WO2006126312A1 - Medical instrument using photocatalyst - Google Patents

Medical instrument using photocatalyst Download PDF

Info

Publication number
WO2006126312A1
WO2006126312A1 PCT/JP2006/302450 JP2006302450W WO2006126312A1 WO 2006126312 A1 WO2006126312 A1 WO 2006126312A1 JP 2006302450 W JP2006302450 W JP 2006302450W WO 2006126312 A1 WO2006126312 A1 WO 2006126312A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
medical device
photocatalyst
plate
infection
Prior art date
Application number
PCT/JP2006/302450
Other languages
French (fr)
Japanese (ja)
Inventor
Wook-Cheol Kim
Yoshinobu Oka
Original Assignee
Wook-Cheol Kim
Yoshinobu Oka
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wook-Cheol Kim, Yoshinobu Oka filed Critical Wook-Cheol Kim
Priority to JP2007517729A priority Critical patent/JPWO2006126312A1/en
Publication of WO2006126312A1 publication Critical patent/WO2006126312A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32

Definitions

  • the present invention relates to a medical device used in contact with the body or a body, and a covering material applied to such a medical device. More particularly, the present invention relates to a medical device and a covering material for a medical device effective for prevention and treatment of infectious diseases.
  • antibiotics are often administered in parallel with external fixation treatment, but as is evident from the emergence of multidrug-resistant bacteria such as MRSA, there is a risk of the appearance of resistant bacteria in the treatment with drugs. Will always follow.
  • Patent Document 1 JP-A-7-102678
  • Patent Document 2 JP 2003-260134 A
  • the present invention has been made in consideration of the above-described problems, and is a medical device that can effectively prevent infection, which is implanted in a mammalian body or with a mammalian body. It is an object of the present invention to provide a medical device excellent in safety and the like that can be used in contact with it and a coating material for the medical device.
  • the present invention relates to a medical device that is used by implanting a part or all of it in the body of a mammal or contacting it with the body of a mammal.
  • the present invention relates to a medical device in which a titanium oxide photocatalyst film is formed on at least a part of a titanium surface without a boundary surface.
  • a photocatalytic film is formed on a titanium substrate by applying a titanium oxide photocatalyst on the titanium substrate, the interface between the coating film and the substrate is clear and easily peeled off.
  • the titanium oxide photocatalyst film is deposited on the titanium without any boundary surface by treating the surface of the titanium with the present invention. not being used. Therefore, it is excellent in durability, and the photocatalyst film is peeled off and the wrinkle remaining in the body is small.
  • metal allergies other than titanium allergies should not be considered when used in living organisms. Titanium and titanium oxide have excellent biocompatibility and high chemical stability, and are therefore very suitable for use in living organisms.
  • the titanium oxide photocatalyst film on the surface of the medical device is irradiated with light, active oxygen species are generated and bacteria attached to the film are decomposed, so that a sterilizing effect is obtained.
  • the anti-fouling effect such as scab adhesion can be expected by the photocatalytic hydrophilization reaction, so the infection prevention effect is higher.
  • the antibacterial activity by the photocatalyst is thought to be based on the organic matter decomposition activity of titanium oxide. Catalytic action is considered to be a bactericidal effect due to the bacteriostatic effect that loses the ability to grow and is difficult to see the difference depending on the bacterial species. Since the medical device according to the present invention does not use antibiotics, there is no need to worry about the emergence of resistant bacteria, and it can be used with peace of mind for patients with low immune functions, such as children and the elderly.
  • the titanium oxide photocatalyst generally reacts with light having a wavelength of 380 ° or less, a patient to whom the medical device according to the present invention is applied can prevent and treat infection by exposing the affected area to sunlight. it can.
  • black light is used, the bactericidal effect can be obtained by local irradiation for about 30 minutes.
  • the effect can be expected even after long-term exposure to fluorescent lamps.
  • treatment can be performed more easily by using titanium oxide that can exhibit a photocatalytic function even in visible light (wavelength range: about 400 ⁇ ! To 800 nm). Visible light is emitted not only from the sun, but also from various types of lighting.
  • a visible light responsive titanium oxide photocatalyst By using a visible light responsive titanium oxide photocatalyst, it is possible to treat highly infected with room light without exposing the affected area to sunlight or black light. A preventive effect can be obtained.
  • using a titanium oxide photocatalyst that is also active in visible light makes the therapeutic effect more effective when treating infectious diseases using sunlight. .
  • visible light is harmless than ultraviolet light, the safety of treatment can be further enhanced by using a visible light responsive titanium oxide photocatalyst.
  • a metal material such as a pin or a sleeve used by being inserted into the body (used for trauma treatment such as a fracture or leg extension), a wound surface, etc.
  • dressing material wound dressing material for covering the skin.
  • the present invention is also a titanium covering material for covering at least a part of a medical device used by embedding a part or all of the body in a mammalian body or contacting the mammalian body with a photocatalytic film.
  • the present invention also relates to a coating material in which an oxide titanium photocatalyst coating is formed on at least a part of the coating material surface without a boundary surface.
  • the covering material according to the present invention By using the covering material according to the present invention, infection can be prevented and treated using an existing medical device. If mechanical strength is required and the desired strength cannot be obtained with titanium alone, infection can be prevented while securing the required strength by using the coating material according to the present invention. be able to.
  • external fixation pins or wires used for the lower limbs are the force that requires mechanical strength. It is also possible to prevent infection by using a pin or wire made of 6A ⁇ 4V titanium alloy and covering the part where they pass through the soft tissue with the coating material according to the present invention formed in a cylindrical shape. It is.
  • the medical device and the covering material of the present invention are effective for the prevention and treatment of infectious diseases. In addition, it has excellent safety and durability, and there is no worry about the occurrence of resistant bacteria, so it can be used safely in living organisms.
  • FIG. 1 is a graph showing the antibacterial action of acid-titanium photocatalyst (10 5 MRSA)
  • FIG. 3 is a graph showing the antibacterial action of acid-titanium photocatalyst (10 5 Pseudomonas aeruginosa)
  • FIG. 4 is a graph showing the relationship between irradiation distance and ultraviolet intensity
  • the titanium oxide photocatalyst coating is formed on the titanium surface without a boundary surface when the surface treatment is performed on titanium that is not obtained by applying a titanium oxide photocatalyst on titanium.
  • This refers to an oxide-titanium photocatalyst film formed on the surface, and can be produced, for example, by the method disclosed in Japanese Patent No. 337 0290.
  • Titanystar registered trademark of Yild Co., Ltd.
  • the titanium constituting the surface of the medical device or the covering material of the present invention is 95% or more, preferably 99% or more of pure titanium, which is not a titanium alloy.
  • the medical device according to the present invention may be composed entirely of titanium force, or the inside may be made of other material forces and only the surface layer portion may be made of titanium.
  • the surface of the medical device according to the present invention is formed of titanium at least at a portion in contact with the living tissue.
  • the medical device to be used by being partially embedded in the body at least of the portion protruding the skin surface force.
  • the part located near the skin surface is made of titanium. More preferred is a medical device in which the entire surface is made of titanium.
  • the titanium oxide photocatalyst film on the titanium surface may be formed only in a portion necessary for preventing infection or the titanium surface. It may be formed in all.
  • the part necessary to prevent infection is, for example, a pin or wire for external fixation, which part passes through soft tissue or part through skin (out of parts located inside or outside the skin). , Part near the skin surface). More preferred is a medical device / coating material in which a photocatalytic film is formed on the entire titanium surface.
  • pins used for external fixation in orthopedic surgery 'pinner' half pins titanium beads for use in wound creation, non-woven fabric for covering the wound surface, mesh-like Examples include dressing materials and implants such as artificial joints. These will be explained in more detail below.
  • Injuries such as broken bones and leg extension are often treated using external fixation, and fractures are generally treated by percutaneous pinning.
  • the most common is infection at the pin insertion site. Bones and soft tissue pierced pins appear on the skin surface, so that bacteria such as resident bacteria can easily settle, and the infectious state is caused by stimulation of surrounding soft tissue or the presence of necrotic tissue. .
  • the presence of foreign bodies on the skin surface is a condition that is not always helpful when infections occur. In fact, infections can occur at a frequency of 70-80%, including minor ones.
  • the area around the pin is cleaned and antibiotics are administered! /, But if it does not respond to these treatments, the pin itself must be removed.
  • the pin and wire used for the upper limb which may be relatively low in strength, can be obtained by using the pin and wire according to the present invention formed entirely of titanium in place of the pin and wire currently used. Good.
  • pins and wires made of stainless steel or titanium alloy are used for those that require a certain level of strength, such as pins and wires used in the lower limbs. Only the necessary parts can be covered with the covering material according to the present invention.
  • an acid-titanium photocatalyst film on the surface of titanium that has been processed into a non-woven fabric or mesh, it can be used as a wound dressing (dressing material). Can prevent and treat infections.
  • chronic osteomyelitis is a very refractory disease, and even if surgery is performed, several surgical treatments and long-term treatment are required.
  • a titanium mesh with a titanium oxide photocatalyst coating on the surface and a titanium non-woven fabric are brought into close contact with the wound surface and irradiated with UV light for a certain period of time (visible light response type
  • UV light response type In the case of using a titanium oxide photocatalyst, it is possible to treat infection by irradiation with visible light.
  • the film material in order to stick and fix each of the above titanium materials ⁇ iij surface Z To maintain a moderately moist environment Z To prevent the entry of new bacteria from the outside of the water, etc.
  • a film material that transmits light wavelength light that can activate the photocatalyst
  • the photocatalyst can be activated without any problem, which is preferable.
  • the transmittance of ultraviolet light visible light in the case of a visible light responsive type
  • a transparent film is used.
  • Adding a photocatalytic function to an implant such as a hip prosthesis or knee prosthesis reduces the chance of the implant being contaminated during the procedure and consequently reduces the infection rate.
  • Surfaces around the sliding surfaces of joints, fracture fixing materials such as plates, screws, and nails, vertebral body spacers for spinal surgery, and instrumentation materials were formed with titanium with an acid-titanium photocatalytic coating.
  • ultraviolet light visible light when visible light-responsive titanium oxide photocatalyst is used
  • ultraviolet light or visible light
  • the antibacterial effect was examined using the bacterial count counting film adhesion method.
  • a plate-like titastar (Titanystar registered trademark) M-to-C (manufactured by Yale Co., Ltd.) was used.
  • the titanium star is manufactured by surface-treating pure titanium, and a titanium oxide photocatalyst film is formed on the pure titanium surface without a boundary surface. An untreated pure titanium plate was used for comparison.
  • Titanium oxide photocatalyst plate (Titastar MI-C)
  • Bacterial fluid MRSA adjusted to 10 5 CFU
  • One pure titanium plate and one photocatalyst plate washed with alcohol and sterilized by pre-irradiation for 1 hour were arranged on a petri dish, and 0.2 ml of the bacterial solution was dropped in the center.
  • the upper and lower sides of the plate were covered with LDPE (low density polyethylene) film to prevent the bacterial solution from drying. Irradiation was performed from above 3 cm with a 15 W black light (ultraviolet intensity of the plate surface: l.lmWZcm 2 ), and the petri dish was allowed to stand at a temperature of 25 degrees.
  • the photocatalyst plate almost killed bacteria on its surface in 60 minutes when irradiated with ultraviolet light, and the bacteria became undetectable in 120 minutes. At half an hour, bacteria were increasing again. From this result, it was found that light irradiation is necessary for the medical device and the covering material according to the present invention to exhibit the antibacterial effect effectively.
  • Table 9 summarizes the UV intensity on the plate surface and the survival rate of the bacteria.
  • UV intensity of sunlight is 2-3 mWZcnT in summer, if a 40 W black light is used, if the distance of 50 mm or more is opened, the patient will be treated without irradiating the patient with UV or more than sunlight. I was able to do what I could do.
  • Model 1 was created, and on the day of the day, 40W of black light was irradiated for 5 days at a distance of 5cm vertically.
  • the UV intensity corresponds to about 3mWZcm 2 on the skin surface, which corresponds to the intensity of ultraviolet rays outdoors in summer.
  • model 2 a model in which a pin made of titastar MI-C is inserted into the right lower leg of the rat and a pin made of pure titanium (no treatment) is inserted into the left lower leg vertically through the bone (hereinafter referred to as model 2). And irradiated with ultraviolet rays under the same conditions.
  • Model 3 a model created in the same way as Model 1 (hereinafter referred to as Model 3) was raised for 1 month, 2 months, and 3 months, and these histological studies were conducted after the period.
  • model 1 and model 2 rats were euthanized, and histological examination of the tissues surrounding the pins was performed.
  • model 3 examined the effects on surrounding tissues after long-term implantation, such as 1 month, 2 months, and 3 months, but even in this case, only the infiltration of inflammatory cells into the surroundings revealed an obvious necrosis image, etc. The negative effects on the surrounding tissues were unseen.

Abstract

It is intended to provide a highly safe medical instrument, by which infection can be effectively prevented and which can be used by embedding in a mammalian body or bringing into contact with a mammalian body, and a coating material for medical instruments. A medical instrument which is to be used by partly or entirely embedding in a mammalian body or bringing into contact with a mammalian body, wherein a part or the whole surface thereof is made of titanium and a titanium oxide photocatalyst film is formed on at least a part of the titanium surface with no boundary.

Description

明 細 書  Specification
光触媒を用いた医療用具  Medical device using photocatalyst
技術分野  Technical field
[0001] 本発明は、体内あるいは体に接触させて用いられる医療用具、及びそのような医療 用具に適用する被覆材に関する。より詳しくは、感染症の予防'治療に有効な医療用 具及び医療用具用被覆材に関する。  [0001] The present invention relates to a medical device used in contact with the body or a body, and a covering material applied to such a medical device. More particularly, the present invention relates to a medical device and a covering material for a medical device effective for prevention and treatment of infectious diseases.
背景技術  Background art
[0002] 医療分野、特に、整形外科の領域では、手術治療で人工物を用いる局面が多いが ため、ひとたび感染を起こすとその治療は非常に難渋する。特に無菌領域である骨、 関節の感染は、非常に大きな問題となっている。整形外科では、治療のために金属 製の医療用具を体内に適用することも多いが、感染により細菌が金属表面にバイオ フィルムを形成するため、抗生物質の効果が得られにくぐ医療用具の抜去が必要と なり、治療を中断せざるを得ないこともある。特に、金属ピンを体外から刺入して行う 経皮鋼線固定や創外固定術では、体表面に露出した金属への皮膚常在菌の付着 (c ◦Ionization)が避けられないため感染率が高ぐ整形外科において、ピン感染は重要 な合併症となっている。  [0002] In the medical field, particularly in the field of orthopedics, there are many situations in which artifacts are used in surgical treatment, so once infection occurs, the treatment is very difficult. In particular, infection of bones and joints, which are sterile areas, is a very big problem. In orthopedics, metal medical devices are often applied to the body for treatment, but because bacteria form a biofilm on the metal surface due to infection, removal of medical devices that are difficult to obtain the effects of antibiotics is difficult. May be necessary and treatment may be interrupted. In particular, in the case of percutaneous steel wire fixation or external fixation performed by inserting a metal pin from outside the body, adherence of skin resident bacteria (c ◦Ionization) to the metal exposed on the body surface is unavoidable. In orthopedic surgeries, pin infection is an important complication.
[0003] このため、感染の予防が肝心となる力 ピンケアの徹底、洗浄によっても感染を完 全に防ぐことは難しい。また、創外固定治療と平行して抗生物質の投与が行われるこ とも多いが、 MRSAに代表される多剤耐性菌の出現からも明らかなように、薬剤による 治療には耐性菌出現の危険が常につきまとう。  [0003] For this reason, it is difficult to prevent infection completely by thorough pin care and cleaning. In addition, antibiotics are often administered in parallel with external fixation treatment, but as is evident from the emergence of multidrug-resistant bacteria such as MRSA, there is a risk of the appearance of resistant bacteria in the treatment with drugs. Will always follow.
[0004] また、抗菌金属材料を用いた感染予防の試みもなされているが、抗生物質、消毒 剤や銀の添加で作用を発揮しているため、安全性やコスト面から問題が残る。  [0004] In addition, attempts have been made to prevent infection using an antibacterial metal material, but there are still problems in terms of safety and cost because the effect is exhibited by the addition of antibiotics, disinfectants and silver.
[0005] 一方、光触媒を利用して院内感染を防ごうとする試みがある。し力 現在は、床、窓 枠等の病院施設自体や、輸液時に用いる力-ユーラ部の内面等が対象となっており 、体内あるいは体に直接接触させて用いる医療用具への適用は報告されて 、な 、。 創外固定ピンのように、体内に直接用いる医療用具に適用するためには、安全性、 耐久性等、様々な問題をクリアする必要がある。 特許文献 1 :特開平 7— 102678号公報 On the other hand, there is an attempt to prevent nosocomial infection using a photocatalyst. Currently, it covers the hospital facilities themselves such as the floor and window frames, and the force used during infusion-the inner surface of the Eulera, etc., and its application to medical devices that are used directly in contact with the body or body has been reported. ,,,. In order to apply to medical devices that are used directly in the body, such as external fixation pins, it is necessary to clear various problems such as safety and durability. Patent Document 1: JP-A-7-102678
特許文献 2：特開 2003 - 260134号公報  Patent Document 2: JP 2003-260134 A
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明は、以上のような問題点を考慮してなされたものであり、感染を有効に防ぐこ とができる医療用具であって、哺乳類の体内に埋め込んで、あるいは哺乳類の体と 接触させて用いることができる安全性等に優れた医療用具及び医療用具用の被覆 材を提供することを課題とする。 [0006] The present invention has been made in consideration of the above-described problems, and is a medical device that can effectively prevent infection, which is implanted in a mammalian body or with a mammalian body. It is an object of the present invention to provide a medical device excellent in safety and the like that can be used in contact with it and a coating material for the medical device.
課題を解決するための手段  Means for solving the problem
[0007] 本発明は、哺乳類の体内に一部あるいは全部を埋め込んで、あるいは哺乳類の体 に接触させて用いられる医療用具であって、表面の一部あるいは全部がチタンで形 成され、さらに該チタン表面の少なくとも一部に酸ィ匕チタン光触媒被膜が境界面なく 形成されている医療用具に関する。  [0007] The present invention relates to a medical device that is used by implanting a part or all of it in the body of a mammal or contacting it with the body of a mammal. The present invention relates to a medical device in which a titanium oxide photocatalyst film is formed on at least a part of a titanium surface without a boundary surface.
[0008] チタン基材上に酸化チタン光触媒を塗布することによってチタン基材上に光触媒 被膜を形成させた場合は、コーティング被膜と基材との境界面が明確で剥がれやす ぐまた、ノインダーゃ分散剤などの使用が不可欠である力 本発明では、チタンを 表面処理することによって、酸ィ匕チタン光触媒被膜をチタンに境界面なく析出させて いるため、剥離の恐れがなぐノインダーゃ分散剤も一切使用されていない。そのた め、耐久性に優れるとともに、光触媒被膜が剥離して体内に残存する虡も小さい。さ らに、バインダーや分散剤を使用していないため、生体に用いてもチタンアレルギー 以外の金属アレルギーを考慮しなくてょ 、。チタン及び酸ィ匕チタンは生体親和性に 優れィ匕学的安定性が高 、ため、生体に用いるのに非常に適して 、る。  [0008] When a photocatalytic film is formed on a titanium substrate by applying a titanium oxide photocatalyst on the titanium substrate, the interface between the coating film and the substrate is clear and easily peeled off. In this invention, the titanium oxide photocatalyst film is deposited on the titanium without any boundary surface by treating the surface of the titanium with the present invention. not being used. Therefore, it is excellent in durability, and the photocatalyst film is peeled off and the wrinkle remaining in the body is small. In addition, since no binders or dispersants are used, metal allergies other than titanium allergies should not be considered when used in living organisms. Titanium and titanium oxide have excellent biocompatibility and high chemical stability, and are therefore very suitable for use in living organisms.
[0009] 医療用具表面の酸化チタン光触媒被膜に光を照射すると、活性酸素種が発生し、 被膜に付着した細菌が分解されるため、殺菌効果が得られる。また、光触媒親水化 反応により痂皮の付着などの防汚効果が期待できるため、感染予防効果がより高ま る。光触媒による抗菌活性は、酸ィ匕チタンの有機物分解活性に基づいていると考え られる。触媒作用は、細菌種による差が見られにくぐ増殖能を失う静菌効果でなぐ 殺菌効果と考えられる。 本発明に係る医療用具は抗生物質を用いないため耐性菌が出現する心配がなぐ 小児や老人等、免疫機能が低い患者にも安心して使用することができる。 [0009] When the titanium oxide photocatalyst film on the surface of the medical device is irradiated with light, active oxygen species are generated and bacteria attached to the film are decomposed, so that a sterilizing effect is obtained. In addition, the anti-fouling effect such as scab adhesion can be expected by the photocatalytic hydrophilization reaction, so the infection prevention effect is higher. The antibacterial activity by the photocatalyst is thought to be based on the organic matter decomposition activity of titanium oxide. Catalytic action is considered to be a bactericidal effect due to the bacteriostatic effect that loses the ability to grow and is difficult to see the difference depending on the bacterial species. Since the medical device according to the present invention does not use antibiotics, there is no need to worry about the emergence of resistant bacteria, and it can be used with peace of mind for patients with low immune functions, such as children and the elderly.
[0010] 酸ィ匕チタン光触媒は一般に 380應以下の波長の光に反応するため、本発明に係る 医療用具を適用した患者は、患部を太陽光にさらすことで感染を予防'治療すること ができる。ブラックライトを用いる場合は、局所に約 30分照射すれば殺菌効果が得ら れる。また、蛍光灯からも微量の紫外線が出ているので、長時間の蛍光灯への暴露 でも効果が期待できる。  [0010] Since the titanium oxide photocatalyst generally reacts with light having a wavelength of 380 ° or less, a patient to whom the medical device according to the present invention is applied can prevent and treat infection by exposing the affected area to sunlight. it can. When black light is used, the bactericidal effect can be obtained by local irradiation for about 30 minutes. In addition, since a very small amount of ultraviolet light is emitted from fluorescent lamps, the effect can be expected even after long-term exposure to fluorescent lamps.
さらに、可視光 (波長範囲:約 400ηπ！〜 800nm)でも光触媒機能を発現できる酸化チ タンを用いることにより、治療をより簡便に行うことができる。可視光線は、太陽だけで なく様々な照明から発せられているため、可視光応答型酸化チタン光触媒を用いる ことにより、患部を太陽光やブラックライトに曝さなくても、室内光により高い感染治療 •予防効果を得ることができる。また、太陽光の 90%以上は可視光であるため、可視 光にも活性な酸化チタン光触媒を用いることにより、太陽光を利用して感染症を治療 する際の治療効果がより高効率になる。また、可視光は紫外光より無害であるため、 可視光応答型酸ィ匕チタン光触媒を用いることにより、治療の安全性をより高めること ができる。  Furthermore, treatment can be performed more easily by using titanium oxide that can exhibit a photocatalytic function even in visible light (wavelength range: about 400 ηπ! To 800 nm). Visible light is emitted not only from the sun, but also from various types of lighting. By using a visible light responsive titanium oxide photocatalyst, it is possible to treat highly infected with room light without exposing the affected area to sunlight or black light. A preventive effect can be obtained. In addition, since more than 90% of sunlight is visible light, using a titanium oxide photocatalyst that is also active in visible light makes the therapeutic effect more effective when treating infectious diseases using sunlight. . In addition, since visible light is harmless than ultraviolet light, the safety of treatment can be further enhanced by using a visible light responsive titanium oxide photocatalyst.
[0011] 本発明に係る医療用具の代表例として、体内に挿入して用いられるピンあるいはヮ ィャ一等の金属材料 (骨折などの外傷治療や脚延長術などに使用される)や、創面 を覆うためのドレッシング材 (創傷被覆材)などを挙げることができる。  [0011] As a representative example of the medical device according to the present invention, a metal material such as a pin or a sleeve used by being inserted into the body (used for trauma treatment such as a fracture or leg extension), a wound surface, etc. And dressing material (wound dressing material) for covering the skin.
[0012] 本発明はまた、哺乳類の体内に一部あるいは全部を埋め込んで、あるいは哺乳類 の体に接触させて用いられる医療用具の少なくとも一部を光触媒被膜で覆うための チタン製被覆材であって、該被覆材表面の少なくとも一部に酸ィ匕チタン光触媒被膜 が境界面なく形成されて ヽる被覆材に関する。  [0012] The present invention is also a titanium covering material for covering at least a part of a medical device used by embedding a part or all of the body in a mammalian body or contacting the mammalian body with a photocatalytic film. The present invention also relates to a coating material in which an oxide titanium photocatalyst coating is formed on at least a part of the coating material surface without a boundary surface.
[0013] 本発明に係る被覆材を用いることにより、既存の医療用具を利用しつつ感染を予防 •治療することができる。また、力学的強度が必要とされ、チタンのみでは所望の強度 が得られない場合は、本発明に係る被覆材を利用することによって、必要とされる強 度を確保しつつ、感染を予防することができる。例えば、下肢に用いる創外固定ピン あるいはワイヤーなどは、力学的強度が必要とされる力 現在流通しているステンレス や 6A卜 4Vチタン合金製のピンもしくはワイヤーを利用し、これらが軟部組織を通過す る部分だけに、筒状に形成した本発明に係る被覆材を被せて感染症の予防を図るこ とも可能である。 [0013] By using the covering material according to the present invention, infection can be prevented and treated using an existing medical device. If mechanical strength is required and the desired strength cannot be obtained with titanium alone, infection can be prevented while securing the required strength by using the coating material according to the present invention. be able to. For example, external fixation pins or wires used for the lower limbs are the force that requires mechanical strength. It is also possible to prevent infection by using a pin or wire made of 6A 卜 4V titanium alloy and covering the part where they pass through the soft tissue with the coating material according to the present invention formed in a cylindrical shape. It is.
発明の効果  The invention's effect
[0014] 本発明の医療用具及び被覆材は、感染症の予防'治療に有効である。また、安全 性、耐久性に優れ、耐性菌発生の心配もないため、生体に安全に用いることができる 図面の簡単な説明  [0014] The medical device and the covering material of the present invention are effective for the prevention and treatment of infectious diseases. In addition, it has excellent safety and durability, and there is no worry about the occurrence of resistant bacteria, so it can be used safely in living organisms.
[0015] [図 1]酸ィ匕チタン光触媒の抗菌作用を示すグラフである（105MRSA) [0015] FIG. 1 is a graph showing the antibacterial action of acid-titanium photocatalyst (10 5 MRSA)
[図 2]酸ィ匕チタン光触媒の抗菌作用を示すグラフである（104MRSA) [Fig. 2] Graph showing the antibacterial action of acid-titanium photocatalyst (10 4 MRSA)
[図 3]酸ィ匕チタン光触媒の抗菌作用を示すグラフである（105緑膿菌） FIG. 3 is a graph showing the antibacterial action of acid-titanium photocatalyst (10 5 Pseudomonas aeruginosa)
[図 4]照射距離と紫外線強度の関係を示すグラフである  FIG. 4 is a graph showing the relationship between irradiation distance and ultraviolet intensity
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0016] チタン表面に酸ィ匕チタン光触媒被膜が境界面なく形成されているとは、チタン上に 酸化チタン光触媒を塗布して得られたものではなぐチタンを表面処理することによつ てチタン表面に酸ィ匕チタン光触媒被膜を形成させたものを指し、例えば特許第 337 0290号に開示された方法で製造することができる。本発明の医療用具および被覆 材の材質に好適なものとして、有限会社ィールド社の Titanystar (登録商標）を挙げる ことができる。本発明の医療用具表面あるいは被覆材を構成するチタンは、チタン合 金ではなぐ 95%以上、好ましくは 99%以上の純チタンである。  [0016] The titanium oxide photocatalyst coating is formed on the titanium surface without a boundary surface when the surface treatment is performed on titanium that is not obtained by applying a titanium oxide photocatalyst on titanium. This refers to an oxide-titanium photocatalyst film formed on the surface, and can be produced, for example, by the method disclosed in Japanese Patent No. 337 0290. As a material suitable for the medical device and the covering material of the present invention, Titanystar (registered trademark) of Yild Co., Ltd. can be mentioned. The titanium constituting the surface of the medical device or the covering material of the present invention is 95% or more, preferably 99% or more of pure titanium, which is not a titanium alloy.
[0017] 本発明に係る医療用具は、全てチタン力 構成されていてもよぐあるいは内部が 他の材質力もなり表層部のみがチタン製であってもよい。また、本発明に係る医療用 具の表面は、少なくとも生体組織と接する部分がチタンで形成されており、体内に一 部埋め込んで用いられる医療用具に関しては、さらに皮膚表面力 突出する部分の うち少なくとも皮膚表面付近に位置する部分がチタンで形成されて 、る。より好まし ヽ のは表面全てがチタンで形成されて 、る医療用具である。  [0017] The medical device according to the present invention may be composed entirely of titanium force, or the inside may be made of other material forces and only the surface layer portion may be made of titanium. In addition, the surface of the medical device according to the present invention is formed of titanium at least at a portion in contact with the living tissue. Regarding the medical device to be used by being partially embedded in the body, at least of the portion protruding the skin surface force. The part located near the skin surface is made of titanium. More preferred is a medical device in which the entire surface is made of titanium.
[0018] 本発明に係る医療用具及び被覆材において、チタン表面の酸ィ匕チタン光触媒被 膜は、感染を防ぐのに必要な部分のみに形成されていてもよぐあるいはチタン表面 全てに形成されていてもよい。感染を防ぐのに必要な部分とは、例えば、創外固定用 のピンやワイヤーで言えば、これらが軟部組織を通過する部分や皮膚を通過する部 分 (皮膚の内外に位置する部分のうち、皮膚表面付近の部分)である。より好ましい のはチタン表面全てに光触媒被膜が形成されて!ヽる医療用具 ·被覆材である。 [0018] In the medical device and the covering material according to the present invention, the titanium oxide photocatalyst film on the titanium surface may be formed only in a portion necessary for preventing infection or the titanium surface. It may be formed in all. The part necessary to prevent infection is, for example, a pin or wire for external fixation, which part passes through soft tissue or part through skin (out of parts located inside or outside the skin). , Part near the skin surface). More preferred is a medical device / coating material in which a photocatalytic film is formed on the entire titanium surface.
[0019] 本発明に係る医療用具の具体例として、整形外科で創外固定に用いられるピン 'ヮ ィヤー'ハーフピン、褥創に用いるためのチタンビーズ、創面を覆うための不織布、メ ッシュ状のドレッシング材、人工関節などのインプラントなどを挙げることができる。以 下これらをより具体的に説明する。  [0019] As specific examples of the medical device according to the present invention, pins used for external fixation in orthopedic surgery 'pinner' half pins, titanium beads for use in wound creation, non-woven fabric for covering the wound surface, mesh-like Examples include dressing materials and implants such as artificial joints. These will be explained in more detail below.
[0020] ピン、ワイヤー、ノヽーフピン  [0020] Pins, wires, noise pins
骨折などの外傷治療や、脚延長術などは創外固定を用いて治療することが多ぐま た、経皮ピンユングにより骨折治療がなされることも一般的である。これらの合併症で もっとも頻度が高 、ものがピン刺入部の感染である。骨ゃ軟部組織に刺さったピンが 皮膚表面に出ていることで容易に常在菌をはじめとする細菌が定着し、周囲の軟部 組織の刺激や壊死組織の存在などにより感染状態が惹起される。皮膚表面に異物 が常に存在するということは感染がいつ起こってもお力しくない状態であり、実際 mino rなものも含めると感染は 70〜80%の頻度で起こり得る。現在はピン周囲の清浄化、 抗生物質の投与で対処して!/、るが、これらの治療に反応しな 、場合はピンそのもの を抜去せざるを得ない。抜去すると固定装置の強度は落ち、ゆるみの原因となり、治 療成績は不良となる。このようなピン、ワイヤーに本発明を適用することにより、感染を 予防することができる。上肢に用いられるピン、ワイヤーのように比較的強度が小さく てよいものは、現在使用されているピン、ワイヤーの代わりに、全体がチタンで形成さ れた本発明に係るピン、ワイヤーを用いればよい。一方、チタンは比較的硬度の小さ い金属であるため、下肢に用いられるピン、ワイヤーのように、有る程度強度が必要と されるものについては、ステンレスやチタン合金製のピン'ワイヤーを使用し、必要部 分のみを、本発明に係る被覆材で覆って使用することができる。  Injuries such as broken bones and leg extension are often treated using external fixation, and fractures are generally treated by percutaneous pinning. Of these complications, the most common is infection at the pin insertion site. Bones and soft tissue pierced pins appear on the skin surface, so that bacteria such as resident bacteria can easily settle, and the infectious state is caused by stimulation of surrounding soft tissue or the presence of necrotic tissue. . The presence of foreign bodies on the skin surface is a condition that is not always helpful when infections occur. In fact, infections can occur at a frequency of 70-80%, including minor ones. Currently, the area around the pin is cleaned and antibiotics are administered! /, But if it does not respond to these treatments, the pin itself must be removed. If it is removed, the strength of the fixing device will drop, causing loosening and poor treatment results. Infection can be prevented by applying the present invention to such pins and wires. The pin and wire used for the upper limb, which may be relatively low in strength, can be obtained by using the pin and wire according to the present invention formed entirely of titanium in place of the pin and wire currently used. Good. On the other hand, since titanium is a metal with relatively low hardness, pins and wires made of stainless steel or titanium alloy are used for those that require a certain level of strength, such as pins and wires used in the lower limbs. Only the necessary parts can be covered with the covering material according to the present invention.
[0021] ドレッシング材、チタンビーズ  [0021] Dressing material, titanium beads
不織布状あるいはメッシュ状に加工したチタンの表面に酸ィ匕チタン光触媒被膜を 形成させて、褥創 '創傷用の被覆材 (ドレッシング材)として使用することにより、創の 感染を予防 ·治療することができる。 By forming an acid-titanium photocatalyst film on the surface of titanium that has been processed into a non-woven fabric or mesh, it can be used as a wound dressing (dressing material). Can prevent and treat infections.
とりわけ、広範囲褥創ゃ慢性骨髄炎は現在も非常に難治性の疾患であり、手術を 行う場合も数回の手術治療と長期間の療養を必要とする。このような組織欠損を伴う 感染に対して、表面に酸ィ匕チタン光触媒被膜を形成させたチタン製メッシュ、チタン 製不織布を徒手的に創表面に密着させ、一定時間紫外線照射 (可視光応答型酸ィ匕 チタン光触媒を用いた場合は可視光照射)することにより、感染を治療することが可 能である。  In particular, chronic osteomyelitis is a very refractory disease, and even if surgery is performed, several surgical treatments and long-term treatment are required. For infections involving such tissue defects, a titanium mesh with a titanium oxide photocatalyst coating on the surface and a titanium non-woven fabric are brought into close contact with the wound surface and irradiated with UV light for a certain period of time (visible light response type In the case of using a titanium oxide photocatalyst, it is possible to treat infection by irradiation with visible light.
さらに、創が深くスぺーサ一としての役割を持たせた ヽ場合には現在用いられて ヽ るセメントビーズではなぐ酸ィ匕チタン光触媒被膜を有する穴あきチタンビーズを用い ることによって耐性菌の心配をせず、感染治療を行うことができる。  Furthermore, when the wound is deep and has a role as a spacer, the use of perforated titanium beads with a titanium photocatalyst coating that is not used in the cement beads currently used can prevent Infection treatment can be performed without worry.
なお、上記各チタン材^ iij面に貼付固定するため Z適度な湿潤環境を維持するた め Z外部からの新たな細菌'水分等の侵入を防止するため、等の目的で、チタン材 の背面 (創傷と直接接触しないほうの面）にフィルム材を設ける場合、使用する光触 媒に対応した光 (光触媒を活性ィ匕できる波長の光）を透過するフィルム材を用いれば 、フィルム材を外すことなく光触媒を活性化させることができ、好ましい。例えば、紫外 光（可視光応答型の場合は可視光）の透過率が高!、透明フィルムを用いる。  In addition, in order to stick and fix each of the above titanium materials ^ iij surface Z To maintain a moderately moist environment Z To prevent the entry of new bacteria from the outside of the water, etc. When the film material is provided on the surface that is not in direct contact with the wound, remove the film material by using a film material that transmits light (wavelength light that can activate the photocatalyst) corresponding to the photocatalyst used. The photocatalyst can be activated without any problem, which is preferable. For example, the transmittance of ultraviolet light (visible light in the case of a visible light responsive type) is high, and a transparent film is used.
また、酸ィ匕チタン光触媒被膜にハイドロキシアパタイトを付着させ、細菌や毒素を光 が当たらな 、時に吸着させてぉ 、て照射時に分解すると 、う方法で治療を行うことも できる。  In addition, when hydroxyapatite is attached to the titanium oxide photocatalyst film, and bacteria and toxins are sometimes adsorbed when exposed to light and then decomposed upon irradiation, treatment can be performed by the method.
インプラント  Implant
人工股関節、人工膝関節などのインプラントに光触媒機能を付加させると、術中に インプラントが汚染される可能性が減少し、結果的に感染率を減らすことができる。関 節の摺動面周囲やプレートやスクリュー、ネイルなどの骨折内固定材料、脊椎手術 用椎体スぺーサ一、 instrumentation用材料などの表面を酸ィ匕チタン光触媒被膜を有 するチタンで形成した場合、感染を起こした場合にも細 ヽファイバーで紫外線光（可 視光応答型酸化チタン光触媒を用いた場合は可視光)を金属表面まで導入するか 創を解放として紫外線 (あるいは可視光)照射することで内固定材料を抜去せずに感 染症の治療が可能となる。 [0023] 以下、実施例に基づき、本発明をより詳細に説明する。 Adding a photocatalytic function to an implant such as a hip prosthesis or knee prosthesis reduces the chance of the implant being contaminated during the procedure and consequently reduces the infection rate. Surfaces around the sliding surfaces of joints, fracture fixing materials such as plates, screws, and nails, vertebral body spacers for spinal surgery, and instrumentation materials were formed with titanium with an acid-titanium photocatalytic coating. In the case of infection, ultraviolet light (visible light when visible light-responsive titanium oxide photocatalyst is used) is introduced to the metal surface even when infection occurs, or ultraviolet light (or visible light) is irradiated by releasing the wound. This makes it possible to treat infectious diseases without removing the internal fixation material. Hereinafter, the present invention will be described in more detail based on examples.
実施例 1  Example 1
[0024] 感 チ の ^ ί [0024] Feeling of ^ ί
本発明に係る医療用具 ·被覆材の感染予防効果を検証するために、菌数測定フィ ルム密着法を用いてその抗菌効果を検討した。本発明の実験用モデルとして、板状 のチタ-スター (Titanystar登録商標) Mト C (有限会社ィールド製）を用いた。チタ- スターは純チタンを表面処理することによって製造されており、純チタン表面に酸ィ匕 チタン光触媒被膜が境界面なく形成されている。比較には無処理の純チタンプレー トを用いた。  In order to verify the infection-preventing effect of the medical device / coating material according to the present invention, the antibacterial effect was examined using the bacterial count counting film adhesion method. As an experimental model of the present invention, a plate-like titastar (Titanystar registered trademark) M-to-C (manufactured by Yale Co., Ltd.) was used. The titanium star is manufactured by surface-treating pure titanium, and a titanium oxide photocatalyst film is formed on the pure titanium surface without a boundary surface. An untreated pure titanium plate was used for comparison.
[0025] 「菌数測定フィルム密着法」 [0025] “Bacteria count film adhesion method”
試料：酸化チタン光触媒プレート（チタ-スター MI-C)  Sample: Titanium oxide photocatalyst plate (Titastar MI-C)
純チタンプレート（無処理）  Pure titanium plate (no treatment)
形状： 5cm X 5cmの板状（厚さ lmm)  Shape: 5cm X 5cm plate (thickness lmm)
菌液： 105CFU入りに調整した MRSA Bacterial fluid: MRSA adjusted to 10 5 CFU
纖棚  Shelf
アルコール洗净し、プレ照射を 1時間施行して滅菌した純チタンプレート、光触媒プ レートをそれぞれシャーレ上に 1枚ずつ並べ、中央に 0.2mlの菌液を滴下した。 LDPE (low density polyethylene)フィルムで菌液ごとプレート上下を覆い、菌液の乾燥を防 いだ。 15Wのブラックライトで 3cm上方 (プレート表面の紫外線強度 l.lmWZcm2)から 照射を行い、 25度の温度条件下でシャーレを静置した。所定時間だけ紫外線照射を 行い、試料表面の菌液を滅菌生理食塩水で洗浄して洗い出し、希釈した。希釈液の 内 0.1mlを採取し、寒天培地に植菌の上 24時間後のコロニー形成をカウントした。菌 液の採取は 30分、 60分、 120分、 180分後にそれぞれ行った。光を照射せずに同 様の手順を経たものを作成し、回収率が 0. 8〜1. 1の場合を信頼できるデータとし て採用し、各時間につき 6つのシャーレ力もデータを得た (N = 6)。酸化チタン光触 媒プレートも純チタンプレートも置かずに LDPEフィルムで細菌を覆 、、光照射したも のをコントロールとした。 One pure titanium plate and one photocatalyst plate washed with alcohol and sterilized by pre-irradiation for 1 hour were arranged on a petri dish, and 0.2 ml of the bacterial solution was dropped in the center. The upper and lower sides of the plate were covered with LDPE (low density polyethylene) film to prevent the bacterial solution from drying. Irradiation was performed from above 3 cm with a 15 W black light (ultraviolet intensity of the plate surface: l.lmWZcm 2 ), and the petri dish was allowed to stand at a temperature of 25 degrees. Ultraviolet irradiation was performed for a predetermined time, and the bacterial solution on the surface of the sample was washed out with sterilized physiological saline and diluted. 0.1 ml of the diluted solution was collected, and colony formation was counted 24 hours after inoculation on the agar medium. Bacteria were collected at 30, 60, 120 and 180 minutes, respectively. The same procedure was made without irradiating light, and the recovery rate of 0.8 to 1.1 was adopted as reliable data, and data were also obtained for 6 petri dishes for each hour ( N = 6). Bacteria were covered with an LDPE film without a titanium oxide photocatalyst plate or pure titanium plate, and the light irradiated was used as a control.
実験の全結果を表 1に、平均値を表 2及び図 1に示す。表中、初期値とはプレート に滴下時の菌液の CFU値である。 The overall results of the experiment are shown in Table 1, and the average values are shown in Table 2 and Fig. 1. In the table, the initial value is the plate This is the CFU value of the bacterial solution when dripping.
[0026] [表 1] 表 1 15WBLB照射 3cm(1.1 mW/cm!) 10'MRSA [0026] [Table 1] Table 1 15WBLB irradiation 3cm (1.1 mW / cm ! ) 10'MRSA
単位: CFU  Unit: CFU
Figure imgf000010_0001
表 2 平均値（10SMRSA 3cm)
Figure imgf000010_0002
Figure imgf000010_0001
Table 2 Average values (10 S MRSA 3cm)
Figure imgf000010_0002
[0027] 表 2に示すように、酸ィ匕チタン光触媒プレートではその表面の細菌を 10万個以上と いう量にもかかわらず 30分で 1Z4以下に、 60分で 2000個台へと激減し、無処理の純 チタンプレートと明らかな差を示した。この結果から、本発明にかかる医療用具およ び被覆材を用いれば細菌の定着 (colonization)自体が予防でき、感染の発症予防に 有効であることが分力つた。 [0027] As shown in Table 2, on the surface of the titanium oxide photocatalyst plate, the amount of bacteria on the surface was dramatically reduced to 1Z4 or less in 30 minutes and 2000 in 60 minutes, despite the amount of 100,000 or more. It showed a clear difference from the untreated pure titanium plate. From these results, it was found that the use of the medical device and the covering material according to the present invention can prevent bacterial colonization itself and is effective in preventing the onset of infection.
実施例 2  Example 2
[0028] 威 の ^ "2 [0028] Weir ^ "2
菌液として 104CFU入りに調整した MRSAを用い、実施例 1と同じ手順で実験を行つ た。観察は 30分、 60分、 120分後に行った。各時間のデータ数は 6とした (N = 6)。 また、光を照射せず同様の手順で実験を行い、光照射しな力つた場合の光触媒プレ ートの抗菌効果を検討した。全結果を表 3に、平均値を表 4及び図 2に示す。表及び 図中、暗条件'コントロールとは、光触媒プレートも純チタンプレートも置かずに LDP Eフィルムで細菌を覆 、、光照射しな力つたものを指す。 Experiments were performed in the same procedure as in Example 1, using MRSA adjusted to 10 4 CFU as the bacterial solution. Observations were made after 30, 60 and 120 minutes. The number of data at each time was 6 (N = 6). In addition, an experiment was conducted in the same procedure without irradiating light, and the antibacterial effect of the photocatalyst plate when the light was not applied was examined. All results are shown in Table 3, and the average values are shown in Table 4 and FIG. In the table and figure, the dark condition 'control' refers to the one that covered bacteria with an LDP E film without the photocatalyst plate or pure titanium plate, and did not irradiate with light.
[¾2] 表 3 1 5WBLB照射 3cm(1.1 mW/cmり 104MRSA [¾2] Table 3 1 5WBLB irradiation 3cm (1.1 mW / cm 10 4 MRSA
単位： CFU  Unit: CFU
Figure imgf000011_0001
平均値（10'MRSA 3cm)
Figure imgf000011_0001
Average value (10'MRSA 3cm)
Figure imgf000011_0002
表 4に示すように、光触媒プレートは紫外線照射時には 60分でその表面の細菌を ほぼ死滅させ、 120分時には細菌は検出不可能となった力 紫外線を照射しなかつ た場合は 60分時には細菌数半減に留まり、 120分時には、細菌が再び増加してい た。この結果から、本発明にかかる医療用具および被覆材が抗菌効果を有効に発揮 するためには、光照射が必要であることが分力つた。
Figure imgf000011_0002
As shown in Table 4, the photocatalyst plate almost killed bacteria on its surface in 60 minutes when irradiated with ultraviolet light, and the bacteria became undetectable in 120 minutes. At half an hour, bacteria were increasing again. From this result, it was found that light irradiation is necessary for the medical device and the covering material according to the present invention to exhibit the antibacterial effect effectively.
実施例 3 [0031] 威 予防効 の検討 3 Example 3 [0031] Examination of threat prevention 3
ブラックライトの照射位置を 5cm (表面紫外線強度 0.65mW/cm2)および 10cm上方（ 表面紫外線強度 0.40mWZcm2)に変更して、実施例 1と同じ手順で実験を行った。 観察は 30分、 60分、 120、 180分後に行った。各時間のデータ数は 6とした (N = 6) 。全結果を表 5および表 6に、平均値を表 7および表 8に示す。 The experiment was performed in the same procedure as in Example 1, except that the irradiation position of the black light was changed to 5 cm (surface ultraviolet intensity 0.65 mW / cm 2 ) and 10 cm above (surface ultraviolet intensity 0.40 mWZcm 2 ). Observations were made after 30, 60, 120 and 180 minutes. The number of data at each time was 6 (N = 6). All results are shown in Tables 5 and 6, and the average values are shown in Tables 7 and 8.
また、プレート表面の紫外線強度と菌の生存率を表 9にまとめた  Table 9 summarizes the UV intensity on the plate surface and the survival rate of the bacteria.
[0032] [表 3] 表 5 15WBLB照射 5cm(0.65mW/cm2) 105MRSA [0032] [Table 3] Table 5 15WBLB irradiation 5cm (0.65mW / cm 2 ) 10 5 MRSA
単位: CFU  Unit: CFU
30分 初期値 1 2 3 4 5 6 光触媒プレート 130000 70000 25000 52000 24000 41000 50000 純チタンプレート 130000 70000 68000 51000 50000 46000 68000 コントロール 130000 53000 70000 140000 50000 80000 51000  30 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 130000 70000 25000 52000 24000 41000 50000 Pure titanium plate 130000 70000 68000 51000 50000 46000 68000 Control 130000 53000 70000 140000 50000 80000 51000
60分 初期値 1 2 3 4 5 6 光触媒プレート 130000 57000 43000 25000 13000 23000 22000 純チタンプレート 130000 76000 64000 12000 35000 1 1000 13000 コントロール 130000 57000 52000 58000 64000 60000 67000 60 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 130000 57000 43000 25000 13000 23000 22000 Pure titanium plate 130000 76000 64000 12000 35000 1 1000 13000 Control 130000 57000 52000 58000 64000 60000 67000
120分 初期値 1 2 3 4 5 6 光触媒プレート 120000 1 100 8000 4500 2000 3200 3300 純チタンプレート 120000 52000 42000 42000 35000 41000 16000 コントロール 120000 130000 84000 1 10000 84000 120000 96000120 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 120000 1 100 8000 4500 2000 3200 3300 Pure titanium plate 120000 52000 42000 42000 35000 41000 16000 Control 120,000 130000 84000 1 10000 84000 120000 96000
180分 初期値 1 2 3 4 5 6 光触媒プレート 120000く 10 く 10 く 10 <10 く 10 く 10 純チタンプレート 120000 9300 5700 4700 3400 16000 24000 コント口一ル 120000 35000 60000 28000 66000 47000 54000 表 6 15WBLB照射 10cm(0.40mWん m2) 105MRSA 180 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 120000 10 10 10 <10 10 10 Pure titanium plate 120000 9300 5700 4700 3400 16000 24000 10 cm (0.40 mW m 2 ) 10 5 MRSA
単位： CFU  Unit: CFU
30分 初期値 1 2 3 4 5 6 光触媒プレート 190000 100000 1 10000 74000 84000 1 10000 71000 純チタンプレート 190000 130000 85000 1 10000 85000 130000 150000 コン卜口一レ 190000 170000 190000 290000 140000 130000 150000  30 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 190000 100000 1 10000 74000 84000 1 10000 71000 Pure titanium plate 190000 130000 85000 1 10000 85000 130000 150000 Single outlet 190000 170000 190000 290000 140000 130000 150000
60分 初期値 1 2 3 4 5 6 光触媒プレート 190000 93000 62000 34000 56000 75000 89000 純チタンプレート 190000 1 10000 140000 150000 120000 120000 170000 コントローレ 190000 220000 200000 150000 240000 240000 150000 60 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 190000 93000 62000 34000 56000 75000 89000 Pure titanium plate 190000 1 10000 140000 150000 120000 120000 170000 Controller 190000 220000 200000 150000 240000 240000 150000
1 20分 初期値 1 2 3 4 5 6 光触媒プレート 180000 7200 5400 10000 2500 7300 4800 純チタンプレート 180000 98000 100000 1 10000 87000 75000 100000 コント口一ノレ 180000 100000 1 10000 130000 160000 120000 1 100001 20 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 180000 7200 5400 10000 2500 7300 4800 Pure titanium plate 180000 98000 100000 1 10000 87000 75000 100000 Control port 10000 180000 100000 1 10000 130000 160000 120000 1 10000
180分 初期値 1 2 3 4 5 6 光触媒プレート 120000 <10 く 10 く 10 く 10 く 10 く 10 純チタンプレート 120000 88000 94000 71000 75000 66000 100000 コントロール 120000 94000 66000 75000 74000 90000 120000 [0033] [表 4] 表 7 平均値（105MRSA 5cm)
Figure imgf000013_0001
表 8 平均値（105MRSA 10cm)
Figure imgf000013_0002
紫外線強度と菌の生存率 (光触媒プレート 15WBLB照射 105MRSA)
Figure imgf000013_0003
180 minutes Initial value 1 2 3 4 5 6 Photocatalyst plate 120000 <10 10 10 10 10 10 Pure titanium plate 120000 88000 94000 71000 75000 66000 100000 Control 120000 94000 66000 75000 74000 90000 120000 [0033] [Table 4] Table 7 Average (10 5 MRSA 5cm)
Figure imgf000013_0001
Table 8 Average value (10 5 MRSA 10cm)
Figure imgf000013_0002
UV intensity and bacterial viability (photocatalyst plate 15WBLB irradiation 10 5 MRSA)
Figure imgf000013_0003
[0034] 表 9に示すように、ブラックライトとの距離が広がり、光触媒プレート表面の紫外線強 度が小さくなるにつれ、各時間における菌の生存率は高くなり、殺菌効果が緩やかに なることが分力つた。しかし、距離を離しても（紫外線強度が落ちても）全体の傾向は 変わらず、光触媒プレート上の細菌数は 60分以降も確実に減少し続け、 120分後に はほぼ 0になった。これに対し、純チタンプレート及びコントロールにおける細菌数は 経時的な変化が一定せず、減少がごくゆるやかになる力若しくは増加する傾向を示 した。この結果から、光触媒プレート表面の紫外線強度を 0.40mWZcm2まで弱めても[0034] As shown in Table 9, as the distance from the black light increases and the UV intensity on the surface of the photocatalyst plate decreases, the survival rate of the bacteria at each time increases and the bactericidal effect decreases. I helped. However, the overall trend did not change even when the distance was increased (even if the UV intensity decreased), and the number of bacteria on the photocatalyst plate continued to decrease reliably after 60 minutes and became almost zero after 120 minutes. In contrast, the number of bacteria in pure titanium plates and controls did not change over time, and showed a tendency for the decrease to be very slow or increased. From this result, even if the UV intensity on the surface of the photocatalyst plate is reduced to 0.40 mWZcm 2
、数時間以内で十分な殺菌効果が得られることが分力つた。 Thus, it was found that a sufficient bactericidal effect was obtained within a few hours.
実施例 4  Example 4
[0035] 感¾予防効果の検討 4  [0035] Examination of preventive effect 4
グラム陰性桿菌の代表として 105CFU入りに調整した緑膿菌を菌液として用い、ブラ ックライトの照射位置を 3cm (表面紫外線強度 l.lmWZcm2)とし、実施例 1と同じ手順 で実験を行った。観察は 30分、 60分、 120、 180分後に行った。各時間のデータ数 は 6とした (N = 6)。全結果を表 10に、平均値を表 11および図 3に示す。 Using P. aeruginosa was adjusted to 10 5 CFU containing as a representative of Gram-negative bacilli as bacteria solution, the irradiation position of the bra backlight and 3 cm (surface ultraviolet intensity l.lmWZcm 2), conducted an experiment by the same procedure as that in Example 1 It was. Observations were made after 30, 60, 120 and 180 minutes. The number of data at each time was 6 (N = 6). All results are shown in Table 10, and the average values are shown in Table 11 and FIG.
[0036] [表 5] 表 1 0 15WBLB照射 3cm(1.1 mW/cm2) 105緑膿菌 [0036] [Table 5] Table 10 0 15 WBLB irradiation 3 cm (1.1 mW / cm 2 ) 10 5 Pseudomonas aeruginosa
位： CFU  Rank: CFU
Figure imgf000014_0001
Figure imgf000014_0001
平均値（105緑臁菌 3cm)Average value (10 5 Pseudomonas aeruginosa 3cm)
Figure imgf000014_0002
Figure imgf000014_0002
[0037] 表 11に示すように、代表的なグラム陰性桿菌である緑膿菌を用いて実験を行った 場合も、酸化チタン光触媒プレートは十分な殺菌効果を示し、その表面の 20万個近 い緑膿菌を 30分で 1Z3以下に、 60分で 5000個台へと激減させ、無処理の純チタン プレートと明らかな差を示した。この結果から、本発明にかかる医療用具および被覆 材が、菌の種類にかかわらず十分な殺菌効果を示すことが分力つた。 [0037] As shown in Table 11, even when an experiment was performed using Pseudomonas aeruginosa, a typical gram-negative bacilli, the titanium oxide photocatalyst plate showed a sufficient bactericidal effect, with nearly 200,000 on its surface. The number of Pseudomonas aeruginosa drastically decreased to 1Z3 or less in 30 minutes and 5000 in 60 minutes, showing a clear difference from the untreated pure titanium plate. From these results, it was found that the medical device and the covering material according to the present invention showed a sufficient bactericidal effect regardless of the type of bacteria.
実施例 5  Example 5
[0038] 対象との距離と紫外線強度の関係を調べるため、紫外線計を用いて照射距離と紫 外線強度の関係を調べた。試験は、 40Wブラックライトを用い、紫外線計との垂直距 離と紫外線強度の関係を調べた。結果を表 12及び図 4に示す。  [0038] In order to investigate the relationship between the distance to the subject and the ultraviolet intensity, the relationship between the irradiation distance and the ultraviolet intensity was examined using an ultraviolet meter. In the test, a 40W black light was used to examine the relationship between the vertical distance from the UV meter and the UV intensity. The results are shown in Table 12 and FIG.
[0039] [表 6] 表 1 2 [0039] [Table 6] Table 1 2
Figure imgf000015_0001
Figure imgf000015_0001
[0040] 太陽光の紫外線強度は夏で 2— 3mWZcnTであるため、 40Wのブラックライトを用 いた場合には、 50mm以上の距離を開ければ、太陽光以上の紫外線を患者に照射 せず治療を行うことができることが分力 た。 [0040] Since the UV intensity of sunlight is 2-3 mWZcnT in summer, if a 40 W black light is used, if the distance of 50 mm or more is opened, the patient will be treated without irradiating the patient with UV or more than sunlight. I was able to do what I could do.
実施例 6  Example 6
[0041] in vivoにおける安全件の枪討  [0041] Review of safety issues in vivo
本発明に係る医療用具及び被覆材の安全性を検証するために、創外固定用ピン モデルを作成し、動物実験でその安全性を調べた。  In order to verify the safety of the medical device and the covering material according to the present invention, a pin model for external fixation was created, and the safety was examined by animal experiments.
[0042] 12週齢の SDラットの右下腿部皮下にチタ-スター MI-Cからなるピン、左下腿部皮 下に純チタン (無処理)カゝらなるピンを挿入したモデル (以下、モデル 1とする）を作成 し、当日力も連日 14日間 40Wのブラックライトを 5cmの距離力 埋没部に垂直に照 射した。紫外線強度は皮膚表面で約 3mWZcm2に該当し、これは夏の屋外での紫 外線強度に相当する。 [0042] A 12-week-old SD rat model in which a pin made of titastar MI-C is inserted under the right lower leg and a pin made of pure titanium (untreated) under the left lower leg skin (hereinafter, referred to as “the rat”). Model 1) was created, and on the day of the day, 40W of black light was irradiated for 5 days at a distance of 5cm vertically. The UV intensity corresponds to about 3mWZcm 2 on the skin surface, which corresponds to the intensity of ultraviolet rays outdoors in summer.
同様にラットの右下腿にチタ-スター MI-Cからなるピン、左下腿に純チタン (無処 理)力 なるピンを骨に垂直に貫通して刺入したモデル (以下、モデル 2とする）を作 成し、同じ条件で紫外線を照射した。  Similarly, a model in which a pin made of titastar MI-C is inserted into the right lower leg of the rat and a pin made of pure titanium (no treatment) is inserted into the left lower leg vertically through the bone (hereinafter referred to as model 2). And irradiated with ultraviolet rays under the same conditions.
さらに、モデル 1と同様に作成したモデル（以下、モデル 3とする）を 1力月、 2力月、 3 力月間それぞれ飼育し、期間終了後にこれらの組織学的検討を行った。  In addition, a model created in the same way as Model 1 (hereinafter referred to as Model 3) was raised for 1 month, 2 months, and 3 months, and these histological studies were conducted after the period.
[0043] 2週間後にモデル 1およびモデル 2のラットを安楽死させ、ピン周囲組織の組織学 的検討を行った。 [0043] Two weeks later, model 1 and model 2 rats were euthanized, and histological examination of the tissues surrounding the pins was performed.
組織学的にはピン周囲に軽度の炎症細胞の浸潤を認めたが、これは純チタンと酸 化チタン光触媒の間で明らかな差はなぐ異物に対する反応と考えられた。また、酸 化チタン光触媒周囲の細胞、組織に壊死は見られず、少なくとも組織学的には酸ィ匕 チタン光触媒表面に発生する活性酸素種による影響はないと考えられる。 Histologically, there was slight infiltration of inflammatory cells around the pin, which was caused by pure titanium and acid. The obvious difference between the titanium fluoride photocatalysts was considered to be a reaction to foreign matter. In addition, necrosis was not observed in the cells and tissues around the titanium oxide photocatalyst, and at least histologically, it is considered that there is no influence by the active oxygen species generated on the surface of the titanium oxide photocatalyst.
また、モデル 3で 1力月、 2力月、 3力月と長期間埋没後の周囲組織への影響を検討 したが、これにおいても周囲への炎症細胞の浸潤のみで、明らかな壊死像など周囲 組織への悪影響は見られな力つた。  In addition, model 3 examined the effects on surrounding tissues after long-term implantation, such as 1 month, 2 months, and 3 months, but even in this case, only the infiltration of inflammatory cells into the surroundings revealed an obvious necrosis image, etc. The negative effects on the surrounding tissues were unseen.
以上の結果から、本発明に係る医療用具および被覆材を生体に用いた際の安全 性を確認することができた。  From the above results, it was possible to confirm the safety when the medical device and the covering material according to the present invention were used in a living body.

Claims

請求の範囲 The scope of the claims
[1] 哺乳類の体内に一部あるいは全部を埋め込んで、あるいは哺乳類の体に接触させ て用いられる医療用具であって、表面の一部あるいは全部がチタンで形成され、さら に該チタン表面の少なくとも一部に酸ィ匕チタン光触媒被膜が境界面なく形成されて いる、医療用具。  [1] A medical device that is used by embedding a part or all of it in the body of a mammal, or in contact with the body of a mammal, wherein part or all of the surface is formed of titanium, and at least the surface of the titanium A medical device in which a part of the titanium oxide photocatalyst film is formed without a boundary surface.
[2] 前記医療用具が、体内に挿入して用いられる金属材料である、請求項 1に記載の 医療用具。  [2] The medical device according to [1], wherein the medical device is a metal material used by being inserted into a body.
[3] 前記医療用具がドレッシング材である、請求項 1に記載の医療用具。  [3] The medical device according to [1], wherein the medical device is a dressing material.
[4] 哺乳類の体内に一部あるいは全部を埋め込んで、あるいは哺乳類の体に接触させ て用いられる医療用具の少なくとも一部を光触媒被膜で覆うためのチタン製被覆材 であって、該被覆材表面の少なくとも一部に酸ィ匕チタン光触媒被膜が境界面なく形 成されている、被覆材。 [4] A titanium covering material for covering at least a part of a medical device to be used by being embedded in or in contact with a mammalian body or being in contact with the mammalian body, the surface of the covering material A coating material in which an acid-titanium photocatalytic film is formed on at least a part of the film without a boundary surface.
[5] 前記医療用具が、体内に挿入して用いられる金属材料である、請求項 4に記載の 被覆材。  [5] The covering material according to claim 4, wherein the medical device is a metal material used by being inserted into a body.
PCT/JP2006/302450 2005-05-25 2006-02-13 Medical instrument using photocatalyst WO2006126312A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007517729A JPWO2006126312A1 (en) 2005-05-25 2006-02-13 Medical device using photocatalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-151822 2005-05-25
JP2005151822 2005-05-25

Publications (1)

Publication Number Publication Date
WO2006126312A1 true WO2006126312A1 (en) 2006-11-30

Family

ID=37451745

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/302450 WO2006126312A1 (en) 2005-05-25 2006-02-13 Medical instrument using photocatalyst

Country Status (3)

Country Link
JP (1) JPWO2006126312A1 (en)
KR (1) KR20080031184A (en)
WO (1) WO2006126312A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080102A (en) * 2006-08-29 2008-04-10 Nagasaki Univ Implant
WO2008103081A1 (en) * 2007-02-22 2008-08-28 Tigran Technologies Ab (Publ) Porous implant grain or granule
WO2008103082A1 (en) * 2007-02-22 2008-08-28 Tigran Technologies Ab (Publ) Treatment of inflammatory and/or bacterial conditions with particles of microstructure

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002272835A (en) * 2001-03-16 2002-09-24 Hisashi Ozawa Blood compatible titanium oxide coated material directly formed with titanium oxide layer on surface by aqueous solution synthesis
JP2004183017A (en) * 2002-11-29 2004-07-02 Ota Kk Surface treatment method for metal titanium based base material and metal titanium based medical material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005272169A (en) * 2004-03-23 2005-10-06 Yield Co Ltd Method for producing titanium-oxide-containing aqueous solution, titanium-oxide-containing aqueous solution obtained thereby, and method for producing titanium oxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002272835A (en) * 2001-03-16 2002-09-24 Hisashi Ozawa Blood compatible titanium oxide coated material directly formed with titanium oxide layer on surface by aqueous solution synthesis
JP2004183017A (en) * 2002-11-29 2004-07-02 Ota Kk Surface treatment method for metal titanium based base material and metal titanium based medical material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080102A (en) * 2006-08-29 2008-04-10 Nagasaki Univ Implant
WO2008103081A1 (en) * 2007-02-22 2008-08-28 Tigran Technologies Ab (Publ) Porous implant grain or granule
WO2008103082A1 (en) * 2007-02-22 2008-08-28 Tigran Technologies Ab (Publ) Treatment of inflammatory and/or bacterial conditions with particles of microstructure
US8821586B2 (en) 2007-02-22 2014-09-02 Tigran Technologies Ab Porous implant grain or granule

Also Published As

Publication number Publication date
JPWO2006126312A1 (en) 2008-12-25
KR20080031184A (en) 2008-04-08

Similar Documents

Publication Publication Date Title
JP5478497B2 (en) Novel compositions and related methods, coatings, and articles
CA2378561C (en) Bacteria resistant medical devices
US6409719B1 (en) Light stint implant device for treatment of long term viral infection
Itabashi et al. Bactericidal and antimicrobial effects of pure titanium and titanium alloy treated with short-term, low-energy UV irradiation
WO2006126312A1 (en) Medical instrument using photocatalyst
CN108926577A (en) A kind of method that electric potential water is used for Wound antibiotic healing cleaning-nursing
US20100331978A1 (en) Antipathogenic Biomedical Implants, Methods and Kits Employing Photocatalytically Active Material
US11628185B2 (en) Stabilized active oxygen-generating antiseptic compositions, irrigation solutions, and articles
Joshi et al. Current Scenario in Anti-Microbial Therapy and Emerging Treatment in Diabetic Foot Ulcer
US20230414491A1 (en) Kits, systems, and methods for reducing surgical site infections
JP2008080113A (en) Medical instrument and its application
Bennie Lindeque et al. Prevalence of methicillin-resistant Staphylococcus aureus among orthopedic patients at a large academic hospital
Thakre et al. The battle against biofilms: understanding the impact on medical devices and patient health
Hafiza et al. The in-vitro and in vivo evaluations of orthopedic metal implant coated with silver composite: Potential treatment modality for implant related infection
DE102006051035A1 (en) Dermatological composition for use in cosmetics or medicine, e.g. for combating decubitus or gangrene, contains photocatalyst, e.g. zinc oxide, to degrade skin or wound contaminants
EP2254609A2 (en) Antipathogenic biomedical implants, methods and kits employing photocatalytically active material
KR200374914Y1 (en) Nano silver contain wound dressing
Jan et al. IN-VIVO ANTIMICROBIAL AND BIOCOMPATIBILITY ANALYSIS OF ORTHOPAEDIC METAL IMPLANT COATED WITH SILVER (OMICS)
Zhao et al. Enhanced osteogenesis of polyvinylpyrrolidone-iodine as a sterilizing agent for preservation of allografts
Schmidt et al. Biofilms in orthopaedic surgery
TR2021012479U5 (en) BONE DETECTION IMPLANT WITH ANTIBIOTIC ABSORBENT SURFACE
RU2324499C2 (en) Method of prevention of purulent process in post-operational osseous defect
JP2023133053A (en) Pathogenic microorganism inactivation treatment in cell infection
KR200394438Y1 (en) Splint for medical
WO2018136934A1 (en) Method and apparatus for using elastomeric materials in surgical applications

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007517729

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

WWE Wipo information: entry into national phase

Ref document number: 1020077029413

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: RU

WWW Wipo information: withdrawn in national office

Ref document number: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06713592

Country of ref document: EP

Kind code of ref document: A1