WO2012153870A1 - Matériau thérapeutique pour glaucome - Google Patents

Matériau thérapeutique pour glaucome Download PDF

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Publication number
WO2012153870A1
WO2012153870A1 PCT/JP2012/062723 JP2012062723W WO2012153870A1 WO 2012153870 A1 WO2012153870 A1 WO 2012153870A1 JP 2012062723 W JP2012062723 W JP 2012062723W WO 2012153870 A1 WO2012153870 A1 WO 2012153870A1
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WO
WIPO (PCT)
Prior art keywords
drug
glaucoma
film
biodegradable
laminate
Prior art date
Application number
PCT/JP2012/062723
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English (en)
Japanese (ja)
Inventor
兼子　博章
由佳子 景山
弘中　克彦
和久 杉山
朋巳 東出
徹彦 奥田
Original Assignee
帝人株式会社
国立大学法人金沢大学
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 帝人株式会社, 国立大学法人金沢大学 filed Critical 帝人株式会社
Priority to JP2013514085A priority Critical patent/JPWO2012153870A1/ja
Publication of WO2012153870A1 publication Critical patent/WO2012153870A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/0012—Galenical forms characterised by the site of application
    • A61K9/0048—Eye, e.g. artificial tears
    • A61K9/0051—Ocular inserts, ocular implants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/337—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having four-membered rings, e.g. taxol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/40—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil
    • A61K31/407—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil condensed with other heterocyclic ring systems, e.g. ketorolac, physostigmine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
    • A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
    • A61K9/7084—Transdermal patches having a drug layer or reservoir, and one or more separate drug-free skin-adhesive layers, e.g. between drug reservoir and skin, or surrounding the drug reservoir; Liquid-filled reservoir patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P27/00—Drugs for disorders of the senses
    • A61P27/02—Ophthalmic agents
    • A61P27/06—Antiglaucoma agents or miotics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F9/00—Methods or devices for treatment of the eyes; Devices for putting-in contact lenses; Devices to correct squinting; Apparatus to guide the blind; Protective devices for the eyes, carried on the body or in the hand
    • A61F9/007—Methods or devices for eye surgery
    • A61F9/00781—Apparatus for modifying intraocular pressure, e.g. for glaucoma treatment

Definitions

  • the present invention relates to a glaucoma treatment material having sustained drug release. More specifically, the drug sustained-release glaucoma treatment with a specific structure that consists of biodegradable polymers and has adhesion to the tissue surface, used in glaucoma surgery (trabeculectomy; trabeculectomy) Regarding materials.
  • a new method for treating glaucoma that does not require the use of mitomycin C (MMC), which has a concern about side effects, can be realized.
  • MMC mitomycin C
  • Glaucoma is said to be an “adult disease of the eye” and is a disease in which the optic nerve is impaired due to causes such as increased intraocular pressure, resulting in narrowing of the visual field and decreased vision. If the intraocular pressure drop is still insufficient even with anti-glaucoma drugs, trabeculectomy (trabectomy; excision of the trabecula and discharge of aqueous humor out of the eye to reduce intraocular pressure) (Surgery to lower the pressure) is performed (see FIG. 1). Thereby, the aqueous humor passes through the scleral flap from the trabeculectomy part and is discharged outside the eye, and a filtering bleb is formed under the conjunctiva.
  • trabeculectomy trabectomy; excision of the trabecula and discharge of aqueous humor out of the eye to reduce intraocular pressure
  • JP-A-2008-136770 discloses a film-like glaucoma surgical material having a honeycomb structure as a highly biocompatible material used for surgery for forming a filtering bleb. It is described that the use of the film may reduce or eliminate the dose of MMC.
  • the problem to be solved by the present invention is to provide a glaucoma therapeutic material that is free from adhesion and scarring around the scleral flap and is excellent in maintaining the formation of filtration follicles.
  • the inventors of the present invention have no inflammation, adhesion, or scarring around the sclera and are excellent in maintaining the formation of filter bleb.
  • the present inventors have found that it is possible to maintain a filtering follicle effective in suppressing scarring of the affected area and effective in treating glaucoma. Furthermore, the inventors of the present invention can also use a laminated material composed of an adhesive film not containing a drug and a layer containing a drug as a protective film for the filtration cell wall directly above the scleral valve. It was found that the adhesion and scarring can be suppressed.
  • the first aspect of the present invention comprises a laminate (A) comprising an adhesive layer to the surface of a biological tissue and a barrier layer, biodegradable and not containing a drug, and a drug-containing matrix (a biodegradable matrix containing a drug ( It is a glaucoma treatment material which is a kit composed of B).
  • the second aspect of the present invention provides a biodegradable adhesive layer (C) containing no drug and having adhesiveness to the surface of a living tissue, and a biodegradable drug-containing layer (D) containing a drug. It is a glaucoma treatment material consisting of a laminate.
  • the present invention includes a step of fixing a biodegradable and drug-free laminate (A) comprising an adhesive layer and a barrier layer to the surface of a biological tissue on a resection surface in a fiber withdrawal operation for glaucoma, A method for treating glaucoma, comprising a step of fixing the containing matrix (B) to a site different from the excision surface.
  • the present invention further includes a method for treating glaucoma, comprising the step of fixing the glaucoma therapeutic material of the second present invention to a resection surface in trabeculectomy for glaucoma.
  • the glaucoma treatment material of the present invention for trabeculectomy, which is an operation for glaucoma, it is possible to suppress inflammation around the scleral flap, adhesion, and scarring and to maintain the formation of healthy filter bleb, Provided is a treatment method that suppresses the recurrence and progression of glaucoma over a long period of time and reduces the risk of side effects such as follicular infection.
  • FIG. 1 is an explanatory diagram of trabeculectomy (travelectomy).
  • FIG. 2 is an explanatory diagram of glaucoma filtration surgery of Example 5.
  • FIG. 3 is an explanatory diagram of glaucoma filtration surgery of Example 9.
  • the first aspect of the present invention comprises a laminate (A) comprising an adhesive layer to the surface of a biological tissue and a barrier layer, biodegradable and containing no drug, and a drug-containing matrix (B) which is a biodegradable matrix containing the drug ) Is a kit composed of glaucoma treatment material.
  • a laminate (A) is a laminate of an adhesive layer and a barrier layer, and each layer is a biodegradable film-like member that does not contain a drug.
  • a barrier layer will be located in the other side of the surface which contacts a tissue surface (adhesion surface) among contact bonding layers.
  • Such a laminate (A) can be obtained by molding a biodegradable polymer, whether it is an adhesive layer or a barrier layer.
  • the second aspect of the present invention is a laminate comprising a biodegradable adhesive layer (C) that does not contain a drug and has adhesiveness to the surface of a living tissue, and a biodegradable drug-containing layer (D) that contains the drug. It is a glaucoma treatment material.
  • the adhesive layer (C) and the drug-containing layer (D) constituting such a laminate can be obtained by molding a biodegradable polymer.
  • biodegradable polymers include polylactic acid, polyglycolic acid, polylactic acid-polyglycolic acid copolymer, polycaprolactone, polyglycerol sebacic acid, polyhydroxyalkanoic acid, and polybutylene succinate.
  • Examples include aliphatic polyesters such as aromatic polyesters, polytrimethylene carbonate, polysaccharide derivatives such as cellulose diacetate, cellulose triacetate, methylcellulose, propylcellulose, and benzylcellulose, proteins such as fibroin, gelatin, and collagen, and derivatives thereof. .
  • polylactic acid, polyglycolic acid, polylactic acid-polyglycolic acid copolymer, polycaprolactone, and polylactic acid-polycaprolactone copolymer are preferable, and polylactic acid and polylactic acid-polycaprolactone copolymer are more preferable.
  • the molecular weight of the biodegradable polymer is 1 ⁇ 10 3 to 5 ⁇ 10 6 , preferably 1 ⁇ 10 4 to 1 ⁇ 10 6 , more preferably 5 ⁇ 10 4 to 5 ⁇ 10 5 .
  • the terminal structure of the biodegradable polymer and the catalyst for polymerizing the polymer can be arbitrarily selected.
  • On the surface (adhesive surface) where the laminate (A) in the first invention and the adhesive layer (C) in the second invention are in contact with the tissue surface (three-dimensional unevenness) on the biodegradable polymer of the material It is preferable that processing has been performed.
  • adhesion to the tissue surface means that when the laminate is placed on the tissue surface, the laminate may not be displaced due to gravity drop or body fluid leakage, and lightly pressed with a finger from above. A state in which the laminate is stuck to the tissue surface without moving. The case where the adhesion is weak enough that the laminated film can be peeled off by sandwiching and lifting the laminated film with an instrument such as tweezers is also included.
  • the laminated film may be partially fixed to the tissue surface with a suture.
  • the tissue surface refers to the tissue surface of the eye where the necessity of surgical operation has occurred. Specifically, sclera, conjunctiva, cornea and the like can be mentioned.
  • the state of the surface is not particularly limited, but is preferably a state without continuous bleeding. Further, such a concavo-convex structure is preferably processed to a size of about 100 nm to 10 ⁇ m, and a preferable example is a honeycomb pattern structure. It is preferable that a honeycomb structure is formed on a part or all of the adhesion surface to the living tissue.
  • the honeycomb-shaped pattern structure means that when forming a film by casting a dope of an organic solvent of a biodegradable polymer onto a glass plate, water droplets are formed on the surface by condensation, so that the water droplets and the mold are formed. This is the structure formed.
  • This honeycomb pattern structure has a structure in which holes of uniform size formed inside the film are connected to each other and are connected in the horizontal direction, so that the blood and body fluid in the affected area move quickly, and the film It has the characteristic that it is easy to stick to an affected part.
  • a phospholipid as described in JP-A-2008-136770 is used as a surfactant to form a honeycomb-like interconnected hole. There is a way to do it.
  • Such phospholipids can be extracted from animal tissues or artificially synthesized.
  • phosphatidylethanolamine phosphatidylcholine, phosphatidylserine, phosphatidylglycerol, and derivatives thereof.
  • Preferred is phosphatidylethanolamine, and more preferred is L- ⁇ -phosphatidylethanolamine dioleoyl.
  • the amount of the phospholipid can be 0.01 to 100 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.
  • the pore diameter and film thickness of the honeycomb are not particularly limited, but preferably the pore diameter is 1 to 10 ⁇ m and the film thickness is 5 to 20 ⁇ m.
  • the barrier layer is a layer made of a biodegradable polymer film that is substantially impermeable to water and air, and examples thereof include a film or a monomolecular film obtained by processing a biodegradable polymer into a flat film.
  • a film can be arbitrarily selected from a solvent cast film, a melt-extruded film, a spin coat film, a wet film formed using a coagulation bath, and is preferably a solution cast film.
  • the method for bonding the barrier layer and the adhesive layer can be arbitrarily selected from thermocompression bonding, pressing, and the like, and is not particularly limited, but is preferably a thermocompression bonding method.
  • An adhesive agent can also be used if desired.
  • the drug-containing matrix (B) may be used in a state where it is in contact with the laminate (A) or in a separated state, but is preferably used in a separated state.
  • the material of the drug-containing matrix can be selected from biodegradable polymers used for the laminate (A). Preferably, polylactic acid or polylactic acid-polyglycolic acid copolymer is used.
  • the shape of the drug-containing matrix (B) is preferably a sheet or a film, but a porous material such as a porous body or a fiber structure can also be used.
  • a material that is not deformed by moisture may be used, or a material that swells by containing moisture may be used.
  • a honeycomb structure is preferably formed on part or all of the surface of the drug-containing matrix (B).
  • At least one drug-containing layer (D) is laminated on the side opposite to the surface (adhesive surface) that adheres to the tissue surface of the adhesive layer (C).
  • the drug-containing layer (D) is a layer made of a biodegradable polymer film that is substantially impermeable to water and air, and includes a film or a monomolecular film obtained by processing a biodegradable polymer into a flat film. It is done.
  • a film can be arbitrarily selected from a solvent cast film, a melt-extruded film, a spin coat film, a wet film formed using a coagulation bath, and is preferably a solution cast film.
  • the adhesion processing method of the adhesive layer (C) and the drug-containing layer (D) in the second aspect of the present invention can be arbitrarily selected from thermocompression bonding or press working, and is not particularly limited, but is preferably a thermocompression bonding method.
  • An adhesive agent can also be used if desired.
  • the honeycomb structure described above may be formed on a part or all of the surface of the drug-containing matrix (B) in the first invention and the surface of the drug-containing layer in the second invention.
  • the drug is contained in the drug-containing matrix (B) in the first invention and the drug-containing layer (D) in the second invention.
  • Such drugs preferably have the effect of suppressing the proliferation of fibroblasts and cancer cells.
  • Taxanes such as paclitaxel, doxetaxel, DHA-paclitaxel, Abraxane, polyglutamated paclitaxel, 5-fluorouracil, mitozantrone, daunorubicin, doxorubicin , Anticancer agents such as cisplatin, carboplatin, methotrexate, and bevacizumab, tacrolimus or analogs thereof, and statins, and paclitaxel and doxetaxel are preferably used. Moreover, a protein formulation and a nucleic acid medicine may be sufficient as long as it can maintain activity in a volatile solvent.
  • the content of the drug is not particularly limited, but is preferably in the range of 0.01 to 10% with respect to the biodegradable polymer.
  • the mixing method of the biodegradable polymer and the drug is not particularly limited, and a uniform mixed solution may be prepared using a solvent that can dissolve both, and this may be molded.
  • the drug may be dispersed and molded into a film shape, or the powder may be mixed and compressed to be molded.
  • medical agent for example, a metal, polysaccharide, a fatty acid, phospholipid, and surfactant, may be further included.
  • the laminate (A) and drug-containing matrix (B) in the first invention, and the adhesive layer (C) and drug-containing layer (D) in the second invention can be prepared by using a suture or a fixture as desired. You may fix to.
  • a suture can be used for suturing, and examples of the fixture include a stapler and a pin.
  • the glaucoma treatment material of the present invention is gradually decomposed and absorbed when applied to a patient. There is no particular limitation on the decomposition period, but it is preferable that it is completely absorbed in about 3 months to 1 year.
  • the release rate of the drug is not particularly limited, but it is preferable that the drug is released for a period of about one month after the operation.
  • Example 2 Production of Cast Film (Barrier Layer)
  • legal dye green No. 202 was mixed at a ratio of 0.3% with respect to the polymer, and was poured onto a glass plate.
  • Example 3 Lamination of Honeycomb Film and Barrier Layer
  • the cast film produced in Example 2 was layered on the smooth surface of the honeycomb film produced in Example 1, and the laminate (A) was treated at 70 ° C. for 10 minutes. Got.
  • Example 4 Preparation of drug-supported matrix (composite film) To the polymer solution containing the blue pigment prepared in Example 2, paclitaxel (manufactured by Enzo Life Sciences) was added to 5 ⁇ g, mixed, and a uniform solution Got. This was poured onto a glass plate and dried without applying humidity to obtain a blue cast film containing paclitaxel.
  • Example 5 Glaucoma Filtration Surgery As shown in FIG. 2, glaucoma filtration surgery was performed on one eye of a rabbit. The conjunctiva at the base of the limbus was incised to create a 3 mm ⁇ 3 mm scleral half-layer flap, and the trabecular meshwork was excised. The paclitaxel-containing composite film (3 ⁇ 6 mm in size) produced in Example 4 was placed so that the honeycomb surface faced inward, and was sutured and fixed with two 10-0 nylon sutures so that the film did not move. .
  • the laminate (A) produced in Example 3 was placed so that the honeycomb surface faced outward, and the film was sewn so as not to move, and fixed at five locations, and the conjunctiva was closed. Sutured. On the 7th, 14th, 21st, and 28th days after the operation, intraocular pressure measurement with tonopenes under eye drop anesthesia and observation of filter cysts with an ultrasonic ecological microscope (UBM) were performed. As a result, until 28 days after the operation, filtration space was observed under the conjunctiva in UBM, the filtering vesicles did not disappear, and the intraocular pressure remained constant.
  • UBM ultrasonic ecological microscope
  • Example 6 In the glaucoma filtration surgery of Example 5, the paclitaxel-containing matrix was not used, and the paclitaxel-containing matrix prepared in Example 4 was installed instead of the laminate (A).
  • Example 7 Production of Cast Film (Drug-Containing Layer) Legal dye green No.
  • Example 8 Production of Paclitaxel-Containing Laminated Film The honeycomb film produced in Example 1 was laminated on the surface of the film obtained in Example 7, and a paclitaxel-containing laminated film having a honeycomb structure on one side was produced.
  • Example 9 Glaucoma Filtration Surgery As shown in FIG.
  • glaucoma filtration surgery was performed on one eye of a rabbit.
  • the conjunctiva at the base of the limbus was incised to create a 3 mm ⁇ 3 mm semi-scleral flap, and the trabecular meshwork was excised.
  • the laminated film containing paclitaxel prepared in Example 8 was placed so that the honeycomb surface faced the outside (filtered cell wall side), and 10-0 nylon suture thread was used so that the film did not move. Five places were fixed, the conjunctiva was closed and sutured.
  • Example 2 In the glaucoma filtration operation of Example 9, the laminate not including paclitaxel prepared in Example 3 was installed. As a result, until 28 days after the operation, the film was in partial contact with the wall of the filtering bleb in the ultrasonic biomicroscope, and a filtration space was observed under the conjunctiva, and the filtering vesicle did not disappear. Intraocular pressure remained constant at a lower level than before surgery.
  • the glaucoma treatment material of the first invention and the glaucoma treatment material of the second invention are superior to the former (see Example 6). It can be seen that cell weakening does not occur, the formation of scar tissue of the scleral flap is suppressed, and it is excellent in maintaining the formation of filtration bleb. Therefore, according to any of the present inventions, an ideal glaucoma treatment that is free from the problem of side effects of MMC is achieved.
  • the glaucoma treatment material of the present invention is used, for example, in the manufacturing industry of medical materials.

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  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
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  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Ophthalmology & Optometry (AREA)
  • Dermatology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention porte sur un matériau thérapeutique pour glaucome, qui est une trousse comprenant un stratifié (A) qui comprend une couche adhésive devant adhérer sur la surface d'un tissu biologique et une couche barrière, est biodégradable et ne contient pas d'agent médicinal et une matrice biodégradable (B) qui contient un agent médicinal, ou qui est un stratifié comprenant une couche adhésive (C) qui est adhésive sur la surface d'un tissu biologique, ne contient pas d'agent médicinal et est biodégradable et une couche (D) contenant un agent médicinal, qui contient un agent médicinal et est biodégradable. Lorsque le matériau thérapeutique pour glaucome est utilisé, toute cicatrice d'inflammation n'est pas laissée autour de la sclérotique, une boursouflure de filtration peut être formée et maintenue de manière satisfaisante, il n'y a pas de problème d'effets secondaires néfastes de mitomycine C, et la fragilisation de cellules épithéliales conjonctivales par un agent médicinal peut être empêchée.
PCT/JP2012/062723 2011-05-11 2012-05-11 Matériau thérapeutique pour glaucome WO2012153870A1 (fr)

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Application Number Priority Date Filing Date Title
JP2013514085A JPWO2012153870A1 (ja) 2011-05-11 2012-05-11 緑内障治療材

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-106715 2011-05-11
JP2011106716 2011-05-11
JP2011106715 2011-05-11
JP2011-106716 2011-05-11

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WO2012153870A1 true WO2012153870A1 (fr) 2012-11-15

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533106A (ja) * 2002-07-15 2005-11-04 アルコン，インコーポレイテッド 眼薬送達のための生体侵食性フィルム
JP2008136770A (ja) * 2006-12-05 2008-06-19 Teijin Ltd 緑内障治療材
JP2008533204A (ja) * 2005-03-21 2008-08-21 マクサイト， インコーポレイテッド 病気又は症状の治療のためのドラッグ送達システム

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005533106A (ja) * 2002-07-15 2005-11-04 アルコン，インコーポレイテッド 眼薬送達のための生体侵食性フィルム
JP2008533204A (ja) * 2005-03-21 2008-08-21 マクサイト， インコーポレイテッド 病気又は症状の治療のためのドラッグ送達システム
JP2008136770A (ja) * 2006-12-05 2008-06-19 Teijin Ltd 緑内障治療材

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