Surgical sutures and needles

Abstract

It emits light efficiently under ultraviolet light and can be easily identified with the naked eye. The excited light-emitting part has fallen off. To provide a surgical suture and a surgical suture needle which have little effect on the human body even in the case of contact with the human body. A surgical suture includes a suture and a coating layer that covers the suture. The coating layer contains graphene quantum dots and / or carbon quantum dots and a biodegradable resin. The surgical suture needle is a needle and a groove in the main body 1 of the needle or a needle inserted into the main body 1. and an excitation light emitting unit 8 provided on the suture 6 side, The composition contains nanoparticles and / or carbon quantum dots, and a biodegradable resin.

Description

[Technical Field]

[0001] The present invention relates to a surgical suture and a surgical suture material having a biodegradable resin containing a luminescent agent in a part thereof. Regarding needles. [Background technology]

[0002] Surgical sutures have been used for a long time, and in recent years, there has been a trend toward in vivo sutures that do not require removal after surgery. Absorbable sutures have come into widespread use. Sutures made from materials such as glycolide (polyglycolic acid) are commercially available.

[0003] Surgical sutures include monofilament sutures made of a single fiber and sutures made of multiple fibers. Multifilament sutures made of fibers are known. It has been proposed to improve workability by applying a coating.

[0004] On the other hand, surgical needles are made of steel metal, and there is a risk of surgical needles being left inside the body. In order to prevent the presence of medical supplies in the surgical field, the presence of medical supplies in the surgical field must be checked based on the status of medical supply use. In particular, surgical sutures and needles are very thin. Or, because they are small, they are difficult to see during surgery and are easily lost, which can lead to stress and prolonged surgery. Furthermore, if the thread and needle become dislodged due to bleeding, the problem will worsen. It's becoming a difficult situation.

[0005] In order to solve this problem, for example, Patent Document 1 discloses a medical product such as a surgical suture needle. The luminescent material contains a luminescent agent on its surface that emits near-infrared fluorescence when irradiated with excitation light. The device has at least one component that can be broken and separated when a part of the component breaks. When the separated piece is separated from the component, the luminescent agent is also contained on the surface of the separated piece. This document also proposes a medical product that emits near-infrared fluorescence. A suture thread in which a luminescent agent that emits light is kneaded into a biodegradable resin such as polyglycolic acid is disclosed. . [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. WO2013 / 180127 Summary of the Invention [Problem to be solved by the invention]

[0007] However, when an organic fluorescent material is used as a light-emitting agent as in Patent Document 1, Generally, the luminous efficiency is not high, so the concentration of phosphor in the resin needs to be increased. Furthermore, as in Patent Document 1, the near-infrared fluorescent material is not suitable for forming a fluorescent layer. When using a luminescent agent, the luminescence state cannot be confirmed with the naked eye, and special equipment is required for observation. When using organic phosphors, the type of phosphor is Depending on the species, there are also concerns about their impact on the human body.

[0008] Therefore, an object of the present invention is to provide a compound that can efficiently emit light by ultraviolet light, can be easily identified by the naked eye, and can be excited Surgical sutures and needles that have minimal impact on the human body even if the light-emitting part falls off The purpose is to provide [Means for solving the problem]

[0009] The present inventors have conducted extensive research to achieve the above object, and have found that graphene quantum dots or By using biodegradable resin containing carbon quantum dots, even a small amount can be efficiently treated with ultraviolet light. They discovered that the light emitted from the material can be easily recognized by the naked eye, and this led to the completion of the present invention.

[0010] That is, the present invention includes the following.

[0011] [1] A suture and a coating layer covering the suture, wherein the coating layer is made of graphene. A surgical suture containing quantum dots and / or carbon quantum dots and a biodegradable resin.

[0012] [2] A suture needle and an excitation groove provided on the main body of the suture needle or on the suture side of the main body. and a light-emitting unit, wherein the light-emitting unit is a graphene quantum dot and / or a carbon quantum dot; and a surgical suture needle containing a biodegradable resin.

[0013] [3] The biodegradable resin is selected from the group consisting of polylactic acid, polyvinyl alcohol, polyglycolic acid, poly Butylene succinate, polybutylene adipate terephthalate, polyhydroxyalkanoate Noate, polyethylene terephthalate succinate, polycaprolactone, starch [1] The resin is at least one selected from the group consisting of a biodegradable resin and a cellulose-based biodegradable resin.

[0023] A surgical suture according to the present invention.

[0014] [4] 0.001 to 0.2 parts by mass of graphite per 100 parts by mass of the biodegradable resin [1] or containing silicon quantum dots or 0.001 to 0.5 parts by mass of carbon quantum dots [3] A surgical suture according to the present invention.

[0015] [5] The biodegradable resin is selected from the group consisting of polylactic acid, polyvinyl alcohol, polyglycolic acid, poly Butylene succinate, polybutylene adipate terephthalate, polyhydroxyalkanoate Noate, polyethylene terephthalate succinate, polycaprolactone, starch [2] The resin is at least one selected from the group consisting of a biodegradable resin and a cellulose-based biodegradable resin.

[0023] A surgical suture needle according to the present invention.

[0016] [6] The biodegradable resin further contains cellulose nanofibers and a cellulolytic enzyme. The surgical suture needle according to [5], which comprises:

[0017] [7] 0.001 to 0.2 parts by mass of graphite per 100 parts by mass of the biodegradable resin [2], [containing silicon quantum dots or 0.001 to 0.5 parts by mass of carbon quantum dots. [5] or [6]. [Effects of the Invention]

[0018] According to the surgical suture of the present invention, graphene quantum dots and / or carbon atoms are used as the luminescent agent. Because it uses electron dots, it is thought to have less of an effect on the human body than general fluorescent materials. Even if the coating layer falls off, it is estimated that there will be little impact on the human body. It has a higher luminous efficiency than other materials, so it can form a coating layer at a low concentration and emit ultraviolet light more efficiently. This allows the material to be easily identified by the naked eye. It emits light more efficiently and can be easily identified with the naked eye, and even if the coating layer falls off, there is no adverse effect on the human body. It is possible to provide a surgical suture with less

[0019] Furthermore, according to the surgical suture needle of the present invention, the luminescent agent is graphene quantum dots and / or Because it uses carbon quantum dots, it is thought to have less of an effect on the human body than general fluorescent materials. Even if the excitation light emitting part falls off, it is estimated that there will be little impact on the human body. Since the luminous efficiency is higher than that of other phosphors, the excited luminous area can be formed at low concentration and the luminous efficiency can be increased by ultraviolet light. Because it can emit light efficiently, it can be easily identified with the naked eye. It efficiently emits light with ultraviolet light and can be easily identified with the naked eye. Even if the excitation light-emitting part falls off, A surgical suture needle that has little effect on the human body can be provided. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a perspective view showing an example of a surgical suture according to the present invention. [Figure 2] FIG. 1 is a perspective view showing an example of a surgical suture needle according to the present invention. [Figure 3] FIG. 1 is a perspective view showing another example of the surgical suture needle of the present invention. [Figure 4] FIG. 1 is a perspective view showing another example of the surgical suture needle of the present invention. [Figure 5] Graph showing the fluorescence spectra of the surgical sutures obtained in Example 2 and Comparative Example 1 [Figure 6] Graph showing the fluorescence spectra of pellets obtained in Examples 6 to 7 and Comparative Example 3 DETAILED DESCRIPTION OF THE INVENTION

[0021] <Surgical sutures> The surgical suture of the present invention comprises a suture and a coating layer that covers the suture. The support layer contains graphene quantum dots and / or carbon quantum dots and a biodegradable resin. It is characterized by the following.

[0022] In this specification, "coating" refers to a state in which 60% or more of the surface area of ​​the object to be coated is covered. It is preferable that 90% or more of the surface is covered, and more preferably 100% of the surface is covered. It is in a state of being covered.

[0023] Fig. 1 is a perspective view showing an example of the surgical suture of the present invention. 1 shows an example of a surgical suture 10 in which the suture 11 is completely covered by a coating layer 12. Although shown, the suture 11 need not be completely covered by the coating layer 12 .

[0024] (Sutures) The suture that forms the coating layer may be a non-absorbable suture that requires removal. It is preferable to use biodegradable and bioabsorbable sutures, which do not require a surgical procedure. Even in such cases, the use of the surgical suture of the present invention can eliminate the problem of the coating layer falling off. This can reduce the amount of stress, making it easier to check the location of the suture during surgery.

[0025] Non-absorbable sutures include, but are not limited to, nylon, polypropylene, polyester, Examples include polyvinylidene fluoride, silk thread, and metal wire.

[0026] Examples of absorbable sutures include polyglycolide, polylactide, and poly-ε-caproate. Lactone, lactide-glycolic acid copolymer, glycolide-ε-caprolactone copolymer , lactide-ε-caprolactone copolymer, polycitric acid, polymalic acid, poly-α-silicone Polyacrylate, Poly-β-hydroxy acid, Polytrimethylene oxalate, Polytetrafluoroethylene Lamethylene oxalate, polyorthoester, polyorthocarbonate, polyethylene Carbonate, Poly-γ-benzyl-L-glutamate, Poly-γ-methyl-L-glutamate Synthetic polymers such as mate, poly-L-alanine, polyglycol sebaceous acid, and starch Polysaccharides such as alginic acid, hyaluronic acid, chitin, pectic acid and their derivatives, and gelatin Examples include natural polymers such as proteins, including cellulose, collagen, albumin, and fibrin. Among them, poly(3-hydroxybutane) is the most popular due to its moderate biodegradability and strength. Polyglycolides such as poly(3-hydroxybutanoic acid) homopolymer or poly(3-hydroxybutanoic acid) copolymer Polyglycolic acid is preferred.

[0027] The structure of the suture may be a multifilament suture made of multiple fibers, From the viewpoint of ease of forming a suture layer, monofilament sutures consisting of only a single fiber are preferred. The diameter of the suture is, for example, 0.01 to 1 mm, but the thickness of the coating layer may vary. Considering the performance, 0.05 to 0.5 mm is preferable.

[0028] (coat layer) The coating layer covering the suture thread comprises graphene quantum dots and / or carbon quantum dots, It also contains a biodegradable resin.

[0029] Quantum dots are nanoscale particles with unique optical properties that obey quantum chemistry and quantum mechanics. It means that the optical properties can be adjusted by the particle size, so it is not particle-dependent. In the present invention, graphene quantum dots and / or Alternatively, carbon quantum dots (hereinafter, both are collectively referred to as "carbon-based quantum dots") are used. In addition, by using multiple quantum dots selected from these and adjusting the content of each, A desired emission wavelength can be obtained.

[0030] Regarding the content of carbon-based quantum dots, in the case of graphene quantum dots, the efficiency is increased by ultraviolet light. From the viewpoint of emitting visible light effectively, the amount of the biodegradable resin forming the coating layer is The content is preferably 0.001 to 0.2 parts by mass, and more preferably 0.0015 to 0.15 parts by mass. When graphene quantum dots are used, ultraviolet light to violet light (200 When excited by light of wavelengths from 445 nm to 410 nm, a coating layer is formed that emits light with a peak at 445 nm. It is preferable to form

[0031] In the case of carbon quantum dots, in order to efficiently emit visible light using ultraviolet light, a coating layer The content is 0.001 to 0.5 parts by mass relative to 100 parts by mass of the biodegradable resin forming the The amount is preferably 0.0075 to 0.45 parts by mass, and more preferably 0.0075 to 0.45 parts by mass. In this case, the excitation light from ultraviolet light to blue light (200 nm to 500 nm) is particularly effective. It is preferable to form a coating layer that emits light with a peak at .beta.

[0032] (carbon-based quantum dots) Carbon-based quantum dots have particle size-dependent luminescence properties due to the π bonds between carbon atoms. Carbon-based quantum dots include graphene quantum dots with a graphene structure. Examples include carbon quantum dots that do not have a graphene structure, and quantum dots that are chemically modified with these. However, from the viewpoint of quantum yield, graphene quantum dots or chemically modified graphene quantum dots are Dots are preferred.

[0033] These carbon-based quantum dots are manufactured by Sigma-Aldrich, Fuji Pigment Co., Ltd., and GS Ara. It is commercially available from companies such as Eance Co., Ltd., Funakoshi Co., Ltd., and Kishida Chemical Co., Ltd. Any of these can be used.

[0034] (Graphene quantum dots) The graphene quantum dots include non-functionalized graphene quantum dots and functionalized graphene quantum dots. quantum dots, pristine graphene quantum dots, and their combinations Examples include:

[0035] The functionalized graphene quantum dots may be functionalized with one or more functional groups. is an oxygen group, a carboxyl group, a carbonyl group, an amorphous carbon, a hydroxyl group, an alkyl group , aryl groups, esters, amines, amides, polymers, poly(propylene oxide), and and combinations thereof.

[0036] Graphene quantum dots also include functionalized graphenes, which are functionalized with one or more alkyl groups. The alkyl groups include methyl, ethyl, propyl, and bromine. ethyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, une In some embodiments, the alkyl group may be a methyl group, a decyl group, a methyl ... contains an octyl group (e.g., octylamine).

[0037] Graphene quantum dots can also be functionalized with one or more polymer precursors. For example, graphene quantum dots can be synthesized using one or more monomers (e.g., vinyl monomers). It can be functionalized.

[0038] Graphene quantum dots can be functionalized with polymer precursors to form polymeric For example, vinyl monomers can be polymerized to form graphene quantum dots. By functionalizing the ends with hydroxybenzoates, end-functionalized polyvinyl adducts can be formed. do.

[0039] Graphene quantum dots are functionalized graphenes that have been functionalized with one or more hydrophilic functional groups. Hydrophilic functional groups include carboxyl groups, carbonyl groups, and hydroxyl groups. groups, hydroxyalkyl groups, poly(ethylene glycol), poly(vinyl alcohol), poly(acrylic acid), and combinations thereof.

[0040] Graphene quantum dots are functionalized graphenes that have been functionalized with one or more hydrophobic functional groups. Hydrophobic functional groups include alkyl groups, aryl groups, and combinations thereof. The hydrophobic functional group may be one or more alkylamides or arylamides. Included.

[0041] The graphene quantum dots include edge-functionalized graphene quantum dots. The graphene quantum dots include one or more of the hydrophobic functional groups described above. The quantum dots include one or more hydrophobic functional groups as described above. The quantum dots also contain one or more hydrophilic functional groups as previously described. Functionalized graphene quantum dots contain one or more oxygen adducts on their edges. Edge-functionalized graphene quantum dots contain one or more amorphous carbons on their edges. It includes the addition of

[0042] Graphene quantum dots are prepared by dissolving one or more alkylamides, such as alkylamides or arylamides. The ends are functionalized with alkyl or aryl groups. The edge functionalization of graphene quantum dots is achieved by alkylating the edges of the graphene quantum dots. This is done by reaction of an amide or arylamide with a carboxylic acid.

[0043] Graphene quantum dots include pristine graphene quantum dots. Pristine graphene quantum dots include graphene quantum dots that are left untouched after synthesis. Pristine graphene quantum dots have not undergone any additional surface modification after synthesis. Contains graphene quantum dots.

[0044] Graphene quantum dots can be obtained from a variety of sources, for example, The dots include coal-derived graphene quantum dots, coke-derived graphene quantum dots, Graphene quantum dots include graphene derived from coke. Graphene quantum dots include those derived from coal. Coal includes, but is not limited to, anthracite, bituminous coal, sub-bituminous coal, modified coal, Bituminous coal, asphaltene, asphalt, peat, lignite, boiler coal, petroleum oil (PETR ified oil), carbon black, activated carbon, and combinations thereof. The carbon source is bituminous coal.

[0045] Graphene quantum dots can have a variety of diameters. The dots preferably have a diameter ranging from about 1 nm to about 100 nm, More preferably, the diameter ranges from about 1 nm to about 20 nm. More preferably, the diameter is in the range of .

[0046] Graphene quantum dots can also have a variety of structures. The quantum dots may have a crystalline structure, for example a crystalline hexagonal structure. The graphene quantum dots may have a single layer or multiple layers, for example, It has from about two layers to about four layers.

[0047] Graphene quantum dots can also have a variety of quantum yields. The graphene content preferably ranges from about 30 to 80%. The fluorescence properties of the water dispersion of quantum dots are at least some of the excitation light wavelengths of 300 nm to 420 nm. For either wavelength, the emission wavelength is preferably 380 nm to 650 nm.

[0048] The graphene quantum dots may be in the form of a powder or pellets. The graphene quantum dots may be in a liquid state, such as a dispersion, a solution, or a melt. Good too.

[0049] Various methods are available for forming graphene quantum dots, for example: The process of forming graphene quantum dots involves exposing a carbon source to an oxidizing agent, resulting in graphene The carbon source can include coal, coke, and and combinations thereof.

[0050] Oxidizing agents include acids, such as sulfuric acid, nitric acid, phosphoric acid, hypophosphorous acid, oleum, and chloride water. Acids include benzoic acid, oleum, chlorosulfonic acid, and combinations thereof. The agent includes potassium permanganate, sodium permanganate, hypophosphorous acid, nitric acid, sulfuric acid, Preferred oxidizing agents include potassium permanganate, potassium nitrate, potassium hydroxide, potassium iodide ... It is a mixture of ammonium nitrate, sulfuric acid and hypophosphorous acid.

[0051] The carbon source is exposed to the oxidizing agent by sonicating the carbon source in the presence of the oxidizing agent. The heating step includes heating a carbon source in the presence of a catalyst. The heating step is performed at a temperature of at least about 100° C. This is carried out.

[0052] Additional methods for forming graphene quantum dots can also be envisioned, for example Further methods for forming graphene quantum dots are disclosed in international patent application PCT / US2004 / 002294. Further suitable methods for producing graphene quantum dots are disclosed in US Pat. No. 5,660,494. This method is also disclosed in the following reference: ACS Appl. Mater. Interfaces 2015, 7, 7041-7048; and Nature Commun. 2013, 4:2943, 1-6.

[0053] (carbon quantum dots) Carbon quantum dots are quantum dots that do not have a ring structure like graphene. The H value affects the emission intensity and peak position more easily than graphene quantum dots. It has the property of being

[0054] Carbon quantum dots can have a variety of diameters. For example, carbon quantum dots have diameters of approximately 1n Preferably, the diameter ranges from about 1 nm to about 100 nm, and more preferably from about 1 nm to about 50 nm. More preferably, the diameter ranges from about 1 nm to about 30 nm. It is more preferable that the diameter of the pores is 1 / 2.

[0055] Carbon quantum dots can also have a variety of quantum yields. It is preferable that the quantum yield is in the range of 0 to 50%. The fluorescent properties of the dispersion are such that the excitation light has at least one wavelength between 300 nm and 420 nm. The emission wavelength is preferably 380 nm to 600 nm.

[0056] The manufacturing method of carbon quantum dots is not very different from that of graphene quantum dots. The only difference is whether the material and manufacturing conditions make it easier to form a graphene structure.

[0057] Therefore, carbon-based quantum dots containing both can be used, for example, by laser ablating a carbon target. A manufacturing method that involves carrying out chemical treatment after laser ablation (Patent Document 20 12-501863) and a method of producing it from candle soot (H. Liu, et al., Angew. Che m.Int. Ed. 2007, 46, 6473-6475.), a method for producing graphite oxide by chemical treatment (G. Eda, et al., Adv. Mater.2010, 22, 505-509.), graphite oxide was used as a precursor. a method for producing fullerenes from a chemical reaction involving the following steps (JP Patent Publication No. 2012-136566); A method for producing it from a substitution reaction (J. Lu, et al., Nature Nanotech. 2011, 6, 247-252.), and , a method of producing carbon nanotubes by chemically processing cheaper carbon raw materials such as carbon fiber and activated carbon (J. Peng, e t al., Nano Lett. 2012, 12, 844-849., ZA Qiao, ChemCommun. 2010, 46,8812-8814. , Y. Dong, et al., Chem. Mater. 2010, 22, 5895-5899. .

[0058] These methods are roughly classified as top-down methods, Bottom-up fabrication of carbon quantum dots from the polymerization of organic precursor molecules -up) method (GA Ozin, et al., J. Mater. Chem., 2012, 22, 1265-1269.) It can be manufactured.

[0059] In addition, the carbon material is mixed with hydrogen peroxide, and the carbon is decomposed by the hydrogen peroxide, and the amount of carbon is reduced. A step of preparing a carbon quantum dot generating solution, and a step of mixing carbon quantum dots in the carbon quantum dot generating solution with water peroxide. and separating the element to stop the decomposition reaction and obtain the carbon quantum dots. It is also possible to manufacture the same by the method for manufacturing a PET bottle (Japanese Patent Application Laid-Open No. 2014-133685).

[0060] (biodegradable resin) The biodegradable resin contained in the coating layer can be any biodegradable resin that can form a coating film. However, from the viewpoint that the coating layer is more difficult to peel off, it is preferable to use a material similar to the suture thread. It is preferable that

[0061] Examples of biodegradable resins include polylactic acid, polyvinyl alcohol, and polyglycolic acid. , polybutylene succinate, polybutylene adipate terephthalate, polyhydroxya Gluconate, polyethylene terephthalate succinate, polycaprolactone, starch and at least one selected from the group consisting of cellulose-based biodegradable resins. When using a cellulose-based biodegradable resin, it is preferable to use a cellulose-degrading enzyme in combination. I wish.

[0062] Sutures are made from poly(3-hydroxybutanoic acid) homopolymer or poly(3-hydroxybutanoic acid). Polyglycolides (polyglycolic acids) such as hydroxybutanoic acid copolymers are preferably used. In this case, the biodegradable resin used for the coating layer is polyglycolic acid, poly Caprolactone, polylactic acid, polyvinyl alcohol, polybutylene succinate, poly Hydroxyalkanoates are preferably used.

[0063] (Formation of coating layer) The method for forming the coating layer includes the steps of: forming graphene quantum dots and / or carbon quantum dots; A coating solution containing a biodegradable resin and a solvent is prepared, and the solution is applied to the suture thread and dried. The coating method can be dip coating, spray coating, coater coating, brush coating, Examples include lacquering.

[0064] The solvent used in the coating solution is one that disperses or dissolves the biodegradable resin used. For example, alcoholic solvents such as ethanol and isopropyl alcohol, acetone, etc. ketone solvents such as methyl ethyl ketone, ether solvents such as diethyl ether and tetrahydrofuran ester solvents such as ethyl acetate and butyl acetate, chloroform, dichloromethane Examples of suitable solvents include halogen-based solvents such as toluene and xylene, aromatic hydrocarbon-based solvents such as toluene and xylene, and water. can be.

[0065] The coating solution for forming the coating layer contains higher fatty acid salts such as calcium stearate. It contains lubricants such as citric acid esters, plasticizers such as fatty acid esters, and surfactants such as Good too.

[0066] Carbon-based quantum dots are available as aqueous dispersions, so the above-mentioned solvents and aqueous solvents are By replacing the carbon-based quantum dots, biodegradable resin, and solvent, A coating solution having the above properties can be easily prepared.

[0067] The thickness of the coating layer is set to 0. The thickness is preferably 5 μm or more, and more preferably 1 μm or more. If it exceeds this limit, the overall thickness will become too large, so it is preferable that it is 20 μm or less, and 10 μm or less is even better. preferable.

[0068] <Surgical suture needle> The surgical suture needle of the present invention comprises a suture needle and a suture needle inserted into a groove in the main body of the suture needle or into the main body. and an excitation and emission unit provided on the yarn side, wherein the excitation and emission unit is a graphene quantum dot and / or The excitation and emission part is characterized by containing carbon quantum dots and a biodegradable resin. It is preferable that the outer diameter is not larger than that of the main body of the needle. When the groove is provided, it is preferable that the thickness of the excitation light emitting portion is smaller than the depth of the groove. When the excitation light emitting unit is provided on the suture side of the needle body, the excitation light emitting unit is It is preferable to provide an excitation light emitting part having a smaller outer diameter than the above.

[0069] The surgical suture needle of the present invention has a sharp needle tip 2 at the tip, a semicircular arc-shaped needle tip, and a needle body. The body 1 has a body portion 3 formed on the suture 6 side, and a base end portion 4 is provided on the body portion 3. The mounting hole 5 is drilled along the length of the body 3 from the base end 4 to the tip end side. The suture 6 inserted into the attachment hole 5 is parallel to the outer surface of the base end 4 and is longer than the base end 4. The shank is crimped by a crimping portion 7 having a reduced diameter outer surface.

[0070] The main body 1 of the suture needle is made of, for example, stainless steel, 4310SS, nickel-titanium (Ni Metal alloys such as Ti)SS and 420SS, or tungsten-rhenium (W-Re) alloys They can be made from sturdy biocompatible materials, including advanced alloys such as refractory alloys and urethane foams.

[0071] In the embodiment shown in FIG. 2, a sleeve-shaped excitation light emitting member 8a is provided as the excitation light emitting unit 8. This excitation light emitting member 8a is molded, for example, into two parts, By adhering this to the suture 6 or the base end 4, it is possible to integrate them. The excitation light emitting member 8a is fixed to the suture thread 6 by adhesive or the like, and the suture thread 6 to which the excitation light emitting member 8a is fixed is attached to the suture needle. It is also possible to caulk it to the main body 1.

[0072] In the embodiment shown in FIG. 3, a sleeve-shaped excitation and light emitting member 8a is provided on the suture thread 6 side. The body 3 is also provided with a belt-shaped excitation light emitting member 8b as an excitation light emitting section 8 around the body 3. The excitation light emitting member 8b is, for example, formed in a groove in the body 3, and a strip-shaped light emitting element is inserted in the groove. The excitation light emitting member 8b can be integrated by adhering or the like. The light-emitting member 8b is formed by applying a coating liquid containing carbon-based quantum dots and a biodegradable resin to the grooves. It can also be formed by drying.

[0073] In the embodiment shown in FIG. 4, a strip-shaped excitation light emitting portion 8 is provided along the longitudinal direction of the body portion 3. This example shows a case where the light emitting member 8c is provided in the longitudinal direction. This excitation light emitting member 8c is, for example, A groove is provided in the body 3 along the longitudinal direction, and a strip-shaped excitation light emitting member 8c is bonded in the groove. In addition, the strip-shaped excitation light emitting member 8c is A coating solution containing carbon quantum dots and biodegradable resin is applied to the grooves and dried. It is also possible to form it by

[0074] In addition, when the outer diameter of the crimped portion 7 is smaller than the outer diameter of the body portion 3, the excitation light emitting portion is It is also possible to form 8 by coating.

[0075] When the excitation light emitting portion 8 is formed using a coating liquid, the surgical suture of the present invention is It is possible to use the same coating solution as the coating layer. When the strip-shaped excitation light-emitting member 8b is produced using the molded excitation light-emitting portion 8, the coating layer It is possible to use the same coating solution as that of the above.

[0076] When molding the sleeve-shaped excitation and light emitting member 8a, carbon-based quantum dots and biodegradable resin are A resin composition containing the compound is extruded from an annular nozzle to form a sleeve-shaped excitation light emitting member 8a. In addition, a nozzle with a C-shaped cross section can be used to manufacture an excitation emission It is possible to form part 8.

[0077] The resin composition contains one or more of the above-mentioned biodegradable resins, and further contains cellulose nanoparticles. The material may contain fibers such as cellulose nanofibers. It is preferable to use a cellulose decomposing enzyme in combination with the lubricant, plasticizer, and interface agent. It is also possible to add an activator, a crystal nucleating agent, etc.

[0078] 2 to 4 show an example in which a normal suture 6 is used, but the surgical suture of the present invention Like sutures, graphene quantum dots and / or carbon quantum dots, and biodegradable resins It is also possible to use a suture covered with a coating layer containing the above. [Example]

[0079] The present invention will be described in detail below using examples, but the present invention will not be limited to the above examples. The evaluation items in the examples are as follows: The measurements were carried out in this manner.

[0080] (1) Measurement of fluorescence spectrum The surgical suture or pellet prepared in the examples was used to insert the surgical suture into the liquid cell. Approximately 10 strands of yarn or approximately 30 pellets were placed in the measurement sample, and the measurement was carried out by fluorescence spectrophotometry. Using a spectrometer (RF-5300PC, Shimadzu Corporation), excitation light wavelength was 375 nm or 435 nm. The fluorescence spectrum was measured by m.

[0081] (2) Evaluation of the durability of the coating layer The coated suture was bent once along a cylinder with a radius of curvature of 10 mm. The presence or absence of peeling or falling off of the coating layer was checked.

[0082] (3) Evaluation of light emission state using UV lamp In a dark place, a UV lamp (wavelength 375 nm) is irradiated onto the prepared sample, and the color tone of the emitted light and The degree was checked visually.

[0083] (4) Evaluation of the load capacity of pellet-shaped molded products One of the molded products is placed on a horizontal metal table as a sample, and a load is applied from above via a metal plate. The load was measured when the sample broke.

[0084] Example 1 (Polylactic acid + graphene QDs → surgical suture) Biodegradable and bioabsorbable commercially available sutures made of polyglycolic acid (Kawano Seisakusho, diameter 0.01 mm) were used. .5mm) was prepared.

[0085] In addition, for 100 parts by mass of polylactic acid PLA (manufactured by Fujifilm Wako Co., Ltd., poly(dl-lactic acid)), The graphene quantum dots were dispersed in water (FUJI QD Graphene 818 manufactured by GS Alliance, Ltd.) 10 parts by mass of 0.15% by mass solids, 1 part by mass of water, 10 parts by mass of ethanol as a solvent The above components were placed in a container and thoroughly mixed with a stirrer to prepare a coating solution for forming a coating layer. .

[0086] The suture was immersed in this coating solution, and after pulling it out, excess coating solution was removed. After that, it was heated at 70°C for 1 The suture was then dried for 10 minutes to form a coating layer (thickness: about 1 μm) that covered the suture. When the durability of the coating layer was evaluated, it was confirmed that the coating layer did not peel or fall off.

[0087] In addition, when the light emitted by a UV lamp was evaluated, it was visually confirmed that the light emitted was blue. Confirmed.

[0088] Example 2 (Polyvinyl alcohol + graphene QDs → surgical suture) In Example 1, polyvinyl alcohol (PV, manufactured by Kuraray Co., Ltd.) was used instead of polylactic acid. A surgical suture was prepared under the same conditions as in Example 1, except that the same amount of A-210 (saponification degree 88%) was used. The durability of the coating layer and the state of light emission under a UV lamp were evaluated. The durability of the coating layer was confirmed to be equivalent to that of Example 1, and blue light was emitted by a UV lamp. The fluorescence spectrum of the surgical suture was measured using an excitation light of 375 nm. The results are shown in Figure 5.

[0089] Example 3 (Polyvinyl alcohol + carbon QDs → surgical suture) In Example 2, instead of polyglycolic acid sutures, biomaterials made of polylactic acid (PLA) were used. Commercially available, biodegradable and absorbable sutures (Kawano Seisakusho, 0.5 mm diameter) were used. Instead of using a water dispersion of quantum dots, a water dispersion of carbon quantum dots (GS Alliance The same procedures were carried out except that 1 part by mass of FUJI QD CARBON 308 manufactured by Fuji Electric Co., Ltd., with a solid content of 0.3% by mass, was used. Surgical sutures were prepared under the same conditions as in Example 2, and the durability of the coating layer and the light emission state under UV lamp were examined. As a result, the durability of the coating layer was equivalent to that of Example 1, and the coating was irradiated with a UV lamp. Green luminescence was confirmed.

[0090] Comparative Example 1 (Untreated surgical suture) A commercially available biodegradable and absorbable suture made of polylactic acid (PLA) (Kawano Seisakusho, diameter 0. Fluorescence spectra were measured using this. The results are shown in Figure 5. Shown below.

[0091] Comparative Example 2 (Polylactic acid + fluorescent substance → surgical suture) In Example 1, instead of using graphene quantum dots, commercially available graphene quantum dots that emit light under UV light were used. Same as Example 1 except that 1 part by mass of a phosphor (rhodamine, CAS RN 81-88-9) was used. Surgical sutures were prepared under these conditions, and the durability of the coating layer and the state of light emission under a UV lamp were evaluated. As a result, the coating layer fell off during the durability evaluation, and the UV lamp It was found that the luminescence intensity of the luminescence tube decreased over time to a level that could not be detected visually.

[0092] The above results are summarized in Table 1.

[0093] [Table 1]

[0094] Example 4 (Polylactic acid + carbon QD → excited light-emitting part) Polylactic acid (Fujifilm Wako) 100 parts by mass, carbon quantum dot water dispersion (GS Alliance FUJI QD CARBON 308, solid content 0.3% by mass) The mixture is kneaded at 90°C using a twin-screw extruder, extruded into strands, and cooled. Afterwards, the molded product was cut into pellets (2 mm diameter x 4 mm length).

[0095] When the load-bearing capacity of this molded product was evaluated, it was found that the load-bearing capacity of the pellet-shaped product made only from polylactic acid was The load was almost the same as that of the molded product. In addition, the light emission state of this molded product was evaluated using a UV lamp. Upon inspection, it was visually confirmed that green light was emitted.

[0096] Example 5 (Polylactic acid + Carbon QD + CNF → Excitation and emission part) In Example 4, cellulose nanofiber (GS CNF manufactured by GS Alliance) was further added. A pellet-shaped molded product was prepared under the same conditions as in Example 4, except that 2 parts by mass of The molded article was evaluated for light emission from a UV lamp. Furthermore, compared to Example 4, there was no decrease in the load capacity of the molded product. .

[0097] Example 6 (Cellulose + Carbon QD → Excitation and Emission Moiety) For 100 parts by mass of cellulose resin (GS Alliance GS BR CELLULOSE), Water dispersion of quantum dots (FUJI QD CARBON 308 manufactured by GS Alliance, solid content 0.3 10 parts by mass of the mixture was kneaded at 190°C using a twin screw extruder, and stranded. The mixture was extruded into a molded form, which was then cooled and cut into pellets (2 mm diameter x 4 mm length). .

[0098] When the load-bearing capacity of this molded product was evaluated, it was found that it was higher than that of pellets made only from cellulose resin. The load was almost the same as that of the molded product. When evaluated, it was visually confirmed that the molded product emitted green light. FIG. 6 shows the results of measuring the fluorescence spectrum when the emission wavelength was measured at 435 nm.

[0099] Example 7 (Cellulose + Carbon QD + CNF → Excitation-Emission Moiety) In Example 6, cellulose nanofiber (GS CNF manufactured by GS Alliance) A pellet-shaped molded product was prepared under the same conditions as in Example 6, except that 2 parts by mass of The molded article was evaluated for light emission from a UV lamp. In addition, compared to Example 6, there was no decrease in the load capacity of the molded product. In addition, the fluorescence spectrum when the emission wavelength was measured using this molded product with an excitation light of 435 nm was The spectrum measurement results are shown in FIG.

[0100] Comparative Example 3 (Cellulose → Excitation-Emission Moiety) The same as Example 6 except that the aqueous dispersion of carbon quantum dots was not used. A pellet-shaped molded product was produced under the conditions described above. Using this molded product, the emission wavelength was measured using an excitation light of 435 nm. The fluorescence spectrum obtained when measuring the length is shown in FIG.

[0101] The above results are summarized in Table 2.

[0102] [Table 2]

[0103] [Explanation of symbols]

[0104] 1. Body of the suture needle 6 sutures 8. Excitation and emission unit 8a Sleeve-shaped excitation light-emitting member 8b: Strip-shaped excitation light-emitting member (circumferential direction) 8c Strip-shaped excitation light-emitting member (longitudinal direction) 10 Surgical sutures 11 Sutures 12 Coating Layer

Claims

1. A suture and a coating layer covering the suture, the coating layer being made of graphene quantum dots. A surgical suture comprising nanoparticles and / or carbon quantum dots and a biodegradable resin.

2. a suture needle and an excitation light emitting element provided in a groove in the body of the suture needle or on the suture side of the body a quantum dot generating unit, the quantum dot generating unit including: a graphene quantum dot and / or a carbon quantum dot; A surgical suture needle containing a biodegradable resin.

3. The biodegradable resin is selected from the group consisting of polylactic acid, polyvinyl alcohol, polyglycolic acid, and polybutylene. succinate, polybutylene adipate terephthalate, polyhydroxyalkanoate Polyethylene terephthalate succinate, polycaprolactone, starch-based biodegradable The resin composition according to claim 1 is at least one selected from the group consisting of a cellulose-based biodegradable resin and a cellulose-based biodegradable resin.

1. A surgical suture as described above.

4. 0.001 to 0.2 parts by mass of graphene quantum dots per 100 parts by mass of the biodegradable resin 0.001 to 0.5 parts by mass of carbon quantum dots or 0.001 to 0.5 parts by mass of carbon quantum dots.

1. A surgical suture as described above.

5. The biodegradable resin is selected from the group consisting of polylactic acid, polyvinyl alcohol, polyglycolic acid, and polybutylene. succinate, polybutylene adipate terephthalate, polyhydroxyalkanoate Polyethylene terephthalate succinate, polycaprolactone, starch-based biodegradable The resin composition according to claim 2 is at least one selected from the group consisting of a cellulose-based biodegradable resin and a cellulose-based biodegradable resin.

1. A surgical needle as described above.

6. The biodegradable resin further contains cellulose nanofibers and a cellulolytic enzyme.

6. The surgical suture needle according to claim 5, wherein

7. 0.001 to 0.2 parts by mass of graphene quantum dots per 100 parts by mass of the biodegradable resin dots, or 0.001 to 0.5 parts by mass of carbon quantum dots, according to claim 2 Surgical suture needle.

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