JP2013192885A - Medical implement and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical implement including a surface lubricant layer having island-shaped projecting parts to exert excellent water holding properties, and to provide a method for producing the same.SOLUTION: A method for producing a medical implement includes processes of preparing a solution B by adding hydrophilic polymers and a substance A into a solvent soluble to the hydrophilic polymer and insoluble to the substance A, and forming a film on a base material layer by coating the base material layer with the solution B, and forming a surface lubricant layer having island-shaped projecting parts by immersing the base material layer formed with the film into a solution C insoluble to the hydrophilic polymer and soluble to the substance A. An average particle diameter of the substance A exceeds a thickness of the film formed on the base material layer.

Description

  The present invention relates to a medical device having a surface lubricating layer having island-shaped convex portions and a method for manufacturing the same.

  A medical device inserted into a living body such as a catheter and a guide wire is required to exhibit excellent lubricity in order to reduce tissue damage such as blood vessels and improve the operability of an operator. For this reason, guide wires and catheters in which a hydrophilic polymer having lubricity is coated on the surface of a substrate have been developed and put into practical use.

  Here, in order for the hydrophilic polymer to exhibit lubricity, the hydrophilic polymer needs to be swollen with an aqueous liquid (such as physiological saline or blood). However, medical devices requiring lubricity are not always used in a wet environment. For example, if the guide wire is placed in a dry environment, such as when the guide wire is inserted into the esophagus in the area of digestive organ intervention, the surface lubricant layer will gradually dry during the operation, making operation difficult. The problem is known. Such drying of the surface lubricating layer can cause pain and injury to the patient. In addition, even in the case of a medical device that is placed in a wet environment in the body, such as cardiovascular intervention, the medical device is frequently moistened with physiological saline or the like in order to prevent the surface lubricant layer from being dried outside the body. Complicated work is required.

  For this reason, it is desirable that the surface lubricating layer has high water retention. As a method for imparting high water retention to the surface lubrication layer, Patent Document 1 discloses a medical treatment that improves the water retention by increasing the surface roughness of the substrate, thereby strengthening the adhesion between the hydrophilic coating and the substrate. A tool is disclosed.

  In addition, as a method for imparting irregularities on a substrate, Patent Document 2 devises a method of forming a mesh-like surface lubricating layer by the polymer in the coating liquid becoming an aggregate dispersion.

Special table 2011-516230 gazette JP-T-2001-523759

  However, the method described in Patent Document 1 has a problem in that the types of medical devices that can be applied are limited because the base material needs to be deformed. Moreover, in patent document 2, since there was a part which a base material exposed to the surface, there existed a problem that sufficient lubricity could not be expressed by wetting.

  Accordingly, the present invention has been made in view of the above circumstances, and provides a medical device having a surface lubricating layer having island-shaped convex portions and exhibiting excellent water retention (lubricity maintenance) and a method for producing the same. The purpose is to do.

  To achieve the above object, the present invention provides (1) adding the hydrophilic polymer and the substance A to a solvent that is soluble in the hydrophilic polymer and insoluble in the substance A. Preparing a solution B, coating the base material layer with the solution B to form a film on the base material layer, insoluble in the hydrophilic polymer and soluble in the substance A Immersing the base material layer on which the film is formed in the solution C to form a surface lubricating layer having island-shaped convex portions, and the average particle size of the substance A is on the base material layer. This is a method for producing a medical device that exceeds the thickness of the film formed on the skin.

  Moreover, this invention for achieving the said objective is (2) The said substance A is a particle | grain of inorganic salt or organic salt, The said solution C is a medical device of Claim 1 which has water as a main component. It is a manufacturing method.

  Furthermore, the present invention for achieving the above object comprises (3) a base material layer and a surface lubricating layer made of a hydrophilic polymer that covers at least a part of the base material layer, and the surface lubricating layer comprises: The medical device has island-shaped convex portions, an average height of the convex portions is 0.8 to 5 μm, and a surface roughness of the surface lubricating layer is 0.15 μm or more.

  The present invention provides a medical device in which the surface lubricating layer has island-shaped convex portions and exhibits excellent water retention, and a method for producing the medical device. Further, according to the production method of the present invention, the surface lubricating layer having island-shaped convex portions is fixed to the base material by a simple method, and exhibits excellent water retention (lubrication maintenance property) even in the air after wetting. A medical device is provided.

It is the fragmentary sectional view which represented typically the laminated structure of the surface of embodiment of the medical device (henceforth abbreviated as medical device only) which has the surface lubrication layer in which the island-shaped convex part of this invention was formed. It is the fragmentary sectional view which represented typically the structural example from which the laminated structure of the surface differs as an application example of this embodiment. It is a schematic diagram showing the manufacturing process of the surface lubricating layer in which the island-shaped convex part of the medical device of this invention was formed. 2 is an ultradeep shape measurement photomicrograph of the surface of the surface lubricant layer of the medical device (sample) obtained in Example 1. FIG. 3D is a three-dimensional image of the surface shape of the surface lubricating layer in FIG. 3A. FIG. 3B is a diagram illustrating a roughness curve of a straight line portion xx of the three-dimensional image in FIG. 3B. It is an ultra-deep shape measurement micrograph of the surface of the surface lubricant layer of the medical device (sample) obtained in Comparative Example 1. It is a graph which shows the result of the convex part height of the surface lubricating layer of the medical device (sample) obtained in Examples 1 and 2C and Comparative Examples 1 and 3. It is a graph which shows the result of the surface roughness of the surface lubricating layer of the medical device (sample) obtained in Examples 2A to 2D and Comparative Examples 2 and 3. It is a schematic diagram of the water retention evaluation test apparatus (friction measuring machine) used by the Example and the comparative example. It is a graph which shows the water retention evaluation test result of the surface lubrication layer of the medical device (sample) obtained in Examples 2A-2D. It is a graph which shows the water retention evaluation test result of the surface lubrication layer of the medical device (sample) obtained by the comparative example 2 and the comparative example 3. FIG.

  In the present invention, a solution B is prepared by adding the hydrophilic polymer and the substance A in a solvent that is soluble in the hydrophilic polymer and insoluble in the substance A. The step of forming a film on the base layer by coating the base layer, and the film was formed in the solution C that is insoluble in the hydrophilic polymer and soluble in the substance A A step of immersing the base material layer to form a surface lubricating layer having island-shaped convex portions, wherein the average particle size of the substance A exceeds the thickness of the film formed on the base material layer And a method of manufacturing a medical device.

  In the present invention, “the average particle diameter of substance A exceeds the thickness of the film formed on the base material layer” means that the average particle diameter of substance A is a film formed in the step of forming a film. It means that the thickness of the thinnest part is exceeded.

  Further, the present invention comprises a base material layer and a surface lubricating layer made of a hydrophilic polymer that covers at least a part of the base material layer, and the surface lubricating layer has island-shaped convex portions, It is related with the medical device whose average height of a convex part is 0.8-5 micrometers, and the surface roughness of the said surface lubrication layer is 0.15 micrometers or more.

  According to the production method of the present invention, first, the base material layer is coated with the solution B containing the dissolved hydrophilic polymer and the solid state substance A, and the hydrophilic weight is coated on the base material layer. A film containing the coalescence and the substance A is formed. Next, the base material layer is immersed in a solution C that dissolves the substance A without dissolving the hydrophilic polymer, so that the substance A in the film is dissolved and has island-shaped protrusions (in other words, The surface lubrication layer is formed on the base material layer. “Solid substance A” in solution B, which is a coating solution for the base material layer, means that substance A is insoluble in solution B and is in a solid state. In the method of the present invention, a film containing the solid state substance A is formed on the base material layer, and in the next step, the substance A serves as a template by dissolving the substance A contained in the film. The island-shaped convex part is formed in the surface lubricating layer. Further, the average height of the convex portions and the surface roughness of the surface lubricating layer can be easily adjusted depending on the size of the substance A. In the present embodiment, a discontinuous island-shaped convex structure composed of independent islands is formed on the entire surface of the surface lubricating layer. Since water can be retained in such an island-like convex structure, that is, a concave portion of the concave-convex structure, the medical device obtained by the production method of the present invention can exhibit excellent lubricity when wet, and after being wet, Long-term lubricity can be maintained even in an environment. Further, according to the present invention, the surface lubricating layer containing the hydrophilic polymer can be fixed to the surface of the base material layer by a simple method, and excellent surface lubricating properties and lubricity maintaining properties can be exhibited.

  FIG. 1A is a partial cross-sectional view schematically showing a laminated structure of a surface of a medical device (hereinafter, also simply referred to as “medical device”) having a surface lubrication layer on which island-shaped convex portions of the present embodiment are formed. is there. FIG. 1B is a partial cross-sectional view schematically showing a configuration example having a different surface layer configuration as an application example of the present embodiment. As shown in FIGS. 1A and 1B, in the medical device 10 of the present embodiment, the base material layer 1 and at least a part of the base material layer 1 are covered (in the figure, the whole base material layer in the drawing is covered). A surface lubrication layer 2), and after the surface lubrication layer 2 forms a film containing the solid substance A, the substance A is immersed in a solution C in which the substance A is dissolved. It is obtained by removing. Moreover, the substance A plays a role like a mold, and island-shaped convex portions are formed on the surface of the surface lubricating layer.

  Hereinafter, the manufacturing method of the medical device of this embodiment is demonstrated in order.

<Method for manufacturing medical device>
The method for producing a medical device of the present embodiment is described as follows: “A hydrophilic polymer in a solvent that is soluble in the hydrophilic polymer and insoluble in the substance A (hereinafter also referred to as“ solvent 1 ”). And a substance A is added to prepare a solution B, and the base material layer is coated with the solution B to form a film on the base material layer (hereinafter, this step is referred to as “hydrophilic weight on the base material layer”). This is also referred to as “the step of coating the solution B containing the union and the substance A”), and “the film was formed on the solution C that is insoluble in the hydrophilic polymer and soluble in the substance A. A step of immersing the base material layer to form a surface lubricating layer having island-shaped convex portions (hereinafter, this step is also referred to as a “step of forming island-shaped convex portions on the surface lubricating layer”); Have

  Hereinafter, it will be described by dividing into “a step of coating the base material layer with the solution B containing the hydrophilic polymer and the substance A” and “a step of forming island-shaped protrusions on the surface lubricating layer”.

“Process for coating base material layer with solution B containing hydrophilic polymer”
(1) In this step, first, a solution B is prepared by adding the hydrophilic polymer and the substance A to the solvent 1 that is soluble in the hydrophilic polymer and insoluble in the substance A.

(Hydrophilic polymer)
The hydrophilic polymer used as the surface lubricating layer of the present embodiment may be anything as long as it absorbs water and exhibits lubricity. Specifically, hydrophilic polymers such as polyvinylpyrrolidone, polyethylene glycol, carboxymethylcellulose, hyaluronic acid, polyacrylamide, polydimethylacrylamide, polyacrylic acid, methyl vinyl ether, and their derivatives absorb water when wet and lubricate. Sex can be expressed. In order to firmly fix these hydrophilic polymers to the base material layer, the hydrophilic polymer is added by adding an appropriate amount of a crosslinking agent or introducing a reactive functional group into the hydrophilic polymer forming the surface lubricating layer. It is preferable to crosslink the functional polymer.

  As a method for introducing a reactive functional group into a hydrophilic polymer, a monomer having a reactive functional group (hereinafter also referred to as “reactive monomer”) and a hydrophilic monomer are copolymerized. The method of letting it be mentioned.

  Here, the reactive monomer means a monomer having a reactive functional group capable of performing a crosslinking reaction or the like. The reactive functional group is not particularly limited, and may be a functional group such as an epoxy group, an acid halide group, an aldehyde group, an isocyanate group, or an acid anhydride group. As the reactive monomer, specifically, a monomer having an epoxy group in its molecule such as glycidyl acrylate, glycidyl methacrylate (GMA), methyl glycidyl methacrylate, allyl glycidyl ether; (meth) acrylic acid chloride , (Meth) acrylic acid bromide, (meth) acrylic acid iodide and other monomers having an acid halide group in the molecule; (meth) acrylaldehyde and other aldehyde groups in the molecule; acryloyloxyethyl isocyanate And monomers having an isocyanate group in the molecule such as (meth) acryloyloxypropyl isocyanate; monomers having an acid anhydride group in the molecule such as maleic anhydride, itaconic anhydride and citraconic anhydride; it can. Among these, as the monomer having a reactive functional group, a monomer having an epoxy group is preferable, and glycidyl acrylate or glycidyl methacrylate, in which the reaction is accelerated by heat or the like and handling is relatively easy, is more preferable. These monomers may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used, the form of the polymer may be a block copolymer or a random copolymer.

  Further, the hydrophilic monomer is not particularly limited. For example, acrylamide and its derivatives, vinyl pyrrolidone, acrylic acid and methacrylic acid and their derivatives, polyethylene glycol acrylate and its derivatives, sugar and phospholipids in the side chain. Examples thereof include water-soluble monomers such as maleic anhydride and maleic anhydride. More specifically, N-methylacrylamide, N, N′-dimethylacrylamide, acrylamide, acryloylmorpholine, N, N′-dimethylaminoethyl acrylate, vinylpyrrolidone, 2-methacryloyloxyethylphosphorylcholine, 2-methacryloyloxy Preferable examples include ethyl-D-glycoside, 2-methacryloyloxyethyl-D-mannoside, methyl vinyl ether, hydroxyethyl methacrylate and the like. From the viewpoint of ease of synthesis and operability, N, N′-dimethylacrylamide and N, N′-dimethylaminoethyl acrylate are preferable, and N, N′-dimethylacrylamide is more preferable. These hydrophilic monomers may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used, the form of the polymer may be a block copolymer or a random copolymer.

  In order to express good lubricity, the hydrophilic polymer is composed of a block formed from a monomer having a reactive functional group (reactive block) and a block formed from a hydrophilic monomer (hydrophilic). A block copolymer having a functional block). With such a block copolymer, good results can be obtained in the strength and lubricity of the surface lubricating layer.

  In a more preferred embodiment of the present invention, the hydrophilic polymer comprises a reactive domain having an epoxy group-containing monomer as at least one structural unit, and the hydrophilic monomer as at least one structural unit. A block copolymer having a hydrophilic domain. When the epoxy group which is a reactive functional group reacts with the adjacent epoxy group, the adjacent hydrophilic polymer forms a crosslinked structure, and the strength of the surface lubricating layer can be increased.

  A block copolymer in which a hydrophilic polymer has a reactive domain whose structural unit is a monomer having a reactive functional group (preferably an epoxy group) and a hydrophilic domain whose structural unit is a hydrophilic monomer The composition of the monomer having a reactive functional group and the hydrophilic monomer in the case of a coalescence is not particularly limited. Considering the formation of the hydrogel layer when it comes into contact with bodily fluids and physiological saline, and further the display of moderate lubricity, the molar ratio between the hydrophilic monomer and the monomer having a reactive functional group is It is preferably 1: 1 to 100: 1, more preferably 3: 1 to 50: 1, still more preferably 5: 1 to 20: 1, and 10: 1 to 15: 1. It is particularly preferred.

  The production method (polymerization method) of the hydrophilic polymer for polymerizing the hydrophilic polymer is not particularly limited, and a known polymerization method can be used, but generally a solvent using a polymerization initiator. The polymerization can be carried out by a method such as polymerization or bulk polymerization. Further, when the hydrophilic polymer of the present embodiment is a block copolymer or a graft copolymer, for example, living polymerization, polymerization using a macromonomer, polymerization using a polymer polymerization initiator, polycondensation However, it is not particularly limited.

  As the hydrophilic polymer (surface lubrication layer) of this embodiment, maleic anhydride-methyl vinyl ether copolymer and glycidyl methacrylate-dimethylacrylamide copolymer are preferable, and glycidyl methacrylate-dimethylacrylamide copolymer (especially block copolymer). Coalescence) is more preferred.

(Substance A)
As the substance A, the average particle diameter exceeds the thickness of the film formed on the base material layer (the thickness of the thinnest part of the film formed in the process of forming the film) and is insoluble in the solvent 1 There is no particular limitation as long as it is soluble in the solution C and can provide the surface lubricating layer with an uneven structure, and examples thereof include inorganic particles and organic particles. Examples of the inorganic particles include metal particles and inorganic salt particles, and examples of the organic particles include polymer particles, organic salt particles, and other organic compound particles. In the present embodiment, the substance A is preferably an inorganic salt or organic salt particle. In the present specification, the substance being insoluble in the solvent (not dissolved in the solvent) means that 1 L or more of the solvent is required for 1 g of the solute to dissolve.

Examples of the metal particles include metals such as iron; oxide particles such as SiO ₂ , Al ₂ O ₃ , TiO ₂ and BaTiO ₂ ; nitride particles such as aluminum nitride and silicon nitride;

Inorganic salt particles include alkali metal, alkaline earth metal or ammonium (NH ₄ ⁺ ) halides (fluoride, chloride, bromide, iodide), hydroxide, carbonate, bicarbonate, phosphoric acid. Examples thereof include particles such as a salt, hydrogen phosphate, nitrate, sulfate, hydrogen sulfate, cyanate or thiocyanate. Specifically, halides such as sodium fluoride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, barium chloride, ammonium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide; sodium hydroxide , Hydroxides such as potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide; carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, ammonium carbonate; sodium hydrogen carbonate, hydrogen carbonate Bicarbonates such as potassium, calcium bicarbonate and ammonium bicarbonate; phosphates such as trisodium phosphate (Na ₃ PO ₄ ) and tripotassium phosphate (K ₃ PO ₄ ); sodium dihydrogen phosphate (NaH ₂₎ PO ₄ ), disodium hydrogen phosphate (Na ₂ HPO ₄ ), hydrogen phosphates such as potassium dihydrogen phosphate (KH ₂ PO ₄ ) and dipotassium hydrogen phosphate (K ₂ HPO ₄ ); nitrates such as sodium nitrate, potassium nitrate and ammonium nitrate; sodium sulfate and potassium sulfate Sulfates such as magnesium sulfate, calcium sulfate and barium sulfate; hydrogen sulfates such as sodium hydrogen sulfate; cyanates such as sodium cyanate, potassium cyanate and ammonium cyanate; sodium thiocyanate, potassium thiocyanate, thiocyanic acid Examples thereof include thiocyanate such as calcium.

  Examples of the polymer particles include particles of polymers such as lactic acid, acrylamide, methyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid, and styrene, and copolymers thereof. It is done.

  Examples of the organic salt particles include alkali metal, alkaline earth metal or organic compound carboxylates (acetates, succinates), hydroxyates (citrates), sulfonates, hydrochlorides, and the like. It is done. Specifically, acetates such as sodium acetate and potassium acetate; succinates such as sodium succinate; citrates such as sodium citrate and potassium citrate; sodium methanesulfonate, sodium benzenesulfonate, p-toluene Examples thereof include particles of sulfonates such as sodium sulfonate; hydrochlorides such as arginine hydrochloride.

  Other organic compound particles include particles of hydroxy acids such as citric acid and glycolic acid, amino acids, monosaccharides, and oligosaccharides.

  Among these, as the substance A, particles of an inorganic salt or an organic salt are preferable from the viewpoint of solubility in water when water is used for the solution C as described later. Sodium sulfate, sodium chloride, potassium chloride Sodium citrate is more preferable.

  The particle size of the substance A correlates with the height of island-shaped protrusions formed on the surface lubricating layer, that is, the protrusions of the uneven structure. The average particle diameter of the substance A is the thickness of the film formed by the solution B (the thickness of the thinnest part of the film formed in the process of forming the film) in order to form convex portions that can exhibit excellent water retention. For example, the average particle size of the substance A is preferably 1.01 to 20 times the thickness of the film, more preferably 1. 5 to 15 times, more preferably 2 to 10 times. Moreover, it is preferable that the average particle diameter of the substance A exceeds 0.7 micrometer, More preferably, it is 1.5-100 micrometers, More preferably, it is 2-75 micrometers, Especially preferably, it is 3-50 micrometers. By making the average particle size of the substance A larger than the thickness of the film, it is possible to sufficiently ensure the size of the convex portion of the concave-convex structure formed on the surface lubricating layer, so water retention by retaining water in the concave portion Is demonstrated. In addition, it is preferable that the particle size distribution of the substance A is small in order to keep the height of the protrusions of the uneven structure of the surface lubricating layer constant. Specifically, the CV value (coefficient of variation) is preferably less than 1.0, more preferably less than 0.7, and even more preferably less than 0.5. In this specification, “particle size” means the equivalent circle diameter of a particle (the diameter of a circle having the same area as the projected area of the particle). The value of “average particle size” is the average value of the particle size of particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted. The particle diameters and average particle diameters of the other constituent components can be defined similarly.

  The substance A used in the present embodiment may be synthesized or a commercially available product can be used. Further, for example, the commercially available substance A may be pulverized using a mill or the like, or classified using a sieve or the like, so as to obtain a desired particle size and particle size distribution.

(Solvent 1)
The solvent 1 constituting the solution B used in the present embodiment is not particularly limited as long as it is soluble in the hydrophilic polymer and insoluble in the substance A. Examples of the solvent 1 include halogen-based organic solvents such as chloroform and dichloromethane; aliphatic hydrocarbons such as butane, pentane and hexane; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate Water-insoluble ketones such as methyl isobutyl ketone; ethers such as tetrahydrofuran (THF), butyl ether and dioxane; aliphatic alcohols such as methanol, ethanol and isopropanol; acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) And carbon disulfide. These solvents may be used alone or as a mixed solvent in which two or more of these solvents are combined.

(Solution B)
The solution B includes the above-described hydrophilic polymer, the substance A, and the solvent 1. At this time, the hydrophilic polymer and the substance A are dissolved in the solution B due to the difference in solubility in the respective solvents 1, and the substance A is in a solid state in the solution B. Is distributed.

  The concentration of the hydrophilic polymer in the solution B is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and further preferably 0.1 to 10% by mass. . When the concentration of the hydrophilic polymer is within the above range, the mechanical strength of the obtained surface lubricating layer is sufficiently exhibited. In addition, a uniform surface lubricating layer having a desired thickness can be easily obtained by one coating, which is preferable in terms of workability (for example, ease of coating) and production efficiency. However, even if it is out of the above range, it can be sufficiently utilized as long as it does not affect the operational effects of the present invention.

  The mass ratio of the hydrophilic polymer and the substance A in the solution B is not particularly limited, but is preferably 20: 1 to 1: 4, more preferably 15: 1 to 1: 4, and even more preferably 10: 1. ~ 1: 3. If the mass ratio between the hydrophilic polymer and the substance A is in the above range, island-shaped convex portions are easily formed on the obtained surface lubricating layer, and the surface roughness of the surface lubricating layer is 0.15 μm or more, and water retention Sex is fully demonstrated. However, even if it is out of the above range, it can be sufficiently utilized as long as it does not affect the operational effects of the present invention. The method for dispersing the substance A in the solvent 1 is not particularly limited, but the substance A is prepared by adding the substance A to the solvent 1 and stirring with a stirrer or the like.

  (2) Next, in this step, the solution B is coated on the base material layer (also referred to as “coating” or “coating”) to form a film on the base material layer.

(Base material layer)
The base material layer used in the present embodiment may be composed of any material, and the material is not particularly limited. Specifically, examples of the material constituting (forming) the base material layer 1 include metal materials, polymer materials, and ceramic materials. Here, the base material layer 1 is composed (formed) of the whole base material layer 1 by any one of the above materials, or, as shown in FIG. The surface layer 1b may be configured (formed) by coating (coating) any of the other materials with a suitable method on the surface of the formed base layer core portion 1a. As an example of the latter case, a metal material is coated (coated) by an appropriate method (a known method such as plating, metal vapor deposition, sputtering) on the surface of the base material layer core portion 1a formed of a polymer material or the like. The surface layer 1b is formed on the surface of the base layer core portion 1a formed of a hard reinforcing material such as a metal material or a ceramic material, and is a polymer that is more flexible than a reinforcing material such as a metal material. The material is coated (coating) by an appropriate method (dipping (dipping), spraying (spraying), application / printing, etc.) or a reinforcing material for the base layer core portion 1a and a polymer material for the surface layer 1b Is formed by forming a surface layer 1b by compounding (appropriate reaction treatment). Therefore, the base layer 1a is a multilayer structure in which different materials are laminated in multiple layers, or a structure (composite) in which members formed of different materials for each part of a medical device are connected. Also good. Further, another middle layer (not shown) may be formed between the base material layer core portion 1a and the surface layer 1b. Further, the surface layer 1b may be a multilayer structure in which different materials are laminated in multiple layers, or a structure (composite) in which members formed of different materials are connected to each part of the medical device.

  Of the materials constituting (forming) the base layer 1, the metal material is not particularly limited, and metal materials generally used for applications such as catheters, guide wires, and indwelling needles are used. The Specifically, various stainless steel (SUS) such as SUS304, SUS316, SUS316L, SUS420J2, and SUS630, gold, platinum, silver, copper, nickel, cobalt, titanium, iron, aluminum, tin, or nickel-titanium (Ni-Ti) ) Alloys, nickel-cobalt (Ni-Co) alloys, cobalt-chromium (Co-Cr) alloys, various alloys such as zinc-tungsten (Zn-W) alloys, and the like. These may be used individually by 1 type and may use 2 or more types together. What is necessary is just to select suitably the metal material optimal as base materials, such as a catheter, a guide wire, an indwelling needle which is a use application, as said metal material.

  Of the materials constituting (forming) the base material layer 1, the polymer material is not particularly limited, and is a polymer generally used for applications such as catheters, guide wires, and indwelling needles. Material is used. Specifically, a polyolefin resin such as a polyamide resin, a linear low density polyethylene (LLDPE), a low density polyethylene (LDPE), a high density polyethylene (HDPE), or a polypropylene resin, a modified polyolefin resin, an epoxy resin, Urethane resin, diallyl phthalate resin (allyl resin), polycarbonate resin, fluororesin, amino resin (urea resin, melamine resin, benzoguanamine resin), polyester resin, styrene resin, acrylic resin, polyacetal resin, vinyl acetate resin, phenol resin, chloride A vinyl resin, a silicone resin (silicon resin), a polyether resin, a polyimide resin, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. What is necessary is just to select suitably the polymeric material optimal as base materials, such as a catheter, a guide wire, and an indwelling needle which are use uses as the said polymeric material.

  Moreover, the shape of the base material layer is not particularly limited, and is appropriately selected depending on the usage mode such as a sheet shape, a linear shape (wire), and a tubular shape (tube).

  In addition, the material that can be used for the middle layer (not shown) is not particularly limited, and a material that can sufficiently express the bonding function between the base layer 1a and the surface layer 1b is appropriately used. Just choose. For example, although the same material as the material of the base material layer 1 can be used, it is not limited to these.

(Coating method)
The method for coating the base material layer with the solution B is not particularly limited, and is a dipping method (dipping method), a coating / printing method, a spraying method (spraying method), a spin coating method, a mixed solution impregnated sponge coating method. Although a conventionally known method can be applied, for example, in the present embodiment, it is preferable to use an immersion method (dipping method).

  Further, when a film (surface lubrication layer) is formed only on a part of the base material layer, only a part of the base material layer is immersed in the solution B, and the solution B is made a part of the base material layer. By coating, a film (surface lubricating layer) can be formed on a desired surface portion of the base material layer.

  When it is difficult to immerse only a part of the base material layer in the solution B, the surface part of the base material layer that does not require the formation of a film (surface lubrication layer) in advance can be attached / detached (attached / detached). It is not necessary to form a film (surface lubrication layer) after the base material layer is dipped in the solution B and coated on the base material layer after being protected (covered) with various members and materials. By removing the protective member (material) from the surface portion of the base material layer and then reacting it by a heating operation or the like, a film (surface lubrication layer) can be formed on a desired surface portion of the base material layer. However, the present invention is not limited to these forming methods, and a film (surface lubricating layer) can be formed by appropriately using conventionally known methods. For example, when it is difficult to immerse only a part of the base material layer in the mixed solution, instead of the immersing method, another coating technique (for example, the solution B is applied to a predetermined surface portion of the medical device, A coating method using a coating apparatus such as a spray device, a bar coater, a die coater, a reverse coater, a comma coater, a gravure coater, a spray coater, or a doctor knife may be applied.

  As mentioned above, after obtaining the base material layer which coat | covered the solution B on the surface, it is made to dry and a membrane | film | coat is formed on a base material layer. The drying method is not particularly limited, and can be dried by heating, for example. The drying treatment temperature (set temperature of a heating device such as a heating furnace) is not particularly limited, but is preferably 40 to 170 ° C., more preferably 50 to 150 ° C., and the drying treatment time is particularly Although not limited, for example, it is preferably 30 minutes to 24 hours, more preferably 1 to 10 hours. As the heating means (device), for example, an oven, a dryer, or the like can be used.

  In this embodiment, when the hydrophilic polymer includes a reactive monomer, when the solution B is evaporated (dried), the reactive functional group (preferably an epoxy group) of the reactive monomer is adjacent. It can react with the reactive functional group of the reactive monomer to form a crosslinked structure. Thereby, it is possible to form a surface lubricating layer that is firmly fixed to the base material layer and has excellent strength. In the case where the hydrophilic polymer contains a reactive monomer, the step of reacting the reactive functional group (preferably an epoxy group) of the reactive monomer is carried out by subjecting the base material layer after being immersed in the solution C to be described later. Although it may be performed when drying and is not particularly limited, it is preferably performed when drying the solution B from the viewpoint of forming the surface lubricating layer on the base material layer more firmly.

  As a method for evaporating (drying) the solution B at that time, any method can be used as long as the reactive functional group can advance (accelerate) the reaction, and it is preferable to perform heat treatment. For example, the heat treatment temperature (set temperature of a heating device such as a heating furnace) is preferably 40 to 170 ° C, more preferably 50 to 150 ° C. If it is such a range, a desired reaction is fully accelerated | stimulated and a desired effect can be acquired in a short time. The heat treatment time is not particularly limited as long as the reaction of the hydrophilic polymer can be promoted, and is preferably 30 minutes to 24 hours, more preferably 1 to 10 hours. When the heating time is in the above range, the reaction proceeds efficiently, and the surface lubricating layer can be firmly fixed to the base material layer. The pressure condition during the heat treatment is not limited at all, and it can be performed under normal pressure (atmospheric pressure), or under pressure or reduced pressure. In addition, when the reactive functional group of the reactive monomer is an epoxy group, a reaction catalyst such as a trialkylamine compound or a tertiary amine compound such as pyridine is hydrophilic so that the reaction can be promoted. An appropriate amount of the solution A may be added to the solution A in which the polymer is dissolved. As the heating means (device), for example, an oven, a dryer, a microwave heating device, or the like can be used. In addition to the heat treatment, the method for promoting the reaction of the reactive functional group is not particularly limited. For example, light irradiation, ultraviolet (UV) irradiation, electron beam irradiation, radiation irradiation, plasma irradiation, etc. Conventionally known methods can be applied.

  Further, the thickness of the film formed in this step is not particularly limited, but the obtained surface lubrication layer is firmly fixed to the base material layer, and has excellent surface lubricity during use and water retention ( It is preferable to have a thickness capable of exhibiting (lubricity maintenance). From such a viewpoint, the thickness of the coating is preferably 0.1 to 10 μm, preferably 0.5 to 5 μm. If it is such thickness, in the surface lubrication layer obtained, surface lubricity and water retention (lubrication maintenance property) can fully be exhibited.

  The thickness of the film is a value obtained by observing a cross section cut perpendicularly to the base material layer and the film with a digital microscope, and a value of a portion having the shortest distance from the base material layer surface to the outermost surface part of the film That is, it means the thickness of the thinnest part of the film formed in the process of forming the film.

“Process of forming island-shaped protrusions on the surface lubricating layer”
In this step, the base material layer on which the film is formed is immersed in a solution C that is insoluble in the hydrophilic polymer and soluble in the substance A, and has island-shaped convex portions (concave / convex structure). A surface lubricating layer is formed.

(Solution C)
The solution C used in the present embodiment is not particularly limited as long as it is insoluble in the hydrophilic polymer and soluble in the substance A, and is appropriately selected according to the type of the hydrophilic polymer and the substance A. Is done. In the present embodiment, the solution C may be composed of only the solvent or may be composed of other components in the solvent.

  In this embodiment, when metal particles are used as the substance A, examples of the solution C include an acidic or basic aqueous solution, a solution containing a complexing agent, and the like. The acidic aqueous solution is not particularly limited, but an aqueous solution of hydrochloric acid, nitric acid, perchloric acid, sulfuric acid, acetic acid, formic acid, carbonic acid, phosphoric acid, citric acid or the like whose pH is less than 7, preferably 6 or less. Can be mentioned. Although it does not restrict | limit especially as basic aqueous solution, The aqueous solution of sodium hydroxide, calcium hydroxide, barium hydroxide, ammonia etc. whose pH of the aqueous solution is larger than 7, Preferably it is 7.5 or more is mentioned. The solution containing the complexing agent is not particularly limited as long as it is a solution containing a compound capable of forming a complex ion by binding with a metal ion. Examples of the complexing agent include ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).

  When inorganic salt particles are used as the substance A, examples of the solution C include the acidic or basic aqueous solution and water.

  Further, when polymer particles are used as the substance A, the solution C includes the above acidic or basic aqueous solution, a solution containing a degrading enzyme, a halogen-based organic solvent such as water, chloroform or dichloromethane; a fat such as butane, pentane or hexane. Aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; water-insoluble ketones such as methyl isobutyl ketone; ethers such as tetrahydrofuran (THF), butyl ether and dioxane; Aliphatic alcohols such as methanol, ethanol and isopropanol; acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like.

  When organic salt particles are used as the substance A, examples of the solution C include the acidic or basic aqueous solution and water.

  When other organic compound particles are used as the substance A, the solution C includes water, methanol, ethanol, and the like.

  Among the above, from the viewpoint that the solution C is easily available and easy to handle, the substance A is an inorganic salt or organic salt particle, and the solution C is preferably a combination containing water as a main component. “Solution C is mainly composed of water” means that the content of water in solution C is 80% by mass or more. By selecting inorganic salt or organic salt particles having high solubility in water as the substance A, a solution containing water as a main component can be selected as the solution C.

(Formation method of convex part)
The method for immersing the base material layer on which the film is formed in the solution C is not particularly limited, and a conventionally known dipping method (dipping method) can be applied. Although it does not restrict | limit especially as temperature of the solution C at the time of immersion, Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC. Moreover, as immersion time, Preferably it is 5 to 60 minutes, More preferably, it is 10 to 30 minutes.

  When the solution C contains a component other than the solvent, for example, when the solution C such as an acidic aqueous solution is used, after the surface lubricating layer is immersed in the solution C and the substance A is dissolved, a hydrophilic polymer is further added. It is preferable to immerse the surface lubricating layer in a solvent that does not dissolve and wash it.

  As described above, after immersing the base material layer on which the film is formed in the solution C, the base material layer is dried to form a surface lubrication layer having island-shaped protrusions (concavo-convex structure) on the base material layer. Let The drying method is not particularly limited, and for example, it can be dried in the air. The drying treatment temperature (set temperature of a heating device such as a heating furnace) is not particularly limited, but is preferably 15 to 170 ° C., more preferably 20 to 150 ° C., and the drying treatment time is particularly Although not limited, for example, it is preferably 1 minute to 24 hours, more preferably 5 minutes to 10 hours. As a drying means (apparatus), in addition to drying in the air, for example, an oven, a dryer, or the like can be used.

  In this embodiment, when the hydrophilic polymer includes a reactive monomer, when the solution C is evaporated (dried), the reactive functional group (preferably an epoxy group) of the reactive monomer is adjacent. It can react with the reactive functional group of the reactive monomer to form a crosslinked structure. Thereby, it is possible to form a surface lubricating layer that is firmly fixed to the base material layer and has excellent strength. When the hydrophilic polymer contains a reactive monomer, the method of reacting the reactive functional group (preferably epoxy group) of the reactive monomer is the same as the method performed when the solution B is dried. Is applicable.

  After the surface lubrication layer is formed in this way, the surplus hydrophilic polymer or the like is washed with an appropriate solvent, and the surface lubrication layer is firmly fixed to the base material layer. Can also be allowed to remain.

  Further, the thickness of the surface lubricating layer formed in this step is not particularly limited, but the obtained surface lubricating layer is firmly fixed to the base material layer, and has excellent surface lubricity during use and water retention. It is preferable to have a thickness that can exhibit the property (lubricity maintenance property). From such a viewpoint, it is desirable that the thickness of the surface lubricating layer is 0.1 to 10 μm, preferably 0.5 to 5 μm. If it is such thickness, in the surface lubrication layer obtained, surface lubricity and water retention (lubrication maintenance property) can fully be exhibited.

  The thickness of the surface lubricating layer is determined by observing a cross section cut perpendicular to the base material layer and the surface lubricating layer with a digital microscope, and the distance from the surface of the base material layer to the outermost surface portion of the surface lubricating layer is the largest. The value of the short part, that is, the thickness of the thinnest part of the surface lubricating layer formed in the step of forming the island-shaped protrusions on the surface lubricating layer, reflects the thickness of the film.

  FIG. 2 is a diagram schematically showing a process of forming the surface lubricating layer of the present embodiment. FIG. 2A shows a medical device 20 in which a film 12 containing the substance A 13 is formed on the base material layer 11. By immersing the film 12 in the solution C, the substance A in the film is dissolved, the region where the substance A exists becomes a convex part, and an island-shaped convex part 14a is formed. As a result, as shown in FIG. 2B, the surface-like lubrication layer 14 having an uneven structure having island-shaped convex portions 14a, that is, convex portions 14a and concave portions 14b is formed. As described above, according to the manufacturing method of the present embodiment, it is understood that the convex portion correlated with the particle size of the substance A is formed on the surface lubricant layer of the medical device.

  Further, in the present embodiment, the height of the convex portions (specifically, island-shaped convex portions) formed on the surface lubricating layer and the surface roughness of the surface lubricating layer are the thickness of the film formed by the solution B. It also correlates with the average particle diameter of the substance A with respect to the ratio of the substance A to the hydrophilic polymer in the film. The higher the average particle diameter of the substance A with respect to the thickness of the film, the higher the height of the convex portion. The higher the ratio of the substance A to the hydrophilic polymer, the higher the surface roughness of the surface lubricating layer. There is a tendency to become coarse.

(Surface lubrication layer)
As described above, according to the manufacturing method of the present embodiment, the surface lubricating layer having island-shaped convex portions is formed. That is, the medical device of the present embodiment includes a base material layer and a surface lubrication layer made of a hydrophilic polymer that covers at least a part of the base material layer, and the surface lubrication layer has island-shaped protrusions. And the average height of the convex portions is 0.8 to 5 μm, and the surface roughness of the convex portions is 0.15 μm or more.

  In the island-shaped convex part (concavo-convex structure), the cross-sectional shape of the convex part is not particularly limited, and is conical, triangular pyramid, quadrangular pyramid (pyramid), frustoconical, triangular frustum, square frustum. Further, it may be a convex portion (concave / convex structure) having an arbitrary shape within a range that does not impair the object of the present invention, such as a tapered shape.

  In the present embodiment, the average height of the convex portions is 0.8 to 5 μm, preferably 1 to 5 μm. If the average height of the convex portions is within the above range, water can be sufficiently retained in the concave portions to be formed. Therefore, even when left in the atmosphere, the water retention effect is exhibited. If the average height of the convex portion is less than 0.8 μm, water cannot be retained in the concave portion, and if it exceeds 5 μm, the durability of the surface lubricating layer is lowered. In addition, in this specification, the average height of a convex part is calculated with the following method. The roughness curve average height Rc value in the linear region (200 μm) on the surface lubrication layer observed with an objective lens 50 times using an ultra-deep shape measurement microscope is measured based on JISB0601: 2001. This measurement is performed at any 10 locations on the surface lubricating layer, and an average value obtained by arithmetically averaging the measured Rc values is defined as the average height of the convex portions.

  In the present embodiment, the surface lubrication layer has a surface roughness of 0.15 μm or more, preferably 0.17 to 0.5 μm. If the surface roughness of the surface lubrication layer is within the above range, water can be sufficiently retained in the formed recess, so that even when left in the air, the water retention effect is exhibited. . When the surface roughness of the surface lubricating layer is less than 0.15 μm, the amount of water that can be held in the recesses is not sufficient, and the water retention is not improved. In the present specification, the surface roughness of the surface lubricating layer is calculated by the following method. An arithmetic average roughness Ra value in a region of 20 μm × 200 μm on the surface lubricating layer observed with an objective lens 50 times is measured using an ultra-deep shape measuring microscope based on JISB0601: 2001. This measurement is performed at any 10 locations on the surface lubricating layer, and an average value obtained by arithmetically averaging the measured Ra values is defined as the surface roughness of the surface lubricating layer.

<Medical tools>
The surface lubrication layer thus formed exhibits surface lubricity and water retention (lubrication maintenance).

  The medical device having surface lubricity and water retention according to the present invention is an instrument used in contact with an aqueous liquid such as body fluid or physiological saline in any of the above-described embodiments. Therefore, it is possible to reliably exhibit lubricity maintenance and to exhibit surface lubricity for a long time. Specific examples include guide wires and catheters used in blood vessels, but the following medical devices are also shown.

  (1) Endoscopic guidewires, gastrointestinal guidewires, gastrointestinal catheters, feeding catheters, tube feeding tubes, guidewires and catheters inserted or placed in the digestive organs orally or nasally Kind.

  (2) Oxygen catheter, oxygen cannula, endotracheal tube, tracheostomy guide wire, tracheostomy tube, guide wire and catheters that are inserted or placed in the trachea or trachea orally or nasally.

  (3) Guide wires and catheters inserted or placed in the urethra or ureter, such as urethral guide wires, urethral catheters, urinary catheters, urethral balloon catheter catheters and balloons.

  (4) Catheters inserted or placed in various body cavities, organs, tissues such as suction catheters, drainage catheters, rectal catheters, or guide wires for these catheters.

  (5) Indwelling needles, IVH catheters, thermodilution catheters, angiographic catheters, vasodilator catheters and catheters inserted or placed in blood vessels such as dilators or introducers, or for these catheters Guide wire, stylet, etc.

  (6) Artificial trachea, artificial bronchi, etc.

  (7) Medical devices for extracorporeal circulation treatment (artificial lung, artificial heart, artificial kidney, etc.) and their circuits.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

<Production method>
Example 1
Block copolymer having polydimethylacrylamide (DMAA) as hydrophilic block and polyglycidyl methacrylate (GMA) as reactive block [p (DMAA-b-GMA)] (DMAA: GMA (molar ratio)) = 12: 1 ) Was dissolved in a DMF solution at a ratio of 4.0% by mass to prepare a coating solution in which 8.0% by mass of sodium sulfate fine particles (Mitajiri Chemical Co., Ltd.) having an average particle size of 8.5 μm were dispersed ( The mass ratio of the hydrophilic polymer to the sodium sulfate fine particles is 1: 2). Nylon elastomer sheet (manufactured by MSK Japan Co., Ltd., Grillamide ELG5660 grade, 10 × 50 × 1 mm) is dipped in the coating solution, dip-coated, dried in an oven at 130 ° C. for 3 hours, and a film (thickness) 2.0 μm). Thereafter, the sheet is immersed in water for 15 minutes and air-dried at 25 ° C. for 60 minutes, whereby the surface lubricating layer has an island-like convex portion (irregular structure) (surface lubricating layer thickness 2. 0 μm) was produced.

  3A and 3B show the results of observing the surface state of the surface lubricating layer obtained in Example 1 using an ultradeep shape measuring microscope (product name VK-X100, manufactured by Keyence Corporation). 3A is an ultra-deep image photograph of the surface of the surface lubricating layer, and FIG. 3B is a three-dimensional image of the surface shape of the surface lubricating layer of FIG. 3A. From the three-dimensional image in FIG. 3B, the shape of the irregularities on the surface can be seen, and it can be seen that island-shaped convex portions are formed on the surface of the surface lubricating layer. 3C is a diagram showing a roughness curve of the surface lubricating layer in a cross section cut perpendicularly to the base material layer and the surface lubricating layer in the linear portion xx (200 μm) of the three-dimensional image of FIG. 3B. .

(Example 2)
Nylon elastomer (manufactured by MSK Japan Co., Ltd., Grillamide ELG5660 grade) was extruded by a conventional method to produce a single-layer tube having an outer diameter of 0.88 mm, an inner diameter of 0.76 mm, and a length of 50 mm.

  Block copolymer having polydimethylacrylamide (DMAA) as hydrophilic block and polyglycidyl methacrylate (GMA) as reactive block [p (DMAA-b-GMA)] (DMAA: GMA (molar ratio)) = 12: 1 ) In a DMF solution at a ratio of 4.0% by mass, sodium sulfate fine particles (Mitajiri Chemical Co., Ltd.) having an average particle diameter of 8.5 μm are 0.5, 2.0, 8.0, and 12 respectively. A coating solution in which 0.0 mass% was dispersed was prepared (mass ratios of hydrophilic polymer and sodium sulfate fine particles were 8: 1, 2: 1, 1: 2, and 1: 3, respectively). The single-layer tube is immersed in the coating solution and dip-coated, and dried in an oven at 130 ° C. for 3 hours to form a film (thickness 1.8 μm, average value of the four mass ratios) on the outer periphery of the tube. did. Thereafter, the tube was immersed in water for 15 minutes and air-dried at 25 ° C. for 60 minutes to produce a tube having an island-like convex portion (concave / convex structure) on the surface lubricating layer. Among these tubes, Examples 2A to 2D are used in descending order of the ratio of the sodium sulfate fine particles. The thickness of the surface lubricating layer of the 2A to 2D tubes was 1.8 μm (average value of 2A to 2D).

(Comparative Example 1)
A sheet having a surface lubricating layer was produced in the same manner as in Example 1 except that the sodium sulfate fine particles were not dispersed in the coating solution. The result of observing the surface state of the surface lubricating layer obtained in Comparative Example 1 using an ultra-deep shape measuring microscope (product name VK-X100, manufactured by Keyence Corporation) is shown in FIG. FIG. 4 is a photograph of the surface state of the surface lubricating layer.

(Comparative Example 2)
A tube having a surface lubricating layer on the outer periphery was produced in the same manner as in Example 2 except that the sodium sulfate fine particles were not dispersed in the coating solution.

(Comparative Example 3)
Block copolymer having polydimethylacrylamide (DMAA) as hydrophilic block and polyglycidyl methacrylate (GMA) as reactive block [p (DMAA-b-GMA)] (DMAA: GMA (molar ratio)) = 12: 1 ) In a DMF solution in which 4.0% by mass is dissolved, a coating solution in which 8.0% by mass of calcium carbonate fine particles having an average particle size of 0.7 μm (Softon 3200, manufactured by Bihoku Powder Chemical Co., Ltd.) is dispersed It was prepared (mass ratio of hydrophilic polymer to calcium carbonate fine particles is 1: 2). The single-layer tube of Example 2 was immersed in this coating solution and dip-coated, and dried in an oven at 130 ° C. for 3 hours to form a film (thickness: 1.9 μm) on the outer periphery of the tube. Thereafter, the tube was immersed in 0.1 mol / L hydrochloric acid for 15 minutes, washed with water, and air-dried at 25 ° C. for 60 minutes, whereby island-like protrusions ( A tube (surface lubrication layer thickness 1.9 μm) having an uneven structure was produced.

<Uneven structure>
The height of the convex portion of the sheet or tube (sample) produced in Example 1, Example 2C, Comparative Example 1, and Comparative Example 3 was calculated by the following method.

  Each sample was observed with an ultra-deep shape measuring microscope (product name VK-X100, manufactured by Keyence Corporation) at an objective lens of 50 times, and the roughness curve average height in a linear region (200 μm) on the surface lubricating layer of each sample. Rc value was measured based on JISB0601: 2001. This measurement was performed at any 10 locations on the surface lubricating layer, and an average value obtained by arithmetically averaging the measured Rc values was defined as the average height of the convex portions. The results are shown in FIG.

  Moreover, the surface roughness of the tube (sample) produced by the said Example 2A-2D, the comparative example 2, and the comparative example 3 was computed with the following method.

  Each sample was observed with an ultra-deep profile measuring microscope (product name VK-X100, manufactured by Keyence Corporation) at an objective lens of 50 times, and an arithmetic average roughness Ra value in a 20 μm × 200 μm region on the surface lubricating layer of each sample. Was measured based on JISB0601: 2001. This measurement was performed at any 10 locations on the surface lubricating layer, and the average value obtained by arithmetically averaging the measured Ra values was defined as the surface roughness of the surface lubricating layer. The results are shown in FIG.

<Water retention evaluation>
Water retention evaluation was performed using the tubes (samples) prepared in Examples 2A to 2D, Comparative Example 2, and Comparative Example 3.

  As shown in FIG. 7, the double-sided tape was affixed on the glass petri dish 31, and the sample 35 which inserted the metal core 32 was fixed to the adhesive surface. The petri dish 31 was filled with PBS and immersed for 1 minute, and then the PBS was removed. After that, it is quickly set on the sample stage of the friction measuring device 30 (manufactured by Trinity Labs, Handy Tribomaster TL201), and a load is applied to the SUS spherical contact terminal 33 by the weight 34, so that the sliding when repeatedly reciprocating is performed. The dynamic resistance value was measured over time. As the surface lubricating layer dries in the atmosphere, the lubricity is lost and the sliding resistance value increases. At this time, the measurement was performed until the sliding resistance value exceeded 5 gf as the lubricity holding time.

  The water retention evaluation results of the tubes prepared in Examples 2A to 2D are shown in FIG. 8A, and the water retention evaluation results of the tubes manufactured in Comparative Examples 2 and 3 are shown in FIG. 8B. In Comparative Examples 2 and 3, the lubricity retention time was about 150 seconds. On the other hand, in Example 2A, the lubricity was maintained for about 1.7 times longer. In Examples 2B to 2D in which the amount of sodium sulfate fine particles added was large, the lubricity was maintained for a longer time.

  From the above results, it was shown that by producing island-shaped convex portions (concave / convex structure) as in the examples of the present invention, a surface lubricating layer that maintains the lubricity for a long time even in the atmosphere can be manufactured. .

1 base material layer,
1a base material layer core part,
1b surface layer,
2 surface lubrication layer,
3 convex parts,
10 Medical tools,
11 base material layer,
12 film,
13 Substance A,
14 surface lubrication layer,
14a convex part,
14b recess,
20 medical devices,
30 Friction measuring machine,
31 Petri dish,
32 core metal 33 SUS spherical contact terminal,
34 Weight,
35 samples.

Claims (3)

A solution B is prepared by adding the hydrophilic polymer and the substance A in a solvent that is soluble in the hydrophilic polymer and insoluble in the substance A, and the solution B is applied to the base material layer. Coating and forming a film on the substrate layer;
The base material layer on which the film is formed is immersed in a solution C that is insoluble in the hydrophilic polymer and soluble in the substance A to form a surface lubricating layer having island-shaped convex portions. And a process of
Including
The method for producing a medical device, wherein an average particle diameter of the substance A exceeds a thickness of a film formed on the base material layer.   The method for producing a medical device according to claim 1, wherein the substance A is particles of an inorganic salt or an organic salt, and the solution C is mainly composed of water. A base material layer;
A surface lubricating layer made of a hydrophilic polymer covering at least a part of the base material layer,
The surface lubricating layer has island-shaped convex portions,
The average height of the convex portions is 0.8 to 5 μm,
A medical device wherein the surface lubrication layer has a surface roughness of 0.15 µm or more.