JP2018000746A - Medical tool - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical tool having a surface lubrication layer exhibiting excellent durability.SOLUTION: A medical tool has a base material, an undercoat layer arranged on the surface of the base material, and a surface lubrication layer which is arranged on the surface of the undercoat layer and contains a hydrophilic polymer, where the undercoat layer is formed form a composition containing a base polymer and a tackifier, and less than 90 pts.mass of the tackifier is contained with respect to 100 pts.mass of the base polymer.SELECTED DRAWING: None

Description

  The present invention relates to a medical device (medical device) coated with a surface lubricating layer.

  Medical devices such as catheters, guide wires, and indwelling needles that are inserted into a living body are required to exhibit excellent lubricity in order to reduce tissue damage such as blood vessels and improve operability for the operator. For this reason, a method of coating the surface of a substrate with a hydrophilic polymer having lubricity has been developed and put into practical use. In such a medical device, it is a problem in terms of maintaining safety and operability that the hydrophilic polymer is eluted and separated from the surface of the base material. For this reason, coating with a hydrophilic polymer requires not only excellent lubricity but also durability against loads such as wear and abrasion.

  From such a viewpoint, Patent Document 1 discloses that a water-soluble or water-swellable polymer is dissolved in a solvent in which a base material of a medical device swells to prepare a polymer solution, and the medical device contains the medical device. A medical device is disclosed in which a surface lubricating layer is formed on the surface of the substrate by dipping and swelling the substrate and further cross-linking or polymerizing the polymer on the surface of the substrate. According to the technique disclosed in Patent Document 1, it is possible to fix a surface lubricating layer exhibiting relatively good lubricity to a substrate.

  Patent Document 2 describes providing a polyisocyanate compound layer between a hydrophilic polymer coating and a support. According to the said method, since isocyanate and a hydrophilic polymer react, it describes that it is excellent in abrasion resistance.

JP-A-8-33704 Japanese translation of Japanese translation of PCT publication No. 5-505125

  Patent Document 1 discloses that it is preferable to use, as the water-soluble or water-swellable polymer, a block copolymer comprising a hydrophilic part that exhibits lubricity and a part having an epoxy group. And when such a block copolymer is used, an epoxy group can be bridge | crosslinked by heating operation and the surface lubrication layer which cannot be peeled comparatively easily can be formed.

  However, in recent years, medical devices have been remarkably reduced in size and diameter, and medical procedures for approaching medical devices to narrow lesion sites are becoming more widespread in vivo. Further, as the operation becomes complicated, the operation may last for a long time. Therefore, in order to keep the operability of the device good even in a complicated lesion site, a technique for further improving the lubricity maintenance property of the device surface (durability of the surface lubrication layer) is required compared with the prior art.

  Therefore, there is a need for a technology that can improve durability and support complicated and sophisticated medical procedures.

  In the technique described in Patent Document 2, it is an essential requirement to provide a polyisocyanate compound layer between the hydrophilic polymer coating and the support. For this reason, there existed a subject that the hydrophilic polymer which comprises hydrophilic polymer coating will be limited to the material which reacts with a polyisocyanate compound.

  Therefore, there is a demand for a technology that can widen the selection range of materials that can be used for the target surface layer (hydrophilic polymer coating) and improve the lubricity maintenance (durability of the surface lubricating layer).

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a medical device having a surface lubricating layer that exhibits excellent durability.

  Another object of the present invention is to provide a medical device excellent in durability of a surface lubricating layer capable of firmly fixing various hydrophilic polymers and a substrate by a simpler method.

  As a result of intensive studies to solve the above problems, the present inventors have provided an undercoat layer containing a base polymer and a specific amount of tackifier between the base material and the surface lubricating layer. The present invention has been completed by finding out that the problems can be solved.

  That is, the above objects are medical devices comprising a base material, an undercoat layer disposed on the surface of the base material, and a surface lubricating layer including a hydrophilic polymer disposed on the surface of the undercoat layer. The undercoat layer is formed from a composition containing a base polymer and a tackifier, and the tackifier is contained in a proportion of less than 90 parts by mass with respect to 100 parts by mass of the base polymer. Achieved with medical tools.

  ADVANTAGE OF THE INVENTION According to this invention, the medical device excellent in durability of a surface lubricating layer can be provided.

FIG. 1 is a schematic diagram of a test apparatus (friction measuring machine) for evaluating the durability of a surface lubricating layer. FIG. 2 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 1 obtained in Example 1-1. FIG. 3 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 2 obtained in Example 1-2. FIG. 4 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 3 obtained in Example 1-3. FIG. 5 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 4 obtained in Example 1-4. FIG. 6 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 5 obtained in Example 1-5. FIG. 7 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 6 obtained in Example 1-6. FIG. 8 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 7 obtained in Example 1-7. FIG. 9 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 8 obtained in Example 1-8. FIG. 10 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 9 obtained in Example 1-9. FIG. 11 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 10 obtained in Example 1-10. FIG. 12 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 11 obtained in Example 1-11. FIG. 13 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 12 obtained in Example 1-12. FIG. 14 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 13 obtained in Example 1-13. FIG. 15 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 14 obtained in Example 1-14. FIG. 16 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 15 obtained in Example 1-15. FIG. 17 is a graph showing the results of a durability evaluation test of the surface lubricating layer of the comparative medical device 1 obtained in Comparative Example 1-1. FIG. 18 is a graph showing the durability evaluation test result of the surface lubricating layer of the comparative medical device 2 obtained in Comparative Example 1-2. FIG. 19 is a graph showing the durability evaluation test result of the surface lubricating layer of the comparative medical device 3 obtained in Comparative Example 1-3. FIG. 20 is a graph showing the durability evaluation test result of the surface lubricating layer of the comparative medical device 4 obtained in Comparative Example 1-4. FIG. 21 is a graph showing the durability evaluation test result of the surface lubricating layer of the comparative medical device 5 obtained in Comparative Example 1-5. FIG. 22 is a graph showing the results of a durability evaluation test of the surface lubricating layer of the comparative medical device 6 obtained in Comparative Example 1-6. FIG. 23 is a graph showing the durability evaluation test result of the surface lubricating layer of the comparative medical device 7 obtained in Comparative Example 1-7. FIG. 24 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 16 obtained in Example 2-1. FIG. 25 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 17 obtained in Example 2-2. FIG. 26 is a graph showing the durability evaluation test result of the surface lubricating layer of the medical device 18 obtained in Example 2-3. FIG. 27 is a graph showing the results of a durability evaluation test of the surface lubricating layer of the comparative medical device 8 obtained in Comparative Example 2-1.

  The present invention is a medical device comprising a base material, an undercoat layer disposed on the surface of the base material, and a surface lubricating layer including a hydrophilic polymer disposed on the surface of the undercoat layer, The undercoat layer is formed from a composition containing a base polymer and a tackifier, and the tackifier is contained in a proportion of less than 90 parts by mass with respect to 100 parts by mass of the base polymer. provide.

  According to the present invention, an undercoat layer formed from a composition containing a base polymer and a specific amount (less than 90 parts by mass with respect to 100 parts by mass of the base polymer) is provided between the substrate and the surface lubricating layer. It is characterized by that. With this configuration, the medical device of the present invention can exhibit the durability (lubricity maintenance) of the surface lubricating layer. In addition, the medical device of the present invention exhibits excellent lubricity on the surface in an aqueous liquid such as body fluid or physiological saline. Although the detailed mechanism by which the medical device according to the present invention exerts the above effects is still unclear, it is considered as follows. The following mechanism is speculative and does not limit the technical scope of the present invention. That is, the undercoat layer is formed from a composition containing a base polymer and a tackifier, and in this case, the content of the tackifier is less than 90 parts by mass with respect to 100 parts by mass of the base polymer. Here, since the base polymer which comprises an undercoat layer is high molecular weight, although film | membrane intensity | strength is high, since it is comparatively hard, it is inferior to adhesiveness (adhesion). On the other hand, the tackifier constituting the undercoat layer has a low molecular weight and is excellent in molecular mobility, but is very brittle as a film. For this reason, the present inventors diligently studied a composition that can balance both properties in a well-balanced manner. As a result, when an undercoat layer is formed by blending a base polymer and a tackifier at a ratio of less than 90 parts by mass with respect to 100 parts by mass of the base polymer, the undercoat layer becomes active in molecular movement and has an appropriate plasticity. Exerts, resulting in increased tackiness. On the other hand, due to the presence of the base polymer, the undercoat layer has an appropriate film strength. Therefore, the surface lubricating layer is firmly fixed to the undercoat layer. The undercoat layer also exhibits high adhesiveness (adhesion) with respect to the substrate. For this reason, a base material, an undercoat layer, and a surface lubrication layer are integrated firmly, and it can suppress / prevent effectively that the surface lubrication layer which exists in the outermost surface detaches | leaves from a base material. Therefore, the medical device of the present invention can maintain its lubricity for a long period of time (durability (lubrication maintenance)) while exhibiting excellent lubricity on the surface in an aqueous liquid such as body fluid and physiological saline. ).

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In this specification, “X to Y” indicating a range includes X and Y, and means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 20 to 80% RH.

[Base material]
The substrate used in the present embodiment may be composed of any material, and the material is not particularly limited, and metal materials, polymer materials, ceramics, and the like can be used. Here, the metal material is not particularly limited, and a metal material generally used for medical devices such as a catheter, a guide wire, and an indwelling needle is used. Specifically, various stainless steels such as SUS304, SUS316, SUS316L, SUS420J2, SUS630, gold, platinum, silver, copper, nickel, cobalt, titanium, iron, aluminum, tin, nickel-titanium alloy, nickel-cobalt alloy, Examples include various alloys such as cobalt-chromium alloy and zinc-tungsten alloy. The polymer material is not particularly limited, and polymer materials generally used for medical devices such as catheters, guide wires, injection needles, and indwelling needles are used. Specifically, polyamide resin, polyamide elastomer, polyolefin resin such as polyethylene resin or polypropylene resin, modified polyethylene resin (modified high density polyethylene, modified low density polyethylene, modified linear low density polyethylene, etc.), modified polypropylene resin, etc. Modified polyolefin resin, cyclic polyolefin resin, epoxy resin, urethane resin (polyurethane), 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, vinyl chloride resin, silicone resin (silicon resin), polyether resin, polyimide resin, polyimide Elastomer and the like. The materials constituting these base materials may be used alone or in a mixture of two or more, or a copolymer of two or more monomers constituting any of the above resins May be used as What is necessary is just to select the material optimal as a base material suitably from the said material according to uses, such as a catheter, a guide wire, and an indwelling needle which are uses.

  The shape of the substrate corresponds to the shape according to the actual use application such as a catheter, a guide wire, or an indwelling needle. For this reason, the shape of the base material is not particularly limited, and is appropriately selected depending on the usage mode, such as a sheet shape, a coil shape, a wire (wire) shape, and a tube (tube) shape. In addition, the base material may be composed of any of the above materials or a combination of different materials as appropriate. As an example of the latter case, a structure or substrate in which a substrate surface layer is formed by coating the surface of a substrate core portion made of any of the above materials with any of the above other materials by an appropriate method. The core-shell structure in which the surface of the material core is coated with any of the above-mentioned materials by an appropriate method to form the base material surface layer, the multilayer structure in which different materials are laminated in multiple layers, or the medical device There is a structure in which members formed of different materials are connected to each other.

[Undercoat layer]
An undercoat layer is arrange | positioned between a base material and a surface lubrication layer, and is formed from the composition which contains a base polymer and a tackifier essential.

  Here, the base polymer is not particularly limited, but in consideration of the kink resistance improvement effect, the influence on the base material, etc., those having flexibility are preferable, and the glass transition point (Tg) is a polymer having a temperature of 20 ° C. or less. More preferably. Specifically, synthetic rubber such as natural rubber, styrene butadiene rubber (SBR), butyl rubber, isoprene rubber, latex rubber, silicone rubber, (meth) acrylic resin, silicone resin, urethane resin, vinyl ether resin, SBS elastomer, SEBS elastomer And olefin elastomers such as ethylene-α-olefin copolymer elastomers. The said base polymer may be used individually by 1 type, or may be used with the form of 2 or more types of mixtures. Of these, (meth) acrylic resin and styrene butadiene rubber (SBR) are preferable. That is, in a preferred embodiment of the present invention, the base polymer is at least one selected from the group consisting of (meth) acrylic resins and styrene butadiene rubber. Further, the (meth) acrylic resin has high solubility in a solvent that does not damage the substrate (for example, an alcohol solvent), and is particularly suitable for the preparation of a coating solution. For this reason, in a more preferred embodiment of the present invention, the base polymer is a (meth) acrylic resin. In a particularly preferred form of the invention, the base polymer is an acrylic resin. Here, the (meth) acrylic resin is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as typified by acrylic and methacrylic monomers. These may be either homopolymers or copolymers. Preferably, the (meth) acrylic resin has (meth) acrylic acid and / or (meth) acrylic acid ester as the main monomer component. As (meth) acrylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate and the like having 1 to 20 carbon atoms, Examples include, but are not limited to, esterified products of alkyl alcohol and (meth) acrylic acid. The said (meth) acrylic acid ester may be used individually by 1 type, or may be used with the form of 2 or more types of mixtures. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid. Similarly, “(meth) acrylate” means acrylate or metallate.

  The base polymer may be obtained by synthesis or a commercially available product may be used. Commercially available products include, for example, Quickmaster, Finetack series (for example, Finetack CT-6020) (all manufactured by DIC Corporation), SK Dyne (manufactured by Soken Chemical Co., Ltd.), Arontack Series (manufactured by Toagosei Co., Ltd.) ), And styrene butadiene rubber (manufactured by Sigma Aldrich Japan G.K., for example, # 182907).

  The undercoat layer includes a tackifier in addition to the base polymer. In the present specification, the “tackifier” is a compound that imparts adhesive force to the base polymer or improves the adhesive force of the base polymer, and is also called a tackifier. The tackifier is not particularly limited, and known compounds such as rosin resin, terpene resin, petroleum resin, alkylphenol resin, and xylene resin can be used. Examples of the rosin resin include natural rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, disproportionated rosin, and disproportionated rosin ester. Examples of the terpene resin include α-pinene resin, β-pinene resin, and terpene phenol resin. The petroleum resin is composed of an unsaturated hydrocarbon (co) polymer having an aliphatic, alicyclic or aromatic hydrocarbon structure, such as styrene resin, α-toluene resin, coumarone-indene resin, α- Examples thereof include methylstyrene resin, α-methylstyrene / styrene copolymer resin, styrene monomer / aliphatic monomer copolymer resin, pentadiene resin, cyclopentadiene resin, hydrogenated hydrocarbon resin, and the like.

  The tackifier is preferably an aromatic tackifier because the effect of improving the adhesive strength of the base polymer is higher (durability can be further improved). That is, according to a preferred embodiment of the present invention, the tackifier is an aromatic tackifier. The aromatic tackifier is not particularly limited as long as it is a compound having an aromatic structure. Examples thereof include rosin resins having dehydroabietic acid, rosin phenol resins, terpene phenol resins, petroleum resins made of homopolymers or copolymers of unsaturated hydrocarbons having an aromatic hydrocarbon structure. Examples of the rosin resin having dehydroabietic acid include a rosin ester derived from a natural resin rosin, and a disproportionated rosin ester obtained by esterifying a disproportionated rosin obtained by disproportionating rosin. Petroleum resins comprising an unsaturated hydrocarbon homopolymer or copolymer having an aromatic hydrocarbon structure include styrene resin, α-toluene resin, coumarone-indene resin, α-methylstyrene resin, α-methylstyrene. / Styrene copolymer resin, styrene monomer / aliphatic monomer copolymer resin (copolymer of styrene monomer and aliphatic monomer), phenol resin, xylene resin and the like. Among these, terpene phenol resin, rosin resin having dehydroabietic acid, and styrene monomer / aliphatic monomer copolymer resin are preferable from the viewpoint of imparting adhesive strength to the base polymer or improving the adhesive strength of the base polymer. . Further, from the viewpoint of suppressing elution of the tackifier from the base polymer, a rosin resin having dehydroabietic acid and a styrene monomer / aliphatic monomer copolymer resin are more preferable, and a rosin resin having dehydroabietic acid, or A mixture of a rosin resin having dehydroabietic acid and a styrene monomer / aliphatic monomer copolymer resin is particularly preferred. According to a preferred embodiment of the present invention, the tackifier is at least one selected from the group consisting of a terpene phenol resin, a rosin resin having dehydroabietic acid, and a styrene monomer / aliphatic monomer copolymer resin. According to a more preferred embodiment of the present invention, the tackifier is at least one selected from the group consisting of a rosin resin having dehydroabietic acid and a styrene monomer / aliphatic monomer copolymer resin. According to a particularly preferred embodiment of the present invention, the tackifier is a rosin resin having dehydroabietic acid or a mixture of a rosin resin having dehydroabietic acid and a styrene monomer / aliphatic monomer copolymer resin.

  In addition, the said tackifier may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

  That is, a preferred combination of the base polymer and the tackifier constituting the undercoat layer is at least one base polymer selected from the group consisting of a (meth) acrylic resin and a styrene butadiene rubber, and an aromatic tackifier. Is a combination of A more preferred combination is a (meth) acrylic resin (base polymer) and at least one of a terpene phenol resin, a rosin resin having dehydroabietic acid, and a styrene monomer / aliphatic monomer copolymer resin (tackifier). It is a combination. An even more preferable combination is a combination of a (meth) acrylic resin (base polymer) and a rosin resin having dehydroabietic acid and / or a styrene monomer / aliphatic monomer copolymer resin (tackifier). A particularly preferred combination is a (meth) acrylic resin (base polymer) and a mixture of a rosin resin having dehydroabietic acid or a rosin resin having dehydroabietic acid and a styrene monomer / aliphatic monomer copolymer resin (tackifier) ).

  The tackifier may be obtained by synthesis or may be a commercially available product. Commercially available products include, for example, YS Polyster Series, YS Resin Series, Chloron Series (all (Yasuhara Chemical Co., Ltd.), Super Ester Series, Pine Crystal Series, Pencel Series (Arakawa Chemical Co., Ltd.), FTR Series ( Mitsui Chemicals).

  The content of the tackifier is less than 90 parts by mass (over 0 part by mass) with respect to 100 parts by mass of the base polymer. Here, when the content of the tackifier is 90 parts by mass or more, the content of the base polymer is too small, and the effect (particularly the film strength) due to the base polymer is excessively lowered. The lubricating layer is inferior in durability (see Comparative Example 2 below). On the contrary, when the undercoat layer is composed only of the base polymer (the content of the tackifier is 0% by mass), the undercoat layer is inferior in tackiness, and the surface lubricating layer is formed via the undercoat layer. The surface lubricant layer of the obtained medical device cannot be sufficiently adhered to the material, and is also inferior in durability (see Comparative Example 1 below). The content of the tackifier is preferably 1 to 70 parts by mass, more preferably 3 parts by mass or more and less than 60 parts by mass, and further preferably 10 to 50 parts by mass with respect to 100 parts by mass of the base polymer. With such a content, a desired adhesive force is imparted to the undercoat layer, and the surface lubricating layer can be firmly integrated with the substrate via the undercoat layer. For this reason, the surface lubrication layer of the obtained medical device can improve durability more.

  In addition, content of the tackifier in the undercoat layer of a medical device is substantially equivalent to content of the tackifier in the coating liquid (solid content total amount) at the time of undercoat layer formation. Moreover, also in the form of the medical device that is the final product, the content of the tackifier in the undercoat layer can be measured by a known method. For example, the content of the base polymer and the tackifier in the undercoat layer is determined by separating the base polymer and the tackifier in the undercoat layer by a known method such as a liquid separation operation, and then the base polymer and the tackifier. The amount of each component can be determined, and the content of each component can be quantified based on the amount extracted. In this specification, the value measured by the following method is adopted. The following method is an example, and the extraction conditions (extraction temperature, extraction time, extraction solvent, number of extractions) are not particularly limited, and are appropriate depending on the type of base polymer or tackifier that constitutes the undercoat layer. Can be selected.

(Measurement method of tackifier content)
After the undercoat layer is extracted with a solvent (solvent A) that is soluble in the base polymer but insoluble in the tackifier, it is soluble in the tackifier but insoluble in the base polymer and with solvent A. A non-miscible solvent (solvent B) is added to carry out a liquid separation treatment. Alternatively, the separation process may be performed in the reverse order of extraction, that is, after extracting the undercoat layer with a solvent (solvent A ′) that is soluble in the tackifier but insoluble in the base polymer. A liquid separation treatment may be performed by adding a solvent (solvent B ′) that is soluble in the base polymer but insoluble in the tackifier and immiscible with the solvent A ′. Moreover, the said liquid separation processing operation is repeatedly performed as needed. By such an operation, a fraction in which the base polymer is selectively dissolved (fraction A) and a fraction in which the tackifier is selectively dissolved (fraction B) are obtained. Each of these fractions is dried and the mass of each dry residue is measured. The dry residues of fractions A and B respectively correspond to the amount of base polymer and tackifier contained in the undercoat layer. Based on these amounts, the content (% by mass) of the tackifier relative to the base polymer can be calculated.

  Moreover, you may use the commercial item containing a base polymer and a tackifier. Examples of such commercially available products include the Oliveline series (for example, BPS6074HTF, BPS6574HTF (manufactured by Toyochem Co., Ltd.), Finetack series (for example, Finetac CT-5020) (manufactured by DIC Corporation), and SK Dyne series (for example, SK). Dyne 1502), etc. In addition, when a commercial product containing a base polymer and a tackifier is used, the content of the tackifier may be unknown. The content of the tackifier (composition with respect to the base polymer) can be measured by the same method as in (Method for measuring the content of tackifier).

  The undercoat layer may be formed from a composition containing only the base polymer and the tackifier as the active ingredient (solid component), or other additive in addition to the base polymer and the tackifier as the active ingredient (solid component). It may be formed from the composition containing this. In the former case, the undercoat layer is substantially composed of only the base polymer and the tackifier. Under the present circumstances, an undercoat layer contains a tackifier in the ratio of less than 90 mass parts with respect to 100 mass parts of base polymers. In the latter case, examples of the other additive include a crosslinking agent for crosslinking the base polymer. These other additives may be used individually by 1 type, or may use 2 or more types together. For example, if the undercoat layer is formed from a composition comprising a base polymer, a tackifier, and a crosslinker, the undercoat layer is a cross-linked base polymer (if any uncrosslinked portion), the base polymer, and Contains a tackifier. Under the present circumstances, an undercoat layer contains a tackifier in the ratio of less than 90 mass parts with respect to 100 mass parts of total amounts of a base polymer and its crosslinked material.

  When the undercoat layer is formed from a composition containing only the base polymer and the tackifier as active ingredients (solid components), the base polymer is surface lubricated when a surface lubrication layer is further formed on the undercoat layer. It may be dissolved in a coating liquid (coating liquid) for layer formation. For this reason, by further crosslinking the base polymer with a crosslinking agent, the film strength is increased, and the durability of the undercoat layer (especially durability under a high load state) can be further improved. Moreover, dissolution of the base polymer during formation of the surface lubricating layer can be effectively suppressed / prevented. Although it does not specifically limit as a crosslinking agent, A well-known polyisocyanate compound, an epoxy resin, an aziridine compound, a polyvalent metal salt, a metal chelate, an organic peroxide etc. can be used. The addition amount of the crosslinking agent when the undercoat layer is formed using a crosslinking agent is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 0. 5 to 20 parts by mass. With such an amount, the base polymer can be sufficiently cross-linked with a cross-linking agent, so that the durability of the undercoat layer, particularly in a high load state, can be further improved. The dissolution of the base polymer during the formation of the surface lubricating layer can be more effectively suppressed / prevented.

[Surface lubrication layer]
The surface lubricating layer is disposed adjacent to the surface of the undercoat layer and includes a hydrophilic polymer.

  Here, the hydrophilic polymer is not particularly limited, and examples thereof include polyvinyl pyrrolidone (PVP), polyvinyl alcohol, polyethylene oxide polymer substances, polysaccharide polymer substances such as carboxymethyl cellulose, hyaluronic acid, chondroitin sulfate, and the like. Examples thereof include acrylamide polymer materials such as acrylamide and polydimethylacrylamide, maleic anhydride polymer materials such as polyacrylic acid and maleic anhydride-methyl vinyl ether copolymer, water-soluble nylon resins, and derivatives thereof. These hydrophilic polymers can absorb water when wet and exhibit lubricity. Moreover, when using a hydrophilic polymer as described above, a crosslinking agent may be used in combination, or a reactive functional group may be introduced into the hydrophilic polymer. As a result, the hydrophilic polymer is cross-linked to increase the film strength of the surface lubricating layer, and the durability of the surface lubricating layer (particularly, durability under high load conditions) can be further improved. The crosslinking agent used in combination with the crosslinking agent is not particularly limited, but known polyisocyanate compounds, epoxy resins, aziridine compounds, polyvalent metal salts, metal chelates, organic peroxides, self-crosslinking polymers (for example, self-crosslinking polymers) Crosslinkable urethane resin). The amount of the crosslinking agent added when the surface lubricating layer is formed using a crosslinking agent is not particularly limited, but is preferably 0.1 to 200 parts by mass, more preferably 0. 5 to 150 parts by mass. With such an amount, the hydrophilic polymer can be sufficiently cross-linked with a cross-linking agent, so that the durability, particularly in a high load state, can be further improved.

  Alternatively, the hydrophilic polymer may be a copolymer of a monomer having a reactive functional group and a hydrophilic monomer. Such a hydrophilic polymer is excellent in lubricity due to the presence of the hydrophilic monomer. Here, the reactive functional group is not particularly limited, but considering reactivity (bonding) with the base polymer of the undercoat layer, an epoxy group, an acid halide group, an aldehyde group, an isocyanate group, an acid anhydride group Etc. Although it does not restrict | limit especially as a monomer which has the above reactive functional groups, For example, epoxy groups, such as glycidyl acrylate, glycidyl methacrylate (GMA), glycidyl ether, methyl glycidyl methacrylate, and allyl glycidyl ether, are in a molecule. Monomers having acid halide groups in the molecule such as (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic acid iodide; (meth) acrylaldehyde, glyoxal, terephthalaldehyde, etc. Monomer having an aldehyde group in the molecule; (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2,2,4-trimethylhexamethylene diisocyanate or 1,3,5-trimethyl Monomers having an isocyanate group such as hexamethylene diisocyanate in the molecule; maleic anhydride, itaconic anhydride, and the like monomer having an acid anhydride group such as citraconic anhydride in the molecule can be exemplified. The monomer having the reactive functional group may be used alone or in the form of a mixture of two or more. Among these, as the monomer having a reactive functional group, a monomer having an epoxy group is preferable, and the reaction is promoted by heat or the like, and handling is relatively easy. Therefore, glycidyl acrylate and glycidyl methacrylate are preferable. Is more preferable, and glycidyl methacrylate is particularly preferable. In addition, a copolymer of a monomer having a reactive functional group having an epoxy group and a hydrophilic monomer has good binding properties with the base polymer of the undercoat layer (particularly the carboxyl group of the acrylic resin). The adhesion (integration) between the undercoat layer and the surface lubricating layer is further improved. Therefore, it is particularly preferable to use such a copolymer as a hydrophilic polymer because the durability of the medical device can be further improved. That is, according to a preferred embodiment of the present invention, the monomer having a reactive functional group is a monomer having an epoxy group. According to a more preferred form of the invention, the monomer having a reactive functional group is glycidyl acrylate and / or glycidyl methacrylate. According to a particularly preferred form of the invention, the monomer having a reactive functional group is glycidyl methacrylate.

  The hydrophilic monomer is not particularly limited, and examples thereof include acrylamide and derivatives thereof, vinylpyrrolidone, acrylic acid and methacrylic acid and derivatives thereof, polyethylene glycol acrylate and derivatives thereof, and a simple substance having a sugar or phospholipid in the side chain. Examples thereof include water-soluble monomers such as monomers and maleic anhydride. More specifically, acrylic acid, methacrylic acid, N-methylacrylamide, N, N′-dimethylacrylamide (DMAA), acrylamide, acryloylmorpholine, N-vinylpyrrolidone, 2-methacryloyloxyethyl phosphorylcholine, 2-methacryloyloxyethyl -D-glycoside, 2-methacryloyloxyethyl-D-mannoside, vinyl methyl ether, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate Diethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane Di (meth) acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 2-hydroxy-3-phenyloxy (meth) acrylate 4-hydroxycyclohexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, poly (ethylene glycol) methyl ether acrylate, and Such as poly (ethylene glycol) methyl ether methacrylate. The said hydrophilic monomer may be used individually by 1 type, or may be used with the form of 2 or more types of mixtures. From the viewpoint of ease of synthesis and operability, N, N-dimethylacrylamide, acrylamide, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, and N-vinylpyrrolidone are preferable. In addition to the above, N, N′-dimethylacrylamide, acrylamide and N-vinylpyrrolidone are more preferable from the viewpoint of further improving the lubricity, and N, N′-dimethylacrylamide is particularly preferable. These hydrophilic monomers can be used alone or in combination of two or more. That is, according to a preferred embodiment of the present invention, the hydrophilic monomer is at least one selected from the group consisting of N, N′-dimethylacrylamide, acrylamide, and N-vinylpyrrolidone. According to a more preferred form of the invention, the hydrophilic monomer is N, N'-dimethylacrylamide and / or N-vinylpyrrolidone. According to a particularly preferred form of the invention, the hydrophilic monomer is N, N'-dimethylacrylamide.

  Specifically, the hydrophilic polymer is preferably polyvinyl pyrrolidone (PVP), a copolymer of a monomer having a reactive functional group and a hydrophilic monomer, and is selected from glycidyl acrylate and glycidyl methacrylate. More preferably, it is a copolymer of a monomer having a reactive functional group and a hydrophilic monomer selected from N, N-dimethylacrylamide and N-vinylpyrrolidone, and is selected from glycidyl acrylate and glycidyl methacrylate. It is more preferable that it is a block copolymer of a monomer having a reactive functional group and a hydrophilic monomer selected from N, N-dimethylacrylamide and N-vinylpyrrolidone, and glycidyl methacrylate and N, It is especially a block copolymer with N-dimethylacrylamide Masui.

The form of the hydrophilic polymer in the case where the hydrophilic polymer is a copolymer of a monomer having a reactive functional group and a hydrophilic monomer is not particularly limited, and a random copolymer, an alternating copolymer, Either a periodic copolymer or a block copolymer may be used. Among these, a block copolymer having a block formed from a monomer having a reactive functional group and a block formed from a hydrophilic monomer (reactive monomer and hydrophilic monomer) And a block copolymer) are more preferable. With such a block copolymer, better results can be obtained in terms of the strength and lubricity of the surface lubricating layer.

  Composition of hydrophilic polymer when the hydrophilic polymer is a copolymer of a monomer having a reactive functional group and a hydrophilic monomer (monomer having a reactive functional group: hydrophilic monomer) (Molar ratio)) is not particularly limited. Considering the formation of the hydrogel layer when it comes into contact with bodily fluids and physiological saline, and also the display of moderate lubricity, the molar ratio of the monomer having a reactive functional group and the hydrophilic monomer is It is preferably 1: 1 to 1: 100, preferably 1: 3 to 1:80, and more preferably 1: 5 to 1:50.

  The method for producing the hydrophilic polymer is not particularly limited, and can be produced by applying a conventionally known polymerization method such as a living radical polymerization method, a polymerization method using a macroinitiator, or a polycondensation method. Among these, the living unit is easy to control the molecular weight and molecular weight distribution of the structural unit (part) derived from the hydrophilic monomer and the structural unit (part) derived from the monomer having a reactive functional group. A radical polymerization method or a polymerization method using a macroinitiator is preferably used. The living radical polymerization method is not particularly limited. For example, the methods described in JP-A-11-263819, JP-A-2002-145971, JP-A-2006-316169, and the like, and atom transfer radical polymerization (ATRP) ) And the like can be applied in the same manner or appropriately modified. In the polymerization method using a macroinitiator, for example, after preparing a macroinitiator having a hydrophobic site having a reactive functional group and a radical polymerizable group such as a peroxide group, the macroinitiator and A block copolymer having a hydrophilic part and a hydrophobic part can be produced by polymerizing a monomer for forming the hydrophilic part.

  Alternatively, a known method such as bulk polymerization, suspension polymerization, emulsion polymerization, or solution polymerization may be used as a method for producing the hydrophilic polymer. Specifically, in the production of the hydrophilic polymer, a method can be used in which a monomer having a reactive functional group and a hydrophilic monomer are copolymerized by stirring and heating together with a polymerization initiator in a polymerization solvent. Here, the polymerization initiator is not particularly limited, and a known one may be used. Preferably, it is a radical polymerization initiator in terms of excellent polymerization stability. Specifically, it is a persulfate such as potassium persulfate (KPS), sodium persulfate, or ammonium persulfate; hydrogen peroxide, t-butyl persulfate. And peroxides such as oxide and methyl ethyl ketone peroxide; azo compounds such as azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyronitrile), azobiscyanovaleric acid, and the like. Further, for example, a reducing agent such as sodium sulfite, sodium hydrogen sulfite, or ascorbic acid may be combined with the radical polymerization initiator and used as a redox initiator. As for the compounding quantity of a polymerization initiator, 0.0001-1 mol% is preferable with respect to a monomer total amount. The polymerization solvent is not particularly limited, but examples thereof include aliphatic organic solvents such as n-hexane, n-heptane, n-octane, n-decane, cyclohexane, methylcyclohexane, liquid paraffin, tetrahydrofuran, dioxane, and the like. Ether solvents, aromatic organic solvents such as toluene and xylene, halogen organic solvents such as 1,2-dichloroethane and chlorobenzene, and polar aprotic organic solvents such as N, N-dimethylformamide and dimethyl sulfoxide can be used. . In addition, the said solvent can also be used individually or in mixture of 2 or more types. The concentration of the monomer in the polymerization solvent (the total concentration of the hydrophilic monomer and the monomer having a reactive functional group) is preferably 5 to 90% by mass, and more preferably 8 to 80% by mass. Preferably, it is 10-50 mass%, and it is especially preferable. In the polymerization, the polymerization conditions are not particularly limited as long as the copolymerization proceeds. For example, the polymerization temperature is preferably 30 to 150 ° C, more preferably 40 to 100 ° C. The polymerization time is preferably 30 minutes to 30 hours, more preferably 3 to 24 hours. Further, during the copolymerization, a chain transfer agent, a polymerization rate adjusting agent, a surfactant, a water-soluble polymer, a water-soluble inorganic compound (alkali metal salt, alkali metal hydroxide, polyvalent metal salt, if necessary) And non-reducing alkali metal salt pH buffer, etc.), inorganic acids, inorganic acid salts, organic acids, organic acid salts and other additives may be used as appropriate. The hydrophilic polymer after copolymerization may be purified by a general purification method such as a reprecipitation method, a dialysis method, an ultrafiltration method, or an extraction method.

  The surface lubricating layer may be composed of only the hydrophilic polymer, or may contain other additives in addition to the hydrophilic polymer. In the latter case, examples of the additive include a crosslinking agent and a drug (a physiologically active substance). Since the form in which the surface lubricating layer contains a crosslinking agent has been described above, the description thereof is omitted here. When the surface lubricant layer contains a drug, the drug is not particularly limited. For example, when the medical device is intended for insertion into a body cavity or lumen such as a catheter, an anticancer agent, an immunosuppressive agent, an antibiotic Antirheumatic drugs, antithrombotic drugs, HMG-CoA reductase inhibitors, ACE inhibitors, calcium antagonists, antihyperlipidemic drugs, integrin inhibitors, antiallergic agents, antioxidants, GPIIbIIIa antagonists, retinoids, Flavonoids, carotenoids, lipid improvers, DNA synthesis inhibitors, tyrosine kinase inhibitors, antiplatelet drugs, vascular smooth muscle growth inhibitors, anti-inflammatory drugs, biomaterials, interferons, and NO production promoters (physiological activities) Substance). Here, the addition amount of a chemical | medical agent is not restrict | limited in particular, The quantity normally used is applied similarly. Ultimately, the addition amount of the drug is appropriately selected in consideration of the severity of the disease to be applied, the weight of the patient, and the like.

As described above, the medical device of the present invention has a substrate, an undercoat layer containing a base polymer and a tackifier, and a surface lubricating layer containing a hydrophilic polymer. Here, the combination of the base polymer and the tackifier constituting the undercoat layer and the hydrophilic polymer constituting the surface lubricating layer is not particularly limited, and can be appropriately selected from the preferred examples described above. Considering the further improvement effect of adhesion (integration) of the undercoat layer and the surface lubricating layer,
An undercoat layer in which the base polymer is at least one of (meth) acrylic resin and styrene butadiene rubber and the tackifier is an aromatic tackifier, and the hydrophilic polymer is polyvinylpyrrolidone (PVP) and a self-crosslinkable polymer Selected from mixtures with (eg self-crosslinkable urethane resins) and monomers with reactive functional groups selected from glycidyl acrylate and glycidyl methacrylate and N, N-dimethylacrylamide and N, N′-dimethylaminoethyl acrylate It is preferably a combination with a surface lubricating layer that is at least one of a block copolymer with a hydrophilic monomer;
The base polymer is at least one of (meth) acrylic resin and styrene butadiene rubber, and the tackifier is selected from the group consisting of terpene phenol resin, rosin resin having dehydroabietic acid, styrene monomer / aliphatic monomer copolymer resin An undercoat layer that is at least one selected from the group consisting of a mixture of polyvinylpyrrolidone (PVP) and a self-crosslinkable polymer (for example, a self-crosslinkable urethane resin) and a reactivity selected from glycidyl acrylate and glycidyl methacrylate. More preferably, it is a combination of a surface lubricating layer that is at least one of a block copolymer of a monomer having a functional group and N, N-dimethylacrylamide (hydrophilic monomer);
An undercoat in which the base polymer is a (meth) acrylic resin and the tackifier is dehydroabietic acid or a mixture of a rosin resin having dehydroabietic acid and a styrene monomer / aliphatic monomer copolymer resin More preferably, the layer is a combination of a surface lubricating layer in which the hydrophilic polymer is a block copolymer of glycidyl methacrylate and N, N-dimethylacrylamide. Such a combination has a more remarkable effect in terms of adhesion between the undercoat layer and the surface lubricating layer. Here, the reason for the above effect is presumed as follows. In addition, the following is estimation and does not restrict | limit the technical scope of this invention. Specifically, the hydrophobic base polymer such as (meth) acrylic resin or styrene butadiene rubber constituting the undercoat layer is different from the hydrophobic part of the block copolymer constituting the surface lubricating layer or the hydrophobic self-crosslinking polymer ( For example, it adheres firmly to a self-crosslinkable urethane resin). Therefore, the combination as described above can further improve the adhesion (integration) between the undercoat layer and the surface lubrication layer, so that the durability of the surface lubrication layer (especially in a high load state) is further improved. The medical device can maintain good lubricity over a long period of time.

[Method for manufacturing medical devices]
The method for producing the medical device of the present invention is not particularly limited, and can be applied in the same manner as a known method or by appropriately modifying it. For example, first, an undercoat layer containing a base polymer and a tackifier at a specific mixing ratio is formed on a substrate (step (1)), and then a surface lubricating layer containing a hydrophilic polymer on the undercoat layer. It is preferable to form (step (2)).

  Hereinafter, a preferred method for producing the medical device of the present invention will be described. The present invention is not limited by the following method.

(Process (1))
In this step, an undercoat layer containing a base polymer and a tackifier at a specific mixing ratio is formed on the substrate. Preferably, the base polymer and the tackifier are dissolved in a solvent at a specific mixing ratio to prepare a mixed solution, and the mixed solution is coated on the substrate to form the undercoat layer on the substrate. In addition, since a base material, a base polymer, and a tackifier are as above-mentioned, description is abbreviate | omitted here.

  In the above method, the solvent used for dissolving the base polymer and the tackifier is not particularly limited as long as it can dissolve the base polymer and the tackifier. Specifically, water, alcohols such as methanol, ethanol, isopropanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate, halides such as chloroform, olefins such as hexane, tetrahydrofuran (THF), ethers such as butyl ether, aromatics such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), sulfoxides such as dimethyl sulfoxide, and the like. There are no restrictions. These may be used alone or in combination of two or more.

  The method for preparing the mixed solution is not particularly limited, and the base polymer and the tackifier are dissolved in the same solvent; after the base polymer is dissolved in the solvent, the tackifier is added; after the tackifier is dissolved in the solvent The base polymer is added; the base polymer and the tackifier are dissolved separately in the same or different solvent, and then mixed.

  The mixing ratio of the base polymer and the tackifier in the mixed solution may be such that the tackifier is less than 90 parts by mass with respect to 100 parts by mass of the base polymer, and the preferable mixing ratio is as described above. The concentration of the base polymer and the tackifier in the mixed solution is not particularly limited, but the concentration of the base polymer (resin content) in the mixed solution is preferably 0.1 to 80 mass from the viewpoint of ease of coating. %, More preferably 1 to 30% by mass.

  As described above, the mixed solution may further contain a crosslinking agent or the like. The addition amount of the crosslinking agent when the mixed solution further contains a crosslinking agent is not particularly limited, but is preferably the amount as described above. In addition, the addition timing of the crosslinking agent is not particularly limited, and may be any of the addition of the base polymer and the tackifier, or at the same time or after the addition of the base polymer and the tackifier. The base polymer and the tackifier are preferably added.

  The mixed solution thus prepared is coated on the substrate. In addition, you may wipe off a base material beforehand with alcoholic solvents, such as acetone, ethanol, and isopropyl alcohol, before the coating to a base material. The method of coating (applying) the liquid mixture on the substrate surface is not particularly limited, and is a coating / printing method, dipping method (dipping method, dip coating method), spray method (spray method), spin coating method. A conventionally known method such as a mixed solution-impregnated sponge coating method can be applied. Of these, the dipping method (dipping method, dip coating method) is preferably used. The dipping conditions for coating the mixed solution on the substrate by the dipping method are not particularly limited. For example, the immersion temperature can be 0-40 ° C. Also, the immersion time can be 0.1 seconds to 5 minutes.

  In the case where an undercoat layer is formed on a narrow and narrow inner surface of a catheter, guide wire, injection needle or the like, the base material may be immersed in the mixed solution, and the inside of the system may be depressurized to be defoamed. By degassing under reduced pressure, the solution can quickly penetrate into the narrow and narrow inner surface, and the formation of the undercoat layer can be promoted.

  Moreover, when forming an undercoat layer only on a part of the substrate, only a part of the substrate is immersed in the mixed solution, and the mixed solution is coated on a part of the substrate, An undercoat layer can be formed on the desired surface portion.

  If it is difficult to immerse only a part of the base material in the mixed solution, use an appropriate member or material that can attach and detach (attach / remove) the surface part of the base material without the need to form an undercoat layer in advance. After protecting (coating, etc.), the substrate is immersed in the mixed solution, and after coating the mixed solution on the substrate, the protective member (material) for the surface portion of the substrate that does not require the formation of an undercoat layer Is removed and then reacted by heat treatment or the like, whereby an undercoat layer can be formed on a desired surface portion of the substrate. However, the present invention is not limited to these forming methods, and the undercoat layer can be formed by appropriately using conventionally known methods. For example, when it is difficult to immerse only a part of the substrate in the mixed solution, instead of the immersing method, another coating technique (for example, spraying the mixed liquid onto a predetermined surface portion of a medical device) For example, a coating method using a coating apparatus such as an apparatus, 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. In addition, when both the outer surface and the inner surface of the cylindrical device need to have an undercoat layer due to the structure of the medical device, it is possible to coat both the outer surface and the inner surface at once. A dipping method (dipping method) is preferably used because it can be used.

  Thus, after immersing a base material in a liquid mixture, a base material is taken out from a liquid mixture and a drying process is performed. Here, the drying conditions (temperature, time, etc.) of the mixed solution are not particularly limited as long as the undercoat layer containing the base polymer and the tackifier can be formed on the substrate. Specifically, the drying temperature is preferably 10 to 200 ° C, more preferably 40 to 160 ° C. The drying time is preferably 10 minutes to 20 hours, more preferably 0.5 to 10 hours. The pressure condition at the time of drying is not limited at all, and it can be performed under normal pressure (atmospheric pressure), or under pressure or reduced pressure. As the heating means (apparatus) for heating, for example, an oven, a dryer, a microwave heating apparatus, or the like can be used. However, in the case of natural drying (air drying), the drying means (apparatus) is not particularly required. is there. Under such conditions, the undercoat layer is firmly bonded (immobilized) to the surface of the base material, and peeling from the base material can be effectively suppressed / prevented.

(Process (2))
In this step, a surface lubricating layer containing a hydrophilic polymer is formed on the undercoat layer of the base material (base material A) on which the undercoat layer is formed on the surface in the above step (1). Preferably, a surface lubricating layer is formed on the undercoat layer by preparing a coating liquid by dissolving a hydrophilic polymer in a solvent and coating the coating liquid on the substrate A (at least the undercoat layer side). In addition, since a hydrophilic polymer is as above-mentioned, description is abbreviate | omitted here.

  In the above method, the solvent used for dissolving the hydrophilic polymer is not particularly limited as long as it can dissolve the hydrophilic polymer. Specifically, water, alcohols such as methanol, ethanol, isopropanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate, halides such as chloroform, olefins such as hexane, tetrahydrofuran (THF), ethers such as butyl ether, aromatics such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), sulfoxides such as dimethyl sulfoxide, and the like. There are no restrictions. These may be used alone or in combination of two or more. The concentration of the hydrophilic polymer in the coating liquid is not particularly limited, but from the viewpoint of ease of coating, the concentration of the hydrophilic polymer in the coating liquid is preferably 0.01 to 30% by mass, more preferably 1 to 10%. % By mass.

  As described above, the coating liquid may further contain a crosslinking agent, a drug, and the like. In the case where the coating liquid further contains a cross-linking agent or a drug, the definition of the cross-linking agent or the drug is the same as described above, and the description thereof is omitted here.

  The substrate A is coated with the coating solution thus prepared. The method for coating (coating) the coating liquid on the surface of the substrate A is not particularly limited, and is a coating / printing method, a dipping method (dipping method, dip coating method), a spraying method (spraying method), or spin coating. Conventionally known methods such as a method and a mixed solution-impregnated sponge coating method can be applied. Of these, the dipping method (dipping method, dip coating method) is preferably used. The dipping conditions for coating the substrate A on the substrate A by the dipping method are not particularly limited. For example, the immersion temperature can be 0-40 ° C. Also, the immersion time can be 0.1 seconds to 5 minutes.

  When forming a surface lubrication layer on the inner surface of a narrow and narrow substrate A such as a catheter, guide wire, injection needle, etc., as in the case of the undercoat layer, the substrate A is dipped in the coating solution. The inside may be degassed under reduced pressure. By degassing under reduced pressure, the solution can quickly penetrate into the narrow and narrow inner surface, and the formation of the surface lubricating layer can be promoted. Further, the method of forming the surface lubricating layer when the surface lubricating layer is formed only on a part of the substrate A is not particularly limited, but for example, the same method as in the case of the undercoat layer can be employed.

  Thus, after immersing the base material A in a coating liquid, the base material A is taken out from a coating liquid, and a drying process is performed. Here, the drying conditions (temperature, time, etc.) of the coating liquid are not particularly limited as long as the undercoat layer containing the base polymer and the tackifier can be formed on the substrate A. Specifically, the drying temperature is preferably 10 to 200 ° C, more preferably 20 to 150 ° C. The drying time is preferably 10 minutes to 20 hours, more preferably 0.5 to 10 hours. The pressure condition at the time of drying is not limited at all, and it can be performed under normal pressure (atmospheric pressure), or under pressure or reduced pressure. As the heating means (apparatus) for heating, for example, an oven, a dryer, a microwave heating apparatus, or the like can be used. However, in the case of natural drying (air drying), the drying means (apparatus) is not particularly required. is there. Under such conditions, the surface lubricating layer is firmly bonded (fixed) to the surface of the undercoat layer, and peeling from the substrate A (undercoat layer) can be effectively suppressed / prevented.

  In this way, the medical device of the present invention is obtained. In the medical device of the present invention, an undercoat layer containing a base polymer and a tackifier in a specific mixing ratio is disposed between the base material and the surface lubricating layer. The medical device having such a structure is a case where the base material and the surface lubricating layer can be firmly adhered (integrated) via the undercoat layer, and therefore, the medical device has a high flexibility and / or is applied to a narrow lesion site. However, good lubricity can be exhibited and maintained. For this reason, by using the medical device of the present invention, it is possible to appropriately support more complicated and sophisticated medical procedures.

  Moreover, since the undercoat layer itself has adhesiveness, the medical device of the present invention is not limited to the materials constituting the base material and the surface lubricating layer, and can be applied to a wide range of materials. Therefore, the surface lubricating layer can be firmly fixed even on a base material made of a modified olefin (for example, modified polyethylene) or a metal material (for example, SUS), which has been difficult to immobilize conventionally (surface of a medical device). Lubricating layer has excellent durability).

(Use of medical device of the present invention)
The medical device of the present invention has a lubricious surface in an aqueous liquid such as a body fluid or physiological saline, and can improve operability and reduce damage to tissue mucous membranes. For this reason, the medical device of this invention can be used conveniently as a device used in contact with a body fluid, blood, etc. Specific examples include catheters, guide wires, indwelling needles, and the like used in blood vessels, but the following medical devices are also shown.

  (A) Catheters inserted or placed in the digestive organs orally or nasally, such as gastric tube catheters, nutritional catheters, tube feeding tubes and the like.

  (B) Oxygen catheters, oxygen canulas, endotracheal tube tubes and cuffs, tracheostomy tube tubes and cuffs, intratracheal suction catheters, and other catheters that are inserted or placed in the trachea or trachea orally.

  (C) Catheters inserted into or placed in the urethra or ureter, such as urethral catheters, urinary catheters, urethral balloon catheter catheters and balloons.

  (D) Catheters that are inserted or placed in various body cavities, organs, and tissues such as suction catheters, drainage catheters, and rectal catheters.

  (E) 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.

  (F) Artificial trachea, artificial bronchi, etc.

  (G) 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. In the following examples, the operation was performed at room temperature (25 ° C.) unless otherwise specified. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively.

Synthesis Example 1: Preparation of Block Copolymer 1 A block copolymer of dimethylacrylamide (DMAA) and glycidyl methacrylate (GMA) (DMAA: GMA = 11: 1 (molar ratio)) was prepared as follows. Hereinafter, the block copolymer prepared above is referred to as “p (DMAA-b-GMA)” or “block copolymer 1”.

  After 29.7 g of triethylene glycol was added dropwise to 72.3 g of adipic acid dichloride at 50 ° C., hydrochloric acid was removed under reduced pressure at 50 ° C. for 3 hours to obtain an oligoester. Next, 4.5 g of methyl ethyl ketone was added to 22.5 g of the obtained oligoester, and this was mixed with 5 g of sodium hydroxide, 6.93 g of 31% by mass hydrogen peroxide, 0.44 g of dioctyl phosphate as a surfactant and 120 g of water. The solution was added dropwise to the solution and reacted at −5 ° C. for 20 minutes. The obtained product was repeatedly washed with water and methanol, and then dried to obtain a polyperoxide having a plurality of peroxide groups in the molecule (PPO).

  Subsequently, 0.5 g of this PPO, 9.5 g of glycidyl methacrylate (GMA), and 30 g of benzene (solvent) were mixed and polymerized while stirring at 65 ° C. for 2 hours under reduced pressure. The reaction product obtained after polymerization was reprecipitated with diethyl ether to obtain polyGMA (PPO-GMA) having a peroxide group in the molecule.

  Subsequently, 0.48 g of the obtained PPO-GMA (corresponding to 3.38 mmol of GMA) was used as a polymerization initiator, 3.34 g (37.1 mmol) of dimethylacrylamide was dissolved in 90 g of dimethyl sulfoxide, and the nitrogen atmosphere was maintained at 80 ° C. for 5 hours. Polymerized below. The reaction product obtained after the polymerization was recovered by reprecipitation with hexane, and a block copolymer having a hydrophilic domain having DMAA as a structural unit and a reactive domain having glycidyl methacrylate as a structural unit (DMAA: GMA = 11: 1 (molar ratio)) (block copolymer (1)).

Reference Example 1: Evaluation of Adhesive Strength A modified polyethylene (Modic (registered trademark) M512 manufactured by Mitsubishi Chemical Corporation) sheet (18 mm × 40 mm × 1 mm) (modified PE sheet) was wiped with acetone to obtain a substrate.

  Separately, an acrylic resin (manufactured by DIC Corporation, Finetack CT-6020) was added to acetone so as to have a resin content of 15% by mass to prepare an undercoat liquid (1). Further, an undercoat fine tack CT-5020 (manufactured by DIC Corporation) containing an aromatic tackifier and an acrylic resin was added to acetone so as to have a resin content of 9% by mass to prepare an acetone solution. . The undercoat liquid (2) was prepared by adding a crosslinking agent (FINECK HARDENER D40, manufactured by DIC Corporation) to the acetone solution so as to be 15% by mass with respect to the acrylic resin. In addition, about undercoat fine tack CT-5020, when content of the aromatic tackifier was measured according to the following method, the tackifier was contained in the ratio of about 42 mass% with respect to the acrylic resin. I confirmed. The aromatic tackifier contained in the undercoat fine tack CT-5020 is a mixture of a rosin resin having dehydroabietic acid and a copolymer resin of a styrene monomer and an aliphatic monomer.

(Quantitative test of tackifier)
A modified polyethylene (Medic Chemical Co., Ltd. Modic (registered trademark) M512) sheet (18 mm × 40 mm × 1 mm) was wiped with acetone to prepare a base material (base material A). Next, acetone is added to undercoat fine tack CT-5020 (manufactured by DIC Corporation) containing an aromatic tackifier and an acrylic resin so as to have a resin content of 20% by mass to prepare an acetone solution. did. The substrate A was dipped in this acetone solution, coated at a speed of 15 mm / sec, and dried for 30 minutes (substrate B). After air drying, the substrate B was heated in an oven at 80 ° C. for 5 hours to form (fix) an undercoat layer on the surface of the substrate A (modified polyethylene sheet) (substrate C). Further, the undercoat layer of the substrate C was extracted in 10 g of N, N-dimethylformamide (DMF) at 40 ° C. for 24 hours. After extraction for a predetermined time, 10 g of hexane was added to the DMF extract, and a liquid separation operation was performed. The above liquid separation operation was repeated 5 times to complete the liquid separation operation. Thus, the acrylic resin is contained in the DMF solution, and the tackifier is contained in the hexane solution.

  After completion of the liquid separation operation, a DMF solution containing an acrylic resin and a hexane solution containing a tackifier were each dried to measure the mass of the dry residue. As a result, the dry residue of the DMF solution containing the acrylic resin was 36.5 mg, and the dry residue of the hexane solution containing the tackifier was 15.0 mg. Therefore, the content of the tackifier in the undercoat layer is 42 parts by mass with respect to 100 parts by mass of the acrylic resin. As described above, the content of the tackifier in the undercoat layer is substantially equivalent to the content of the tackifier in the acetone solution. For this reason, undercoat fine tack CT-5020 (made by DIC Corporation) contains a tackifier in the ratio of about 42 mass parts with respect to 100 mass parts of acrylic resins.

  The block copolymer (DMAA: GMA = 11: 1 (molar ratio)) (block copolymer 1) produced in Synthesis Example 1 was added to tetrahydrofuran (THF) to a concentration of 3.5% by mass, and the coating solution Was prepared.

  In the undercoat liquids (1) and (2) prepared above, the substrate was dipped, and immediately after the coating was performed at a speed of 15 mm / sec, it was air-dried for 30 minutes (substrate ( 1-1) and base material (2-1)). After air drying, the substrate (1-1) and the substrate (2-1) are each heated in an oven at 60 ° C. for 1 hour to form an undercoat layer on the surface of the substrate (modified polyethylene sheet). (Immobilized) (base material (1-2), base material (2-2)). Thereafter, the substrate (1-2) and the substrate (2-2) were each immersed in the coating solution prepared in the coating solution, and soon after being pulled up at a speed of 15 mm / sec. And air-dried for 30 minutes (base material (1-3), base material (2-3)). After air drying, the base (1-3) and the base (2-3) were each reacted in an oven at 80 ° C. for 5 hours to form a surface lubricating layer on the undercoat layer (medical device) (1), medical device (2)). As described above, in the medical device (2), the content of the aromatic tackifier in the undercoat layer is about 42% by mass with respect to the acrylic resin.

  For the medical devices (1) and (2) obtained as described above, an undercoat layer and a hydrophilic polymer were added based on the crosscut test (JIS K5600-5-6: 1999 (ISO2409: 1992)). The adhesion strength with the surface lubricating layer was evaluated.

  The results are shown in Table 1 below. In Table 1 below, the cross-cut test score is classified into 6 levels, and the smaller the numerical value, the less the peeling (the higher the adhesion).

  As shown in Table 1 below, the medical device (2) having an undercoat layer containing a tackifier and an acrylic resin is a medical device having an undercoat layer containing only an acrylic resin without containing a tackifier ( Compared with 1), it is shown that the adhesion between the undercoat layer and the surface lubricating layer is high.

Example 1-1: Manufacture of medical device 1 Modified polyethylene (Modic (registered trademark) M512 manufactured by Mitsubishi Chemical Corporation) sheet (18 mm × 40 mm × 1 mm) (modified PE sheet) was wiped with acetone to form a substrate. (Substrate 1).

  Undercoat BPS6074HTF containing non-aromatic tackifier and acrylic resin (Toyochem Co., Ltd., content of non-aromatic tackifier: 5 to 15% by mass (catalog value) with respect to acrylic resin) Undercoat liquid 1 was prepared by adding to tetrahydrofuran (THF) so that the concentration of the resin content was 10% by mass.

  The block copolymer (DMAA: GMA = 11: 1 (molar ratio)) (block copolymer 1) produced in Synthesis Example 1 was added to tetrahydrofuran (THF) to a concentration of 3.5% by mass, and the coating solution A was prepared.

  Soon after the substrate 1 was immersed in the undercoat solution 1 prepared above, the coating was performed at a speed of 15 mm / sec, followed by air drying for 30 minutes (substrate 1-1). After air drying, this base material 1-1 was heated in an oven at 60 ° C. for 1 hour to form (fix) an undercoat layer on the surface of the base material 1 (modified polyethylene sheet) (base material 1-2). . Thereafter, the base material 1-2 was dipped in the coating solution A prepared above, and soon, it was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 1-3). After air drying, the base material 1-3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubricating layer on the undercoat layer (medical device 1).

Example 1-2: Manufacture of medical device 2 Undercoat BPS6574HTF (produced by Toyochem Co., Ltd., an aromatic tackifier containing rosin resin (aromatic tackifier) having dehydroabietic acid and acrylic resin : 10-20 mass% (catalog value) with respect to the acrylic resin was added to tetrahydrofuran (THF) so as to have a resin content of 10 mass%, thereby preparing an undercoat liquid 2. In Example 1-1, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-1 except that the undercoat solution 2 prepared above was used instead of the undercoat solution 1. Formed on the material 1 (medical device 2).

Example 1-3: Manufacture of medical device 3 Modified polyethylene (Medic Chemical Co., Ltd. Modic (registered trademark) M512) sheet (18 mm x 40 mm x 1 mm) (modified PE sheet) was wiped with acetone to form a substrate. (Substrate 1).

  Acrylic resin (DIC Corporation, FineTac CT-6020) was added to acetone so as to have a resin content of 15% by mass, and then terpene phenol resin (Yasuhara Chemical Co., Ltd., which is an aromatic tackifier). Undercoat liquid 3 was prepared by adding 1 part by mass of YS polyster K125) to 100 parts by mass of acrylic resin.

  The block copolymer (DMAA: GMA = 11: 1 (molar ratio)) (block copolymer 1) produced in Synthesis Example 1 was added to tetrahydrofuran (THF) to a concentration of 3.5% by mass, and the coating solution A was prepared.

  Soon after the substrate 1 was immersed in the undercoat solution 3 prepared above, the coating was performed at a speed of 15 mm / sec, followed by air drying for 30 minutes (substrate 3-1). After air drying, the substrate 3-1 was heated in an oven at 60 ° C. for 1 hour to form (fix) an undercoat layer on the surface of the substrate 1 (modified polyethylene sheet) (substrate 3-2). . Thereafter, the base material 3-2 was immediately immersed in the coating solution A prepared above, was coated at a speed of 15 mm / sec, and air-dried for 30 minutes (base material 3-3). After air drying, this base material 3-3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubricating layer on the undercoat layer (medical device 3).

Example 1-4: Manufacture of medical device 4 After adding acrylic resin (manufactured by DIC Corporation, Finetack CT-6020) to acetone so as to have a resin content of 15% by mass, an aromatic tackifier A terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar U115) was added to 3 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare an undercoat liquid 4. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the undercoat solution 4 prepared above was used instead of the undercoat solution 3. Formed on the material 1 (medical device 4).

Example 1-5: Production of medical device 5 After adding an acrylic resin (manufactured by DIC Corporation, Finetac CT-6020) to acetone so as to have a resin content of 15% by mass, an aromatic tackifier Terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar T100) was added to 10 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare an undercoat solution 5. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the undercoat solution 5 prepared above was used instead of the undercoat solution 3. Formed on the material 1 (medical device 5).

Example 1-6: Manufacture of medical device 6 After adding acrylic resin (manufactured by DIC Corporation, Finetack CT-6020) to acetone so as to have a resin content of 15% by mass, an aromatic tackifier A terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar T100) was added so as to be 20 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare an undercoat liquid 6. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the undercoat solution 6 prepared above was used instead of the undercoat solution 3. Formed on the material 1 (medical device 6).

Example 1-7: Manufacture of medical device 7 After adding an acrylic resin (manufactured by DIC Corporation, Finetac CT-6020) to acetone so as to have a resin content of 15% by mass, an aromatic tackifier A terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar T100) was added to 50 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare an undercoat liquid 7. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the undercoat solution 7 prepared above was used instead of the undercoat solution 3. Formed on the material 1 (medical device 7).

Example 1-8: Production of medical device 8 After adding an acrylic resin (manufactured by DIC Corporation, Finetac CT-6020) to acetone so as to have a resin content of 15% by mass, an aromatic tackifier The undercoat liquid 8 was prepared by adding the terpene phenol resin (YS Hara Chemical Co., Ltd., YS Polystar T100) that is 60 parts by mass with respect to 100 parts by mass of the acrylic resin. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the undercoat solution 8 prepared above was used instead of the undercoat solution 3. Formed on the material 1 (medical device 8).

Example 1-9: Production of medical device 9 After adding an acrylic resin (manufactured by DIC Corporation, Finetac CT-6020) to acetone so as to have a resin content of 15% by mass, an aromatic tackifier A terpene phenol resin (YS Hara Chemical Co., Ltd., YS Polystar T100) was added to 70 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare an undercoat liquid 9. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the undercoat solution 9 prepared above was used instead of the undercoat solution 3. Formed on the material 1 (medical device 9).

Example 1-10: Manufacture of Medical Device 10 Modified polyethylene (Modic (registered trademark) M512 manufactured by Mitsubishi Chemical Corporation) sheet (18 mm × 40 mm × 1 mm) (modified PE sheet) was wiped with acetone to form a substrate. (Substrate 1).

  Undercoat fine tack CT-5020 (produced by DIC Corporation, content of aromatic tackifier: about 42% by mass with respect to acrylic resin; the same applies hereinafter) containing an aromatic tackifier and an acrylic resin Then, it was added to acetone so that the concentration of the resin content was 9% by mass to prepare an undercoat solution 10. In addition, as above-mentioned, undercoat fine tack CT-5020 contains an aromatic tackifier in the ratio of about 42 mass% with respect to an acrylic resin (refer the said reference example 1). The aromatic tackifier contained in the undercoat fine tack CT-5020 is a mixture of a rosin resin having dehydroabietic acid and a copolymer resin of a styrene monomer and an aliphatic monomer (the same applies hereinafter). .

  The block copolymer (DMAA: GMA = 11: 1 (molar ratio)) (block copolymer 1) produced in Synthesis Example 1 was added to tetrahydrofuran (THF) to a concentration of 3.5% by mass, and the coating solution A was prepared.

  Soon after the substrate 1 was immersed in the undercoat solution 10 prepared above, coating was performed by pulling up at a speed of 15 mm / sec and air-dried for 30 minutes (substrate 10-1). After air drying, this base material 10-1 was heated in an oven at 60 ° C. for 1 hour to form (fix) an undercoat layer on the surface of the base material 1 (modified polyethylene sheet) (base material 10-2). . Thereafter, the base material 10-2 was dipped in the coating solution A prepared above and soon after coating was performed at a speed of 15 mm / sec and air-dried for 30 minutes (base material 10-3). After air drying, the base 10-3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubricating layer on the undercoat layer (medical device 10).

Example 1-11: Manufacture of medical device 11 Undercoat Finetack CT-5020 (manufactured by DIC Corporation) containing an aromatic tackifier and an acrylic resin was added with acetone so as to have a resin content of 9% by mass. To prepare an acetone solution. Undercoat liquid 11 was prepared by adding a polyisocyanate compound (FINECK HARDENER D40, manufactured by DIC Corporation) to the acetone solution so as to be 15% by mass with respect to the acrylic resin. In Example 1-10, an undercoat layer and a surface lubricating layer were sequentially formed in the same manner as in Example 1-10 except that the undercoat solution 11 prepared above was used instead of the undercoat solution 10. Formed on the material 1 (medical device 11).

Example 1-12: Manufacture of medical device 12 Polyamide elastomer (Grill Flex (registered trademark) ELG5660, manufactured by Emschemie Japan Co., Ltd.) sheet (18 mm × 40 mm × 1 mm) was wiped with acetone to form a base material (base material) 2).

  In Example 1-11, an undercoat layer and a surface lubricating layer were sequentially formed on the substrate 2 in the same manner as in Example 1-11 except that the substrate 2 was used instead of the substrate 1. (Medical device 12).

Example 1-13: Production of medical device 13 A SUS304 sheet (18 mm x 40 mm x 1 mm) was wiped with acetone to form a base material (base material 3).

  In Example 1-11, an undercoat layer and a surface lubricating layer were sequentially formed on the substrate 3 in the same manner as in Example 11 except that the substrate 3 was used instead of the substrate 1 (medical) Tool 13).

Example 1-14: Manufacture of medical device 14 Polyvinylpyrrolidone (PVP) (manufactured by Tokyo Chemical Industry Co., Ltd., K-90) and self-crosslinkable aqueous urethane resin (manufactured by Mitsui Chemicals, Takelac (registered trademark) WS-) 5000) were added to ethanol so as to have a concentration of 3.5% by mass, respectively, to prepare a coating liquid B (PVP: urethane resin = 1: 1 (mass ratio)).

  In Example 1-11, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-11 except that the coating liquid B prepared above was used instead of the coating liquid A. Formed above (medical device 14).

Example 1-15: Production of medical device 15 Modified polyethylene (Modic (registered trademark) M512 manufactured by Mitsubishi Chemical Corporation) sheet (18 mm × 40 mm × 1 mm) (modified PE sheet) was wiped with acetone to obtain a substrate. (Substrate 1).

  After adding styrene butadiene rubber (manufactured by Sigma Aldrich Japan GK, product number: 182907) to tetrahydrofuran (THF) so as to have a resin content of 4% by mass, terpene phenol resin (aromatic tackifier) An undercoat solution 15 was prepared by adding 20 parts by mass of YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd. to 100 parts by mass of styrene butadiene rubber.

  The block copolymer (DMAA: GMA = 11: 1 (molar ratio)) (block copolymer 1) produced in Synthesis Example 1 was added to tetrahydrofuran (THF) to a concentration of 3.5% by mass, and the coating solution A was prepared.

  Soon after the substrate 1 was immersed in the undercoat solution 15 prepared above, coating was performed by pulling it up at a speed of 15 mm / sec and air-dried for 30 minutes (substrate 15-1). After air drying, this base material 15-1 was heated in an oven at 60 ° C. for 1 hour to form (fix) an undercoat layer on the surface of the base material 1 (modified polyethylene sheet) (base material 15-2). . After that, the base material 15-2 was dipped in the coating solution A prepared above, and soon it was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 15-3). After air drying, this base material 15-3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubricating layer on the undercoat layer (medical device 15).

Comparative Example 1-1: Manufacture of Comparative Medical Device 1 An acrylic resin (manufactured by DIC Corporation, Finetack CT-6020) was added to acetone so as to have a resin content of 15% by mass, and a comparative undercoat solution 1 Was prepared. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the comparative undercoat solution 1 prepared above was used instead of the undercoat solution 3. It formed on the base material 1 (comparative medical device 1).

Comparative Example 1-2: Manufacture of Comparative Medical Device 2 Acrylic resin (FineTac CT-6020, manufactured by DIC Corporation) was added to acetone so as to have a resin content of 15% by mass, and then aromatic tackifying was performed. A comparative undercoat solution 2 was prepared by adding 90 parts by mass of a terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar T100) as an agent to 100 parts by mass of the acrylic resin. In Example 1-3, the undercoat layer and the surface lubricating layer were sequentially formed in the same manner as in Example 1-3 except that the comparative undercoat solution 2 prepared above was used instead of the undercoat solution 3. It formed on the base material 1 (comparative medical device 2).

Comparative Example 1-3: Production of Comparative Medical Device 3 A modified polyethylene (Modic (registered trademark) M512 manufactured by Mitsubishi Chemical Corporation) sheet (18 mm × 40 mm × 1 mm) (modified PE sheet) was wiped with acetone, (Substrate 1).

  The block copolymer (DMAA: GMA = 11: 1 (molar ratio)) (block copolymer 1) produced in Synthesis Example 1 was added to tetrahydrofuran (THF) to a concentration of 3.5% by mass, and the coating solution A was prepared.

  Soon after the substrate 1 was immersed in the coating solution A prepared above, the coating was performed at a speed of 15 mm / sec, followed by air drying for 30 minutes (Comparative substrate 3). After air drying, the comparative base material 3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubricating layer on the base material 1 (comparative medical device 3).

Comparative Example 1-4: Production of Comparative Medical Device 4 Polyamide elastomer (Grill Flex (registered trademark) ELG5660 manufactured by EMS) sheet (18 mm × 40 mm × 1 mm) was wiped with acetone to form a base material (base material 2).

  In Comparative Example 1-3, a surface lubricating layer was formed on the base material 2 in the same manner as in Comparative Example 1-3 except that the base material 2 was used instead of the base material 1 (Comparative Medical Device 4 ).

Comparative Example 1-5: Production of Comparative Medical Device 5 A SUS304 sheet (18 mm × 40 mm × 1 mm) was wiped with acetone to form a base material (base material 3).

  In Comparative Example 1-3, a surface lubricating layer was formed on the base material 3 in the same manner as in Comparative Example 1-3 except that the base material 3 was used instead of the base material 1 (Comparative Medical Device 5 ).

Comparative Example 1-6: Production of Comparative Medical Device 6 Polyvinylpyrrolidone (PVP) (Tokyo Chemical Industry Co., Ltd., K-90) and self-crosslinkable aqueous urethane resin (Mitsui Chemicals, Takelac (registered trademark) WS- 5000) were added to ethanol so as to have a concentration of 3.5% by mass, respectively, to prepare a coating liquid B (PVP: urethane resin = 1: 1 (mass ratio)).

  In Comparative Example 1-3, a surface lubricating layer was formed on the substrate 1 in the same manner as in Comparative Example 1-3 except that the coating liquid B prepared above was used instead of the coating liquid A ( Comparative medical device 6).

Comparative Example 1-7: Production of Comparative Medical Device 7 Styrene butadiene rubber (manufactured by Sigma Aldrich Japan G.K., product number: 182907) was added to tetrahydrofuran (THF) so as to have a resin content of 4% by mass, A comparative undercoat solution 7 was prepared.

  In Example 1-14, the undercoat layer and the surface lubricating layer were successively formed in the same manner as in Example 14 except that the comparative undercoat solution 7 prepared above was used instead of the undercoat solution 14. 1 (Comparative medical device 7). That is, this comparative example is the same as Example 1-14 except that the aromatic tackifier (YS Polystar T100) was not added in Example 1-14.

Example 2-1: Production of medical device 16 Modified polyethylene (manufactured by Tosoh Corporation, Nitipolon ZF260) tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to form a substrate. (Substrate 4).

  In Example 1-11, an undercoat layer and a surface lubricating layer were sequentially formed on the substrate 4 in the same manner as in Example 1-11 except that the substrate 4 was used instead of the substrate 1. (Medical device 16).

Example 2-2: Production of medical device 17 Modified polyethylene (Nichipolon ZF260 manufactured by Tosoh Corporation) A tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to obtain a base material ( Substrate 4).

  In Example 1-10, an undercoat layer and a surface lubricating layer were sequentially formed on the base material 4 in the same manner as in Example 1-10 except that the base material 4 was used instead of the base material 1. (Medical device 17).

Example 2-3: Manufacture of medical device 18 Modified polyethylene (Nichipolon ZF260, manufactured by Tosoh Corporation) A tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to form a substrate ( Substrate 4).

  In Example 1-14, an undercoat layer and a surface lubricating layer were sequentially formed on the base material 4 in the same manner as in Example 1-14 except that the base material 4 was used instead of the base material 1. (Medical device 18).

Comparative Example 2-1 Production of Comparative Medical Device 8 Modified polyethylene (Nichipolon ZF260 manufactured by Tosoh Corporation) Tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to form a base material (Substrate 4).

In Comparative Example 1-3, an undercoat layer and a surface lubricating layer were sequentially formed on the base material 4 in the same manner as in Comparative Example 1-3 except that the base material 4 was used instead of the base material 1. (Comparison medical device 8)
Medical devices 1 to 18 manufactured in Examples 1-1 to 1-15 and 2-1 to 2-3 and Comparative medical devices 1 to 8 manufactured in Comparative Examples 1-1 to 1-7 and 2-1 According to the following method, durability (durability of the surface lubricating layer) was evaluated.

[Durability evaluation]
For each medical device (hereinafter simply abbreviated as “sample”), the sliding resistance value (gf) of the surface lubricating layer was measured using the friction measuring device 20 shown in FIG. Sex was evaluated.

  That is, each sample 16 was fixed in the petri dish 12 and immersed in water 17 having a height that the entire sample 16 was immersed. This petri dish 12 was placed on the moving table 15 of the friction measuring machine (manufactured by Trinity Lab, Handy Tribomaster TL201) 20 shown in FIG. A cylindrical polyethylene (PE) terminal (φ10 mm, R1 mm) 13 was brought into contact with the sample 16, and a load 14 of 450 g was applied to the terminal 13 when the sample 16 was a sheet shape and 50 g when the sample 16 was a tube shape. . The sliding resistance value (gf) when the moving table 15 was reciprocated horizontally 50 times at a speed of 16.7 mm / sec and a moving distance of 2 cm was measured. The sliding resistance value from the first reciprocation to the 50th reciprocation was averaged for each reciprocation, and plotted as a sliding resistance value (gf) on a graph to evaluate the lubricity durability against 50 repeated sliding operations. In each test, one sample was tested. Moreover, it means that it is excellent in surface lubricity, so that sliding resistance value (gf) is low.

  The results of the medical devices 1 to 18 and the comparative medical devices 1 to 8 are shown in FIGS. Moreover, the results of FIGS. 2 to 27 are evaluated according to the following criteria, and the results are summarized in Table 2 below. In Table 2 below, “modified PE” indicates modified polyethylene. In Table 2 below, “p (DMAA-b-GMA)” represents block copolymer 1 (DMAA: GMA = 11: 1 (molar ratio)) produced in the same manner as in Synthesis Example 1.

(Judgment criteria when sample 16 has a sheet shape)
X: The number of sliding is 5 to 29 and the sliding resistance is 30 gf or more;
(Triangle | delta): The frequency | count of sliding is 30 to 49 times, and sliding resistance value is 30 gf or more;
A: The number of sliding times is 50, and the sliding resistance value does not reach 30 gf.

(Criteria when sample 16 is tube-shaped)
× Sliding frequency reaches 1 to 5 times and sliding resistance reaches 10 gf or more. △ Sliding frequency reaches 6 to 49 and sliding resistance reaches 10 gf or more. ○ Number of sliding times is 50. Sliding resistance value does not reach 10gf

  From Table 2 and FIGS. 2 to 7, the medical devices 1 to 15 of the present invention have comparative medical devices 1 and 7 having an undercoat layer that does not contain a tackifier, and an undercoat layer that contains an excessive amount of the tackifier. It can be seen that the lubricity and durability (lubrication maintenance) are significantly improved as compared with the comparative medical device 2 and the comparative medical devices 3 to 6 and 8 having no undercoat layer.

  In FIG. 2, in the medical device 1 (Example 1) having an undercoat layer containing a non-aromatic tackifier and an acrylic resin, the sliding resistance value gradually increases after 50 reciprocations, and the number of sliding operations The sliding resistance value exceeds 30 gf around 35 times. On the other hand, in FIG. 3, in the medical device 2 (Example 2) which has an undercoat layer containing an aromatic tackifier and an acrylic resin, good lubricity is maintained even after 50 reciprocations. From this, it is considered that the durability (effect of maintaining lubricity) of the surface lubricating layer can be further improved by using an aromatic tackifier as the tackifier.

  4 to 10, when the content of the tackifier is 1 to 70 parts by mass with respect to 100 parts by mass of the acrylic resin, the medical device maintains good lubricity even after 50 reciprocations (medical treatment). It can be seen that the surface lubrication layer of the device is excellent in durability). On the other hand, as shown in FIGS. 17 and 18, when the tackifier content is 0 part by mass or 90 parts by mass with respect to 100 parts by mass of the acrylic resin, the sliding resistance value exceeds 30 gf at the initial stage. The effect of maintaining lubricity is low. From this, it is necessary that the tackifier content is less than 90 parts by mass with respect to 100 parts by mass of the acrylic resin, and particularly 1 to 70 parts by mass, the surface lubricant layer of the medical device has sufficiently good lubricity. In addition, it is considered that durability can be exhibited.

  12-14, it turns out that the favorable lubricity is maintained even after 50 reciprocations in all the medical devices whose base material is a modified polyethylene sheet, a polyamide elastomer sheet, and a SUS304 sheet. Moreover, it turns out by each comparison with FIGS. 12-14 and FIGS. 19-21 that durability of a surface lubricating layer can be improved significantly by providing an undercoat layer. From the above results, it is considered that the surface lubricant layer of the medical device of the present invention can exhibit excellent lubricity and durability by providing an undercoat layer regardless of the type of the substrate.

  In FIGS. 11 and 12, there is no significant difference in durability regardless of whether a cross-linking agent is added to the undercoat layer. On the other hand, in comparison with FIGS. 24 and 25, it can be seen that the addition of a crosslinking agent to the undercoat layer (FIG. 24) is superior in durability. Therefore, when a higher load is applied, the use of a block copolymer of DMAA and GMA as the hydrophilic polymer makes the durability more remarkable by adding a crosslinking agent to the undercoat layer. It is considered that it can be improved.

  FIG. 15 shows that even when polyvinylpyrrolidone is used as the hydrophilic polymer, good lubricity can be maintained even after 50 reciprocations. On the other hand, as shown in FIG. 22, when the undercoat layer is not provided, the sliding resistance value is increased from the first time. From the above results, it is considered that the surface lubricant layer of the medical device of the present invention can exhibit excellent lubricity and durability by providing an undercoat layer regardless of the type of the hydrophilic polymer. In addition, in the comparison with FIG.12 and FIG.15, the difference of durability in a hydrophilic polymer is not recognized so much. On the other hand, from the comparison with FIGS. 24 and 26, when a higher load is applied (under a higher load on the contacted area), the block copolymer of DMAA and GMA as the hydrophilic polymer is used. It is considered that the use of the polymer can exhibit excellent durability as compared with the case of using polyvinylpyrrolidone.

  FIG. 16 shows that even when styrene butadiene rubber is used as the base polymer, good lubricity can be maintained even after 50 reciprocations. On the other hand, as shown in FIG. 23, when no tackifier is added to the undercoat layer, the sliding resistance value exceeds 30 gf at the initial stage (the number of sliding times is about 15). From the above results, it is considered that the surface lubricating layer of the medical device of the present invention can exhibit excellent lubricity and durability by providing an undercoat layer regardless of the type of the base polymer.

12 Petri dish,
13 Cylindrical polyethylene terminal,
14 load,
15 Moving table,
16 Medical device (sample),
17 Water,
20 Friction measuring machine.

Claims (4)

A medical device comprising: a base material; an undercoat layer disposed on a surface of the base material; and a surface lubricating layer including a hydrophilic polymer disposed on a surface of the undercoat layer,
The undercoat layer is formed from a composition comprising a base polymer and a tackifier,
The said tackifier is a medical device contained in the ratio below 90 mass parts with respect to 100 mass parts of said base polymers.   The medical device according to claim 1, wherein the base polymer is at least one selected from the group consisting of (meth) acrylic resins and styrene butadiene rubber.   The medical device according to claim 1 or 2, wherein the tackifier is an aromatic tackifier.   The said tackifier is a medical device of any one of Claims 1-3 contained in the ratio of 1-70 mass parts with respect to 100 mass parts of said base polymers.