JP6776029B2 - Medical equipment - Google Patents

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 the living body are required to exhibit excellent lubricity in order to reduce tissue damage such as blood vessels and improve the operability of the operator. Therefore, a method of coating the surface of a base material with a hydrophilic polymer having lubricity has been developed and put into practical use. In such a medical device, the dissolution and peeling of the hydrophilic polymer from the surface of the base material is a problem in terms of maintaining safety and operability. Therefore, the coating with a hydrophilic polymer is required not only to have excellent lubricity but also to have durability against loads such as abrasion and abrasion.

From this point of view, Patent Document 1 describes a polymer solution prepared by dissolving a water-soluble or water-swellable polymer in a solvent in which the base material of a medical device swells, and the polymer solution is used to prepare a polymer solution. A medical device in which a surface lubricating layer is formed on the surface of a base material by immersing and swelling the base material and further cross-linking or polymerizing the polymer on the surface of the base material is disclosed. According to the technique disclosed in Patent Document 1, a surface lubrication layer exhibiting relatively good lubricity can be fixed to a base material.

Further, Patent Document 2 describes that a polyisocyanate compound layer is provided between the hydrophilic polymer coating and the support. According to this method, since isocyanate and a hydrophilic polymer react with each other, it is described that the abrasion resistance is excellent.

Japanese Unexamined Patent Publication No. 8-33704 Special Table No. 5-505125

Patent Document 1 discloses that it is preferable to use a block copolymer composed of a hydrophilic moiety exhibiting lubricity and a moiety having an epoxy group as the water-soluble or water-swellable polymer. Then, when such a block copolymer is used, the epoxy group can be crosslinked by a heating operation, and a surface lubricating layer that is relatively difficult to peel off can be formed.

However, in recent years, the miniaturization and diameter of medical devices have been remarkably reduced, and medical techniques for approaching medical devices to narrow lesions with higher flexibility in the living body are becoming widespread. In addition, as the operation becomes more complicated, the operation may last for a long time. Therefore, in order to maintain good operability of the device even in a complicated lesion site, a technique for further improving the lubricity retention property (durability of the surface lubrication layer) of the device surface is required as compared with the conventional technique.

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

Further, in the technique described in Patent Document 2, it is an essential requirement that the polyisocyanate compound layer is provided between the hydrophilic polymer coating and the support. Therefore, there is a problem that the hydrophilic polymer constituting the hydrophilic polymer coating is limited to the material that reacts with the polyisocyanate compound.

Therefore, there is a need for a technique that allows a wide selection of materials that can be used for the target surface layer (hydrophilic polymer coating) and improves lubrication maintenance (durability of the surface lubrication layer).

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

Another object of the present invention is to provide a medical device having excellent durability of a surface lubricating layer capable of firmly immobilizing various hydrophilic polymers and a base material by a simpler method.

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

That is, the above object is a medical device including a base material, an undercoat layer arranged on the surface of the base material, and a surface lubricating layer containing a hydrophilic polymer arranged 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 by medical devices.

According to the present invention, it is possible to provide a medical device having excellent durability of the surface lubricating layer.

FIG. 1 is a schematic view of a test device (friction measuring machine) for evaluating the durability of the surface lubrication layer. FIG. 2 is a graph showing the durability evaluation test results of the surface lubricating layer of the medical device 1 obtained in Reference Example 1-1. FIG. 3 is a graph showing the durability evaluation test results of the surface lubrication layer of the medical device 2 obtained in Example 1-2. FIG. 4 is a graph showing the durability evaluation test results of the surface lubricating layer of the medical device 3 obtained in Example 1-3. FIG. 5 is a graph showing the results of the durability evaluation test of the surface lubricating layer of the medical device 4 obtained in Examples 1-4. FIG. 6 is a graph showing the durability evaluation test results 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 results 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 results 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 results 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 results 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 results 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 results 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 results 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 results 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 results of the surface lubrication layer of the medical device 14 obtained in Example 1-14. FIG. 16 is a graph showing the durability evaluation test results of the surface lubricating layer of the medical device 15 obtained in Example 1-15. FIG. 17 is a graph showing the durability evaluation test results 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 results of the surface lubricating layer of the comparative medical device 2 obtained in Comparative Example 1-2. FIG. 19 is a graph showing the results of the durability evaluation test 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 results of the surface lubrication layer of the comparative medical device 4 obtained in Comparative Example 1-4. FIG. 21 is a graph showing the durability evaluation test results of the surface lubricating layer of the comparative medical device 5 obtained in Comparative Example 1-5. FIG. 22 is a graph showing the durability evaluation test results of the surface lubricating layer of the comparative medical device 6 obtained in Comparative Example 1-6. FIG. 23 is a graph showing the results of the durability evaluation test 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 results 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 results 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 results of the surface lubricating layer of the medical device 18 obtained in Example 2-3. FIG. 27 is a graph showing the durability evaluation test results of the surface lubricating layer of the comparative medical device 8 obtained in Comparative Example 2-1.

The present invention is a medical device including a base material, an undercoat layer arranged on the surface of the base material, and a surface lubricating layer containing a hydrophilic polymer arranged 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.

In 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) of a tackifier is provided between the base material and the surface lubricating layer. It is characterized by that. With this configuration, the medical device of the present invention can exhibit the durability (lubrication maintainability) of the surface lubrication layer. In addition, the medical device of the present invention exhibits excellent lubricity on the surface in aqueous liquids such as body fluids and physiological saline. The detailed mechanism by which the medical device according to the present invention exerts the above effects is still unknown, but 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 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 constituting the undercoat layer has a high molecular weight, the film strength is high, but since it is relatively hard, the adhesiveness (adhesion) is inferior. On the other hand, the tackifier that constitutes the undercoat layer has excellent molecular motility because it is a small molecule, but it is very brittle as a film. Therefore, the present inventors have diligently studied a composition capable of achieving both characteristics in a well-balanced manner. As a result, when the base polymer and the tackifier are blended in a ratio of less than 90 parts by mass with respect to 100 parts by mass of the base polymer to form an undercoat layer, the movement of molecules of the undercoat layer becomes active and appropriate plasticity is obtained. It exerts, resulting in increased stickiness. On the other hand, due to the presence of the base polymer, the undercoat layer has an appropriate film strength. Therefore, the surface lubrication layer is firmly fixed to the undercoat layer. In addition, the undercoat layer exhibits high adhesiveness (adhesion) to the substrate. Therefore, the base material, the undercoat layer, and the surface lubrication layer are firmly integrated, and it is possible to effectively suppress / prevent the surface lubrication layer existing on the outermost surface from being separated from the base material. Therefore, the medical device of the present invention can maintain its lubricity for a long period of time while exhibiting excellent lubricity on the surface in an aqueous liquid such as a body fluid or physiological saline (durability (lubrication retention) can be improved). ).

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments. In addition, 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, operations and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 20 to 80% RH.

[Base material]
The base material 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 or nickel-titanium alloy, nickel-cobalt alloy, Examples thereof include various alloys such as cobalt-chromium alloy and zinc-tungsten alloy. The polymer material is not particularly limited, and a polymer material generally used for medical devices such as a catheter, a guide wire, an injection needle, and an indwelling needle is used. Specifically, polyamide resins, polyamide elastomers, polyolefin resins such as polyethylene resins and polypropylene resins, modified polyethylene resins (modified high density polyethylene, modified low density polyethylene, modified linear low density polyethylene, etc.), modified polypropylene resins, etc. Modified polyolefin resin, cyclic polyolefin resin, epoxy resin, urethane resin (polyurethane), diallyl phthalate resin (allyl resin), polycarbonate resin, fluororesin, amino resin (ureia resin, melamine resin, benzoguanamine resin), polyester resin, styrol resin, Examples thereof include acrylic resin, polyacetal resin, vinyl acetate resin, phenol resin, vinyl chloride resin, silicone resin (silicon resin), polyether resin, polyimide resin, and polyimide elastomer. The materials constituting these base materials may be used alone, in combination of two or more, or a copolymer of two or more monomers constituting any of the above resins. May be used as. From the above materials, the most suitable material as a base material may be appropriately selected according to the intended use such as a catheter, a guide wire, and an indwelling needle.

The shape of the base material corresponds to the shape of the catheter, the guide wire, the indwelling needle, etc. according to the actual usage. Therefore, 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 shape, and a tube shape. Further, the base material may be composed of any of the above materials as a whole, or may be formed by appropriately combining different materials. As an example of the latter case, a structure or a base formed by coating the surface of a base material core portion made of any of the above materials with any of the above materials by an appropriate method to form a base material surface layer. A core-shell structure in which the surface of a material core is coated with any of the above materials by an appropriate method to form a base material surface layer, a multi-layer structure in which different materials are laminated in multiple layers, or a medical device. There is a structure in which members made of different materials are joined together for each part.

[Undercoat layer]
The undercoat layer is disposed between the substrate and the surface lubrication layer and is formed from a composition that essentially contains a base polymer and a tackifier.

Here, the base polymer is not particularly limited, but is preferably a polymer having flexibility in consideration of the effect of improving kink resistance, the influence on the substrate, and the like, and a polymer having a glass transition point (Tg) of 20 ° C. or less. More preferably. Specifically, natural rubber, styrene-butadiene rubber (SBR), butyl rubber, isoprene rubber, latex rubber, synthetic rubber such as silicone rubber, (meth) acrylic resin, silicone resin, urethane resin, vinyl ether resin, SBS elastomer, SEBS elastomer. Such as styrene-based elastomer, olefin-based elastomer such as ethylene-α-olefin copolymer elastomer, and the like can be mentioned. The base polymer may be used alone or in the form of a mixture of two or more. 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 resin and styrene-butadiene rubber. Further, the (meth) acrylic resin has high solubility in a solvent (for example, an alcohol solvent) that does not damage the substrate, and is particularly suitable for preparing a coating solution. Therefore, in a more preferred embodiment of the present invention, the base polymer is a (meth) acrylic resin. In a particularly preferred embodiment of the present 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 an acrylic-based or methacrylic-based monomer. These may be either homopolymers or copolymers. Preferably, the main monomer component of the (meth) acrylic resin is (meth) acrylic acid and / or (meth) acrylic acid ester. Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and lauryl (meth) acrylate having 1 to 20 carbon atoms. There are but not limited to esterified products of alkyl alcohol and (meth) acrylic acid. The (meth) acrylic acid ester may be used alone or in the form of a mixture of two or more. In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid. Similarly, "(meth) acrylate" means acrylate or metalylate.

The base polymer may be obtained synthetically or may be commercially available. Commercially available products include, for example, Quick Master, Fine Tuck Series (for example, Fine Tuck CT-6020) (all manufactured by DIC Corporation), SK Dyne (manufactured by Soken Chemical Co., Ltd.), and Aron Tuck Series (manufactured by Toagosei Co., Ltd.). ) And the like, styrene-butadiene rubber (manufactured by Sigma-Aldrich Japan GK, for example, # 182907) and the like.

The undercoat layer contains a tackifier in addition to the base polymer. As used herein, the "tacking agent" is a compound that imparts adhesive strength to a base polymer or improves the adhesive strength of a base polymer, and is also referred to as a tack fire. 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, terpene phenol resin and the like. The petroleum resin is composed of a (co) polymer of an unsaturated hydrocarbon having an aliphatic, alicyclic or aromatic hydrocarbon structure, and is, for example, a styrene resin, an α-toluene resin, a kumaron-inden resin, or an α-. Examples thereof include methyl styrene resin, α-methyl styrene / styrene copolymer resin, styrene monomer / aliphatic monomer copolymer resin, pentadiene resin, cyclopentadiene resin, and hydrogenated hydrocarbon resin.

Further, the tackifier is preferably an aromatic tackifier because it has a higher effect of improving the adhesive strength of the base polymer (it can further improve durability). That is, according to the 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. For example, a rosin resin having dehydroabietic acid, a rosin phenol resin, a terpene phenol resin, a petroleum resin composed of a homopolymer or a copolymer of an unsaturated hydrocarbon having an aromatic hydrocarbon structure, and the like can be mentioned. Examples of the rosin resin having dehydroabietic acid include a rosin ester derived from a natural resin rosin, a disproportionate rosin ester obtained by esterifying a disproportionate rosin obtained by asymmetricalizing the rosin, and the like. Examples of the petroleum resin composed of a monopolymer or copolymer of an unsaturated hydrocarbon having an aromatic hydrocarbon structure include styrene resin, α-toluene resin, kumaron-inden resin, α-methylstyrene resin, and 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 can be mentioned. Of these, terpenephenol resins, rosin resins having dehydroabietic acid, and styrene-based monomer / aliphatic monomer copolymer resins 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-based monomer / aliphatic monomer copolymer resin are more preferable, and a rosin resin having dehydro-abietic acid, or A mixture of a rosin resin having dehydroabietic acid and a styrene-based monomer / aliphatic monomer copolymer resin is particularly preferable. According to the 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-based monomer / aliphatic monomer copolymer resin. Further, according to a more preferable form 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-based monomer / aliphatic monomer copolymer resin. Further, according to a particularly preferable form 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-based monomer / aliphatic monomer copolymer resin.

The tackifier may be used alone or in the form of a mixture of two or more.

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

The tackifier may be obtained synthetically or a commercially available product may be used. Commercially available products include, for example, YS Polystar series, YS resin series, Croaron series (all manufactured by Yasuhara Chemical Co., Ltd.), Super Ester series, Pine Crystal series, Pencel series (manufactured by Arakawa Chemicals Co., Ltd.), FTR series (all). Mitsui Chemicals Co., Ltd.)

The content of the tackifier is less than 90 parts by mass (more than 0 parts 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 of the base polymer (particularly the film strength) is excessively lowered, so that the surface of the obtained medical device is obtained. The lubricating layer is inferior in durability (see Comparative Example 2 below). On the contrary, when the undercoat layer is composed of only the base polymer (the content of the tackifier is 0% by mass), the undercoat layer is inferior in adhesiveness and the surface lubricating layer is based on the undercoat layer. The surface lubricating layer of the obtained medical device is still inferior in durability because it cannot be sufficiently adhered to the material (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, the undercoat layer can be imparted with a desired adhesive force, and the surface lubrication layer can be firmly integrated with the base material via the undercoat layer. Therefore, the surface lubrication layer of the obtained medical device can further improve the durability.

The content of the tackifier in the undercoat layer of the medical device is substantially the same as the content of the tackifier in the coating liquid (total solid content) at the time of forming the undercoat layer. Further, even in the form of the final product, the medical device, 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 after the base polymer and the tackifier in the undercoat layer are separated by a known method such as a liquid separation operation, and then the base polymer and the tackifier are separated. The content of each component can be quantified based on the extracted amount. In the present 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 and tackifier constituting the undercoat layer. Can be selected.

(Method of measuring the content of tackifier)
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. An immiscible solvent (solvent B) is added to perform a liquid separation treatment. Alternatively, the liquid separation treatment may be performed in the reverse order of extraction, that is, after the undercoat layer is extracted with a solvent (solvent A') that is soluble in the tackifier but insoluble in the base polymer. , A solvent (solvent B') that is soluble in the base polymer but insoluble in the tackifier and is immiscible with the solvent A'may be added to carry out the liquid separation treatment. In addition, the liquid separation treatment operation is repeated as necessary. 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) can be obtained. Each of these fractions is dried to dryness and the mass of each dry residue is measured. The dry residues of fractions A and B correspond to the amount of base polymer and tackifier contained in the undercoat layer, respectively. Based on these amounts, the content (mass%) of the tackifier with respect to the base polymer can be calculated.

In addition, a commercially available product containing a base polymer and a tackifier may be used. Examples of such commercially available products include Oliveine series (for example, BPS6074HTF, BPS6574HTF (manufactured by Toyochem Co., Ltd.), Finetack series (for example, Finetack CT-5020) (manufactured by DIC Corporation), and SK Dyne series (for example, SK). Dyne 1502) and the like. In addition, when a commercially available product containing a base polymer and a tackifier is used, the content of the tackifier may be unknown. Even in such a case, the above The content of the tackifier (composition to the base polymer) can be measured by the same method as (Method for measuring the content of the tackifier).

The undercoat layer may be formed from a composition containing only the base polymer and tackifier as the active ingredient (solid ingredient), or other additives in addition to the base polymer and tackifier as the active ingredient (solid ingredient). It may be formed from a composition containing. In the former case, the undercoat layer is substantially composed only of the base polymer and the tackifier. At this time, the undercoat layer contains the tackifier at a ratio of less than 90 parts by mass with respect to 100 parts by mass of the base polymer. In the latter case, other additives include cross-linking agents for cross-linking the base polymer and the like. These other additives may be used alone or in combination of two or more. For example, if the undercoat layer is formed from a composition comprising a base polymer, a tackifier and a crosslinker, the undercoat layer may be a crosslinked product of the base polymer, the base polymer (if any uncrosslinked portions), and Contains tackifier. At this time, the undercoat layer contains the tackifier at a ratio of less than 90 parts by mass with respect to 100 parts by mass of the total amount of the base polymer and the crosslinked product thereof.

When the undercoat layer is formed from a composition containing only the base polymer and the tackifier as the active ingredient (solid component), the base polymer surface lubricates when a surface lubrication layer is further formed on the undercoat layer. It may dissolve in the coating liquid (coating liquid) for layer formation. Therefore, by further cross-linking the base polymer with a cross-linking agent, the film strength can be increased, and the durability of the undercoat layer (particularly the durability under a high load state) can be further improved. Further, the dissolution of the base polymer at the time of forming the surface lubricating layer can be effectively suppressed / prevented. The cross-linking agent is not particularly limited, but known polyisocyanate compounds, epoxy resins, aziridine compounds, polyvalent metal salts, metal chelates, organic peroxides and the like can be used. When the undercoat layer is formed by using a cross-linking agent, the amount of the cross-linking agent added is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 0, with respect to 100 parts by mass of the base polymer. It is 5 to 20 parts by mass. With such an amount, the base polymer can be sufficiently crosslinked with a cross-linking agent, so that the durability of the undercoat layer, particularly the durability under a high load state can be further improved. It is possible to more effectively suppress / prevent the dissolution of the base polymer during the formation of the surface lubricating layer.

[Surface lubrication layer]
The surface lubrication layer is arranged adjacent to the surface of the undercoat layer and contains a hydrophilic polymer.

Here, the hydrophilic polymer is not particularly limited, and for example, a polysaccharide polymer substance such as polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyethylene oxide polymer substance, carboxymethyl cellulose, hyaluronic acid, chondroitin sulfate, and poly. Examples thereof include acrylamide-based polymer substances such as acrylamide and polydimethylacrylamide, polyacrylic acid, maleic anhydride-based polymer substances such as maleic anhydride-methylvinyl ether copolymer, water-soluble nylon resins, and derivatives thereof. These hydrophilic polymers can absorb water when wet and exhibit lubricity. When the hydrophilic polymer as described above is used, a cross-linking agent may be used in combination, or a reactive functional group may be introduced into the hydrophilic polymer. As a result, the hydrophilic polymer can be crosslinked to increase the film strength of the surface lubricating layer, and the durability of the surface lubricating layer (particularly, durability under a high load state) can be further improved. The cross-linking agent used in combination with the cross-linking agent is not particularly limited, but is limited to known polyisocyanate compounds, epoxy resins, aziridine compounds, polyvalent metal salts, metal chelate, organic peroxides, and self-crosslinking polymers (for example, self). Crosslinkable urethane resin) and the like. When the surface lubricating layer is formed by using a cross-linking agent, the amount of the cross-linking agent added is not particularly limited, but is preferably 0.1 to 200 parts by mass, more preferably 0, with respect to 100 parts by mass of the hydrophilic polymer. It is 5 to 150 parts by mass. With such an amount, the hydrophilic polymer can be sufficiently crosslinked with a cross-linking agent, so that durability, particularly durability under 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 in consideration of the reactivity (bondability) of the undercoat layer with the base polymer and the like, an epoxy group, an acid halide group, an aldehyde group, an isocyanate group, and an acid anhydride group. And so on. The monomer having a reactive functional group as described above is not particularly limited, and for example, an epoxy group such as glycidyl acrylate, glycidyl methacrylate (GMA), glycidyl ether, methyl glycidyl methacrylate, or allyl glycidyl ether is contained in the molecule. Monomer having; Monomer having an acid halide group in the molecule such as (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic acid iodide; (meth) acrylic aldehyde, glioxal, terephthalaldehyde, etc. Monomer having an aldehyde group in the molecule; (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,3,5-trimethylhexamethylene diisocyanate, etc. Monomer having an isocyanate group in the molecule; a monomer having an acid anhydride group in the molecule such as maleic anhydride, itaconic anhydride, citraconic anhydride and the like can be exemplified. The monomer having a reactive functional group may be used alone or in the form of a mixture of two or more kinds. Of these, as the monomer having a reactive functional group, a monomer having an epoxy group is preferable, the reaction is promoted by heat or the like, and handling is relatively easy. Therefore, glycidyl acrylate and glycidyl methacrylate are used. Is more preferable, and glycidyl methacrylate is particularly preferable. Further, since the copolymer of the monomer having a reactive functional group having an epoxy group and the hydrophilic monomer has a good bondability with the base polymer of the undercoat layer (particularly the carboxyl group of the acrylic resin), 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 the 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 embodiment of the present invention, the monomer having a reactive functional group is glycidyl methacrylate.

The hydrophilic monomer is not particularly limited, but for example, acrylamide and its derivatives, vinylpyrrolidone, acrylic acid and methacrylic acid and their derivatives, polyethylene glycol acrylate and its derivatives, sugars and phospholipids are simply contained in the side chains. Examples thereof include a metric, a water-soluble monomer such as maleic anhydride, and the like. More specifically, acrylic acid, methacrylic acid, N-methylacrylamide, N, N'-dimethylacrylamide (DMAA), acrylamide, acryloylmorpholin, 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 (Meta) 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, trimethylolpropandi (meth) acrylate, trimethylol ethanedi (meth) ) Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 2-hydroxy-3-phenyloxy (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, cyclohexanedi Examples thereof include methanol mono (meth) acrylate, poly (ethylene glycol) methyl ether acrylate, and poly (ethylene glycol) methyl ether methacrylate. The hydrophilic monomer may be used alone or in the form of a mixture of two or more. 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, from the viewpoint of further improving the lubricity, N, N'-dimethylacrylamide, acrylamide, and N-vinylpyrrolidone are more preferable, 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 the 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 embodiment of the present invention, the hydrophilic monomer is N, N'-dimethylacrylamide.

Specifically, the hydrophilic polymer is preferably polyvinylpyrrolidone (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, A block copolymer with N-dimethylacrylamide is particularly preferable.

When the hydrophilic polymer is a copolymer of a monomer having a reactive functional group and the hydrophilic monomer, the form of the hydrophilic polymer is not particularly limited, and a random copolymer, an alternating copolymer, etc. It may be either a periodic copolymer or a block copolymer. 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). It is more preferable that it is a block copolymer with. With such a block copolymer, better results can be obtained in terms of the strength and lubricity of the surface lubrication layer.

When the hydrophilic polymer is a copolymer of a monomer having a reactive functional group and a hydrophilic monomer, the composition of the hydrophilic polymer (monomer having a reactive functional group: hydrophilic monomer) (Moral ratio)) is not particularly limited. Considering the formation of a hydrogel layer when in contact with body fluids and physiological saline, and the exertion of appropriate lubricity, the molar ratio of the monomer having a reactive functional group to 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 the hydrophilic polymer can be produced by applying a conventionally known polymerization method such as a living radical polymerization method, a polymerization method using a macro initiator, or a polycondensation method. Of these, the living room is easy to control the molecular weight and molecular weight distribution of the structural unit (site) derived from the hydrophilic monomer and the structural unit (site) 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, but is described in, for example, JP-A-11-263819, JP-A-2002-145971, JP-A-2006-316169, and the like, and atom transfer radical polymerization (ATRP). ) Method can be applied in the same manner or modified as appropriate. Further, in the polymerization method using a macroinitiator, for example, a macroinitiator having a hydrophobic moiety having a reactive functional group and a radical polymerizable group such as a peroxide group is prepared, and then the macroinitiator is used. By polymerizing a monomer for forming a hydrophilic moiety, a block copolymer having a hydrophilic moiety and a hydrophobic moiety can be produced.

Alternatively, as a method for producing the hydrophilic polymer, a known method such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization or the like may be used. Specifically, in the production of a 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 with a polymerization initiator in a polymerization solvent. Here, the polymerization initiator is not particularly limited, and known ones may be used. It is preferably a radical polymerization initiator in that it is excellent in polymerization stability, and specifically, a persulfate such as potassium persulfate (KPS), sodium persulfate, ammonium persulfate; hydrogen peroxide, t-butylper. Peroxides such as oxides and methylethylketone peroxides; azo compounds such as azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile) and azobiscyanovaleric acid can be mentioned. Further, for example, the radical polymerization initiator may be used as a redox-based initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, or ascorbic acid. The blending amount of the polymerization initiator is preferably 0.0001 to 1 mol% with respect to the total amount of the monomers. The polymerization solvent is not particularly limited, and for example, an aliphatic organic solvent such as n-hexane, n-heptane, n-octane, n-decane, cyclohexane, methylcyclohexane, and liquid paraffin, tetrahydrofuran, dioxane, and the like. Ether-based solvents, aromatic organic solvents such as toluene and xylene, halogen-based organic solvents such as 1,2-dichloroethane and chlorobenzene, and polar aproton organic solvents such as N, N-dimethylformamide and dimethylsulfoxide can be used. .. The solvent may be used alone or in combination of two or more. The concentration of the monomer in the polymerization solvent (total concentration of the hydrophilic monomer and the monomer having a reactive functional group) is preferably 5 to 90% by mass, more preferably 8 to 80% by mass. It is preferably 10 to 50% by mass, particularly preferably. In the above-mentioned polymerization, the polymerization conditions are also not particularly limited as long as the above-mentioned 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, at the time of copolymerization, if necessary, a chain transfer agent, a polymerization rate adjuster, a surfactant, a water-soluble polymer, and a water-soluble inorganic compound (alkali metal salt, alkali metal hydroxide, polyvalent metal salt). , And non-reducing alkali metal salt pH buffers, etc.), inorganic acids, inorganic acid salts, organic acids and 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 the hydrophilic polymer alone, or may contain other additives in addition to the hydrophilic polymer. In the latter case, examples of the additive include a cross-linking agent and a drug (physiologically active substance). Since the form in which the surface lubricating layer contains a cross-linking agent has been described above, the description thereof will be omitted here. When the surface lubricating layer contains a drug, the drug is not particularly limited, but for example, when the medical device is intended to be inserted into a body cavity or a lumen such as a catheter, an anticancer agent, an immunosuppressant, an antibiotic, etc. , Anti-rheumatic drugs, antithrombotic drugs, HMG-CoA reductase inhibitors, ACE inhibitors, calcium channel blockers, antihyperlipidemic drugs, integrin inhibitors, antiallergic agents, antioxidants, GPIIbIIIa antagonists, retinoids, Drugs such as flavonoids, carotinoids, lipid improvers, DNA synthesis inhibitors, tyrosine kinase inhibitors, antithrombotic drugs, vascular smooth muscle growth inhibitors, anti-inflammatory drugs, biogenic materials, interferons, and NO production promoters (physiological activity) Substance) and the like. Here, the amount of the drug added is not particularly limited, and the amount usually used is applied in the same manner. Ultimately, the amount of the drug added is appropriately selected in consideration of the severity of the applied disease, the weight of the patient, and the like.

As described above, the medical device of the present invention has a base material, 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 forming the undercoat layer and the hydrophilic polymer forming the surface lubricating layer is not particularly limited and can be appropriately selected from the above preferred examples. Considering the effect of further improving the adhesion (integration) of the undercoat layer and the surface lubrication 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-crosslinking polymer. Select from N, N-dimethylacrylamide and N, N'-dimethylaminoethyl acrylate with monomers having reactive functional groups selected from mixtures with (eg, self-crosslinking urethane resins) and glycidyl acrylates and glycidyl methacrylates. It is preferably in combination with a surface lubricating layer which is at least one of the block copolymers with the hydrophilic monomer to be formed;
Select from the group consisting of at least one of (meth) acrylic resin and styrene butadiene rubber as the base polymer, terpenphenol resin as the tackifier, rosin resin having dehydroavietic acid, and styrene-based monomer / aliphatic monomer copolymer resin. The undercoat layer, which is at least one kind of layer, and the hydrophilic polymer are a mixture of polyvinylpyrrolidone (PVP) and a self-crosslinking polymer (for example, a self-crosslinking urethane resin), and a reactivity selected from glycidyl acrylate and glycidyl methacrylate. More preferably, it is a combination of a monomer having a functional group and a surface lubricating layer which is at least one of block copolymers of N, N-dimethylacrylamide (hydrophilic monomer);
An undercoat in which the base polymer is a (meth) acrylic resin and the tackifier is a rosin resin having dehydroabietic acid, or a mixture of a rosin resin having dehydroabietic acid and a styrene-based 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 exerts a more remarkable effect in terms of adhesion between the undercoat layer and the surface lubrication layer. Here, the reason for achieving the above effect is presumed as follows. The following is speculation and does not limit the technical scope of the present invention. Specifically, the hydrophobic base polymer such as (meth) acrylic resin or styrene-butadiene rubber constituting the undercoat layer is used as the hydrophobic part of the block copolymer constituting the surface lubricating layer or the hydrophobic self-crosslinking polymer ( For example, it adheres firmly to (self-crosslinking urethane resin). Therefore, with the combination as described above, the adhesion (integration) between the undercoat layer and the surface lubrication layer can be further improved, so that the durability of the surface lubrication layer (particularly the durability under a high load state) can be further improved. It can be improved and the medical device can maintain good lubricity for a long period of time.

[Manufacturing method of medical equipment]
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, an undercoat layer containing a base polymer and a tackifier at a specific mixing ratio is first formed on the substrate (step (1)), and then a surface lubricating layer containing a hydrophilic polymer is formed on the undercoat layer. (Step (2)) is preferably formed.

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

(Step (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 base material to form an undercoat layer on the base material. Since the base material, the base polymer, and the tackifier are as described above, description thereof will be omitted here.

In the above method, the solvent used to dissolve the base polymer and the tackifier is not particularly limited as long as it can dissolve the base polymer and the tackifier. Specifically, alcohols such as water, 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 and tetrahydrofuran. Examples thereof include ethers such as (THF) and butyl ether, aromatics such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), and sulfoxides such as dimethyl sulfoxide. 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; the base polymer is dissolved in the solvent, and then the tackifier is added; after the tackifier is dissolved in the solvent. , The base polymer is added; the base polymer and the tackifier may be separately dissolved in the same or different solvents and then mixed, and the like.

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 (resin content) of the base polymer in the mixed solution is preferably 0.1 to 80% by mass from the viewpoint of ease of coating and the like. %, More preferably 1 to 30% by mass.

As described above, the mixed solution may further contain a cross-linking agent or the like. When the mixed solution further contains a cross-linking agent, the amount of the cross-linking agent added is not particularly limited, but is preferably the above-mentioned amount. The timing of adding the cross-linking agent is not particularly limited, and may be at the same time as or after the addition of the base polymer and the tackifier, or during the addition of the base polymer and the tackifier. , Preferably after the addition of the base polymer and tackifier.

The mixed solution prepared in this manner is coated on the base material. Before coating the base material, the base material may be wiped with an alcohol solvent such as acetone, ethanol or isopropyl alcohol in advance. The method of coating (coating) the mixed solution on the surface of the base material is not particularly limited, and is a coating / printing method, a dipping method (dip method, dip coating method), a spray method (spray method), and a spin coating method. , Conventionally known methods such as a mixed solution impregnated sponge coating method can be applied. Of these, it is preferable to use the dipping method (dip method, dip coating method). When the mixed solution is coated on the substrate by the dipping method, the dipping conditions are not particularly limited. For example, the immersion temperature can be 0-40 ° C. The immersion time can be 0.1 seconds to 5 minutes.

When the undercoat layer is formed on a thin and narrow inner surface of a catheter, a guide wire, an injection needle, or the like, the base material may be immersed in the mixed solution to reduce the pressure inside the system to defoam. By defoaming under reduced pressure, the solution can be quickly permeated into the narrow and narrow inner surface, and the formation of the undercoat layer can be promoted.

When the undercoat layer is formed only on a part of the base material, the base material is coated by immersing only a part of the base material in the mixed solution and coating the mixed solution on a part of the base material. An undercoat layer can be formed on the desired surface portion of the above.

If it is difficult to immerse only a part of the base material in the mixed solution, use an appropriate member or material that allows the surface part of the base material to be attached / detached (attached / detached) without the need to form an undercoat layer in advance. After protecting (coating, etc.), the base material is immersed in the mixed liquid, the mixed liquid is coated on the base material, and then a protective member (material) for the surface portion of the base material that does not need to form an undercoat layer. The undercoat layer can be formed on a desired surface portion of the base material by removing the material and then reacting it by heat treatment or the like. However, the present invention is not limited to these forming methods, and the undercoat layer can be formed by appropriately using a conventionally known method. For example, if it is difficult to immerse only part of the substrate in the mixed solution, instead of the dipping method, another coating method (eg, spraying the mixed solution onto a given surface portion of the medical device). A method of applying using an apparatus, a bar coater, a die coater, a reverse coater, a comma coater, a gravure coater, a spray coater, a doctor knife, or the like) may be applied. If it is necessary for both the outer surface and the inner surface of the cylindrical device to have an undercoat layer due to the structure of the medical device, both the outer surface and the inner surface can be coated at once. The dipping method is preferably used because it can be used.

After immersing the base material in the mixed solution in this way, the base material is taken out from the mixed solution and dried. 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 carried out under normal pressure (atmospheric pressure), or under pressurization or reduced pressure. As the heating means (device) for heating, for example, an oven, a dryer, a microwave heating device, or the like can be used, but in the case of natural drying (air drying), no particular drying means (device) is required. is there. Under such conditions, the undercoat layer is firmly bonded (fixed) to the surface of the base material, and peeling from the base material can be effectively suppressed / prevented.

(Step (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 hydrophilic polymer is dissolved in a solvent to prepare a coating liquid, and the coating liquid is coated on the base material A (at least on the undercoat layer side) to form a surface lubricating layer on the undercoat layer. Since the hydrophilic polymer is as described above, the description thereof is 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, alcohols such as water, 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 and tetrahydrofuran. Examples thereof include ethers such as (THF) and butyl ether, aromatics such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), and sulfoxides such as dimethyl sulfoxide. 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 the concentration of the hydrophilic polymer in the coating liquid is preferably 0.01 to 30% by mass, more preferably 1 to 10 from the viewpoint of ease of coating and the like. It is mass%.

As described above, the coating liquid may further contain a cross-linking agent, a chemical, or the like. The specifications of the cross-linking agent and the drug when the coating liquid further contains the cross-linking agent and the drug are the same as described above, and thus the description thereof will be omitted here.

The coating liquid prepared in this manner is coated on the base material A. The method of coating (coating) the coating liquid on the surface of the base material A is not particularly limited, and is a coating / printing method, a dipping method (dip method, dip coating method), a spray method (spray method), and a spin coating method. Conventionally known methods such as a method and a sponge coating method impregnated with a mixed solution can be applied. Of these, it is preferable to use the dipping method (dip method, dip coating method). The dipping conditions when the coating liquid is coated on the base material A by the dipping method are not particularly limited. For example, the immersion temperature can be 0-40 ° C. The immersion time can be 0.1 seconds to 5 minutes.

When forming a surface lubrication layer on the inner surface of a thin and narrow base material A such as a catheter, a guide wire, or an injection needle, the base material A is immersed in the coating liquid as in the case of the undercoat layer. The inside may be depressurized to defoam. By defoaming under reduced pressure, the solution can be quickly permeated into the narrow and narrow inner surface, and the formation of the surface lubricating layer can be promoted. Further, the method for forming the surface lubricating layer when the surface lubricating layer is formed only on a part of the base material A is also not particularly limited, but for example, the same method as in the case of the undercoat layer can be adopted.

After immersing the base material A in the coating liquid in this way, the base material A is taken out from the coating liquid and dried. 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 base material 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 carried out under normal pressure (atmospheric pressure), or under pressurization or reduced pressure. As a heating means (device) for heating, for example, an oven, a dryer, a microwave heating device, or the like can be used, but in the case of natural drying (air drying), a drying means (device) 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 base material A (undercoat layer) can be effectively suppressed / prevented.

In this way, the medical device of the present invention can be 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 arranged between a base material and a surface lubricating layer. A medical device having such a structure can be applied to a highly flexible and / or narrow lesion site because the base material and the surface lubrication layer can be firmly adhered (integrated) through the undercoat layer. However, it can exhibit and maintain good lubricity. Therefore, by using the medical device of the present invention, it is possible to appropriately support more complicated and sophisticated medical procedures.

Further, since the undercoat layer itself has adhesiveness, the medical device of the present invention can be applied to a wide range of materials without limiting the materials constituting the base material and the surface lubricating layer. Therefore, the surface lubrication layer can be firmly immobilized 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 in the past (the surface of a medical device). The lubricating layer has excellent durability).

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

(A) Catheter that is orally or nasally inserted or placed in the digestive organs such as a gastric tube catheter, a feeding catheter, and a tube for tube feeding.

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

(C) Catheter types such as urethral catheters, urinary catheters, urethral balloon catheters and balloons that are inserted or placed in the urethra or urethra.

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

(E) For indwelling needles, IVH catheters, thermodilution catheters, angiographic catheters, vasodilator catheters and catheters inserted or indwelled into blood vessels such as dilators or introducers, or for these catheters. Guide wires, stylets, etc.

(F) Artificial trachea, artificial bronchus, etc.

(G) Medical devices (artificial lungs, artificial hearts, artificial kidneys, etc.) for extracorporeal circulation treatment and their circuits.

The effects of the present invention will be described with reference to the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the following examples, the operation was performed at room temperature (25 ° C.) unless otherwise specified. Unless otherwise specified, "%" and "parts" mean "mass%" and "parts by mass", respectively.

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

After dropping 29.7 g of triethylene glycol at 50 ° C. in 72.3 g of adipic acid dichloride, 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, which were added to 5 g of sodium hydroxide, 6.93 g of 31 mass% hydrogen peroxide, 0.44 g of dioctyl phosphate as a surfactant, and 120 g of water. It was added dropwise to the solution and reacted at −5 ° C. for 20 minutes. The obtained product was washed with water and methanol repeatedly, 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 at 65 ° C. for 2 hours with stirring under reduced pressure. The reaction product obtained after the polymerization was reprecipitated with diethyl ether to obtain a poly GMA (PPO-GMA) having a peroxide group in the molecule.

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

Reference Example 1: Evaluation of Adhesion 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 prepare a base material.

Separately, an acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) 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 Tuck 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. .. A cross-linking agent (FINETACK HARDENER D40 manufactured by DIC Corporation) was added to this acetone solution so as to be 15% by mass with respect to the acrylic resin to prepare an undercoat solution (2). When the content of the aromatic tackifier was measured for Undercoat Fine Tuck CT-5020 according to the following method, the tackifier was contained in a proportion of about 42% by mass with respect to the acrylic resin. I confirmed that it was there. 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-based monomer and an aliphatic monomer.

(Quantitative test of tackifier)
A base material (base material A) was prepared by wiping a modified polyethylene (Modic (registered trademark) M512 manufactured by Mitsubishi Chemical Corporation) sheet (18 mm × 40 mm × 1 mm) with acetone. Next, undercoat Finetack CT-5020 (manufactured by DIC Corporation) containing an aromatic tackifier and an acrylic resin is added with acetone so as to have a resin content of 20% by mass to prepare an acetone solution. did. The base material A was immersed in this acetone solution, pulled up at a speed of 15 mm / sec, coated, and air-dried for 30 minutes (base material B). After air-drying, the base material B was heated in an oven at 80 ° C. for 5 hours to form (immobilize) an undercoat layer on the surface of the base material A (modified polyethylene sheet) (base material C). Further, the undercoat layer of the base material 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 liquid separation operation was repeated 5 times to complete the liquid separation operation. As a result, the DMF solution contains an acrylic resin, and the hexane solution contains a tackifier.

After the liquid separation operation was completed, the DMF solution containing the acrylic resin and the hexane solution containing the tackifier were dried to dryness, and the mass of the dry residue was measured. 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. Therefore, Undercoat Fine Tuck CT-5020 (manufactured by DIC Corporation) contains a tackifier at a ratio of about 42 parts by mass with respect 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) so as to have a concentration of 3.5% by mass, and a coating solution was added. Was prepared.

Immediately after the base material was immersed in the undercoat liquids (1) and (2) prepared above, the base material was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material (base material (base material)). 1-1), base material (2-1)). After air-drying, the base material (1-1) and the base material (2-1) are each heated in an oven at 60 ° C. for 1 hour to form an undercoat layer on the surface of the base material (modified polyethylene sheet). (Fixed) (base material (1-2), base material (2-2)). Then, shortly after the base material (1-2) and the base material (2-2) were immersed in the coating liquid prepared above, they were pulled up at a speed of 15 mm / sec to coat the coating. This was performed and air-dried for 30 minutes (base material (1-3), base material (2-3)). After air-drying, the base material (1-3) and the base material (2-3) were each reacted in an oven at 80 ° C. for 5 hours to form a surface lubrication layer on the undercoat layer (medical equipment). (1), medical equipment (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 a cross-cut test (JIS K5600-5-6: 1999 (ISO2409: 1992)). The adhesion with the surface lubricating layer including it was evaluated.

The results are shown in Table 1 below. In Table 1 below, the cross-cut test scores are classified into 6 levels, and the smaller the value, the less the peeling (higher 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 a tackifier (2). It is shown that the adhesion between the undercoat layer and the surface lubricating layer is higher than that of 1).

Reference Example 1-1: Manufacture of medical device 1 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 form a base material. (Base material 1).

Undercoat BPS6074HTF containing non-aromatic tackifier and acrylic resin (manufactured by Toyochem Co., Ltd., content of non-aromatic tackifier: 5 to 15% by mass (catalog value) with respect to acrylic resin). The undercoat liquid 1 was prepared by adding to tetrahydrofuran (THF) so that 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) so as to have a concentration of 3.5% by mass, and a coating solution was added. A was prepared.

Immediately after immersing the base material 1 in the undercoat liquid 1 prepared above, the base material 1 was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 1-1). After air-drying, the base material 1-1 was heated in an oven at 60 ° C. for 1 hour to form (immobilize) an undercoat layer on the surface of the base material 1 (modified polyethylene sheet) (base material 1-2). .. Then, shortly after the base material 1-2 was immersed in the coating liquid A prepared above, 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 lubrication layer on the undercoat layer (medical device 1).

Example 1-2: Production of medical device 2 Content of undercoat BPS6574HTF (manufactured by Toyochem Co., Ltd., aromatic tackifier) containing rosin resin (aromatic tackifier) having dehydroabietic acid and acrylic resin. : 10 to 20% by mass (catalog value) with respect to the acrylic resin) was added to tetrahydrofuran (THF) so as to have a resin content of 10% by mass to prepare an undercoat liquid 2. In Reference Example 1-1, the undercoat layer and the surface lubrication layer are sequentially based in the same manner as in Reference Example 1-1, except that the undercoat liquid 2 prepared above is used instead of the undercoat liquid 1. Formed on material 1 (medical device 2).

Example 1-3: Production of 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 to prepare a base material. (Base material 1).

Acrylic resin (Fine Tuck CT-6020, manufactured by DIC Corporation) is added to acetone so that the resin content is 15% by mass, and then terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd.), which is an aromatic tackifier. YS Polystar K125) was added so as to be 1 part by mass with respect to 100 parts by mass of the acrylic resin to prepare the undercoat liquid 3.

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

Immediately after immersing the base material 1 in the undercoat liquid 3 prepared above, the base material 1 was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 3-1). After air-drying, the base material 3-1 was heated in an oven at 60 ° C. for 1 hour to form (immobilize) an undercoat layer on the surface of the base material 1 (modified polyethylene sheet) (base material 3-2). .. Then, shortly after the base material 3-2 was immersed in the coating liquid A prepared above, it was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 3-3). After air-drying, the base material 3-3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubrication layer on the undercoat layer (medical device 3).

Example 1-4: Production of medical device 4 Acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) is added to acetone so as to have a resin content of 15% by mass, and then an aromatic tackifier. The terpene phenol resin (YS Polystar U115 manufactured by Yasuhara Chemical Co., Ltd.) was added so as to be 3 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare the undercoat liquid 4. In Example 1-3, the undercoat layer and the surface lubrication layer are sequentially based in the same manner as in Example 1-3, except that the undercoat liquid 4 prepared above is used instead of the undercoat liquid 3. Formed on the material 1 (medical device 4).

Example 1-5: Production of Medical Device 5 Acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) is added to acetone so as to have a resin content of 15% by mass, and then an aromatic tackifier. The terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd.) was added so as to be 10 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare the undercoat liquid 5. In Example 1-3, the undercoat layer and the surface lubrication layer are sequentially based in the same manner as in Example 1-3, except that the undercoat liquid 5 prepared above was used instead of the undercoat liquid 3. Formed on material 1 (medical device 5).

Example 1-6: Production of medical device 6 Acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) is added to acetone so as to have a resin content of 15% by mass, and then an aromatic tackifier. The terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd.) 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 lubrication layer are sequentially based in the same manner as in Example 1-3, except that the undercoat liquid 6 prepared above was used instead of the undercoat liquid 3. Formed on the material 1 (medical device 6).

Example 1-7: Production of Medical Device 7 Acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) is added to acetone so as to have a resin content of 15% by mass, and then an aromatic tackifier. The terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd.) was added so as to be 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 lubrication layer are sequentially based in the same manner as in Example 1-3, except that the undercoat liquid 7 prepared above is used instead of the undercoat liquid 3. Formed on the material 1 (medical device 7).

Example 1-8: Production of medical device 8 Acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) is added to acetone so as to have a resin content of 15% by mass, and then an aromatic tackifier is applied. The terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd.) was added so as to be 60 parts by mass with respect to 100 parts by mass of the acrylic resin to prepare an undercoat liquid 8. In Example 1-3, the undercoat layer and the surface lubrication layer are sequentially based in the same manner as in Example 1-3 except that the undercoat liquid 8 prepared above is used instead of the undercoat liquid 3. Formed on the material 1 (medical device 8).

Example 1-9: Production of Medical Device 9 Acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) is added to acetone so as to have a resin content of 15% by mass, and then an aromatic tackifier is applied. The terpene phenol resin (YS Polystar T100 manufactured by Yasuhara Chemical Co., Ltd.) was added so as to be 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 lubrication layer are sequentially based in the same manner as in Example 1-3 except that the undercoat liquid 9 prepared above was used instead of the undercoat liquid 3. Formed on the material 1 (medical device 9).

Example 1-10: Manufacture of medical device 10 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 prepare a base material. (Base material 1).

Undercoat Fine Tack CT-5020 containing an aromatic tackifier and an acrylic resin (manufactured by DIC Corporation, content of the aromatic tackifier: about 42% by mass based on the acrylic resin; the same applies hereinafter). , The undercoat liquid 10 was prepared by adding to acetone so that the resin content was 9% by mass. As described above, the undercoat Finetack CT-5020 contains an aromatic tackifier at a ratio of about 42% by mass with respect to the acrylic resin (see Reference Example 1 above). The aromatic tackifier contained in the Undercoat Fine Tuck CT-5020 is a mixture of a rosin resin having dehydroabietic acid and a copolymer resin of a styrene-based 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) so as to have a concentration of 3.5% by mass, and a coating solution was added. A was prepared.

Immediately after immersing the base material 1 in the undercoat liquid 10 prepared above, the base material 1 was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 10-1). After air-drying, the base material 10-1 was heated in an oven at 60 ° C. for 1 hour to form (immobilize) an undercoat layer on the surface of the base material 1 (modified polyethylene sheet) (base material 10-2). .. Then, shortly after the base material 10-2 was immersed in the coating liquid A prepared above, it was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 10-3). After air-drying, the substrate 10-3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubrication layer on the undercoat layer (medical device 10).

Example 1-11: Manufacture of Medical Device 11 Undercoat Fine Tuck CT-5020 (manufactured by DIC Corporation) containing an aromatic tackifier and an acrylic resin is mixed with acetone so as to have a resin content of 9% by mass. Was added to prepare an acetone solution. A polyisocyanate compound (FINETACK HARDENER D40, manufactured by DIC Corporation) was added to this acetone solution as a cross-linking agent so as to be 15% by mass with respect to the acrylic resin to prepare an undercoat solution 11. In Example 1-10, the undercoat layer and the surface lubrication layer were sequentially based in the same manner as in Example 1-10, except that the undercoat liquid 11 prepared above was used instead of the undercoat liquid 10. Formed on the material 1 (medical device 11).

Example 1-12: Manufacture of medical device 12 Polyamide elastomer (Grillflex (registered trademark) ELG5660 manufactured by MSM 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, the undercoat layer and the surface lubrication layer were sequentially formed on the base material 2 in the same manner as in Example 1-11 except that the base material 2 was used instead of the base material 1. (Medical device 12).

Example 1-13: Production of Medical Device 13 A SUS304 sheet (18 mm × 40 mm × 1 mm) was wiped with acetone to prepare a base material (base material 3).

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

Example 1-14: Production of medical device 14 Polyvinylpyrrolidone (PVP) (manufactured by Tokyo Chemical Industry Co., Ltd., manufactured by K-90) and self-crosslinkable water-based urethane resin (manufactured by Mitsui Chemicals Co., Ltd., Takelac (registered trademark) WS- 5000) was 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 lubrication layer were sequentially applied to the base material 1 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 on top (medical device 14).

Example 1-15: Manufacture of medical device 15 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 prepare a base material. (Base material 1).

Styrene-butadiene rubber (manufactured by Sigma Aldrich Japan LLC, product number: 182907) is added to tetrahydrofuran (THF) so as to have a resin content of 4% by mass, and then a terpene phenol resin (terpene phenol resin) which is an aromatic tackifier. YS Polystar T100) manufactured by Yasuhara Chemical Co., Ltd. was added so as to be 20 parts by mass with respect to 100 parts by mass of styrene-butadiene rubber to prepare an undercoat liquid 15.

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

Immediately after immersing the base material 1 in the undercoat liquid 15 prepared above, the base material 1 was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (base material 15-1). After air-drying, the base material 15-1 was heated in an oven at 60 ° C. for 1 hour to form (immobilize) an undercoat layer on the surface of the base material 1 (modified polyethylene sheet) (base material 15-2). .. Then, shortly after the base material 15-2 was immersed in the coating liquid A prepared above, 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, the substrate 15-3 was reacted in an oven at 80 ° C. for 5 hours to form a surface lubrication layer on the undercoat layer (medical device 15).

Comparative Example 1-1: Production of Comparative Medical Device 1 Acrylic resin (Fine Tuck CT-6020 manufactured by DIC Corporation) was added to acetone so as to have a resin content of 15% by mass, and the comparative undercoat liquid 1 was added. Was prepared. In Example 1-3, the undercoat layer and the surface lubrication 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 was formed on the base material 1 (comparative medical device 1).

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

Comparative Example 1-3: Manufacture 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 to form a base material. (Base material 1).

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

Immediately after immersing the base material 1 in the coating liquid A prepared above, the base material 1 was pulled up at a speed of 15 mm / sec for coating and air-dried for 30 minutes (comparative base material 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 A polyamide elastomer (EMS grill flex (registered trademark) ELG5660) sheet (18 mm × 40 mm × 1 mm) was wiped with acetone to prepare 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 prepare 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: Manufacture of Comparative Medical Device 6 Polyvinylpyrrolidone (PVP) (manufactured by Tokyo Chemical Industry Co., Ltd., K-90) and self-crosslinkable water-based urethane resin (manufactured by Mitsui Chemicals, Inc., Takelac (registered trademark) WS- 5000) was 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, the surface lubricating layer was formed on the base material 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: Manufacture of Comparative Medical Device 7 Styrene-butadiene rubber (manufactured by Sigma-Aldrich Japan GK, 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 Examples 1-14, the undercoat layer and the surface lubrication layer were sequentially used as a base material in the same manner as in Example 14 except that the comparative undercoat liquid 7 prepared above was used instead of the undercoat liquid 14. Formed on 1 (comparative medical device 7). That is, in this comparative example, it is the same as in Example 1-14 except that the aromatic tackifier (YS Polystar T100) was not added in Example 1-14.

Example 2-1: Manufacture of medical device 16 A modified polyethylene (Tosoh, Nichiporon ZF260) tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to prepare a base material. (Base material 4).

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

Example 2-2: Manufacture of medical device 17 A modified polyethylene (Nichiporon ZF260 manufactured by Tosoh) tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to form a base material ( Base material 4).

In Example 1-10, the undercoat layer and the surface lubrication 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 A modified polyethylene (Nichiporon ZF260 manufactured by Tosoh) tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to prepare a base material (modified polyethylene tube). Base material 4).

In Example 1-14, the undercoat layer and the surface lubrication 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: Manufacture of Comparative Medical Device 8 A modified polyethylene (Nichiporon ZF260 manufactured by Tosoh) tube (diameter (φ) 1.0 mm, length 5 cm) (modified polyethylene tube) was wiped with acetone to prepare a base material. (Base material 4).

In Comparative Example 1-3, the undercoat layer and the surface lubrication 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. (Comparative medical device 8) .
It was produced by the medical devices 1 to 18 produced in Reference Example 1-1 and Examples 1-2 to 1-15 and 2-1 to 2-3, and in Comparative Examples 1-1 to 1-7 and 2-1. The durability (durability of the surface lubricating layer) of the comparative medical devices 1 to 8 was evaluated according to the following method.

[Durability evaluation]
For each medical device (hereinafter, also simply abbreviated as "sample"), the sliding resistance value (gf) of the surface lubrication layer is measured by using the friction measuring machine 20 shown in FIG. 1 according to the following method, and the durability is achieved. Gender was evaluated.

That is, each sample 16 was fixed in a petri dish 12 and immersed in water 17 at a height at which the entire sample 16 was immersed. The petri dish 12 was placed on the moving table 15 of the friction measuring machine (Handy Tribomaster TL201 manufactured by Trinity Lab) 20 shown in FIG. A columnar 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 had a sheet shape and 50 g when the sample 16 had a tube shape. .. The sliding resistance value (gf) when the moving table 15 was horizontally reciprocated 50 times at a speed of 16.7 mm / sec and a moving distance of 2 cm was measured. The lubrication durability against repeated sliding 50 times was evaluated by averaging the sliding resistance values from the first round trip to the 50th round trip for each number of round trips and plotting them as a sliding resistance value (gf) on a graph. In each test, one sample was tested. Further, the lower the sliding resistance value (gf), the better the surface lubricity.

The results of the medical devices 1 to 18 and the comparative medical devices 1 to 8 are shown in FIGS. 2 to 22, respectively. In addition, 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. Further, in Table 2 below, “p (DMAA-b-GMA)” indicates a block copolymer 1 (DMAA: GMA = 11: 1 (molar ratio)) produced in the same manner as in Synthesis Example 1 above.

(Criteria when sample 16 has a sheet shape)
X: The number of sliding times is 5 to 29 times, and the sliding resistance value is 30 gf or more;
Δ: The number of sliding times is 30 to 49 times, and the sliding resistance value is 30 gf or more;
◯: The number of sliding times is 50, and the sliding resistance value does not reach 30 gf.

(Criteria when sample 16 has a tube shape)
× The number of sliding times is 1 to 5 times and the sliding resistance value reaches 10 gf or more △ The number of times of sliding is 6 to 49 times and the sliding resistance value reaches 10 gf or more ○ The number of times of sliding is 50 times Sliding resistance value does not reach 10 gf

From Table 2 and FIGS. 2 to 7 above, 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 excess of a tackifier. It can be seen that the lubricity and durability (lubrication maintainability) 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 ( Reference Example 1-1 ) having an undercoat layer containing a non-aromatic adhesive and an acrylic resin, the sliding resistance value gradually increases after 50 reciprocating movements, and the sliding resistance value gradually increases. The sliding resistance value exceeds 30 gf when the number of movements is around 35. On the other hand, in FIG. 3, the medical device 2 having an undercoating layer containing an aromatic tackifier and acrylic resins (Example 1 2), is maintained even good lubricity after reciprocating 50 times .. 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.

From FIGS. 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 round trips (medical treatment). The surface lubrication layer of the instrument has excellent durability). On the other hand, as shown in FIGS. 17 and 18, when the content of the tackifier is 0 parts 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, the content of the tackifier needs to be less than 90 parts by mass with respect to 100 parts by mass of the acrylic resin, and particularly when it is 1 to 70 parts by mass, the surface lubricating layer of the medical device has sufficiently good lubricity. And it is considered that durability can be exhibited.

From FIGS. 12 to 14, it can be seen that all the medical devices whose base materials are the modified polyethylene sheet, the polyamide elastomer sheet and the SUS304 sheet maintain good lubricity even after 50 round trips. Further, by comparing FIGS. 12 to 14 and 19 to 21, it can be seen that the durability of the surface lubrication layer can be significantly improved by providing the undercoat layer. From the above results, it is considered that the surface lubrication layer of the medical device of the present invention can exhibit excellent lubricity and durability by providing the undercoat layer regardless of the type of the base material.

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

From FIG. 15, it can be seen that even when polyvinylpyrrolidone is used as the hydrophilic polymer, good lubricity can be maintained even after 50 round trips. On the other hand, as shown in FIG. 22, it is shown that the sliding resistance value increases from the first time when the undercoat layer is not provided. 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 hydrophilic polymer. In comparison with FIGS. 12 and 15, there is not much difference in durability between the hydrophilic polymers. On the other hand, from the comparison with FIGS. 24 and 26, when a higher load is applied (under a condition where the load on the contacted area is higher), both the blocks of DMAA and GMA as hydrophilic polymers are used. It is considered that the use of the polymer can exhibit superior durability as compared with the case of using polyvinylpyrrolidone.

From FIG. 16, it can be seen that even when styrene-butadiene rubber is used as the base polymer, good lubricity can be maintained even after 50 round trips. On the other hand, as shown in FIG. 23, when the tackifier is not added to the undercoat layer, it is shown that the sliding resistance value exceeds 30 gf in the initial stage (the number of sliding times is about 15 times). From the above results, it is considered that the surface lubrication layer of the medical device of the present invention can exhibit excellent lubricity and durability by providing the undercoat layer regardless of the type of the base polymer.

12 petri dish,
13 Cylindrical polyethylene terminals,
14 load,
15 moving table,
16 Medical equipment (sample),
17 water,
20 Friction measuring machine.

Claims (4)

A medical device comprising a base material, an undercoat layer arranged on the surface of the base material, and a surface lubricating layer containing a hydrophilic polymer arranged on the surface of the undercoat layer.
The undercoat layer is formed from a composition comprising a base polymer and a tackifier.
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.
The tackifier is a medical device , which is a terpene phenol resin, a rosin resin having dehydroabietic acid, or a mixture of a rosin resin having dehydroabietic acid and a styrene-based monomer / aliphatic monomer copolymer resin . The medical device according to claim 1, wherein the base polymer is at least one selected from the group consisting of (meth) acrylic resin and styrene-butadiene rubber. The medical device according to claim 1 or 2 , wherein the tackifier is contained in a ratio of 1 to 70 parts by mass with respect to 100 parts by mass of the base polymer. The medical device according to any one of claims 1 to 3, wherein the tackifier is contained in a ratio of 10 to 50 parts by mass with respect to 100 parts by mass of the base polymer .