US-12623006-B2 - Medical instrument

US12623006B2US 12623006 B2US12623006 B2US 12623006B2US-12623006-B2

Abstract

The present disclosure can improve durability (particularly, sliding durability) of a surface lubricating layer while maintaining flexibility of a medical instrument. The medical instrument can include: a base whose surface is partially made of a polyester resin; an intermediate layer formed on at least a part of the surface of the base and containing a (meth)acrylic-modified polyester resin and a polyurethane resin; and a surface lubricating layer formed on an upper part of the intermediate layer and containing a block copolymer having a structural unit (A) derived from a hydrophobic monomer and a structural unit (B) derived from a hydrophilic monomer, in which at least one of the hydrophobic monomer and the hydrophilic monomer has a (meth)acryloyl group.

Inventors

Takashi Okuhara

Assignees

TERUMO KABUSHIKI KAISHA

Dates

Publication Date: 20260512
Application Date: 20220315
Priority Date: 20190917

Claims (14)

1 . A medical instrument comprising: a base whose surface is partially made of a polyester resin; an intermediate layer formed on at least a part of the surface of the base and containing a (meth)acrylic-modified polyester resin and a polyurethane resin; a surface lubricating layer formed on an upper part of the intermediate layer and containing a block copolymer having a structural unit (A) derived from a hydrophobic monomer and a structural unit (B) derived from a hydrophilic monomer; wherein at least one of the hydrophobic monomer and the hydrophilic monomer has a (meth)acryloyl group, and wherein the (meth)acrylic-modified polyester resin contains terephthalic acid and isophthalic acid; and wherein a molar ratio of a structural unit derived from the terephthalic acid to a structural unit derived from the isophthalic acid is 1.5 or more and 4.5 or less.
2 . The medical instrument according to claim 1 , wherein a mass ratio of the (meth)acrylic-modified polyester resin to the polyurethane resin in the intermediate layer is (meth)acrylic-modified polyester resin/polyurethane resin is 70/30 to 30/70.
3 . The medical instrument according to claim 1 , wherein a (meth)acrylic modification ratio of the (meth)acrylic-modified polyester resin is between 10 mol % and 60 mol % based on a total number of moles of monomers constituting the (meth)acrylic-modified polyester resin.
4 . The medical instrument according to claim 1 , wherein a content of a structural unit derived from the terephthalic acid is 12.5 mol % to 40 mol % based on a total number of moles of monomers constituting a (meth)acrylic resin segment and monomers constituting a polyester resin segment.
5 . The medical instrument according to claim 1 , wherein the hydrophobic monomer contains at least one selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and β-methylglycidyl methacrylate.
6 . The medical instrument according to claim 1 , wherein the hydrophilic monomer contains at least one selected from the group consisting of N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylamide, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate.
7 . The medical instrument according to claim 1 , wherein the medical instrument is a catheter.
8 . A catheter comprising: a surface that is partially made of a polyester resin; an intermediate layer formed on at least a part of the surface and containing a (meth)acrylic-modified polyester resin and a polyurethane resin; a surface lubricating layer formed on an upper part of the intermediate layer and containing a block copolymer having a structural unit derived from a hydrophobic monomer and a structural unit derived from a hydrophilic monomer; at least one of the hydrophobic monomer and the hydrophilic monomer has a (meth)acryloyl group, and wherein the (meth)acrylic-modified polyester resin contains terephthalic acid and isophthalic acid, and a molar ratio of a structural unit derived from the terephthalic acid to a structural unit derived from the isophthalic acid is 1.5 or more and 4.5 or less; and wherein the hydrophobic monomer contains at least one selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and β-methylglycidyl methacrylate, and the hydrophilic monomer contains at least one selected from the group consisting of N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylamide, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate.
9 . The catheter according to claim 8 , wherein a mass ratio of the (meth)acrylic-modified polyester resin to the polyurethane resin in the intermediate layer is (meth)acrylic-modified polyester resin/polyurethane resin is 70/30 to 30/70.
10 . The catheter according to claim 8 , wherein a (meth)acrylic modification ratio of the (meth)acrylic-modified polyester resin is between 10 mol % and 60 mol % based on a total number of moles of monomers constituting the (meth)acrylic-modified polyester resin.
11 . The catheter according to claim 8 , wherein a content of a structural unit derived from the terephthalic acid is 12.5 mol % to 40 mol % based on a total number of moles of monomers constituting a (meth)acrylic resin segment and monomers constituting a polyester resin segment.
12 . A method of coating a medical instrument, the method comprising: applying an intermediate layer containing a (meth)acrylic-modified polyester resin and a polyurethane resin on at least a part of a surface of a base, the surface being partially made of a polyester resin, the (meth)acrylic-modified polyester resin containing terephthalic acid and isophthalic acid, and a molar ratio of a structural unit derived from the terephthalic acid to a structural unit derived from the isophthalic acid is 1.5 or more and 4.5 or less; and applying a surface lubricating layer on an upper part of the intermediate layer, the surface lubricating layer containing a block copolymer having a structural unit derived from a hydrophobic monomer and a structural unit derived from a hydrophilic monomer, and wherein at least one of the hydrophobic monomer and the hydrophilic monomer has a (meth)acryloyl group.
13 . The method according to claim 12 , wherein a mass ratio of the (meth)acrylic-modified polyester resin to the polyurethane resin in the intermediate layer is (meth)acrylic-modified polyester resin/polyurethane resin is 70/30 to 30/70.
14 . The method according to claim 12 , wherein a (meth)acrylic modification ratio of the (meth)acrylic-modified polyester resin is between 10 mol % and 60 mol % based on a total number of moles of monomers constituting the (meth)acrylic-modified polyester resin.

Description

CROSS-REFERENCES TO RELATED APPLICATIONS This application is a continuation of International Application No. PCT/JP2020/035074 filed on Sep. 16, 2020, which claims priority to Japanese Application No. 2019-168683 filed on Sep. 17, 2019, the entire content of which is incorporated herein by reference. TECHNOLOGICAL FIELD The present disclosure relates to a medical instrument. BACKGROUND DISCUSSION Medical instruments such as catheters and guide wires which are to be inserted into a living body are required to exhibit an excellent lubricating property in order to reduce damage to tissues such as blood vessels and to improve operability by an operator. Therefore, a method of coating a surface of a base layer of a medical instrument with a hydrophilic polymer having a lubricating property has been developed and put into practical use. Meanwhile, in order to maintain the operability by an operator, it is also important that the hydrophilic polymer having a lubricating property can be maintained on the surface of the base layer when the operator uses the medical instrument. Therefore, not only an excellent lubricating property but also durability against loads such as abrasion and scratch is required in coating with the hydrophilic polymer. From such viewpoints, Japanese Patent Application Publication 8-33704 A discloses a medical instrument in which a water-soluble or water-swellable polymer is dissolved in a solvent in which a base of the medical instrument swells to produce a polymer solution, the base of the medical instrument is immersed in the polymer solution to swell, the polymer is cross-linked or polymerized on a surface of a base layer, whereby a surface lubricating layer is formed on the surface of the base layer. According to the technique disclosed in Japanese Patent Application Publication No. 8-33704 A, the surface lubricating layer exhibiting a favorable lubricating property can be fixed to the base. Japanese Patent Application Publication No. 8-33704 A discloses that it is preferable to use, as the water-soluble or water-swellable polymer, a block copolymer having a hydrophilic site exhibiting a lubricating property and a site having an epoxy group. Further, in a case where such a block copolymer is used, the epoxy group of the block copolymer can be cross-linked by a heating operation, and the surface lubricating layer that is relatively difficult to peel off can be formed. However, a favorable lubricating property and excellent durability are in a trade-off relationship, and there is a need for a technique that enables compatibility of a favorable lubricating property and excellent durability. In particular, in recent years, medical procedures allowing medical instruments with higher bendability to approach narrow lesion areas in a living body have been spreading. Operations with medical instruments continue for a relatively long time in some cases along with complication of the medical procedures. Therefore, in order to maintain favorable operability with devices even in a case of complicated lesion areas, there is a need for a technique that can further improve a lubrication retaining property (durability) of a device surface as compared with techniques in the related art. More specifically, there is a need for devices having excellent sliding durability that can maintain flexibility, and can maintain a relatively high lubricating property even in a case where sliding on a device surface is repeated. Accordingly, there is a need for a technique that can improve durability (particularly, sliding durability) and can support medical procedures that are more complicated and sophisticated while maintaining flexibility of a medical instrument. SUMMARY The present disclosure provides means that can improve durability (particularly, sliding durability) of a surface lubricating layer while maintaining flexibility of a medical instrument. In accordance with an exemplary embodiment, the present disclosure provides means that can improve durability (particularly, sliding durability) of a surface lubricating layer while maintaining flexibility of a medical instrument by providing, between a base whose surface is partially made of a polyester resin and a surface lubricating layer, an intermediate layer containing a (meth)acrylic-modified polyester resin and a polyurethane resin. A medical instrument is disclosed, which includes: a base whose surface is partially made of a polyester resin; an intermediate layer formed on at least a part of the surface of the base and containing a (meth)acrylic-modified polyester resin and a polyurethane resin; and a surface lubricating layer formed on an upper part of the intermediate layer and containing a block copolymer having a structural unit (A) derived from a hydrophobic monomer and a structural unit (B) derived from a hydrophilic monomer, in which at least one of the hydrophobic monomer and the hydrophilic monomer has a (meth)acryloyl group. A catheter is disclosed