Flexible tube for endoscope, endoscope-type medical device, and method for manufacturing the same

Abstract

The present invention provides a flexible tube for endoscope, an endoscopic medical device using the same, and methods for manufacturing the flexible tube for endoscope and the endoscopic medical device, respectively. The flexible tube for endoscope comprises a flexible tube substrate made of metal and a coating layer covering the outer periphery of the flexible tube substrate, wherein a primer layer containing at least one of a specific silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound and a titanium alkoxide compound is provided between the flexible tube substrate and the coating layer, and the coating layer contains a polyester having a naphthalene structure at least on the side in contact with the primer layer.

Description

Technical Field

[0001] The present invention relates to an endoscope flexible tube, an endoscope type medical device and methods for manufacturing the same. Background Art

[0002] An endoscope is a medical device used to observe the body cavity, digestive tract, esophagus, etc. of a patient. Since it is inserted into the body for use, it is hoped that it will not damage the organs and will not cause pain or discomfort to the patient. Based on such requirements, the flexible tube constituting the insertion portion of the endoscope adopts a spiral tube formed by spirally winding a soft and curved metal strip. In addition, it is covered with a soft resin around it to prevent irritation or damage to the inner surface of the esophagus, digestive tract or body cavity.

[0003] Endoscopes used for observing the human body are used repeatedly. In order to smoothly and reliably deliver the endoscope insertion portion to the affected part, the endoscope insertion portion is bent repeatedly. Therefore, the endoscope insertion portion is required to have a property that the flexible tube substrate and the coating layer of the flexible tube substrate are not easily peeled off even if it is bent repeatedly (bending durability).

[0004] As a technology to solve this problem, Patent Document 1 describes a flexible tube for endoscope, which is formed by covering the outer periphery of a flexible tube material formed by embedding a mesh tube on the outer periphery of a spiral tube with an outer skin of a thermoplastic elastomer, wherein the flexible tube material and the outer skin are formed by bonding with a silane-based, titanate-based, aluminum-based, zirconium-based or other coupling agent having a function of bonding with both inorganic and organic substances. In addition, Patent Document 2 describes a flexible tube for endoscope, which has a flexible tube base material made of metal and a resin coating layer covering the outer periphery of the flexible tube base material, wherein a primer containing a specific silane compound is provided between the flexible tube base material and the resin coating layer, and the resin coating layer contains a polyurethane elastomer at least on the side in contact with the primer layer, so that the resin coating layer is difficult to be peeled off from the flexible tube base material.

[0005] In addition, the flexible tube constituting the insertion portion of the endoscope needs to be cleaned and sterilized with medicine each time it is used. In particular, when inserting into a site with a high possibility of infection such as a bronchus, cleanliness exceeding the sterilization level of disinfection is required. Therefore, the flexible tube for an endoscope is required to have a high degree of durability that can withstand repeated sterilization treatments.

[0006] Regarding the cleaning durability of the flexible tube, for example, Patent Document 3 describes a flexible tube for an endoscope, which is formed by covering the surface of the flexible tube material with a sheath, wherein polybutylene naphthalate is used in the hard segment of the polyester elastomer constituting the sheath, thereby suppressing the deterioration of the sheath caused by a cleaning solution or a disinfectant, and also improving the durability to sterilization treatment using an autoclave.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 11-42205

[0010] Patent Document 2: International Publication No. 2019 / 013243

[0011] Patent Document 3: Japanese Patent Application Publication No. 2004-141487 Summary of the invention

[0012] Technical issues to be solved by the invention

[0013] Improving the adhesion between the flexible tube base material and its coating layer is an important requirement for the durability of endoscope products, and further improvement of the adhesion is required.

[0014] In addition, regarding the sterilization durability of the flexible tube for endoscopes, in recent years, from the viewpoint of suppressing the wet-heat deterioration of the flexible tube for endoscopes, chemical sterilization treatments such as hydrogen peroxide plasma and ethylene oxide gas have been widely implemented instead of autoclave treatment. In addition, sterilization treatment using ozone water prepared by dissolving a small amount of ozone (O3) in water has recently begun. This ozone water produces potent active species such as hydroxyl radicals, and its oxidizing ability is stronger than that of hydrogen peroxide gas. Therefore, as an organic material that can withstand the sterilization treatment of ozone water, it is at the stage of known fluorine resins.

[0015] In view of the above, an object of the present invention is to provide an endoscope flexible tube and an endoscope type medical device using the same, wherein the endoscope flexible tube can sufficiently maintain the close contact between the flexible tube base material and the coating layer covering the flexible tube even when the flexible tube is repeatedly bent, and the close contact between the flexible tube base material and the coating layer is unlikely to be reduced even by a strong sterilization treatment using ozone water. In addition, an object of the present invention is to provide a method for manufacturing the above-mentioned endoscope flexible tube and the above-mentioned endoscope type medical device.

[0016] Means for solving technical problems

[0017] The present inventors have repeatedly conducted intensive studies in view of the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by using a polyester assembled with a naphthalene structure as a constituent material of a coating layer (outer skin) constituting a flexible tube for an endoscope, providing a primer layer comprising at least one of an aluminum alkoxide compound, a zirconium alkoxide compound, a titanium alkoxide compound and a specific silane coupling agent on the periphery of a flexible tube substrate in the preparation of the flexible tube for an endoscope, and providing the above-mentioned coating layer via the primer layer, thereby completing the present invention.

[0018] The above objects can be achieved by the following method.

[0019] <1>

[0020] A flexible tube for an endoscope comprises a flexible tube base material made of metal and a coating layer covering the outer periphery of the flexible tube base material, wherein:

[0021] A primer layer containing at least one of a silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound and a titanium alkoxide compound is provided between the flexible tube substrate and the coating layer, and the coating layer contains a polyester having a naphthalene structure at least on a side in contact with the primer layer.

[0022] The above silane coupling agent does not include vinyl silane coupling agent, (meth) acrylic silane coupling agent, epoxy silane coupling agent, amino silane coupling agent and sulfanyl silane coupling agent.

[0023] <2>

[0024] according to <1> The flexible tube for endoscope, wherein:

[0025] The above-mentioned silane coupling agent includes a compound represented by the following general formula (1):

[0026] [Chemical formula 1]

[0027] General formula (1)

[0028] In the formula, LL 1 represents a univalent substituent or an n1-valent connecting group; L 1 represents a single bond or a divalent connecting group; Y 1 ~Y 3 represents a substituent; n1 is an integer from 1 to 4,

[0029] Among them, Y 1 ~Y 3 At least one of them is a group selected from an alkoxy group and a hydroxyl group, and when n1 is 1, all LL 1 LL 1 -L 1 and Y 1 ~Y 3 The compounds represented by the general formula (1) above do not include vinyl silane coupling agents, (meth) acrylic silane coupling agents, epoxy silane coupling agents, amino silane coupling agents and sulfanyl silane coupling agents.

[0030] <3>

[0031] according to <2> The flexible tube for endoscope, wherein the compound represented by the general formula (1) includes a compound represented by any one of the following general formulas (2) to (4),

[0032] [Chemical formula 2]

[0033] General formula (2)

[0034] General formula (3)

[0035] General formula (4)

[0036] In the formula, LL 1a represents a hydrogen atom, an alicyclic group, a heterocyclic group, a hydroxyl group, a sulfanyl group, an isocyanate group, a thiocyanate group, a urea group, a cyano group, an acid anhydride group, an azido group, a carboxyl group, an acyl group, a thiocarbamoyl group, a phosphoric acid group, a phosphino group, a sulfonic acid group or an amoyl group;

[0037] L 2 represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, an ester bond, a thioester bond, an amide bond, a sulfamide bond or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds;

[0038] L 3 ~L 5 represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, an ester bond, a thioester bond, an amide bond, a sulfamide bond, a urea bond, a thiourea bond or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds;

[0039] LL 1b represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, a divalent heterocyclic group, an amide bond, an ester bond, a thioester bond, a divalent phosphate group, a phosphanediyl group or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds;

[0040] LL 1c represents an n2-valent alkane, an n2-valent olefin, an n2-valent alkyne, an n2-valent aromatic hydrocarbon, an n2-valent heterocyclic group, a trivalent phosphoric acid group, a phosphane triyl group, or an isocyanurate group, or a combination of these groups and an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NR a -, an n2-valent group consisting of a group or a combination of two or more of an ester bond, a thioester bond, an amide bond, a sulfamide bond and a sulfonyl group;

[0041] R a represents a hydrogen atom or a substituent;

[0042] Y 4 , Y 7 , Y 10 and Y13 represents a hydroxyl group or an alkoxy group; Y 5 , Y 6 , Y 8 , Y 9 , Y 11 , Y 12 , Y 14 and Y 15 represents a hydroxyl group, an alkoxy group, an alkyl group or a ketoximate group;

[0043] n2 is 3 or 4;

[0044] The compound represented by any one of the general formulae (2) to (4) above does not include a vinyl silane coupling agent, a (meth)acrylic silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, and a sulfanyl silane coupling agent.

[0045] <4>

[0046] according to <1> ~ <3> The flexible tube for endoscope described in any one of the preceding claims, wherein:

[0047] The aluminum alkoxide compound includes a compound represented by the following general formula (a) or (b):

[0048] General formula (a): R 1a m1 -Al-(OR 2a ) 3-m1

[0049] General formula (b): O-[Al-(OR 2a )2]2

[0050] R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group;

[0051] R 2a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S1 ; R S1 represents a substituent;

[0052] m1 is an integer from 0 to 2.

[0053] <5>

[0054] according to <4> The flexible tube for endoscope, wherein:

[0055] In the above general formulae (a) and (b), OR 2a At least one of the compounds has an acetonate structure or an acetate structure.

[0056] <6>

[0057] according to <1> ~ <5> The flexible tube for endoscope described in any one of the preceding claims, wherein:

[0058] The zirconium alkoxide compound includes a compound represented by the following general formula (c) or (d):

[0059] General formula (c): R 1b m2 -Zr-(OR 2b ) 4-m2

[0060] General formula (d): O-[Zr-(OR 2b )3]2

[0061] R 1b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group;

[0062] R 2b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S2 ; R S2 represents a substituent;

[0063] m2 is an integer from 0 to 3.

[0064] <7>

[0065] according to <6> The flexible tube for endoscope, wherein:

[0066] In the above general formulae (c) and (d), OR 2b At least one of the compounds has an acetonate structure, an acetate structure or a lactate structure.

[0067] <8>

[0068] according to <1> ~ <7> The flexible tube for endoscope described in any one of the preceding claims, wherein:

[0069] The titanium alkoxide compound includes a compound represented by the general formula (e) or (f),

[0070] General formula (e): R 1c m3 -Ti-(OR 2c ) 4-m3

[0071] General formula (f): O-[Ti-(OR 2c )3]2

[0072] R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group;

[0073] R 2crepresents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S3 ; R S3 represents a substituent;

[0074] m3 is an integer from 0 to 3.

[0075] <9>

[0076] according to <8> The flexible tube for endoscope, wherein:

[0077] The compound represented by the general formula (e) or (f) contains at least one atom of N, P and S.

[0078] <10>

[0079] according to <1> ~ <9> The flexible tube for endoscope described in any one of the preceding claims, wherein:

[0080] The metal constituting the base material of the above-mentioned flexible tube is stainless steel.

[0081] <11>

[0082] according to <1> ~ <10> The flexible tube for endoscope described in any one of the preceding claims, wherein:

[0083] The metal constituting the flexible tube base material has a passivation film on the surface.

[0084] <12>

[0085] An endoscopic medical device having <1> ~ <11> The endoscope flexible tube according to any one of the above.

[0086] <13>

[0087] A method for manufacturing a flexible tube for an endoscope, comprising:

[0088] forming a primer layer including at least one of a silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound on at least the outer periphery of a flexible tube substrate made of metal; and

[0089] a step of forming a coating layer on the primer layer formed on the outer periphery of the flexible tube substrate using a coating layer forming material containing a polyester having a naphthalene structure;

[0090] The above silane coupling agent does not include vinyl silane coupling agent, (meth) acrylic silane coupling agent, epoxy silane coupling agent, amino silane coupling agent and sulfanyl silane coupling agent.

[0091] <14>

[0092] A method for manufacturing an endoscopic medical device, comprising:

[0093] By following <13> The method for manufacturing the flexible tube for an endoscope includes a step of obtaining the flexible tube for an endoscope; and

[0094] A step of assembling the obtained endoscope flexible tube to an insertion portion of an endoscope type medical device.

[0095] <15>

[0096] A method for manufacturing an endoscopic medical device, comprising:

[0097] Will <1> ~ <11> Any one of the endoscope flexible tubes is assembled to an insertion portion of an endoscope type medical device.

[0098] In the description of this specification, "metal alkoxide compound (specifically, for example, aluminum alkoxide compound, zirconium alkoxide compound and titanium alkoxide compound described later)" means a compound having a structure in which at least one alkoxy group is bonded to a metal atom. The alkoxy group may have a substituent. The substituent may be monovalent or divalent (for example, an alkylidene group). In addition, two alkoxy groups bonded to one metal atom may be bonded to each other to form a ring.

[0099] In the description of this specification, unless otherwise specified, when there are multiple groups with the same symbol in the general formula representing the compound, these groups may be the same or different from each other. In addition, the group represented by each group (for example, an alkyl group) may further have a substituent.

[0100] In the description of this specification, “to” is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0101] Effects of the Invention

[0102] The flexible tube for endoscope of the present invention can fully maintain the close contact between the flexible tube substrate and the coating layer covering the flexible tube substrate even when the bending action is repeated, and the close contact between the flexible tube substrate and the coating layer is not easily reduced by the strong sterilization treatment using ozone water. The endoscopic medical device of the present invention is an instrument having a flexible tube for endoscope having the above-mentioned excellent characteristics. In addition, according to the manufacturing method of the flexible tube for endoscope of the present invention, the flexible tube for endoscope of the present invention having the above-mentioned characteristics can be obtained. According to the manufacturing method of the endoscopic medical device of the present invention, the endoscopic medical device having the flexible tube for endoscope of the present invention having the above-mentioned characteristics can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0103] Figure 1 This is an external view showing the structure of an electronic endoscope.

[0104] Figure 2 This is a partial cross-sectional view showing a schematic structure of an endoscope flexible tube. DETAILED DESCRIPTION

[0105] The flexible tube for endoscope of the present invention (hereinafter, the flexible tube for endoscope may be simply referred to as "flexible tube") is a flexible tube for endoscope having a flexible tube substrate composed of metal and a coating layer covering the outer periphery of the flexible tube substrate, a primer layer containing at least one of a silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound and a titanium alkoxide compound is provided between the flexible tube substrate and the coating layer, and the coating layer contains a polyester having a naphthalene structure at least on the side in contact with the primer layer.

[0106] However, in the present invention, when simply referred to as a "silane coupling agent", vinyl silane coupling agents, (meth) acrylic silane coupling agents, epoxy silane coupling agents, amino silane coupling agents and sulfanyl silane coupling agents are not included.

[0107] <Base Coating>

[0108] In the present invention, a primer layer (not shown) is provided on the outer periphery of the flexible tube substrate. By providing the primer layer, the adhesion between the flexible tube substrate and the coating layer described later provided to cover the outer periphery thereof can be effectively improved. In the present invention, the primer layer comprises at least one of a silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound. From the perspective of peeling resistance and sterilization durability, the primer layer preferably comprises at least one of an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound, and more preferably comprises a titanium alkoxide compound.

[0109] (Silane coupling agent)

[0110] As the silane coupling agent used in the present invention, a common silane coupling agent that can be used as a primer of an endoscope flexible tube can be widely used. However, the silane coupling agent does not include a vinyl silane coupling agent, a (meth) acrylic silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, and a sulfanyl silane coupling agent. As shown in the [Examples] described later, the present inventors found out based on experimental facts that the target effect cannot be obtained when these silane coupling agents are used.

[0111] The term "vinyl silane coupling agent" refers to a silane coupling agent having a vinyl group (CH2=CH-) and the vinyl group is directly bonded to a silicon atom. That is, for example, in the general formula (2) described below, "LL 1a -L 2 -" does not use "CH2=CH-".

[0112] The “(meth)acrylic silane coupling agent” means a silane coupling agent having a (meth)acryloyl group.

[0113] The “epoxy silane coupling agent” means a silane coupling agent having an epoxy group.

[0114] The "aminosilane coupling agent" means a silane coupling agent having an amino group (-NH2 group).

[0115] The "sulfanylsilane coupling agent" means a silane coupling agent having a sulfanyl (mercapto) group (-SH group).

[0116] The silane coupling agent preferably contains a compound represented by the following general formula (1). The content ratio of the compound represented by the following general formula (1) in the silane coupling agent is not particularly limited, and can be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and can also be 100% by mass.

[0117] [Chemical formula 3]

[0118] General formula (1)

[0119] In the formula, LL 1 represents a univalent substituent or an n1-valent linking group. 1 represents a single bond or a divalent linking group. 1 ~Y 3 represents a substituent. n1 is an integer from 1 to 4. (When n1 is 1, LL 1 When n1 is an integer from 2 to 4, LL 1 represents a 2- to 4-valent connecting group. )

[0120] Among them, Y 1 ~Y 3 At least one of them is a group selected from an alkoxy group and a hydroxyl group. When n1 is 1, all LL 1 LL 1 -L 1 and Y 1 ~Y 3 Both represent a group selected from an alkoxy group and a hydroxy group.

[0121] The compound represented by the general formula (1) above preferably includes a compound represented by any one of the following general formulas (2) to (4), and more preferably includes a compound represented by the following general formula (3) or (4) from the viewpoint of peeling resistance and sterilization durability.

[0122] [Chemical formula 4]

[0123] General formula (2)

[0124] General formula (3)

[0125] General formula (4)

[0126] In the formula, LL 1a represents a hydrogen atom, an alicyclic group, a heterocyclic group, a hydroxyl group, a sulfanyl group, an isocyanate group, a thiocyanate group, a urea group, a cyano group, an acid anhydride group, an azido group, a carboxyl group, an acyl group, a thiocarbamoyl group, a phosphoric acid group, a phosphine group, a sulfonic acid group or a sulfamoyl group.

[0127] L 2 represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, ester bond (-C(=O)-O-, -OC(=O)-), thioester bond (-S(=O)-O-, -OS(=O)-), amide bond (-NH-C(=O)-, -C(=O)-NH-), sulfamide bond (-NH-S(=O)-, -S(=O)-NH-) or sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds.

[0128] L 3 ~L 5 represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, an ester bond, a thioester bond, an amide bond, a thioamide bond, a urea bond, a thiourea bond or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds.

[0129] LL 1b represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, a divalent heterocyclic group, an amide bond, an ester bond, a thioester bond, a divalent phosphoric acid group (a divalent group obtained by removing two hydrogen atoms from phosphoric acid), a phosphanediyl group or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds.

[0130] LL 1c represents an n2-valent alkane, an n2-valent olefin, an n2-valent alkyne, an n2-valent aromatic hydrocarbon, an n2-valent heterocyclic group, a trivalent phosphoric acid group, a phosphane triyl group, or an isocyanurate group, or a combination of these groups with an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NR a -, an n2-valent group formed by a combination of two or more groups or bonds selected from the group consisting of an ester bond, a thioester bond, an amide bond, a sulfamide bond and a sulfonyl group.

[0131] R a represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom.

[0132] Y 4 , Y 7 , Y 10 and Y 13Y represents a hydroxyl group or an alkoxy group. 5 , Y 6 , Y 8 , Y 9 , Y 11 , Y 12 , Y 14 and Y 15 represents a hydroxyl group, an alkoxy group, an alkyl group or a ketoximate group.

[0133] n2 is 3 or 4.

[0134] Also, do not remove part of the amide bond ("-NH-") and interpret it as -NR a -, do not take out a part of the structure ("-O-") in the ester bond and interpret it as "-O-". In addition, even if the acid anhydride group has a heterocyclic ring, the acid anhydride group should not be interpreted as a heterocyclic group.

[0135] Regarding the compounds represented by the general formula (2), the compounds corresponding to LL 1a -L 2 - structure, according to LL 1a , L 2 Apply the structure in the order specified.

[0136] However, in the presence of LL 1a The groups and LL 1a The groups represented by L 2 In the case of any combination of groups (e.g., hydroxyl, sulfanyl, thiocyanato, urea, anhydride, carboxyl, acyl, carbamoyl) representing a bond, these groups are preferably understood as LL 1a In addition, in L 2 Alkylene, alkenylene, alkynylene, arylene, -O-, -S-, -NR a In the case of a combination of two or more of -, an ester bond, a thioester bond, an amide bond, a sulfamide bond and a sulfonyl group, it is understood that the number of groups (bonds) constituting the combination is the smallest.

[0137] The following is an example of compound K-11, LL 1a represents thiocyanate, L 2 represents an alkylene group.

[0138] Regarding the compounds represented by the general formula (3), the compounds corresponding to -L 3 -LL 1b -L 4 - structure, according to L 3 , L 4 LL 1b In this case, select L 3 and L4 , so that L 3 The number of groups (bonds) represented and L 4 The number of combinations of groups (bonds) represented is the smallest.

[0139] The following is an explanation using the exemplary compound K-24 as an example. 3 represents an alkylene group, L 4 represents alkylene, LL 1b In addition, when the exemplary compound K-25 described later is used as an example, L 3 represents an alkylene group, L 4 Represents alkylene, LL 1b It represents a combination of two ester bonds and an alkenylene group.

[0140] Among them, in the equivalent of -L 3 -LL 1b -L 4 - When the structure is a group (for example, an alkylene group), L 3 and L 4 Represents a single bond.

[0141] In addition, regarding the compound represented by the general formula (4), the corresponding LL 1c -(L 5 ) n2 - structure, according to L 5 LL 1c In this case, select L 5 , so that L 5 The number of combinations of groups etc. represented is the smallest.

[0142] Among them, in the equivalent of LL 1c -(L 5 ) n2 - When the structure is a group (for example, an n2-valent alkane), n2 L 5 Represents a single bond.

[0143] Optional as LL 1a The alicyclic group is preferably an alicyclic hydrocarbon group, which may be any of a cycloalkyl group, a cycloalkenyl group and a cycloalkynyl group. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15, and further preferably 5 to 10. The number of carbon atoms in the cycloalkenyl group and the cycloalkynyl group is preferably 6 to 20, more preferably 6 to 15, more preferably 6 to 10, and further preferably 6.

[0144] The composition can be selected as LL 1aThe heterocyclic ring of the heterocyclic group may be a saturated or unsaturated aliphatic heterocyclic ring, or an aromatic heterocyclic ring, and may be a monocyclic ring or a condensed ring. In addition, it may also be a bridged ring. The heteroatoms constituting the heterocyclic ring may include, for example, oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms contained in a heterocyclic ring is not particularly limited, and is preferably 1 to 3, more preferably 1 or 2. The number of carbon atoms in the heterocyclic ring is preferably 2 to 10, more preferably 4 or 5. The heterocyclic ring is preferably a 3-7-membered ring, more preferably a 3-6-membered ring, and further preferably a 3-5-membered ring. Specific examples of the heterocyclic ring include an epoxy ring, a 3,4-epoxycyclohexane ring, a furan ring, and a thiophene ring.

[0145] Optional as LL 1a The number of carbon atoms of the acyl group is preferably 0 to 40, more preferably 0 to 30, more preferably 0 to 20, more preferably 0 to 15, and further preferably 0 to 10. In the present invention, the acyl group includes formyl, carbamoyl, alkylcarbonyl, alkenylcarbonyl and arylcarbonyl.

[0146] As an optional LL 1a The acid anhydride group is preferably a monovalent group having a carboxylic anhydride structure, and examples thereof include maleic anhydride groups such as 3,4-dihydro-2,5-furandione group, succinic anhydride groups, glutaric anhydride groups, adipic anhydride groups, and citraconic anhydride groups.

[0147] Optional as L 2 The alkylene group may be any of a straight chain and a branched chain. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 25, more preferably 1 to 20, and more preferably 1 to 15. Specific examples of the alkylene group include methylene, ethylene, isopropylene, butylene, pentylene, cyclohexylene, heptylene, octylene, nonylene, decylene, and undecylene.

[0148] Optional as L 2 The alkenylene group may be either linear or branched. The number of carbon atoms in the alkenylene group is preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10, and further preferably 2 to 6. Specific examples of the alkenylene group include vinylene and propenylene.

[0149] Optional as L 2 The alkynylene group may be either linear or branched. The number of carbon atoms in the alkynylene group is preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10, and further preferably 2 to 6. Specific examples of the alkynylene group include ethynylene and propynylene.

[0150] Optional as L 2 The carbon number of the arylene group is preferably 6 to 20, more preferably 6 to 15, more preferably 6 to 12, and further preferably 6 to 10. Specific examples of the arylene group include a phenylene group and a naphthylene group.

[0151] As an optional L 2 -NR a -R a The substituents on the alkyl group include alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms), aryl groups (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms) and heterocyclic groups. a The heterocyclic ring of the heterocyclic group can be selected as LL 1a The heterocyclic ring of the heterocyclic group is preferably selected as LL 1a The preferred manner for the heterocyclic group is the same as that for the

[0152] AS-NR a -, for example -NH-.

[0153] The composition can be selected as L 2 A divalent group formed by combining two or more of the above groups or bonds (hereinafter, also referred to as "a group that can be selected as L 2 The number of the combined groups or bonds is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.

[0154] In addition, L 2 The molecular weight of the group formed by the combination of is preferably 20 to 1,000, more preferably 30 to 500, and further preferably 40 to 200.

[0155] As an optional L 2 Examples of the group formed by the combination of urea bonds, thiourea bonds, carbamate groups, sulfoneamide bonds, arylene-alkylene groups, -O-alkylene groups, -NR a -alkylene, amide-alkylene, -S-alkylene, alkylene-O-amide-alkylene, alkylene-amide-alkylene, alkenylene-amide-alkylene, alkylene-ester-alkylene, arylene-ester-alkylene, -(alkylene-O)-, alkylene-O-(alkylene-O)-alkylene ("(alkylene-O)" are all repeating units), arylene-sulfonyl-O-alkylene and ester-alkylene ("group" is omitted. The same may be used hereinafter.).

[0156] As an optional L 3 ~L 5 Alkylene, alkenylene, alkynylene, arylene and -NR a -, the above mentioned can be used as L 2 Alkylene, alkenylene, alkynylene, arylene and -NR a -, preferably also with optional L2 Alkylene, alkenylene, alkynylene, arylene and -NR a - is preferred in the same manner.

[0157] Optional as LL 1b The alkylene group may be any of a linear, branched or cyclic group. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 25, more preferably 1 to 20, and further preferably 1 to 15. Specific examples of the alkylene group include methylene, ethylene, isopropylene, butylene, pentylene, cyclohexylene, heptylene, octylene, nonylene, decylene and undecylene.

[0158] Optional as LL 1b The alkenylene group may be any of linear, branched and cyclic. The number of carbon atoms in the alkenylene group is preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10, and further preferably 2 to 6. Specific examples of the alkenylene group include vinylene and propenylene.

[0159] Optional as LL 1b The alkynylene group may be any of linear, branched and cyclic. The number of carbon atoms in the alkynylene group is preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10, and further preferably 2 to 6. Specific examples of the alkynylene group include ethynylene and propynylene.

[0160] Optional as LL 1b The arylene group that can be used as L can be exemplified by 2 The arylene group is preferably the same as that which can be used as L 2 The preferred manner for the arylene group is the same.

[0161] The composition can be selected as LL 1b The heterocyclic ring of the divalent heterocyclic group can be selected as LL. 1a The heterocyclic ring of the heterocyclic group is preferably selected as LL 1a The preferred embodiment of the heterocyclic group is the same as that of the heterocyclic group. 1b -NR a -, the above mentioned ones can be selected as L 2 -NR a -, preferably also with optional L 2 -NR a - is preferred in the same manner.

[0162] The composition can be selected as LL 1b The above-mentioned group or a divalent group composed of two or more of the above-mentioned bonds (hereinafter, also referred to as "LL 1b The number of the combined groups or bonds is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.

[0163] In addition, you can choose LL 1b The molecular weight of the combined group is preferably 20 to 1,000, more preferably 30 to 500, and further preferably 40 to 200.

[0164] As an optional LL 1b Examples of the combination of groups include urea bonds, carbonate groups, sulfoneamide bonds, disulfide bonds, ester bonds-alkenylene-ester bonds, -(alkylene-O)- and -O-(alkylene-O)- ("(alkylene-O)" are all repeating units).

[0165] Optional as LL 1c The trivalent alkane among the n2-valent alkanes, that is, the alkane triyl group, preferably has 1 to 20 carbon atoms, more preferably 3 to 15, more preferably 4 to 12, and further preferably 5 to 10 carbon atoms.

[0166] Optional as LL 1c The number of carbon atoms in the tetravalent alkane among the n2-valent alkane, that is, the alkane tetrayl group, is preferably 1 to 20, more preferably 3 to 15, more preferably 4 to 12, and further preferably 5 to 10.

[0167] Optional as LL 1c The trivalent olefin among the n2-valent olefins, that is, the olefin triyl group, preferably has 2 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and further preferably 5 to 10 carbon atoms.

[0168] Optional as LL 1c The number of carbon atoms of the tetravalent olefin among the n2-valent olefins, that is, the olefin tetrayl group, is preferably 2-20, more preferably 3-15, more preferably 4-12, and further preferably 5-10.

[0169] Optional as LL 1c The trivalent alkyne among the n2-valent alkynes, that is, the alkyne triyl group, preferably has 3 to 20 carbon atoms, more preferably 3 to 15, more preferably 4 to 12, and further preferably 5 to 10 carbon atoms.

[0170] Optional as LL 1c The number of carbon atoms in the tetravalent alkyne among the n2-valent alkynes, that is, the alkyne tetrayl group, is preferably 3-20, more preferably 3-15, more preferably 4-12, and further preferably 5-10.

[0171] Optional as LL 1c The carbon number of the trivalent aromatic hydrocarbon among the n2-valent aromatic hydrocarbons, that is, the arene triyl group, is preferably 6 to 20, more preferably 6 to 15, more preferably 6 to 12, and further preferably 6 to 10. Specific examples of the arene triyl group include benzene triyl and naphthalene triyl.

[0172] Optional as LL 1cThe carbon number of the tetravalent aromatic hydrocarbon among the n2-valent aromatic hydrocarbons, that is, the arene tetrayl group, is preferably 6 to 20, more preferably 6 to 15, more preferably 6 to 12, and further preferably 6 to 10. Specific examples of the arene tetrayl group include benzene tetrayl group and naphthalene tetrayl group.

[0173] The composition can be selected as LL 1c The heterocyclic ring of the n2-valent heterocyclic group can be selected as LL 1a The heterocyclic ring of the heterocyclic group is preferably selected as LL 1a The preferred embodiment of the heterocyclic ring is the same as that of 1c -NR a -, the above mentioned ones can be selected as L 2 -NR a -, preferably also with optional L 2 -NR a - is preferred in the same manner.

[0174] The composition can be selected as LL 1c The above groups are combined with alkylene, alkenylene, alkynylene, arylene, -O-, -S-, -NR a -, ester bond, thioester bond, amide bond, thioamide bond and sulfonyl group or bond combination of two or more groups (hereinafter, also referred to as "LL 1c The number of the combined groups or bonds is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.

[0175] In addition, you can choose LL 1c The molecular weight of the group formed by the combination of is preferably 20 to 1,000, more preferably 30 to 500, and further preferably 40 to 200.

[0176] As an optional LL 1c Examples of the group formed by a combination of include a glyceryl group, a trimethylolpropyl group, a 1,3,5-triazine group, and an isocyanurate group (1,3,5-triazine-2,4,6(1H,3H,5H)-trione-1,3,5-triyl group).

[0177] The composition can be selected as Y 4 ~Y 15 The alkyl group of the alkoxy group may be any of a straight chain, a branched chain, and a cyclic group, or may be a combination of these forms. In the present invention, the alkyl group is preferably a straight chain alkyl group. The number of carbon atoms of the alkyl group constituting the alkoxy group is preferably 1 to 15, more preferably 1 to 10, more preferably 1 to 5, and further preferably 1 or 2. Specific examples of the alkyl group constituting the alkoxy group include a methyl group, an ethyl group, a propyl group, a tert-butyl group, a pentyl group, and a cyclohexyl group.

[0178] As an optional 5, Y 6 , Y 8 , Y 9 , Y 11 , Y 12 , Y 14 and Y 15 The alkyl group that can be selected as Y can be listed as 4 ~Y 15 The alkyl group of the alkoxy group is preferably also selected as Y 4 ~Y 15 The preferred manner is the same as that of the alkyl group of the alkoxy group.

[0179] The ketoximo group is a substituent having the following structure.

[0180] [Chemical formula 5]

[0181]

[0182] In the above structure, R 11 and R 12 represents a substituent, and * represents a bonding portion to a silicon atom.

[0183] As R 11 and R 12 The substituents that can be used include the above R a The substituents in the preferred embodiment can also be selected as R a The preferred manner for the substituents is the same.

[0184] Examples of the ketoxime group include a dimethylketoxime group, a methylethylketoxime group, and a diethylketoxime group.

[0185] The silane coupling agent may have a substituent within a range that does not impair the effects of the present invention. Examples of the substituent include the LL 1a In addition, as its substituent, an unsubstituted silyl group and a substituted silyl group not having an alkoxy group or a hydroxyl group as a substituent can be mentioned.

[0186] In the general formula (2), LL 1a or L 2 With Y 5 and Y 6 At least any of them may be linked to each other to form a ring. The number of atoms constituting the ring is preferably 3 to 10, more preferably 4 to 8, and even more preferably 5 or 6.

[0187] In the general formula (3), LL 1b or L 3 With Y 8 and Y 9At least any of them may be linked to each other to form a ring. The number of atoms constituting the ring is preferably 3 to 10, more preferably 4 to 8, and further preferably 5 or 6. 1b or L 4 With Y 11 and Y 12 At least any of them may be linked to each other to form a ring. The number of atoms constituting the ring is preferably 3 to 10, more preferably 4 to 8, and further preferably 5 or 6. In addition, two or more of these rings may be formed simultaneously.

[0188] In the general formula (4), LL 1c or L 5 With Y 13 and Y 14 At least any of them may be linked to each other to form a ring. The number of atoms constituting the ring is preferably 3 to 10, more preferably 4 to 8, and even more preferably 5 or 6.

[0189] In the general formula (2), LL 1a represents a hydrogen atom, an alicyclic group, a heterocyclic group, a hydroxyl group, a sulfanyl group, a thiocyanate group, an acid anhydride group, a carboxyl group, an acyl group or a sulfonic acid group. 2 represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, an ester bond, a thioester bond, an amide bond or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds.

[0190] In the general formula (2), LL 1a represents a hydrogen atom, a hydroxyl group, a carboxylic anhydride group, a carboxyl group, an acyl group or a sulfonic acid group. 2 represents an alkylene group, an alkenylene group, -O-, or -NR a -, an ester bond or an amide bond, or a divalent group formed by combining two or more of these groups or bonds.

[0191] As LL 1a -L 2 -Specific examples include hydrogen atom-alkenylene (except hydrogen atom -CH=CH-), hydrogen atom-arylene-alkylene, alicyclic-alkylene, heterocyclic-alkylene, acyl-O-alkylene, acyl-NR a -alkylene, sulfanyl-alkylene, heterocyclic-S-alkylene, thiocyanate-alkylene, hydroxy-alkylene, hydroxy-alkylene-amide bond-alkylene, carboxyl-alkylene, acyl-alkylene-amide bond-alkylene, anhydride-alkylene, hydrogen atom-arylene-ester bond-alkylene, hydrogen atom-alkylene-ester bond-alkylene, hydrogen atom-alkylene-O-(alkylene-O)-alkylene, sulfonic acid-alkylene and hydrogen atom-arylene-sulfonyl-O-alkylene, etc.

[0192] In the general formula (2), preferably Y 4 ~Y 6 At least two of Y are alkoxy or hydroxy, and more preferably all Y 4 ~Y 6 All are alkoxy or hydroxy.

[0193] In the general formula (3), LL 1b represents an alkylene group, an alkenylene group, an arylene group, -O-, -S-, an ester bond, a thioester bond, an amide bond or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds. 3 and L 4 It represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, an ester bond, a thioester bond, an amide bond or a sulfonyl group, or a divalent group formed by a combination of two or more of these groups or bonds, and more preferably represents a single bond, an alkylene group, an alkenylene group, -O-, an ester bond or an amide bond.

[0194] As-L 3 -LL 1b -L 4 -Specific examples include alkylene, alkylene-ester bond-O-alkylene, alkylene-ester bond-alkenylene-ester bond-alkylene, alkylene-O-(alkylene-O)-alkylene, alkylene-arylene-alkylene, alkylene-SS-alkylene, and the like.

[0195] In the general formula (3), preferably Y 7 ~Y 9 At least two of them are alkoxy or hydroxy.

[0196] In the general formula (3), preferably Y 10 ~Y 12 At least two of them are alkoxy or hydroxy.

[0197] In the general formula (4), preferably n2 is 3, LL 1c represents an isocyanurate group. In addition, preferably L 5 represents an alkylene group.

[0198] In the general formula (4), preferably Y 13 ~Y 15 At least two of Y are alkoxy or hydroxy, and more preferably all Y 13 ~Y 15 All are alkoxy or hydroxy.

[0199] In the general formula (4), n2 is preferably 3.

[0200] The compound of the general formula (1) used in the present invention is a single molecule and is a compound that contributes to the adhesion between the flexible tube substrate and the coating layer. The thickness of the primer layer is extremely thin compared to a general adhesive layer (in other words, it is so thin that the concept of thickness is unimaginable). That is, the primer layer containing the compound of the general formula (1) is different from the adhesive layer that requires a certain thickness and flexibility for the adhesion between the flexible tube substrate and the coating layer. Therefore, the primer layer does not substantially affect the rebound resilience of the flexible tube, and the flexible tube of the present invention also has excellent rebound resilience.

[0201] In the present invention, "containing a silane coupling agent" means including a form in which the silane coupling agent is contained in a state after reacting with the flexible tube base material and a form in which the silane coupling agent is contained in a state after reacting with the coating layer. That is, for example, the silane coupling agent is at least partially hydrolyzed to expose hydroxyl groups, and is a substance that can react with a constituent metal of the flexible tube base material or react with a group on the surface of the coating layer.

[0202] In addition, for example, as described later, in the case of forming a primer layer using a coating solution prepared to be acidic or alkaline in pH, a portion of the silane coupling agent may also exist as a salt or ion. As the form of the above-mentioned ion, for example, a group (anionic group) that can form anions as anions can be cited. In addition, as the form of the above-mentioned salt, the above-mentioned anionic group can be cited as a salt-type group having alkaline metal ions such as sodium ions and potassium ions as counter cations.

[0203] The same applies to the metal alkoxide compound described later.

[0204] Specific examples of the silane coupling agent are listed below, but the present invention is not limited to these specific examples.

[0205] In the following structures, Me represents a methyl group, and Et represents an ethyl group. In the structure of the compound K-20, ( ) represents a repeating unit having a repeating number of 6 to 9. In the structure of the compound K-26, ( ) represents a repeating unit having a repeating number of 6 to 9.

[0206] In the following chemical structural formula, regarding compounds in which an alkoxy group is listed as a substituent bonded to a silicon atom, specific examples of silane coupling agents include compounds having a structure in which a part or all of the alkoxy group is a hydroxyl group. In the exemplified compounds, R represents an alkyl group.

[0207] [Chemical formula 6]

[0208]

[0209] [Chemical formula 7]

[0210]

[0211] [Chemical formula 8]

[0212]

[0213] [Chemical formula 9]

[0214]

[0215] As the aluminum alkoxide compound used in the present invention, a wide range of common aluminum alkoxide compounds that can be used as a primer layer of an endoscope flexible tube can be adopted.

[0216] The aluminum alkoxide compound preferably contains at least one of the compounds represented by the following general formula (a) or (b), and more preferably contains at least one of the compounds represented by the following general formula (a). The total content ratio of the compounds represented by the following general formula (a) or (b) in the above-mentioned aluminum alkoxide compound is not particularly limited, and can be set to, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and can also be 100% by mass.

[0217] General formula (a): R 1a m1 -Al-(OR 2a ) 3-m1

[0218] General formula (b): O-[Al-(OR 2a )2]2

[0219] R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0220] Optional R 1a The alkyl group includes a linear alkyl group, a branched alkyl group, and an aralkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, particularly preferably 1 to 8, and preferably 7 to 30 in the case of an aralkyl group. Preferred specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a tridecyl group, an octadecyl group, a benzyl group, and a phenethyl group.

[0221] Optional R 1a The alkyl group of R also preferably has an ethylene oxide ring. 1a The number of ring members of the cycloalkyl group (cycloalkyl group having a structure in which an oxirane ring is condensed) in the cyclooxyalkyl group is preferably 4 to 8, more preferably 5 or 6, and further preferably 6 (ie, cyclohexyl oxide).

[0222] In addition, R 1aThe alkyl group also preferably has a group selected from an amino group, an isocyanate group, a mercapto group, an ethylenically unsaturated group and an acid anhydride group.

[0223] Optional R 1a The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 3 to 15, further preferably 3 to 10, and particularly preferably 3 to 8. Preferred specific examples of the cycloalkyl group include cyclopropyl, cyclopentyl and cyclohexyl.

[0224] Optional R 1a The acyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, further preferably 2 to 20 carbon atoms, and particularly preferably 2 to 18 carbon atoms.

[0225] Optional R 1a The carbon number of the aryl group is preferably 6 to 20, more preferably 6 to 15, further preferably 6 to 12, particularly preferably 6 to 10. Preferred specific examples of the aryl group include phenyl and naphthyl, and phenyl is further preferred.

[0226] Optional R 1a The number of carbon-carbon unsaturated bonds of the unsaturated aliphatic group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. The unsaturated aliphatic group may contain a heteroatom, and is also preferably a hydrocarbon group. When the unsaturated aliphatic group is a hydrocarbon group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 10, further preferably 2 to 8, and also preferably 2 to 5. The unsaturated aliphatic group is more preferably an alkenyl group or an alkynyl group.

[0227] R 1a A hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group is preferred, and an alkyl group or a cycloalkyl group is more preferred.

[0228] In the compound of general formula (a) having two or more R 1a In the case of two R 1a They can be connected to each other to form a ring.

[0229] R 2a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group (phosphonic acid group), or -SO2R S1 . R S1 represents a substituent.

[0230] Optional R 2a The alkyl, cycloalkyl, acyl and aryl groups are respectively 1a The alkyl, cycloalkyl, acyl and aryl groups have the same meanings, and the preferred forms of each group are also the same. 2a The alkyl group also preferably has an amino group as a substituent.

[0231] Optional R 2aThe alkenyl group includes a straight-chain alkenyl group and a branched alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 18, more preferably 2 to 7, and further preferably 2 to 5. Preferred specific examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, and hexenyl. The alkenyl group is preferably a substituted alkenyl group.

[0232] Optional R 2a The phosphonate group is -P(=O)(-OR P1 )OR P2 The group represented by R P1 and R P2 represents a hydrogen atom or a substituent, and the substituent is preferably an alkyl group or a phosphonate group. P1 and R P2 The alkyl group of the above-mentioned group can be selected as R 1a The alkyl group has the same meaning as R and the preferred forms of the alkyl group are also the same. P1 and R P2 The phosphonate group and the optional R 2a The phosphonate group has the same meaning and the same preferred method. P1 or R P2 In the case of a phosphonate group, R constituting the phosphonate group P1 and R P2 An alkyl group is preferred.

[0233] Optional R 2a The phosphonate group is preferably R P1 and R P2 are all alkyl, or R P1 is a hydrogen atom, R P2 It is a phosphonate group.

[0234] In addition, a phosphonate group and a phosphite group (phosphite group) are tautomerisms, and therefore, in the present invention, a phosphonate group is meant to include a phosphite group.

[0235] In the optional R 2a -SO2R S1 In, as R S1 Alkyl or aryl is preferred. S1 The preferred embodiments of the alkyl and aryl groups of R include the above-mentioned 1a The preferred embodiment of the alkyl group and aryl group of S1 Phenyl groups having an alkyl group as a substituent are preferred. The preferred embodiment of the alkyl group is the same as that of the above-mentioned alkyl group which can be selected as R 1a The preferred manner for the alkyl group is the same.

[0236] The compound represented by the general formula (a) has two or more R 2a In the case of two R 2aIn the compound represented by the general formula (b), two R 2a They can be connected to each other to form a ring.

[0237] m1 is an integer from 0 to 2.

[0238] In the above general formulae (a) and (b), preferably OR 2a At least one of them has an acetonato structure. The acetonato structure means a structure in which a hydrogen ion is removed from acetone or a compound having a structure in which acetone has a substituent and coordinated to Al. The coordinating atom coordinated to the Al is usually an oxygen atom. The acetonato structure preferably has an acetylacetone structure ("CH3-C(=O)-CH2-C(=O)-CH3") as a basic structure, from which a hydrogen ion is removed, and a structure in which an oxygen atom is coordinated to Al (i.e., an acetylacetone structure). The above-mentioned "structure based on the acetylacetone structure" means that in addition to the above-mentioned acetylacetone structure, it also includes a structure in which the hydrogen atom of the above-mentioned acetylacetone structure is replaced by a substituent. As OR 2a Examples of the compound having an acetonide structure include compounds A-2 and A-3 described below.

[0239] In the above general formulae (a) and (b), preferably OR 2a At least one of them has an acetate structure. In the present invention, the acetate structure means a structure in which a hydrogen ion is removed from acetic acid or an acetate ester or a compound thereof having a structure with a substituent (including a form in which the methyl group of acetic acid has an alkyl group as a substituent) and coordinated to Al. The coordinating atom coordinated to the Al is generally an oxygen atom. The acetate structure is preferably in the form of an alkyl acetoacetate structure ("CH3-C(=O)-CH2-C(=O)-OR alk ”(R alk Represents an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms). )) is a basic structure, from which a hydrogen ion is removed, and an oxygen atom is coordinated to Al as a coordinating atom (i.e., an alkyl acetoacetate structure). The above-mentioned "based on an alkyl acetoacetate structure" means that in addition to the above-mentioned alkyl acetoacetate structure, it also includes a structure in which the hydrogen atom of the above-mentioned alkyl acetoacetate structure is replaced by a substituent. As OR 2a Examples of the form having an acetate structure include compounds A-3, A-4, and A-5 described below.

[0240] Can be selected as above R 1a or R 2aEach group may also have an anionic group (salt-type substituent) having a counter cation as a substituent. Anionic groups refer to groups that can form anions. As anionic groups having the above-mentioned counter cations, for example, groups of carboxylic acid ions with ammonium ions as counter cations can be cited. In this case, the above-mentioned counter cation only needs to exist in the compound represented by the above-mentioned general formula (a) or (b) to make the overall charge of the compound 0. This situation is also the same for the compounds represented by the general formula (c) or (d) described later and the compounds represented by the general formula (e) or (f).

[0241] Specific examples of the aluminum alkoxide compound used in the present invention are listed below, but the present invention is not limited to these specific examples.

[0242] Aluminum triethoxide

[0243] Aluminum triisopropoxide

[0244] Aluminum tri-sec-butylate

[0245] Aluminum tris(ethyl acetoacetate)

[0246] Aluminum diisopropyl acetoacetate

[0247] Aluminum monoacetylacetonate bis(ethyl acetoacetate)

[0248] Aluminum tris(acetylacetonate)

[0249] Diisopropoxyaluminum-9-octadecenyl acetoacetate

[0250] Diisopropoxyaluminum monoacetoacetate

[0251] Aluminum mono-sec-butoxydiisopropylate

[0252] Aluminum Isopropyl Diacetoacetate

[0253] Ethyl bisacetoacetate Aluminum monoacetylacetonate

[0254] Octadecyl Aluminum Diisopropyl Acetoacetate

[0255] (Zirconium alkoxide compound)

[0256] As the zirconium alkoxide compound used in the present invention, a wide range of common zirconium alkoxide compounds that can be used as a primer layer for an endoscope flexible tube can be adopted.

[0257] The zirconium alkoxide compound preferably contains at least one of the compounds represented by the following general formula (c) or (d), and more preferably contains at least one of the compounds represented by the following general formula (c). The total content ratio of the compounds represented by the following general formula (c) or (d) in the above-mentioned zirconium alkoxide compound is not particularly limited, and can be set to, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and can also be 100% by mass.

[0258] General formula (c): R 1b m2 -Zr-(OR 2b ) 4-m2

[0259] General formula (d): O-[Zr-(OR 2b )3]2

[0260] R 1b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0261] As the alkyl group, cycloalkyl group, acyl group, aryl group and unsaturated aliphatic group, for example, R 1a Alkyl, cycloalkyl, acyl, aryl and unsaturated aliphatic groups.

[0262] R 2b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S2 . R S2 represents a substituent.

[0263] As the alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group and phosphonate group, for example, R 2a An alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group. S2 The substituents may be selected from the above general formula (a) R S1 substituent.

[0264] m2 is an integer from 0 to 3.

[0265] In the above general formulae (c) and (d), preferably OR 2b At least one of them has an acetonato structure. The acetonato structure has the same meaning as the acetonato structure described in general formula (a). 2b Examples of the compound having an acetonide structure include compounds Z-3 and Z-6 described below.

[0266] In the above general formula (c), preferably OR 2bAt least one of them has an acetate structure. The acetate structure has the same meaning as the acetate structure described in the general formula (a). 2b The form having an acetate structure includes, for example, Z-7 described below. In addition, compound Z-5 corresponds to R in general formula (c). 2b In the form of acyl group.

[0267] In the above general formulae (c) and (d), it is preferred that OR 2b At least one of them has a lactate structure. The lactate structure means a structure with lactate ion (lactate ester) as the basic structure, from which one hydrogen ion is removed and coordinated to Zr. The above-mentioned "with lactate ion as the basic structure" means a structure in which the hydrogen atom of the lactate ion is replaced by a substituent in addition to the lactate ion. The coordinating atom coordinated to the Zr is usually an oxygen atom. 2b Examples of the form having a lactate structure include the compound Z-4 described below.

[0268] Specific examples of the zirconium alkoxide compound used in the present invention are listed below, but the present invention is not limited to these specific examples.

[0269] Tetrapropoxyzirconium (also known as tetra-n-propoxide zirconium)

[0270] Zirconium Tetrabutoxide (also known as Zirconium Tetra-n-Butoxide)

[0271] Zirconium Tetraacetylacetonate

[0272] Zirconium tributyloxyacetylacetonate

[0273] Zirconium dibutoxybis(acetylacetonate)

[0274] Dibutoxybis(ethyl acetoacetate)zirconium

[0275] Zirconium tributoxyacetoacetate

[0276] Zirconium monobutoxyacetylacetonate bis(ethyl acetoacetate)

[0277] Zirconium tri-butoxy monostearate (also known as zirconium tri-n-butyl stearate)

[0278] Zirconium stearate

[0279] Ammonium zirconium lactate

[0280] Zirconium monoacetylacetonate

[0281] (Titanium alkoxide compound)

[0282] As the titanium alkoxide compound used in the present invention, a wide range of common titanium alkoxide compounds that can be used as a primer layer for an endoscope flexible tube can be adopted.

[0283] The titanium alkoxide compound preferably contains at least one of the compounds represented by the following general formula (e) or (f), and more preferably contains at least one of the compounds represented by the following general formula (e). The total content ratio of the compounds represented by the following general formula (e) or (f) in the titanium alkoxide compound is not particularly limited, and can be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and can also be 100% by mass.

[0284] General formula (e): R 1c m3 -Ti-(OR 2c ) 4-m3

[0285] General formula (f): O-[Ti-(OR 2c )3]2

[0286] R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0287] As the alkyl group, cycloalkyl group, acyl group, aryl group and unsaturated aliphatic group, for example, R 1a Alkyl, cycloalkyl, acyl, aryl and unsaturated aliphatic groups.

[0288] R 2c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S3 . R S3 represents a substituent.

[0289] As the alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group and phosphonate group, for example, R 2a An alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group. S3 The substituents may be selected from the above general formula (a) R S1 substituent.

[0290] m3 is an integer from 0 to 3.

[0291] The compound represented by the general formula (e) or (f) preferably contains at least one atom of N, P and S. When the compound represented by the general formula (e) or (f) has N, it preferably has the N as an amino group.

[0292] When the compound represented by the general formula (e) or (f) has P, it preferably has P as a phosphate group (phosphoric acid group) or a phosphonate group (phosphonic acid group).

[0293] When the compound represented by the general formula (e) or (f) has S, it preferably has the S as a sulfonyl group (—SO 2 —).

[0294] In addition, the compound represented by the above general formula (e) or (f) also preferably has an acyl group as R 2c , i.e., having the above acetate structure as OR 2c .

[0295] Specific examples of the titanium alkoxide compound used in the present invention are listed below, but the present invention is not limited to these specific examples.

[0296] Isopropyl triisostearoyl titanate

[0297] Isopropyl tri(dodecylbenzenesulfonyl) titanate

[0298] Isopropyl trioctanoyl titanate

[0299] Isopropyl tri(dioctyl phosphite) titanate

[0300] Isopropyl tri(dioctyl pyrophosphate) titanate

[0301] Isopropyl tri(dioctyl sulfate) titanate

[0302] Isopropyl tricumylphenyl titanate

[0303] Isopropyl tri(N-aminoethyl-aminoethyl) titanate

[0304] Isopropyl dimethacryloyl isostearyl titanate

[0305] Isopropyl isostearyl diacryloyl titanate

[0306] Isobutyl trimethyl titanate

[0307] Diisostearyl Ethylene Titanate

[0308] Diisopropyl bis(dioctyl pyrophosphate) titanate

[0309] Dioctyl bis(di-tridecyl phosphate) titanate

[0310] Dicumylphenyloxyacetate titanate

[0311] Bis(dioctyl pyrophosphate)oxyacetate titanate

[0312] Bis(dioctyl pyrophosphate)ethylene titanate

[0313] Tetraisopropyl titanate

[0314] Tetrabutyl titanate

[0315] Tetraoctyl titanate

[0316] Tetrastearyl Titanate

[0317] Tetraisopropyl bis(dioctylphosphite) titanate

[0318] Tetraoctylbis(di-tridecylphosphite) titanate

[0319] Tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate

[0320] Butyl Titanate Dimer

[0321] Titanium Tetraacetylacetonate

[0322] Titanium acetoacetate

[0323] Titanium Oxyethylene Glycolate

[0324] Bis(2-ethyl-3-hydroxyhexyl)titanium

[0325] The content of the silane coupling agent and the metal alkoxide compound in the primer layer is not particularly limited, but is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, particularly preferably 99% by mass or more, and may be 100% by mass.

[0326] The silane coupling agent, the aluminum alkoxide compound, the zirconium alkoxide compound, and the titanium alkoxide compound contained in the primer layer may be one kind or two or more kinds, respectively.

[0327] The primer layer may contain additives such as a surfactant, a thickener, a leveling agent, a stabilizer, and a defoaming agent in addition to the silane coupling agent and the metal alkoxide compound within a range that does not impair the effects of the present invention.

[0328] Furthermore, the primer layer may be a single layer or a multi-layer layer, but is preferably a single layer.

[0329] <Coating layer>

[0330] The flexible tube of the present invention has a coating layer on the outer periphery of a flexible tube base material provided with a primer layer.

[0331] In the present invention, the coating layer may be a single layer or a multilayer structure of two or more layers, preferably a single layer. In the present invention, when the coating layer is a single layer, the single layer of the coating layer contains a polyester having a naphthalene structure. In addition, when the coating layer is a multilayer structure of two or more layers, at least the innermost layer contains a polyester having a naphthalene structure. That is, in the present invention, the coating layer contains a polyester having a naphthalene structure in the innermost layer.

[0332] (Polyester with naphthalene structure)

[0333] Examples of the polyester having a naphthalene structure include polyester resins having a naphthalene structure and polyester elastomers having a naphthalene structure.

[0334] Preferred examples of the polyester having a naphthalene structure include polyesters composed of a dicarboxylic acid component including a naphthalene dicarboxylic acid component and a diol component.

[0335] A specific example of a dicarboxylic acid component that is preferable as the naphthalene dicarboxylic acid component is a 2,6-naphthalene dicarboxylic acid component.

[0336] First, the polyester resin having a naphthalene structure will be described.

[0337] The polyester resin having a naphthalene structure preferably has a naphthalene dicarboxylic acid component. The polyester resin having a naphthalene dicarboxylic acid component may have a dicarboxylic acid component other than the naphthalene dicarboxylic acid component as the dicarboxylic acid component.

[0338] The above-mentioned dicarboxylic acid components other than the naphthalene dicarboxylic acid component are not particularly limited, and substances generally used as dicarboxylic acid components constituting polyester resins can be widely used. For example, constituent components derived from terephthalic acid, isophthalic acid, phthalic acid (ortho-isomer), sodium 5-sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and cyclohexanedicarboxylic acid can be mentioned. One or more of these dicarboxylic acid components can be used.

[0339] The polyester resin having a naphthalene structure can be widely used as a diol component generally used as a polyester resin. For example, constituent components derived from ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, triethylene glycol, bisphenol A, and bisphenol S can be mentioned. One or more of these diol components can be used.

[0340] The polyester resin having a naphthalene structure may also have a hydroxycarboxylic acid component as a constituent component. Examples of the hydroxycarboxylic acid component include constituent components derived from ε-caprolactone, lactic acid, 4-hydroxybenzoic acid, etc. One or more of these hydroxycarboxylic acid components may be used.

[0341] The polyester resin having a naphthalene structure may be a homopolymer or a copolymer composed of the above components, and may further contain a small amount of a trifunctional compound component such as trimellitic acid, trimesic acid, pyromellitic acid, trimethylolpropane, glycerol, and pentaerythritol.

[0342] Furthermore, as the polyester resin having a naphthalene structure, two or more homopolymers or copolymers composed of the above components may be used in combination.

[0343] Next, the polyester elastomer having a naphthalene structure will be described.

[0344] The polyester elastomer having a naphthalene structure preferably has a naphthalene dicarboxylic acid component. More preferably, it is a copolymer consisting of a hard segment and a soft segment, wherein the hard segment is composed of a crystalline polyester chain having a dicarboxylic acid component including a naphthalene dicarboxylic acid component and a low molecular weight diol component as constituent components, and the soft segment is at least any one of the following (i) to (iii).

[0345] (i) a soft segment consisting of an aliphatic polyester chain;

[0346] (ii) a soft segment composed of an aliphatic polymer diol component;

[0347] (iii) a soft segment composed of a polyester chain composed of an aliphatic polymer diol component and a dicarboxylic acid component including an aromatic dicarboxylic acid

[0348] That is, the naphthalene structure may be introduced into any one or both of the hard segment and the soft segment, but is preferably introduced into at least the hard segment.

[0349] A specific example of a dicarboxylic acid component that is preferable as the naphthalene dicarboxylic acid component is a 2,6-naphthalene dicarboxylic acid component. The polyester elastomer having a naphthalene structure in the hard segment will be described below.

[0350] The polyester elastomer with a naphthalene structure preferably has a naphthalene dicarboxylic acid component in the hard segment. In the case where the hard segment has a naphthalene dicarboxylic acid component, all dicarboxylic acid components of the hard segment can be naphthalene dicarboxylic acid components, and the hard segment can also have dicarboxylic acid components other than the naphthalene dicarboxylic acid component. As dicarboxylic acid components other than the naphthalene dicarboxylic acid components constituting the hard segment, substances commonly used as dicarboxylic acid components of the hard segment constituting the common polyester elastomer can be widely used. For example, dicarboxylic acid components other than the naphthalene dicarboxylic acid components described in the description of the polyester resin with a naphthalene structure can be cited, and one or more of these dicarboxylic acid components can be included. Among them, the dicarboxylic acid components other than the naphthalene dicarboxylic acid components constituting the hard segment preferably include aromatic dicarboxylic acid components (dicarboxylic acid components with aromatic rings), preferably 50% or more of the dicarboxylic acid components other than the naphthalene dicarboxylic acid components (preferably 70% or more, more preferably 80% or more, more preferably 90% or more) are aromatic dicarboxylic acid components. In addition, all dicarboxylic acid components other than the naphthalene dicarboxylic acid components constituting the hard segment are also preferably aromatic dicarboxylic acid components.

[0351] As the diol component constituting the hard segment, a wide range of diol components generally used as diol components constituting polyester resins can be used, for example, the diol components described for the polyester resin having a naphthalene structure, and the hard segment may contain one or more of these diol components.

[0352] The hard segment may include one or two or more of the hydroxycarboxylic acid components described in the description of the polyester resin having a naphthalene structure as a constituent component.

[0353] The hard segment may be a homopolymer composed of the above-described components, or may be a copolymer.

[0354] When the soft segment is (i) an aliphatic polyester chain, the dicarboxylic acid component constituting the aliphatic polyester chain is not particularly limited as long as it is an aliphatic dicarboxylic acid component. For example, the aliphatic polyester chain may include components derived from oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexanedicarboxylic acid, etc. The aliphatic polyester chain may include one or more of these dicarboxylic acid components.

[0355] The diol component of the aliphatic polyester chain constituting the above-mentioned soft segment is not particularly limited as long as it is an aliphatic diol component. Examples thereof include aliphatic diol components such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 1,3-propanediol, 1,4-butanediol, 1,9-nonanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decanediol and cyclohexanedimethanol. It may contain one or more of these diol components. In addition, the aliphatic polyester chain also preferably contains an aliphatic polymer diol component as a diol component. Examples of the aliphatic polymer diol component include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, and it may contain one or more of these aliphatic polymer diol components. In the present invention, the polyalkylene glycol is HO-[(CH2) m O] n Here, m is preferably 1 to 12, more preferably 2 to 10, further preferably 2 to 8, further preferably 2 to 6. In addition, n is preferably 5 to 100, and more preferably 10 to 50.

[0356] In addition, when the soft segment is (ii) an amorphous soft segment derived from an aliphatic polymer diol, the aliphatic polymer diol is not particularly limited as long as it is an aliphatic polymer diol. Examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. The polyester elastomer may be configured to have a structure having aliphatic polymer diol components derived from one or more of these as soft segments. The structure of the polyalkylene glycol is as described above.

[0357] In addition, when the soft segment is (iii) a soft segment composed of a polyester chain, and the polyester chain is composed of an aliphatic polymer diol component and a dicarboxylic acid component containing an aromatic dicarboxylic acid, the aliphatic polymer diol component is not particularly limited, and for example, the constituent components derived from the aliphatic polymer diol described in (ii) above can be cited. In addition, as the aromatic dicarboxylic acid component, the constituent components derived from naphthalene dicarboxylic acid can be cited. In addition, in the case of containing a dicarboxylic acid component other than the aromatic dicarboxylic acid component, as the dicarboxylic acid component, the dicarboxylic acid component described in (i) above can be cited.

[0358] Examples of commercially available polyesters having a naphthalene structure include TQB-KET30 (manufactured by Teijin Chemicals Co., Ltd.) and PELPRENE EN type (manufactured by Toyobo Co., Ltd.).

[0359] The polyester having a naphthalene structure may be used alone or in combination of two or more.

[0360] The content of the polyester having a naphthalene structure in the covering layer when the covering layer is a single layer and the content of the polyester having a naphthalene structure in the innermost layer when the covering layer is a plurality of layers are preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more. In addition, the covering layer when the covering layer is a single layer may be a layer composed of the polyester having a naphthalene structure, and in addition, the innermost layer when the covering layer is a plurality of layers may be a layer composed of the polyester having a naphthalene structure.

[0361] When the coating layer is a single layer and the innermost layer is a blend of a polyester having a naphthalene structure and a polymer other than a polyester having a naphthalene structure, a wide range of polymers commonly used as coating materials constituting an endoscope flexible tube can be used as the polymer. Examples of such polymers include polyesters, polyurethanes, and polyamides that do not have a naphthalene structure.

[0362] In addition, the coating layer may contain various commonly used additives as appropriate within the range that does not impair the effects of the present invention. Examples of such additives include heat stabilizers, inorganic fillers, impact modifiers, plasticizers, lubricants, metal soaps, light fastness aids, and colorants. The content of the above additives in the coating layer may also be appropriately adjusted. Such additives may be derived from the material of the polyester having a naphthalene structure used, or may be added separately from the polyester having a naphthalene structure.

[0363] When the covering layer is a multi-layer structure, the layers other than the innermost layer also preferably contain a polyester having a naphthalene structure.

[0364] The above-mentioned polymers that can be used for the coating layer of the present invention preferably have a molecular weight of 10,000 to 1,000,000, more preferably 20,000 to 500,000, and even more preferably 50,000 to 300,000.

[0365] In the present invention, unless otherwise specified, the molecular weight of the polymer constituting the coating layer means the weight average molecular weight. The weight average molecular weight can be measured as a molecular weight in terms of polystyrene by gel permeation chromatography (GPC). Specific measurement conditions are shown below.

[0366] The measurement can be performed using a GPC apparatus HLC-8220 (trade name, manufactured by Tosoh Corporation), chloroform as an eluent, and G3000HXL+G2000HXL (both trade names, manufactured by Tosoh Corporation) as chromatographic columns, at 23°C and a flow rate of 1 mL / min, by gel permeation chromatography using an RI (differential refractive index) detector.

[0367] In the present specification, the number average molecular weight can be measured under the same conditions as the weight average molecular weight. In the present specification, when a numerical range of the weight average molecular weight of a compound is recorded, the numerical range is also preferably used as the numerical range of the number average molecular weight of the compound.

[0368] The flexible tube of the present invention makes the flexible tube base material and the coating layer closely adhere to each other through the primer layer, thereby making it possible to sufficiently maintain the close adhesion between the flexible tube base material and the coating layer covering the flexible tube even when the flexible tube is repeatedly bent, and the close adhesion between the flexible tube base material and the coating layer is unlikely to be reduced even by a strong sterilization treatment using ozone water. The reason for this is not clear, but it is considered as follows.

[0369] It is believed that polyester having a naphthalene structure can be strongly bonded to the flexible tube substrate via the primer layer because of its high affinity with a specific silane coupling agent or metal alkoxide compound. In addition, it is considered that the naphthalene structure-specific molecules can be configured such that the polyester is not easily peeled off even during bending due to the planar structure of the naphthalene ring.

[0370] It is also believed that the naphthalene structure has barrier properties due to the size of its molecular area, which hinders the movement and penetration of active species such as hydroxyl radicals that exhibit sterilization function in the above-mentioned coating layer. When the polyester having this structure is bonded to the flexible tube substrate via an alkoxide metal compound, not only can the adhesion between the coating layer and the flexible tube substrate be improved to a high level, but also, depending on the situation, due to the main reason such as π-π interaction, the naphthalene structure can be arranged in a position in the coating layer that can effectively hinder the movement and penetration of the above-mentioned active species.

[0371] <Top coating>

[0372] In the flexible tube of the present invention, a topcoat (not shown) may be provided as needed on the outer periphery of the coating layer 15. The material of the topcoat is not particularly limited, and urethane paint, acrylic paint, fluorine paint, silicone paint, epoxy paint, polyester paint, etc. may be used.

[0373] The main purpose of using the topcoat layer is to protect or polish the surface of the flexible tube, impart lubricity, and impart chemical resistance. Therefore, the topcoat layer is preferably a layer with a high elastic modulus, a smooth surface, and excellent chemical resistance.

[0374] <Method for manufacturing flexible tube>

[0375] (Formation of Primer Layer)

[0376] In the production of the flexible tube of the present invention, first, a primer layer is formed on the outer periphery of the flexible tube substrate. The primer layer can be formed by dissolving at least one of a silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound in a solvent to prepare a coating liquid, applying or spraying the coating liquid on the outer periphery of the flexible tube substrate, or immersing the flexible tube substrate in the coating liquid, etc., forming a coating film on at least the outer periphery of the flexible tube substrate, and then drying the coating film by a common method (e.g., high-temperature drying at 100° C. to 170° C.).

[0377] As the solvent used for the coating liquid, alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate; hydrocarbon solvents such as toluene; or a mixture of these solvents can be used. In addition, in order to promote the hydrolysis of the alkoxy group possessed by at least one of the aluminum alkoxide compound, the zirconium alkoxide compound and the titanium alkoxide compound, it is preferred to mix water with these solvents. The same is true for the case where the silane coupling agent has an alkoxy group. In addition, the pH of the coating liquid is not particularly limited. For example, by using a pH adjuster, it can be appropriately adjusted to acidic (e.g., pH 1 to 4 at 25°C) or alkaline (e.g., pH 9 to 11 at 25°C).

[0378] The content of at least one of the silane coupling agent, aluminum alkoxide compound, zirconium alkoxide compound and titanium alkoxide compound in the coating liquid is not particularly limited, and can be, for example, 0.01 to 2 mass %, preferably 0.05 mass % or more and less than 1.5 mass %, more preferably 0.1 mass % or more and less than 1.0 mass %.

[0379] The coating liquid may contain, in addition to a silane coupling agent, at least one of an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound, a solvent, and a pH adjuster, a surfactant, a catalyst, etc. The coating liquid is more preferably composed of a silane coupling agent, at least one of an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound, and a solvent.

[0380] In the present invention, a portion of the outer circumference of the flexible tube base material may have a portion not covered by the primer layer (that is, a defect may be formed in a portion of the primer layer) within a range not impairing the effects of the present invention.

[0381] Before forming the primer layer, the flexible tube substrate is preferably preliminarily degreased and cleaned with an alkaline solution, an aqueous surfactant solution, an organic solvent, etc. In addition, it is preferably preliminarily cleaned with water or warm water after the above cleaning. In addition, it is preferably preliminarily dried (for example, at 100° C. for 10 minutes) after the above cleaning with water or warm water.

[0382] (Formation of coating layer)

[0383] The manufacture of the flexible tube for endoscope of the present invention includes a step of forming a coating layer. The step of forming the coating layer includes: using a coating layer forming material containing polyester having a naphthalene structure, forming a coating layer on a primer layer formed on the outer periphery of the above-mentioned flexible tube substrate (in a manner of being in contact with the primer layer). The formation of the coating layer using the coating layer forming material itself can be carried out by a common method, for example, the coating layer can be formed by extrusion coating (forming temperature: 150 to 250° C.) the coating layer forming material. In addition, in the case where the above-mentioned coating layer forming material contains components other than the polyester having a naphthalene structure, the coating layer can be formed, for example, by mixing the components for the coating layer forming material using a twin-screw mixer and extruding the mixture.

[0384] <Endoscopic medical equipment>

[0385] The flexible tube of the present invention can be widely used for endoscopic medical equipment. It can also be applied to, for example, an instrument equipped with a clamp or a wire at the tip of an endoscope, or an instrument equipped with a basket or a brush. In addition, endoscopic medical equipment refers to medical equipment with an endoscope as the basic structure, and in a broad sense also includes medical and diagnostic equipment such as remote-operated medical equipment with a flexible insertion portion and introduced into the body for use.

[0386] The endoscopic medical device of the present invention has the endoscopic flexible tube of the present invention assembled in its insertion portion. That is, the manufacturing method of the endoscopic medical device of the present invention includes assembling the endoscopic flexible tube of the present invention or the endoscopic flexible tube obtained by the manufacturing method of the endoscopic flexible tube of the present invention in the insertion portion of the endoscopic medical device.

[0387] The preferred embodiment of the endoscopic medical device of the present invention is described by taking an electronic endoscope as an example. The electronic endoscope can be used as a medical device that is assembled with an endoscope flexible tube and the flexible tube is inserted into a body cavity to observe the body cavity. Figure 1In the example shown, the electronic endoscope 2 includes an insertion portion 3 inserted into a body cavity, a main body operation portion 5 connected to the base end portion of the insertion portion 3, and a universal cord 6 connected to a processor device or a light source device. The insertion portion 3 is composed of a flexible tube 3a connected to the main body operation portion 5, an angle portion 3b connected to the flexible tube 3a, and a top portion 3c connected to the front end of the angle portion 3b and having a built-in imaging device (not shown) for imaging in the body cavity. The flexible tube 3a, which occupies most of the length of the insertion portion 3, is flexible over almost the entire length, and in particular, the portion inserted into the interior of the body cavity is a more flexible structure.

[0388] <Flexible pipe>

[0389] The flexible tube has a flexible tube base material made of metal as an innermost layer.

[0390] like Figure 2 As shown, the flexible tube substrate 14 is preferably configured as follows: on the spiral tube 11 formed by winding the metal strip 11a into a spiral shape at the innermost side, a cylindrical mesh 12 formed by weaving metal wires is coated and a pipe head 13 is respectively embedded at both ends. The metal constituting the flexible tube substrate 14 is preferably subjected to a passivation treatment on its surface to prevent corrosion. That is, the flexible tube substrate 14 preferably has a passivation film on its periphery. The passivation treatment can be performed by a common method. For example, a passivation film can be formed on the metal surface by immersing in a solution containing a strong oxidant such as nitric acid, or heating in air (oxygen) or water (steam), or performing anodization in a solution containing an oxidant.

[0391] The metal constituting the flexible tube substrate 14 is preferably stainless steel. The surface of stainless steel is usually in a state where chromium and oxygen are bonded to form a passive film. However, even when stainless steel is used as the constituent material of the flexible tube substrate 14, it is preferable to perform the above-mentioned passivation treatment on the stainless steel in order to more reliably form a more uniform passive film on the entire stainless steel surface.

[0392] In the present embodiment, the coating layer 15 is formed with a substantially uniform thickness in the longitudinal direction (axial direction) of the flexible tube substrate 14. The thickness of the coating layer 15 is, for example, 0.1 to 0.6 mm, and the outer diameter D of the flexible tube 3a is, for example, 1.7 to 13.5 mm, preferably 3.0 to 8.0 mm. In addition, the outer diameter of the flexible tube substrate 14 is, for example, 1.6 to 12.5 mm, preferably 2.2 to 7.8 mm. In addition, when the flexible tube of the present invention is used for insertion into a bronchus, the thickness of the coating layer 15 is preferably 0.1 to 0.3 mm, the outer diameter D of the flexible tube 3a is preferably 3.0 to 5.0 mm, and the outer diameter of the flexible tube substrate 14 is preferably 2.4 to 4.8 mm.

[0393] [Example]

[0394] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not to be construed as being limited to these Examples.

[0395] <Preparation of coating layer forming materials>

[0396] In Examples 1 to 28 and 32, polyesters (R) having a naphthalene structure described in Tables 1-1 to 1-3 (hereinafter, at least one of Tables 1-1 to 1-3 is referred to as Table 1) described later were used.

[0397] In Examples 29 to 31, samples prepared as follows were used.

[0398] A composition prepared by mixing the polyester (R) having a naphthalene structure and other polymers (Q) described in Table 1 below in the proportions described in Table 1 below was introduced into a twin-screw kneader (KZW15-30MG, trade name, manufactured by TECHNOVEL) with the barrel temperature and die head temperature set at 220° C., and kneaded at a screw speed of 100 rpm. The molten strands discharged from the twin-screw kneader were cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped sample.

[0399] <Preparation of flexible tube base material>

[0400] Reference Figure 2 The flexible tube substrates used in Examples and Comparative Examples are described.

[0401] A spiral tube 11 is formed using a stainless steel metal strip 11a, and a flexible tube substrate in the form of the spiral tube 11 is covered with a cylindrical mesh 12 in which stainless steel fibers are woven. The flexible tube substrate has a length of 80 cm and a diameter of 12 mm. The stainless steel flexible tube substrate has a passivation layer formed on the surface by annealing (heat treatment) when forming the spiral tube and the cylindrical mesh.

[0402] <Preparation of coating solution for forming undercoat layer>

[0403] The undercoat layer-forming components listed in Table 1 below were dissolved in a solution prepared by mixing water and ethanol at a mass ratio of 5:75 to a concentration of 8.9 g / kg to prepare an undercoat layer-forming coating solution.

[0404] <Formation of Primer Layer>

[0405] The flexible tube substrate was immersed in a 7.5% sodium hydroxide aqueous solution at 60°C for 1 minute, washed and rinsed with distilled water. The flexible tube substrate was dried in an oven at 100°C for 10 minutes, immersed in the above-prepared coating solution for forming a primer layer at room temperature for 1 minute, and then dried in an oven at 160°C for 10 minutes. In this way, a flexible tube substrate having a primer layer on the outer periphery and the inner periphery was prepared.

[0406] <Formation of Coating Layer>

[0407] The outer circumference of the flexible tube substrate provided with the primer layer was extrusion-coated with the coating layer forming material prepared above (molding temperature: 220° C.) to produce an endoscope flexible tube having a coating layer. The coating layer had a thickness of 0.4 mm.

[0408] [Test Example 1 (peel resistance)]

[0409] The endoscope flexible tube manufactured as described above was subjected to bending operation.

[0410] Specifically, a cylindrical rod was placed against the center of the length direction of the endoscope flexible tube (40 cm from one end of the flexible tube in the axial direction), bent into a U-shape with a curvature radius of 5 cm, and then restored to a straight shape. This action was considered as one reciprocation, and 5,000 reciprocations were performed.

[0411] The coating layer of the endoscope flexible tube after the bending operation was cut with a width of 1 cm perpendicular to the axial direction (length direction) at a position 40 cm away from one end of the flexible tube (the center of the length direction) so that the incision reached the flexible tube base material. From both ends of the incision, a length of 10 cm was cut along the axial direction of the flexible tube so that the incision reached the flexible tube base material.

[0412] The flexible tube was subjected to a 90° peel test using a peel tester (trade name FGS-500TV, manufactured by Nidec Shinpo Co., Ltd.). The end of the cut was grasped and peeled in the axial direction at a constant speed of 2 mm / min to measure the peel strength (measured value X1 (N / cm)). The peel strength was measured using a dynamometer.

[0413] The 90° peel test was also performed on the endoscope flexible tube that was not subjected to the bending operation, and the peel strength (measured value Y1 (N / cm)) was measured. The value (%) obtained according to the following formula 1) was evaluated against the following criteria. "C" or above was considered acceptable.

[0414] Formula 1) 100×X1 / Y1(%)

[0415] <Evaluation Criteria>

[0416] AA: above 80%

[0417] A: 60% or more and less than 80%

[0418] B: 40% or more and less than 60%

[0419] C: 20% or more and less than 40%

[0420] D: Less than 20% (including completely peeled state)

[0421] [Test Example 2 (sterilization durability)]

[0422] The endoscope flexible tube produced as described above was subjected to ozone water treatment.

[0423] Specifically, an endoscope flexible tube was placed in the flow path of an ozone water generator ("OWM-10L10P" (trade name) manufactured by EcoDesign), and ozone water having an ozone concentration of 3 ppm was flowed at a flow rate of 1 L / min for 3 hours for treatment.

[0424] The above bending operation is applied to the flexible tube for endoscope after the ozone water treatment. The flexible tube for endoscope after the bending operation is cut into the incision in the same manner as above, and the peel strength is measured (measured value X2 (N / cm)). The value (%) obtained according to the following formula 2) is evaluated against the following criteria. "C" or above is qualified.

[0425] Formula 2) 100×X2 / Y1(%)

[0426] In Formula 2), Y1 has the same meaning as Y1 in Formula 1).

[0427] <Evaluation Criteria>

[0428] A: More than 80%

[0429] B: 60% or more and less than 80%

[0430] C: 40% or more and less than 60%

[0431] D: Less than 40% (including the state of peeling during processing)

[0432] [Table 1-1]

[0433]

[0434] [Table 1-2]

[0435]

[0436] [Table 1-3]

[0437]

[0438] <Explanation of terms in the table>

[0439] Example

[0440] Ratio: Comparative Example

[0441] [Polyester having a naphthalene structure (R)]

[0442] (R-1) A polyester elastomer having polybutylene naphthalate in a structural unit (manufactured by Toyobo Co., Ltd., trade name "PELPRENE EN-5000", weight average molecular weight 119,000)

[0443] (R-2) A polyester elastomer having polybutylene naphthalate in a structural unit (manufactured by Toyobo Co., Ltd., trade name "PELPRENE EN-1000", weight average molecular weight 131,000)

[0444] [Other polymers (Q)]

[0445] (Q-1) A polyester elastomer having polybutylene terephthalate in a structural unit (manufactured by Toyobo Co., Ltd., trade name "PELPRENE P-280B", weight average molecular weight 128,000)

[0446] (Q-2) Ether polyurethane elastomer (manufactured by Nippon Polyurethane Co., Ltd., trade name "MIRACTRAN E574PNAT", weight average molecular weight 145,000)

[0447] (Q-3) Polyamide elastomer (manufactured by Arkema, trade name "PEBAX 7233", weight average molecular weight 48,000)

[0448] <Silane coupling agent (S)>

[0449] -Compounds used in Examples-

[0450] (S-1): p-Styryltrimethoxysilane (trade name: KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0451] (S-2): 3-ureidopropyltrialkoxysilane (trade name: KBE-585A, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0452] (S-3): 3-isocyanatepropyltriethoxysilane (trade name: KBM-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0453] (S-4): Bis(3-trimethoxysilylpropyl)fumarate (trade name "SIB1834.5", manufactured by Gelest)

[0454] (S-5): tris(trimethoxysilylpropyl)isocyanurate (trade name: KBM-9659, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0455] (S-6): 3-trimethoxysilylpropylsuccinic anhydride (trade name: X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0456] -Compounds used in Comparative Examples-

[0457] (S-7): Vinyltrimethoxysilane (trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0458] (S-8): (3-methacryloxypropyl)trimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0459] (S-9): 3-Glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0460] (S-10): 3-aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0461] (S-11): 3-mercaptopropyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0462] <Titanium alkoxide compound (T)>

[0463] (T-1): Tetra-n-butyl titanate (trade name: ORGATICS TA-21, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0464] [Chemical formula 10]

[0465]

[0466] (T-2): n-butyl titanate dimer (trade name: ORGATICS TA-23, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0467] [Chemical formula 11]

[0468]

[0469] (T-3): Isopropyl triisostearoyl titanate (trade name: PLENACT TTS, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0470] [Chemical formula 12]

[0471]

[0472] (T-4): Dioctylbis(di-tridecyl phosphate) titanate (trade name: PLENACT 46B, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0473] [Chemical formula 13]

[0474]

[0475] (T-5): diisopropyl bis(dioctyl pyrophosphate) titanate (trade name: PLENACT 38S, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0476] [Chemical formula 14]

[0477]

[0478] (T-6): Bis(dioctyl pyrophosphate)oxyacetato titanate (trade name: PLENACT 138S, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0479] [Chemical formula 15]

[0480]

[0481] (T-7): Bis(dioctyl pyrophosphate)ethylene titanate (trade name: PLENACT 238S, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0482] [Chemical formula 16]

[0483]

[0484] (T-8): Isopropyl tris(N-aminoethyl-aminoethyl) titanate (trade name: PLENACT 44, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0485] [Chemical formula 17]

[0486]

[0487] (T-9): Isopropyl tri(dodecylbenzenesulfonyl) titanate (trade name: PLENACT 9SA, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0488] [Chemical formula 18]

[0489]

[0490] (T-10): Bis-2-ethylhexyloxybis(2-ethyl-3-hydroxyhexyl)titanium (trade name: ORGATICS TC-201, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0491] [Chemical formula 19]

[0492]

[0493] <Aluminum Alkoxide Compound (A)>

[0494] (A-1): Aluminum sec-butoxide (trade name: ASBD, manufactured by Kawaken Fine Chemicals Co., Ltd.)

[0495] [Chemical formula 20]

[0496]

[0497] (A-2): Aluminum triacetylacetonate (trade name: ORGATICS AL-3100, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0498] [Chemical formula 21]

[0499]

[0500] (A-3): Ethyl bisacetoacetate aluminum monoacetylacetonate (trade name: ORGATICS AL-3200, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0501] [Chemical formula 22]

[0502]

[0503] (A-4): Aluminum triacetoacetate (trade name: ORGATICS AL-3215, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0504] [Chemical formula 23]

[0505]

[0506] (A-5): Octadecyl aluminum diisopropyl acetoacetate (trade name: PLENACT AL-M, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0507] [Chemical formula 24]

[0508]

[0509] <Zirconium Alkoxide Compound (Z)>

[0510] (Z-1): Zirconium tetrapropoxide (trade name: ORGATICS ZA-45, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0511] [Chemical formula 25]

[0512]

[0513] (Z-2): Zirconium tetra-n-butoxide (trade name: ORGATICS ZA-65, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0514] [Chemical formula 26]

[0515]

[0516] (Z-3): Zirconium tetraacetylacetonate (trade name: ORGATICS ZC-150, manufactured by Matsumoto Fine Chemicals Co., Ltd.) [Chemical formula 27]

[0517]

[0518] (Z-4): ammonium zirconium lactate (trade name: ORGATICS ZC-300, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0519] [Chemical formula 28]

[0520]

[0521] (Z-5): tri-n-butyl zirconium stearate (trade name: ORGATICS ZC-320, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0522] [Chemical formula 29]

[0523]

[0524] (Z-6): tri-n-butoxymonoacetylacetonate zirconium (trade name: ORGATICS ZC-540, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0525] [Chemical formula 30]

[0526]

[0527] (Z-7): di-n-butoxybis(ethyl acetoacetate)zirconium (trade name: ORGATICS ZC-580, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0528] [Chemical formula 31]

[0529]

[0530] As shown in Table 1, since Comparative Example 1 did not use any of the silane coupling agent and the metal alkoxide compound specified in the present invention, its peeling resistance and sterilization durability were unacceptable.

[0531] Comparative Examples 2 to 6 failed at least in sterilization durability because they used silane coupling agents that did not meet the requirements of the present invention. This is probably because the sterilization durability of the silane coupling agents that did not meet the requirements of the present invention was low, or the bonding between the silane coupling agents and at least one of the flexible tube base material and the coating layer was easily cut.

[0532] The results of Comparative Examples 7 to 9 show that even when the metal alkoxide compound specified in the present invention is used, the peeling resistance and sterilization durability are unacceptable unless a polyester having a naphthalene structure is used in the coating layer.

[0533] In contrast, the peeling resistance and sterilization durability of Examples 1 to 32 of the present invention are all qualified. In particular, the results of Examples 7 to 32 show that the sterilization durability can be improved to a higher level (all evaluated as "B" or above) by using the alkoxide metal compound specified in the present invention in the primer layer.

[0534] The present invention has been described together with its embodiments, but we believe that our invention is not limited to any details described unless otherwise specified, and should be broadly interpreted without violating the spirit and scope of the invention set forth in the attached claims.

[0535] This application claims priority based on Japanese Patent Application No. 2020-111755 filed in Japan on June 29, 2020, the contents of which are incorporated herein by reference as a part of the description of this specification.

[0536] Explanation of symbols

[0537] 2Electronic endoscope (endoscope)

[0538] 3 Insertion

[0539] 3a Flexible pipe

[0540] 3b corner

[0541] 3c Top

[0542] 5Main operating unit

[0543] 6 Universal Cord

[0544] 11 spiral tube

[0545] 11a Metal strip

[0546] 12 cylindrical mesh

[0547] 13 Tube Head

[0548] 14 Flexible tube base material

[0549] 15 Coating layer

Claims

1. A flexible tube for an endoscope, comprising: Flexible pipe base material made of metal, and a coating layer covering the outer periphery of the flexible tube base material, in, A primer layer containing at least one of a silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound and a titanium alkoxide compound is provided between the flexible tube substrate and the coating layer, and the coating layer contains a polyester having a naphthalene structure at least on one side in contact with the primer layer. The silane coupling agent does not include vinyl silane coupling agent, (meth) acrylic silane coupling agent, epoxy silane coupling agent, amino silane coupling agent and sulfanyl silane coupling agent.

2. The endoscope flexible tube according to claim 1, wherein: The silane coupling agent includes a compound represented by the following general formula (1): [Chemical formula 1] General formula (1) In the formula, LL 1 represents a univalent substituent or an n1-valent connecting group; L 1 represents a single bond or a divalent connecting group; Y 1 ~Y 3 represents a substituent; n1 is an integer from 1 to 4, Among them, Y 1 ~Y 3 At least one of them is a group selected from an alkoxy group and a hydroxyl group, and when n1 is 1, all LL 1 LL 1 -L 1 and Y 1 ~Y 3 All represent groups selected from alkoxy and hydroxy groups; the compound represented by the general formula (1) does not include vinyl silane coupling agents, (meth) acrylic silane coupling agents, epoxy silane coupling agents, amino silane coupling agents and sulfanyl silane coupling agents.

3. The endoscope flexible tube according to claim 2, wherein: The compound represented by the general formula (1) includes a compound represented by any one of the following general formulas (2) to (4), [Chemical formula 2] General formula (2) General formula (3) General formula (4) In the formula, LL 1a represents a hydrogen atom, an alicyclic group, a heterocyclic group, a hydroxyl group, a sulfanyl group, an isocyanate group, a thiocyanate group, a urea group, a cyano group, an acid anhydride group, an azido group, a carboxyl group, an acyl group, a thiocarbamoyl group, a phosphoric acid group, a phosphino group, a sulfonic acid group or an amoyl group; L 2 represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, an ester bond, a thioester bond, an amide bond, a sulfamide bond or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds; L 3 ~L 5 represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, an ester bond, a thioester bond, an amide bond, a sulfamide bond, a urea bond, a thiourea bond or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds; LL 1b represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, a divalent heterocyclic group, an amide bond, an ester bond, a thioester bond, a divalent phosphate group, a phosphanediyl group or a sulfonyl group, or a divalent group formed by combining two or more of these groups or bonds; LL 1c represents an n2-valent alkane, an n2-valent olefin, an n2-valent alkyne, an n2-valent aromatic hydrocarbon, an n2-valent heterocyclic group, a trivalent phosphoric acid group, a phosphane triyl group, or an isocyanurate group, or a combination of these groups with an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NR a -, an n2-valent group consisting of a group or a combination of two or more of an ester bond, a thioester bond, an amide bond, a sulfamide bond and a sulfonyl group; R a represents a hydrogen atom or a substituent; Y 4 , Y 7 , Y 10 and Y 13 represents a hydroxyl group or an alkoxy group; Y 5 , Y 6 , Y 8 , Y 9 , Y 11 , Y 12 , Y 14 and Y 15 represents a hydroxyl group, an alkoxy group, an alkyl group or a ketoximate group; n2 is 3 or 4; The compound represented by any one of the general formulae (2) to (4) does not include a vinyl silane coupling agent, a (meth)acrylic silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, and a sulfanyl silane coupling agent.

4. The endoscope flexible tube according to any one of claims 1 to 3, wherein The aluminum alkoxide compound includes a compound represented by the following general formula (a) or (b), General formula (a): R 1a m1 -Al-(OR 2a ) 3-m1 General formula (b): O-[Al-(OR 2a )2]2 R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group; R 2a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S1 ; R S1 represents a substituent; m1 is an integer from 0 to 2.

5. The endoscope flexible tube according to claim 4, wherein: In the general formulae (a) and (b), OR 2a At least one of the compounds has an acetonate structure or an acetate structure.

6. The endoscope flexible tube according to any one of claims 1 to 3, wherein The zirconium alkoxide compound includes a compound represented by the following general formula (c) or (d), General formula (c): R 1b m2 -Zr-(OR 2b ) 4-m2 General formula (d): O-[Zr-(OR 2b )3]2 R 1b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group; R 2b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S2 ; R S2 represents a substituent; m2 is an integer from 0 to 3.

7. The endoscope flexible tube according to claim 6, wherein: In the general formulae (c) and (d), OR 2b At least one of the compounds has an acetonate structure, an acetate structure or a lactate structure.

8. The endoscope flexible tube according to any one of claims 1 to 3, wherein The titanium alkoxide compound includes a compound represented by the general formula (e) or (f), General formula (e): R 1c m3 -Ti-(OR 2c ) 4-m3 General formula (f): O-[Ti-(OR 2c )3]2 R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group; R 2c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S3 ; R S3 represents a substituent; m3 is an integer from 0 to 3.

9. The endoscope flexible tube according to claim 8, wherein: The compound represented by the general formula (e) or (f) contains at least one atom of N, P and S.

10. The endoscope flexible tube according to any one of claims 1 to 3, wherein The metal constituting the base material of the flexible tube is stainless steel.

11. The endoscope flexible tube according to any one of claims 1 to 3, wherein The metal constituting the flexible tube base material has a passivation film on the surface. 12 . An endoscopic medical device comprising the endoscopic flexible tube according to claim 1 .

13. A method for manufacturing a flexible tube for an endoscope, wherein: include: forming a primer layer including at least one of a silane coupling agent, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound on at least the outer periphery of a flexible tube substrate made of metal; and a step of forming a covering layer on the primer layer formed on the outer periphery of the flexible tube substrate by using a covering layer forming material containing a polyester having a naphthalene structure, The silane coupling agent does not include vinyl silane coupling agent, (meth) acrylic silane coupling agent, epoxy silane coupling agent, amino silane coupling agent and sulfanyl silane coupling agent.

14. A method for manufacturing an endoscopic medical device, wherein: include: A step of obtaining the flexible tube for an endoscope by the method for manufacturing the flexible tube for an endoscope according to claim 13; as well as A step of assembling the obtained endoscope flexible tube to an insertion portion of an endoscope type medical device.

15. A method for manufacturing an endoscopic medical device, wherein: include: The endoscope flexible tube according to any one of claims 1 to 11 is assembled to an insertion portion of an endoscope type medical device.

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