JP2018068811A - Tracheal tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tracheal tube capable of sucking and removing phlegm or the like in the trachea without placing any burden on a patient.SOLUTION: The tracheal tube includes: a distal end 16 disposed at a lung side in the trachea; a proximal end at an opposite side of the distal end; and a lumen body 12 provided with an airway securing lumen 20 penetrating from the proximal end to the distal end. The lumen body includes suction lumens 40, 42, 46, and 48 formed in a wall along the airway securing lumen and opened to a wall surface of an end part in the distal end side of the airway securing lumen. Further, the suction lumens include: water-repellent membranes 40b, 42b, 46b, and 48b on at least parts of wall surfaces of end parts in the distal end side; and hydrophilic membranes 40a, 42a, 46a, and 48a at least parts of the wall surfaces in the proximal end side with respective to the water-repellent membranes thereof.SELECTED DRAWING: Figure 3

Description

  The present invention relates to tracheal tubes such as tracheostomy tubes and endotracheal tubes.

For patients who have difficulty in spontaneous breathing or who have difficulty in draining sputum on their own, methods for securing an airway for breathing or sputum discharge include, for example, tracheal intubation, tracheostomy, cricoid incision In addition, methods such as cricoid puncture are known.
Tracheal intubation is a method of inserting a tracheal tube from the mouth or nose into the trachea via the pharynx. Tracheostomy (surgical tracheostomy) is a method for cases where endotracheal intubation is prolonged or when tracheal intubation is not possible. It is a method of inserting a tube for trachea called. Annular thyroid incision is a method for urgently securing an airway, and is a method of incising an annular thyroid membrane (annular thyroid ligament) and inserting a tracheal cannula. Furthermore, the cricoid puncture is a method of inserting a tracheal cannula by puncturing the cricoid thyroid.

Medical personnel connect a ventilator to such a tracheal tube (tracheal cannula) to maintain patient breathing, or insert a suction catheter into the tracheal tube to aspirate foreign material such as stored sputum It has been removed.
In such a tracheal tube, various proposals have been made to reduce the burden on the patient.

For example, Patent Document 1 discloses that in a tracheal tube (tracheal cannula) having a cuff for fixing the tracheal tube at a predetermined position of the trachea, in addition to the airway securing lumen (respiratory tract), there A tracheal tube is described in which a suction path is provided for sucking air, and the suction path opens to the tip side of the cuff of the tube wall surface.
By having such a configuration, the tracheal tube of Patent Document 1 enables suction of sputum at an early stage after the occurrence of sputum, and also enables suction of sputum that has entered the lumen for securing the airway. I have to.

Further, in Patent Document 2, as in Patent Document 1, in the tracheal tube (tracheal tube) provided with a suction path for sucking sputum in the tube wall separately from the airway securing lumen, the suction path is A tracheal tube that opens only on the inner wall surface of the tracheal tube is described.
By having such a configuration, the tracheal tube of Patent Document 2 prevents mucosal damage due to the tracheal mucosa being continuously sucked into the suction port of the sputum.

International Publication No. 2006/035769 JP 2011-156246 A

According to the tracheal tube of Patent Document 1 and Patent Document 2, the burden on the patient wearing the tracheal tube can be reduced by preventing rapid suction of sputum and damage to the tracheal mucosa.
However, the burden on the patient wearing the tracheal tube is preferably small, and the appearance of a tracheal tube capable of sucking sputum generated in the trachea is desired.

  An object of the present invention is to solve such problems of the prior art, and to provide a tracheal tube that can more appropriately suck the soot generated in the trachea.

  As a result of intensive studies by the present inventors, it has been found that the above object can be achieved by adopting the following configuration.

That is, the tracheal tube of the present invention has a distal end portion disposed on the lung side in the trachea, a proximal end portion provided on the opposite side of the distal end portion, and an airway securing lumen penetrating from the proximal end portion to the distal end portion. A tracheal tube having a provided luminal body,
The lumen body has a suction lumen that is formed in the wall along the airway securing lumen and that opens to the wall surface of the end portion of the distal end side of the airway securing lumen;
Further, a water repellent film is provided on at least a part of the wall surface at the distal end side of the suction lumen, and a hydrophilic film is provided on at least a part of the wall surface on the proximal end side of the water repellent film of the suction lumen. A tracheal tube is provided.

In such a tracheal tube of the present invention, the hydrophilic film has a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), and It is preferable that the copolymer A contains 0.6 to 7 mol% of the repeating unit (A) with respect to all repeating units.
However, in Formula (1), R < ¹¹ > is a hydrogen atom or a methyl group, Z is an oxygen atom or -NH-, R < ¹² > is a C1-C6 alkylene group, R <^13> and R ¹⁴ is independently an alkyl group having 1 to 4 carbon atoms, and R ¹⁵ is an alkylene group having 1 to 6 carbon atoms.
In Formula (2), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkylene group having 1 to 6 carbon atoms, and R ²³ is an alkyl group having 1 to 4 carbon atoms.
Moreover, it is preferable that a hydrophilic membrane | film | coat crosslinks the polymer B which has the site | part which expresses lubricity, and the site | part which has crosslinkability.
Moreover, it is preferable that the site | part which expresses lubricity is a site | part originating in (meth) acrylamide or a (meth) acrylamide derivative.
Moreover, it is preferable that the site | part which has crosslinkability is a site | part which has an epoxy group.
The tracheal tube is preferably used as a tracheostomy tube.
The tracheal tube is preferably used as a double-tube tracheotomy tube.
Further, the tracheal tube is preferably used as an endotracheal tube.
The tracheal tube is suitably used as a tracheal cannula that can be inserted into the trachea through a puncture hole or an incision hole in an annular thyroid membrane.
The tracheal tube is suitably used as a tracheal cannula that can puncture the annular thyroid membrane.
The tracheal tube is preferably used as a small tracheostomy tube.

  ADVANTAGE OF THE INVENTION According to this invention, the tube for trachea which can perform the suction | suction of a sputum suitably can be provided.

It is a figure which shows notionally the state with which the patient was equipped with an example of the tracheostomy tube which is the tube for trachea of this invention. It is sectional drawing which shows notionally the principal part of the tracheostomy tube shown in FIG. It is sectional drawing which shows notionally the front-end | tip part of the tracheostomy tube shown in FIG. (A) And (B) is a figure which shows notionally the cross section of the lumen body of an example of the tracheostomy tube of this invention. (A) And (B) is sectional drawing which shows typically an example of the water layer of the hydrophilic membrane | film | coat A. FIG. (A) And (B) is sectional drawing which shows typically an example of the water layer of the hydrophilic membrane | film | coat B. FIG.

  Hereinafter, the tube for trachea of the present invention will be described in detail based on a preferred embodiment shown in the accompanying drawings.

  In the present invention, “痰” is a kind of mucus and is a viscous fluid showing a slimy property secreted from mucous membranes such as trachea. When pulling up, it has the property of pulling a thread) and viscoelasticity (like rubber, it stretches when it is grabbed and lifted, returns to its original shape when released, and breaks when stretched more than a certain amount) . Examples of the main components of koji include water and glycoproteins such as mucin.

FIG. 1 conceptually shows an example in which the tracheal tube of the present invention is used as a tracheostomy tube, which is attached to a patient. FIG. 2 conceptually shows a cross-sectional view of the tracheostomy tube shown in FIG.
A tracheostomy tube 10 shown in FIGS. 1 and 2 is an instrument for performing respiratory management of a patient, and is used in a state where the tracheostomy tube is directly inserted into the trachea B through an incision hole formed by incising the trachea.
The tracheostomy tube 10 includes a lumen body 12 constituting a main part of the tracheostomy tube 10 and a fixing portion 14 for fixing the lumen body 12 to a patient.

The luminal body 12 has a cylindrical shape having both ends opened and a uniform outer diameter and inner diameter along the length direction, and a distal end portion that becomes the lung side in the trachea B when attached to a patient. 16, a proximal end portion 18 on the opposite side of the distal end portion 16, and a curved portion 17 between the distal end portion 16 and the proximal end portion. However, as shown in FIG. 2 and FIG. 3 to be described later, the end portion on the tip end portion 16 side has a tapered shape (taper portion 16a) in which the outer diameter is gradually reduced toward the end portion. .
The curved portion 17 is curved so that the central axis of the distal end portion 16 and the central axis of the proximal end portion 18 intersect at an angle θ. In FIG. 2A, the lumen body 12 is formed in a substantially L shape. That is, the angle θ is about 90 °.
In addition, the lumen body 12 has such flexibility that the θ can be changed in a range from about 90 ° to about 120 ° in accordance with a change in the posture of the patient. The hydrophilic film described later does not peel off or drop off from the suction lumen described later even when the θ changes within this range.

  As described above, the lumen body 12 has a cylindrical shape and includes the airway securing lumen 20 penetrating from the end portion on the proximal end portion 18 side to the end portion on the distal end portion 16 side.

The tracheostomy tube 10 has a cuff (cuff balloon) 24 for fixing the distal end portion 16 of the tracheostomy tube 10 at a predetermined position of the trachea B at the distal end portion 16 as a preferred embodiment.
The cuff 24 is a known one provided on the tracheostomy tube 10 and can be inflated or deflated by introducing and discharging air. Although illustration is omitted, in the tracheostomy tube 10, the lumen body 12 is provided with a tube communicating with the cuff 24 for introducing and discharging air to the cuff 24.

The lumen body 12 and the cuff 24 may be formed of various materials used for a tracheostomy tube (tracheal tube). As an example, synthetic resins such as silicone, polycarbonate, polypropylene, polyethylene, and polyvinyl chloride can be exemplified.
In this case, the inner surface of the lumen body 12 that forms the airway securing lumen 20 is also formed of the synthetic resin. The lumen body 12 and the cuff 24 may be formed of the same material or different materials.

As shown in FIGS. 1 and 2, the tracheostomy tube 10 incises the wall of the trachea B and the skin S above the trachea B for a patient who is lying on his back (the supine position). The distal end portion 16 of the luminal body 12 is inserted into the trachea B through the tracheostomy hole formed in (1).
At this time, the distal end portion 16 of the luminal body 12 inflates the cuff 24 so as to be spaced apart from the mucous membranes (skin-side tracheal mucosa Ba, body inner tracheal mucosa Bb) constituting the tube wall of the trachea B. And placed in the trachea B toward the lung side and fixed.

Further, the proximal end portion 18 of the lumen body 12 is exposed to the outside through the tracheostomy hole, and a ventilator (not shown) is attached to the proximal end portion 18.
By operating the ventilator, exhaled air and inhaled air (respiratory air) pass through the lumen 20 for airway maintenance. Thereby, the patient's breathing is sustained and respiratory management is performed. As a result, it is possible to prevent the airway, which is a passage for oxygen necessary for breathing, from being blocked, and to manage the patient's breathing.

The fixing portion 14 is attached to the proximal end portion 18 of the lumen body 12. The fixing portion 14 fixes the distal end portion 16 at an appropriate position in the trachea B by contacting the skin S when the lumen body 12 is attached to the patient. 32.
The fixed plate 30 is a flat plate member, and a storage hole 34 penetrating the fixed plate 30 is formed at the center. And the adhesion part 32 is attached to the surface of the fixing plate 30, and the back surface of the fixing plate 30 contacts the skin S of the patient.
The bonding portion 32 is for bonding the lumen body 12 to the fixing portion 14 and has a ring shape in which a substantially circular through hole 36 is formed at the center. The through hole 36 of the bonding portion 32 communicates with the storage hole 34 of the fixing plate 30, and the size of the through hole 36 is set according to the outer diameter of the lumen body 12.
The lumen body 12 passes through the accommodation hole 34 of the fixing plate 30 and the through hole 36 of the bonding portion 32 and is fixed by, for example, an adhesive.

FIG. 3 conceptually shows the vicinity of the tip on the tip 16 side.
As described above, the end of the lumen body 12 on the distal end portion 16 side is a tapered portion 16a having an outer diameter that gradually decreases toward the end.
As shown in FIGS. 2 and 3, the first suction lumen 40, the second suction lumen 42, the third suction lumen 46, and the fourth suction are arranged in the wall of the lumen body 12 along the airway securing lumen 20. Lumen 48 is formed. The first suction lumen 40, the second suction lumen 42, the third suction lumen 46, and the fourth suction lumen 48 are preferably provided in parallel (substantially parallel) to the airway securing lumen 20.

The first suction lumen 40 opens to the tapered portion 16a at the end on the distal end portion 16 side (opening 40a). The second suction lumen 42 opens at the end surface of the end portion on the distal end portion 16 side (opening 42a). The third suction lumen 46 is a characteristic part of the present invention and opens to the wall surface of the airway securing lumen 20 (inner wall surface of the lumen body 12) in the vicinity of the end portion on the distal end portion 16 side (opening 46a). Further, the fourth suction lumen 48 opens slightly to the outer wall surface of the lumen body 12 on the proximal end portion 18 side than the cuff 24 of the distal end portion 16 (opening 48a).
Each suction lumen is formed along the airway securing lumen 20 from the respective opening to the bonding portion 32. Each suction lumen is bent toward the outer wall surface of the lumen body 12 at a position corresponding to the bonding portion 32 in the longitudinal direction of the airway securing lumen 20, penetrates the bonding portion 32, and passes through the outer wall surface of the bonding portion 32. Open to.
A suction tube 40 t is connected to the opening of the outer wall surface of the adhesive portion 32 of the first suction lumen 40. A suction tube 42 t is connected to the opening of the outer wall surface of the adhesive portion 32 of the second suction lumen 42. A suction tube 46 t is connected to the opening of the outer wall surface of the bonding portion 32 of the third suction lumen 46. Further, a suction tube 48 t is connected to the opening of the outer wall surface of the adhesive portion 32 of the fourth suction lumen 48. Note that the suction tube is omitted in FIG.

Therefore, by performing suction from the suction tube connected to each suction lumen, the wrinkles near the end on the distal end portion 16 side can be sucked and removed from the opening of each suction lumen.
Specifically, by performing suction from the suction tube 40t connected to the first suction lumen 40, it adheres to the tracheal mucosa near the end on the distal end portion 16 side from the opening 40a formed in the tapered portion 16a. The sputum can be removed by suction.
By performing suction from the suction tube 42t connected to the second suction lumen 42, from the opening 42a formed on the end face on the end portion 16 side, the ridge near the end portion on the end portion 16 side, The wrinkles adhering to the end surface of the end portion on the tip end portion 16 side can be sucked and removed.
By performing suction from the suction tube 46t connected to the third suction lumen 46, the soot adhering to the wall surface of the airway securing lumen 20 in the vicinity of the end portion on the distal end portion 16 side can be removed by suction.
Furthermore, by sucking from the suction tube 48 t connected to the fourth suction lumen 48, the patient's aspiration can be sucked and removed.

  That is, according to the tracheostomy tube 10, the patient is burdened with wrinkles and foreign matter that are difficult to be sucked by the suction catheter, such as wrinkles adhering to the vicinity of the end of the tracheostomy tube 10 on the distal end portion 16 side and aspiration of the patient. Can be removed by suction without giving.

In FIG. 2 and FIG. 3, four suction lumens are shown on the diameter of the cylindrical lumen body 12 in order to clearly show the configuration of the suction lumens. It is formed at a different position in the circumferential direction of the body 12.
In the tracheostomy tube 10, it is preferable that the lumen body 12 has a smaller outer diameter, and the lumen, that is, the airway securing lumen 20, is thicker. That is, it is preferable that the thickness of the wall forming the lumen body 12, that is, the tube thickness of the lumen body 12, be thinner. Therefore, normally, the four suction lumens are arranged around the periphery of the cylindrical lumen body 12 as conceptually shown in the sectional view of the lumen body 12 in FIG. 4A (cross section taken along line AA in FIG. 2). They are formed at different positions.
However, the present invention is not limited to this. For example, as conceptually shown in the cross-sectional view of the luminal body 12 in FIG. May be formed on the diameter of the lumen body 12, and the other two suction lumens may be formed at different circumferential positions of the cylindrical lumen body 12. Alternatively, when the wall thickness of the lumen body 12, that is, the tube wall thickness of the lumen body 12 is sufficient, four suction lumens are formed on the diameter of the lumen body 12 as shown in FIGS. May be provided.

Here, in the tracheostomy tube (tracheal tube) of the present invention, a water-repellent film is formed on the wall surface of the end portion (on the end portion and in the vicinity of the end portion) on the distal end portion 16 side of the suction lumen. Further, a hydrophilic film is formed on the side of the base end portion 18 side of the water repellent film on the wall of the suction lumen. In the following description, the “end on the tip 16 side” of the suction lumen is also simply referred to as “tip”.
The water-repellent film may be formed on at least a part of the wall surface of the distal end portion of the suction lumen, but is preferably formed on the entire wall surface of the distal end portion of the suction lumen. Further, the hydrophilic film may be formed on at least a part of the wall surface of the suction lumen on the side of the base end part 18 from the water repellent film, but preferably the wall surface of the suction lumen on the side of the base end part 18 side. Form on the entire surface.

Specifically, as conceptually shown in FIG. 3, a water repellent coating 40 b is formed on the wall surface of the distal end portion of the first suction lumen 40. Further, a hydrophilic film 40c is formed on the wall surface of the first suction lumen 40 on the proximal end portion 18 side from the water repellent coating 40b from the end portion on the proximal end portion 18 side of the water repellent coating 40b to the adhesive portion 32. .
A water repellent coating 42 b is formed on the wall surface of the distal end portion of the second suction lumen 42. Further, a hydrophilic film 42c is formed on the wall surface of the second suction lumen 42 on the proximal end 18 side from the water repellent film 42b from the end of the water repellent film 42b on the proximal end 18 side to the adhesive portion 32. .
A water repellent film 46 b is formed on the wall surface of the tip of the third suction lumen 46. A hydrophilic film 46 c is formed on the wall surface of the third suction lumen 46 closer to the base end 18 than the water repellent film 46 b from the end of the water repellent film 46 b on the base end 18 side to the adhesive portion 32. .
Further, a water repellent film 48 b is formed on the wall surface at the tip of the fourth suction lumen 48. Further, a hydrophilic film 48c is formed on the wall surface of the fourth suction lumen 48 on the base end 18 side from the water repellent film 48b from the end of the water repellent film 48b on the base end 18 side to the adhesive portion 32. .

In the present invention, water repellency is a property of repelling water, and a water repellent coating is a surface on which water droplets roll when an inclination angle is 30 ° and water droplets are dropped by 100 μL each.
More preferably, the water-repellent film has repellency. The repellency refers to the property of repelling wrinkles. Specifically, the water-repellent coating (repellent coating) is preferably a surface on which the wrinkles roll when an inclination angle is 30 ° and 100 μL of the wrinkles are dropped there.

In the tracheostomy tube 10 (tracheal tube) of the present invention, the third suction lumen 46, preferably all the suction lumens, have such a water-repellent film and a hydrophilic film, so that the water-repellent film at the tip is provided. The suction lumen can be easily taken into the suction lumen near the opening of the suction lumen, and the suction lumen can be partially filled with soot by the hydrophilic film. It can suck out the sputum with force and discharge it from the suction lumen.
As will be described later, since the suction lumen has a hydrophilic film (water layer), it is possible to prevent the suction lumen from being attached to the suction lumen and blocking the suction lumen.

In the present invention, the end of the suction lumen that forms the water-repellent film on the tip 16 side (the end and the vicinity of the end), that is, the tip of the suction lumen that forms the water-repellent film refers to the suction lumen. One of the regions selected from the region of 1 to 20 mm from the opening on the distal end portion 16 side to the proximal end portion 18 side is shown. Therefore, in the present invention, the distal end portion of the suction lumen forming the water repellent film has a region extending from the opening on the distal end portion 16 side of the suction lumen to 3 mm on the proximal end portion 18 side, from the opening on the distal end portion 16 side of the suction lumen. What is necessary is just to set suitably between the area | region from 1-20 mm to the base end part 18 side from the opening by the side of the front-end | tip part 18 side of a suction lumen, such as an area | region to 18 mm on the base end part 18 side.
In the present invention, the distal end portion of the suction lumen is preferably any region selected from an opening of 1 to 10 mm on the proximal end portion 18 side from the opening on the distal end portion 16 side of the suction lumen. It is.
When the suction lumen opens at a tapered position like the opening 40a, the tip of the suction lumen forming the water repellent film is positioned on the tip side of the opening on the tip 16 side of the suction lumen. To any one of the areas of 1 to 20 mm on the base end 18 side with the position closest to the base end 18 of the opening as a base point. That is, in FIG. 3, from the position on the lower side in the drawing of the opening 40a of the first suction lumen 40 to the base end portion 18 side starting from the position on the upper side in the drawing of the opening 40a of the first suction lumen 40. Any region selected between regions up to 20 mm is defined as the tip of the first suction lumen 40 that forms the water-repellent film.

  In the present invention, the water-repellent coatings 40b, 42b, 46b, and 48b are not particularly limited, and a known water-repellent coating (water-repellent coating layer) such as a fluorine-based resin coating or a silicone-based resin coating, Various types are available.

  As a preferable water-repellent film, a water-repellent film having metal oxide composite particles composed of metal oxide particles and a fluorine-based resin formed on the surface thereof is exemplified.

  The metal oxide particles are not particularly limited as long as they can serve as the core of the metal oxide composite particles. For example, particles such as silicon oxide (silica), titanium oxide (titania), aluminum oxide (alumina), and zinc oxide ( At least one of (powder) can be used. In the present invention, the metal oxide particles are preferably at least one selected from the group consisting of silicon oxide (silica) particles, titanium oxide (titania) particles and aluminum oxide (alumina) particles, and silicon oxide (silica) particles. Is more preferable.

  The shape of the particles is not particularly limited, and may be various shapes such as a spherical shape, a spheroid shape, a cylindrical shape, a rod shape, and a plate shape.

  Moreover, the average primary particle diameter of the metal oxide particles is not particularly limited, but is preferably 5 to 50 nm, and more preferably 7 to 30 nm. When the average primary particle diameter of the metal oxide particles is within this range, more excellent repellency can be obtained.

Known or commercially available metal oxide particles can be used.
Examples of the silicon oxide particles include AEROSIL ^(R) 200 (average primary particle size: about 12 nm), AEROSIL ^(R) 200 FAD (average primary particle size: about 12 nm), AEROSIL ^(R) 130 (average primary particles). diameter: about ^{16nm), AEROSIL (R) 300} ( average primary particle diameter: about ^{7nm), AEROSIL (R) 50} ( average primary particle diameter: about ^{30nm), AEROSIL (R) 380} ( average primary particle diameter: Examples thereof include fumed silica products sold under a trade name such as about 7 nm (above, manufactured by Nippon Aerosil Co., Ltd.).
Examples of the titanium oxide particles include fumed titania products sold under trade names such as AEROXIDE ^(R) TiO ₂ T805 (average primary particle size: about 21 nm) (manufactured by Evonik Degussa). .
Examples of the aluminum oxide particles include fumed alumina products sold under trade names such as AEROXIDE ^(R) Alu C 805 (Evonik Degussa).

  The metal oxide composite particles constituting this water-repellent film contain a fluororesin. By using a fluororesin, it is possible to form a strong coating layer with relatively high adhesion on the surface of the metal oxide particles because of its excellent affinity with metal oxide particles (particularly silicon oxide particles), High water repellency (repellency) can also be expressed.

The fluorine-based resin is not particularly limited as long as it can be a coating layer of the metal oxide composite particles, and examples thereof include a fluorine-containing acrylic resin, a fluorine-containing urethane resin, and a fluorine-containing acrylic urethane resin.
The fluorine-containing acrylic resin is not particularly limited, but a homopolymer of fluoroalkyl (meth) acrylate or a copolymer containing fluoroalkyl (meth) acrylate as a monomer is preferable, and a copolymer containing fluoroalkyl methacrylate as a monomer is preferable. A polymer (polyfluoroalkyl methacrylate resin) is more preferable.
In the tracheostomy tube 10 of the present invention, the water-repellent film may be formed using only these resins without using metal oxide particles.

  A known or commercially available polyfluoroalkyl methacrylate resin can be used. Examples of commercially available products include CHEMINOX FAMAC-6 (manufactured by Unimatec), Zonyl TH Fluoromonomer code 421480 (manufactured by Sigma Aldrich), SCFC-65530-66-7 (manufactured by Maya High Purity Chem), FC07-04-10. (Manufactured by Fluori Co., Ltd.), CBINDEX: 58 (manufactured by Wilshire Chemical Co., Ltd.), Asahi Guard AG-E530, Asahi Guard AG-E060 (manufactured by Asahi Glass Co., Ltd.), TEMAc-N (manufactured by Top Fluor Chem), Zonyl 7950 ( Sigma-RBI), 61000840-6100902 (Weibo Chemical), CB INDEX: 75 (ABCR) and the like.

  Among these, for example, polyfluorooctyl methacrylate, 2-N, N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, and 2,2′-ethylenedioxydiethyldimethacrylate can be obtained from the point that superior water repellency can be achieved. Can be suitably employed as the polyfluoroalkylmethacrylic acid resin. These may also be commercial products as described above.

  The method for producing the metal oxide composite particles is not particularly limited. If the coating layer is formed according to a known coating method, granulation method, etc., using a fluorine-based resin as a coating material for the metal oxide particles (powder). Good.

  If a polyfluoroalkyl methacrylate resin is used as the fluororesin, for example, a step of coating a metal oxide particle with a coating solution in which a liquid polyfluoroalkyl methacrylate resin is dissolved or dispersed in a solvent (coating step) The metal oxide composite particles can be suitably prepared by a production method including a step of removing the solvent from the coating solution by heat treatment (heat treatment step).

  The solvent used in the coating liquid is not particularly limited, and organic solvents such as alcohol and toluene can be used in addition to water. In the present invention, it is preferable to use toluene. That is, it is preferable to use a coating solution in which a polyfluoroalkyl methacrylate resin is dissolved and / or dispersed in toluene as the coating solution.

  The method for applying the coating liquid onto the surface of the metal oxide particles is not particularly limited, and may be a known method, and for example, any of a spray method, a dipping method, a stirring granulation method, and the like can be applied. In particular, in the present invention, application by a spray method is particularly preferable in terms of excellent uniformity and the like.

After applying the coating solution, the metal oxide composite particles can be obtained by removing the solvent by heat treatment.
The atmosphere during the heat treatment is not particularly limited, but an inert gas (non-oxidizing) atmosphere such as nitrogen gas or argon gas is preferable.

A method for forming the water-repellent film containing such metal oxide composite particles is not particularly limited, and a known method or the like can also be applied.
As an example, in the present invention, the water-repellent film may be formed by a method including a step of applying a dispersion containing metal oxide composite particles to the wall surface of the tip of the suction lumen. That is, a water-repellent film can be formed on the tip wall surface of the suction lumen by applying the dispersion liquid on the tip wall surface of the suction lumen in a wet manner and then removing the solvent.

  The solvent used in the dispersion is not particularly limited. For example, in addition to water, alcohol (ethanol), cyclohexane, toluene, acetone, IPA (isopropyl alcohol), propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol , Normal pentane, normal hexane, hexyl alcohol and the like. By using water or alcohol as the solvent, the burden on the environment can be kept low.

  The dispersion may contain an adhesive (adhesive resin) such as a polyolefin resin, a polyester resin, a polyurethane resin, an epoxy resin, an acrylic resin, or a vinyl resin.

The method for applying the dispersion liquid to the wall surface of the tip of the suction lumen is not particularly limited, and a known method can be employed.
For example, the dispersion liquid may be applied to the wall surface of the distal end portion of the suction lumen by immersing the distal end portion of the tracheostomy tube 10 in the dispersion liquid and sucking as necessary.

After the dispersion is applied to the wall surface of the tip of the suction lumen, the dispersion is dried to form a water repellent film.
Drying may be either natural drying or heat drying. When the dispersion is heated and dried, the heating temperature and the heating and drying time are set so as not to adversely affect the tracheostomy tube 10.

  In addition to this, as a water-repellent film, Unexamined-Japanese-Patent No. 2016-131831, Unexamined-Japanese-Patent No. 2016-131893, International Publication No. 2013/146377, International Publication No. 2016/052336, International Publication No. 2016/052340 Water repellent films (repellent layers) described in International Publication No. 2016/052350 and International Publication No. 2016/117462 can also be suitably used.

  The water repellent coatings 40b, 42b, 46b and 48b may be the same coating or different coatings.

In the present invention, the hydrophilic films 40c, 42c, 46c, and 48c are not particularly limited, and various known films having hydrophilicity can be used.
Specific examples of the hydrophilic film include the following hydrophilic film A and hydrophilic film B. In the tracheostomy tube (tracheal tube) of the present invention, it is preferable that the hydrophilic film A or the hydrophilic film B is also formed on the wall surface of the lumen 20 for securing the airway.
In the following description, after the hydrophilic film A is described in detail, the hydrophilic film B is described in detail.

<Hydrophilic film A>
The hydrophilic film A is a hydrophilic film containing at least a copolymer A described below.
The content of the copolymer A in the hydrophilic film A is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, and 98% by mass or more. Is particularly preferred.

<< Copolymer A >>
Copolymer A has a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), and a repeating unit ( It is a copolymer having a content of A) of 0.6 to 7 mol%.

However, in Formula (1), R < ¹¹ > is a hydrogen atom or a methyl group, Z is an oxygen atom or -NH-, R < ¹² > is a C1-C6 alkylene group, R <^13> and R ¹⁴ is independently an alkyl group having 1 to 4 carbon atoms, and R ¹⁵ is an alkylene group having 1 to 6 carbon atoms.
In Formula (2), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkylene group having 1 to 6 carbon atoms, and R ²³ is an alkyl group having 1 to 4 carbon atoms.

  The terminal of the copolymer A is not particularly limited and is appropriately defined depending on the type of raw material used, but is usually a hydrogen atom. Copolymer A may be any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer.

The weight average molecular weight of the copolymer A is preferably 1,000 to 1,000,000, more preferably 50,000 to 500,000.
The “weight average molecular weight” is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance and tetrahydrofuran (THF) as a mobile phase.

  Hereinafter, each structural unit (repeating unit) of the copolymer A will be described.

(Repeating unit (A))
The copolymer A essentially contains the repeating unit (A) represented by the formula (1).

In formula (1), R ¹¹ is a hydrogen atom or a methyl group, preferably a methyl group.

  In formula (1), Z is an oxygen atom or -NH-. From the viewpoint of durability, it is preferable that Z is —NH—. When Z is —NH—, an amide structure is formed in the formula (1). Therefore, it is superior in hydrolysis resistance than when Z is an oxygen atom (that is, when an ester structure is formed in Formula (1)), and is suitable for use in contact with biological components over a long period of time.

In the formula (1), R ¹² is a linear or branched alkylene group having 1 to 6 carbon atoms, and specifically includes a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentane group. A methylene group, a hexamethylene group, etc. are mentioned. Of these, a linear or branched alkylene group having 1 to 4 carbon atoms is preferable, a methylene group, an ethylene group, or a trimethylene group is more preferable, and an ethylene group or a trimethylene group is further preferable. preferable.

In the formula (1), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. And a linear or branched alkyl group of a group, sec-butyl group, and tert-butyl group. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms (methyl group, ethyl group) is more preferable, and a methyl group More preferably.

In the formula (1), R ¹⁵ is a linear or branched alkylene group having 1 to 6 carbon atoms, and specific examples thereof include the same groups as those exemplified in the description of R ¹² . Of these, a linear or branched alkylene group having 1 to 4 carbon atoms is preferable, a methylene group, an ethylene group, or a trimethylene group is more preferable, and a trimethylene group is still more preferable.

As described above, in the repeating unit (A), in the formula (1), R ¹¹ is a methyl group, Z is an oxygen atom or —NH—, R ¹² is an alkylene group having 1 to 4 carbon atoms, R ¹³ and R ¹⁴ are each independently an alkyl group having 1 or 2 carbon atoms, and R ¹⁵ is preferably an alkylene group having 1 to 4 carbon atoms. In the formula (1), R ¹¹ is a methyl group, R ¹² is an alkylene group having 2 or 3 carbon atoms, Z is an oxygen atom or —NH—, and R ¹³ and R ¹⁴ are carbon atoms. More preferably, it is an alkyl group of 1 (methyl group), and R ¹⁵ is an alkylene group of 3 carbon atoms.

  The copolymer A is also referred to as a monomer that forms the repeating unit (A) (hereinafter also referred to as “monomer a”) and a monomer that forms the repeating unit (B) described in detail below (hereinafter also referred to as “monomer b”). ) And a polymerization reaction.

  As the monomer a, for example, when Z is an oxygen atom or when Z is -NH-, the following compounds can be used. The following monomers may be used alone or in combination of two or more. Moreover, you may mix and use the compound whose Z is an oxygen atom, and the compound whose Z is -NH-.

  When Z is an oxygen atom, examples of the monomer a include [2- (methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide, [2- (acryloyloxy) ethyl] dimethyl- (3- Sulfopropyl) ammonium hydroxide, {2-[(meth) acryloyloxy] ethyl} dimethyl- (2-sulfoethyl) ammonium hydroxide, {2-[(meth) acryloyloxy] ethyl} diethyl- (2-sulfoethyl) ammonium Hydroxide, {2-[(meth) acryloyloxy] ethyl} diethyl- (3-sulfopropyl) ammonium hydroxide, {3-[(meth) acryloyloxy] propyl} dimethyl- (2-sulfoethyl) ammonium hydroxide, {3-[(meta) a Liloyloxy] propyl} dimethyl- (3-sulfopropyl) ammonium hydroxide, {3-[(meth) acryloyloxy] propyl} diethyl- (2-sulfoethyl) ammonium hydroxide, {3-[(meth) acryloyloxy] propyl } Diethyl- (3-sulfopropyl) ammonium hydroxide and the like can be mentioned, and [2- (methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide is preferable.

  When Z is —NH—, examples of the monomer a include [3- (methacryloylamino) propyl] dimethyl (3-sulfopropyl) ammonium hydroxide, [3- (acryloylamino) propyl] dimethyl (3 -Sulfopropyl) ammonium hydroxide, {2-[(meth) acryloylamino] ethyl} dimethyl (2-sulfoethyl) ammonium hydroxide, {2-[(meth) acryloylamino] ethyl} dimethyl (3-sulfopropyl) ammonium Hydroxide, {2-[(meth) acryloylamino] ethyl} diethyl (2-sulfoethyl) ammonium hydroxide, {2-[(meth) acryloylamino] ethyl} diethyl (3-sulfopropyl) ammonium hydroxide, {3 -[(Meta) Ac Roylamino] propyl} dimethyl (2-sulfoethyl) ammonium hydroxide, {3-[(meth) acryloylamino] propyl} diethyl (2-sulfoethyl) ammonium hydroxide, {3-[(meth) acryloylamino] propyl} diethyl ( Examples thereof include [3-sulfopropyl) ammonium hydroxide, and [3- (methacryloylamino) propyl] dimethyl (3-sulfopropyl) ammonium hydroxide is preferable.

  In the present specification, “(meth) acryl” means “acryl” and / or “methacryl”, and “(meth) acryloyl” means “acryloyl” and / or “methacryloyl”. "(Meth) acrylate" means "acrylate" and / or "methacrylate".

(Repeating unit (B))
The copolymer A essentially contains the repeating unit (B) represented by the formula (2).

In the formula (2), R ²¹ is a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the formula (2), R ²² is a linear or branched alkylene group having 1 to 6 carbon atoms, specifically, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentane. A methylene group, a hexamethylene group, etc. are mentioned. Of these, a linear or branched alkylene group having 1 to 3 carbon atoms is preferable, a methylene group or an ethylene group is more preferable, and an ethylene group is still more preferable.

In the formula (2), R ²³ is a linear or branched alkyl group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group. , Sec-butyl group, and tert-butyl group linear or branched alkyl group. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms (methyl group, ethyl group) is more preferable, and a methyl group More preferably.

From the above, in the repeating unit (B), in formula (2), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkylene group having 1 to 3 carbon atoms, and R ²³ is a carbon atom. It is preferably an alkyl group of the number 1 or 2. In the formula (2), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkylene group having 2 carbon atoms (ethylene group), and R ²³ is an alkyl group having 1 carbon atom ( More preferably, it is a methyl group).

  Examples of the monomer b constituting the repeating unit (B) include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, (meth) Ethoxymethyl acrylate, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, ethoxybutyl (meth) acrylate, propoxymethyl (meth) acrylate, propoxyethyl (meth) acrylate, (meth) acrylic acid Examples include propoxypropyl, propoxybutyl (meth) acrylate, butoxymethyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxypropyl (meth) acrylate, butoxybutyl (meth) acrylate.

The monomer b is preferably methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and is easily available. More preferably, it is methoxyethyl acrylate (MEA).
The said monomer may be used individually by 1 type or in mixture of 2 or more types.

(Content of each repeating unit)
Copolymer A contains 0.6 to 7 mol% of repeating units (A) in all the structural units (100 mol%) of copolymer A. The repeating unit (A) is preferably 0.8 to 6 mol%, more preferably 0.9 to 4.7 mol%, and more preferably 1 to 4 mol% in all the structural units. Further preferred.

  In all the structural units of the copolymer A, the repeating unit (B) is preferably contained, for example, at 60 mol% or more, more preferably 80 mol% or more, and 90 mol% or more. More preferably, it is particularly preferably contained in an amount of 93 mol% or more. On the other hand, the upper limit is 99.4 mol% from the relationship with the repeating unit (A).

  The copolymer A may contain structural units other than the repeating units (A) and (B), but is preferably composed of only the repeating units (A) and (B). That is, in the copolymer A, the total amount of the repeating unit (A) and the repeating unit (B) is preferably 100 mol%.

As the content (ratio) of each repeating unit in the copolymer A, a value determined by an NMR (nuclear magnetic resonance) method is adopted (the same applies to the polymer B described later).
For example, in the case of the copolymer A composed of the repeating unit (A) and the repeating unit (B), an alkylene group on the nitrogen atom which is a characteristic structure in each of the repeating units (A) and (B) (That is, R ¹⁵ ) and the ¹ H-NMR integrated value of the alkoxy group (ie, —OR ²³ ) are obtained, and the repeating unit (A) in the copolymer A is repeated based on the ratio of the integrated value. The ratio with the unit (B) can be analyzed. Moreover, in the measurement of ¹ H-NMR, when the peaks overlap, it can be calculated using ¹³ C-NMR.

(Other repeat units)
As described above, the copolymer A preferably comprises only the repeating units (A) and (B), but may contain other repeating units. That is, the copolymer A includes structural units (repeating units) derived from the monomer a, the monomer b, and other monomers copolymerizable therewith (hereinafter also simply referred to as “other monomers”). May be.

  Examples of other monomers copolymerizable with the monomer a and the monomer b include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, aminomethyl (meth) acrylate, Aminoethyl (meth) acrylate, aminoisopropyl (meth) acrylate, diaminomethyl (meth) acrylate, diaminoethyl (meth) acrylate, diaminobutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, ethylene, propylene, N-vinylacetamide, N-isopropenylacetamide, N- (meta There is acryloyl morpholine.

  The ratio of the repeating unit derived from the other monomer is not particularly limited in the total structural unit of the copolymer A, but is, for example, more than 0 mol% and less than 39 mol%, preferably more than 0 mol%. It is less than 33 mol%, more preferably more than 0 mol% and less than 9 mol%, and particularly preferably more than 0 mol% and less than 3 mol%.

(Method for producing copolymer A)
The ratio of the repeating unit derived from the repeating unit (A), the repeating unit (B), or other monomer in the copolymer A can be arbitrarily adjusted by changing the ratio of the monomer used in the polymerization. More specifically, the monomer a for constituting the repeating unit (A) may be added at a ratio of 0.6 to 7 mol% with respect to the total number of moles of all monomers used in the polymerization. Further, at this time, it is preferable to add the monomer b for constituting the repeating unit (B) at a ratio of 93 to 99.4 mol% with respect to the total number of moles of all monomers used. Basically, when the molecular weight fractionation or the like is not performed for the copolymer A obtained by copolymerization of the monomer a, the monomer b, and other monomer optionally added, the monomer used for the copolymerization is charged. The ratio is the content of each repeating unit in the copolymer A to be obtained.

The production method of the copolymer A is not particularly limited. For example, known polymerization methods such as radical polymerization, anionic polymerization, and cationic polymerization can be employed, and radical polymerization that is easy to produce is preferably used.
Further, as a method of producing the copolymer A, plasma polymerization using radiation or ultraviolet rays is adopted, and the hydrophilic film A containing the copolymer A is formed on the inner surface forming the lumen for securing the airway of the lumen of the tracheal tube. You may form in.

  The monomer polymerization method is usually one or more of monomer a corresponding to repeating unit (A), one or more of monomer b corresponding to repeating unit (B), and other if necessary. The monomer is copolymerized by stirring and heating together with a polymerization initiator in a polymerization solvent.

  The polymerization temperature is preferably 30 to 100 ° C. from the viewpoint of controlling the molecular weight. The polymerization reaction is usually performed for 30 minutes to 24 hours.

  The polymerization solvent is preferably water; alcohols such as methanol, ethanol, propanol, n-butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; and the like, and more preferably methanol. , Ethanol, or propanol. These may be used alone or in combination of two or more.

  The monomer concentration (solid content concentration) in the polymerization solvent is usually 10 to 90% by mass, preferably 15 to 80% by mass, based on the entire reaction solution. In addition, the monomer concentration with respect to the polymerization solvent is the monomer a, the monomer b, and other monomers copolymerizable with these (hereinafter referred to as “monomer a, monomer b, and optional copolymerized with these”). “Other possible monomers” are also referred to as “polymerization monomers”)).

  The polymerization solvent to which the polymerization monomer is added may be subjected to a degassing treatment before the addition of the polymerization initiator.

For the production of the copolymer A, a known polymerization initiator can be used, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethyl). Examples thereof include, but are not limited to, azo polymerization initiators such as valeronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile).
The compounding quantity of a polymerization initiator is 0.0001-1 mol with respect to all the monomers (1 mol) used for manufacture of the copolymer A, for example.

  Furthermore, if necessary, a chain transfer agent, a polymerization rate adjusting agent, a surfactant, and other additives may be appropriately used in the polymerization.

The atmosphere in which the polymerization reaction is performed is not particularly limited, and can be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas or argon gas. Further, during the polymerization reaction, the reaction solution may be stirred.
The copolymer A after polymerization can be purified by a general purification method such as a reprecipitation method, a dialysis method, an ultrafiltration method, or an extraction method.

  The purified copolymer A can be dried by any method such as freeze drying, reduced pressure drying, spray drying, or heat drying. However, from the viewpoint of little influence on the physical properties of the polymer, Vacuum drying is preferred.

<< Formation of hydrophilic film A >>
As a method of forming the hydrophilic film A containing the copolymer A, for example, a method of performing plasma polymerization by applying a polymerization solvent containing a monomer for obtaining the copolymer A to the wall surface of the suction lumen; A method obtained using a coating agent A containing a copolymer A; Among these, from the viewpoint of ease of production, the latter method, that is, the method of obtaining the hydrophilic film A using the coating agent A is preferable.

  When the hydrophilic film A is obtained using the coating agent A, specifically, the coating agent A containing the copolymer A is applied to the wall surface of the suction lumen by a known method, and then dried. A hydrophilic film A is formed. The drying temperature is appropriately selected and is, for example, 15 to 50 ° C. The atmosphere during drying is not particularly limited, and examples include an air atmosphere or an inert gas atmosphere such as nitrogen gas or argon gas.

The coating agent A is preferably a coating agent in which the copolymer A is dissolved in a solvent. The solvent used for the coating agent A is not particularly limited as long as it can dissolve the copolymer A. For example, alcohol solvents such as methanol, ethanol, isopropanol, and butanol; water; chloroform, tetrahydrofuran, acetone, dioxane, Non-proton donating organic solvents such as benzene; These solvents may be used alone or in combination of two or more.
The amount of the copolymer A contained in the coating agent A can be arbitrarily set, and can be used as a solution in which the copolymer A is dissolved up to a saturation amount. -50 mass% is preferable and 0.1-50 mass% is more preferable.
The coating agent A may optionally further contain other components such as a crosslinking agent, a thickener, a preservative, and a pH adjuster.

<< Thickness of hydrophilic film A >>
The thickness of the hydrophilic film A may be appropriately set and is not particularly limited, but is formed within a range of 1 to 1000 nm, for example.

<Hydrophilic film B>
The hydrophilic film B is a hydrophilic film formed by crosslinking a polymer B described below.
The content of the polymer B in the hydrophilic film B is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, and 98% by mass or more. Particularly preferred.

<< Polymer B >>
The polymer B is a polymer having a site that exhibits lubricity and a site that has crosslinkability. Examples of the mode of the polymer B include modes such as a copolymer or a macromonomer.
The weight average molecular weight of the polymer B is preferably 1,000 to 1,000,000, more preferably 50,000 to 500,000.

Examples of the site exhibiting lubricity include, for example, (meth) acrylamide, (meth) acrylamide derivatives, N, N-dimethylaminoethyl (meth) acrylate, monomers having sugars and phospholipids in the side chain, maleic anhydride The site | part derived from etc. is mentioned, Especially, it is preferable that it is a site | part derived from (meth) acrylamide or a (meth) acrylamide derivative. Examples of the (meth) acrylamide derivative include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like.
The site having crosslinkability is not particularly limited, and examples thereof include a site having a crosslinkable group that is crosslinked by heat treatment or a catalyst. Specific examples thereof include a site having an epoxy group and a (meth) acryloyl group. And the like. In addition, as a site | part which has an epoxy group, the site | part derived from glycidyl (meth) acrylate is mentioned, The polyglycidyl (meth) acrylate which is a polymer of glycidyl (meth) acrylate is mentioned as the specific example.

When the polymer B is a copolymer having a site exhibiting lubricity and a site having crosslinkability, the molar ratio is preferably 1: 5 to 10, and more preferably 1: 6 to 9.
As the polymer B as such a copolymer, for example, polyglycidyl (meth) acrylate, which is a polymer of glycidyl (meth) acrylate, and (meth) acrylamide or a (meth) acrylamide derivative are polymerized. A copolymer (block copolymer) is mentioned. The polymerization conditions are not particularly limited. For example, the reaction is performed in a solvent such as dimethyl sulfoxide at a temperature of 65 to 85 ° C. for about 15 to 20 hours.

Examples of the polymer B that is a macromonomer include a macromonomer of glycidyl (meth) acrylate and dimethyl (meth) acrylamide; a macro of glycidyl (meth) acrylate and maleic anhydride / hydroxyethyl (meth) acrylate copolymer Monomer; macromonomer of glycidyl (meth) acrylate and maleic anhydride / (meth) acrylamide copolymer; and the like.
Specific examples of such a macromonomer include the following polymer (2).
First, 10 g of dimethylacrylamide, 1 g of iodoacetic acid as a chain transfer agent, and 0.05 g of t-butyl peroctoate as an initiator are reacted under reduced pressure at 80 ° C. for 8 hours to obtain a polymer (1). 5 g of the obtained polymer (1) and 1 g of glycidyl methacrylate are dissolved in 90 g of benzene and reacted in a nitrogen atmosphere at 60 ° C. for 8 hours in the presence of a small amount of hydroquinone. The reaction product is purified using diethyl ether as a poor solvent and tetrahydrofuran as a good solvent to obtain a polymer (2).

<< Formation of hydrophilic film B >>
Examples of the method for forming the hydrophilic film B formed by crosslinking the polymer B include a method obtained using a coating agent B containing the polymer B. In this case, more specifically, the coating agent B containing the polymer B is applied to the wall surface of the suction lumen by a known method, and then heated, for example, to crosslink the polymer B so as to be hydrophilic. Film B is formed.
In the case of heating, the heating conditions are not particularly limited. For example, the heating is performed at a temperature of more than 50 ° C. and 80 ° C. or less for about 5 to 20 hours.

The solvent used for the coating agent B is not particularly limited as long as the polymer B can be dissolved, and examples thereof include 1,4-dioxane, tetrahydrofuran, chloroform and the like.
The amount of the polymer B contained in the coating agent B can be arbitrarily set, and is, for example, 0.01 to 50% by mass, preferably 0.1 to 25% by mass with respect to the entire coating agent B, 1-10 mass% is more preferable.

In the coating agent B, a known catalyst such as pyridine or azobisisobutyronitrile is preferably selected and blended appropriately according to the site having crosslinkability.
Although the compounding quantity of a catalyst is not specifically limited, For example, it is the range of 0.001-1 mass part with respect to 1 mass part polymer B, The range of 0.005-0.5 mass part is preferable.

<< Thickness of hydrophilic film B >>
The thickness of the hydrophilic film B may be adjusted as appropriate and is not particularly limited, but is formed within a range of 1 to 1000 nm, for example.

[Water layer]
Such hydrophilic film A and hydrophilic film B hold an aqueous layer on the surface by moisture in breathing air or moisture in sputum. Since the hydrophilic film A and the hydrophilic film B have such an aqueous layer, the tracheostomy tube 10 can remove the wrinkle sucked into the suction lumen by suitably sucking it from the suction lumen.

<Water in polymer>
Polymers such as PMEA (2-methoxyethyl polyacrylate) take up and retain water. The water retained in the polymer has properties different from, for example, water in a cup (bulk water: freezes at 0 ° C.).
Water (hydration water) in such a polymer is classified into non-freezing water (non-freezing water) and freezing water (freezing water) as a result of differential scanning calorimetry (DSC) measurement. Antifreeze water is water that does not freeze even when cooled to minus 100 ° C. (water that has a strong interaction with the polymer). Freezing water includes water that freezes around 0 ° C (free water: very little interaction with polymer) and water that freezes at minus tens of degrees (intermediate water: water that has moderate interaction with the polymer). (For example, "M. Tanaka; A. Mochizuki, Effect of water structure on blood compatibility-thermal analysis of water in poly (meth) acrylate, J. Biomed. Mat. Res. Part A 68A (4 ), 684-695 (2004)).

  For example, when the process of water adsorption on PMEA is observed by time-resolved infrared spectroscopy (in situ ATR-IR), antifreeze water, intermediate water and free water are observed at different adsorption times. Specifically, antifreeze water forms hydrogen bonds with carbonyl groups in the early stage of adsorption, intermediate water interacts with side chain terminal methoxy groups in the middle stage of adsorption, and forms a hydrogen bond structure similar to that of bulk water in the late stage of adsorption. It is observed that the free water it has is bound.

<Water layer of hydrophilic film A>
Presence of antifreeze water and intermediate water is confirmed from the hydrophilic film A in a state where respiratory air is in contact. In addition, the presence of antifreeze water, intermediate water and free water is confirmed from the hydrophilic film A in the state where the sputum is in contact with the breath.

  The relative quantitative ratios of antifreeze water, intermediate water and free water in the hydrophilic film A are shown in Table 1 below. In Table 1, the greater the number of “+”, the greater the amount of water. In addition, “-” in Table 1 indicates that there is no water (here, free water). The amount of intermediate water and free water differs depending on the presence or absence of sputum in the respiratory air, and the presence of sputum in the respiratory air increases the intermediate water and free water.

In this specification, when the presence of at least antifreeze water and intermediate water is confirmed from the hydrophilic film A, it is assumed that a water layer is retained in the hydrophilic film A.
For this reason, an aqueous layer derived from moisture in breathing air is held in the hydrophilic film A. In addition, when sputum is present in breathing air, the hydrophilic film A retains water in sputum and water layers derived from water in breathing.
By forming such an aqueous layer on the hydrophilic film A, the soot does not adhere to the hydrophilic film A, and moves according to the flow of breathing air or is easily removed by suction.

  From the viewpoint of the strength of interaction with the polymer, the water layer made of antifreeze water is a “strongly fixed layer” relatively strongly fixed to the hydrophilic film A, and the water layer made of intermediate water is relative to the hydrophilic film A. In particular, the “medium fixing layer” fixed to a medium level and the water layer made of free water can be defined as “weak fixing layer” fixed relatively weakly to the hydrophilic film A.

For example, when breathing air does not include sputum, as shown conceptually in FIG. 5A, the strong fixed layer W is formed on the hydrophilic film A (indicated by reference numeral 52 in FIG. 5A). ₁ and the middle fixed layer W ₂ are preferably formed in this order. In FIG. 5A, the strong fixed layer W ₁ is present on the smooth surface of the hydrophilic film A indicated by reference numeral 52, and the middle fixed layer W ₂ is present on the strong fixed layer W ₁ . aqueous layer on the middle fixed layer W ₂ is absent, the middle fixed layer W ₂ is relatively thicker than the reinforced fixed layer W _1.
Further, when breathing air includes sputum, as shown conceptually in FIG. 5B, the strongly fixed layer W _{1 is formed} on the hydrophilic film A (indicated by reference numeral 52 in FIG. 5B). The middle fixed layer W ₂ and the weak fixed layer W ₃ are preferably formed in this order. In FIG. 5 (B), the strong fixed layer W ₁ exists on the smooth surface of the hydrophilic film A (reference numeral 52), the middle fixed layer W ₂ exists on the strong fixed layer W ₁ , there exists a weak fixed layer W ₃ on the middle fixed layer W _2, the aqueous layer on top of the weak anchoring layer W ₃ being absent, the strength the thickness of the fixed layer W ₁ and weakly fixed layer W ₃ being equal Thus, the middle fixed layer W ₂ is relatively thicker than the strong fixed layer W ₁ and the weak fixed layer W ₃ .
Thereby, the strong fixed layer W ₁ is protected by the intermediate fixed layer W ₂ , or the intermediate fixed layer W ₂ and the weak fixed layer W ₃ , and the hydrophilic strong film A ₁ is wrinkled by the protected strong fixed layer W ₁ . Adhesion is suppressed.

<Water layer of hydrophilic film B>
Presence of antifreeze water and free water is confirmed from the hydrophilic film B in a state where respiratory air is in contact. Similarly, the presence of antifreeze water and free water is confirmed from the hydrophilic film B in a state in which breathing air containing sputum is in contact.

  The relative quantitative ratios of antifreeze water, intermediate water and free water in the hydrophilic film B are shown in Table 2 below. In Table 2, the greater the number of “+”, the greater the amount of water. In addition, “-” in Table 2 indicates that there is no water (in this case, intermediate water). When the breathing air contains sputum, free water is increased compared to the case where sputum does not contain sputum.

In this specification, when the presence of at least antifreeze water and free water is confirmed from the hydrophilic film B, it is assumed that an aqueous layer is held in the hydrophilic film B.
For this reason, an aqueous layer derived from moisture in breathing air is held in the hydrophilic film B. In addition, when soot is present in breathing air, the hydrophilic film B retains the water layer in the soot and the water layer derived from the moisture in the breathing air.
By forming such an aqueous layer on the hydrophilic film B, as described in Test Example 2 below, the simulated soot does not adhere to the hydrophilic film B, depending on the flow of breathing air. It moves or is easily removed by suction.

  From the viewpoint of the strength of interaction with the polymer, the water layer composed of antifreeze water is a “strongly fixed layer” relatively strongly fixed to the hydrophilic film B, and the water layer composed of intermediate water is relative to the hydrophilic film B. In particular, the “medium fixing layer” fixed to a medium level and the water layer made of free water can be defined as “weak fixing layer” fixed relatively weakly to the hydrophilic film B.

For example, when breathing air does not include sputum, as shown conceptually in FIG. 5A, the strong fixed layer W is formed on the hydrophilic film B (indicated by reference numeral 54 in FIG. 5A). ₁ and the weak fixed layer W ₃ are preferably formed in this order. In FIG. 5A, the strong fixed layer W ₁ is present on the smooth surface of the hydrophilic film A indicated by reference numeral 52, and the weak fixed layer W ₃ is present on the strong fixed layer W ₁ . aqueous layer on top of the weak anchoring layer W ₃ being absent, weak fixed layer W ₃ being strong relatively thinner than the fixed layer W _1.
Similarly, when breathing air includes sputum, as shown conceptually in FIG. 5B, the strongly fixed layer W is formed on the hydrophilic film B (indicated by reference numeral 52 in FIG. 5B). ₁ and the weak fixed layer W ₃ are preferably formed in this order. In FIG. 5 (B), the strong fixed layer W ₁ exists on the smooth surface of the hydrophilic film A indicated by reference numeral 52, and the weak fixed layer W ₃ exists on the strong fixed layer W ₁ . aqueous layer on top of the weak anchoring layer W ₃ being absent, the thickness of the reinforced fixed layer W ₁ and weakly fixed layer W ₃ being equal.
Thereby, the strong fixing layer W ₁ is protected by the weak fixing layer W ₃ , and the adhesion of wrinkles to the hydrophilic film B is suppressed by the protected strong fixing layer W ₁ .

In the tracheostomy tube 10 of the present invention, the hydrophilic coating is not limited to this, and other coatings that exhibit surface lubricity when wet, for example, a known coating described in International Publication No. 2006/037626. Various hydrophilic coatings can be used.
Further, the hydrophilic films 40c, 42c, 46c and 48c may be the same film or different films.

When removing the fistula in the trachea B from the tracheostomy tube 10 of the present invention, the suction catheter is inserted into the trachea B from the lumen 20 for securing the airway of the tracheostomy tube 10 in the same manner as a general tracheostomy tube. It is only necessary to insert and suck and remove the wrinkles in the trachea B with a suction catheter.
Here, the tracheostomy tube 10 of the present invention has a third suction lumen 46. Accordingly, by sucking the inside of the third suction lumen 46 from the suction tube 46t, the soot adhering to the wall surface in the vicinity of the end of the airway securing lumen 20 on the distal end portion 16 side of the tracheostomy tube 10 is also preferably sucked. Can be removed.
Furthermore, since the tracheostomy tube 10 of the present invention includes not only the third suction lumen 46 but also the first suction lumen 40, the second suction lumen 42, and the fourth suction lumen 48, the suction catheter 601 suctions and removes them. Difficulty such as wrinkles adhering to the vicinity of the end portion of the tracheostomy tube 10 on the distal end portion 16 side can be easily sucked and removed.

The tracheostomy tube 10 in the illustrated example includes a first suction lumen 40 that opens to a tapered portion 16a formed at an end portion on the distal end portion 16 side of the lumen body 12, and a second suction that opens to a distal end surface on the distal end portion 16 side. The lumen 42, the third suction lumen 46 that opens to the wall surface of the airway securing lumen 20 near the end on the distal end 16 side, and the first opening that opens to the outer wall surface of the lumen body 12 on the proximal end 18 side from the cuff 24. The four suction lumens 48 have four suction lumens.
However, the present invention is not limited to this, and various configurations can be used as long as the third suction lumen 46 opens to the wall surface of the airway securing lumen 20.
That is, the tracheostomy tube 10 of the present invention (tracheal tube of the present invention) has a configuration having only the third suction lumen 46, a configuration having the third suction lumen 46 and the first suction lumen 40, and a third suction lumen 46. And a second suction lumen 42, a third suction lumen 46 and a fourth suction lumen 48, a first suction lumen 40, a second suction lumen 42 and a third suction lumen 46, a first Various configurations can be used as long as they have the third suction lumen 46, such as a configuration having the first suction lumen 40, the third suction lumen 46, and the fourth suction lumen 48.
Furthermore, if the tracheostomy tube of the present invention has the third suction lumen 46 opened to the wall surface of the airway securing lumen 20, it opens at a position different from the first suction lumen 40 to the fourth suction lumen 48. You may have a suction lumen.

Further, the tracheal tube of the present invention is not limited to a tracheostomy tube as shown in the drawing.
That is, the tracheal tube of the present invention is, for example, a multi-tube tracheotomy tube, an endotracheal tube, a puncture hole or an incision hole of a cricoid thyroid membrane shown in FIGS. 6 to 10 of International Publication No. 2016/052340. It can be used for various known tracheal tubes, such as a tracheal cannula that can be inserted into the trachea via a trachea, a tracheal cannula that can puncture the ring-shaped thyroid membrane, and a small tracheostomy tube.

[Example 1]
<Formation of water-repellent film>
(1) Preparation of Metal Oxide Composite Particles 100 g of vapor phase method silica powder (product name “AEROSIL 200” manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle size of 12 nm and a BET specific surface area of 200 m ² / g is placed in a reaction vessel, and nitrogen is added. While stirring in a gas atmosphere, 500 g of the surface treatment agent was sprayed, then stirred at 200 ° C. for 30 minutes, and then cooled. Thereby, powder of surface-modified silica fine particles (metal oxide composite fine particles) was obtained.
As the treatment agent, an aqueous dispersion of a copolymer of polyfluorooctyl methacrylate, 2-N, N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate and 2,2′-ethylenedioxydiethyldimethacrylate (solid content concentration: 20 % By mass) was used as a treating agent.
(2) Preparation of dispersion A dispersion was prepared by adding and mixing 30 parts by mass of surface-modified silica fine particles and commercially available thermal adhesion to 200 parts by mass of an organic solvent (toluene).

(3) Formation of water-repellent coating A tracheostomy tube having a third suction lumen 46 and a suction tube 46t that open to the wall surface of the airway securing lumen 20 in the vicinity of the end on the distal end portion 16 side was prepared.
The distal end 16 side of the airway securing lumen 20 of the tracheostomy tube is masked by opening the portion 46a of the third suction lumen 46, and the distal end 16 side of the tracheostomy tube is immersed in the dispersion. . Subsequently, the water-repellent film 46b was formed in the region of 0 to 5 mm on the wall surface of the tip of the third suction lumen 46 (distance from the opening 46a) by heating in an oven at 180 ° C. for 15 seconds.

<Formation of hydrophilic film A>
(1) Preparation of copolymer A 5 g (38.4 mmol) of methoxyethyl acrylate (MEA) and 0.55 g (1.9 mmol) of [3- (methacryloylamino) propyl] dimethyl (3-sulfopropyl) ammonium hydroxide Was dissolved in 22 g of methanol, placed in a four-necked flask, and N ₂ bubbling was performed at 50 ° C. for 1 hour to obtain a methanol solution 1.
Next, a methanol solution obtained by dissolving 0.006 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) in 1 mL of methanol in methanol solution 1 2 was added and polymerized at 50 ° C. for 5 hours to obtain a polymerization solution.
The obtained polymerization solution was added dropwise to diethyl ether, and the precipitated copolymer A1 was recovered.
Content of the repeating unit (A) in copolymer A1 was 4.7 mol% with respect to all the repeating units. This was the same value as the content calculated from the charged amount.

(2) Preparation of coating agent A About copolymer A1, the 0.5 mass% methanol solution was prepared and this was made into coating agent A1.

(3) Formation of hydrophilic coating A The tip of the tracheostomy tube having the water-repellent coating 46b formed on the wall surface of the tip of the third suction lumen 46 is dipped in the prepared coating agent A1. Then, suction was performed from the suction tube 46t, and the coating agent A1 was applied to the wall surface of the third suction lumen 46. Note that the coating agent A1 did not adhere to the water-repellent coating 46b formed on the wall surface of the tip of the suction lumen.
Subsequently, coating agent A1 was dried at room temperature (25 degreeC), and the hydrophilic membrane | film A was formed as the hydrophilic membrane | film 46c.
Accordingly, the water repellent film 46 b is provided on the wall surface on the distal end side of the third suction lumen 46, and the hydrophilic film 46 c (hydrophilic film A) is formed on the wall surface closer to the base end portion 18 than the water repellent film of the third suction lumen 46. A tracheostomy tube was prepared.

<Suction of simulated sputum>
An 8% by weight aqueous paste solution (viscosity: 5000 to 10000 cP) was prepared as a simulated soot.
The simulated soot was attached to the surface of the glass plate and sucked from the suction tube 46t while being in contact with the opening 46a of the third suction lumen 46. As a result, the simulated soot adhering to the surface of the glass plate could be suitably sucked and removed.

[Example 2]
(1) Preparation of polymer B 29.7 g of adipic acid dichloride was dropped into 29.7 g of triethylene glycol at 50 ° C., and then the oligoester obtained by removing hydrochloric acid under reduced pressure at 50 ° C. for 3 hours. 4.5 g of methyl ethyl ketone was added to 22.5 g. This was added dropwise to a solution consisting of 5 g of sodium hydroxide, 6.93 g of 31% hydrogen peroxide, 0.44 g of surfactant dioctyl phosphate and 120 g of water and reacted at −5 ° C. for 20 minutes to obtain a reaction product. It was.
The obtained reaction product was repeatedly washed with water and methanol, and then dried to obtain a polyperoxide having a plurality of peroxide groups in the molecule.
Using 0.5 g of the obtained polyperoxide as an initiator and 30 g of benzene as a solvent, 9.5 g of glycidyl methacrylate (GMA) was polymerized with stirring at 80 ° C. for 2 hours under reduced pressure. After the polymerization, purification was performed using diethyl ether as a poor solvent and tetrahydrofuran as a good solvent to obtain polyglycidyl methacrylate (PPO-GMA) having a plurality of peroxide groups in the molecule.
Next, 9.0 g of dimethylacrylamide and 90 g of dimethyl sulfoxide as a solvent were charged into 1.0 g of the obtained PPO-GMA, sealed under reduced pressure, and then heated to 80 ° C. to carry out a polymerization reaction for 18 hours.
After the polymerization reaction, purification was carried out using diethyl ether as a poor solvent and tetrahydrofuran as a good solvent to obtain a block polymer having an epoxy group in the molecule. The obtained block polymer was confirmed to have an epoxy group in the molecule by NMR and IR measurements. The resulting block polymer was designated as Polymer B.

(2) Preparation of coating agent B Polymer B (2 parts by mass) and pyridine (1 part by mass) as a catalyst were dissolved in 1,4-dioxane, and the resulting solution was used as coating agent B.

(3) Formation of Hydrophilic Film B In the same tracheotomy catheter as in Example 1, a water repellent film 46 b was formed on the wall surface on the distal end side of the third suction lumen 46 in the same manner as in Example 1. Further, the coating agent B was applied to the wall surface of the third suction lumen 46 on which the water repellent coating 46b was formed in the same manner as in Example 1.
Subsequently, the hydrophilic membrane | film | coat B was formed by heating at 60 degreeC for 18 hours.
Accordingly, the water repellent film 46 b is provided on the wall surface on the distal end side of the third suction lumen 46, and the hydrophilic film 46 c (hydrophilic film B) is formed on the wall surface closer to the base end portion 18 than the water repellent film of the third suction lumen 46. A tracheostomy tube was prepared.

<Suction of simulated sputum>
As in Example 1, when the simulated soot adhered to the surface of the glass plate was sucked, the simulated soot attached to the surface of the glass plate could be suitably sucked and removed.

  Tracheostomy tube, multi-tube tracheostomy tube, endotracheal tube, tracheal cannula that can be inserted into the trachea through the puncture hole or incision hole of the cricoid thyroid, tracheal cannula that can puncture the cricoid thyroid membrane, small tracheostomy tube, etc. Can be suitably used.

DESCRIPTION OF SYMBOLS 10 Tracheostomy tube 12 Lumen 14 Fixed part 16 Tip part 17 Curved part 18 Base end part 20 Airway securing lumen 24 Cuff 30 Fixing plate 32 Adhesion part 34 Storage hole 40 1st suction lumen 40a, 42a, 46a, 48a Opening 40b, 42b, 46b, 48b Water repellent coating 40c, 42c, 46c, 48c Hydrophilic coating 40t, 42t, 46t, 48t Suction tube 42 Second suction lumen 46 Third suction lumen 48 Fourth suction lumen 52 Hydrophilic coating A
54 Hydrophilic film B
B Trachea Ba Skin side tracheal mucosa Bb Body tracheal mucosa S Skin W ₁ Strong fixed layer W ₂ Medium fixed layer W ₃ Weak fixed layer

Claims (11)

A lumen body provided with a distal end portion disposed on the lung side in the trachea, a proximal end portion provided on the opposite side of the distal end portion, and an airway securing lumen penetrating from the proximal end portion to the distal end portion A tracheal tube having
The lumen body has a suction lumen that is formed in the wall along the airway securing lumen and that opens to a wall surface of an end portion on the distal end side of the airway securing lumen;
Further, a water repellent film is provided on at least a part of the wall surface at the distal end side of the suction lumen, and at least a part of the wall surface closer to the base end part than the water repellent film of the suction lumen is provided. A tracheal tube provided with a hydrophilic film. The hydrophilic film has a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), and the repeating unit (A The tube for trachea of Claim 1 containing the copolymer A whose content of) is 0.6-7 mol%.
However, in Formula (1), R < ¹¹ > is a hydrogen atom or a methyl group, Z is an oxygen atom or -NH-, R < ¹² > is a C1-C6 alkylene group, R <^13> and R ¹⁴ is independently an alkyl group having 1 to 4 carbon atoms, and R ¹⁵ is an alkylene group having 1 to 6 carbon atoms.
In Formula (2), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkylene group having 1 to 6 carbon atoms, and R ²³ is an alkyl group having 1 to 4 carbon atoms.   The tracheal tube according to claim 1, wherein the hydrophilic film is obtained by crosslinking a polymer B having a site exhibiting lubricity and a site having crosslinkability.   The tracheal tube according to claim 3, wherein the site exhibiting lubricity is a site derived from (meth) acrylamide or a (meth) acrylamide derivative.   The tracheal tube according to claim 3 or 4, wherein the crosslinkable site is a site having an epoxy group.   The tracheal tube according to any one of claims 1 to 5, which is a tracheostomy tube.   The tracheal tube according to any one of claims 1 to 5, which is a double-tube tracheotomy tube.   The tracheal tube according to any one of claims 1 to 5, which is an endotracheal tube.   The tracheal tube according to any one of claims 1 to 5, which is a tracheal cannula that can be inserted into the trachea through a puncture hole or an incision hole in a ring-shaped thyroid membrane.   The tracheal tube according to any one of claims 1 to 5, wherein the tracheal cannula is a tracheal cannula that can puncture the cricoid thyroid membrane.   The tracheal tube according to any one of claims 1 to 5, which is a small tracheostomy tube.