JP2021183078A - Catheter and method for producing the same - Google Patents

Abstract

To provide a catheter that has excellent lubricity at the initial stage and keeps it over the long term.SOLUTION: A catheter 10 has a catheter tube 11 composed of silicone rubber. The surface of the catheter tube 11 is provided with a crosslinked polyurethane netlike body 30 formed by crosslinking and drying a composition containing polyol, blocked polyisocyanate with a dissociation temperature of blocking agent of 100°C or higher, water-soluble polymer, and organic solvent.SELECTED DRAWING: Figure 1

Description

The present invention relates to a catheter and a method for manufacturing the same.

In the medical field, for example, a Foley catheter is used for the purpose of guiding urine of a patient who has difficulty in urinating, guiding urine during surgery or absolute rest, measuring the amount of residual urine, and the like. A Foley catheter is used by passing a flexible tube portion through the urethra, and after insertion, inflating and indwelling a balloon at the tip in the bladder. The Foley catheter is usually made of silicone or the like, and is required to have low friction on the surface portion so as not to damage the urethra. To meet such demands, a method of forming a coating containing a water-soluble polymer that imparts lubricity to the surface of a catheter is known. For example, Patent Document 1 discloses a method for forming an interpolymer of polyvinylpyrrolidone and polyurethane on the surface.

Japanese Unexamined Patent Publication No. 5-156203

Usually, unblocked polyisocyanate is used as a raw material for polyurethane. When polyurethane formed with unblocked polyisocyanate is used for coating, the surface of the coating becomes sticky and the initial lubricity may not be sufficient. In addition, the Foley catheter is removed after a certain period of time has passed since it was placed in the body, but there is a problem that the lubricity is lost over time and pain is felt when the catheter is removed.
On the other hand, since the composition containing the water-soluble polymer easily absorbs water, the water content is affected by the storage condition, and there is a problem that it is difficult to produce a stable product.
The present invention has been made in view of the above circumstances, and manufactures a catheter having good initial lubricity and long-term lubricity, and a catheter capable of stably manufacturing such a catheter. The purpose is to provide a method.

As a result of diligent studies by the present inventors, when unblocked isocyanate was used for the production of polyurethane, the water incorporated in the composition and the isocyanate group reacted with each other, and the unreacted isocyanate group was originally supposed to react with the isocyanate group. It was found that the polyol in the above causes stickiness. Further, by reacting water with an isocyanate group, a polyurethane having few cross-linking points is formed, and a water-soluble polymer such as polyvinylpyrrolidone is separated from the network of the cross-linked polymer, and the original lubricity of the water-soluble polymer can be exhibited. It turned out not.
Therefore, the present inventors used a blocked polyisocyanate having a dissociation temperature of a blocking agent of 100 ° C. or higher, which is the boiling point of water, as the polyisocyanate as a raw material of polyurethane to form a polyurethane having many cross-linking points, and formed a network thereof. It has been found that the lubricity of the crosslinked polyurethane network can be improved and a catheter having lubricity for a long period of time can be realized by retaining the water-soluble polymer well, and the present invention has been made.

That is, the present invention is a catheter provided with a catheter tube made of silicone rubber, which is produced from the reaction of a blocked polyisocyanate with a polyol in the presence of a water-soluble polymer and a water-soluble polymer on the surface of the catheter tube. It is a catheter provided with a cross-linked polyurethane reticulum.

The water-soluble polymer is preferably polyvinylpyrrolidone.

The thickness of the crosslinked polyurethane network is preferably 5 μm or less.

The catheter of the present invention may have a balloon portion.

The method for producing a catheter of the present invention includes a step of producing a catheter tube having at least one lumen using a silicone rubber composition, and a block having a dissociation temperature of a polyol and a blocking agent of 100 ° C. or higher on the outer periphery of the catheter tube. It comprises a step of applying a composition containing a modified polyisocyanate, a water-soluble polymer, and an organic solvent, and then cross-linking and drying to form a cross-linked polyurethane network.

In the method for producing a catheter of the present invention, the water-soluble polymer is preferably polyvinylpyrrolidone.

According to the catheter of the present invention, the initial lubricity is good and the lubricity is maintained for a long period of time.
Further, according to the method for manufacturing a catheter of the present invention, it is possible to stably manufacture a catheter having good initial lubricity and lubricity for a long period of time.

It is a top view which shows the balloon catheter of one Embodiment of this invention. FIG. 1 is a cross-sectional view taken along the line AA of FIG.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The following embodiments are presented for purposes of illustration only, and the present invention is not limited to the embodiments shown below.

[catheter]
The Foley catheter 10 as an embodiment of the present invention will be described.
As shown in FIG. 1, the Foley catheter 10 has a catheter tube 11 and a balloon portion 20. Further, a side hole 12 for taking in urine is formed at the tip of the catheter tube 11.
As shown in FIG. 2, the catheter tube 11 has a first lumen 14 and a second lumen 15 inside. The first lumen 14 is an internal conduction hole that communicates with the side hole 12. The urine in the bladder taken in from the side hole 12 is discharged to a urine collection bag (not shown) via the urination funnel 17. The second lumen 15 is an internal conduction hole through which a medium for inflating the balloon tube 21 (see FIG. 2), for example, physiological saline, sterilized purified water, air, etc. is sent and discharged. The second lumen 15 has a through hole 13 extending from the inside of the second lumen 15 to the outer wall of the catheter tube 11. For example, air is press-fitted into the second lumen 15 by a valve 18 into the second lumen 15, and the press-fitted air passes from the second lumen 15 through the through hole 13 between the catheter tube 11 and the balloon tube 21. Will be supplied. As a result, the balloon tube 21 expands and air stays inside to form a balloon.

A contrast portion 16 in which a contrast agent is mixed linearly along the longitudinal direction X may be provided on the side surface of the catheter tube 11.

(Catheter tube)
The catheter tube 11 is made of silicone rubber. The rubber hardness (JIS K 6253-3) of the catheter tube 11 is preferably A30 or more and A80 or less, and more preferably A40 or more and A70 or less, from the viewpoint of reducing pain at the time of insertion into the body.

The catheter tube 11 can be manufactured by extrusion molding, for example, using a known addition-curing type miraculous silicone rubber composition. The silicone rubber composition may contain a curing agent such as a cross-linking agent and a catalyst.

(Cross-linked polyurethane network)
As shown in FIG. 1, the Foley catheter 10 according to an embodiment of the present invention includes a crosslinked polyurethane network 30 (see FIG. 2) on the surfaces of the catheter tube 11 and the balloon portion 20.
The crosslinked polyurethane network 30 is a composition containing a polyol, a blocked polyisocyanate having a dissociation temperature of a blocking agent of 100 ° C. or higher, a water-soluble polymer, and an organic solvent on the outer periphery of the catheter tube 11 (hereinafter, crosslinked polyurethane network). It is formed by applying (described as a composition for body formation), cross-linking and drying.

The thickness of the crosslinked polyurethane network 30 is preferably 5 μm or less, and more preferably 2 μm or less, from the viewpoint of maintaining lubricity for a long period of time.

Hereinafter, each component of the crosslinked polyurethane network-forming composition will be described.

-Polyol-
The polyol may be any of various polyols usually used in the preparation of polyurethane, and is preferably at least one polyol selected from a polyether polyol, a polyester polyol, a polyacrylate polyol, and a polycarbonate polyol.

Examples of the polyether polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol, polytetramethylene ether glycols, copolymerized polyols of tetrahydrofuran and alkylene oxide, various modified products thereof, and mixtures thereof. Can be mentioned.

Polyester polyols have two or more ester bonds and two or more hydroxyl groups in the molecule. Examples of the polyester polyol include a condensation reaction product of a dicarboxylic acid and a polyol. Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acids such as adipic acid and sebacic acid.

Polyacrylate polyols are hydroxyl group-containing monomers and other olefinically unsaturated monomers such as (meth) acrylic acid esters, styrene, α-methylstyrene, vinyltoluene, vinyl esters, maleic acid monoalkyl esters and maleic acid dialkyl esters. , Fumaric acid monoalkyl esters and fumaric acid dialkyl esters, α-olefins and copolymers with other unsaturated oligomers and unsaturated polymers.

Polycarbonate polyols have two or more carbonate bonds and two or more hydroxyl groups in the molecule. Examples of the polycarbonate polyol include a condensation reaction product of the polyol and the carbonate compound. Moreover, as a carbonate compound, for example, a dialkyl carbonate, a diallyl carbonate, an alkylene carbonate and the like can be mentioned. Examples of the polyol used as a raw material for the polycarbonate polyol include diols such as hexanediol and butanediol, and triols such as 2,4-butanediol.
The polyol preferably has a number average molecular weight of 1000 to 8000, and more preferably 1000 to 5000, in terms of excellent compatibility with isocyanate and the like, which will be described later. The number average molecular weight is the molecular weight when converted to standard polystyrene by gel permeation chromatography (GPC).

-Blocked polyisocyanate-
The blocked polyisocyanate used in the present invention is a blocked polyisocyanate in which the dissociation temperature of the blocking agent is 100 ° C. or higher. More preferably, the dissociation temperature of the blocking agent is 110 ° C. or higher.
Examples of the blocking agent include 3,5-dimethylpyrazole (DMP), methylethylketone oxime (MEKO), ε-caprolactam and the like.
Examples of the various isocyanate compounds usually used for the preparation of polyurethane of the blocked polyisocyanate include polyisocyanate monomers and polyisocyanate derivatives. Examples of the polyisocyanate monomer include polyisocyanates such as aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of the aromatic polyisocyanate include toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or a mixture thereof) (TDI), phenylenedi isocyanate (m-, p-phenylenedi isocyanate or a mixture thereof), 4, 4'-Diphenyldiisocyanate, 1,5-naphthalenediocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), Examples thereof include aromatic diisocyanates such as 4,4'-toluene diisocyanate (TODI) and 4,4'-diphenyl ether diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI) and tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Examples thereof include methylxylylene diisocyanate (or a mixture thereof) (TMXDI), aromatic aliphatic diisocyanates such as ω, ω'-diisocyanate-1,4-diethylbenzene and the like.
Examples of the aliphatic isocyanate compound include hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornene diisocyanatomethyl (NBDI), xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate. (TMXDI) and the like can be mentioned. Further, examples of the alicyclic isocyanate include transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6XDI (hydrogenated XDI), H12MDI (hydrogenated MDI), and 4,4'-dicyclohexylmethane diisocyanate. And so on.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate, Trans, Trans- (H ₁₂ MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate), norbornandiisocyanate. (Various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (H ₆ XDI) and other alicyclic groups Diisocyanate can be mentioned. These polyisocyanate monomers can be used alone or in combination of two or more.

Examples of the polyisocyanate derivative include a multimer of the above-mentioned polyisocyanate monomer (for example, a dimer and a trimer (for example, an isocyanurate modified form and an iminooxadiazidinedione modified form), a pentamer and 7). Measures, etc.), allophanate modified products (for example, allophanate modified products produced by the reaction of the above-mentioned polyisocyanate monomer with a low molecular weight polyol described later), polyol modified products (for example, polyisocyanate monomer and described later). A polyol modified product (alcohol adduct) produced by reaction with a low molecular weight polyol, etc.), a biuret modified product (for example, a biuret modified product produced by reaction of the above-mentioned polyisocyanate monomer with water or amines, etc. ), Urea modified product (for example, urea modified product produced by the reaction of the above-mentioned polyisocyanate monomer and diamine), oxadiazine trione modified product (for example, the above-mentioned polyisocyanate monomer and carbon dioxide gas). Examples thereof include oxadiazine trione produced by the reaction), a carbodiimide modified product (such as a carbodiimide modified product produced by the decarbonation condensation reaction of the polyisocyanate monomer described above), a uretdione modified product, and a uretonimine modified product.
Further, examples of the polyisocyanate derivative include polymethylene polyphenyl polyisocyanate (crude MDI, polypeptide MDI) and the like.
These polyisocyanate derivatives can be used alone or in combination of two or more. These polyisocyanate compounds can be used alone or in combination of two or more.

In the present invention, since blocked polyisocyanate is used as a raw material for polyurethane, the viscosity of the crosslinked polyurethane network-forming composition does not increase even after a lapse of time after preparation, and the composition is crosslinked. Good workability when forming a polyurethane network. Further, in the preparation of the composition, the compatibility between the blocked polyisocyanate and other components is maintained well, and curing failure does not occur.

The cross-linked polyurethane network-forming composition may be used in combination with an auxiliary agent usually used for the reaction between the polyol and the blocked polyisocyanate, for example, a chain extender, a cross-linking agent, or the like. Examples of the chain extender and the cross-linking agent include glycols, hexanetriol, trimethylolpropane, amines and the like.

The mixing ratio of the polyol and the blocked polyisocyanate in the mixture is such that the molar ratio (NCO / OH) of the hydroxyl group (OH) contained in the polyol and the isocyanate group (NCO) contained in the polyisocyanate is 0.7 or more. It is preferably 15 or less. This molar ratio (NCO / OH) is more preferably 0.85 or more and 1.10 or less in that hydrolysis of polyurethane can be prevented. Actually, in consideration of the work environment and work error, an amount equivalent to 3 to 4 times the appropriate molar ratio may be blended.

-Water-soluble polymer-
Water-soluble polymers include, but are not limited to, polyethylene oxide (PEO), polyethylene glycol (PEG), polysaccharides, hyaluronic acid and its salts and derivatives, sodium alginate, chondroitin sulfate, cellulose, chitin, chitosan, and agarose. , Xantane, Dermatane Sulfate, Keratin Sulfate, Emilzan, Gellan, Curdran, Agarose, Carrageenan, Amylopectin, Dextran, Glycogen, Stardust, Heparin Sulfate, and Limit Dextrin and Fragments thereof, Synthetic Hydrophilic Polymers, Poly (Vinyl Alcohol), And polyvinylpyrrolidone (PVP). The preferred water-soluble polymer for use in the present invention is polyvinylpyrrolidone.
The type of the water-soluble polymer contained in the crosslinked polyurethane network may be one type or two or more types.

-Organic solvent-
The organic solvent does not react with polyols, blocked polyisocyanates and water-soluble polymers, but must be able to dissolve all. The organic solvent is preferably free of reactive amines, hydroxyl and carboxyl groups. Specifically, methylene bromide, methylene chloride, methane dibromide, chloroform, ethane dichloride, n-propyl bromide, acetonitrile, ethane dibromide, methylbenxoate, benzyl acetate, n-propyl bromide, It is selected from the group consisting of cyclohexanone, dichloromethane, 1,3-dioxolane and N-methylpyrrolidone.

The crosslinked polyurethane network-forming composition may contain components other than polyols, blocked polyisocyanates, water-soluble polymers and organic solvents. Examples of other components include catalysts, antioxidants and the like.

-Catalyst-
Non-limiting examples of suitable catalysts include tertiary amines such as N, N-dimethylaminoethanol, N, N-dimethyl-cyclohexamine-bis (2-dimethylaminoethyl) ether, N-ethylmorpholin, N, N, N', N', N "-pentamethyl-diethylene-triamine, and 1-2 (hydroxypropyl) imidazole, as well as metal catalysts such as tin, tin octanate, dibutyltin dilaurate, dioctyltindilaurate, dibutyltin merca. Examples thereof include petitdo, ferric acetylacetone, lead octanoate, dibutyltin dilysinolate, calcium carbonate, iron (III) acetylacetonate and the like. Preferred catalysts are dibutyltin dilysinolate, tin. The most preferable catalyst is. Dioctyltin dilaurate. The catalyst is preferably in the range of 0.05% by mass or more and 0.5% by mass or less in the polyol and the blocked polyisocyanate.

-Antioxidant-
Antioxidants are effective in improving the oxidative stability of the cured coating. Antioxidants include vitamin E, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,2'-methylenebis (4methyl-6-t-butylphenol), 1,3. 5 trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, butyl hydroxytoluene, octadecyl 3,5, di-t-butyl 4-hydroxyhydrocin namemate, 4 , 4'methylenebis (2,6-di-t-butylphenol), p, p'-dioctyldiphenylamine, 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane However, it is not limited to these. The antioxidant is preferably 0.01% by mass or more and 1% by mass or less in the polyol and the blocked polyisocyanate.

An adhesive layer or a primer layer made of a silane coupling agent may be provided between the catheter tube 11 and the crosslinked polyurethane network 30 in order to improve the adhesive strength. Further, the composition for forming a crosslinked polyurethane network may contain a silane coupling agent from the viewpoint of improving the adhesion with the crosslinked polyurethane network 30.

In the above embodiment, the catheter having the balloon portion has been described, but the present invention may be a catheter having no balloon portion.

The catheter of the present invention uses a blocked polyisocyanate having a dissociation temperature of 100 ° C. or higher as the isocyanate component for forming urethane. That is, since the blocking agent dissociates at a temperature of 100 ° C. or higher, more preferably 110 ° C. or higher, which is the boiling point of water, the blocking agent is blocked when the water content evaporates due to heating and the water content of the crosslinked polyurethane network-forming composition decreases. The agent dissociates and an isocyanate group is expressed. As a result, the reaction between water and the isocyanate group is suppressed, and unreacted polyol does not remain, so that there is no stickiness. Further, since the reaction between water and the isocyanate group is suppressed, polyurethane having many cross-linking points can be formed, and the water-soluble compound can be retained in the network, so that the original lubricity as a hydrophilic coat is sufficiently exhibited. .. Therefore, the catheter of the present invention is not sticky and has good lubricity in the initial stage and for a long period of time.

[Catheter manufacturing method]
The method for producing a catheter of the present invention includes a step of producing a catheter tube having at least one lumen using a silicone rubber composition, and a block having a dissociation temperature of a polyol and a blocking agent of 100 ° C. or higher on the outer periphery of the catheter tube. It comprises a step of applying a composition containing a modified polyisocyanate, a water-soluble polymer, and an organic solvent, and then cross-linking and drying to form a cross-linked polyurethane network.
Hereinafter, a method for manufacturing a Foley catheter, which is an embodiment of the method for manufacturing a catheter of the present invention, will be described. The Foley catheter described in this embodiment is the same as the Foley catheter 10 described above, and the same elements will be described with the same reference numerals.

(Making a catheter tube)
The catheter tube 11 can be made by primary extrusion molding and vulcanization treatment of a silicone rubber composition. The primary extrusion molding can be performed by a known horizontal extrusion molding machine and vertical extrusion molding machine. In the extrusion molding process and the vulcanization treatment, it is preferable to use a vertical extruder and a vulcanizer. By using the vertical extruder and the vulcanizer, since no fine contact trace is left on the surface of the tube, eccentricity does not occur when the balloon is inflated, or the balloon can be prevented from bursting.
Examples of the silicone rubber composition include an addition-curing type mirable type silicone rubber composition.

(Formation of cross-linked polyurethane network)
The composition for forming a crosslinked polyurethane network can be applied by a roll coating method, a dipping method or the like. In the case of a catheter having a balloon portion 20 as in the present embodiment, the balloon tube 21 constituting the balloon portion 20 is attached to the catheter tube 11, a crosslinked polyurethane network-forming composition is applied, and then crosslinked and dried. To form a crosslinked polyurethane network 30.

In the present embodiment, the Foley catheter 10 having the balloon portion 20 has been described, but a catheter having no balloon portion 20 may be used. In that case, a crosslinked polyurethane network may be formed on the outer periphery of the catheter tube 11. preferable.

According to the method for manufacturing a catheter of the present invention, since a blocked polyisocyanate having a dissociation temperature of a blocking agent of 100 ° C. or higher is used as a raw material for polyurethane of a crosslinked polyurethane network, a composition for forming a crosslinked polyurethane network is used. It is possible to stably provide high quality catheters without the need for strict storage management or equipment with high water content.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to the examples shown below.

[Example 1]
(Making a catheter tube)
A silicone rubber composition for a catheter tube was prepared from the following raw materials.
-Silicone rubber (trade name "KE-561 (U)", manufactured by Shin-Etsu Chemical Co., Ltd.)
100 parts by mass ・ Vulcanizing agent (trade name “C-25A”, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass ・ Vulcanizing agent (trade name “C-25B”, manufactured by Shin-Etsu Chemical Co., Ltd.) 2. 0 parts by mass

Next, a catheter tube having a first lumen and a second lumen was produced by extrusion molding using the above silicone rubber composition. In the area where the balloon of the catheter tube is formed, a through hole from the second lumen to the outer wall of the catheter tube was formed with forceps. The hardness of the catheter tube (JIS K 6253-3) was A60.

Finally, a one-component room temperature curable silicone rubber composition (for example, trade name "KE-45RTV", manufactured by Shin-Etsu Chemical Co., Ltd.) is used as an adhesive on the tip of the catheter tube, and the tip sealing portion is attached. And completed the catheter.

(Formation of cross-linked polyurethane network)
A composition for forming a crosslinked polyurethane network was prepared from the following raw materials.
(1) Polypropylene glycol (trade name "Uniol D-2000", manufactured by NOF CORPORATION) 100 parts by mass (2) Blocked polyisocyanate (Coronate BI-301 ", manufactured by Tosoh Corporation) 40 parts by mass (3) ) Polyvinylpyrrolidone (trade name "K-90", manufactured by Nippon Shokubai Co., Ltd.)
330 parts by mass (4) Catalyst dibutyltin laurate 0.6 parts by mass (5) Solvent dibromomethane 23000 parts by mass

The molar ratio [NCO / OH] of the isocyanate group (NCO) contained in the blocked polyisocyanate and the hydroxyl group (OH) contained in the polyol was 1.1 / 1.

Normally, the water content of the composition is reduced to less than 0.5% in order to prevent the reaction between water and isocyanate, but the crosslinked polyurethane network of the present invention did not perform such work.
The composition was applied to the surface of the catheter tube by the dipping method, crosslinked and dried to form a crosslinked polyurethane network.

[Example 2]
A catheter similar to that in Example 1 was prepared, and a composition for forming a crosslinked polyurethane network was prepared from the following raw materials.
(1) Polypropylene glycol (trade name "Uniol D-2000", manufactured by NOF CORPORATION) 100 parts by mass (2) Blocked polyisocyanate (Coronate 2507 ", manufactured by Tosoh Corporation) 39 parts by mass (3) Polyvinyl Pyrrolidone (trade name "K-90", manufactured by Nippon Shokubai Co., Ltd.)
330 parts by mass (4) Catalyst dibutyltin laurate 0.6 parts by mass (5) Solvent dibromomethane 22,500 parts by mass

The molar ratio [NCO / OH] of the isocyanate group (NCO) contained in the blocked polyisocyanate and the hydroxyl group (OH) contained in the polyol was 1.1 / 1.
The composition was applied to the surface of the catheter tube by the dipping method, crosslinked and dried to form a crosslinked polyurethane network.

[Example 3]
A catheter similar to that in Example 1 was prepared, and a composition for forming a crosslinked polyurethane network was prepared from the following raw materials.
(1) Polypropylene glycol (trade name "Uniol D-2000", manufactured by NOF CORPORATION) 100 parts by mass (2) Blocked polyisocyanate (Coronate 2554 ", manufactured by Tosoh Corporation) 44 parts by mass (3) Polyvinyl Pyrrolidone (trade name "K-90", manufactured by Nippon Shokubai Co., Ltd.)
340 parts by mass (4) 0.6 parts by mass of catalyst dibutyltin laurate (5) 23000 parts by mass of solvent dibromomethane

The molar ratio [NCO / OH] of the isocyanate group (NCO) contained in the polyisocyanate and the hydroxyl group (OH) contained in the polyol was 1.1 / 1.
The composition was applied to the surface of the catheter tube by the dipping method, crosslinked and dried to form a crosslinked polyurethane network.

[Comparative Example 1]
A catheter was prepared in the same manner as in Example 1 except that an unblocked polyisocyanate (trade name "Millionate MR-200", manufactured by Tosoh Corporation) was used instead of the blocked polyisocyanate.

[Comparative Example 2]
A catheter was prepared in the same manner as in Example 1 except that an unblocked polyisocyanate (trade name "Coronate L", manufactured by Tosoh Corporation) was used.

[evaluation]
For the above Examples and Comparative Examples, the coefficient of static friction was measured as an evaluation of lubricity.

(Measurement of coefficient of static friction)
The catheters produced in Examples and Comparative Examples are immersed in warm water at 60 ° C. for 30 seconds, then taken out from the hot water, and the coefficient of static friction is measured using a portable friction meter (TYPE: 94i-II) manufactured by Shinto Kagaku Co., Ltd. bottom. After that, the measurement site was rubbed 50 times with strong acupressure in running water, immersed in warm water at 60 ° C. for 30 seconds, taken out from the warm water, and the coefficient of static friction at the same location was measured again.

As shown in Table 1, it was found that the catheter of the present invention had good initial lubricity and long-term lubricity.

10 Foley catheter 11 Catheter tube 12 Side hole 13 Through hole 14 1st lumen 15 2nd lumen 16 Contrast part 17 Urination funnel 18 Valve 20 Balloon part 21 Balloon tube 30 Cross-linked polyurethane mesh

Claims (6)

A catheter equipped with a catheter tube made of silicone rubber.
A catheter provided with a water-soluble polymer and a crosslinked polyurethane network produced by the reaction of a blocked polyisocyanate with a polyol in the presence of the water-soluble polymer on the surface of the catheter tube. The catheter according to claim 1, wherein the water-soluble polymer is polyvinylpyrrolidone. The catheter according to claim 1 or 2, wherein the crosslinked polyurethane network has a thickness of 5 μm or less. The catheter according to any one of claims 1 to 3, which has a balloon portion. The process of making a catheter tube with at least one lumen using a silicone rubber composition and
A composition containing a polyol, a blocked polyisocyanate having a dissociation temperature of 100 ° C. or higher, a water-soluble polymer, and an organic solvent is applied to the outer periphery of the catheter tube, and then crosslinked and dried to form a crosslinked polyurethane network. The process of forming the body and
A method for manufacturing a catheter having a catheter. The method for manufacturing a catheter according to claim 5, wherein the water-soluble polymer is polyvinylpyrrolidone.

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