JPH01195863A - Medical instrument and manufacture thereof - Google Patents

Abstract

PURPOSE:To make frictional resistance at the time of application in a wetting state smaller as well as to improve the persistence by installing the specified material on the surface of a base material constituting a medical instrument. CONSTITUTION:A covered layer 1 is formed on each outer surface of an olive 21 of an ED (for tubing nutrition) tube 2 connected to a connector 24 and a body tube 22. This covered layer 1 is formed by covalently binding a reactive functional group, cellulose polymeric material, polyethylene oxide polymer material and water soluble polymeric material selected out of water soluble nylon or its derivative.

Description

[Detailed description of the invention]

I. BACKGROUND OF THE INVENTION Technical Field The present invention relates to a medical device and a surface treatment method thereof. Prior art and its problems Medical instruments such as catheters inserted into the respiratory tract, trachea, gastrointestinal tract, urethra, blood vessels, other body cavities or tissues, and medical instruments such as guide wires and stylets inserted into these Various medical devices such as instruments are required to be smooth so that they do not damage tissues and can be inserted reliably to the target site, and they also need to be smooth enough to avoid damaging mucous membranes due to friction while being placed in tissues. It is required to exhibit excellent lubricity to avoid causing irritation or inflammation. For this reason, the base materials for these medical devices have conventionally been made of general low-friction resistance materials such as fluororesin or polyethylene, or have surface coats such as fluororesin coats or silicone coats applied to the surface of the base material, or silicone Oil, olive oil, glycerin, xylocaine jelly, etc. are applied to the surface. However, all of these conventional cases are insufficient in terms of effectiveness. For example, when using low-friction resistance materials such as Teflon or high-density polyethylene, or applying a surface coating with them,
There are problems such as the coefficient of friction not being sufficiently low. Also,
Surface application of oil lowers the coefficient of dynamic friction, but has the disadvantage that the effect is not sustainable and the oil etc. wash away. Alternatively, oil coating makes the surface sticky and makes it difficult to store as a product, so the coating must be done immediately before use, making handling complicated. On the other hand, US Pat. No. 4,100,309 discloses the use of an interpolymer of polyvinylzorollidone and polyurethane as the coating layer. This coating exceeds conventional coatings in terms of frictional resistance and durability. However, an incyanate group is essential as a reactive functional group, and polyurethane must be used as a base material or an underlayer formed on a base material, which is undesirable because it limits usable base materials and applications of medical devices. For example, even if polyamide resin is treated with such a coating layer, it is difficult to directly introduce isocyanate groups, and even if polyurethane is used as a base layer, the adhesion to the base material is low, making it difficult to maintain a durable coating. You can't expect layers. Also, polyvinylpyrrolidone is relatively expensive. In addition, polyvinyl, lolidone, and isocyanate groups are
It is thought to contain an ion complex, and therefore the bond state is not stable in body fluids such as saliva, digestive juices, blood, etc., or in aqueous solutions such as physiological saline, and There is a tendency to dissolve, and satisfactory sustainability cannot be expected.In addition, JP-A-53-106778 discloses a polyurethane resin surface wire characterized in that a fibrinolytic active substance is immobilized on the polyurethane resin surface. A method for imparting solubility activity has been disclosed, in which a polymer containing maleic anhydride units is used as an intermediate bonding layer for fixing fibrinolytic active substances to the surface of a polyurethane resin, and such coating layer There is no disclosure or suggestion that the lubricity of medical devices is improved by eluting the liquid from the outer surface of the medical device. ■ Purpose of the Invention When used in a wet state, i.e., wet with an aqueous liquid, the frictional resistance during insertion is low, the durability is good, the storage stability is good, and there are many types of substrates that can be used. An object of the present invention is to provide a medical device having a rich coating layer and a method for manufacturing the same. Covalently bonding a reactive functional group present on at least the surface of the base material to a water-soluble polymer material or a derivative thereof selected from a cellulose-based polymer material, a polyethylene oxide-based polymer material, and a water-soluble nylon; The medical device is characterized in that the surface thereof has lubricity when wetted.A second invention also provides a medical device in which a base material constituting the medical device is treated with a solution of a compound having a reactive functional group. A base layer is formed so that a reactive functional group is present on at least the surface of the base material, and then a water-soluble polymer selected from a cellulose-based polymer material, a polyethylene oxide-based polymer material, and a water-soluble nylon is formed. covalently bonding the reactive functional group and the water-soluble polymeric substance by treatment with a substance or a derivative thereof;
This method of manufacturing a medical device is characterized in that a coating layer of a water-soluble polymer substance is formed on the base layer so that the surface has lubricity when wetted. Furthermore, in a third invention, a base material constituting a medical device is treated with a solution of a compound having a reactive functional group, a base layer is formed so that the reactive functional group is present on at least the surface of the base material, and then , treated with a water-soluble polymer material or a derivative thereof selected from a cellulose-based polymer material, a polyethylene oxide-based polymer material, and a water-soluble nylon, so that the reactive functional group and the water-soluble polymer material share combine,
This method of manufacturing a medical device is characterized in that a coating layer of a water-soluble polymer substance is formed on the base layer, and then water treatment is performed so that the surface has lubricity when wet. Moreover, it is preferable that the reactive functional group is an aldehyde group, an epoxy group, an isocyanate group, or an amino group. Medical devices according to the present invention include catheters inserted into the respiratory tract, trachea, gastrointestinal tract, urethra, blood vessels, and other body cavities or tissues. A guide device that can be introduced into or removed from the body is preferred. ■Specific structure of the invention The specific structure of the present invention will be explained in detail below. The water-soluble polymeric substance used to form the lubricious surface coating layer of the medical device of the present invention is covalently fixed onto the medical device substrate. As a general rule, such water-soluble polymeric substances are chain-like and non-crosslinked polymeric substances. -〇〇NHI, -COOH, -NH,. -〇 〇 〇 -, -SOs -, -NRs'', etc. Natural water-soluble polymers 1) Starch-based carboxymethyl starch, dialdehyde starch 2) Cellulose-based CMC, MC, HEC %HPC 3) Tannin, nignin-based tannin, nignin 4) Polysaccharide-based alginic acid, gum arabic, guar gum, gum tragacanth, tamarind seeds 5) Protein gelatin, casein, glue, collagen synthesis Water-soluble polymer 1) PVA-based polyvinyl alcohol 2) Polyethylene oxide-based polyethylene oxide, polyethylene glycol 3) Acrylic acid-based polysodium acrylate 4) Maleic anhydride-based methyl vinyl ether maleic anhydride copolymer 5) Phthalic acid-based polyhydroxyethyl phthalate ester 6) Water-soluble polyester polydimethyl roll Propionate ester 7) Ketone aldehyde resin Methyl isopropyl ketone formaldehyde resin 8) Acrylamide polyacrylamide 9) Polyvinylpyrrolidone vP 10) Polyaminopolyethyleneimine 11) Polyelectrolyte polystyrene sulfonate 12) Others include water-soluble nylon. In addition, the derivatives are not limited to water-soluble ones, and there are no particular restrictions as long as they have the above-mentioned water-soluble polymeric substance as their basic composition.
As for the insolubilized material, it is sufficient that the molecular chain has a degree of freedom and contains water as described below. For example, esterified products, salts, amidated products, anhydrides, halides, etherified products, hydrolyzed products, acetalized products, formalized products obtained by condensation, addition, substitution, oxidation, reduction reactions, etc. of the above water-soluble polymeric substances, Alkylorated products, quaternized products, diazotized products, hydrazidated products, sulfonated products, nitrated products, ion complexes. With substances that have two or more reactive functional groups such as diazonium groups, azide groups, isocyanate groups, acid chloride groups, acid anhydride groups, imino carbonate groups, amino groups, carboxyl groups, epoxy groups, hydroxyl groups, alrahide groups, etc. Crosslinked product. Examples include copolymers with vinyl compounds, acrylic acid, methacrylic acid, diene compounds, maleic anhydride, and the like. Such water-soluble polymer substances dissolve well in water, and when the solution is present between certain objects, the frictional resistance between the two can be significantly reduced, and it can be used as a lubricant. In addition, derivatives obtained by condensation, addition reactions, substitution reactions, etc. of these water-soluble polymer substances, as well as those that have been partially crosslinked, so-called insolubilized, are similarly effective as lubricants between two layers. It is. By covalently bonding these with reactive functional groups present or introduced in the base material or on the base material surface, it is possible to obtain a lubricating layer supported on the base material, which is durable and does not dissolve in water. A lubricious surface can be obtained. The water-soluble polymeric substance is not particularly limited, but the most representative ones include cellulose, maleic anhydride, acrylamide, polyethylene oxide, and water-soluble nylon. In particular, hydroxypropyl cellulose, methyl vinyl ether, maleic anhydride copolymer, polyacrylamide, polyethylene glycol, water-soluble nylon (AQ-Nylon P-70 manufactured by Toshi Co., Ltd.)
) are cheap and easy to obtain (and are also good in terms of safety). The average molecular weight of these water-soluble polymer substances is not particularly limited, but those of about 3 to 5 million have high lubricity and are suitable for It is preferable to obtain a lubricating layer with a thick thickness and a significantly thick swelling degree when it contains water.Also, the degree of swelling when it contains water can be adjusted as described above (by using an insolubilized material or by using a base material). The same treatment may be carried out after supporting the material on the material.The reactive functional group present or introduced into the substrate or on the surface of the substrate reacts with the water-soluble polymer substance and forms bonds or crosslinks. There is no particular restriction as long as it is immobilized, such as diazonium group, azide group, isocyanate group, acid chloride group, acid anhydride group, imino carbonate group, amino group, carboxyl group, epoxy group, hydroxyl group, aldehyde group, etc. are considered, and isocyanate groups, amino groups, aldehyde groups, and epoxy groups are particularly suitable. Therefore, polyurethane, polyamide, etc. are suitable as the base material containing reactive functional groups. Also, the outer walls of various medical devices, Substrates that do not contain these reactive functional groups are usually used as the base material constituting the inner walls, etc. In such cases, they are treated with a substance that has reactive functional groups as described above to remove the reactive functional groups. A group is present in a base material, and a water-soluble polymeric substance (as in the present invention) is covalently bonded thereon.There are various forms of bonding, such as covalent bonding, ionic bonding, and physical attachment, but sustainability must be taken into consideration. In this case, covalent bonding is most preferred.These are not limited to direct bonding to the surface of the substrate, but the outermost layer can be bonded to the water-soluble polymer layer by the presence or introduction of a reactive functional group in or on the polymer layer, as described above. A surface with sustained lubricity may be obtained by covalently fixing a reactive polymeric substance. Examples of substances having such reactive functional groups include ethylene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate. , polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, cyclohexylene diisocyanate, triphenylmethane triisocyanate, and toluene diisocyanate, and adducts or prepolymers of these polyisocyanates and polyols. For example, low molecular weight polyaminos include ethylene diamino, trimethylene diamino, and 1,2-diaminopropane. Tetramethylenediamino, 1,3-diaminobutane, 2
．． 3-diaminobutane, pentamethylenediamino, 2.
4-diaminobencune, hexamethylenediamino, octamethylenediamino, nonamethylenediamino, decamethylenediamino, undecamethylenediamino, dodecamethylenediamino, tridecamethylenediamino, octadecamethylenediamino, N,N-dimethylethylenediamino,
N,N-diethyltrimethylenediamino, N,N-dimethyltrimethylenediamino, N,N-dibutyltrimethylenediamino, N,N,N'-triethylethylenediamino, N-methyltrimethylenediamino, N,N-dimethyl -p-phenylenediamino, N,N-dimethylhexamethylenediamino, diethylenetriamino, triethylenetetramine, tetraethylenepentamine, hebutaethyleneoctamine, nonamethylenediamino, 1.3-
Bis(2'-aminoethylamino)propane, bis(3
-aminopropal)amino, 1,3-bis(3'-aminopropylamino)propane, 1,2,3. -triaminopropane, tris(2-aminoethyl)amino, tetra(aminomethyl)methane, methyliminobispropylamino, methyliminobisethylamino, ethyliminobisethylamino, N-aminopropyl-2morpholine, N-aminobripyl -2-pipecoline, N-(2-hydroxyethyl)trimethylenediamino, xylylenediamino, phenylenediamino, piperazine, N-methylbiperazine, N-(2-aminoethyl)ethanolamino, N-aminoethylpiperazine, N,N ,N'N
'-Tetramethylethylenediamino, N, N, N'
Examples include N'-tetramethyltetramethylene diamino, etc. Poly(alkylene polyamino) synthesized from [11 amino and alkylene civalide or epichlorohydrin]

[Encyclopedia of Polymer Science and Technology]
erScience and Technology
) Vol. 10, p. 616 1, [II] Alkylene imine polymers obtained by ring-opening polymerization of alkylene imines such as ethyleneimine and propylene imine [Ensalacrobidia of Polymer Science and Technology, Vol. 1, Page 734], [I[1] Others, polyamino such as polyvinylamino and polylysine. In addition, glutaraldehyde, terephthalaldehyde,
Isophthalaldehyde, dialdehyde, starch, gallyoxal, malonaldehyde, succinic aldohyde,
Azibaldehyde, pimelindialdehyde, superingialdehyde, malealdehyde, 2-pentene-1,
Polyaldehydes such as 5-dialdehyde, as well as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polybrobylene diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. There is polyepoxide. Among these, 4,4'-diphenylmethane diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolpropane, or a trimer thereof, and diethylenetriamino are most preferred. 1゜In the present invention, as the base material applied to the outermost layer, a particularly low friction resistance base material is used, or a low friction resistance treatment agent such as silicone oil, olive oil, glycerin, or xylocaine jelly is applied before use. However, when it comes into contact with an aqueous liquid such as the one described above, a low frictional resistance (lubricity) surface condition is immediately obtained, making it possible to use it as a medical device. There are also very few restrictions on the base material. Therefore, the base materials to be used include, for example, polyamide, polyester, polyvinyl chloride, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, polyacrylamide, polyacrylic acid, polymethacrylate. Acids, polyethylene, polypropylene, polyvinyl alcohol, polymaleic anhydride, polyethyleneimine. Various organic polymer base materials such as polyurethane, polyvinyl acetate, silicone resins, various latexes, and various copolymers and blends of these, It may be any of various inorganic or metal base materials such as glass, ceramics, stainless steel, etc. These base materials may contain various additives as necessary. Note that as the base material, In particular, organic polymer resins have a high long-lasting lubricity effect, and among these, polyvinyl chloride, polyurethane, polyamide, latex, and polyester resins have the highest effect. Therefore, other resins such as these Alternatively, when using metal, glass, etc. as a base material, a layer made of various organic polymer resins similar to those used for the above-mentioned base material is formed on the surface of the base material in advance, and reactive functional groups are introduced. More favorable results can be obtained if a lubricating layer is provided by blending the resin with a substance having a reactive functional group.To form the coating layer of the present invention on such a base material,
You can do as follows. When using an ordinary base material that does not contain reactive functional groups, first, a base layer is formed. To form the base layer, the base material may be immersed in a solution containing the above-mentioned compound having a reactive functional group, and then dried. In such a case, examples of solvents used include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate, methyl cellosolve, ethyl cellosolve, and tetrahydrofuran. Any of ether systems such as ether systems, aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, alcohol systems, etc. may be used. However, the solvent is preferably one that dissolves or swells the resin base material (in some cases, the resin coating layer previously formed on the surface of the base material). This is because the adhesion strength of the coating layer improves and the lasting effect becomes greater. Particularly suitable solvents include methyl ethyl ketone, cyclohyxanone, tetrahydrofuran, xylene, and methyl alcohol. In addition to dipping treatment, brush painting, spinner coating, etc. are also possible. The subsequent drying step is to evaporate the solvent, and is usually carried out at room temperature to about 80° C. for about 5 minutes to 48 hours. Note that, as described above, when coating the surface of the base material with an adhesive layer in advance, a conventional method may be followed. Next, the substrate on which the underlayer has been formed (or without forming the underlayer as the case may be) is treated with a solution containing the water-soluble polymeric substance of the present invention. The solvent used in this case is one that does not react with the reactive functional groups present in the base material or the adhesive layer, that is, one that does not react with incyanate groups and amino groups, and methyl ethyl ketone, THF, acetone, etc. are particularly preferred. Particularly suitable are those that have solubility and swelling properties in the base material. And its concentration is 0.1-15%, especially 0.5-10%
It is preferable to set it as approximately. Further, the treatment is usually performed by dipping treatment as described above, but various coating methods can also be used. The processing temperature is room temperature to 80°C, and the processing time is 1 second to 48°C.
It should be about an hour. Then, continue (the drying process is at room temperature to about 80°C,
It may be done for about 5 minutes to 48 hours. In this way, the water-soluble polymeric substance of the present invention is covalently bonded to the reactive functional group to form a coating layer. In the present invention, when the coating layer thus formed is further subjected to water treatment, an even more favorable result can be obtained in that affinity with water can be obtained in a short time. Water treatment usually involves immersing the material in water and then drying it. In this case, the immersion time is about 10 minutes to 2 hours, the processing temperature is room temperature to 60°C, and the drying is 30 minutes at room temperature to 80°C.
Do this for about 48 hours. In addition, as the water treatment, steam treatment or the like is also possible. Although the detailed mechanism is not clear, the reason why the water-soluble polymer coating layer covalently fixed to the base material of the present invention maintains extremely excellent lubricity over a long period of time is as follows. Conceivable. Water-soluble polymers are generally in an aqueous solution or gel state,
Hydrates through hydrophilic groups such as -NH2, -COOH, and -○H. Although the state of hydration is not fully understood, it is thought that there are two types of water: bound water, which is incorporated into the polymer and has relatively little movement, and water with a high degree of freedom. It is thought that one of the reasons for the development of lubricity when wetted with water is the presence of this free water. Although they absorb water and swell very well, they have poor lubricity, and the reason why some materials with relatively low molecular weights have low lubricity is due to this lack of free water, and this is affected by the structure and polarity of the polymer. It is thought that In other words, those with a crystalline molecular structure do not have a large amount of free water, and the movement of the entire molecule is not smooth compared to those with a chain structure. This is thought to be the reason why polymer substances have good lubricity.In addition, even those with a chain structure and hydrophilic groups, those that are bonded to the base material at various places, and those whose molecules are cross-linked are ,
The molecules themselves lose their degree of freedom, resulting in poor lubricity. Furthermore, a strong bond such as a covalent bond with the base material is very advantageous for maintaining lubricity. Therefore, the best lubricity is achieved when chain molecules having a hydrophilic group are fixed to the base material by covalent bonds and extend relatively long. In the present invention, the medical device having the base material subjected to the surface treatment as described above as its inner or outer surface is, as described above, wetted with the above-mentioned aqueous liquid when inserted. It has a surface that requires low frictional resistance when sliding and when indwelling in the body. Therefore, as the medical device of the present invention, there are the following medical devices provided with the coating layer of the present invention on the surface as described below. 1) The outer or inner surface of catheters that are inserted or indwelled into the gastrointestinal tract orally or nasally, such as gastric tube catheters, feeding catheters, and ED (enteral feeding) tubes. For example, in FIG.
An example is shown in which the coating layer 1 of the present invention is formed on the outer surface of the olive 21 of the tube 2 and the main tube 22. At this time, insertion becomes easier, and the patient's own swallowing becomes easier. 2) Catheters that are inserted or indwelled into the airway or trachea orally or nasally, such as oxygen catheters, oxygen cameras, tubes and cuffs for endotracheal tubes, tubes and cuffs for tracheostomy tubes, and endotracheal suction catheters. surface or inner surface. 3) Urethra - The outer or inner surface of catheters for insertion or indwelling into the urethra or ureter, such as catheters, urinary catheters, and balloon catheters. For example, FIG. 2 shows a side hole 31, a balloon 32, a main body tube 33, a balloon branch pipe 34, a main body connector 3
An example is shown in which the coating layer of the present invention is formed on the outer surfaces of the balloon 32 and the main body tube 33 of a balloon catheter 3 consisting of 5. At this time, since the frictional resistance is low, insertion is easy and pain to the patient is reduced. Furthermore, during indwelling within tissue, frictional resistance with mucous membranes is low, reducing the risk of inflammation or damage. Note that in the present invention, the balloon 32
Even if it is applied to an elastic body such as, the physical properties of the balloon 32 can be applied to an elastic body (in addition, the balloon 32 is a site where resistance during insertion is extremely large, so the effect is great. 4) Suction catheter, liquid drainage The outer or inner surface of catheters for insertion or indwelling into various body cavities or tissues, such as catheters and rectal catheters. In addition, by forming the coating layer of the present invention on the inner surface of these catheters 1) to 4), there are advantages such as reducing adhesion of nutrients, tissue fluid, etc., and not inhibiting the lumen flow path. 5) Outer or inner surfaces of catheters for insertion or indwelling into blood vessels, such as indwelling needles, IVH catheters, thermodilution catheters, angiography catheters, dilators, and introducers. Or the outer surface of guide wires, stylets, etc. for these catheters. For example, FIG. 3 shows an example in which the coating layer of the present invention is formed on the outer and inner surfaces of a Judkin style catheter 5 for coronary angiography. FIG. 4 also shows a guide wire 6 inserted into the catheter 5 and used to introduce the catheter 5 into a blood vessel site.
An example is shown in which the coating layer of the present invention is formed on the outer surface of. This reduces the insertion resistance of the catheter into the blood vessel and the coronary insertion resistance of the guide wire. 6) Surfaces of medical devices that require low frictional resistance during insertion, sliding, or indwelling in the body, such as the outer surface of endoscopes for insertion into various body cavities. 7) Other surfaces such as condoms and contact lenses. Specific effects of the rv invention According to the first invention, the frictional resistance on the surface of the medical device becomes extremely small. In particular, when wet with body fluids such as saliva, digestive juices, and blood, or aqueous liquids such as physiological saline and water, the frictional resistance is extremely low, and as a medical device,
It provides extremely great advantages such as ease of insertion, alleviation of patient pain, and prevention of damage to mucous membranes and vascular intima. In addition, the frictional resistance does not increase due to repeated use or storage under poor conditions, which is extremely advantageous in terms of long-lasting effects and storage stability. Because it is compatible with reactive functional groups,
Since there are few restrictions on the base materials to which it can be applied, it can be used in various medical devices and has excellent versatility. Furthermore, the coating layer can be manufactured at a lower cost than by conventional means. According to the second invention, a coating layer that exhibits lubricity, that is, low frictional resistance in a wet state is obtained. Furthermore, when water treatment is carried out as in the third invention, water is incorporated into the new aqueous group of the water-soluble polymer substance in the coating layer as water contained or bound, and one end is fixed to the base material by a covalent bond. The polymeric substances are aligned to form an orderly water-containing coating layer. Even if this is dried, the next time it comes into contact with an aqueous system, the affinity for water has increased, so that it becomes a lubricious coating layer in a short time. Although the as-treated coating layer of the second invention tends to develop lubricity somewhat slower than the water-treated coating layer of the third invention, the difference in lubricity can be seen over time. Therefore, the device having the coating layer according to the second invention may be used in devices that do not require quick development of lubricity. [Example 1], Soft polyvinyl chloride 3 cmX 5 cmX 0.4
After drying 4.tmm of 4'-diphenylmethane diisocyanate for 1 hour, methyl vinyl ether maleic anhydride copolymer (
GANTREZ AN-139, MW=750,000G
(manufactured by AF) 1.25% MEK solution for 10 seconds,
It was dried at 60° C. for 2 hours to obtain a surface lubricity treated sample (1). As a result of performing the frictional resistance and durability test described below on sample (1), the value of frictional resistance μ=0.02 was maintained even after continuous water washing for 6 hours. However, the surface did not reach a low frictional resistance state immediately after the sample was wetted with water, but the above-mentioned good state was obtained after some time had elapsed. After preparing sample (1), it was immersed in water at room temperature for about 30 minutes, and
After drying at °C for 24 hours, sample (2) was obtained. As a result of conducting the same test as (1) on sample (2), even after continuous water washing for 6 hours at μ=0.02,
We were able to maintain this value. Furthermore, in sample (2), sample (
Unlike 1), the surface lubricity developed relatively quickly after getting wet with water and was good. After preparing sample (1), immerse it in water for about 1 hour or more at room temperature,
After drying at 60° C. for 24 hours, sample (3) was obtained. Sample (3
) As a result of conducting tests similar to (1) and (2),
Similarly, this value could be maintained even after continuous water washing for 6 hours with frictional resistance μ=0.02. Furthermore, in sample (3),
Compared with Samples (1) and (2), the surface lubricity was developed immediately after getting wet with water and was very good. [Example 2] Soft polyvinyl chloride 3 cmX 5 cmX O. 4t
6 mm in an aqueous solution of 5 wt% diethylenetriamino and 5 wt% tetra-n-butylammonium iosite.
After dipping at 0°C for 10 minutes and drying at 60°C for 30 minutes, methyl vinyl ether maleic anhydride copolymer (GANTREZ A
N-139) Immerse in 2.5% MEK solution for 10 seconds and dry at 60°C for 2 hours. Thereafter, it was immersed in water for about 1 hour, and after water treatment, it was dried at 60° C. for 24 hours to obtain a surface lubricity treated sample (4). [Example 3] 10 g of polyethylene glycol (MW=1000). A polyurethane resin having terminal incyanate groups was synthesized by reacting with 4 g of penryerythritol and 16 g of toluene diisocyanate. This polyurethane resin is 3 cm x 5 cm x 0.
The sheet was molded to 4 tmm, and this sheet was dissolved in a 1.25% MEK solution of methyl vinyl ether maleic anhydride copolymer.
After being immersed for 0 seconds, dried at 60°C for 2 hours, immersed in water at room temperature for about 1 hour or more, and dried at 60°C for 24 hours, a surface lubricity treated sample (5) was obtained. In the friction resistance test and durability test, like sample (3),
It was very good. [Example 4] A 7 Fr (outer diameter 2.3 mm, inner diameter 1.4 mm) nylon 6 angiography catheter was immersed in dilute hydrochloric acid at 30°C for 60 minutes, and after thoroughly rinsing with water, a 210% aqueous solution of polyethylene trash and dicyclohexyl carbonimide 5 were soaked. 1.25% methyl vinyl ether maleic anhydride copolymer.
It was immersed in MEK solution for 10 minutes, dried at 60°C for 2 hours, immersed in water at room temperature for about 1 hour or more, and dried at 60°C for 24 hours to obtain a surface-lubricated catheter (6). It showed very good lubricity and durability in friction resistance tests and durability tests. [Example 5] A stainless steel rod with a diameter of 0.87 and a length of 100 cm was immersed in a 1:1 mixed solution of 4.4'-diphenylmethane diisocyanate and 5% polyurethane (5% T) IP warm solution, and dried at 60°C for 1 hour. After doing 2
．． 5% methyl vinyl ether maleic anhydride copolymer (
GANTREZ AN-169 MW = 1.5 million manufactured by GAF) Immersed in MEK solution for 1 minute, 60℃3
After drying for 0 minutes, immerse in water for about 3 hours, and after water treatment at 60℃2
It was dried for 4 hours to impart surface lubricity, and a catheter guide wire (7) was obtained. When the guide wire (7) wetted with physiological saline was inserted into a 7Fr angiography catheter and operated, the sliding resistance was very low (good. [Example 6] 18Fr (outer diameter 6 mm) Natural rubber balloon catheter with 4,4'-diphenylmethane diisocyanate 1
% MEK solution for 1 hour and dried at 60°C for 30 minutes,
Methyl vinyl ether maleic anhydride copolymer (GAN
TREZ AN-169 Mw = 1,500,000 GAF) Immersed in 1% MEK solution for 1 second, dried at 60°C for 30 minutes, then immersed in water for about 3 hours, treated with water, dried at 60°C for 24 hours to impart surface lubricity. A balloon catheter (8) was obtained. The surface lubricity was good as in the previous example. [Example 7] Soft polyvinyl chloride 3 cmX 5 cmX O. 4t
mm to 4,4'-diphenylmethane diisocyanate 1
%ME for 1 minute, and after drying at 60°C for 30 minutes, methyl vinyl ether maleic anhydride copolymer (GA
NTREZ AN-170, MW=800,000 GAF
Ethyl ester (degree of esterification: 40-50%)
It was immersed in the solution for 10 seconds and dried at 60°C for 2 hours to obtain a surface lubricity treated sample (21). As a result of performing frictional resistance and durability tests separately shown on sample (21), a value of frictional resistance μ=0.02 was maintained even after 6 hours of continuous water washing. However, the surface did not reach a low frictional resistance state immediately after the sample was wetted with water, but the above-mentioned good state was obtained after some time had elapsed. After preparing the sample (21), it was immersed in water at room temperature for about 30 minutes, and then
After drying at 0° C. for 24 hours, a sample (22) was obtained. As a result of performing the same test as (21) on sample (22), it was found that μ=0.02 and this value could be maintained even after continuous water washing for 6 hours. Furthermore, unlike sample (21), sample (22) exhibited good surface lubricity relatively quickly after getting wet with water. death,
After drying at 60° C. for 24 hours, a sample (23) was obtained. sample(
Regarding 23), tests similar to those in (21) and (22) were conducted, and as a result, the frictional resistance μ = 0.02 and this value could be maintained even after continuous water washing for 6 hours. Furthermore, in comparison with samples (21) and (22), sample (23) showed very good surface lubricity immediately after getting wet with water. [Example 8] Soft polyvinyl chloride 3 cmX 5 cmX 0.4t
6 mm in an aqueous solution of 5 wt% diethylenetriamino and 5 wt% tetra-n-butylammonium iosite.
After soaking at 0°C for 10 minutes and drying at 60°C for 30 minutes, methyl vinyl ether maleic anhydride copolymer ethyl ester 4%T
Dip in HF solution for 10 seconds and dry at 60°C for 2 hours.
Thereafter, it was immersed in water for about 1 hour, and after water treatment, it was dried at 60° C. for 24 hours to obtain a surface lubricity treated sample (24). Similarly, a friction resistance test and a durability test were conducted, and the results were favorable. [Example 9] Polyethylene glycol (MW = 1000) log
, 4 g of penryerythritol, and 16 g of toluene diisocyanate to synthesize a polyurethane resin having terminal isocyanate groups. This polyurethane resin is 3 cm x 5 cn x 0.
This sheet was immersed in a 4% THF solution of half ethyl ester (degree of esterification: 40-50%) of methyl vinyl ether maleic anhydride copolymer for 10 seconds, dried at 60°C for 2 hours, and then dried at room temperature for about 1 After soaking in water for more than an hour and drying at 60°C for 24 hours, the surface lubricity treated sample (25
) was obtained. Like sample (23), it performed very well in the friction resistance test and durability test. [Example 101] A 7 Fr (outer diameter 2.3 mm, inner diameter 1.4 mm) nylon 6 angiography catheter was immersed in dilute hydrochloric acid at 30°C for 60 minutes, thoroughly washed with water, and then diluted with a 10% aqueous solution of polyethyleneimine and 5% dicyclohexyl carbonimide. It was immersed in a 1:2 mixed solution of methanol solution at 30°C for 5 hours, washed with water, and then immersed in a 4% THF solution of half ethyl ester of methyl vinyl ether maleic anhydride copolymer (degree of esterification 40-50%) for 10 minutes. , dried at 60°C for 2 hours, dried at room temperature for about 1
After treatment with water by immersing it in water for more than an hour, it was dried at 60° C. for 24 hours to obtain a surface-lubricated catheter (26). It showed very good lubricity and durability in friction resistance tests and durability tests. [Example 11] A stainless steel rod with a diameter of 0.87 mm and a length of 100 cm,
It was immersed in a 1:1 mixed solution of polyurethane 5% THF solution and 4.4'-diphenylmethane diisocyanate 2% MEK solution and dried at 60°C for 1 hour. 40-50%) immersion in 4% THF solution for 1 minute,
After drying at 60° C. for 30 minutes, it was immersed in water for about 3 hours, and after water treatment, it was dried at 60° C. for 24 hours to obtain a surface lubricity-imparted catheter guide wire (27). When the guide wire (27) wetted with physiological saline was inserted into the 7Fr angiography catheter and operated, the sliding resistance was very low and the results were good. [Example 12] An 18Fr (outer diameter 6 mm) natural rubber balloon catheter was coated with 4.4'-diphenylmethane diisocyanate 1
After drying, half ethyl ester of methyl vinyl ether maleic anhydride copolymer (degree of esterification 40-50%)
) 1% T) Immersed in IF solution for 1 second and dried at 60'C for 30 minutes, then immersed in water for about 3 hours, after water treatment, at 60'C24
Balloon catheter with time-dry surface lubricity (28)
I got it. The surface lubricity was good as in the previous example. Examples 1 to 6 of the present invention [sample numbers (1) to (8)] and Examples 7 to 12 of the present invention [sample numbers (21) to (2)]
g) ] did not produce any significant difference in the friction resistance and continuous water washing tests, but as a more severe test method, when the test results were repeatedly squeezed with a finger under running water, Examples 7 to 12 showed better results. The durability of surface lubricity was slightly better, and even better results were obtained. [Example 13] Polyurethane resin 3 cmX 5 cmX 0.4tm
4,4'-diphenylmethane diisocyanate 0.6% MEK solution for 1 minute, and heated at 60℃30.
After drying for a minute, water-soluble nylon (AQ Nylon P-7
0) in 10% chloroform solution for 1 second at 60℃6
After drying for a period of time and water treatment, a surface lubricity treated sample (31) was obtained. Good results were observed in both wet lubricity and durability. [Example 14] A polyurethane resin sheet similar to (13) was 4.4'-
Diphenylmethane diisocyanate 0.01% MEK
After immersing in the solution for 1 minute and drying at 60°C for 30 minutes, hydroxypropyl cellulose () IPC: Hercules H
type) immersed in 0.75% chloroform solution for 1 second,
After drying at 60°C for 6 hours and water treatment, the surface lubricity treated sample (3
2) was obtained. Good results were confirmed in both wet lubricity and durability. [Comparative Example 1] Soft polyvinyl chloride 3 cmX 5 cmX 0.4t
Samples of (12) low-density polyethylene, (13) high-density polyethylene, and (14) tetrafluoroethylene of the same size as the sample pieces whose mm surface is (9) glycerin coated, (10) olive oil coated, and (11) non-coated. Prepare the pieces;
Friction resistance and durability test with invention examples (1) to (8)-■
As a result of carrying out the following procedure, it was found that the friction resistance was originally large on the side other than the side of the present invention, or the initial lubricity was lost after about 10 minutes of continuous water washing, and the effectiveness of the present invention was confirmed. . [Comparative Example 2] A nylon angiography catheter and sheet similar to those used in Example 4 were coated with a polyurethane resin having terminal isocyanate groups synthesized in Example 3, and polyvinylpyrrolidone (K-90, average molecular weight 360,000, G
After immersion in a 5% chloroform solution (manufactured by AF) and drying, a sample (15) that was not supported on the substrate by covalent bonding was obtained.
16) was obtained. Inventive samples (1) to (5), friction resistance test of sheet (61) obtained in the same manner as Example 10 and sample (15),
In Sustainability Test-I, although there was a slight difference in the latter, good surface lubricity was observed in all cases. However, in the sustainability test-H, sample (16) had a clear loss of lubricity, whereas the present inventions (1) to (5) (61
) was still found to have lubricity. Furthermore, when both catheters were bent, peeling of the urethane layer occurred around the catheter side hole and at the boundary of the untreated portion only in sample (15), and no abnormality was observed in sample (6) prepared in Example 4. Therefore, the effectiveness of the present invention was confirmed. [Friction resistance test] As shown in FIG. 5, polyvinyl chloride or polyurethane sheets 41 treated to have coatings according to the examples of the present invention and comparative examples are fixed on an inclined plate, and a sheet made of polyamide resin is placed on the bottom surface. When a cylindrical iron weight 44 with a sheet 43 attached and weighing approximately 100 g is placed on it and the inclination angle θ of the plate 41 is gradually increased, the angle θ at which the weight starts to slide is determined, μ = tanθ The friction coefficient was calculated as follows. The results are shown in Table 1. Glycerin coat (8) and olive oil coat (9)
For this, a polyvinyl chloride sheet was immersed in the coating solution, and the sample surface was obtained by shaking it off to the extent that the solution would not drip. [Durability test-I (change in friction coefficient over time)] A sample having the coated surface described in the example of the present invention, olive oil, and glycerin coated surface was immersed in II2 water.
The mixture was stirred at rpm, and the friction coefficient was determined by the test method shown in FIG. 5, and its change over time was investigated. The results are shown in Table 1 and Figure 6. [Durability test - (change in lubricity due to severe friction)] The sample surfaces as described in the examples and comparative examples of the present invention were
The durability of the lubricity was checked by rubbing strongly with a finger moistened with water. The results are shown in Table-1. Table-1 Surface lubricity various evaluation tables

[Brief explanation of the drawing]

1, 2, 3, and 4 show configuration examples of the medical device of the present invention, and are a side view and a side view of an ED tube, a balloon catheter, a coronary angiography catheter, and a guide wire, respectively. 6 is a diagram showing a method of measuring the friction coefficient, and FIG. 6 is a graph showing changes in the friction coefficient over time. Explanation of symbols l...Covering layer 2 of the present invention...HD tube 21...Olive 22...Body tube 24...Connector 31...Side hole 32...Balloon 33...Body Tube 34... Balloon branch tube 35... Main body connector 41... Sample plate 42... Inclined plate 43... Bottom plate 44... Weight 5... Coronary angiography catheter 6... Guide Wire diagram 5

Claims (7)

[Claims] (1) A reactive functional group present at least on the surface of the base material constituting the medical device and a water-soluble polymeric substance selected from cellulose-based polymeric substances, polyethylene oxide-based polymeric substances, and water-soluble nylon, or its 1. A medical device characterized in that the surface thereof has lubricity when wetted by covalently bonding a derivative with a derivative. (2) The medical device according to claim 1, wherein the cellulosic polymer material is hydroxypropyl cellulose. (3) The medical device according to claim 1, wherein the polyethylene oxide polymeric substance is polyethylene glycol. (4) Claim 1, wherein the reactive functional group is an aldehyde group, an epoxy group, an isocyanate group, or an amino group.
Medical equipment listed in section. (5) The medical device according to claim 1, which comprises a rod-shaped body that can be inserted into a medical tube, and is a guide tool that allows the medical tube to be introduced into or removed from the body. (6) Treat a base material constituting a medical device with a solution of a compound having a reactive functional group to form a base layer so that the reactive functional group is present on at least the surface of the base material, and then Treating with a water-soluble polymer substance selected from molecular substances, polyethylene oxide-based polymer substances, and water-soluble nylon or derivatives thereof to covalently bond the reactive functional group and the water-soluble polymer substance; 1. A method for manufacturing a medical device, comprising forming a coating layer of a water-soluble polymer substance on a base layer so that the surface has lubricity when wetted. (7) Treat a base material constituting a medical device with a solution of a compound having a reactive functional group to form a base layer so that the reactive functional group is present on at least the surface of the base material, and then Treating with a water-soluble polymer substance selected from molecular substances, polyethylene oxide-based polymer substances, and water-soluble nylon or derivatives thereof to covalently bond the reactive functional group and the water-soluble polymer substance; 1. A method for manufacturing a medical device, comprising forming a coating layer of a water-soluble polymer substance on a base layer, and then performing water treatment so that the surface has lubricity when wet.