JPH07101B2 - Catheter tube - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is applied to the field of medical catheter tubes, particularly catheter tubes for digestive organs that are inserted into the body nasally or catheter tubes for urology. It

[Prior art]

There are gastrointestinal catheters, gastrointestinal catheters, gastrointestinal catheters, gastrointestinal catheters, esophageal tubes, Zengstangen breakmore tubes, nutrition tubes, etc., for gastrointestinal catheters that are inserted into the body via the nasal passage. There are urinary catheters, urethral catheters, etc., for catheters and tubes, all of which are made of polyvinyl chloride silicone rubber, latex, polyethylene,
Made from polyurethane, etc.

Since most of these catheters are hydrophobic, the resistance and irritation to the mucous membrane are great if they are left as they are, which may make it difficult to insert the catheter, cause laceration of the mucous membrane, and cause pain to the patient.

Therefore, in the past, water or jelly was used as a lubricant to facilitate insertion, and a local anesthetic such as lidocaine was further mixed to reduce pain, and it was applied to the tip of the catheter. It was These methods are cumbersome and have insufficient efficacy in reducing patient distress. On the other hand, a method of forming a hydrophilic film to impart lubricity has been proposed. (U.S. Pat. Nos. 4,100,309 and 4,119,094) In these methods, the material of the coating is vinylpyrrolidone polymer or the like, and these methods only form the coating, and the surface of the catheter / tube is activated. Therefore, even if lubricity is imparted, there is a high risk that the hydrophilic coating may peel off or fall off during insertion or during use.

[Object of the Invention]

The present invention is to provide a catheter tube which exhibits high lubricity when used by being inserted into the human body and which reduces irritation to the human body, while having high safety.

[Structure of Invention]

The present invention, a part or all of the tubular outer surface made of plastic is plasma treatment, corona discharge treatment, or an ultraviolet treatment is activated, further N, N dimethyl on the activated surface. The present invention relates to a catheter tube coated with a copolymer of acrylamide and methoxytetraethylene glycol methacrylate and having a water lubrication rate of 50% or less.

To measure the water lubrication rate, insert a metal round bar along the inner diameter of the tube to be measured and fix it, and make a silicone rubber sheet with a width of 25 mm and a thickness of 2 mm perpendicular to the measurement area as shown in Fig. 1. To make contact. (1/4 of the outer surface of the tube measurement part is in surface contact with the silicone rubber sheet.) A load of 200 g is applied to one end of the silicone rubber sheet, and the other end is connected to the load cell through a pulley. Lubricate the contact surface between the tube and the silicone rubber sheet with water beforehand, measure the 50 mm tensile load at a speed of 300 mm / min with a crosshead directly connected to the load cell, and read the maximum and minimum values. Further, rotate the measurement part of the tube 180 ° and measure in the same way, read the maximum and minimum values, and average them to obtain Wt.

Next, let W _B be the result of performing the same measurement in a tube of the same shape that has not been activated and covered with the copolymer of N, N dimethylacrylamide and methoxytetraethylene glycol methacrylate.

The water lubrication rate is expressed by equation (1).

In the present invention, the material of the tube is made of plastic and may be a single or multi-component material, and the tube shape is not particularly limited, such as the size of the diameter, the same diameter or the different diameter. In order to improve the wettability of the hydrophilic polymer to be coated and the adhesiveness after coating, a part or all of the surface of the tube is activated. As the activation treatment, plasma treatment,
Either corona discharge treatment or ultraviolet treatment may be used. Since these processes change with time, it is better to move to the next step as soon as possible. A plasma-initiated polymerization method is preferable as a method for producing a copolymer of N, N dimethylacrylamide and methoxytetraethylene glycol methacrylate.
Since plasma functions as a polymerization initiator in this method, it contains no reagents other than monomers and is suitable for application in the medical field. According to this method, N, N dimethylacrylamide has a slow polymerization rate and methoxytetraethylene glycol methacrylate has a high polymerization rate. The former polymer is relatively easy to handle, but the latter polymer is sticky and poor in workability.

Copolymerization is carried out in order to make up for the drawbacks of both, but when the weight ratio of N, N dimethylacrylamide / weight of methoxytetraethylene glycol methacrylate = D / M ratio, this ratio is 0.05 to 0.95, preferably 0.5 to 0.9. . If the D / M ratio is biased, each of the above-mentioned drawbacks will appear. It is known that the plasma-initiated polymerization method accelerates the polymerization rate by the presence of water, and water is added as a polymerization solvent from the viewpoint of handling after the polymerization. The concentration of the whole monomer with respect to water is 5 to 30%, preferably 10 to 15%. If this concentration is low, the polymerization rate will decrease, and if it is high, it will increase and control by time will be difficult. After compounding, the dissolved oxygen is removed by blowing nitrogen gas or by freeze degassing. The degree of vacuum inside the container is important for plasma generation.
01-1 torr, preferably 0.05-0.5 torr. After completion of plasma irradiation, post-polymerization proceeds. 1.5-10 after polymerization
The residual monomer is separated and purified by diluting with water in a range of preferably 2 to 3 times. For the purification, a polymer is used as a poor solvent monomer and a good solvent such as methylene chloride is used according to a conventional method to obtain a coating solution. Next, the coating solution is applied to a catheter tube whose surface has been activated. Apply 1
The coating is thicker and the lubrication effect is improved and the reproducibility is improved when the coating is applied more than once. After coating, it is dried by air drying, heating, reduced pressure, etc. Thereafter, for example, post-treatment such as immersion treatment is performed in a mixed solution of water, ethanol and the like by weight. After the post-treatment, it is dried to obtain a product.

The product according to the invention is evaluated, for example, by a water lubricity test.
The water lubrication rate is defined by the equation (1), but it must be at least 50% or less. If it is 50% or more, the lubricity at the time of being inserted into the human body for use becomes insufficient and the irritation to the human body becomes large, so that the object of the present invention cannot be achieved.

〔The invention's effect〕

The surface of the catheter tube according to the present invention is activated, and the surface is coated with a high-molecular weight hydrophilic copolymer from which residual monomers have been removed. The rate is less than 50%.

Therefore, it is suitable for a gastrointestinal catheter tube or a urological catheter tube.

Examples will be described below.

Example 1 Equipment used: plasma treatment of equipment; plasma polymerization equipment manufactured by Shimadzu LCVD-12 type, plasma-initiated polymerization of monomers; high frequency oscillator JEH-005D manufactured by JEOL Ltd. Materials used: equipment; extruded polyurethane (Takeda Yakuhin) T-850 manufactured by Co., Ltd. Tube outer diameter 5 mm Inner diameter 2.5 mm Monomer; N, N Dimethylacrylamide Co., Ltd. Kojin's methoxytetraethylene glycol methacrylate Shin-Nakamura Chemical Co., Ltd. Activation condition: 100 W with argon gas 10 minutes Plasma-initiated polymerization: Monomer aqueous solution formulated as prescribed was frozen and degassed, and then plasma irradiation was performed for 200 W for 2 minutes. After polymerization, close the vacuum cock at 40 ° C for 48 hours.

Removal of residual monomers: Excess methylene chloride is added, and the mixture is stirred, separated, and concentrated under reduced pressure to obtain a coating solution.

Coating: The tube within 1 week after the activation treatment is immersed in the coating solution and pulled up.

Post-treatment: After air-drying overnight, 50 in water / ethanol etc.
After treatment at ℃ for 2 hours, air-dry for 1 hour. Vacuum dry at 50 ℃ for 4 hours.

The water lubricity test was performed using the apparatus shown in FIG. The results are shown in Table 1.

Example 2 As the activation treatment, a HFS-402 type corona discharge treatment device manufactured by Kasuga Electric Co., Ltd. was used, and the primary voltage was 220 V, the primary current was 17 A, and the transfer speed was 3
Same as Example 1 except that the belt was passed three times at m / min.

Example 3 Example 1 was repeated except that the activation treatment was carried out twice by using a commercially available mercury lamp (2 KW) at a transport speed of 2 m / min.
Same as

Comparative Example 1 Same as Example 1 except that the activation treatment was not performed.

Comparative Example 2 A tube not subjected to activation treatment and coating.

Example 4 and Comparative Example 3 A soft vinyl chloride resin containing 55 parts by weight of DOP as a plasticizer was extrusion-molded, the tip was heated to seal and rounded, and the same plasma as that of Example 1 as shown in FIG. Processed. Then, the copolymer synthesized in Example 1 was applied by dipping from the catheter tip to a portion of 200 mm, and 1
After overnight air drying, it was immersed in a mixed solution of water, ethanol and the like at 50 ° C. for 90 minutes and vacuum dried at 40 ° C. for 3 hours. After that, one side hole of 1 mmφ was opened 5 mm away from the tip of the catheter to prepare a urinary catheter. (Example 4).

We made a prototype urinary catheter made of soft vinyl chloride resin with the same shape and without plasma treatment and copolymer coating. (Comparative example 3).

First, Comparative Example 3 was performed using these catheters in a small miscellaneous dog.
Subsequently, they were inserted into the urethra in the order of Example 4 to check the operability.

The catheter of Comparative Example 3 had 2 catheters in the urethra near the penis bone and in the urethra near the origin of the urethral penis where the urethra makes a U-turn.
There was some resistance, especially during insertion. On the other hand, when the catheter of Example 4 was inserted, it could be easily inserted with almost no resistance. After that, urination was forcibly conducted with a syringe, and it was confirmed that the tip of the catheter reached the inside of the bladder. Then, the catheter of Example 4 was taken out, and the water lubrication rate was measured. As a result, the lubricity was extremely high at 27%.

[Brief description of drawings]

FIG. 1 shows a water lubrication rate measuring apparatus, in which 1 is a sample tube in which a metal round bar is inserted and fixed, 2 is a silicone rubber sheet, 3 is a weight, 4 is a pulley, and 5 is a load cell. FIG. 2 shows the details of 1. 1a is a tube, 1b is a metal rod, and 1c is an adhesive tape. FIG. 3 shows the shape of the sample tube of Example 4, and the hatched portion shows the copolymer-coated portion.

Claims (2)

[Claims] 1. A tube-shaped outer surface made of plastic is partially or wholly activated by a plasma treatment, a corona discharge treatment, or an ultraviolet treatment, and N, N is further applied on the activated surface. It is coated with a copolymer of dimethylacrylamide and methoxytetraethylene glycol methacrylate, and has a water lubrication rate represented by the following formula (1).
A catheter tube characterized by being 50% or less. Here, Wt: In the cross-sectional shape of the tube coated with the activation treatment and the copolymer, the width is 2 so that it touches the surface of 1/4 circumference.
Attach a silicone rubber sheet with a thickness of 5 mm and a thickness of 2 mm.
After applying a load of 0 g and lubricating the contact surfaces of both the tube and the silicone rubber sheet with water in advance,
Measure the maximum and minimum values of the load when pulling 50 mm at a speed of 0 mm / min, rotate the tube 180 °, and measure the maximum and minimum values in the same way. The average of the four numerical values. W _B : Average value of the above measurements when using a tube not subjected to activation treatment / copolymer coating. 2. A copolymer of N, N dimethylacrylamide and methoxytetraethylene glycol methacrylate is copolymerized by a plasma initiation polymerization method, and the weight ratio of N, N dimethylacrylamide / methoxytetraethylene glycol methacrylate is 0.05 to A catheter tube according to claim 1 having a value of 0.95.