JPH10118176A - Medical equipment - Google Patents

Abstract

(57) [Problem] To provide a medical device having permanent lubricity when wet. SOLUTION: At least one compound represented by the general formulas [1a] and [1b], and [2a] and [2]
b] and a repeating unit containing at least one compound represented by [2c], and [1a]: [1b]
Is in the range of 70:30 to 95: 5 wt% by weight, and [1a] + [1b]: [2a] + [2b] + [2
c] is in the range of 99: 1 to 60:40 wt% by weight, and GPC using tetrahydrofuran as a solvent
Polystyrene reduced number average molecular weight by measurement is 2,000
A medical device coated with a copolymer having a molecular weight of up to 100,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a medical device, and more particularly to a medical device such as a catheter having lubricity when wet.

[0002]

2. Description of the Related Art In recent years, a technique of percutaneously inserting a catheter or the like without incising an affected part when administering a drug to a blood vessel, a ureter, a trachea, or the like or inserting a stent is known. Has been adopted. These medical devices require smoothness that allows accurate insertion to a target site without damaging mucous membranes or tissues. In addition, excellent lubricity is required to avoid damaging tissues and mucous membranes and causing inflammation due to friction during placement in tissues.

[0003] Therefore, a low friction material is used as a base material of these medical devices, and a hydrophilic polymer is coated on the surface of the base material. For example, a low friction material such as a fluororesin or polyethylene is used as a base material of a medical device, or a fluororesin, silicone oil, glycerin, olive oil, or the like is applied to the surface of these materials. In JP-A-6-7426, a polymer material is swollen with a polar solvent, the polymer material is impregnated with a hydrophilic polymer compound dissolved in the polar solvent, and treated with water, so that a swellable surface is obtained when wet. A method of forming is disclosed. However, these methods have drawbacks such as the coefficient of friction not being sufficiently low.Permanent lubricity cannot be expected with these surface coatings, and elution and peeling of lubricating substances from the substrate surface There was a problem in terms of safety.

Further, US Pat. No. 4,100,309 discloses a method of fixing a hydrophilic polymer polyvinylpyrrolidone to a substrate via an isocyanate.
Discloses a method using a hydrophilic polymer obtained by copolymerizing a reactive functional group and isocyanate, and JP-A-58-193766 discloses a method of fixing polyethylene oxide to a substrate via isocyanate. These surface lubrication methods require at least two coating operations (for example, coating of a crosslinkable compound such as isocyanate and coating of a substance having lubricity), which is not preferable in operation. In addition, since bifunctional reactive groups generally have high reactivity, the use of these substances is not preferable from the viewpoint of safety.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide a medical device surface with permanent lubricity (low friction) when wet, such as when contacting a body fluid, and a plurality of coatings. An object of the present invention is to provide a highly safe medical device that requires no operation.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned problems of the prior art, and have reached the present invention. That is, the present invention provides the following general formula [1]
a], [1b], and [2a], [2b], [2c]
Wherein the weight ratio of [1a]: [1b] is 7
0:30 to 95: 5, [1a] + [1b]: [2
a] + [2b] + [2c] in a weight ratio of 99: 1 to 60:
The present invention relates to a medical device coated with a copolymer of No. 40.

[0007]

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(In the formula [1a], R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 200.)

[0009]

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(In the formula [1b], R ³ is a hydrogen atom or a methyl group, Xa is an atom or a group which can be a monovalent cation species, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms,
b represents a hydroxyl group, an amino group, or an amide group. )

[0011]

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(In the formula [2a], R ⁵ represents a hydrogen atom or a methyl group, and Xc represents an alkyl group having 4 to 30 carbon atoms.)

[0013]

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(In the formula [2b], R ⁶ is a hydrogen atom or a methyl group, and Xd is a perfluoroalkyl group-containing group having 4 to 20 carbon atoms.)

[0015]

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(In the formula [2c], R ⁷ is a hydrogen atom or a methyl group, R ^{8 is} an alkylene group or a modified alkylene group having 1 to 20 carbon atoms, R ⁹ is an alkyl group or a modified alkyl group having 1 to 20 carbon atoms, m represents an integer of 5 to 80.) Hereinafter, the present invention will be described in detail.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, [1a], [1
b] both have the effect of imparting hydrophilicity to the copolymer and reducing the friction of the surface coated with the copolymer. In particular, [1a] is a highly hydrophilic monomer and has a low glass transition temperature, so that it is possible to impart flexibility to the coating surface.
In addition, since the polyethylene oxide chains have good mobility, the interaction with blood components is low, and lubricity can be imparted. In the general formula [1a], n represents an integer of 1 to 200, preferably n is in the range of 5 to 100. n is 20
If it is larger than 0, the solution viscosity during polymerization becomes high, which is not preferable. Examples of the general formula [1a] include the following polyethylene oxide-containing (meth) acrylates.

[0018]

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Also, a vinyl monomer represented by the general formula [1b] is copolymerized to impart hydrophilicity and high molecular weight. In the general formula [1b], Xa can be a monovalent cation species, and specific examples of the compound include (meth) acrylic acid, or a sodium, potassium or ammonium salt thereof. Further, the other vinyl copolymer is a conventionally known radical polymerizable monomer having a hydrophilic group, wherein the hydrophilic group-containing group is,
It means a group having a hydrophilic group such as a hydroxyl group, an amino group, an amide group and a carboxyl group. Specific examples of the monomer having a hydrophilic group include hydroxy (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. These may be used in combination of two or more kinds of monomers. [1a]:
The ratio of [1b] is a polymerization ratio of 70:30 to 95: 5, preferably 75:25 to 90:10, and more preferably 80:
It is preferred to copolymerize at 20 to 85:15. [1b] is 3
If it exceeds 0 wt%, the hydrophilicity is slightly lowered to increase the coefficient of friction, and if it is less than 5 wt%, the polymerizability becomes poor.
[2a], [2b] and [2c] are hydrophobic monomers, and one or more of them can be used according to the base material constituting the medical device. Examples of the alkyl group-containing vinyl monomer of the general formula [2a] include the following alkyl group-containing (meth) acrylates.

[0020]

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Examples of the perfluoroalkyl group-containing vinyl monomer represented by the general formula [2b] include the following perfluoroalkyl group-containing (meth) acrylates.

[0022]

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In the present invention, particularly preferred perfluoroalkyl group-containing vinyl monomers are the following perfluoroalkyl (meth) acrylates. In the following formula, o shows the integer of 6-10.

[0024]

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Examples of the vinyl monomer of the general formula [2c] include the following silicone-containing (meth) acrylates.

[0026]

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It has been found that the use of these hydrophobic monomers in an appropriate range has an effect of suppressing the elution of the copolymer without impairing the lubricity of the copolymer. [1
The ratio of a] + [1b]: [2a] + [2b] + [2c] is 99: 1 to 60:40 by weight, preferably 98:
2-70: 30, more preferably 97: 3-80: 2
0. When [2a] + [2b] + [2c] is less than 1 wt%, the copolymer has high hydrophilicity and the copolymer is easily eluted, and when it exceeds 40 wt%, the copolymer has poor hydrophobicity. It becomes bigger and stickiness of the coating film occurs,
Also, friction increases.

The copolymer of the present invention has the general formula [1]
a), [1b] and at least one of the compounds represented by [2a], [2b], and [2c] are obtained by copolymerization in the presence of a radical initiator. Examples of a method of coating the above-mentioned copolymer on a medical device include dipping, coating, and spraying methods, and dipping is effective. As the immersion liquid, it is preferable to use the copolymer dissolved in a polar solvent, and as the polar solvent, for example, methyl ethyl ketone, methyl isobutyl ketone, acetone,
Examples thereof include tetrahydrofuran, dioxane, dimethylformamide, alcohols, and dimethyl sulfoxide. Further, the concentration of the immersion liquid is preferably 1 to 30% by weight. If the concentration of the immersion liquid is less than 1% by weight, sufficient lubricity will not be exhibited, and if it is more than 30% by weight, the viscosity of the immersion liquid is too high to uniformly coat, which is not preferable. After immersion, it is preferable to dry at 50 to 85 ° C. for 3 to 50 hours.

The shape of the medical device of the present invention includes a flat membrane,
Hollow fibers, sheets, tubes, nonwoven fabrics, woven fabrics, or composites thereof are conceivable. In particular, it is preferably a tube-shaped, so-called catheter that can be inserted into a blood vessel, other body cavity, or tissue. Examples of the form of the medical device of the present invention include an artificial kidney membrane, a plasma separation membrane, a catheter,
Materials for artificial lungs, artificial blood vessels, adhesion preventing films, materials for implants, and the like can be exemplified. Especially in blood vessels and other body cavities,
Alternatively, a catheter inserted into tissue is preferable. Further, as the base material constituting the medical device used in the present invention, depending on the target medical device, for example,
Examples include polyurethane, polyamide, and polyacrylate.

[0030]

Embodiments of the present invention will be described below, but the present invention is not limited thereto. The coefficient of friction was measured by applying a load of 100 g in water using an automatic friction and wear analyzer DFPM-SS manufactured by Kyowa Interface Chemical Co., Ltd., and measuring the static friction coefficient (μS) and the dynamic friction coefficient (μK). The durability was measured by measuring the change in the coefficient of static friction after five times of friction in the measurement of the coefficient of friction. O when the change rate is 10% or less, 10 to 20%
The following cases were rated as Δ, and the cases with 20% or more were rated as x.

Example 1 6.3 g of polyethylene glycol methacrylate (041MA, manufactured by Kyoeisha Chemical Co., Ltd.) and 0.68 of acrylic acid were placed in a flask equipped with a stirring blade, a reflux condenser, and a gas inlet.
g, heptadecafluorodecyl acrylate (Viscoat 17F, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 0.61 g, t-
Butyl peroxyisopropyl carbonate 57.4m
g and 17.71 g of methyl isobutyl ketone, and polymerized at 110 ° C. for 8 hours under a nitrogen stream. 1 g of the copolymer solution was dissolved by stirring in 9 g of methyl ethyl ketone, and a polyurethane film (Pelesen 2363-80AE manufactured by Dow Chemical Company) was immersed in the obtained solution for about 1 minute,
Dry at 0 ° C. for 10 hours. The film immediately became slimy when wet with water, and had a static friction coefficient of 0.021 and a dynamic friction coefficient of 0.018. Also,
There was no change in the coefficient of friction after 5 rubs.

Examples 2 and 3 Polymerization and coating were carried out in the compositions shown in Table 1 in the same manner as in Example 1, and the friction coefficient was measured. Table 1 shows the results of each example.

[0033]

[Table 1]

041MA: Polyethylene glycol methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) (n ≒ 30 in formula [1a]) MAE400: Polyethylene glycol methacrylate (manufactured by NOF Corporation) (n ≒ 9 in formula [1a]) HBA : Hydroxybutyl acrylate AA: acrylic acid 17F: heptadecafluorodecyl acrylate (Osaka Organic Chemical Industry Co., Ltd. Si: silicone-containing methacrylate DM: dodecyl methacrylate)

Comparative Example 1 Polyethylene glycol methacrylate (# 30 in formula [1a]) (041MA, manufactured by Kyoeisha Chemical Co., Ltd.) was placed in a flask equipped with a stirring blade, a reflux condenser, and a gas inlet.
g, t-butyl peroxyisopropyl carbonate 5
mg, 18.67 g of methyl isobutyl ketone,
Polymerization was carried out at 110 ° C. for 8 hours under a nitrogen stream. 1 g of the copolymer solution was stirred and dissolved in 9 g of methyl ethyl ketone,
A polyurethane film (Pelesen 2363-80AE manufactured by Dow Chemical Company) was immersed in the obtained solution for about 1 minute,
Dried at 70 ° C. for 10 hours. The film immediately felt slimy when wet with water, but disappeared slimy after 5 minutes. The coefficient of static friction was 0.235 and the coefficient of dynamic friction was 0.214.

Comparative Example 2 Polyethylene glycol methacrylate (# 30 in formula [1a]) (041MA, manufactured by Kyoeisha Chemical Co., Ltd.) was placed in a flask equipped with a stirring blade, a reflux condenser, and a gas inlet.
5 g, acrylic acid 0.5 g, dodecyl methacrylate 7
g, t-butyl peroxyisopropyl carbonate 3
2 mg and 23.33 g of methyl isobutyl ketone were charged and polymerized at 110 ° C. for 8 hours under a nitrogen stream. 1 g of the copolymer solution was dissolved by stirring in 9 g of methyl ethyl ketone, and a polyurethane film (Pelecene 2363-80AE manufactured by Dow Chemical Company) was immersed in the obtained solution for about 1 minute, and dried at 70 ° C. for 10 hours. The film was tacky in air and peeled off during rubbing.

[0037]

As is apparent from the above description, it is possible to extremely easily obtain a desired medical device having lubricity when moistened without using a compound harmful to the human body.

Claims (2)

[Claims] 1. At least one compound represented by the following general formulas [1a] and [1b], and [2a],
It consists of a repeating unit containing at least one compound represented by [2b] and [2c], and [1a]: [1
b] is 70:30 to 95: 5, and [1a]
The weight ratio of + [1b]: [2a] + [2b] + [2c] is 99: 1 to 60:40, and the number average molecular weight in terms of polystyrene by GPC measurement using tetrahydrofuran as a solvent is 2,000 to 100. A medical device coated with a copolymer having a molecular weight of 2,000. Embedded image (In the formula [1a], R ¹ is a hydrogen atom or a methyl group, R ²
Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n is 1
Shows an integer of ~ 200. ) (In the formula [1b], R ³ is a hydrogen atom or a methyl group, Xa
Is an atom or group that can be a monovalent cationic species;
⁴ is an alkylene group having 1 to ⁴ carbon atoms, and Xb represents any one of a hydroxyl group, an amino group and an amide group. ) (In the formula [2a], R ⁵ is a hydrogen atom or a methyl group, Xc
Represents an alkyl group having 4 to 30 carbon atoms. ) (In the formula [2b], R ⁶ is a hydrogen atom or a methyl group, Xd
Represents a perfluoroalkyl group-containing group having 4 to 20 carbon atoms. ) (Wherein [2c], R ⁷ is a hydrogen atom or a methyl group, R ⁸
An alkylene group having 1 to 20 carbon atoms or a modified alkylene group,
R ⁹ represents an alkyl group having 1 to 20 carbon atoms or a modified alkyl group, and m represents an integer of 5 to 80. ) 2. The medical device according to claim 1, wherein the medical device is a catheter.