JP3314451B2 - Surface treatment method for polymer materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a surface of a polymer material. More specifically, the present invention relates to a surface treatment method for a polymer material suitable as a material for various medical devices such as a blood bag, a blood transfusion bag, a catheter, and a blood tube.

[0002]

2. Description of the Related Art As a method for imparting hydrophilicity to a surface of a polymer material, conventionally, a surface of a hydrophobic polymer material is subjected to a treatment such as an acid or alkali treatment, a corona discharge treatment, a plasma treatment, and a sputtering treatment. It has been known. However, in the acid or alkali treatment, the corona discharge treatment, and the plasma treatment, the surface is temporarily given hydrophilicity, but is not permanent, and it is known that the hydrophilicity decreases with time. Further, in the sputtering treatment using an inorganic oxide, there is a problem that the adhesion between the inorganic oxide film formed on the surface and the polymer becomes insufficient, and the film is easily peeled. Further, JP-A-46-
42759, JP-A-50-150793,
Japanese Patent Application Laid-Open No. 51-24651 discloses a poly (2
An antithrombotic material comprising a hydrogel obtained by cross-linking a hydrophilic polymer such as (-hydroxyethyl) methacrylate or polyvinyl alcohol has been disclosed, but all have the drawback of low strength.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antithrombotic material having permanent hydrophilicity without impairing the inherent properties of a polymer such as mechanical strength, flexibility and heat resistance. It is an object of the present invention to provide a method for treating a surface of a polymer material used for the above.

[0004]

According to the present invention, the object is to provide polybutadiene, polyethylene and styrene butane.
Table of polymer materials selected from tadiene block copolymer
After irradiation or low-temperature plasma treatment of the surface,
A (meth) acrylate having two or more hydroxyl groups and / or a structure represented by the following general formula (1) on the surface;
Is achieved by a surface treatment method for a polymer material characterized by polymerizing (meth) acrylamide .

[0005]

Embedded image Wherein R1 represents a hydrogen atom or a methyl group, and n is 1
Represents an integer of ~ 100]

Hereinafter, the present invention will be described in detail, which will clarify the objects, configurations and effects of the present invention. As the polymer material used in the present invention,
Polybutadiene, polyethylene, styrene butadiene
Lock copolymers and blends thereof can be mentioned, and these polymeric materials include stabilizers against heat, light, oxidation, etc., crosslinking agents, crosslinking agents, dyes, fillers, reinforcing agents, plasticizers. , Dyes, pigments and the like may be added. The shape is a film, a sheet, a tube, a fibrous material, or various molded products, and is not particularly limited.

In the present invention, first, a process of forming radicals by irradiating the surface of a polymer material with radiation,
Alternatively, a process of forming radicals by low-temperature plasma (hereinafter, these are collectively referred to as “pretreatment”) is performed.

[0008] The radiation used in the method is 1
Ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and a carbon arc lamp having a wavelength range of 600 to 4000 angstroms, and γ-rays can be used.

When the above-mentioned ultraviolet rays are used, in particular,
Ultraviolet light at a wavelength of 2050 Angstroms or 2350-2750 Angstroms is preferred. UV irradiation can be performed in the presence or absence of oxygen or ozone,
Usually, it is desirable to perform the irradiation at a dose of 0.005 to 10 J / cm ² . Here, the absence of oxygen or ozone refers to the presence or absence of inert gas such as nitrogen or argon.
Although it is under a vacuum of 0 Torr or less, oxygen may be contained in less than 1% by volume and ozone may be contained in less than 0.1% by volume.

In the case of using γ-rays, 0.01 to 50
It is preferable to perform the irradiation at a dose of kilogray, preferably 0.05 to 25 kilogray.

In these methods, a sensitizer may be used to promote the formation of radicals. Examples of the sensitizer include benzoin ethers such as benzoin methyl ether, azo compounds such as azobisisobutyrovaleronitrile, and ketones such as Michler's ketone. The method of adding the sensitizer to a solution of the hydrophilic unit to be graft-polymerized after the pretreatment can also be adopted, but in this case, the polymer is not graft-polymerized with the polymer surface, and the hydrophilic unit is polymerized with each other. In general, it is preferable that the sensitizer is previously applied or impregnated on the surface of the polymer before the irradiation with radiation, since a problem arises that a large amount of coalescence is formed. When applying or impregnating a sensitizer, a solution in which the sensitizer is dissolved in an organic solvent such as benzene, toluene, or tetrahydrofuran is applied or impregnated on the polymer surface, and then dried to remove the organic solvent. Is preferred. The amount of the sensitizer used is generally 1 per m ² of the polymer material.
１０００1000 g, preferably 5-300 g.

The low-temperature plasma treatment in the method of
As already known, a low-temperature plasma is generated by applying a high-frequency electric field, a microwave electric field, or a DC electric field to a low-pressure gas of 100 Torr or less, and the low-temperature plasma is generated on the surface of the polymer material in the plasma gas or the plasma atmosphere. This is performed by generating active species generated by plasma. The plasma treatment is argon, nitrogen, air, in an atmosphere such as hydrogen, generally 10 ^@ 3 to 10 Torr, preferably ^10-2 2 ～1Torr generally 5 seconds to 60 minutes said low temperature plasma under a pressure of, preferably 10 The irradiation is performed by irradiating the surface of the polymer material for 10 seconds to 10 minutes.

After the above pretreatment, the hydrophilic monomer is subjected to graft polymerization.

Examples of structural units having two or more hydroxyl groups used for graft polymerization include di (hydroxymethyl) (meth) acrylamide, di (hydroxyethyl) (meth) acrylamide, tris (hydroxymethyl) ( Examples thereof include (meth) acrylamide, tris (hydroxyethyl) (meth) acrylamide, and glycerol mono (meth) acrylate. In addition, the above-mentioned structural unit is obtained by graft-polymerizing the surface of a polymer material and then post-treating with an acid or an alkali to obtain 1
It may be a compound having two or more hydroxyl groups per monomer. Such compounds include glycidyl (meth) acrylate, (2,2-dimethyl-1,3-
Dioxolan-4-yl) methyl methacrylate and the like.

Representative examples of the monomer having a structural unit represented by the formula (1) used in the present invention include methoxyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxy nonaethylene glycol. (Meth) acrylate, methoxytetradecaethylene glycol (meth) acrylate, methoxytriacontanethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate, butoxynonaethylene glycol (meth) acrylate, Butoxytetradecaethylene glycol (meth) acrylate, butoxyacontan ethylene glycol (meth) acrylate, triethylene glycol di (meth) acryle G, nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, triacontan ethylene glycol di (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy Examples include nonapropylene glycol (meth) acrylate, methoxytetradecapropylene glycol (meth) acrylate, and methoxytriacontan propylene glycol (meth) acrylate. These hydrophilic units can be used alone or in combination of two or more.

In the present invention, the hydrophilic unit is generally 0.1
It is used in a solvent solution having a concentration of １００100% by weight, preferably 1-40% by weight. As the solvent used here,
Examples of the solvent include a solvent in which the hydrophilic monomer is dissolved and the polymer material is not dissolved or swelled, such as water, methyl alcohol, ethyl alcohol, dioxane, and dimethylformamide. In the graft polymerization in the present invention, the polymer material is placed in a solvent in which these hydrophilic units are dissolved, and the reaction temperature is generally 0 to 10 under a nitrogen atmosphere.
The reaction is carried out at a temperature of 0 ° C., preferably 20 to 80 ° C., and the reaction time is generally 2 minutes to 96 hours, preferably 30 minutes to 6 hours. Incidentally, the hydrophilic unit is the polymer material 1 cm ² per reacting 1 to 10 ³ [mu] g.

[0016]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Here, the performance evaluation of each material was performed in the following manner. Contact angle: Kyowa Interface Science Co., Ltd. contact angle measuring instrument (CA-
(DT-A type). The numerical value of the contact angle is a measure of water wettability, and the smaller the numerical value, the better the water wettability. Water absorption: The water absorption of the test piece immediately after the graft polymerization of the hydrophilic monomer was measured according to the following formula. Water absorption (%) = (W−W _O ) / W _O × 100 In the above equation, W is the weight (g) of the test piece in an equilibrium water-containing state, and W _O is the weight (g) of the test piece in a dry state. Represents

Safety test: Film after surface treatment (1c
(m × 1 cm), and a heavy metal test and an eluate test were performed based on “Disposable Blood Transfusion Set and Infusion Set Standard” of the Ministry of Health and Welfare. Platelet adhesion test: After contacting a predetermined number of platelets obtained by separating the surface-treated film from fresh human blood for 5 minutes, immobilizing with glutaraldehyde, dehydrating, and then using a scanning electron microscope, The film surface was observed at a magnification of 300 times, and the number of adherent platelets per 1 cm ² was counted.

Example 1 1.2—Polybutadiene having a binding amount of 92% (RB820
0.2mm thick, 50 length of Japan Synthetic Rubber Co., Ltd.)
mm square film under an argon gas flow for 0.5 mm
Plasma treatment was performed for 5 minutes while maintaining the high-frequency power at 40 W at ~ 0.6 Torr. After the treatment, the film was returned to normal pressure with air, the film was taken out, placed in a 10% by weight aqueous solution of methoxytriethylene glycol methacrylate, and kept under a nitrogen atmosphere while maintaining the aqueous solution temperature at 60 ° C.
Graft polymerization was performed while stirring for 5 hours. The film after polymerization was sufficiently washed with water and then dried. Table 1 shows the evaluation results of various properties of this film.

Comparative Example 1 The film treated in Example 1 was returned to normal pressure with air and then taken out. After the reaction, the film was sufficiently washed with water and dried. Table 1 shows the evaluation results of various properties of this film.

Example 2 The film treated with plasma in Example 1 was returned to normal pressure with air, the film was taken out, placed in a 10% by weight aqueous solution of glycerol monomethacrylate, and the temperature of the aqueous solution was maintained at 60 ° C. under a nitrogen atmosphere. The reaction was continued while stirring for 5 hours. The film after polymerization was sufficiently washed with water and then dried. Table 1 shows the evaluation results of various properties of this film.

Example 3 A film of low-density polyethylene (density 0.925 g / cm ² ) having a thickness of 0.2 mm and a length of 50 mm square was placed under an argon gas flow at 0.5 to 0.6 Torr and high frequency power of 80 W The plasma treatment was performed for 5 minutes while maintaining the temperature. After the treatment, the film was returned to normal pressure with air, the film was taken out, placed in a 10% aqueous solution of glycerol monomethacrylate, and subjected to graft polymerization under a nitrogen atmosphere while stirring at an aqueous solution temperature of 60 ° C. for 5 hours. The film after polymerization was sufficiently washed with water and then dried. Table 1 shows the evaluation results of various properties of this film.

Example 4 Styrene-butadiene block copolymer (TR2000
0.2mm thick, 50m long, manufactured by Japan Synthetic Rubber Co., Ltd.
Using a UV lamp VUV-040 / A-2.2U manufactured by Oak Co., Ltd., an m-square film was irradiated with ultraviolet light of 2357 angstroms in air from a distance of 30 mm in a distance of 10 mm.
The light was irradiated for minutes. The light-irradiated film was placed in a 5% by weight aqueous solution of glycerol monomethacrylate, and subjected to graft polymerization under a nitrogen atmosphere while stirring at 60 ° C. for 5 hours. After the reaction, the film was sufficiently washed with water and dried. Table 1 shows the evaluation results of various properties of this film.

Comparative Examples 2 to 4 Table 1 shows the results of evaluating various performances of RB820 (Comparative Example 2), polyethylene (Comparative Example 3) and TR2000 (Comparative Example 4) which were not subjected to pretreatment.

[0024]

[Table 1]

[0025]

According to the surface treatment method for a polymer material of the present invention, an anti-polymer having a permanent hydrophilic property without impairing the performance such as the mechanical strength, flexibility and heat resistance inherent in the polymer material. A polymer material useful as a thrombus material can be provided. Also,
The polymer material obtained according to the present invention is suitably used as various medical device materials such as a blood bag, a blood transfusion bag, a catheter, and a blood tube.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J ^7/ 00-7/18

Claims (2)

(57) [Claims] 1. A polybutadiene, polyethylene and polyethylene
Polymer selected from Tylene butadiene block copolymer
Irradiation treatment or low-temperature plasma treatment of the material surface
Then, on the surface , two or more hydroxyl groups and / or a (meth) acryle having a structure represented by the following general formula (1)
A method for surface treating a polymer material, comprising polymerizing a salt or (meth) acrylamide . Embedded image Wherein R1 represents a hydrogen atom or a methyl group, and n is 1
Represents an integer of ~ 100] 2. The method according to claim 1, wherein the polymer material is a medical device material.
The surface treatment method according to claim 1, wherein: