JPS597725B2 - Surface modification method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to surface modification of substrates made of natural or synthetic polymers.

Today, natural and synthetic polymers are used in a wide range of fields and have become extremely important base materials.

For example, they are used in various forms in a wide range of fields, including textiles and plastics. However, these base materials have various drawbacks, and the current situation is that these materials are used in spite of these drawbacks.

In particular, it is a well-known fact to those who handle these base materials that the surfaces of these base materials have extremely difficult defects. The surface of the base material has many drawbacks, such as poor dyeability in fibers, easy generation of static electricity, poor adhesive performance in plastic films, and poor printing performance. However, it is thought that these can be improved by modifying the surface of the base material, and that the functions of the base material can be fully exhibited.

Many surface modification methods have been proposed to date, but none have yet been satisfactory.

The most commonly used modification method at present is a method of coating a substrate with polymers having various properties. However, as mentioned above, the surface of the base material has extremely poor adhesion, and coatings often peel off during use, and soluble coatings dissolve and wash away during use, reducing their performance. At the same time, it is necessary to apply the coating extremely thinly to the extent that the function of the base material is not deteriorated, and this technical difficulty is also an important problem. Radiation grafting is a method that solves these various drawbacks. This is a surface modification method in which radicals are generated in the base material by irradiating the base material with radiation, and various monomers are graft-polymerized using the radicals as starting points. Since the modified layer formed by this method is grafted, there is no deterioration in performance due to peeling or dissolution, and since the graft layer is thin, there is no deterioration in the functionality of the base material, and it has an excellent surface. Although it is said to be a reforming method, this method has the following fatal disadvantages. Because the energy of the radiation is extremely large, the radiation is injected not only onto the surface of the base material but also into the interior, damaging the base material and impairing its functionality. Another serious problem with radiation irradiation equipment is that great care must be taken in handling and safety of the equipment. Furthermore, a method has been proposed in which the base material is exposed to high voltage discharge and then exposed to polymerizable monomer vapor to graft-polymerize the monomer onto the base material to modify the surface.

As a result of the inventors' studies on this method, it has become clear that there are the following problems. Many polymerizable monomers have high boiling points and are difficult to supply as monomer vapor.

Furthermore, when the monomer is heated to increase its vapor pressure, thermal polymerization easily occurs because the monomer is held in a vacuum. Even if the monomer has a low boiling point and can be supplied as monomer vapor, a graft polymerization layer of sufficient thickness to exhibit reforming performance cannot be formed.

When supplying the 111 monomer in the form of vapor, it is not possible to supply two or more monomers at the same time because the vapor pressures of the monomers are different, so graft polymerization consisting of copolymerization of monomers is performed. The improved surface properties are limited.

The present invention is a surface modification method that eliminates the various drawbacks mentioned above and easily imparts surface properties suitable for various uses to a substrate. In order to achieve this object, the present invention has the following configuration.

That is, after exposing the surface of a base material made of a single polymer such as a natural polymer or a synthetic polymer or a mixture thereof to a high voltage discharge, the base material is treated with one or more types of polymers without exposing it to the atmosphere. Contact with a liquid consisting of a monomer capable of radical polymerization and having a vapor pressure of 20m71LH9 or less at 20°C to form a graft polymerized layer of the monomer on the surface of the base material,
It modifies the surface of the base material. In the present invention, natural polymers include, for example, cotton, hemp, silk, wood, etc., and synthetic polymers include, for example, polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene,
Examples include fibers and resins such as polystyrene, polycarbonate, vinyl chloride, vinylidene chloride, cellulose acetate, and cellophane, as well as plastic resins such as ABS, acrylic, methacrylic, phenol, elastomer, melamine, and epoxy.

Such polymeric substances may be used alone or in combination,
Further, it may be in any shape such as fibrous, plate, sheet, cylindrical, block, etc., but the present invention is suitable for plate-like and sheet-like products, particularly films, woven fabrics, and knitted fabrics. The high voltage discharge of the present invention is 0.2mmH9
Higher than 50mmH9 preferably 0.3m77! H
It discharges under the pressure of various gases of 9 or more and 20 mmH or less.

When a base material is exposed to an electric discharge under a pressure of 0.1 m11LH9 or less, the base material deteriorates, and a base material with a low melting point and softening point, such as a polypropylene film, may melt or soften.

C-H-BAMFORD et al. 0.1
Discharge treatment is performed under hydrogen gas on Pilgrimage H9 (NATUR
EvOll 86, p. 72l, 1960), these problems probably did not occur because they used crystalline resin powder. Coleman (J-H-COLEMAN)
) is 150m77! Discharge treatment is carried out under various gases at substantially atmospheric pressure above H9 (Japanese Patent Publication No. 13640/1983), but in this pressure region, the discharge becomes a spark discharge, which is extremely unstable, non-sustained discharge, and localized. The discharge damages the base material and causes pinholes in the base material, and the base material deteriorates so much that it shows yellowing. In the discharge pressure range of the present invention, the discharge exhibits extremely uniform and stable sustained discharge, and the surface of the substrate is uniformly and efficiently activated without damaging the substrate. The gas used for high-voltage discharge is preferably a relatively inert gas such as air, nitrogen dioxide, hydrogen, argon, helium, chlorine fluoride, chlorinated carbon, carbon fluoride, or a mixture of these gases. It is not particularly limited to these as long as active points such as radicals can be formed.

The base material whose surface has been activated by such discharge treatment is then exposed to one or more radically polymerizable liquid monomers or their solvent solutions to form a graft polymerized layer of the monomers on the surface of the base material. do.

The monomer applied to the present invention is capable of radical polymerization and has a vapor pressure of 201 LmH9 or less at room temperature (200 C). BRADLEX (A-BRADLEX)
The base material is exposed to acrylic acid vapor after discharge treatment, and the monomer is graft-polymerized onto the surface of the base material (CHEMICA).
LTECHNOLOGY, vOll, page 232, 197
1), but the vapor pressure of acrylic acid is 5 m at room temperature (2'C).
mH is 9 or less, the monomer molecular density in the monomer atmosphere with which the surface of the substrate comes into contact is extremely low, and the growth rate of the graft polymerized layer formed on the surface of the substrate is extremely slow. For this reason, the processing speed of the substrate is slow, which is a major drawback in processing on an industrial scale. According to experiments conducted by the present inventors, the residence time of the base material in an acrylic acid solution to form a graft layer of similar thickness is approximately 1/1/1 of the residence time in acrylic acid vapor.
I should have given it 10. Furthermore, the vapor pressure of many radically polymerizable monomers is even lower than that of acrylic acid at room temperature (2'C), and the method of forming a graft layer using monomer vapor poses a difficult problem. . Raising the temperature when exposing the substrate to the monomer can be considered, but this is often technically difficult in large-scale equipment, and it is often difficult to maintain radically polymerizable monomers at high temperatures. However, it is accompanied by difficult problems such as thermal polymerization. The radically polymerizable monomer used in the present invention is one that is itself liquid during treatment or can form a solution with an appropriate solvent, and has a vapor pressure of 20 mmH9 or less at 20°C. .

For example, styrene compounds such as sodium parastyrene sulfonate, maleic anhydride, maleic acid compounds such as dimethyl maleate, diethyl maleate, dibutyl maleate, itaconic acid, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc. compounds, allyl compounds such as sodium allylsulfonate, methallyl compounds such as sodium methallylsulfonate, vinyl compounds such as divinylbenzene, 2-vinylpyridine, N-vinyl-2-pyrrolidone, acrylamide, N-N-butoxymethyl Acrylamide, acrylamide compounds such as N-methylol acrylamide, acrylic acid, ethyl acrylate, N-butyl acrylate, cyanoethyl acrylate, glycidyl acrylate, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2,3-dibromopropyl acrylate,
Acrylic compounds such as ethylene glycol diacrylate, diethylene glycol diacrylate, 2-hydroxyethyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, glycidyl methacrylate, ethylene glycol monomethacrylate, 2-dimethylaminoethyl methacrylate , 2-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 3-chloro-2-
Hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, trimethylol Propane trimethacrylate, (NEWMERl) acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, 2-(1-aziridinyl) ethyl methacrylate,
These include methacrylic compounds such as 2-cyanoethyl methacrylate and sodium methacrylpropylsulfonate.

In particular, sodium parastyrene sulfonate, maleic anhydride, dimethyl itaconate, diethyl itaconate, divinylbenzene, 2-vinylpyridine, N-vinyl-2-pyrrolidone, acrylamide, N-N-butoxymethylacrylamide, acrylic acid, ethyl acrylate. , N-butyl acrylate, cyanoethyl acrylate, glycidyl acrylate, 2-dimethylaminoethyl acrylate, 2,3-dibromopropyl acrylate, ethylene glycol diacrylate, 2-hydroxyethyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, glycidyl methacrylate , ethylene glycol monomethacrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-dimethylaminoethyl methacrylate
-Hydroxypropyl methacrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate,
Examples include ethylene glycol dimethacrylate, acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, 2-cyanoethyl methacrylate, and sodium methacrylpropylsulfonate, which can be treated in various ways by the method of the present invention. It can be graft-polymerized well to the base material of , giving it excellent surface properties. Of course, the monomers of the present invention are not limited to the above-mentioned monomers, but any monomer that can undergo radical polymerization and has a vapor pressure of 20 or less at room temperature (20°C) can be used. good. The monomer solution referred to in the present invention may be the liquid monomer itself, or may be a solution made with various solvents.

In particular, sodium parastyrenesulfonate, maleic anhydride, itaconic acid, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, sodium allylsulfonate, sodium methallylsulfonate, acrylamide, 2-hydroxy-3-methacryloxypropyltrimethyl Monomers that are solid at room temperature (20°C), such as ammonium chloride and sodium methacrylpropylsulfonate, can be subjected to discharge graft polymerization for the first time using the method of the present invention, and the monomers are dissolved in an appropriate solvent. The solution obtained is reacted on the surface of the substrate. It goes without saying that such a solvent should be selected from one that is compatible with the monomers, but generally water, methyl alcohol, ethyl alcohol, N-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide , benzene, dimethylformamide, ethyl acetate, etc. were excellent solvents. Of course, the solvents used in the present invention are not limited to the above solvents. The monomer solution of the present invention may be a solution containing only a single monomer, or may be a solution containing two or more types of monomers.

In the present invention, processing is performed using a liquid as described above, and therefore, it is easy to control the composition ratio of the graft polymer composed of each monomer, which can be said to be one major advantage.

When a surface-activated base material is exposed to a solution containing two or more types of monomers, it is not clear what the structural form of the graft layer is, but the characteristics of each monomer are When applied to the surface of the substrate, the substrate has excellent surface properties. For example, a polypropylene film surface-activated by high-voltage discharge is prepared with a mixed solution of acrylic acid and 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride (80 mol 70:20 mol %), or 60% by weight of the mixed solution? When the monomer is graft-polymerized by contacting with a methyl alcohol solution of
) and acid dyes (e.g. AcidOrange). Monomers such as maleic anhydride, maleic acid compounds, itaconic acid, itaconic acid compounds, and N-vinyl-2-pyrrolidone are difficult to graft polymerize alone, but they can be used as a mixed solution with other monomers that are easily graft polymerized. When used, graft polymerization becomes extremely easy.

Further, as in the above-mentioned example, as a solvent for the solid monomer, it is also possible to use another monomer in the form of a solution that is compatible with the solid monomer.

General commercially available radically polymerizable monomers inhibit polymerization caused by heat or light during storage, so
Polymerization inhibitors such as hydroquinone or methoxyhydroquinone of several thousand P or more are often mixed in, but even if a commercially available monomer mixed with a polymerization inhibitor is used as a monomer solution, the graft polymerization in the present invention cannot be carried out. It was not a serious problem.

For example, when commercially available acrylic acid (manufactured by Takeuchi Pharmaceutical Co., Ltd.) is used as the monomer solution, and when the acrylic acid purified by distillation is used as the monomer solution, the surface modification layer There was almost no difference in performance. Next, the method of the present invention will be explained using an example of the apparatus shown in FIG. 1 for carrying out the present invention.

The apparatus shown in FIG. 1 is an example of an apparatus for surface modification of plastic films, textiles, and the like. The apparatus illustrated in FIG.
2. It consists of a monomer chamber 13, a heating chamber 14, and a base material winding chamber 15.

Each chamber is evacuated through exhaust pipes 1, 2, 3, 4, 5, and 6 and maintained at a desired pressure. In carrying out the present invention, it is an extremely serious problem that the base material comes into contact with oxygen, which serves as a radical scavenger, in the apparatus, particularly in the process from the high voltage discharge treatment chamber 11 to the monomer chamber 13. Therefore, it is necessary to sufficiently remove oxygen from each chamber using an exhaust system. According to the inventors' experiments, the oxygen partial pressure is 107! The above problem could be solved if LmH was 9 or less, preferably 0.2 mmH9 or less. In addition, in the monomer chamber 13, in order to prevent evaporation of the monomer and diluting solvent, N2, Ar, and
, He, or other inert gas may be introduced to maintain the inside at an appropriate pressure. Base material derivation chamber 10, base material winding chamber 15
A lead-out roll 16 and a take-up roll 1 provided in the
5 may be installed outside the apparatus, and the base material may be introduced into the apparatus through a chamber whose pressure gradually becomes low or high.

The base material led out from the lead-out roll 16 is discharged from air trapped between the base materials in the lead-out chamber 10, and subjected to a high-voltage discharge treatment in the high-voltage discharge treatment chamber 11 to activate its surface. In the high voltage discharge treatment chamber 11, the target gas is introduced through the gas introduction pipe 7, and from 0.2mmH9 to 507!1mH by the gas introduction pipe 7 and the exhaust pipe 2 from the exhaust system.
The target gas pressure within 9 is maintained. Power is power supply 2
2 to the secondary side through the coupling coil 21, matched by the matching circuit 20, and applied to the electrode 19. Various power sources can be used as the power source 22. For example, a power source that generates periodic waves such as a sine wave, triangular wave, pulse wave, or square wave, or a power source that generates intermittent waves can be used. Moreover, stable discharge can be maintained if the power supply frequency is several hundred hertz (z) or higher. Various conductive metals can be used for the electrode 19. For example, Cu. Al. Fe. Ni. W,
Examples include carbon rods and carbon fibers. Further, electrodes made of these metals coated with a dielectric material such as glass are extremely excellent electrodes. When discharging continuously for a long time, it is better to flow water or a coolant into the electrode tube to prevent the temperature of the electrode 19 from rising. The shape of the electrode is not particularly limited, and electrodes of various shapes can be used depending on the shape of the base material. For example, wire rods, flat plates, nets, etc. Further, the opposing electrodes do not necessarily have to have the same shape; for example, one side may be rod-shaped and the other may be mesh-shaped. The substrate whose surface has been activated in the high voltage discharge treatment chamber 11 is introduced into the monomer chamber 13 through the high vacuum chamber 12 .

In the chamber 12, the monomer in the monomer chamber 13 is in the high voltage discharge treatment chamber 11.
A chamber to prevent water from flowing into the air, but is not necessarily essential. The surface-activated base material in the monomer chamber 13 comes into contact with the monomer liquid in the container 18, and forms a graft-polymerized layer of the monomer on the surface. Furthermore, by using a heated monomer solution, the formation of a graft polymerization layer can be promoted. Next, the base material leaving the monomer chamber 13 is heated by an infrared lamp 23 or an ultraviolet lamp 23 in a heating chamber 14 to promote the growth of the graft layer and at the same time volatilize and remove unreacted monomers and solvents. It will be done. However, the heating chamber 14 is not necessarily essential. Further, a washing chamber may be provided between chambers 13 and 14 or between chambers 14 and 15 in order to remove unreacted monomers. The substrate treated in each chamber up to chamber 14 and on which a graft layer has been formed is wound up on a winding roll 17 in a substrate winding chamber 15 . The device shown in Figure 1 is only one example of the device;
The device for carrying out the present invention is not limited to this. Next, the advantages of the present invention will be listed.

(1) As mentioned above, the present invention allows the surface of various polymers to be modified in an extremely simple manner.

(2) The surface modified by the method of the present invention has no peeling or dissolution of the modified layer, and there is no deterioration in its performance. (3) The graft polymerized layer formed by the method of the present invention is extremely Since it is thin and does not damage the base material during the process of forming the graft polymerization layer, the essential properties of the base material are not impaired by simply modifying the surface.

(4) In the method of the present invention, a monomer solution is used in the step of exposing to monomers, so it is possible to use many high-boiling monomers or solid monomers, and to use two or more types of monomers. It is possible to expose the materials simultaneously, and various surface properties can be imparted to the substrate, expanding the range of applications of the high-pressure discharge graft polymerization method.

(5) Many monomers can be used in the method of the present invention, and the monomer can be selected depending on the purpose, allowing surface modification suitable for the purpose.

As described above, the method of the present invention has extremely excellent advantages, and can utilize an extremely large number of monomers. Depending on the selection of monomers, various surface properties such as adhesiveness and heat-sealability can be achieved. , antistatic property (antistatic property), hydrophilicity, water repellency, stain removal property, antifogging property, water absorption property, hygroscopicity, staining property, chemical resistance, oil resistance, bactericidal activity, permselectivity, anticoagulation property etc. can be applied to various polymeric base materials.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 1 m of polyester fiber woven fabric (11 tetron taffeta)
After discharge treatment at a treatment speed of 180 m/Hr under N2 gas at mH9 using a relaxation oscillation type high voltage power supply, the sample was exposed to a 50% by weight 70% aqueous solution of sodium methacrylpropylsulfonate for 30 seconds, taken out from the apparatus, and The mixture was left in hot water at ℃ for 2 hours with stirring to remove unreacted substances and homopolymer.

The treated fiber woven fabric is extremely hydrophilic and has a basic dye (A
strazOnBlueBG), and it was possible to identify that the monomer was graft-polymerized. However, in the case of the untreated polyester fiber woven fabric, it was dyed at the same time as the treated polyester fiber woven fabric, but it was not dyed at all.
After surface activation under the same conditions, a mixed solution of acrylic acid and methacrylpropylsulfonic acid (50 mol%: 50 mol%)
50 weight? The fibers graft-polymerized with the monomer exposed to an aqueous solution for 30 seconds were extremely hydrophilic and dyed with base dyeing (AstrazOnBlueBG) more deeply than when methacrylpropylsulfonic acid was used alone as the monomer. . Note that since the monomer is a powder and has no vapor pressure, it is impossible to carry out graft polymerization using the conventional method of exposing the monomer to monomer vapor after discharge treatment. Example 2 1 ml of polypropylene film (11 Trephane W)
After discharge treatment using a crystal oscillation type high voltage power supply of 13.56 Hz under Ar gas at LH9, it was immersed in a 5070 tetrahydrofuran solution of glycidyl methacrylate for 1 minute, taken out into the apparatus, and placed in a cyclohexane solution at 80 °C.
Unreacted monomers and homopolymers were removed by standing for a period of time.

The treated film was coated with a disperse dye (DldnlXRedF3B).
FS), and an ester absorption peak was observed at 1730cTn-1 in the total reflection infrared absorption spectrum, making it possible to identify that the monomer was graft polymerized. A polypropylene film was exposed to the monomer vapor generated from the monomer solution heated to 60° C. for 20 minutes under the same conditions, and then taken out, and the homopolymer etc. were removed in the same manner. When the film thus obtained was observed using a total reflection infrared absorption spectrum, it was found that 173
The absorption peak of 0cfn-1 ester is extremely small;
It was difficult to determine whether graft polymerization occurred. Example 3 A polyethylene film was subjected to a discharge treatment for 10 seconds at an output power of 50 W using a 13.56 MHz crystal oscillation type high voltage power supply under 0.6T0rr0Ar gas, and then treated with a mixed solution of 2-vinylpyrrolidone and acrylic acid (50 mol%: 50 moles 7
0) for 2 minutes, the sample was taken out of the apparatus, and left in hot water at 80°C for 2 hours with stirring to remove unreacted monomers and homopolymers.

The treated film was dyed with an acid dye (AcidOrange) and a basic dye (AstrazOnBlueBG), resulting in orange and sky blue dyes, respectively. Compared to a film treated under the same conditions using only 2-vinylpyrrolidone as a monomer solution, the treated film was dyed more deeply by the acid dye, and the monomer concentration was higher when using a mixed solution of 2-vinylpyrrolidone with acrylic acid than using 2-vinylpyrrolidone alone. It was found that the body undergoes graft polymerization well. Moreover, untreated polyethylene film dyed at the same time could not be dyed with either dye at all. Under the same conditions, polyethylene film was heated to 60°C after discharge treatment.
After being exposed for 20 minutes to monomer vapor consisting of 2-vinylpyrrolidone vapor heated to 2-vinylpyrrolidone and vapor generated from acrylic acid kept at room temperature, it was taken out and unreacted monomers etc. were removed in the same manner. . When the polyethylene film graft-polymerized in this manner was similarly dyed with acidic dyes and basic dyes, it was stained only with the basic dyes and could not be dyed with the acidic dyes. This suggests that only acrylic acid was graft-polymerized in the polyethylene film. Example 4 Polyester film (11
After discharging a 110KHz tuned self-oscillation type high voltage power supply under 0.6mlLH9 of N2-02 mixed gas (99mol%: 1mol%), acrylamide and acrylic acid mixed solution ( 50 moles 70:50 moles 7
After exposing it to a 50 weight 70 methyl alcohol solution of
After standing for a period of time, unreacted monomers and homopolymers were removed.

The treated film was extremely hydrophilic and could be dyed with acidic and basic dyes. When 50% by weight of acrylamide is used as the monomer solution, only the acidic dye dyes. Moreover, untreated polyester film dyed at the same time was not dyed by either dye at all. Note that acrylamide is a solid and cannot be graft-polymerized by the conventional method of supplying it as monomer vapor. Example 5 0.4 m of polyester film (11 Lumira-11)
After discharge treatment using a 30 KHz pulse oscillation type high voltage power supply under N2 gas at mH9, a mixed solution of crystals of quaternary aminated dimethylaminoethyl methacrylate produced from methyl iodide and dimethylaminoethyl methacrylate and acrylic acid (10 Mol 70: 50 weight 70 of 90 mol 70)
After being exposed to a methyl alcohol solution, the mixture was left in hot water at 80°C for 2 hours with stirring to remove unreacted monomers and homopolymers.

The treated film was extremely hydrophilic and could be dyed with acidic and basic dyes. 50 weight of quaternary aminated dimethylaminoethyl methacrylate as monomer solution? When a methyl alcohol solution was used, the treated film was hydrophilic and could be dyed with acidic dyes, but not with basic dyes. Furthermore, when dimethylaminoethylmethacrylate was used as the monomer solution, it was water repellent and stained only with acid dyes. Untreated polyester film was completely unstained by both dyes. Example 6 Methyl methacrylate resin plate (8 Torreglass 1) 1m71LH
After discharge treatment using a 13.56 MHz crystal oscillation type high voltage power supply under Ar gas of 9, 2-hydroquine-3-methacryloxypropyltrimethylammonium chloride C
50 weight of Bremma Qft (manufactured by Nihon Yushi)? After exposing it to methyl alcohol solution, take it out of the device and heat it to 8'C.
The mixture was left in hot water for 2 hours with stirring to remove unreacted monomers and homopolymers.

The treated plastic board was extremely hydrophilic and could be dyed with acid dyes. The untreated methyl methacrylate board was water repellent and could not be dyed at all with acid dyes.
Note that 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride is a solid and cannot be graft-polymerized by the conventional method of supplying it as monomer vapor. Example 7 Polypropylene film (Wl Trefan 1) 1 mm thick
After discharge treatment using a 10 KHz (7) CR oscillating high voltage power supply under H9 air, the sample was immersed in an acrylic acid solution for 20 seconds, taken out of the apparatus, and left in hot water at 80°C for 2 hours with stirring to ensure that no reaction occurred. Monomers and homopolymers were removed.

The treated film could be dyed with basic dyes. A treated film exposed to acrylic acid vapor generated at 30°C after discharge treatment under the same conditions should be exposed to acrylic acid vapor for 4 minutes to dye with a basic dye to the same concentration as the treated film exposed to an acrylic acid solution. I needed to expose it. Furthermore, untreated polypropylene film could not be dyed with basic dyes at all. Example 8 Silk woven fabric 0.4m77! Hg under argon gas 110
Using a KHz tuned self-oscillation high voltage power supply, a mixed solvent of acrylic acid and crystals of quaternary aminated dimethylaminoethyl methacrylate produced from methyl iodide and diethylaminoethyl methacrylate after discharge treatment (10 mol 70: 50 weight of 90 moles 70)? After being exposed to a methyl alcohol solution, the mixture was left in hot water at 80°C for 2 hours with stirring to remove unreacted monomers and homopolymers.

The antistatic performance of the treated fabric was evaluated using ElectrOstaticpa.
The examination was conducted using peranalyzer MODEL sp-428 (manufactured by Kawaguchi Electric Seisakusho). The treated cloth and the untreated cloth were corona charged at -6K for 5 seconds, and the charged voltage on the cloth surface at that time and the charged voltage 10 seconds after the corona charge was stopped were examined, and the results shown in Table 1 were obtained. As shown in Table 1, the untreated fabric has almost no antistatic property, whereas the treated fabric has excellent antistatic properties.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of an example of an apparatus for implementing the present invention. 1, 2, 3, 4, 5, 6... Exhaust pipe, 7, 25
......Gas inlet pipe, 8,9... Monomer solution introduction pipe and outlet pipe, 10...Base material outlet chamber,
11... High voltage discharge treatment chamber, 12...
High vacuum chamber, 13... Monomer chamber, 14...
・Heating chamber, 15...Base material winding chamber, 16,1
7...Base material lead-out roll and take-up roll,
18... Monomer solution holding container, 19...
・Discharge electrode, 20... Matching circuit, 21...
...Coupling coil, 22...High voltage power supply, 23.
...Infrared lamp or ultraviolet lamp, 24.
...Power source for infrared lamps or ultraviolet lamps.

Claims (1)

[Claims] 1 After exposing the surface of a base material made of a single polymer such as a natural polymer or a synthetic polymer or a mixture thereof to a high voltage discharge, the base material is exposed to one or more types of radicals without being exposed to the atmosphere. A surface modification method comprising exposing a substrate to a liquid consisting of a monomer that can be polymerized and having a vapor pressure of 20 mmHg or less at 20° C. to form a craft polymerized layer of the monomer on the surface of the substrate.