JPH10292058A - Production of graft polymer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a graft polymer material which is not limited in the kind of the substrate polymer, of which the substrate polymer is not damaged, and in which a staining substance (e.g. a sensitizer) does not remain after the completion of polymn. by forming peroxy groups on the surface of a polymer material by a lowtemp. plasma treatment and exposing the surface to light in the presence of a polymerizable monomer to cause the graft polymn. of the monomer. SOLUTION: Peroxy groups are formed on the surface of a polymer material by subjecting the surface to a low-temp. plasma treatment in the presence of an oxygen-contg. gas or by subjecting the surface to a low-temp. plasma treatment in the presence of an inert gas or a nonpolymerizable gas and then exposing the treated surface to an oxygen-contg. gas. The objective graft polymer material is prepd. by subjecting a polymerizable monomer to graft polymn. onto the surface under the exposure to light while utilizing the peroxy groups as the photopolymn. initiation sites. The polymer material used can be in the form of film, plates, rods, particles, fibers, porous bodies, molded articles, etc. The monomer can be selected from among many kinds of monomers in accordance with the desired surface properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to adhesiveness, printability, paintability, and the like of various forms of polymer materials such as films, plates, rods, particles, fibers, and porous materials. The present invention relates to a method for producing a polymer material in which a polymerizable monomer having a functional group exhibiting a function is graft-polymerized on the surface in order to impart desired properties such as hydrophilicity and hydrophobicity.

[0002]

2. Description of the Related Art Grafting the surface of a polymer material and controlling its surface properties are widely used as one method of modifying the surface of a polymer. As such a grafting method, a base polymer is irradiated with γ-rays, electron beams, ultraviolet rays, or the like to generate radical species capable of initiating polymerization on the base material surface. The reaction is carried out by reacting the monomers to form a graft polymer. Such a graft polymerization treatment has an advantage that it can be directly applied to various shaped polymer materials.

[0003] However, when graft polymerizing a polymer material using γ-rays and electron beams, the base polymer material is damaged by irradiation with γ-rays and electron beams, and the polymer chains are cut or cross-linked. Therefore, there is a problem that physical properties such as strength and elongation of the base material are greatly reduced. Furthermore, depending on the type of the polymer, such a deterioration reaction occurs remarkably, so that there is a problem that the polymer material that can be treated is restricted.

[0004] When graft polymerization is carried out on a polymer material using ultraviolet rays, the substrate suffers less damage than when grafting is performed by irradiating with γ-rays or electron beams. In addition, the sensitizer is supported by a method such as applying the sensitizer to the substrate surface. Then, it is necessary to determine an appropriate combination of the sensitizer depending on the type of the base polymer and the type of the polymerizable monomer used for the polymerization, and depending on the type of the base and the polymerization system,
There is a problem that it is difficult to select an appropriate sensitizer. Further, after the polymerization treatment, a sensitizer and a binder for supporting the sensitizer on the substrate surface remain on the substrate surface. There is a possibility that a problem such as contamination may occur, and a problem that it is not suitable for the intended use may occur.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a graft polymerization process capable of controlling the surface properties of a polymer material.
There is no restriction on the type of the base polymer that has been a problem in the conventional technique, there is no damage to the base polymer, and further, a polymer material that does not contain contaminants such as sensitizers remaining after completion of polymerization. It is an object of the present invention to provide a method for producing the same.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the graft polymerization, and is not limited to the form and type of the polymer base material, and furthermore, the polymerization can be completed without damaging the base material. After that, they have been made as a result of earnestly studying a method of a graft polymerization treatment that does not include impurities such as a sensitizer.

According to the present invention, a peroxy group is directly generated on the surface of a polymer substrate by oxygen plasma treatment or the like, or radical species are generated on the surface of the substrate by argon plasma treatment or the like and then exposed to the air. It reacts with oxygen gas in the atmosphere to generate a peroxy group, and then is immersed in a radical polymerizable monomer alone or in a mixture with a solvent or the like, or is immersed in a gas phase in the presence of a polymerizable monomer. Irradiation, and by performing the graft polymerization with the peroxy group as the photopolymerization starting point, the graft polymerization was carried out without being limited to the form and type of the polymer base material, causing no damage or deterioration of the base material, and further containing no impurities. It has been found that a polymer material can be obtained. That is, the polymer material obtained by the present invention has no limitation on the type of the base polymer, does not deteriorate the properties of the base material due to the treatment, and does not contain impurities after the treatment. After introducing a peroxy group on the surface of the polymer material substrate by low-temperature plasma treatment, light is irradiated in the presence of a polymerizable monomer, and the peroxy group is subjected to graft polymerization as a photopolymerization starting point. Is a manufacturing method.

The polymer material used in the present invention can be used without any particular limitation as long as it can introduce a peroxy group by plasma treatment. Examples of such polymer materials include polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and derivatives thereof, polymethyl methacrylate, polymethacrylates such as polyethyl methacrylate,
Polyacrylates such as polymethyl acrylate and polyethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, polybutadiene, polychloroprene, polyisoprene, styrene-acrylonitrile-butadiene copolymer, nylons, Kevlar Polyamides such as Kapton, Ubilex, etc., Polyesters such as polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ethers, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, ethylene vinyl Alcohol copolymer, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene Fluororesin of the polymer such as silicone, polyurethane, phenol resins, urea resins, melamine resins, epoxy resins, diallyl phthalate resins, cellulose and its derivatives, starch and its derivatives, natural substances such as other polysaccharides. These polymers can be used singly or as a copolymer or / and alloy of two or more components. In addition, various forms of materials such as films, plates, rods, particles, fibers, porous materials, and molded products can be used.

The plasma processing apparatus used in the present invention uses a DC power supply, a commercial frequency power supply, or a microwave, and an external electrode system or an internal electrode system can be used without any particular limitation. The introduced gas used for the plasma treatment is an inert gas such as helium, argon, neon, krypton, or xenon, an oxygen-containing gas composed of air and oxygen, a non-polymerized gas such as nitrogen, hydrogen, carbon monoxide, carbon dioxide, and water vapor. One or a mixture of two or more types of reactive gases can be used. When the plasma treatment is performed using an oxygen-containing gas, the peroxy group is directly introduced to the surface of the substrate, so that the process can proceed to the next step as it is. On the other hand, when plasma treatment is performed using an inert gas or a non-polymerizable gas that does not contain oxygen, such as helium and argon, after the plasma treatment, the substrate is exposed to an oxygen-containing gas to react oxygen with radical species generated on the surface. It is necessary to generate a peroxy group. The peroxy group thus introduced into the surface is cleaved by light irradiation to become a polymerization initiation point, and the polymerization proceeds.

[0010] A method is known in which a peroxy group introduced by plasma treatment is thermally decomposed and graft-polymerized with a polymerizable monomer. However, in this method, polymerization of polymerizable monomers not involved in graft polymerization is also performed. There is a problem that a large number of them occur and a large number of homopolymers are produced. However, according to the method using light of the present invention, polymerization can be performed at a low temperature at which a homopolymer is not generated, so that production efficiency is high and economical. The polymerization temperature can be appropriately selected in consideration of the above-mentioned homopolymer formation, in relation to the type of the polymerizable monomer, the reaction time, and the grafting ratio.

The polymerizable monomer used in the present invention can be selected according to the desired surface properties. Normally,
General radical polymerizable monomers can be used. Examples of such a polymerizable monomer include styrene and o-chlorostyrene, p-chlorostyrene, 3,4-dichlorostyrene, pt-butylstyrene, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, p
-Styrene sulfonic acid, styrene derivatives such as divinylbenzene, ethylene-based monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl chlorides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; and vinyl acetate. Vinyl esters of organic acids such as vinyl, propionate and vinyl benzoate, acrylic acid salts such as acrylic acid, aluminum acrylate, zinc acrylate, sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate, and acrylic acid Methyl, ethyl acrylate, t-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, dimethylaminoethyl acrylate, isobutyl acrylate, cetyl acrylate, 4-phenyl acrylate Rokishibuchiru, acrylic acid 2-
Methoxyethyl, 3-methoxybutyl acrylate, lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl 3-methoxyacrylate Polyfunctional acrylic acid derivatives such as tripropylene glycol diacrylate, trimethylolpropane triacrylate, neopentyl glycol hydroxypivalate diacrylate, methacrylic acid and its salts, methyl methacrylate, ethyl methacrylate, etc. Propyl methacrylate, n-methacrylic acid
-Butyl, isobutyl methacrylate, t-methacrylate
Butyl, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate Methacrylic acid derivatives such as aminoethyl, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene dimethacrylate, pentacontahector ethylene glycol dimethacrylate, dimethacrylic acid Diethylene glycol, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol dimethacrylate Pentadecaethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, allyl methacrylate, triethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, polyfunctional methacrylic acid derivatives such as diethylene glycol phthalate phthalate, vinyl Vinyl ethers such as methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone;
N-vinyl compounds such as N-vinylformamide, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, vinylnaphthalenes, vinylpyridine, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid , Diacetone acrylamide, N-methylol acrylamide, N,
Examples thereof include polymerizable monomers such as N'-methylenebis (acrylamide), acrylonitrile, methacrylonitrile, acrylolein, vinylsulfonic acid and salts thereof, and pentaerythritol allyl ether. These polymerizable monomers can be used alone or in combination of two or more.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the following examples. The grafting ratio used in the examples was calculated by the following equation, and the strength was relatively evaluated using a Tensilon tensile tester. Grafting rate (%) = (weight of polymer material after grafting−weight of polymer material before grafting) × 100 / (weight of polymer material before grafting)

Example 1 A 10 cm × 10 cm polyethylene terephthalate film (trade name: Fuji PT Film, manufactured by Fuji Photo Film Co., Ltd., thickness: 50 μm) was subjected to plasma processing using the parallel plate internal electrode type plasma processing apparatus of FIG. gave. The parallel plate internal electrode type plasma processing apparatus shown in FIG. 1 has a bell jar 1 in which two electrode plates 2 are opposed to each other in parallel, a sample 3 is placed on a lower electrode 2, and an upper electrode 2 is placed. Is connected to the RF power source 4 and the lower electrode 2
Is grounded. A gas introduction pipe 5 is provided in the bell jar 1 so that gas can be released to the upper surface of the sample, and an exhaust pipe 7 is provided below the bell jar 1. Reference numeral 6 denotes a support for supporting an upper electrode mounting plate, and reference numeral 8 denotes a support for supporting the electrodes. The plasma treatment was performed by using such an apparatus and introducing oxygen gas from the gas introduction pipe 5 into the bell jar 1 under the conditions of a pressure in the system of 20 Pa, a frequency of 13.56 Hz, an output of 100 W, and a processing time of 1 min. The plasma-treated film was immersed in 500 g of a 10% aqueous solution of acrylic acid (manufactured by Wako Pure Chemical Industries),
Irradiation was performed for 60 minutes using high pressure mercury (manufactured by Sen Special Light Source Co., Ltd., output 120 W) in a nitrogen gas atmosphere for polymerization. After the polymerization, the film was sufficiently washed with hot water to obtain a grafted film having a grafting rate of 250%. Further, the strength of the film by grafting was maintained at 90% of the film before grafting.

Example 2 A grafted film was obtained in the same manner as in Example 1 except that the light irradiation time for the plasma-treated film was changed to 10 minutes. The grafting ratio of this film was 35%, and the strength of the film by grafting maintained 90% of the film before grafting.

Example 3 Polyethylene naphthalate film (manufactured by Teijin Limited, trade name: Theonex, thickness 25 μm)
m) was used, and a grafted film was obtained in the same manner as in Example 1 except that p-vinylbenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the polymerizable monomer. The grafting ratio of this film was 50%, and the strength of the film by grafting maintained 90% of the film before grafting.

Example 4 Polyethersulfone film (trade name: TALPA1000, manufactured by Mitsui Toatsu Chemicals, Inc.)
A grafted film was obtained in the same manner as in Example 1 except that The degree of grafting of this film was 150%, and the strength of the film by grafting maintained 95% of the film before grafting.

Example 5 Polyetheretherketone film (manufactured by Mitsui Toatsu Chemicals, trade name: TALPA20)
A grafted film was obtained in the same manner as in Example 1 except that (00) was used. The grafting ratio of this film was 100%, and the strength of the film by grafting was maintained at 95% of the film before grafting.

<Example 6> Sodium carboxymethylcellulose (manufactured by Daicel, trade name: CMC Daicel)
1202) was prepared and cast into a glass plate to obtain a film having a thickness of about 30 μm. Except for using this film with argon gas as the plasma processing gas,
A plasma-treated film was obtained in the same manner as in Example 1. After this plasma treatment, the film was exposed to the air for one hour to generate peroxy groups on the surface. The film was immersed in 500 g of a 10% toluene solution of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and irradiated with a high-pressure mercury lamp (manufactured by Sen Special Light Source, output 120 W) for 60 minutes in a nitrogen gas atmosphere to polymerize. . After the polymerization, the film was sufficiently washed with toluene to obtain a film having a grafting ratio of 20%. Further, the strength of the film by the grafting was maintained at 95% of the film before the grafting.

<Example 7> Polyimide film (manufactured by Toray DuPont, trade name: Kapton 100V, thickness 25μ)
A plasma-treated film was obtained in the same manner as in Example 1, except that m) was used. After the plasma treatment, the film was exposed to acrylic acid vapor generated by bubbling a 10% aqueous solution of acrylic acid with nitrogen gas, and a high-pressure mercury lamp (120 W output, manufactured by Sen Special Light Source Co., Ltd.)
Irradiation was carried out for 60 minutes to carry out polymerization. After the polymerization, the film was sufficiently washed with hot water to obtain a grafted film having a grafting ratio of 120%. Further, the strength of the film by the grafting was maintained at 95% of the film before the grafting.

<Example 8> Polypropylene non-woven fabric (manufactured by Tonen Tapils, trade name: Tapils P020SW-00)
A grafted nonwoven fabric was obtained in the same manner as in Example 1, except that X) was used. The grafting ratio of this nonwoven fabric was 350%, and the strength of the nonwoven fabric by grafting was maintained at 90% before the grafting.

Example 9 Nylon nonwoven fabric (manufactured by Tonen Tapils, trade name: Tapils N050SS-00X) was used, and acrylamide (manufactured by Wako Pure Chemical Industries) was used as a polymerizable monomer.
A grafted non-woven fabric was obtained in the same manner as in Example 1, except for using. The grafting ratio of this nonwoven fabric was 110%, and the strength of the nonwoven fabric by grafting was maintained at 90% before the grafting.

<Example 10> A polytetrafluoroethylene sheet (trade name: TOMY FINEREC FSS R-250, manufactured by Hamakawa Paper Co., Ltd.) was used, and sodium vinyl sulfonate (Tokyo Kasei Co., Ltd.) was used as a polymerizable monomer. A grafted sheet was obtained in the same manner as described in Example 1 except that the above-mentioned method was used. The grafting ratio of this sheet was 15%, and the strength of the sheet by grafting was maintained at 99% before grafting.

Example 11 50 g of styrene (manufactured by Wako Pure Chemical Industries) in which 0.05 g of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries) was dissolved was completely saponified polyvinyl alcohol (degree of polymerization: 1700, acetic acid group (1 mol%), 2.5 g of partially saponified polyvinyl alcohol (polymerization degree: 1700, acetic acid group: 10 mol%) was suspended in an aqueous solution of 250 ml of water, and suspended at 60 ° C. for 6 hours and then at 80 ° C. for 2 hours. The mixture was reacted for a period of time to obtain a polystyrene powder. 50 g of the polystyrene powder was subjected to plasma processing using the external electrode type powder plasma processing apparatus shown in FIG. In the external electrode type powder plasma processing apparatus of FIG. 2, a single-necked flask-shaped processing reactor 11 is attached to a support 16 at an angle, a sample is placed inside the reactor 11, and two parallel The electrodes 12, 12 are provided outside, the upper electrode is connected to an RF power source, and the lower electrode is grounded. Above the electrode 12, there is provided a rotary gas introducing device 16 having a gas introducing thin tube 15 at the center, 13 is an opening for connection to a vacuum pump, and 14 is a vacuum gauge head. On the lower side, a reaction rotation motor 17 is connected so that the processing reactor 11 can be rotated. Reference numeral 18 denotes a support for supporting the rotation introducing machine 16. Reference numeral 19 denotes a powder sample to be processed.

In the plasma processing, oxygen gas is introduced into the processing reactor 11 by using such an apparatus, and the reaction vessel is set at 30 rpm.
m, the pressure in the system is 20 Pa and the frequency is 13.5.
Plasma processing was performed under the conditions of 6 Hz, output of 100 W, and processing time of 1 min. The plasma-treated powder was immersed in 500 g of a 10% acetone solution of acrylonitrile, and irradiated with a high-pressure mercury lamp (manufactured by Sen Special Light Source Co., output 120 W) for 60 minutes in a nitrogen gas atmosphere to carry out polymerization. After polymerization,
The powder was sufficiently washed with acetone to obtain a grafted powder having a grafting ratio of 50%. No deformation, cracking, chipping or the like due to the grafting was observed in the grafted particles.

Example 12 Polyethylene / polypropylene sheath-core composite fiber (manufactured by Chisso Corporation, trade name: ESC) was used, and acrylic acid (manufactured by Wako Pure Chemical Industries) 2 was used as a polymerizable monomer.
% And potassium p-styrenesulfonate 8% (manufactured by Wako Pure Chemical Industries), except that a grafted fiber having a grafting rate of 120% was obtained in the same manner as in Example 11.
No defects such as deformation and cutting were observed in the grafted fibers.

Example 13 An aromatic polyamide fiber (manufactured by Dupont Toray Kevlar Co., trade name: Kevlar chopped fiber (fiber length 6 mm)) was used, and acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a polymerizable monomer. )), Except that the grafting ratio was 150% in the same manner as in Example 11.
Was obtained. For the grafted fibers,
No defects such as deformation and cutting were observed.

Comparative Example 1 The polypropylene nonwoven fabric used in Example 8 was irradiated with 100 kGy of γ-rays, immersed in 500 g of a 10% aqueous solution of acrylic acid, and subjected to graft polymerization at room temperature for 12 hours. After the polymerization, the nonwoven fabric was sufficiently washed with hot water to obtain a grafted nonwoven fabric having a grafting ratio of 30%. Further, the strength of the nonwoven fabric by the grafting was 70% before the grafting.

Comparative Example 2 A polymerization temperature of 80 ° C. and a polymerization time of 3
The same treatment as in the method described in Comparative Example 1 was performed except that the graft polymerization was performed under the conditions of time. After the polymerization, the viscosity of the aqueous acrylic acid solution was significantly increased. Further, since a large number of gel-like homopolymers adhered to the nonwoven fabric, the gel was sufficiently washed with hot water to remove the adhered homopolymers. The graft ratio of this nonwoven fabric was 300%, and the strength was 60% before grafting.

<Comparative Example 3> The procedure of Comparative Example 1 was repeated, except that the polytetrafluoroethylene sheet used in Example 10 was used. This sheet showed a significant decrease in strength after γ-ray irradiation, and could not proceed to the next grafting step.

Comparative Example 4 The polypropylene nonwoven fabric used in Example 8 was irradiated with an electron beam at a dose of 200 kGy under a nitrogen gas atmosphere at an acceleration voltage of 2 MeV and an electron beam current of 15 mA. 50% aqueous solution
0 g, and graft-polymerized at room temperature for 12 hours.
After the polymerization, the nonwoven fabric was sufficiently washed with hot water, and the graft ratio was 30%.
% Of the grafted nonwoven fabric was obtained. The strength of the nonwoven fabric by the grafting was 60% before the grafting.

Comparative Example 5 Example 6 was repeated except that the polyethylene terephthalate film used in Example 1 was used.
A plasma-treated film was obtained in the same manner as described in (1). 500 g of a 10% aqueous solution of acrylic acid
The polymer was immersed in the solution and graft-polymerized at 80 ° C. for 12 hours. After the polymerization, the viscosity of the aqueous acrylic acid solution was significantly increased.
Further, since a large number of gel-like homopolymers had adhered to the film surface, the film was sufficiently washed with hot water to remove the homopolymer adhered to the surface. The grafting ratio of this film was 20%, and the strength was maintained at 90% before the grafting.

[0032]

According to the present invention, a grafted polymer material which is not restricted by the type of the base polymer, does not deteriorate in physical properties such as the strength of the base polymer, and does not contain contaminants can be easily prepared. Can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of an internal electrode type plasma processing apparatus.

FIG. 2 is an explanatory view showing an example of an external electrode type plasma processing apparatus.

[Explanation of symbols]

 Reference Signs List 1 bell jar 2 electrode 3 sample 4 RF power supply 5 gas introduction pipe 6 support 7 exhaust pipe 8 support supporting electrode 11 processing reactor 12 electrode 13 vacuum pump 14 vacuum gauge head 15 gas introduction thin tube 16 rotating gas introduction machine 17 reactor rotating motor 18 Prop 19 Powder sample to be processed

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[Procedure amendment]

[Submission date] April 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

The polymerizable monomer used in the present invention can be selected according to the desired surface properties. Normally,
General radical polymerizable monomers can be used. Examples of such a polymerizable monomer include styrene and o-chlorostyrene, p-chlorostyrene, 3,4-dichlorostyrene, pt-butylstyrene, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, p
-Styrene sulfonic acid, styrene derivatives such as divinylbenzene, ethylene monoolefins such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl halides such as vinyl fluoride, vinyl acetate, Organic acid vinyl esters such as vinyl propionate and vinyl benzoate, acrylic acid such as acrylic acid, aluminum acrylate, zinc acrylate, sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate, and methyl acrylate , Ethyl acrylate, t-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, dimethylaminoethyl acrylate, isobutyl acrylate, cetyl acrylate, 4-h-acrylate Rokishibuchiru, acrylic acid 2-
Methoxyethyl, 3-methoxybutyl acrylate, lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl 3-methoxyacrylate Polyfunctional acrylic acid derivatives such as tripropylene glycol diacrylate, trimethylolpropane triacrylate, neopentyl glycol hydroxypivalate diacrylate, methacrylic acid and its salts, methyl methacrylate, ethyl methacrylate, etc. Propyl methacrylate, n-methacrylic acid
-Butyl, isobutyl methacrylate, t-methacrylate
Butyl, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate Methacrylic acid derivatives such as aminoethyl, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene dimethacrylate, pentacontahector ethylene glycol dimethacrylate, dimethacrylic acid Diethylene glycol, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol dimethacrylate Pentadecaethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, allyl methacrylate, triethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, polyfunctional methacrylic acid derivatives such as diethylene glycol phthalate phthalate, vinyl Vinyl ethers such as methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone;
N-vinyl compounds such as N-vinylformamide, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, vinylnaphthalenes, vinylpyridine, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid , Diacetone acrylamide, N-methylol acrylamide, N,
Examples thereof include polymerizable monomers such as N'-methylenebis (acrylamide), acrylonitrile, methacrylonitrile, acrylolein, vinylsulfonic acid and salts thereof, and pentaerythritol allyl ether. These polymerizable monomers can be used alone or in combination of two or more. Light irradiation used in the present invention,
Low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide
Unlimited use of general-purpose light sources such as mercury lamps
However, depending on the type of polymer, short wavelength
There is a case where the light of the part deteriorates and the characteristics such as strength are reduced.
The light source is a high-pressure mercury lamp or meta
Luhalide mercury lamps are preferred.

Claims (4)

[Claims] In a method of photografting a polymerizable monomer onto the surface of a solid polymer material, a peroxy group is introduced into the surface of the polymer material by low-temperature plasma treatment, and then the peroxy group is subjected to photopolymerization. As a point, a method for producing a grafted polymer material, which comprises irradiating with light and performing graft polymerization in the presence of a polymerizable monomer. 2. The method for producing a grafted polymer material according to claim 1, wherein an oxygen-containing gas is used as an introduction gas for the low-temperature plasma treatment. 3. The method according to claim 1, wherein after the treatment with the inert gas as the introduction gas for the low-temperature plasma treatment, the substrate is exposed to an oxygen-containing gas to generate a peroxy group. Manufacturing method of molecular material. 4. The grafting method according to claim 1, wherein the non-polymerizable gas is used as an introduction gas for the low-temperature plasma treatment, and then exposed to an oxygen-containing gas to generate a peroxy group. A method for producing a polymer material.