JPH04132713A - Graft polymerization and device therefor - Google Patents

Abstract

PURPOSE:To obtain the title polymer useful for immobilizing substrate of physiologically active substance by subjecting a monomer to graft polymerization onto a substrate to be treated, in a vacuum atmosphere, removing the unreacted monomer and grafting another monomer onto to the substrate to uniformly form graft chains on the surface. CONSTITUTION:A substrate 25 (e.g. porous film made of polypropylene) to be treated is held between bobbins 33 and 36, fixed in a main body 11 of a vacuum tank, the main body 11 of a vacuum tank is evacuated while winding the substrate film 25, an argon gas is introduced from a plasma gas inlet 22 to the main body, the substrate is irradiated with plasma, the argon gas is removed under reduced pressure, a first monomer (e.g. methoxyethyl acrylate) is fed from a monomer inlet 23, graft polymerization is carried out in a vacuum atmosphere, the unreacted monomer is removed, a second monomer (e.g. 4- vinylpyridine) is sent and subjected to graft polymerization in a vacuum atmosphere so that plural kinds of the monomers are subjected to graft polymerization on the substrate 25 to give the objective polymer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a graft polymerization method and apparatus for forming graft chains on a substrate to be treated such as a porous membrane film.
In particular, the present invention relates to a graft polymerization method and apparatus for carrying out graft polymerization using two or more types of monomers separately.

[Conventional technology]

In recent years, processing techniques for improving the surfaces of existing polymer materials by processing them using various methods, that is, techniques for improving the functionality of material surfaces, have become popular.

As one method, a graft polymerization method is used to introduce a molecular structure that exhibits the desired function into a polymer membrane. In this graft polymerization method, a polymer radical serving as a polymerization initiation point is generated in a base material, and then a monomer is supplied to carry out graft polymerization from the polymerization initiation point. Graft polymerization differs from plasma polymerization, in which monomers are polymerized in the presence of plasma and deposited on a substrate. Since the polymer is polymerized while maintaining its structure, it is advantageous for expressing the functions resulting from the molecular structure.

Conventionally, apparatuses for graft polymerization have been designed to irradiate plasma while winding a film in one direction to graft-polymerize monomers. Furthermore, in order to improve the processing capacity, the film has been continuously introduced into and discharged from the vacuum apparatus from an atmospheric state (eg, US Pat. No. 3,959.104).

[Problem to be solved by the invention]

However, such conventional graft polymerization equipment
Using limited monomers with low boiling points (high vapor pressure),
Although it can be applied to qualitative graft polymerization on the surface of a non-porous film to improve "hydrophilicity", "dyeability", "adhesion", etc., it is not suitable for porous membranes, selectively permeable membranes, or selectively adsorbent membranes. However, it could not be applied to membranes that require advanced functions such as . -For example, in order to impart wood-philicity, permselectivity, and selective adsorption to a porous membrane,
It is necessary to uniformly and abundantly introduce graft chains not only onto the outer surface of the membrane but also onto the pore surface inside the membrane. To this end, it is important to supply monomers with low vapor pressure in gaseous form to allow graft polymerization to proceed over a long period of time, but this has been difficult with conventional high vapor pressure limited equipment. In addition, in a device that winds a porous membrane in one direction, the winding speed can be slowed down to lengthen the graft polymerization time, but such a configuration not only greatly reduces processing capacity, but also increases the graft polymerization time. This method has the disadvantage that the amount of grafting is uneven between the beginning and end of the film to be treated.

This causes gas (dissolved air) to escape from the substrate over time.
This is because the formation of the graft polymer layer is inhibited and the concentration (pressure) of the monomer decreases due to the release of air or the introduction of external air from the sealed portion.

In addition, in conventional graft polymerization equipment, although it is possible to simultaneously supply multiple monomers to the graft polymerization chamber for graft polymerization, it is possible to perform graft polymerization by supplying multiple monomers separately and to perform graft polymerization. It was impossible to form chains and have multiple functions.

This is because, in order to perform graft polymerization with two types of monomers separately, two graft polymerization chambers must be provided, which increases the size of the apparatus. In addition, even if two graft polymerization chambers are provided, the time and process required to sufficiently remove the first monomer between the two graft polymerization chambers so that the first monomer does not mix with the second monomer. , which was difficult to implement in reality. If the first monomer is not sufficiently removed and the two monomers are mixed in the second grafting chamber, the rate of grafting will usually be extremely slow and the graft chain consisting of the second monomer will The problem was that the formation of was very slow.

The present invention was made in view of these problems, and its purpose is to form a graft chain using multiple types of monomers, to add multiple functions to the substrate to be treated, and furthermore, to An object of the present invention is to provide a graft polymerization method and an apparatus for the same, which can form a uniform graft polymerization layer on a substrate to be treated.

[Means to solve the problem]

The graft polymerization method according to the present invention includes a step of preparing at least two or more types of monomers and performing graft polymerization by supplying one monomer to a substrate to be treated in a vacuum atmosphere; A step of removing unreacted monomers under reduced pressure;
After removing unreacted monomers, the method includes a step of supplying other monomers to the substrate to be treated in a vacuum atmosphere to perform graft polymerization, and graft polymerization is performed separately with multiple types of monomers. It is something to do.

According to the graft polymerization method of the present invention, it is possible to graft polymerize at least two types of monomers separately and continuously without exposing them to the atmosphere, and to produce a large amount of composite functional materials having two types of graft chains. can. In addition, since graft polymerization is carried out in a series of vacuum processes in which the substrate to be treated does not come into contact with the atmosphere (oxygen), it is possible to
The bond between the graft chain and the other graft chain is not an ether bond via a peroxy radical, but is polymerized by a vinyl group, so heat and hydrolysis are less likely to occur, and detachment of the graft chain is reduced. Become.

Additionally, homopolymer by-products are a problem with graft polymerization via peroxy radicals (hydroxyl radicals, which are decomposition products of peroxy radicals, act as polymerization initiators).
This eliminates problems such as deterioration of graft efficiency, deterioration of physical properties (disassembly of molecular chains), etc.

As the substrate to be treated, for example, bubble point 0.1
~10 [kg/CffI] and a porous membrane film having a porosity of 20 to 90% can be used.

Here, "bubble point" refers to a value measured by ASTM-F316 method using isopropyl alcohol as a solvent. Furthermore, "porosity" refers to a value expressed as a percentage of the volume of the pores to the total volume of the membrane (including the pores).

In the graft polymerization method of the present invention, it is preferable that each step is performed by moving the substrate to be treated, especially reciprocating, and repeating each step multiple times. Thereby, graft chains can be uniformly formed on the surface of a large amount of substrates to be treated.

Further, the graft polymerization method of the present invention is preferably configured such that the substrate to be treated is in the form of a film, a plurality of protrusions are formed on the surface of the substrate, and the substrate to be treated is wound up and conveyed. Furthermore, increase the height of the protrusion from 10 to 100.
It is preferable to set it to 0 μm.

When there are protrusions on the surface of the substrates to be treated, the protrusions serve as spacers and gaps are formed between the substrates to be treated, so that the monomer can be efficiently supplied or removed.

The material of the protrusion is not particularly limited, and may or may not be the same as the base material. The shape is not particularly limited, and may be dot-shaped or
Line shapes, grid shapes, etc. are applied.

The height of the protrusion is 10 to 1000 μm, more preferably 60 to 200 μm. In addition, the area occupied by the protrusions is 0.5 to 50% of the surface of the substrate to be treated, preferably 1
．． It is 0-20%. Although the method for forming the dots is not particularly limited, an example is a method in which protrusions of arbitrary shapes are printed on a porous film using a UV-curable resin and then cured with ultraviolet (UV) light.

In ordinary film rolls, the films are in close contact with each other, making it difficult to remove gas existing between the films or impurities such as dissolved gas, adsorbed gas, and moisture inside the rolls. On the other hand, in the graft polymerization method of the present invention, by using a film-like base material having protrusions with a height of 10 to 1000 μm on the surface, it is possible to efficiently remove impurities from between the films, and it is possible to uniformly remove impurities from between the films. can form a large number of graft chains.

Further, the graft polymerization apparatus according to the present invention includes a vacuum chamber body having a graft polymerization chamber therein, an exhaust means for evacuating the inside of the vacuum chamber body, a plasma generation means for generating plasma in the graft polymerization chamber, and a vacuum chamber body having a graft polymerization chamber therein. A monomer gas supply means for separately supplying at least two types of monomer gas for graft polymerization to the polymerization chamber, and a transfer mechanism for reciprocatingly transporting the substrate to be treated in the graft polymerization chamber. We are prepared.

Specifically, the transfer mechanism includes a pair of winding/unwinding mechanisms that are arranged on both sides of the graft polymerization chamber and wind up and unwind the film-like substrate to be processed;
and a speed control mechanism that controls the running speed of the substrate to be processed that is transported by these winding and unwinding mechanisms.

According to the graft polymerization apparatus of the present invention, it is possible to reciprocate the substrate multiple times in a vacuum atmosphere, so that the substrate to be treated can be irradiated with plasma multiple times. Therefore, plasma irradiation is not only used as a means to generate polymer radicals that serve as polymerization initiation points on the substrate to be treated, but also as a pretreatment of the substrate to be treated, such as desorption of adsorbed gas, crosslinking of the substrate surface, or This can be usefully used as a post-treatment after graft polymerization. Furthermore, since the substrate to be treated can be treated under a series of vacuum conditions without being exposed to the atmosphere, operability is improved. Further, since radicals generated on the base material are not converted into peroxy radicals by oxygen in the atmosphere, it is possible to form a desired surface structure.

In addition, this device is capable of reciprocating the substrate to be treated multiple times under vacuum, so by reciprocating the device where monomer gas is present multiple times, the surface of a large amount of substrate to be treated can be transferred multiple times. It becomes possible to uniformly form graft chains. Further, it becomes possible to remove unreacted monomer gas by an exhaust means and to perform surface modification operations such as plasma polymerization in a continuous series of vacuum processes. Furthermore, if the substrate to be treated is a porous membrane, it is possible to perform graft polymerization for a long time with a low monomer concentration. In addition, a large amount of graft chains can be introduced onto the surface, and a porous membrane having excellent permeability and selective adsorption properties can be uniformly produced.

The plasma generating means may be any means that generates low-temperature plasma, and generally generates it by a capacitive coupling method or a floating method using a high frequency power source and electrodes. In order to uniformly perform low-temperature plasma treatment on a large area (width) of a sheet-like object to generate polymerization initiation points, it is preferable that the electrode be of a parallel plate type.

The evacuation means is a vacuum pump such as a rotary pump, a mechanical booster pump, a turbo molecular pump, a cryopump, or an oil diffusion pump, which brings the inside of the apparatus into a vacuum state. Here, "vacuum" refers to a pressure state lower than atmospheric pressure (atmospheric pressure), preferably 100
Torr or less.

Although this device is intended for graft polymerization, it can also perform other surface treatments, such as plasma treatment, plasma polymerization treatment, or chemical reactions in vacuum, and can also be integrated with a sputtering device. You may also do so. By incorporating a sputtering device into a graft polymerization device, it is possible to perform two types of surface functionalization treatments in a series of vacuum processes without bringing the substrate into contact with the atmosphere, which solves the problems caused by peroxy radicals mentioned above. can.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 shows the internal structure of a functional film manufacturing apparatus in which a graft polymerization apparatus is integrated with a sputtering apparatus as an embodiment of the present invention, and FIG. 2 shows its external structure. In the figure, 11 is a vacuum chamber body, and this vacuum chamber body 1
Preparation chambers 12 and 13 are provided on both sides of the interior of 1, and a graft polymerization chamber 14 is provided between these preparation chambers 12 and 13.
and a sputtering chamber 15 are provided adjacent to each other. Preparation room 12.13, graft polymerization room 14 and sputtering room 1
5 are provided with exhaust ports 16a, 16b, 17a117b connected to vacuum pumps (not shown), respectively, to exhaust the inside of the vacuum chamber body 11. The degree of vacuum is preferably a high vacuum atmosphere of 10-'Torr or less, and the vacuum pump is preferably a dry pump such as a turbomolecular pump or a cryopump to prevent contamination with hydrocarbons. .

A graft polymerization device 18 is provided in the graft polymerization chamber 14 . This graft polymerization device 18 includes a flat plate electrode 19
．． 20, which has a trigger electrode 21, a plasma gas inlet 22, and a monomer gas inlet 23, and generates plasma discharge between the plate electrodes 19 and 20 by a power source 24 provided outside the vacuum chamber body 11 to generate a plasma discharge to be treated. Graft chains are formed on the outermost surface of a membrane, for example, a porous membrane film 25 of polypropylene. The monomer gas inlet 23 is arranged near the porous membrane film 25. A first monomer gas supply section 55a1 and a second monomer gas supply section 55b are connected to the monomer gas inlet 23 via two pipes 54a and 54b, and the monomer gas is supplied from either one. is being supplied. Switching between the first monomer gas supply section 55a and the second monomer gas supply section 55b is performed by valves 56a and 56b provided in the pipes 54a and 54b.

The main parameters of plasma graft polymerization are the type and flow rate of the supply gas, the discharge operating pressure, etc., and the apparatus must be able to independently control these parameters. Precise control of these parameters is performed in the following manner.

(1) Supply Gas Argon (Ar) is supplied as an inert gas for plasma from the plasma gas inlet 22, and a gas necessary for graft polymerization, such as methoxyethyl acrylate (MEA), is supplied from the monomer gas inlet 23. The purpose of introducing argon gas is not only to dilute the supply gas for graft polymerization, but also to expose the porous membrane film 25 to argon plasma discharge to perform plasma cleaning of the membrane surface. In addition, when changing the gas in graft polymerization, argon plasma discharge is performed without setting the porous membrane film 25, and the walls of the vacuum chamber and various devices in the vacuum are cleaned to remove foreign gases and reaction products. Reduce interference due to residual components as much as possible.

(2) Supplied gas flow rate The flow rate of the gas used for graft polymerization is accurately controlled by a mass flow controller (MFC). The mass flow controller is disposed between the vacuum chamber body 11 and a gas cylinder (not shown), and a heater installed in the flow path detects the amount of heat taken away depending on the amount of gas flowing through a change in resistance value, and keeps this value constant at all times. Adjust the gas amount so that

(3) Discharge operating pressure While flowing argon from the plasma gas inlet 22 and gas necessary for graft polymerization, such as methoxyethyl acrylate, from the monomer gas inlet 23 into the vacuum chamber body 11, the pressure is maintained constant. It is necessary to perform plasma discharge by Normally, the operating pressure is 0.01 to several Torr
The main pump for vacuum evacuation at this time is a mechanical booster pump (MBP) which has a large evacuation capacity in this range.
) is used. Maintaining this pressure constant is related to the gas flow rate, and the gas flow rate is adjusted by providing a variable opening valve (conductance valve) in the exhaust system and adjusting the conductance.

On the other hand, a parallel plate type sputtering device 2 is provided in the sputtering chamber 15.
6 are arranged. This sputtering device 26 has an anode electrode 27 and a cathode electrode 28 opposite thereto,
A target 29 made of, for example, silver (Ag) is disposed on the cathode electrode 28 side, and a plasma discharge is generated between the anode electrode 27 and the cathode electrode 28 by a power source 30 disposed outside the vacuum chamber body 11. Let, target 2
9 is performed, thereby forming a thin silver film on the surface of the porous membrane film 250 to impart antibacterial properties. The rest of the configuration is the same as that of the plasma polymerization chamber 14, so a description thereof will be omitted.

Each of the preparation rooms 12 and 13 has a pair of winding/unwinding mechanisms 3.
1.32 is installed. One winding/unwinding mechanism 31
is composed of an aluminum bobbin 33 for winding the porous membrane film 25 and guide rollers 34 and 35 for guiding the porous membrane film 25. The other winding/unwinding mechanism 32 includes a bobbin 36, guide rollers 37, 38, 39, and a tension control mechanism 40. The tension control mechanism 40 includes the guide roller 3
8 rotatably supported by a shaft 41, and rotatably supported by a support member 43 at the center thereof by a shaft 42; a weight 45 attached to the other end of this arm 44; Consisted of. This tension control mechanism 40 sets the tension of the moving porous membrane film 25 using a weight 45, and detects the magnitude using a tension arm 44. The torque of a back tension motor (not shown) is automatically adjusted so that the tension of the membrane film 25 is always constant.

Further, the running speed of the porous membrane film 25 is an important parameter that determines the exposure time to plasma. This running speed is arbitrarily selected within the range of 1 to 10 (mm/m1n).

Detection of the traveling speed is performed by an encoder (not shown) attached coaxially with the guide roller 35.

The output of this encoder and the set value of the motor drive circuit are constantly compared and fed back, so that the porous membrane film 25 is transported at a constant speed.

Partition plates 46 as partition means are provided between the graft polymerization chamber 14 and the sputter chamber 15, between the graft polymerization chamber 14 and the preparation chamber 12, and between the sputter chamber 15 and the preparation chamber 13.
．． 47 and 48 are provided, and these partition plates 46 to 48 are provided.
48 prevents each process from affecting other processes. Windows 49 through which the porous membrane film 25 can pass are formed in each of these partition plates 46 to 48. The upper halves of the partition plates 47 and 48 on both sides can be opened and closed toward the preparation chambers 12 and 13 around the axis 5o using air cylinders (not shown), thereby evacuating the inside of the vacuum chamber body 11. And cleaning is easier.

Further, an opening/closing door 52 is provided on the front surface of the vacuum chamber body 11 and is movable up and down along a rail 51.
is provided with an observation window 53.

Next, an experimental example in which a porous membrane film was specifically functionalized using the above functional membrane manufacturing apparatus will be described.

Experimental Example 1 A polypropylene porous membrane film with surface projections (width 170 mm, length 100 m,
A pore diameter of 0.45 μm, a film thickness of 80 μm, a porosity of 68%, a bubble point of 0, 9 [kg/ctl E, protrusion height of 80 μm) was wound between the bobbins 33 and 36, and this was installed inside the vacuum chamber body 11. While winding up the porous membrane film, the inside of the vacuum chamber main body 11 is pumped 5 times using a vacuum pump.
The pressure was reduced to X 10' Torr. After that, argon gas is introduced from the plasma gas inlet 22 to 0.
Plasma irradiation was performed at 5 Torr while winding at a speed of 5 m/min. Subsequently, after removing the argon gas under reduced pressure using a vacuum pump, methoxyethyl acrylate gas was supplied from the monomer gas inlet 23 to reduce the argon gas to zero. 6 Torr
The film was then wound up twice at a speed of 10 m/min, and graft polymerization was carried out for 40 minutes. Subsequently, unreacted monomer gas was removed under reduced pressure while winding the film back and forth at a speed of 10 m/min, and then the apparatus was returned to atmospheric pressure and the porous membrane filter was taken out. After thoroughly washing this porous membrane film with methanol, the water permeability and moisture content of CASTM4189-82
(methodB>), the average water permeability was 3
．． lXl0” [mm/m1n/m”/mmHg”
J, and the average wetting time was 20 seconds.

(Comparative Example 1) Graft polymerization conditions were set to 0. 2. in one direction under a monomer gas pressure of 6 Torr. Winding at a speed of 5m/min,
A polypropylene porous membrane film with surface protrusions was graft-polymerized in the same manner as in Example 1, except that the graft polymerization was carried out for 40 minutes. In the obtained porous membrane film, methoxyethyl acrylate was not sufficiently graft-polymerized on the pore surface, and the heating time was 5 minutes or more.

In addition, although the surface of this porous membrane film was made hydrophilic as it was, the amount of water permeation could not be measured because the surface of the pores of the membrane was not sufficiently made hydrophilic.

Experimental Example 2 Using the above manufacturing apparatus, a polypropylene porous membrane film similar to that of Example 1 was wound at a speed of 10 m/min, silver was targeted, and the film was heated at 0.1 Torr and 500 W.
High frequency sputtering was performed under the following conditions. Subsequently, in the same manner as in Example 1, methoxyethyl acrylate as the first monomer was graft-polymerized for a predetermined time while winding up the porous membrane film, and unreacted materials were removed under reduced pressure. Furthermore, 4-vinylpyridine as the second monomer was supplied in gaseous form (0.5 Torr) to
Graft polymerization was carried out by making two reciprocations (40 ml) at a speed of n. The obtained porous membrane film is composed of graft-polymerized polymethoxyethyl acrylate and poly(4
-vinylpyridine) provides hydrophilicity and 250 (μeq
It is a composite functional porous membrane film that has both the weak basic anion exchange ability of /g) and the antibacterial property of sputtered silver. was placed on an agar medium and the growth of the bacteria planted on the agar medium was observed. Antibacterial properties prevent the growth of bacteria, so bacteria do not grow around the membrane.
A blocker is formed. In addition, aeruginosa bacteria and Staphylococcus were used as antibacterial indicator bacteria.

Experimental Example 3 Similarly to Experimental Example 1, a polypropylene porous membrane film (width 170 mm, length 100 m, pore diameter 0° 45 μm 1 film thickness 1
00 μm, porosity 61%, bubble point 1.0 [kg
/cI11]) was attached to the above manufacturing equipment, and while winding up the porous membrane film, 5 x 10
'The pressure was reduced to Torr. Thereafter, while winding at a speed of 5 m/min, 0. Plasma irradiation was performed by introducing argon gas from the plasma gas inlet 22 at 5 Torr. Subsequently, after removing the argon gas, ethyl acrylate gas is supplied from the monomer residue inlet 23 to
, 8 Torr, porous membrane film at 10 m/mi
Graft polymerization was carried out for 80 minutes by winding the film back and forth four times at a speed of n. Next, unreacted monomer gas was removed under reduced pressure while winding back and forth at a speed of 5 m/min, and then methoxyethyl acrylate was supplied as the second monomer.
Graft polymerization was carried out for 40 minutes while winding the porous membrane film back and forth twice at a speed of 10 n/min at 5 Torr. Subsequently, after removing unreacted monomer gas, the inside of the vacuum chamber main body 11 was returned to atmospheric pressure and the porous membrane film was taken out. After thoroughly washing this porous membrane film with a methanol/dichloromethane azeotropic mixed solvent, its thermal properties were examined using the method described above, and the heating time was approximately 3 minutes. This porous membrane film is graft-polymerized with polyethyl acrylate that has rubber elasticity, so the elongation at break is 1.
It had rubber-like physical properties with a recovery rate of 96% at 100% elongation.

Comparative Example 2 The polypropylene porous membrane film itself used in Example 3 was water exchangeable and did not get wet.

Furthermore, the elongation at break was 13%, and it did not have rubber-like physical properties.

Experimental Example 4 Polypropylene porous membrane film (width 170 mm, length 100 m) wound around bobbin 33.36.

While winding up the film (pore diameter 0.6 μm, film thickness 80 μm, porosity 67%, bubble point 0.7 [kg/crl]),
The inside of the vacuum chamber body 11 is heated to 5X10-5 Torr using a vacuum pump.
The pressure was reduced to After that, argon gas is introduced from the plasma gas inlet 22 to spread the porous membrane film at a rate of 5 m/min.
While winding at a speed of 0. Plasma irradiation was performed at ITorr. Subsequently, after removing the argon gas, methoxyethyl acrylate gas is supplied from the monomer gas inlet 23 to a temperature of 0. 5Torr, 10m/mi
Graft polymerization was carried out for 60 minutes by winding the film back and forth three times at a speed of n. Next, while winding the porous membrane film twice at a speed of 10 m/min, unreacted monomer gas was removed under reduced pressure, and then 1-vinyl-2-imidacillin was supplied as the second monomer. Te 0. Graft polymerization was carried out for 40 minutes at a pressure of 5 Torr while winding the porous membrane film back and forth twice at a speed of 1 Qm/min. Next, unreacted monomer gas was removed under reduced pressure while winding the porous membrane film twice at a speed of 10 m/min, and then glycidyl acrylate was supplied as the third monomer to 0°5 T.
orr, and graft polymerization was carried out for 40 minutes while winding the porous membrane film back and forth twice at a speed of 10 m/min. Subsequently, after removing unreacted monomer gas under reduced pressure, the porous membrane film was taken out and thoroughly washed with methanol to dissolve polymethoxyethyl acrylate and poly (1
-Vinyl-2-imidacyline) and polyglycidyl acrylate were graft-polymerized to obtain a porous membrane film.

This porous membrane film had hydrophilicity due to polymethoxyethyl acrylate, cationicity due to poly(1-vinyl-2-imidacyline), and reactivity due to the glycidyl group of polyglycidyl acrylate. Therefore, this porous membrane film can be made by ionically bonding an anionic substance in an aqueous solution to the membrane surface and pore surface through electrostatic interaction, and then strongly covalently bonding it with glycidyl groups. Therefore, it was found to be useful as an immobilization substrate for anionic physiologically active substances.

〔Effect of the invention〕

As described above, according to the graft polymerization method according to claim 1,
Since graft polymerization is carried out separately using multiple types of monomers, it is possible to add complex functions to the substrate to be treated using multiple types of graft chains, and the substrate to be treated is exposed to the atmosphere (oxygen). Since the graft polymerization is carried out through a series of vacuum processes without contact with the polymer, stable graft chains can be formed.

Further, according to the graft polymerization method according to claims 2 and 3, the graft polymerization is performed while moving the substrate to be treated back and forth, so that graft chains can be uniformly formed on the surface of a large amount of substrates to be treated. be able to.

Furthermore, according to the graft polymerization method according to claims 4 and 5, the substrate to be treated is formed into a film, a plurality of protrusions are formed on the surface of the substrate, and the substrate to be treated is wound and conveyed. Therefore, gaps are formed between the substrates to be treated, and therefore it becomes possible to efficiently supply and remove monomers, and it is possible to uniformly and stably form graft chains.

Further, according to the graft polymerization apparatus according to claims 6 and 7, the substrate to be treated can be reciprocated multiple times in a vacuum atmosphere, and at least two types of monomer gases can be separately supplied. Since it is possible, claims 1 to 3
The described graft polymerization method can be easily realized,
Composite functions can be added to a large amount of substrates to be processed.

[Brief explanation of drawings]

The drawings show one embodiment of the present invention, and FIG. 1 is a longitudinal sectional view of a functional film manufacturing apparatus, and FIG. 2 is a perspective view showing the external appearance. Fig. 2 1... Vacuum chamber body 4... Graft polymerization chamber 5... Sputtering chamber 2... Plasma gas inlet 3... Monomer gas inlet 9.30... Winding... Unwinding mechanism 5a...first monomer gas supply port 5b...second monomer gas supply port

Claims (1)

[Claims] 1. A step of preparing at least two or more types of monomers and performing graft polymerization by supplying one monomer to a substrate to be treated in a vacuum atmosphere; Of these, there is a step of removing unreacted monomers under reduced pressure, and a step of supplying other monomers to the substrate to be treated in a vacuum atmosphere to carry out graft polymerization after removing unreacted monomers. A graft polymerization method characterized in that the graft polymerization is carried out separately using a plurality of types of monomers. 2. The graft polymerization method according to claim 1, wherein each of the steps is performed while transporting the substrate to be treated. 3. The graft polymerization method according to claim 2, wherein the substrate to be treated is moved back and forth and each step is repeated a plurality of times. 4. The graft polymerization method according to claim 2 or 3, wherein the substrate to be treated is in the form of a film, a plurality of protrusions are formed on the surface of the substrate, and the substrate to be treated is wound and conveyed. . 5. The graft polymerization method according to claim 4, wherein the height of the protrusion is 10 to 1000 μm. 6. A vacuum chamber body having a graft polymerization chamber therein, an exhaust means for evacuating the inside of the vacuum chamber body, a plasma generation means for generating plasma in the graft polymerization chamber, and at least two types for the graft polymerization chamber. monomer gas supply means for separately supplying monomer gases for graft polymerization; and a transfer mechanism for reciprocatingly transporting the membrane substrate to be treated in the graft polymerization chamber. Graft polymerization equipment. 7. The transfer mechanism includes a pair of winding/unwinding mechanisms that are respectively disposed on both sides of the graft polymerization chamber and wind up and unwind the film-like substrate to be processed;
7. The graft polymerization apparatus according to claim 6, further comprising a speed control mechanism for controlling the traveling speed of the substrate to be processed transported by these winding/unwinding mechanisms.