JP2008525566A - Chemically modified organic polymer material, method for producing the same, and apparatus - Google Patents

Abstract

When synthesizing functional materials by introducing chemicals induced by radicals into organic polymer base materials and synthesizing functional materials, phenomena that cause the expected functions to be obtained from the amount of target substances introduced, etc. A functional material and a synthesis method and apparatus for the same are disclosed.
One embodiment of the present invention is an organic polymer material obtained by chemically modifying a base material made of an organic polymer material, and is based on the chemical modification by X-ray photoelectron spectroscopy (XPS) in a surface layer of the base material Provided is an organic polymer material characterized in that a response is detected.
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Description

  The present invention was introduced to a method and apparatus for introducing a chemical substance by performing a chemical reaction induced by radicals on a molded organic polymer base material, and a product after introducing the chemical substance. By measuring the abundance distribution of the target substance in the depth direction from the surface of the product toward the inner direction by means capable of analyzing the atoms or atomic groups constituting the target substance, the necessary function can be obtained. It is related with the technology which confirms that it was introduced.

  Methods for imparting various functions to a molded organic polymer material include a method in which functional groups are directly introduced to the material surface by plasma irradiation or sulfonation, or a surface containing a functional functional group by a cross-linking polymerization method. Various methods have been attempted, such as a method of chemically modifying the polymer, or a method of graft-polymerizing a monomer to a polyolefin substrate.

  Among these, as disclosed in Japanese Patent Publication No. 6-55995, various kinds of compounds are produced by irradiating an organic polymer substrate with ionizing radiation to generate radicals and performing chemical reactions induced by the radicals. The method of introducing this function into the substrate can be applied to substrates of various shapes, and since the shape of the substrate can be maintained after the reaction, it can be said to be a highly versatile method. And since the functional group which expresses a desired function is chemically bonded to the base material, they hardly diffuse or dissociate from the base material. The description of Japanese Patent Publication No. 6-55995 is incorporated herein by reference.

  In recent years, in the course of research by the present inventors, the amount of a target substance introduced into a substrate in an organic polymer material in which a desired function is introduced into the substrate based on a chemical reaction induced by radicals as described above. Compared with the expected function (theoretical value), there were some cases where the actually observed function was insufficient or the function was hardly expressed. For example, surface wettability (contact angle) in a thin film material (film) introduced with a hydrophilic functional group; ion conduction (diffusion) speed in a film thickness direction in a thin film material (film) introduced with an ion exchange group; The above-mentioned phenomenon was observed with respect to functions such as the water absorption rate in the nonwoven fabric into which the group was introduced; the metal ion adsorption rate in the nonwoven fabric into which the cation exchange group was introduced.

  And why does the above phenomenon occur, what is the state of the material after the introduction of the functional group, and how to synthesize functional materials while avoiding the above phenomenon Neither of these is clear.

  The object of the present invention is to obtain a function expected from the amount of target substance introduced when a functional material is synthesized by conducting a chemical reaction induced by radicals on an organic polymer base material. It is an object to provide a functional material, a method for synthesizing the functional material, and an apparatus in which such a phenomenon is clarified, and in which such a phenomenon is avoided. The “chemical modification” as used in the present invention refers to introduction of a target substance by forming a chemical bond such as a covalent bond, an ionic bond, or a coordinate bond with respect to a substrate.

  As a result of diligent research, the present inventors first have an extremely low target substance introduction amount in the region of 1 nm to 100 nm in the depth direction from the surface of the material where the expected (theoretical value) function is not obtained, or We found for the first time that there was an area that was not introduced. In addition, when the region not chemically modified exists at such a depth, the present inventors have a region of 1 nm to 100 nm in a scanning electron microscope (SEM-XMA) or infrared spectroscopy (IR). It is extremely difficult to confirm the existence of the surface because it cannot be analyzed, and its existence can only be confirmed by analyzing the surface using X-ray photoelectron spectroscopy (XPS) or transmission electron microscope (TEM). I found it. As a result of further studies, the present inventors have found that the cause of such a region is oxygen molecules present in a trace amount in the system during the reaction. Furthermore, in the process from the irradiation process of ionizing radiation to the completion of the reaction, it was found that the above-mentioned problems can be solved by controlling the oxygen concentration to a lower concentration than before, and the present invention has been completed. It was.

  Conventionally, when a graft polymerization reaction induced by radicals is performed on an organic polymer substrate, for example, if the oxygen concentration is usually less than 1000 ppm, a part of the radical on the substrate is consumed by oxygen molecules. Even if there is, there is basically no problem because the radical remaining in the crystalline part of the base material migrates inside the base material and then the polymerization reaction proceeds as the starting point. I came. For example, when a sulfonic acid group is introduced into a polyethylene fiber by grafting the polyethylene fiber with glycidyl methacrylate by an impregnation gas phase method and then sulfonating, the oxygen concentration in the gas phase is 1000 ppm. Even in the case of 100 ppm, almost no difference was observed in the results of analysis of the amount of introduced sulfonic acid groups and the element distribution by SEM-XMA.

  The present inventors have conducted a detailed analysis on materials for which functions as expected (theoretical values) have not been obtained. And, from the analysis result of element distribution on the material surface by XPS or TEM, we found for the first time that there is a region where there is little or no element distribution derived from the target substance in a very narrow region of 1 nm to 100 nm in the depth direction. It was. In particular, when the depth of such a region is 1 μm or less, it is extremely difficult to find it by analysis of element distribution by SEM-XMA.

  Furthermore, the present inventors consider that the above-described region exists because a desired reaction does not proceed only in that region, and the cause thereof is a trace amount of oxygen molecules that has not been considered a problem in the past. I thought it was. The reason why such a phenomenon occurs even when the oxygen concentration is less than 1000 ppm as in the past is considered to be because the reaction rate between oxygen molecules and radicals on the polymer substrate is extremely high.

  Therefore, the present inventors introduced the target substance while controlling the oxygen concentration of at least one of the radical generation step and the reaction step induced by the radical further lower than before, and obtained polymer When the material was analyzed by XPS (or TEM), it was found that such a region does not exist by controlling the oxygen concentration as such. Further, regarding the polymer material thus obtained, the wettability (contact angle) of the surface of the thin film material (film) introduced with hydrophilic functional groups; the film thickness of the thin film material (film) introduced with ion exchange groups Ion conduction (diffusion) speed in the direction; water absorption speed in the nonwoven fabric introduced with hydrophilic functional groups; metal ion adsorption speed in the nonwoven fabric introduced with cation exchange groups; It was also found to show good results.

  By appropriately introducing the desired function as described above, the organic polymer material according to the present invention can be suitably used for various applications. For example, when the target substance to be introduced is a cation exchange group, the organic polymer material according to the present invention is a solid polymer fuel cell because the cation exchange group is also introduced into a region having a depth of 20 nm or less of the substrate. It can be suitably used as an electrolyte membrane for (PEFC). Moreover, since the cation exchange group is also introduced into a region having a depth of 50 nm or less, the organic polymer material according to the present invention can be suitably used as a separator for a secondary battery or an electrolyte membrane for electrodialysis. Furthermore, when the target substance to be introduced is an ion exchange group or a chelate group, the organic polymer material according to the present invention is a metal ion removing material because those functional groups are also introduced into a region having a depth of 50 nm or less. Can be suitably used.

Hereinafter, various aspects of the present invention will be described in detail.
The present invention relates to a method of introducing a chemical substance by performing a chemical reaction induced by radicals on an organic polymer base material, and the abundance distribution of the introduced target substance to the product after the introduction. It was confirmed that necessary functions were introduced into the base material by measuring by means capable of analyzing atoms or atomic groups constituting the target substance in the depth direction from the surface of the product toward the inside. The present invention relates to a product, a manufacturing method, and an apparatus.

  The present invention generates radicals by radical generating means for the organic polymer base material, or both of the organic polymer base material and the target substance to be introduced simultaneously, or for the target substance to be introduced, In a method of introducing a target substance having various additional functions by forming a chemical bond such as a covalent bond, an ionic bond, or a coordination bond to an organic polymer base material by a reaction starting from a radical. The oxygen concentration in the radical generating step or the chemical reaction step induced by the radical is controlled. By maintaining the oxygen concentration in each step at 1 to 200 ppm in the radical generation step and 1 to 100 ppm in the chemical reaction step induced by radicals, the oxygen concentration in the depth direction extends from the surface of the substrate toward the inside. The target substance can also be introduced in the range of 1 to 100 nm.

  Furthermore, another aspect of the present invention relates to an atomic group constituting a functional target substance introduced into a product produced by the above method, using X-ray photoelectron spectroscopy (XPS). The presence of the atomic group is confirmed by measuring the amount of atoms constituting the atomic group introduced in the depth direction from the product surface to the inside, and the organic polymer base material is used for the intended use. On the other hand, it is characterized by measuring the presence of a sufficient amount of atomic groups compared to before the reaction.

In the present invention, as the radical generating means, any excitation means such as heating, ultraviolet rays, ionizing radiation, laser, ion beam, etc. may be used. 10- 2 ^eV or less, often in the range of 3~10eV in commercial ultraviolet irradiation device, for introducing from the product surface toward the inside direction in the depth direction in the present invention, the energy level that can be provided Is low, and an agent such as an initiator for assisting the generation of radicals may be required, which is not preferable. Lasers and ion beams have a sufficient energy level, but the apparatus is complicated and expensive, the irradiation area and depth are narrow and structural restrictions are imposed, and the constituent materials may be activated. It is not so preferable because of certain things. In the use of ionizing radiation, the energy level that can be applied is 10 ³ to 10 ⁶ eV, which is sufficiently higher than the binding energy of the covalent bond of the organic polymer substrate or the target substance, It is suitable because it is used industrially and does not require the use of an initiator.

  According to one aspect of the present invention, a method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material isolates the substrate from the external environment and keeps the oxygen concentration lower than the outside. In a container capable of generating radicals on the base material in a part of the container, and then moving the base material to another part of the container to cause chemical reaction by a reaction induced by the radicals. The oxygen concentration of the atmosphere to be chemically modified is 1 ppm or more and 100 ppm or less.

  According to another aspect of the present invention, a method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material isolates the substrate from the external environment and controls the oxygen concentration from the outside. It is placed in a container that can be kept low, and radicals are generated in the base material in a part of the container, and then the base material is moved to another part in the container to be induced by the radicals. Including chemical modification by reaction, wherein the oxygen concentration in the atmosphere for generating the radical is 1 ppm or more and 200 ppm or less.

  Furthermore, according to another aspect of the present invention, a method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material isolates the substrate from the external environment and controls the oxygen concentration from the outside. It is placed in a container that can be kept low, and radicals are generated in the base material in a part of the container, and then the base material is moved to another part in the container to be induced by the radicals. Including chemical modification by a reaction, wherein the oxygen concentration of the atmosphere to be chemically modified is 1 ppm to 100 ppm, and the oxygen concentration of the atmosphere in which the radical is generated is 1 ppm to 200 ppm.

  In addition, as said container, the thing in which the part which generate | occur | produces a radical in a base material and the part to chemically modify in one container can be used. The container includes a container for generating radicals on the base material and a separate container for chemically modifying the base material, and the base material is isolated from the external environment and moved while maintaining the oxygen concentration in the atmosphere at 1 ppm or more and 100 ppm or less. It is also possible to use a device having a connection portion that can be made to operate.

  That is, in the method for producing an organic polymer material described above, the container includes a container that generates radicals on the base material and a separate container that chemically modifies the base material, and the base material is isolated from the external environment and is in an atmosphere. The method may further include moving the base material from a container that generates radicals to a container that is chemically modified through a connection portion that can be moved while maintaining the oxygen concentration at 1 ppm or more and 100 ppm or less.

  Furthermore, in the method of the present invention, radical generation and chemical modification can be performed simultaneously. That is, according to another aspect of the present invention, a method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material isolates the substrate from the external environment and controls the oxygen concentration from the outside. Including in a container that can be kept low, generating radicals on the base material while contacting the base material and the chemical modification reactant in a part of the container, and adjusting the oxygen concentration of the atmosphere to be chemically modified 1 ppm or more and 100 ppm or less.

Examples of the chemical reaction induced by radicals include graft polymerization.
The oxygen concentration in the atmosphere in which chemical modification is performed is preferably 1 ppm to 80 ppm, more preferably 1 ppm to 50 ppm, and still more preferably 1 ppm to 30 ppm. The oxygen concentration in the atmosphere in which radicals are generated is preferably 1 ppm to 100 ppm, more preferably 1 ppm to 80 ppm, and still more preferably 1 ppm to 50 ppm.

  Using a sheet-like material of an aggregate of fibers such as a film or a woven or non-woven fabric as a substrate, a step of supplying the substrate to the space where the reaction is performed, a step of generating radicals on the substrate, a substrate At least one or more selected from the step of chemically modifying and the step of discharging the product can be performed continuously.

  As a method of maintaining a reaction space for performing chemical modification by a chemical reaction or a space for generating radicals at a predetermined oxygen concentration, the oxygen concentration in the space is in the range of 1 ppb to 100 ppm, or higher A method of supplying an inert gas having a low oxygen concentration to replace the internal gas in the space can be employed. As another method, an inert gas having an oxygen concentration in the range of 0.1 ppm or more and 100 ppm or less in the range of oxygen concentration or lower than this is supplied to the space, and the internal gas in the space is discharged. Then, after performing the deoxygenation treatment, it is possible to adopt a method of circulating and replacing the internal gas by returning to the space. Here, as the deoxygenation treatment, it is possible to employ a method such as gas passing through an oxygen adsorption tower or electron beam irradiation. The gas replacement or circulation replacement described above is preferably performed continuously during the radical irradiation and chemical reaction. As the inert gas, nitrogen gas having a purity of 99.99% or more can be used.

  Examples of ionizing radiation that can be used in the present invention include neutron rays, α rays, β rays, γ rays, X rays, and electron beams. However, the use of radioisotopes is necessary for neutron rays, α rays, β rays, or γ rays, and there are restrictions on the structure of the irradiation apparatus. X-rays and electron beams are widely used industrially, and because the degree of freedom of the irradiation chamber shape is high, it is easy to design the process, and therefore the oxygen concentration in the radical generation process is also easy to control. The electron beam with high application efficiency is most preferable. The dose is preferably 10 to 500 kGy, more preferably 50 to 200 kGy.

  In the method of generating radicals by radiation in the present invention, radicals are generated in advance on the organic polymer substrate, and after the radicals generated in the organic polymer substrate are stored, the target substance and the organic polymer on which radicals have been generated are stored. There are a pre-irradiation method in which a substrate is brought into contact and a reaction, and a simultaneous irradiation method in which radicals are generated in the coexistence of an organic polymer substrate and a target substance. Any method can be used in the present invention. Also, the simultaneous irradiation method and the pre-irradiation method can be combined and performed continuously. In order to suppress radical decay, the storage temperature of the radical-generated organic polymer substrate in the pre-irradiation method is not preferably 40 ° C. or higher, and is preferably in the range of −196 ° C. to 40 ° C., and −80 ° C. to 30 ° C. Is more desirable. As the storage time, the lower the storage temperature is, the longer the storage is possible, but 2 to 6 months is desirable, and 1 to 30 minutes is desirable in the vicinity of room temperature of 15 to 30 ° C. The oxygen concentration at the time of storage is desirably lower than the oxygen concentration in the atmosphere, preferably 0.1 to 5%, preferably 1 to 200 ppm, more preferably 1 to 100 ppm, and still more preferably 1 to 100 ppm. 80 ppm, and more preferably 1-50 ppm.

  In the present invention, the contact method between the organic polymer substrate and the chemical substance when performing a chemical reaction induced by radicals is a liquid phase method in which the reaction is performed by immersing the organic polymer substrate in a solution of the chemical substance, A gas phase method in which an organic polymer substrate is brought into contact with the vapor of a chemical substance to perform a reaction, and after the organic polymer substrate is immersed in a chemical solution, it is removed from the solution and remains in the organic polymer substrate An impregnation gas phase method in which a reaction is performed in a gas phase using a chemical solution, or a coating method in which a solution containing a chemical substance or a solid containing the chemical substance is applied to the surface of an organic polymer substrate to perform a reaction. Any of these methods can be preferably used.

In the present invention, as a method for controlling the oxygen concentration in the step of generating radicals, for example, an organic polymer base material piece having an oxygen permeability coefficient of 10 ⁻⁵ mol · cm / m ² · sec · Pa or less is used. In this method, the inner gas is replaced with an inert gas such as nitrogen or argon, or the irradiation chamber of the radiation irradiation device is covered with a wall that can be isolated from the atmosphere. A method of replacing the air in the irradiation chamber with an inert gas by introducing and exhausting the irradiation chamber, or a method of reducing the oxygen partial pressure in the irradiation chamber by exhausting the irradiation chamber and reducing the internal pressure of the irradiation chamber Etc. can be adopted. In addition, as a method for measuring the oxygen concentration, for example, when replacing the internal gas of the irradiation container, the oxygen gas in the glove box is replaced with oxygen gas in a glove box into which an inert gas is introduced. A method of measuring the concentration, a method of measuring the pressure in the irradiation container and calculating from the oxygen partial pressure, or an oxygen concentration in the irradiation chamber of 10 ⁻⁵ mol · cm / m ² · sec · Pa as an oxygen transmission coefficient A method of monitoring with an oxygen concentration measuring means connected by a sampling pipe (stainless steel, Teflon (registered trademark), nylon, etc.) made of the following materials can be employed. This monitoring may be measured continuously during the irradiation. As oxygen concentration in a radical generation | occurrence | production process, 1-200 ppm is desirable in this invention, 1-100 ppm is suitable, 1-80 ppm is more preferable, More desirably, it is 1-50 ppm.

  In the radical generation step, in order to maintain the above oxygen concentration, the oxygen concentration in the irradiation container is continuously monitored by the oxygen concentration measuring means during the irradiation, and the oxygen concentration in the irradiation container is arbitrarily set. When approaching the set value (upper limit value of the predetermined concentration range), the oxygen concentration can be increased by increasing the flow rate of the inert gas introduced into the container by opening and closing the solenoid valve, etc. The range can be kept within any set value.

As a method of controlling the oxygen concentration in the chemical reaction process induced by radicals,
A method similar to the step of generating radicals can be used. For example, in the above-mentioned glove box, it is possible to use a method in which an irradiated organic polymer base material and a chemical solution are introduced and sealed in a reaction vessel under an oxygen concentration measurement. As an oxygen concentration in a chemical reaction process, 1-100 ppm is desirable, 1-80 ppm is suitable, More preferably, it is 1-50 ppm, More preferably, it is 1-30 ppm.

In the chemical reaction step, in order to maintain the above oxygen concentration, for example, a method similar to the step of generating radicals can be used.
In the case of constructing a mass production process industrially, for example, a continuous conveyance reaction process (US Pat. No. 6,659,751) by the present inventors can be used. The description of US Pat. No. 6,659,751 is incorporated herein by reference. A configuration example of such a continuous conveyance type reaction process is shown in FIG. This continuous transport reaction process is for generating radicals by the pre-irradiation method and for reacting by contacting the roll-shaped organic polymer substrate and the chemical substance by the impregnation gas phase method. It consists of four steps as a central element that can also be adopted in the system. First, a roll-shaped organic polymer base material is unwound, and then a continuous unwinding step. Second, the organic polymer base material unwound is irradiated with ionizing radiation to generate radicals. Ionizing radiation irradiation process, third, chemical reaction process in which an organic polymer substrate irradiated with ionizing radiation and a chemical substance are brought into contact with each other to carry out a chemical reaction induced by radicals, and fourth, a product that has reacted. This is a winding process for finishing into a roll. As shown in FIG. 1, the chemical reaction process can be divided into an impregnation process in which a base material is impregnated with a chemical substance and a reaction process in which a chemical reaction induced by radicals proceeds. The route and device from the device for performing the irradiation process for performing ionizing radiation irradiation for generating radicals to the device for performing the reaction process for performing a chemical reaction induced by radicals include the transport route for the organic polymer substrate and the inside of the device. In order to control the oxygen concentration, a container-like structure covered with a wall that is shielded from the atmosphere is used, and an inert gas is introduced into the interior and exhausted to replace the internal gas. At this time, an internal circulation device such as a fan may be installed in the apparatus in order to increase the internal gas replacement efficiency. The replacement of the internal gas is preferably performed continuously. In addition, an oxygen concentration meter that measures the oxygen concentration in the apparatus is attached to the apparatus that performs the above steps (in FIG. 1, a radiation irradiation apparatus, an impregnation apparatus, and a reaction apparatus), and the oxygen concentration in the apparatus is continuously adjusted. When the oxygen concentration in the device approaches the set value (upper limit value of the predetermined concentration range), the flow rate of the inert gas introduced into the device is switched according to the approach. Etc., the oxygen concentration range can be kept within an arbitrary set value.

Regarding the device, the connection between the devices that perform each step may be covered with a wall that shields from the atmosphere, and by providing a sealing structure or the like at the connection portion, the device that performs each step is in a separate airtight state. As well as reducing the amount of inert gas used, the effect of maintaining a predetermined oxygen concentration in each step can also be expected. Japanese Patent Application No. 2004-203507 is a more specific example of the seal structure as a prior patent example by the inventors. The description of Japanese Patent Application No. 2004-203507 is incorporated herein by reference. As a method for measuring the oxygen concentration inside the apparatus according to the present invention, as in the irradiation chamber, a sampling pipe made of a material having an oxygen transmission coefficient of 10 ⁻⁵ mol · cm / m ² · sec · Pa or less (stainless steel, Teflon (registered) Trademark), nylon, etc.) can be used for monitoring with an oxygen concentration measuring means connected. The measurement of the oxygen concentration may be continuously monitored as in the irradiation step.

The present invention also relates to an apparatus for producing a chemically modified organic polymer material by performing the above-described method of the present invention.
That is, another aspect of the present invention is an apparatus for producing a film-like organic polymer material obtained by chemically modifying a base material made of an organic polymer material,
An ionizing radiation irradiating unit for generating radicals in a base material made of an organic polymer material, which is disposed in a first container capable of isolating the base material from the external environment and maintaining an oxygen concentration lower than the outside. ;
A chemical modification portion that is chemically modified by a reaction induced by the radical, disposed in a second container that can isolate the substrate from the external environment and keep the oxygen concentration lower than the outside;
A container in which the ionizing radiation irradiation unit is disposed and a chemical modification unit are disposed in a third container that can isolate the substrate from the external environment and keep the oxygen concentration lower than the outside. A connecting portion for connecting the container to which the base material is moved and the base material is movable;
In any one of the first container in which the ionizing radiation irradiation unit is disposed, the second container in which the chemical modification unit is disposed, and the third container in which the connection unit is disposed, 1st or more inert gas supply port which supplies an inert gas in a container, One or more exhaust port which exhausts the internal gas of a container, The 1st which the said ionizing radiation irradiation part is arrange | positioned The oxygen concentration of the internal gas of the container is maintained at 1 ppm or more and 200 ppm or less, and / or the oxygen concentration of the internal gas of the second container in which the chemical modification unit is disposed is maintained at 0.1 ppm or more and 100 ppm or less. An organic polymer material chemical modification device characterized by having a function.

  It is also possible to divide the chemical modification part into an impregnation part and a reaction part, arrange them in separate containers, and connect them with a connection part. In this case, both the container in which the impregnation part is arranged and the container in which the reaction part is arranged have a mechanism for maintaining the oxygen concentration of the internal gas at 1 ppm or more and 100 ppm or less.

  Moreover, an ionizing radiation irradiation part, a chemical modification part, and a conveyance part can also be arrange | positioned in one container. That is, another aspect of the present invention is an apparatus for producing a film-like organic polymer material obtained by chemically modifying a substrate made of an organic polymer material, isolating the substrate from the external environment and oxygen concentration A container capable of holding the substrate lower than the outside; an ionizing radiation irradiating unit disposed in the container for generating radicals on a substrate made of an organic polymer material; disposed in the container A chemical modification unit that chemically modifies the base material by a reaction induced by the radical; a transport unit that is disposed in the container and transports the base material from the ionizing radiation irradiation unit to the chemical modification unit And an inert gas supply port for supplying an inert gas to the inside of the container and an exhaust port for exhausting the internal gas of the container, and the oxygen concentration of the internal gas of the container is 0.1 ppm or more Hold at 100 ppm or less The present invention also relates to an apparatus for chemically modifying an organic polymer material characterized by having a mechanism.

  In the above apparatus, as a mechanism for maintaining the oxygen concentration of the internal gas of the container below a predetermined range, for example, an oxygen concentration meter that continuously monitors the oxygen concentration of the internal gas is attached to each container. Inert gas to be introduced into the container according to the approach of oxygen concentration continuously monitored, when the oxygen concentration in the container approaches the set value (upper limit value of the predetermined concentration range) It is possible to employ a mechanism that increases the flow rate by opening and closing the electromagnetic valve.

  The organic polymer material chemical modification apparatus includes an oxygen concentration meter that continuously monitors the oxygen concentration of the internal gas of the ionizing radiation irradiation unit and / or the chemical modification unit, and the oxygen concentration is within a predetermined concentration range. It is possible to further provide a function of issuing an alarm when deviating from. Further, the apparatus includes an oxygen concentration meter that continuously monitors the oxygen concentration of the internal gas of the ionizing radiation irradiation unit and / or the chemical modification unit, and is ionized when the oxygen concentration deviates from a predetermined concentration range. It may further have a function of stopping the actinic radiation and / or stopping the chemical modification reaction. Furthermore, the apparatus includes an oxygen concentration meter that monitors the oxygen concentration of the internal gas of the ionizing radiation irradiation unit and the chemical modification unit, and the ionizing radiation irradiation unit and the chemical modification when the operation of the chemical modification device is started. It is possible to further have a control function that can be started when the oxygen concentration of the internal gas of each part is in a predetermined concentration range.

  The invention also relates to a program for operating the device described above. That is, another aspect of the present invention is a computer-readable operation program of the above-described organic polymer material chemical modification device, wherein the internal gas in the ionizing radiation irradiation unit, the chemical modification unit, and the connection unit is oxygenated. By substituting with an inert gas whose concentration is within a predetermined concentration range, the oxygen concentration of each internal gas is set to a predetermined concentration range or less, and the substrate carried from the substrate supply unit is moved to the ionizing radiation irradiation unit to It contains chemical species necessary for chemical modification induced by radicals by irradiating a predetermined amount of ionizing radiation by adjusting the irradiation time, generating radicals on the base material, moving the base material where the radicals were generated to the chemical modification part Contact with a predetermined reaction solution, perform chemical modification according to a predetermined reaction temperature and time, manufacture a chemically modified product, and carry out the chemically modified product by a product transport unit. A computer-readable device operation program for executing the process. In the above program, a program for executing a step of issuing an alarm when the oxygen concentration deviates from the predetermined concentration range can be incorporated. Furthermore, a program for executing a process of stopping ionizing radiation and / or stopping the chemical modification device when the oxygen concentration deviates from a predetermined concentration range may be incorporated. Furthermore, when starting the operation of the chemical modification device, a program for enabling start-up when the oxygen concentration of the internal gas of the ionizing radiation irradiation unit and the chemical modification unit is within a predetermined concentration range can be incorporated. .

  The reaction time used in the radical-induced chemical reaction step varies depending on the combination of the organic polymer substrate and the chemical substance, but is preferably 5 minutes to 24 hours, preferably 10 minutes to 6 hours, Desirably 15 minutes to 2 hours. The reaction temperature used in this step can be from -20 ° C to the decomposition temperature of the chemical substance, but it is preferably 20 ° C to 120 ° C, preferably 30 ° C to 80 ° C, more preferably 40 ° C. To 70 ° C.

  The oxygen concentration measuring means used in the present invention may be any commercially available oxygen concentration meter, but it must be able to measure an oxygen concentration range of 100 ppm or less. Formats include magnetic (Japan Air Gases POM6E, Fuji Electric Instruments ZKG, etc.), zirconia (Toray Engineering LC-750, Iijima Electronics IS-700, etc.), galvanic (Iijima Electronics MC-7G, Japan Air Gases MKI-50 etc.). However, from the oxygen concentration measurement range required in the present invention, the magnetic type has insufficient sensitivity. In addition, a flammable gas may be mixed in the sample gas from the chemical reaction step, and in this case, the oxygen concentration cannot be accurately measured by the zirconia method. Therefore, in the present invention, a galvanic system that has a sufficient oxygen concentration measurement range and that does not hinder measurement even when a flammable gas is mixed in the sample gas is preferable. In addition, when monitoring chemical reactors, installing a cold trap or mist separator in the middle of the gas sampling pipe extends the life of the oximeter to prevent contamination due to evaporation and scattering of chemical substances. be able to.

  The reaction solution used in the present invention needs to be aerated with an inert gas of the solvent before use to reduce the dissolved oxygen concentration in the solvent, and the dissolved oxygen concentration is measured by the oxygen concentration measuring means. It is desirable. The concentration of dissolved oxygen in the reaction solvent used in the present invention is preferably 0.1 to 8 ppm, preferably 0.1 to 4 ppm, and more preferably 0.1 to 1 ppm. In addition, in order to prevent oxygen from being mixed into the apparatus from inside the pipe when transferring the reaction solution from the container having the function of storing the reaction solution and blocking from the atmosphere to the apparatus performing the reaction, an inert gas is put in the pipe. By sending the aerated reaction solution, the gas staying in the pipe is driven out, and oxygen can be prevented from being mixed into the apparatus from the pipe. More preferably, it is possible to employ a method in which the inside of the pipe is replaced with an inert gas and then the reaction solution is fed.

  As the organic polymer base material that can be used in the present invention, any organic polymer material capable of generating radicals can be used. For example, it is easy to process the shape and is generally widely distributed. Polyolefin resins, halogenated polyolefin resins, etc. are suitable. General-purpose plastics such as polyethylene, polypropylene and engineering plastics such as fluororesins (Teflon (registered trademark) made by Mitsui / DuPont Fluorochemical, Daikin neoflon series, etc.) Is easy to use. Also, polyvinyl alcohol resins (Nippon Synthetic Chemical's Boblon, etc.), polyvinyl alcohol-ethylene copolymer resins (Kuraray's Eval, etc.), polyvinyl chloride resins, polyester resins, nylon resins, etc. may be used in the same manner. it can. The shape can be any shape such as granular, rod-like, woven / non-woven, film / sheet, fiber / yarn, hollow fiber, straw, foam, etc. When the process is adopted, a shape that can be formed into a roll is optimal.

  As the chemical substance that can perform a chemical reaction with the radical-induced organic polymer substrate used in the present invention, for example, any polymerizable monomer having a carbon-carbon double bond is used. be able to. For example, (meth) acrylic acid, sodium styrenesulfonate, sodium vinylsulfonate, vinylbenzyltrimethylammonium chloride, diethylaminoethyl methacrylate, which is a polymerizable monomer having a functional atomic group such as an ion exchange group or a hydrophilic group, Examples include acrylamide, hydroxyethyl methacrylate, N-vinylacetamide, and N-vinylpyrrolidone. When these chemical substances are used, the target substance can be introduced into the organic polymer substrate only by the chemical reaction step. In addition, the present invention uses a polymerizable monomer having an atomic group as a precursor that does not itself have a target functional atomic group but can be converted into a target substance by adding a post-process. A product having the target substance can be formed by performing a chemical reaction induced by the radical and then causing a predetermined drug to act. Examples of the polymerizable monomer that can be used in this method include glycidyl methacrylate, styrene, chloromethylstyrene, and vinyl acetate. For example, after introducing glycidyl methacrylate as a polymer side chain into an organic polymer substrate by a radical-induced chemical reaction, for example, by reacting with dimethylamine or iminodiethanol, a weakly basic amino group is introduced on the polymer side. The product you have on the chain can be formed. Similarly, after introducing styrene as a polymer side chain into an organic polymer base material, a cation exchange group can be introduced by sulfonation with a chlorosulfuric acid solution or the like. Furthermore, after introducing chloromethylstyrene into the organic polymer base material as a polymer side chain, an anion exchange group can be introduced by quaternization with trimethylamine or the like. Further, when a chelating agent such as iminodiacetic acid is allowed to act after a radical-induced chemical reaction, a chelating group such as an iminodiacetic acid group can be introduced. In addition, the polymer obtained by polymerizing the polymerizable monomer is brought into contact with the organic polymer base material in a solution or solid state by a coating method, and radicals are generated by the simultaneous irradiation method to generate chemicals on the surface of the base material. Substances or target substances can also be introduced.

  As a method of operation control using measured oxygen concentration values for applying the method according to the present invention to a continuous transport reaction process, for example, the method shown in FIG. 2 as a flowchart and the conceptual diagram as an application example in FIG. Can be mentioned. In the example shown in FIG. 2 and FIG. 3, an arbitrary limit value of the oxygen concentration range to be maintained is input to the oximeter main body as a set value, and a signal is output when the oxygen concentration exceeds the set value. The control panel of the irradiation device and the reaction device receives signals and issues an alarm or stops the operation of the device. In this method, only the actual measured value of oxygen concentration is sent from the oximeter to the control panel, and compared with an arbitrary set value input in advance into the control panel, an alarm is issued when the set value is exceeded. A method of issuing a notification or stopping the operation may be adopted, and any format can be selected. When stopping the operation, it is better to stop the operation of the reaction apparatus after stopping the irradiation and confirming that the radiation irradiation has stopped. This is to prevent deformation or cutting of the organic polymer substrate due to excessive irradiation with ionizing radiation. Furthermore, if it is set so that the operation of the apparatus can be started only when the oxygen concentration falls below an arbitrary set value, an operation error can be prevented. Further, the oxygen concentration in the apparatus can be kept constant by using the actually measured oxygen concentration value. When the oxygen concentration range approaches the vicinity of an arbitrary set value, the flow rate of the inert gas introduced into each device is changed to a preset flow rate using an electromagnetic valve, etc., depending on the approach. Thus, the oxygen concentration range can be kept within an arbitrary set value.

The organic polymer material subjected to chemical modification that can be obtained by the method of the present invention includes the following embodiments.
1. It is an organic polymer material obtained by chemically modifying a base material made of an organic polymer material, and a response based on the chemical modification by X-ray photoelectron spectroscopy (XPS) is detected in a surface layer of the base material. A characteristic organic polymer material.
2. 2. The organic polymer material as described in 1 above, wherein a region of 1 nm to 100 nm is chemically modified in the depth direction of the surface layer of the substrate.
3. 3. The organic polymer material as described in 1 or 2 above, wherein the substrate contains polyolefin and / or halogenated polyolefin.
4). 4. The organic polymer material according to any one of 1 to 3, wherein the organic polymer material is a film-shaped organic polymer material obtained by chemically modifying a film-shaped substrate made of an organic polymer material. Molecular material.
5. A film-like organic polymer material obtained by chemically modifying a film-like substrate made of an organic polymer material, and having a thickness of 0.02% to 0.5% in the depth direction of the surface layer of the substrate 5. The organic polymer material as described in 4 above, wherein the following region is chemically modified.
6). 6. The organic polymer material as described in 4 or 5 above, wherein the surface layer is a layer on both surfaces.
7). 7. The organic polymer material as described in any one of 4 to 6 above, wherein the film-like substrate contains polyolefin and / or halogenated polyolefin.
8). An organic polymer material of a fiber or an aggregate of fibers obtained by chemically modifying a substrate made of an organic polymer material in the form of a fiber or an aggregate of fibers, wherein X-ray photoelectron spectroscopy ( An organic polymer material, wherein a response based on the chemical modification by XPS is detected.
9. 9. The organic polymer material as described in 8 above, wherein a region of 1 nm to 100 nm is chemically modified in the depth direction of the fiber substrate surface layer.
10. A fiber or fiber aggregate organic polymer material obtained by chemically modifying a substrate made of an organic polymer material in the form of fibers or fibers, and the fiber diameter in the depth direction of the fiber substrate surface layer The organic polymer material as described in 8 or 9 above, wherein 0.02% to 0.5% is chemically modified.
11. 11. The organic polymer material as described in any one of 8 to 10 above, wherein the substrate contains a polyolefin and / or a halogenated polyolefin.
12 12. The organic polymer material according to any one of 1 to 11, wherein the organic polymer material subjected to the chemical modification includes a chemical reaction induced by radicals.
13. 13. The organic polymer material as described in 12 above, wherein the means for generating radicals is irradiation with ionizing radiation.
14 14. The organic polymer material as described in 12 or 13 above, wherein the chemical reaction induced by the radical is graft polymerization.
15. 15. The organic polymer material as described in 14 above, wherein the graft side chain introduced into the substrate by graft polymerization is chemically modified.
16. 16. The organic polymer material according to any one of 1 to 15 above, wherein the chemical modification includes introduction of an ion exchange group in the chemically modified organic polymer material.
17. 16. The organic polymer material according to any one of 1 to 15 above, wherein in the organic polymer material subjected to the chemical modification, the chemical modification includes introduction of a ligand.
18. 17. The electrolyte membrane comprising the organic polymer material according to any one of 1 to 16, wherein an ion exchange group is introduced into a base material comprising an organic polymer material, wherein the ion exchange group is induced by radicals. The electrolyte membrane introduced by a reaction including a reaction.
19. An electrolyte membrane in which an ion exchange group is introduced into a base material made of an organic polymer material, and a response based on the introduction of the ion exchange group by X-ray photoelectron spectroscopy (XPS) is detected in the surface layer of the base material An electrolyte membrane characterized by that.
20. 20. The electrolyte membrane as described in 19 above, wherein an ion exchange group is introduced in a region of 1 nm to 10 nm in the depth direction of the surface layer of the substrate.
21. An electrolyte membrane in which an ion exchange group is introduced into a base material made of an organic polymer material, and ions are present in a region of 0.003% to 0.05% of the film thickness in the depth direction of the surface layer of the base material. 21. The electrolyte membrane as described in 19 or 20 above, wherein an exchange group is introduced.
22. The electrolyte membrane according to any one of 19 to 21, wherein the surface layer is a layer on both surfaces.
23. 23. The electrolyte membrane according to any one of 19 to 22, wherein the base material made of the organic polymer contains polyolefin and / or halogenated polyolefin.
24. 17. A secondary battery separator comprising the organic polymer material according to any one of 1 to 16, wherein an ion exchange group is introduced into a base material comprising an organic polymer material, wherein the ion exchange group is induced by a radical. The separator for a secondary battery introduced by a reaction including a chemical reaction to be performed.
25. A separator for a secondary battery in which an ion exchange group is introduced into a base material made of an organic polymer material, and a response based on the introduction of the ion exchange group by X-ray photoelectron spectroscopy (XPS) in the surface layer of the base material Is detected, a separator for a secondary battery.
26. 26. The separator for a secondary battery as described in 25 above, wherein an ion exchange group is introduced in a region of 1 nm to 50 nm in the depth direction of the surface layer of the substrate.
27. 26. The secondary battery separator as described in 25 above, wherein an ion exchange group is introduced in a region of 0.003% to 0.25% of the film thickness in the depth direction of the surface layer of the substrate.
28. The secondary battery separator according to any one of 25 to 27, wherein the surface layer is a layer on both surfaces.
29. 29. The separator for a secondary battery according to any one of 25 to 28, wherein the base material contains polyolefin and / or halogenated polyolefin.

When the substrate is an aggregate of fibers such as a woven fabric or a non-woven fabric, the “surface layer of the substrate” means a surface layer of fibers forming the substrate.
In the present invention, for a product produced by subjecting a base material to radical generation and radical-induced chemical reaction, an atomic group or a part of atoms constituting the introduced target substance is directed inward from the surface. As a means for measuring in the depth direction, for example, in the total reflection measurement method of Fourier transform infrared spectroscopy, a method of measuring by changing the incident angle of infrared rays, a method using a transmission electron microscope, and X-ray photoelectron In order to analyze the distribution of some atoms constituting the target substance in the depth direction from 1 to 100 nm in the depth direction from the surface to the inside of the product according to the present invention, there is a method by a spectroscopic method, X-ray photoelectron spectroscopy is preferred. In X-ray photoelectron spectroscopy, for example, in measurement of organic polymers, etching using Ar ions or the like is performed, and qualitative or quantitative information of atoms existing near the cutting position is obtained while cutting from the surface. It is a method that can be. For example, when a sulfonic acid group is introduced as a functional atomic group, measurement regarding the abundance of sulfur atoms contained in the sulfonic acid group is performed by irradiating X-rays in the depth direction from the surface of the product to the inside, By measuring the energy of the excited secondary electrons and the number of each secondary energy, the abundance of sulfur atoms in the range from the surface to the inside or the bonding state with other atoms can be obtained. The results measured in this way can be used for quality control of products by comparing with the required amount of functional atomic groups according to the intended use.

The following examples further illustrate the present invention. The following description shows specific examples of the present invention, and the present invention is not limited to these descriptions.
Example 1
The inside of the glove box shown in FIG. 4 is placed in a nitrogen atmosphere, and continuous measurement is performed using a galvanic cell type oxygen concentration meter (manufactured by Iijima Electronics Co., Ltd., model number: MC7G-L) as an oxygen concentration measuring means, and the oxygen concentration is maintained at 5 to 30 ppm. As it was, 0.87 g (100 mm × 150 mm) of a film made of poly (chlorotrifluoroethylene) resin (Daikin NEOFLON, average film thickness 25 μm, average weight 55 g / m ² ) was put in a polyethylene bag. Next, the film was taken out from the glove box while being put in a polyethylene bag and irradiated with an electron beam at 200 kGy. The mixture of styrene monomer (70 ml) and toluene (30 ml) was aerated with nitrogen gas for 30 minutes at an oxygen concentration of 10 ppm in the glove box. The irradiated film and the aerated mixture were sealed in a glass container in a glove box at an oxygen concentration of 5 to 10 ppm, and graft polymerization was performed at 60 ° C. for 2 hours. Thereafter, the graft-reacted film was taken out, and after removing the homopolymer for 2 hours with a Soxhlet extractor using acetone as an extraction solvent, it was dried at 70 ° C. for 30 minutes to obtain 1.15 g of a styrene graft film. The graft ratio determined from the change in weight was 32.2%.

The obtained graft-reacted film was immersed in a mixed solution of chlorosulfonic acid / dichloromethane = 2/98 (wt%) and subjected to sulfonation reaction at 5 ° C. for 2 hours. The film was taken out, washed successively with a mixed solution of methanol / dichloromethane = 10/90 (% by weight), methanol and pure water, and dried to obtain a sulfonic acid type film A having an ion exchange capacity of 170 meq / m ² .

Comparative Example 1
As in Example 1 above, 0.88 g (100 mm × 150 mm) of a film made of the same poly (chlorotrifluoroethylene) resin as used in Example 1 in a glove box in an atmosphere of nitrogen at an oxygen concentration of 10 to 25 ppm. ) Was put in a polyethylene bag, taken out of the glove box while being put in the bag, and irradiated with an electron beam at 200 kGy. The mixed solution of styrene monomer (70 ml) and toluene (30 ml) subjected to aeration with this irradiated film and nitrogen gas for 30 minutes is put in a glass container at an oxygen concentration of 100 to 110 ppm in the glove box of Example 1 above. After sealing, graft polymerization was performed at 60 ° C. for 2 hours. The graft-reacted film was taken out, the homopolymer was removed for 2 hours in a Soxhlet extractor using acetone as an extraction solvent, and then dried at 70 ° C. for 30 minutes to obtain 1.12 g of a styrene graft film. The graft ratio obtained from the weight change was 27.3%.

The obtained graft-reacted film was immersed in a mixed solution of chlorosulfonic acid / dichloromethane = 2/98 (wt%) and subjected to sulfonation reaction at 5 ° C. for 2 hours. The film was taken out, washed successively with a mixed solution of methanol / dichloromethane = 10/90 (% by weight), methanol and pure water, and dried to obtain a sulfonic acid type film B having an ion exchange capacity of 168 meq / m ² .

Example 2
Non-woven fabric made of polyethylene fibers (Asahi DuPont Flash Spun Products Co., Ltd., trade name Tyvek: average fiber diameter 0.5 to 10 μm, basis weight 65 g / m ² , thickness 0.17 mm, 300 mm width × 200 m length roll) In addition, the impregnation gas phase graft polymerization reaction was carried out using the continuous transport reactor shown in FIG. Performs continuous measurement using a galvanic cell type oxygen concentration meter (manufactured by Japan Air Gases, model number: MKI-50) as the oxygen concentration measuring means under a nitrogen atmosphere in the radiation irradiation chamber, and maintains the oxygen concentration at 25 to 50 ppm. As it was, the nonwoven fabric was irradiated with an electron beam at 150 kGy. After the polymerization inhibitor was adsorbed and removed by treating chloromethylstyrene (CMS-AM made by Seimi Chemical) with basic alumina, toluene was added and a solution of chloromethylstyrene / toluene = 80/20 (wt%) was added. Prepared and introduced into impregnation apparatus after nitrogen aeration for 30 minutes. While continuously measuring the oxygen concentration in the impregnation apparatus and the reaction apparatus with an oxygen concentration meter (MC7G-L manufactured by Iijima Electronics Co., Ltd.), the oxygen concentration in the impregnation apparatus is 5 to 15 ppm, and the oxygen concentration in the reaction apparatus is 15 to 25 ppm. While being held, the irradiated nonwoven fabric obtained above was transported into the impregnation apparatus at a transport speed of 0.6 m / min to impregnate the nonwoven fabric with the solution, and subsequently transported into the reaction apparatus at 40 ° C. at 40 ° C. Graft polymerization was performed for a minute. In the length direction of the manufactured grafted non-woven fabric (product length = 162 m), three samples at 80 m intervals and a product width x 300 mm size were cut out and treated in toluene at 60 ° C for 3 hours to remove the homopolymer. Went. The nonwoven fabric was further washed with acetone and then dried at 60 ° C. for 2 hours to obtain a chloromethylstyrene graft nonwoven fabric. Table 1 shows the graft ratio according to the change in the weight per unit area of the obtained sample. The average graft ratio was 47.6%.

The obtained chloromethylstyrene grafted nonwoven fabric was immersed in a mixed solution of isopropanol / 30% trimethylamine aqueous solution / pure water = 30/30/40 (volume%), and subjected to quaternary ammonium reaction at 60 ° C. for 6 hours. The nonwoven fabric was taken out, washed three times with pure water at 40 ° C., and dried at 50 ° C. for 1 hour to obtain an anion exchange type nonwoven fabric C. Table 2 shows the ion exchange capacity of the obtained non-woven fabric C. The average ion exchange capacity was 184 meq / m ² .

Comparative Example 2
The same impregnation gas phase graft polymerization reaction as in Example 2 was performed on the nonwoven fabric made of the same polyethylene fiber as that used in Example 2. The nonwoven fabric was irradiated with 150 kGy of an electron beam while maintaining the oxygen concentration of the radiation irradiation apparatus at 250 ppm. A purified chloromethylstyrene (CMS-AM manufactured by Seimi Chemical) / toluene = 80/20 (wt%) solution was aerated with nitrogen for 30 minutes and then introduced into the impregnation apparatus. While maintaining the oxygen concentration in the impregnation apparatus at 5 to 14 ppm and the oxygen concentration in the reaction apparatus at 9 to 37 ppm, the irradiated nonwoven fabric is conveyed into the impregnation apparatus at 0.6 m / min to impregnate the nonwoven fabric with the solution. Subsequently, it was conveyed to a reactor and graft polymerization was carried out at 60 ° C. for 40 minutes. In the length direction of the produced grafted nonwoven fabric, samples having a size of 3 points and a product width × 300 mm were cut out at intervals of 80 m, and the homopolymer was removed by treatment in toluene at 60 ° C. for 3 hours. Further, the nonwoven fabric was washed with acetone and then dried at 60 ° C. for 2 hours to obtain a chloromethylstyrene graft nonwoven fabric. Table 3 shows the graft ratio according to the change in the weight per unit area of the graft nonwoven fabric obtained. The average graft ratio was 45.6%.

The obtained chloromethylstyrene-grafted nonwoven fabric was immersed in a mixed solution of isopropanol / 30% trimethylamine aqueous solution / pure water = 30/30/40 (volume%) in the same manner as in Example 2, and grade 4 at 60 ° C. for 6 hours. An ammoniumation reaction was performed. The nonwoven fabric was taken out, washed three times with pure water at 40 ° C., and dried at 50 ° C. for 1 hour to obtain an anion exchange type nonwoven fabric D. Table 4 shows the ion exchange capacity of the obtained non-woven fabric D. The average ion exchange capacity was 176 meq / m ² .

Example 3
The inside of the glove box shown in FIG. 4 is placed in a nitrogen atmosphere, and continuous measurement is performed using a galvanic cell type oxygen concentration meter (manufactured by Iijima Electronics Co., Ltd., model number: MC7G-L) as an oxygen concentration measuring means, and the oxygen concentration is maintained at 5 to 30 ppm. As it is, non-woven fabric made of polyethylene fiber (Asahi DuPont Flash Spun Products Co., Ltd., trade name Tyvek: average fiber diameter 0.5 to 10 μm, basis weight 65 g / m ² , thickness 0.17 mm) 3.94 g (200 mm × 300 mm) ) In a polyethylene bag. The nonwoven fabric was taken out from the glove box while being put in a polyethylene bag, and irradiated with an electron beam at 150 kGy. The ethanol solution (weight ratio: 1/19) of lithium p-styrenesulfonate (trade name LiSS, manufactured by Tosoh Corporation) was subjected to aeration with nitrogen gas at an oxygen concentration of 10 ppm for 30 minutes in the glove box. After immersing the irradiated nonwoven fabric obtained above in this aerated solution, the liquid is wiped off from the nonwoven fabric to a total weight of 7.80 g. In the glove box, the oxygen concentration is 5 to 10 ppm in the glass container. The mixture was sealed in and graft-polymerized at 60 ° C. for 3 hours. Thereafter, the graft-reacted non-woven fabric is taken out, washed with pure water at 60 ° C. to remove the homopolymer, wiped off the water, and then dried at 50 ° C. for 1 hour to obtain a lithium styrene sulfonate grafted non-woven fabric. 4.22 g was obtained. The graft ratio determined from the change in weight was 7.1%.

The obtained graft-reacted nonwoven fabric was washed twice with 0.5 mol / L hydrochloric acid (500 ml), further washed twice with pure water (500 ml) at 60 ° C. and then wiped off, and then at 50 ° C. for 1 hour. By drying, 4.19 g of a cation exchange nonwoven fabric E was obtained. The resulting nonwoven fabric E had an ion exchange capacity of 10.1 meq / m ² .

Comparative Example 3
As in Example 1 above, a non-woven fabric made of polyethylene fibers (trade name Tyvek: manufactured by Asahi DuPont Flash Spun Products Co., Ltd., average fiber diameter of 0.5- 10 μm, basis weight 65 g / m ² , thickness 0.17 mm) 3.89 g (200 mm × 300 mm) was introduced into a polyethylene bag, and an electron beam was irradiated with 150 kGy while still in the bag. The irradiated nonwoven fabric was immersed in an ethanol solution of lithium p-styrenesulfonate (weight ratio: 1/19) that was aerated with nitrogen gas for 30 minutes, and then wiped to a total weight of 7.80 g. In the same glove box as used in Example 1, after sealing in a glass container at an oxygen concentration of 100 to 110 ppm, graft polymerization was performed at 60 ° C. for 3 hours. The graft-reacted nonwoven fabric was taken out, washed with pure water at 60 ° C. to remove the homopolymer, wiped, and then dried at 50 ° C. for 1 hour to obtain 4.16 g of a lithium styrenesulfonate grafted nonwoven fabric. . The graft ratio determined from the amount of change in weight was 6.9%.

The obtained graft-reacted nonwoven fabric was washed twice with 0.5 mol / L hydrochloric acid (500 ml), further washed twice with pure water (500 ml) at 60 ° C., and then dried at 50 ° C. for 1 hour. By doing this, 4.13 g of the cation exchange nonwoven fabric F was obtained. The obtained nonwoven fabric F had an ion exchange capacity of 9.8 meq / m ² .

Example 4
The elemental distribution on the surface of the sulfonic acid type film A produced in Example 1 and the sulfonic acid type film B produced in Comparative Example 1 were measured by XPS.

  After the film surface was washed with acetone, Al Kα rays (1,486.6 eV) were irradiated as incident X-rays in an elliptical shape having a major axis of 200 μm and a width of 20 to 30 μm. The photoelectrons generated thereby were measured by a wide scan, and when the atomic% of the element existing in a range of 10 nm from the surface was determined, the abundance of S in the sulfonic acid type film A was 1 to 2 atomic%. . On the other hand, in the sulfonic acid type film B, no response based on S was detected.

Example 5
For the sulfonic acid type films A and B obtained in Example 1 and Comparative Example 1 and Nafion N115 manufactured by DuPont, the voltage at constant current is measured using the ion permeability measuring device shown in FIG. Was used to measure the ion permeability. FIG. 6 shows a graph of the results, in which the horizontal axis represents current and the vertical axis represents the required voltage under constant current indicating ion permeability. From this result, it was found that the ion permeability was better when the oxygen concentration during the reaction was lower.

Example 6
Eight of the anion exchange nonwoven fabrics C and D obtained in Example 2 and Comparative Example 2 and the cation exchange nonwoven fabrics E and F obtained in Example 3 and Comparative Example 3 in a strip shape of 4 mm × 25 mm, respectively. Cut out one by one. Next, these were immersed in pure water, washed and wiped, and then dried in a hot air dryer at 50 ° C. for 2 hours. By the method of measuring the water absorption speed shown in FIG. 7, pure water was put into a groove having a depth of 1 mm, and the sample taken out from the dryer was quickly stood so that the long side was vertical and the lower end was placed in the groove, The change with time of the height at which pure water reached was measured. At this time, the room temperature was 25 ° C. and the relative humidity was 55%. The average value of the results is shown in Table 5. In addition, there was no sample which absorbed pure water 10 mm or more in the anion exchange type nonwoven fabric D. From the above, it was confirmed that an ion-exchange nonwoven fabric having a high liquid absorption rate can be obtained by controlling the oxygen concentration during electron beam irradiation to be low.

Example 7
FIG. 3 shows a conceptual diagram of an application example to the continuous transfer type graft reactor installed based on the oxygen concentration control method flowchart shown in FIG. Using this device, when the operation test was performed with the oxygen concentration set value set to 200 ppm on the radiation irradiation device side and 50 ppm on the reaction device side, the operation could not be started above the set value, and the simulated operation started after the set value was reached When the oxygen concentration was increased, a buzzer and Patlite (Registered Trademark) lighting alarm were issued, and a warning message was displayed on the touch panel in the control panel. At that time, the irradiation was stopped, and it was confirmed that the conveyance stopped after that.

FIG. 1 is a diagram illustrating a configuration example of a graft reaction apparatus using a continuous conveyance method. FIG. 2 is a flowchart of an operation control method using oxygen concentration measurement values for applying the method according to the present invention to a continuous transport reaction process. FIG. 3 is a conceptual diagram of an operation control method using an oxygen concentration measurement value for applying the method according to the present invention to a continuous transport reaction process. FIG. 4 is a diagram illustrating a form of the glove box used in the example. FIG. 5 is a diagram showing the configuration of the ion permeability measuring apparatus used in the examples. FIG. 6 is a graph showing the results of the ion permeability test of Example 5. FIG. 7 is a diagram showing an outline of the water absorption rate measuring method used in the examples.

Claims (49)

  It is an organic polymer material obtained by chemically modifying a base material made of an organic polymer material, and a response based on the chemical modification by X-ray photoelectron spectroscopy (XPS) is detected in a surface layer of the base material. A characteristic organic polymer material.   2. The organic polymer material according to claim 1, wherein a region of 1 ppm to 100 nm in the depth direction of the surface layer of the substrate is chemically modified.   The organic polymer material according to claim 1, wherein the base material contains a polyolefin and / or a halogenated polyolefin.   The organic polymer material according to any one of claims 1 to 3, wherein the organic polymer material is a film-shaped organic polymer material obtained by chemically modifying a film-shaped substrate made of an organic polymer material. Polymer material.   A film-like organic polymer material obtained by chemically modifying a film-like substrate made of an organic polymer material, and having a thickness of 0.02% to 0.5% in the depth direction of the surface layer of the substrate The organic polymer material according to claim 4, wherein the following region is chemically modified.   The organic polymer material according to claim 4, wherein the surface layer is a layer on both surfaces.   The organic polymer material according to any one of claims 4 to 6, wherein the film-like substrate contains polyolefin and / or halogenated polyolefin.   An organic polymer material of a fiber or an aggregate of fibers obtained by chemically modifying a substrate made of an organic polymer material in the form of a fiber or an aggregate of fibers, wherein X-ray photoelectron spectroscopy ( An organic polymer material, wherein a response based on the chemical modification by XPS is detected.   The organic polymer material according to claim 8, wherein a region of 1 nm to 100 nm is chemically modified in the depth direction of the fiber base material surface layer.   A fiber or fiber aggregate organic polymer material obtained by chemically modifying a substrate made of an organic polymer material in the form of fibers or fibers, and the fiber diameter in the depth direction of the fiber substrate surface layer The organic polymer material according to claim 8 or 9, wherein 0.02% to 0.5% is chemically modified.   The organic polymer material according to claim 8, wherein the substrate contains a polyolefin and / or a halogenated polyolefin.   The organic polymer material according to any one of claims 1 to 11, wherein the chemically modified organic polymer material includes a chemical reaction induced by radicals.   The organic polymer material according to claim 12, wherein the means for generating radicals is irradiation with ionizing radiation.   The organic polymer material according to claim 12 or 13, wherein the chemical reaction induced by the radical is graft polymerization.   The organic polymer material according to claim 14, wherein a chemical modification is applied to a graft side chain introduced into the base material by graft polymerization.   The organic polymer material according to claim 1, wherein the chemical modification includes introduction of an ion exchange group in the chemically modified organic polymer material.   The organic polymer material according to claim 1, wherein the chemical modification includes introduction of a ligand in the organic polymer material subjected to the chemical modification.   The electrolyte membrane made of an organic polymer material according to any one of claims 1 to 16, wherein an ion exchange group is introduced into a base material made of the organic polymer material, wherein the ion exchange group is induced by a radical. The electrolyte membrane introduced by a reaction including a chemical reaction.   An electrolyte membrane in which an ion exchange group is introduced into a base material made of an organic polymer material, and a response based on the introduction of the ion exchange group by X-ray photoelectron spectroscopy (XPS) is detected in the surface layer of the base material An electrolyte membrane characterized by that.   20. The electrolyte membrane according to claim 19, wherein an ion exchange group is introduced in a region of 1 nm to 10 nm in the depth direction of the surface layer of the substrate.   An electrolyte membrane in which an ion exchange group is introduced into a base material made of an organic polymer material, and ions are present in a region of 0.003% to 0.05% of the film thickness in the depth direction of the surface layer of the base material. 21. The electrolyte membrane according to claim 19 or 20, wherein an exchange group is introduced.   The electrolyte membrane according to any one of claims 19 to 21, wherein the surface layer is a layer on both surfaces.   The electrolyte membrane according to any one of claims 19 to 22, wherein the base material made of the organic polymer contains polyolefin and / or halogenated polyolefin.   The secondary battery separator made of an organic polymer material according to any one of claims 1 to 16, wherein an ion exchange group is introduced into a base material made of an organic polymer material, wherein the ion exchange group is a radical. The separator for a secondary battery introduced by a reaction including an induced chemical reaction.   A separator for a secondary battery in which an ion exchange group is introduced into a base material made of an organic polymer material, and a response based on the introduction of the ion exchange group by X-ray photoelectron spectroscopy (XPS) in the surface layer of the base material Is detected, a separator for a secondary battery.   26. The separator for a secondary battery according to claim 25, wherein an ion exchange group is introduced in a region of 1 nm to 50 nm in the depth direction of the surface layer of the substrate.   26. The separator for a secondary battery according to claim 25, wherein an ion exchange group is introduced in a region of 0.003% to 0.25% of the film thickness in the depth direction of the surface layer of the substrate. .   The secondary battery separator according to any one of claims 25 to 27, wherein the surface layer is a layer on both surfaces.   The secondary battery separator according to any one of claims 25 to 28, wherein the base material contains polyolefin and / or halogenated polyolefin.   A method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material, the container being capable of isolating the substrate from the external environment and maintaining an oxygen concentration lower than the outside And after generating radicals in the base material in a part of the container, the base material is moved to another part in the container and chemically modified by a reaction induced by the radical, A method for producing an organic polymer material, characterized in that the oxygen concentration of the atmosphere to be chemically modified is 1 ppm or more and 100 ppm or less.   A method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material, the container being capable of isolating the substrate from the external environment and keeping the oxygen concentration lower than the outside And after generating radicals in the base material in a part of the container, the base material is moved to another part in the container and chemically modified by a reaction induced by the radical, A method for producing an organic polymer material, wherein an oxygen concentration in an atmosphere for generating radicals is 1 ppm or more and 200 ppm or less.   A method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material, the container being capable of isolating the substrate from the external environment and keeping the oxygen concentration lower than the outside And after generating radicals in the base material in a part of the container, the base material is moved to another part in the container and chemically modified by a reaction induced by the radical, A method for producing an organic polymer material, characterized in that the oxygen concentration of the atmosphere for chemical modification is 1 ppm to 100 ppm, and the oxygen concentration of the atmosphere for generating radicals is 1 ppm to 200 ppm.   The method for producing an organic polymer material according to any one of claims 30 to 32, wherein the container is divided into a portion that generates radicals on the substrate and a portion that is chemically modified.   The container includes a container for generating radicals on the base material and a separate container for chemically modifying the base material, and the base material is moved away from the external environment while maintaining the oxygen concentration in the atmosphere at 1 ppm or more and 100 ppm or less. The organic polymer material according to any one of claims 30 to 32, further comprising moving the base material from a container for generating radicals to a container for chemical modification through a connecting portion capable of Production method.   A method for producing an organic polymer material by chemically modifying a substrate made of an organic polymer material, the container being capable of isolating the substrate from the external environment and keeping the oxygen concentration lower than the outside And generating radicals on the base material while contacting the base material and the chemical modification reactant in a part of the container, and the oxygen concentration of the atmosphere to be chemically modified is 1 ppm or more and 100 ppm or less A method for producing an organic polymer material.   36. The method for producing an organic polymer material according to any one of claims 30 to 35, wherein the means for generating radicals is irradiation with ionizing radiation.   37. The method for producing an organic polymer material according to any one of claims 30 to 36, wherein the chemical modification includes graft polymerization.   The said base material contains polyolefin and / or halogenated polyolefin, The manufacturing method of the organic polymer material in any one of Claims 30-37 characterized by the above-mentioned.   The base material is a sheet-like material in the form of a film or an aggregate of fibers, and the step of supplying the base material to the reaction space, the step of generating radicals, the step of chemical modification, and the step of discharging the product The method for producing an organic polymer material according to any one of claims 30 to 38, wherein at least one selected from the above is continuously performed.   40. The oxygen concentration in the space for performing the reaction is kept lower than the outside by supplying an inert gas having an oxygen concentration of 1 ppb or more and 100 ppm or less to the space in which the reaction is performed to replace the internal gas in the reaction space. The manufacturing method of the organic polymer material in any one.   An inert gas having an oxygen concentration of 0.1 ppm or more and 100 ppm or less is supplied to the space in which the reaction is performed, the internal gas in the reaction space is discharged, deoxygenation treatment is performed, and then the reaction space is returned to the internal space. The method for producing an organic polymer material according to any one of claims 30 to 40, wherein the oxygen concentration in the space in which the reaction is performed is maintained lower than the outside by circulating and replacing the gas. The method for producing an organic polymer material according to claim 40 or 41, wherein the inert gas is a nitrogen gas having a purity of 99.99% or more.   A method for inspecting a film-like organic polymer material in which a base material made of an organic polymer material is chemically modified, wherein the surface layer of the produced film-like organic polymer material has a depth direction of 1 nm to 100 nm. A method for inspecting a film-like organic polymer material, wherein the region is chemically modified by X-ray photoelectron spectroscopy (XPS).   An apparatus for producing a film-like organic polymer material in which a base material made of an organic polymer material is chemically modified, and can isolate the base material from the external environment and keep the oxygen concentration lower than the outside. An ionizing radiation irradiation unit that generates radicals on a base material made of an organic polymer material, which is disposed in the first container; can isolate the base material from the external environment and keep the oxygen concentration lower than the outside A chemical modification portion disposed in the second container and chemically modified by the radical-induced reaction; a third capable of isolating the substrate from the external environment and maintaining the oxygen concentration lower than the outside; Connecting the container in which the ionizing radiation irradiating part is disposed and the container in which the chemical modification part is disposed and the base material is movable; The ionizing radiation irradiation unit is arranged. An inert gas is supplied to the inside of any of the first container, the second container in which the chemical modification unit is disposed, and the third container in which the connection unit is disposed. One or more inert gas supply ports to perform and one or more exhaust ports for exhausting the internal gas of the container, and the oxygen concentration of the internal gas of the first container in which the ionizing radiation irradiation unit is disposed Is maintained at 0.1 ppm or more and 200 ppm or less, and / or has a function of maintaining the oxygen concentration of the internal gas of the second container in which the chemical modification unit is disposed at 0.1 ppm or more and 100 ppm or less. Chemical modification equipment for organic polymer materials. An apparatus for producing a film-like organic polymer material in which a base material made of an organic polymer material is chemically modified, and can isolate the base material from the external environment and keep the oxygen concentration lower than the outside. A container; and an ionizing radiation irradiating part for generating radicals in a base material made of an organic polymer material, disposed in the container; and the radicals induced in the base material, disposed in the container A chemical modification part that is chemically modified by a reaction, and a transport part that is disposed in the container and transports the base material from the ionizing radiation irradiation part to the chemical modification part. And an inert gas supply port for supplying an inert gas and an exhaust port for exhausting the internal gas of the container, and has a function of maintaining the oxygen concentration of the internal gas of the container at 0.1 ppm or more and 100 ppm or less. Characteristic existence Chemical modification equipment for polymer materials.   An oxygen concentration meter that continuously monitors the oxygen concentration of the internal gas of the ionizing radiation irradiation unit and / or the chemical modification unit, and further has a function of issuing an alarm when the oxygen concentration deviates from a predetermined concentration range. Item 44. The chemical modification device for an organic polymer material according to Item 44 or 45.   An oxygen concentration meter for continuously monitoring the oxygen concentration of the internal gas of the ionizing radiation irradiation unit and / or the chemical modification unit, and stopping the ionizing radiation irradiation when the oxygen concentration deviates from a predetermined concentration range; The chemical modification apparatus for organic polymer materials according to any one of claims 44 to 46, further having a function of stopping the chemical modification reaction.   An oxygen concentration meter that monitors the oxygen concentration of the internal gas of the ionizing radiation irradiation unit and / or the chemical modification unit, and the internal gas of the ionizing radiation irradiation unit and the chemical modification unit when starting the operation of the chemical modification device 48. The organic polymer material chemical modification device according to any one of claims 44 to 47, further comprising a control function capable of being started when each of the oxygen concentrations is in a predetermined concentration range.   49. The chemical modification device for an organic polymer material according to claim 44, wherein each internal gas of the ionizing radiation irradiation unit, the chemical modification unit, and the connection unit is an inert gas having an oxygen concentration in a predetermined concentration range. By substituting the oxygen concentration of each internal gas to a predetermined concentration range or less, the substrate carried in from the substrate supply unit is moved to the ionizing radiation irradiation unit, and a predetermined amount of ionizing property is adjusted by adjusting the irradiation source and irradiation time. Radiation is generated, radicals are generated on the base material, the base material where the radicals are generated is moved to the chemical modification part, and contacted with a predetermined reaction solution containing chemical species necessary for chemical modification induced by the radicals. Computer reading for performing each step of chemically modifying the reaction temperature and time, producing a chemically modified product, and carrying out the chemically modified product by the product transport unit. A device capable operation program.

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