JP7095231B2 - Gas Separation Membranes, Laminates, and Gas Separation Modules - Google Patents

Description

The present invention is a gas separation membrane capable of selectively permeating gases such as hydrogen, helium, methane, carbon monoxide, carbon dioxide, nitrogen, oxygen, ethane, ethylene, propane, propylene, butane, and hydrogen sulfide. The present invention relates to a laminate and a gas separation module.

Selective permeability of gas has traditionally been an important requirement in various technical fields. For example, selectively recovering carbon dioxide from large-scale carbon dioxide sources such as thermal power plants and steel mill blast furnaces with as little energy as possible, or from carbon dioxide sources emitted from internal combustion engine systems such as automobiles and ships. Is also required to selectively recover carbon dioxide as much as possible.

In addition, biogas treatment of natural gas, naphtha, liquefied natural gas, liquefied petroleum gas, and other supply gas mixtures such as off-gas derived from the petroleum chemical industry, sludge from sewage treatment facilities, and waste from waste treatment plants. It is required to selectively recover energy sources such as hydrogen and methane from the biogas generated by petroleum.

Furthermore, for general industrial use and household use, oxygen-enriched membranes for improving the combustion efficiency of vehicles, oxygen-enriched membranes for various air conditioning equipment, and increasing the concentration of oxygen in the air for the purpose of maintaining and promoting health. Gas separation films with gas selectivity, such as oxygen-enriched films used in products that have been used, antioxidant and corrosion-preventing, explosion-proof applications, and nitrogen-enriched films used in products aimed at improving the freshness of foods, are available. It has a wide variety of uses, including the types of gases.

As a method for selectively permeating a specific gas from a mixture of gases, a distillation method using a phase change, an absorption method in which an absorbent absorbs a characteristic gas, and adsorption / desorption to a porous adsorbent are used. Examples include the adsorption method used and the selective permeation membrane method utilizing the difference in the permeation rate of the gas depending on the membrane, but the method using the selective permeation membrane composed of a polymer material is only to pass the gas mixture. Since it is possible to selectively take out a specific gas, it is excellent from the viewpoint of energy saving. In addition, since polymer materials have good workability, they can be processed into flat membranes, hollow fiber membranes, laminated membranes, etc., and can be miniaturized when modularized, from the viewpoint of space saving. Are better.

Here, as the basic required performance of the gas separation membrane using the polymer material,
(1) Gas selectivity between the target gas and other components (2) Gas permeability (3) Physical and chemical properties such as membrane strength, heat resistance, moisture resistance, and solvent resistance can be mentioned. Of these, the gas permeability (2) of the gas separation membrane is a characteristic that mainly controls the required membrane area, the membrane module, and the size of the device, that is, the initial cost. By thinning a film with high gas selectivity, industrially practical performance is realized. On the other hand, the gas selectivity (1) of the membrane is essentially a characteristic peculiar to the membrane material, and is a characteristic that mainly controls the yield with respect to the required gas, that is, a characteristic that controls the running cost.

From this point of view, developments have been made using various polymer materials such as polyimide gas separation membranes and acrylic gas separation membranes having specific substituents (Patent Documents 1 to 4).

However, there is a trade-off relationship in which the gas separation membrane generally reduces the gas selectivity when trying to increase the gas permeability, and the gas permeability decreases when the gas selectivity is increased. At present, a polymer gas separation film that has both gas permeability and gas selectivity at a high level has not yet been obtained, and the conventional polymer type gas separation film has a polymer orientation. Although the permeability was good due to the irregularity and the large free volume, the selectivity was still poor. In addition, the widely used polyimide-based gas separation membrane is inferior in processability, and the membrane formation also requires treatment at a high temperature, so that the industrial productivity is significantly inferior.

To solve such a problem, the development of a film material containing a non-polymerizable liquid crystal compound has been studied by several methods (Patent Documents 5 to 10). For example, a technique is known in which a non-polymerizable liquid crystal compound is mixed with a polymer material such as a vinyl halide polymer or polyarylene to form a polymer gas separation membrane (Patent Documents 5 and 7). Further, a technique is known in which a non-polymerized liquid crystal compound is included in the pores of a porous polymer membrane to form a gas separation membrane. (Patent Documents 6 and 8).

However, these non-polymerizable liquid crystal compounds are inferior in gas separation performance because the non-polymerizable liquid crystal compound is not immobilized, and the denseness changes greatly depending on the temperature, so that the gas permeability depends on the temperature. Due to its high properties, it was difficult to use in a high temperature environment and was restricted in its use.

Further, a technique of forming an organic-inorganic hybrid permeable membrane using a non-polymerizable liquid crystal compound in a porous inorganic matrix is also known (Patent Document 9). However, such a technique requires excessive heat and time in the process of firing the film, and thus has a problem in terms of energy saving. Further, since the film is not flexible, there remains a problem that it is difficult to modularize it.

Japanese Unexamined Patent Publication No. 6-269650 Japanese Unexamined Patent Publication No. 2007-21128 Japanese Unexamined Patent Publication No. 10-156157 Japanese Unexamined Patent Publication No. 2006-314944 Japanese Unexamined Patent Publication No. 59-21347 Japanese Unexamined Patent Publication No. 60-10291 Japanese Unexamined Patent Publication No. 62-163710 Japanese Unexamined Patent Publication No. 02-175737 Japanese Unexamined Patent Publication No. 2004-029719 Japanese Unexamined Patent Publication No. 8-073572

Therefore, the problem to be solved by the present invention is a gas separation membrane which is excellent in gas selectivity while maintaining good gas permeability and can be produced by an industrially simple method, and a gas separation membrane based on the same. It is an object of the present invention to provide a laminated body laminated with a material and a gas separation module having excellent separation performance.

As a result of diligent studies to solve the above problems, the inventors of the present application have a film-forming property of a polymerizable liquid crystal composition using a polymerizable liquid crystal compound capable of polymerizing while maintaining a constant arrangement state of molecules. As a result of the fact that the polymerized film has a crosslinked structure and the orientation is firmly fixed, it has been found that excellent gas separation performance is exhibited, and the present invention has been made.

That is, the present invention is a gas separation film containing the polymer in which at least one kind of polymerizable liquid crystal compound is optically arranged in one axis or more, and the polymer is obliquely incident X-ray scattering. In the scattering profile obtained by the measurement method, the scattering angle 2θ has a maximum peak at 5 to 15 °, and the scattering angle 2θ is integrated in the range of 5 ° around the peak, and the azimuth angle of the scattering profile is 5 to 175 °. The gas separation membrane is characterized in that the width of the azimuth angle indicating more than half of the integrated value in the range of (the sum of the two or more maximum peaks) is in the range of 30 to 108 °. ..

The present invention further relates to a laminate in which the gas separation membrane is laminated on a gas permeable substrate.

Further, in the present invention, the gas separation membrane is formed in the shape of a hollow fiber, and a plurality of the hollow fibers are arranged in a container, and one of the inside of the hollow fiber and the outside of the hollow fiber is a mixed gas or a dissolved gas supply port. The present invention relates to a gas separation module characterized in that the other is communicated with a separated gas outlet.

According to the present invention, a gas separation film which is excellent in gas selectivity while maintaining good gas permeability and can be produced by an industrially simple method, and a laminate obtained by laminating the gas separation film with a substrate. It is possible to provide a gas separation module having excellent body and separation performance. Furthermore, it can also exhibit features such as low gas separation ability and low temperature dependence of gas permeability. Therefore, carbon dioxide recovery from thermal power plants and steel mill blast furnaces, carbon dioxide recovery from carbon dioxide sources emitted from internal combustion engine systems such as automobiles and ships, natural gas, naphtha, liquefied natural gas, liquefied petroleum gas, etc. , To recover energy sources such as hydrogen and methane from feed gas mixture such as off-gas derived from the petrochemical industry, sludge from sewage treatment facilities, and biogas generated from waste treatment plants, and to improve the combustion efficiency of vehicles. Oxygen-enriched film, oxygen-enriched film for various air-conditioning equipment, oxygen-enriched film used for products aimed at maintaining and promoting health by increasing the concentration of oxygen in the air, antioxidant, corrosion prevention, and explosion-proof It can be used for applications, nitrogen-enriched membranes used in products aimed at improving the freshness of food, and the like.

FIG. 1 is a schematic diagram of a gas separation membrane containing a polymer obtained by polymerizing the polymerizable compounds to be used in a state of being arranged uniaxially in the horizontal direction with respect to the surface of the membrane. Here, the molecular major axis of the rod-shaped molecule constituting the polymer is in the horizontal direction with respect to the surface of the membrane. FIG. 2 is a schematic diagram of a gas separation membrane containing a polymer obtained by polymerizing the polymerizable compounds used in a state of being arranged uniaxially in the direction perpendicular to the plane of the membrane. Here, the molecular major axis of the rod-shaped molecule constituting the polymer is in the direction perpendicular to the plane of the membrane. In FIG. 3, the polymerizable compounds used are arranged in one axis in the horizontal direction only with respect to one surface (back surface) of the membrane, and the arrangement changes to a slightly inclined state from the front surface of the membrane to the inside of the membrane. It is a schematic diagram of a gas separation membrane containing a polymer obtained by polymerizing in the state of being polymerized. Here, the molecular major axis of the rod-shaped molecule constituting the polymer is horizontal only with respect to one surface of the membrane. FIG. 4 shows a polymer obtained by arranging the polymerizable compounds used horizontally with respect to the surface of the membrane and polymerizing them in an arrangement state having a constant periodic spiral structure in the thickness direction of the membrane. It is a schematic diagram of the gas separation membrane containing. The molecular major axis of the rod-shaped molecule constituting the polymer forms a spiral shape in the horizontal direction with respect to the surface of the membrane and in the thickness direction of the membrane. In FIG. 5, the polymerizable compound used has a long-distance order with a constant periodicity in the direction perpendicular to the surface of the membrane, and has no or long order in the horizontal direction with respect to the surface of the membrane. It is a schematic diagram of a gas separation membrane containing a polymer obtained by polymerizing in a state having a short-distance order rather than a distance. The molecular major axis of the rod-shaped molecule constituting the polymer is horizontal to the surface of the membrane. In FIG. 6, the polymerizable compound used has a long-distance order with a certain periodicity in the horizontal direction with respect to the surface of the membrane, and has no order or has a length in the direction perpendicular to the surface of the membrane. It is a schematic diagram of a gas separation membrane containing a polymer obtained by polymerizing in a state having a short-distance order rather than a distance. Here, the molecular major axis of the rod-shaped molecule constituting the polymer is in the direction perpendicular to the plane of the membrane. FIG. 7 is a two-dimensional X-ray diffraction scattering image of SPring 8 (small angle X-ray) of the polymer according to Example 1. FIG. 8 is a one-dimensional scattering spectrum obtained from a two-dimensional X-ray diffraction scattering image of SPring 8 (small-angle X-ray) of the polymer according to Example 1. FIG. 9 is a two-dimensional X-ray diffraction scattering image of SPring 8 (wide-angle X-ray) of the polymer according to Example 1. FIG. 10 is a one-dimensional scattering spectrum obtained from a two-dimensional X-ray diffraction scattering image of SPring 8 (wide-angle X-ray) of the polymer according to Example 1. FIG. 10 is a profile showing the X-ray diffraction intensity distribution in the azimuth direction of the polymer according to Example 1.

(Molecular arrangement of one or more axes)
The gas separation membrane of the present invention is a permeable membrane having gas selectivity, and contains a polymer in which at least one kind of polymerizable compound is used and the molecules are optically arranged on one axis or more. The gas separation membrane of the present invention forms a composition containing a polymerizable compound having at least one polymerizable group, a hard segment having three or more ring structures, and, if necessary, a soft segment. Obtained by polymerization.

Specifically, the permeable membrane containing a polymer optically arranged on one axis or more is, for example,
a) A molecular arrangement in which the molecular major axis of the rod-shaped molecule constituting the polymer is oriented in a uniform direction and has only an arrangement order, and the long-range order regarding the center of gravity of the molecule is the same as that of a liquid. situation,
b) A molecular arrangement state having a spiral structure in which the molecular arrangement of the polymer is twisted at a uniform period.
c) A molecular arrangement state in which the molecular major axis of the rod-shaped molecule constituting the polymer is oriented in a uniform direction and has a layered structure in units of the molecular major axis of the rod-shaped molecule.
d) A molecular arrangement state in which the disk-shaped molecules constituting the polymer are laminated to form a columnar structure.
e) A molecular arrangement state in which columnar structures formed by laminating disk-shaped molecules constituting the polymer and columnar structures are arranged at regular intervals.
f) Examples thereof include a permeable membrane having a molecular arrangement state of the polymer such as a molecular arrangement state having no molecular order other than that the disk-shaped molecules constituting the polymer are oriented in a uniform direction.

Here, in the case of the molecular arrangement states of a) and b), the rod-shaped molecules may be arranged horizontally in the major axis direction with respect to the surface of the membrane, or may be arranged in which the inclination angle is continuously changed. Alternatively, they may be arranged in the direction perpendicular to the plane of the membrane. Further, in the case of the molecular arrangement state of c), the rod-shaped molecules may be arranged horizontally in the major axis direction with respect to the surface of the membrane, may be arranged in the direction perpendicular to the plane of the membrane, or are constant. It may be an array having an inclination angle. Furthermore, the rod-shaped molecules forming the layered structure may be arranged at regular intervals. In the case of the molecular arrangement states of d) and e), the disk-shaped molecules may be arranged horizontally with respect to the plane of the membrane, may be arranged perpendicular to the plane of the membrane, or have a constant inclination. It may be an array with an angle. In the case of the molecular arrangement state of f), the disk-shaped molecules may be arranged horizontally with respect to the surface of the membrane, arranged perpendicularly with respect to the plane of the membrane, or the inclination angle changes continuously. It may be an array.

Specific examples of the molecular arrangement state shown by the gas separation membrane of the present invention include the molecular arrangement states shown in FIGS. 1 to 6. Here, the molecular arrangement of the polymer contained in the gas separation membrane of the present invention considers the dissolution of gas molecules on the surface of the organic membrane and the diffusion of gas molecules into the organic membrane, depending on the type of permeated gas. However, in the present invention, a preferable molecular arrangement state can be applied as appropriate, but in the present invention, as shown in FIGS. Those containing a polymer obtained by polymerizing in an arranged state are preferable, and in particular, the polymerizable compound used shown in FIG. 6 has a length with a constant periodicity in the horizontal direction with respect to the surface of the membrane. Those having a so-called smectic phase having a distance order, specifically, having a long-distance order with a certain periodicity in the horizontal direction with respect to the membrane surface and in a direction perpendicular to the membrane surface. It has an unordered SmA phase or SmC phase, or a long-distance order with a certain periodicity in the horizontal direction with respect to the membrane surface, and a short-distance order in the direction perpendicular to the membrane surface. A gas separation membrane forming a higher-order smectic phase (SmB phase) is particularly preferable from the viewpoint of gas separation ability.

Next, the molecular arrangement of the polymer contained in the gas separation membrane of the present invention can be confirmed by oblique entry angle small angle / wide angle X-ray scattering measurement. The oblique angle small angle / wide angle X-ray scattering measurement described here is a method of measuring X-ray scattering generated by incidenting incident X-rays at a minute angle of about 0.1 ° with respect to the sample surface.

Small Angle X-ray Scattering (SAXS) is a method of obtaining structural information of a substance by irradiating the substance with X-rays and measuring the scattered X-rays with a small scattering angle. Yes, the size, shape, regularity, and dispersibility of the internal structure can be evaluated. The smaller the scattering angle, the larger the size of the corresponding structure. Further, wide-angle X-ray scattering (WAXS) is to obtain structural information of a substance by irradiating the substance with X-rays and measuring the X-rays having a large scattering angle. This is a method, and structural information smaller than that of small-angle X-ray scattering can be obtained. In addition to being used for crystal structure analysis, information on the degree of orientation of the sample can also be obtained.

In order to accurately determine the maximum peak position of the scattering profile by oblique incident X-ray scattering measurement, it is necessary to measure more scattering. However, when a general X-ray diffractometer is used, the gas separation film having an organic layer containing a polymer such as the polymerizable compound and showing gas selectivity has a higher scattering intensity than an inorganic crystal material or the like. small. Therefore, in order to measure more scattering, the exposure time must be lengthened, and the sample is damaged by long-term X-ray exposure, which has a large effect on the measured value.
Therefore, it is desirable to use a high-intensity X-ray source capable of measuring more scattering in a short time for the oblique incident X-ray scattering measurement of the polymerizable compound. In order to obtain a high-intensity X-ray source, a large-scale radiation facility, for example, a light source such as SPring-8 in Hyogo Prefecture or Photon Factory in Ibaraki Prefecture can be used.
The obliquely incident X-ray scattering device in the radiation facility is installed on the sample table by monochromaticizing the white light taken out from a circular accelerator called a storage ring with a two-crystal spectroscope and using the wavelength in the X-ray region (for example, 1 Å) as the radiation source. A two-dimensional scattered image can be obtained by exposing the scattered light to a two-dimensional detector in a short time of about several seconds.
The structure of the film can be obtained from the obtained two-dimensional X-ray scattering image. The center position of the reflected X-ray beam in the two-dimensional scattered image is determined from the X-ray incident angle at the time of measurement, and the scattering / diffraction intensity I on a straight line in the horizontal direction when viewed from the center of the reflected beam is taken, and the scattering angle from the center of the reflected beam is taken. A one-dimensional scattering profile H can be obtained as the scattering intensity I with respect to 2θ. Similarly, the scattering / diffraction intensity I on a straight line in the vertical upward direction when viewed from the center of the reflected beam can be obtained, and the scattering profile V having one dimension as the scattering intensity I with respect to the scattering angle 2θ from the center of the reflected beam can be obtained. From the measurement principle of oblique incident small angle / wide-angle X-ray scattering, information on the periodic structure in the direction perpendicular to the surface of the film can be obtained from the scattering profile H, and the period in the horizontal direction with respect to the surface of the film can be obtained from the scattering profile V. Information on the structure can be obtained. That is, from the scattering profile H, a period length derived from the periodic structure having an orientation substantially orthogonal to the molecular chain in the molecular arrangement structure in the film can be obtained, and from the scattering profile V, a period derived from the molecular length can be obtained. The length is calculated.
In the present invention, as described above, in the scattering profile when the polymer optically arranged on one or more axes is subjected to oblique incident wide-angle X-ray scattering measurement, the scattering angle 2θ has a maximum peak at 5 to 15 °. It has, and the scattering angle 2θ is integrated in the range of 5 ° around the same peak, and the width of the azimuth angle indicating more than half of the integrated value in the azimuth angle of 5 to 175 ° of the scattering profile (the maximum peak is 2). If there are two or more, the total of them) is in the range of 30 to 108 °, but the half value or more is shown below from the oblique incident wide-angle X-ray scattering measurement (S1). The process up to the derivation of the width of the azimuth angle (S5) will be described.

As a specific measurement procedure, first, a sample smoothly prepared on a substrate is placed on a sample table of an obliquely incident wide-angle X-ray scattering device, and then each scattering angle (2θ) and each azimuth angle (φ). ), The scattering profile of the scattering intensity is measured (S1). In the oblique incident X-ray scattering measurement method, when the azimuth is horizontal to the sample surface φ = 0 ° or 180 °, the scattering intensity becomes very high due to the influence of X-ray reflection from the sample surface, so the maximum peak is searched for. It is desirable to exclude it from the target. More preferably, the target azimuth is in the range of φ = 5 ° to 175 °. Hereinafter, the range of the target azimuth angle is referred to as the target azimuth angle range. In the azimuth target range, the maximum peak is searched for in the range where the scattering angle 2θ is 5 to 15 ° (S2). The integrated value at each azimuth angle is calculated in the range of the scattering angle of 5 ° centering on the corresponding scattering angle 2θ of the searched maximum peak (S3). Next, in the azimuth target range, the maximum value and the minimum value of those integrated values are extracted, and the half value by (integrated maximum value + integrated minimum value) / 2 is calculated (S4). In the azimuth target range, a range of azimuths having an integrated value larger than the half value is derived. The range of the azimuth is defined as "the width of the azimuth indicating a half price or more" (S5). Here, when two maximum peaks of the scattering profile appear as shown in FIGS. 9 and 11, the "width of the azimuth angle indicating more than half the value" (S5) in the present invention means the total of these.

In the present invention, the width of the azimuth is preferably 30 ° to 108 °, more preferably 30 ° to 104 °, and particularly preferably 30 ° to 100 °. When the width of the azimuth is 30 ° or less, the gas permeation is remarkably small, and when the width is 108 ° or more, the gas selectivity is small.

The gas separation membrane of the present invention requires at least one polymerizable group, hard segment, and mainly used to change the dissolution and diffusion of the gas in the membrane depending on the type of gas that selectively permeates. It is preferable to appropriately change the polymerizable compound having a soft segment according to the above, or to apply a polymer using a composition in which the polymerizable compound and the additives to be used are appropriately mixed at an appropriate ratio. Alternatively, it is preferable to apply a polymer having a preferable molecular arrangement state as appropriate.

In the gas separation membrane of the present invention, a preferable film thickness can be appropriately applied depending on the type of gas permeating in order to improve gas selectivity. Specifically, the thickness of the permeable membrane is preferably 0.005 μm or more and 50 μm or less. In the gas separation membrane of the present invention, if the film thickness is too thin, fine pores and the like are likely to be generated when the permeable membrane is manufactured, and on the surface of the base material used for strengthening the strength of the permeable membrane. Defects are likely to occur in the structure of the membrane due to the slight unevenness and the influence of dust, and as a result, the gas selection performance of the gas separation membrane of the present invention may not be sufficiently exhibited. Therefore, the permeable membrane having gas selectivity of the present invention is preferably 0.01 μm or more and 45 μm or less, more preferably 0.05 to 40 μm, and further preferably 0.1 μm or more and 30 μm or less. It is preferably 0.2 μm or more and 10 μm or less, and it is particularly preferable.

In order to obtain a polymer having such a thin film thickness and excellent orientation without cissing or pinholes by various coating methods, a solution containing a polymerizable liquid crystal compound having a low solid content concentration is used. After coating, the polymerizable liquid crystal composition is solvent-dried at a lower temperature within the temperature range indicating the liquid crystal phase (step 1), and further, the temperature is equal to or lower than the solvent drying temperature, and the polymerizable liquid crystal composition forms the liquid crystal phase. Examples thereof include a method of aligning at a temperature within the indicated temperature range (step 2) and then irradiating with UV at the same temperature as that of step 2 (step 3).

Further, the gas separation membrane of the present invention is preferably a laminated body laminated on a base material in order to improve mechanical strength and processability at the time of modularization. The substrate to be used is preferably one having the same or higher gas permeability than the gas separation membrane, and preferably one having lower gas selectivity than the gas separation membrane. Further, the interface between the gas separation membrane and the base material may be recognized independently as a laminated body from the viewpoint of adhesion, or the gas separation membrane and a part of the base material may be compatible with each other. good. The compatibility means that the polymer forming the gas separation membrane and the material forming the base material are mixed at the base material / gas separation membrane interface.

The gas separation membrane of the present invention has gas selectivity for hydrogen, helium, methane, carbon monoxide, carbon dioxide, nitrogen, oxygen, ethane, ethylene, propane, propylene, butane, hydrogen sulfide, sulfur oxides, nitrogen oxides and the like. Has. Therefore, it has good gas selectivity for these mixed gases or liquefied dissolved mixed gases. Further, for example, when the gas separation membrane of the present invention is used for an artificial lung or the like, it can also function as a gas exchange between carbon dioxide in blood and oxygen in air. Among these, it is preferable to have gas selectivity for hydrogen, helium, methane, carbon dioxide, nitrogen, oxygen, ethane and propane, and for hydrogen, helium, methane, carbon dioxide, nitrogen and oxygen. It is particularly preferable to have gas selectivity.

In particular, it is suitable for separating carbon dioxide from a mixed gas of methane and carbon dioxide, separating hydrogen from a mixed gas of hydrogen and carbon dioxide, and separating nitrogen from a mixed gas of nitrogen and oxygen.

The gas separation membrane of the present invention can be appropriately applied as long as the mechanical strength of the gas separation membrane or the laminate does not change extremely. Specifically, −100 ° C. to 250 ° C. is preferable, −50 ° C. to 150 ° C. is more preferable, and −20 ° C. to 100 ° C. is particularly preferable.

Next, the polymerizable liquid crystal compound used in the present invention which can be optically arranged on one or more axes is a polymerizable compound having at least two or more polymerizable groups and hard segments having three or more ring structures. Examples thereof include a polyfunctional bicyclic polymerizable compound and a monofunctional polycyclic polymerizable compound.
(Polymerizable compound having at least two or more polymerizable groups and a hard segment having three or more ring structures: polyfunctional polycyclic polymerizable compound)
A compound having at least two or more polymerizable groups, a hard segment having three or more ring structures, and a soft segment, if necessary, used in the present invention (hereinafter, abbreviated as "polyfunctional polycyclic polymerizable compound"). ) Has a hard segment in which two or more polymerizable functional groups and three or more ring structures are bonded to each other by a linking group and / or a single bond, and the polymerizable group is hard. Either it is directly bonded to the ring structure contained in the segment, or the polymerizable group is bonded to the ring structure contained in the hard segment via the soft segment.

The polyfunctional polycyclic polymerizable compound used in the present invention is specifically represented by the general formula (1).

(In the formula, Sf ¹ and Sf ² each independently represent a soft segment, but when a plurality of Sf ¹ and Sf ² exist, they may be the same or different, and P ¹ and P ² are respectively. Although they independently represent polymerizable groups, when a plurality of P ¹ and P ² are present, they may be the same or different, and HD is a hard segment having three or more ring structures, and n1 and n2 are. Each of them independently represents an integer of 0 to 3, but when either n1 or n2 becomes 0, the bond on HD is bonded to a hydrogen atom, and also represents n1 + n2 ≧ 1).
Examples of P ¹ and P ² include radically polymerizable ones and cationically polymerizable ones.

As P ¹ and P ² , any polymerizable group may be used as long as it is a heat initiator, a photoinitiator, or one that undergoes a polymerization reaction by heat or active energy rays, but each of them independently has the following formula (P). A polymerizable group selected from -1) to (P-20) is preferable.

(Me represents a methyl group and Et represents an ethyl group.) In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), the formula (P-2), the formula (P-3), Formula (P-4), formula (P-5), formula (P-7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferable. , Formula (P-1), formula (P-2), formula (P-7), formula (P-11) or formula (P-13) is more preferable, and formula (P-1), formula (P-). 2) or the formula (P-3) is more preferable, and the formula (P-1) or the formula (P-2) is particularly preferable.

Examples of Sf ¹ and Sf ² include linear and branched ones.

Sf ¹ and Sf ² independently represent a single bond or an alkylene group having 1 to 18 carbon atoms (one or two or more hydrogen atoms bonded to the alkylene group are independent halogen atoms, respectively. , CN group, alkyl group having 1 to 8 carbon atoms, or alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or _Two or more CHs that are not adjacent to each other are independent of each other _, and oxygen atoms do not directly bond to each other. -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH -Or-may be replaced by -C≡C-.) Is preferable.

When n1 and / or n2 is 0, HD has a terminal group, and the terminal groups are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and pentafluorosulfuranyl group. , Cyano group, nitro group, isocyano group, thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -S-, -CO -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- It represents a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

Examples of the HD include rod-shaped, disk-shaped, and bent-shaped ones.

Specifically, HD may have three or more ring structures bonded to each other by a linking group and / or a single bond as described above. Examples of the ring structure include 3- to 8-membered rings, heterocycles, and fused rings, and even if one or two or more hydrogen atoms bonded to each ring are independently substituted with substituents. good.

More specifically, the HD is preferably a hard segment represented by the general formula (1-a).

(In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ are independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group and tetrahydro, respectively. Piran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydro Naphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2, 3,4-Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3 4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b'] dithiophene-2,6-diyl group, Benzo [1,2-b: 4,5-b'] diselenovene-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] Represents a selenophen-2,7-diyl group or a fluorene-2,7-diyl group and binds to the respective rings of A ¹ , A ² , A ³ , A ⁴ and A ⁵ . One or more hydrogen atoms may be independently substituted with the substituent ^LHD , and the substituent ^LHD includes F, Cl, CF ₃ , OCF ₃ , CN group, nitro group and carbon atom. Alkyl group of 1 to 8, alkoxy group of 1 to 8 carbon atoms, alkanoyl group, alkanoyloxy group, carbamoyl group, sulfamoyl group, alkenyl group of 2 to 8 carbon atoms, alkenyloxy of 2 to 8 carbon atoms Group, alkenoyl group, alkenoyloxy group, or group represented by the general formula (1-c).

(In the formula, P ³ represents a polymerizable group, but represents the same as defined in P ¹ and P ² above, and A ⁶ represents -O-, -COO-, -OCO-, and -OCH ₂ . -, -CH ₂ O-, -CH ₂ CH ₂ OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- ,} or a single bond, and Sf ³ is defined by Sf ¹ and Sf ² above. They represent the same thing, q represents 0 or 1, and r represents 0 or 1). ).

A ¹ , A ² , A ³ , A ⁴ and A ⁵ may each independently have one or more hydrogen atoms bonded to the ring substituted with the above-mentioned substituent ^LHD 1, A group selected from a 4-phenylene group, a 1,4-cyclohexylene group and a 2,6-naphthylene group is preferable, and the 1,4-phenylene group, 1,4-cyclohexylene group and 2,6 are independent of each other. -A group selected from naphthylene groups is more preferred.

Z ¹ , Z ² , Z ³ and Z ⁴ are independent of -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO, respectively. -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-,- Represents CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond.
l, m and k each independently represent an integer of 0 to 4, and represent 1 ≦ l + m + k ≦ 8. ).

Further, it is also preferable that the HD is a hard segment represented by the general formula (1-b).

(During the ceremony,
A ¹¹ and A ¹² are independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, naphthalene-2,6-diyl, respectively. Represents a group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group. The groups may be unsubstituted or substituted with ^one or more L1, but if multiple A ¹¹ and / or A ¹² appear, they may be the same or different.
Z ¹¹ and Z ¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO -, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-,- It represents C≡C- or a single bond, but when multiple Z ¹¹ and / or Z ¹² appear, they may be the same or different.
M is from the following equation (M-1) to equation (M-11)

Represents groups selected from, but these groups may be unsubstituted or substituted with ^one or more L1s.
G is the following formula (G-1) to formula (G-6)

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, but the alkyl group may be linear or branched, and may be arbitrary in the alkyl group. The hydrogen atom of the hydrogen atom may be replaced with a fluorine atom, and one -CH _2- or _two or more non-adjacent-CH 2- in the alkyl group are independently -O-, -S-, respectively. , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- May be replaced by
W ⁸¹ represents a group having 5 to 30 carbon atoms and having at least one aromatic group, which groups may be unsubstituted or substituted with ^one or more L1s.
W ⁸² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be a fluorine atom. One -CH _2- or _two or more non-adjacent-CH 2- in the alkyl group may be substituted with-O-, -S-, -CO-,-, respectively. COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = It may be replaced by CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, or W ⁸² is W. It may have the same meaning as ⁸¹ , W ⁸¹ and W ⁸² may be connected to each other to form the same ring structure, or W ⁸² may be represented by the general formula (1-c).

(In the formula, P ³ represents a polymerizable group, but represents the same as those defined in P ¹ and P ² above, and A ⁶ represents -O-, -COO-, -OCO-, and -OCH ₂ . -, -CH ₂ O-, -CH ₂ CH ₂ OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- ,} or a single bond, and Sf ³ is defined by Sf ¹ and Sf ² above. They represent the same thing, q represents 0 or 1, r represents 0 or 1), and W ⁸³ and W ⁸⁴ independently represent a halogen atom, a cyano group, a hydroxy group, a nitro group, and a carboxyl group, respectively. , Carbamoyloxy group, amino group, sulfamoyl group, group having 5 to 30 carbon atoms having at least one aromatic group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, carbon. Alkenyl groups with 2 to 20 atoms, cycloalkenyl groups with 3 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, acyloxy groups with 2 to 20 carbon atoms, 2 to 20 carbon atoms or alkyl Represents a carbonyloxy group, but one of the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy group, alkylcarbonyloxy group-or _two or more non-adjacent groups. -CH ₂ -independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-,- It may be replaced by CO-NH-, -NH-CO- or -C≡C-, where G is an equation (G) when the above M is selected from equations (M-1) to (M-10). It is selected from G-1) to the formula (G-5), and when M is the formula (M-11), G represents the formula (G-6).
L ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group and a diisopropylamino. A group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms is represented, and the alkyl group may be linear or branched, and any hydrogen atom may be used. May be substituted with a fluorine atom, and one -CH _2- or _two or more non-adjacent-CH 2- in the alkyl group are independently -O-, -S-, -CO. -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, Substituted by a group selected from -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- However, if there are multiple ^L1s in the compound, they may be the same or different.
j11 represents an integer from 1 to 5, j12 represents an integer from 1 to 5, and j11 + j12 represents an integer from 2 to 5. ), R ¹¹ and R ³¹ are hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, thioisocyano group, or carbon atom number 1 to 20. The alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and the alkyl group may be substituted with a fluorine atom. One -CH _2- or two or more non-adjacent -CH ₂ -s are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S- , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-, where m11 represents an integer from 0 to 8 and m2. ~ M7, n2 ~ n7, l4 ~ l6, k6 each independently represent an integer of 0 to 5. )
The polyfunctional polycyclic polymerizable compound represented by the general formula (1) is more specifically described in the following general formula (1-a) when HD is a hard segment represented by the general formula (1-a). The compounds represented by a-1) to (1-a-7) are preferable.

In the above general formulas (1-a-1) to (1-a-7), P11 to ^P76 represent polymerizable groups, but each of them is independently derived from the following formulas (P- ¹ ) to formula (P-). 20)

It is preferable to represent a group selected from the above, and among these polymerizable groups, from the viewpoint of enhancing the polymerizable property and the storage stability, the formula (P-1), the formula (P-2), the formula (P-7), and the like. The formula (P-12) or the formula (P-13) is preferable, and the formula (P-1), the formula (P-2), the formula (P-7), or the formula (P-12) is more preferable. (P-1) or the formula (P-2) is more preferable.

In the general formulas (1-a-1) to (1-a-7),-(S ¹¹ -X ¹¹ )-to-(S ⁷⁶ -X ⁷⁶ )-independently form a soft segment or a single bond. show.

S ¹¹ to S ⁷⁶ each independently represent a spacer group or a single bond, but when a plurality of S ¹¹ to S ⁷⁶ are present, they may be the same or different. The spacer group represents an alkylene group having 1 to 18 carbon atoms, and one or two or more hydrogen atoms bonded to the alkylene group independently have a halogen atom, a CN group, and a carbon atom number. It may be substituted with an alkyl group of 1 to 8 or an alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or two or more not adjacent to each other. CH ₂ groups are independent of each other _, and oxygen atoms are not directly bonded to each other. It may be replaced by OH)-, -CH (COOH)-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and one CH ₂ existing in the alkylene group. Preferably, an alkylene group having 3 to 12 carbon atoms in which two or more CH ₂ groups that are not adjacent or adjacent to each other may be replaced with —O—.

In the general formulas (1-a-1) to (1-a-7), X ¹¹ to X ⁷⁶ are independently -O-, -S-, -OCH _2- , -CH ₂ O-,-, respectively. CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond, but when there are a plurality of ^X11 to ^X76 , they may be the same or different. Further, from the viewpoint of easy availability of raw materials and ease of synthesis, when a plurality of raw materials exist, they may be the same or different from each other, and each of them may be independently -O-, -S-, -OCH _2- ,. -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, each independently of -O-, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH _2- It is more preferable to represent OCO- or a single bond, and when a plurality of ^X11 to ^X76 are present, they may be the same or different, and they are independently -O-, -COO-, and -OCO. -Or it is particularly preferred to represent a single bond.

In the above general formulas (1-a-1) to (1-a-7), each P- (SX)-does not include an -O-O- bond.

In the general formulas (1-a-1) to (1-a-7), A ¹¹ to A ⁷² and M ¹¹ to M ⁷¹ are independently 1,4-phenylene groups and 1,4-cyclohexylene, respectively. Group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydro Representing a naphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, although these groups may be unsubstituted or substituted with one or more substituents, ^A11 . When a plurality of A ⁷² appear, they may be the same or different. Even if A ¹¹ to A ⁷² and M ¹¹ to M ⁷¹ are independently substituted or substituted with one or more substituents L ¹ and L ² from the viewpoint of availability of raw materials and ease of synthesis, respectively. It is preferable to represent a good 1,4-phenylene group, 1,4-cyclohexylene group or naphthalene-2,6-diyl, and each of them independently represents the following formulas (A-1) to (A-16).

It is more preferable to represent the groups selected from the formulas (A-1), and it is further preferable to represent the groups selected from the formulas (A-1) to the formulas (A-13) independently. It is particularly preferable to represent a group selected from the formula (A-4).

In the general formulas (1-a-1) to (1-a-7), Z ¹¹ to Z ⁷² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, and -CH, respectively. ₂ CH _2- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-,- OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, It represents -C≡C- or a single bond, but when a plurality of Z ¹¹ to Z ⁷² appear, they may be the same or different. From the viewpoint of availability of raw materials and ease of synthesis, Z ¹¹ to Z ⁷² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, and -O-CO. -O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond is preferable, and Z ¹¹ to Z ⁷² are independently -OCH _2- , respectively. -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF ₂ -, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ --OCO-, -CH = CH-, -C≡C- or It is more preferable to represent a single bond, and Z ¹¹ to Z ⁷² are independently -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH. It is more preferred to represent -CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, respectively. Independently -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or single bond It is particularly preferable to represent it.

In the above general formula (1-a-2), the terminal group R ²¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, or a thioisocyano group. , Or one -CH _2- or two or more non-adjacent -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO. A straight line having 1 to 20 carbon atoms which may be substituted by -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-. Representing a state or branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. From the viewpoint of ease of synthesis, R ²¹ has a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or one -CH _2- or two or more non-adjacent-CH ₂ -independently. It preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with O-, -COO-, -OCO-, -O-CO-O-, and preferably represents a hydrogen atom, a fluorine atom, or chlorine. It is more preferable to represent an atom, a cyano group, or a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms, and it may represent a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms. Especially preferable.

In the above general formulas (A-1) to (A-16), the substituents L ¹ and L ² are independently fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group and nitro. Group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyanogroup, or one -CH _2- or adjacent. Two or more -CH _2- that are not used independently of -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O -CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, Represents a linear or branched alkyl group with 1 to 20 carbon atoms which may be substituted with -CH = CH-, -CF = CF- or -C≡C- and any hydrogen atom in the alkyl group. May be substituted with a fluorine atom, or represents a group represented by the above general formula (1-c). From the viewpoint of ease of synthesis, the substituents L ¹ and L ² are a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or , Any hydrogen atom may be replaced with a fluorine atom, and one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -O-, -S-, -CO. -, -COO-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- may be substituted with a group having 1 carbon atom. It is preferable to represent a linear or branched alkyl group from 20 to 20 or a group represented by the above general formula (1-c), and a fluorine atom, a chlorine atom, or any hydrogen atom is replaced with a fluorine atom. May be done, and one -CH _2- or two or more non-adjacent -CH ₂ -s are each independently substituted with a group selected from -O-, -COO- or -OCO-. It is more preferable to represent a linear or branched alkyl group having 1 to 12 carbon atoms, and a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted with a fluorine atom from 1 carbon atom. It is more preferable to represent 12 linear or branched alkyl groups or alkoxy groups, and it is particularly preferable to represent a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms. ..

In the above general formulas (1-a-1) to (1-a-7), n11 to n76 each independently represent an integer of 0 to 6, but the characteristics of the compound, the availability of raw materials, and the synthesis thereof. From the viewpoint of ease, it is preferable to represent an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0 or 1.

In the above general formulas (1-a-1) to (1-a-7), j11, j12, j21, j22, j31, j32, j41, j42, j51, j52, j61, j62, j71, and j72 are independent of each other. And j11 + j12 represents an integer from 2 to 7, j21 + j22 represents an integer from 2 to 7, j31 + j32 represents an integer from 2 to 7, and j41 + j42 represents an integer from 2 to 7. , J51 + j52 represent an integer from 2 to 7, j61 + j62 represent an integer from 2 to 7, and j71 + j72 represent an integer from 2 to 7. From the viewpoint of ease of synthesis and storage stability, j11, j21, j22, j31, j32, j41, j42, j51, j52, j61, j62, j71, and j72 each independently represent an integer of 1 to 4. Is preferable, it is more preferable to represent an integer of 1 to 3, and it is particularly preferable to represent 1 or 2. j11 + j12, j21 + j22, j31 + j32, j41 + j42, j51 + j52, j61 + j62, j71 + j72 each preferably represent an integer of 2 to 4, and particularly preferably 2 or 3.

Specific examples of the compound represented by the general formula (1-a-1) include the following general formulas (1-a-1-1) to the general formula (1-a-1-25). The compound to be used is preferable.

(In the equation, t and u each independently represent an integer of 1 to 18, and L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , and L ⁸ independently represent a hydrogen atom and a fluorine atom, respectively. Chlorine atom, bromine atom, iodine atom, nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, carbon number 1 to 6 An alkyl group and an alkoxy group having 1 to 6 carbon atoms are shown. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, a hydrogen atom bonded to the alkyl group or the alkoxy group is shown. May be unsubstituted or substituted with one or more halogen atoms.) These compounds may be used alone or in admixture of two or more. can.

Specific examples of the compound represented by the general formula (1-a-2) are represented by the following formulas (1-a-2-1) to (1-a-2-11). Compounds are preferred.

These compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (1-a-3) include the following general formulas (1-a-3-1) to the general formula (1-a-3-23). The compound to be used is preferable.

(In the equation, t, u and v each independently represent an integer of 1 to 18. L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ and L ⁸ independently represent a hydrogen atom and a fluorine atom, respectively. , Chlorine atom, bromine atom, iodine atom, nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, carbon number 1 to 6 The alkyl group and the alkoxy group having 1 to 6 carbon atoms are shown. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, hydrogen bonded to the alkyl group or the alkoxy group is shown. Atoms may be unsubstituted or substituted with one or more halogen atoms.) These compounds may be used alone or in admixture of two or more. You can also.

Specific examples of the compound represented by the above general formula (1-a-4) are represented by the following general formulas (1-a-4-1) to general formulas (1-a-4-20). Compounds are preferred.

(In the equation, t independently represents an integer of 1 to 18, and L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , and L ⁸ independently represent a hydrogen atom, a fluorine atom, and a chlorine atom, respectively. , Bromine atom, iodine atom, nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, alkyl group with 1 to 6 carbon atoms. , An alkoxy group having 1 to 6 carbon atoms. If these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is not yet present. It may be substituted or substituted with one or more halogen atoms.) These compounds may be used alone or in admixture of two or more.

Specific examples of the compound represented by the above general formula (1-a-5) are represented by the following general formulas (1-a-5-1) to general formulas (1-a-5-18). Compounds are preferred.

(In the equation, t, u, v and w each independently represent an integer of 1 to 18. L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ and L ⁸ are independent hydrogen atoms, respectively. , Fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, carbon number It indicates an alkyl group of 1 to 6 and an alkoxy group having 1 to 6 carbon atoms. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the alkyl group or the alkoxy group may be used. The hydrogen atom to be bonded may be unsubstituted or substituted with one or more halogen atoms.) These compounds may be used alone or in admixture of two or more. It can also be used.

Specific examples of the compound represented by the general formula (1-a-6) are represented by the following general formulas (1-a-6-1) to the general formula (1-a-6-21). Compounds are preferred.

(In the formula, L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ and L ⁸ are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, cyano group and isocyano. A group, a carboxyl group, a carbamoyl group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a trimethylsilyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are shown. When the group is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is unsubstituted or one or more halogens. These compounds may be substituted with atoms.) These compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the above general formula (1-a-7) are represented by the following general formulas (1-a-7-1) to general formulas (1-a-7-18). Compounds are preferred.

(In the formula, t, u, v, w, x and y each independently represent an integer of 1 to 18. L ³ and L ⁴ independently represent a hydrogen atom, a fluorine atom, a chlorine atom and a bromine atom, respectively. , Iodine atom, nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, alkyl group with 1 to 6 carbon atoms, carbon number 1 to 6 alkoxy groups are shown. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is unsubstituted. Alternatively, they may be substituted with one or more halogen atoms.) These compounds may be used alone or in admixture of two or more.

The polyfunctional polycyclic polymerizable compound represented by the general formula (1) is more specifically described in the following general formula (1-b) when HD is a hard segment represented by the general formula (1-b). The compounds represented by b-1) to (1-b-5) are preferable.

In the above general formulas (1-b-1) to (1-b-5), P11 to ^P76 represent polymerizable groups, but each of them is independently derived from the following formulas (P- ¹ ) to formula (P-). 20)

It is preferable to represent a group selected from the above, and among these polymerizable groups, from the viewpoint of enhancing the polymerizable property and the storage stability, the formula (P-1), the formula (P-2), the formula (P-7), and the like. The formula (P-12) or the formula (P-13) is preferable, and the formula (P-1), the formula (P-2), the formula (P-7), or the formula (P-12) is more preferable. (P-1) or the formula (P-2) is more preferable.

In the above general formulas (1-b-1) to (1-b-5),-(S ¹¹ -X ¹¹ )-to-(S ⁶² -X ⁶² )-are independently soft segments or single bonds, respectively. Represents.

S ¹¹ to S ⁶² each independently represent a spacer group or a single bond, but when a plurality of S ¹¹ to S ⁶² are present, they may be the same or different. The spacer group represents an alkylene group having 1 to 18 carbon atoms, and one or two or more hydrogen atoms bonded to the alkylene group independently have a halogen atom, a CN group, and a carbon atom number. It may be substituted with an alkyl group of 1 to 8 or an alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or two or more not adjacent to each other. CH ₂ groups are independent of each other _, and oxygen atoms are not directly bonded to each other. It may be replaced by OH)-, -CH (COOH)-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and one CH ₂ existing in the alkylene group. Preferably, an alkylene group having 3 to 12 carbon atoms in which two or more CH ₂ groups that are not adjacent or adjacent to each other may be replaced with —O—.

In the general formulas (1-b-1) to (1-b-5), X ¹¹ to X ⁶² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, and -CO, respectively. -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-,- OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-,- It represents C≡C- or a single bond, but if there are a plurality of X ¹¹ to X ⁶² , they may be the same or different. Further, from the viewpoint of easy availability of raw materials and ease of synthesis, when a plurality of raw materials exist, they may be the same or different from each other, and each of them may be independently -O-, -S-, -OCH _2- ,. -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, each independently of -O-, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH _2- It is more preferable to represent OCO- or a single bond, and when a plurality of X ¹¹ to X ⁶² are present, they may be the same or different, and they are independently -O-, -COO-, and -OCO. -Or it is particularly preferred to represent a single bond.

In the above general formulas (1-b-1) to (1-b-5), each P- (SX)-does not include an -O-O- bond.

In the general formulas (1-b-1) to (1-b-5), A ¹¹ to A ⁶² are independently 1,4-phenylene group, 1,4-cyclohexylene group, and pyridine-2,5-. Diyl group, pyrimidin-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group Alternatively, it represents a 1,3-dioxane-2,5-diyl group, but these groups may be unsubstituted or substituted with one or more substituents, but if a plurality of ^A11 to ^A62 appear. Each may be the same or different. A ¹¹ to A ⁶² are 1,4-phenylene groups which may be substituted or substituted with one or more substituents L ¹ and L ² , respectively, independently from the viewpoint of availability of raw materials and ease of synthesis. , 1,4-Cyclohexylene group or naphthalene-2,6-diyl, respectively, independently of the following formulas (A-1) to (A-16).

It is more preferable to represent the groups selected from the formulas (A-1), and it is further preferable to represent the groups selected from the formulas (A-1) to the formulas (A-13) independently. It is particularly preferable to represent a group selected from the formula (A-4).

In the above general formulas (A-1) to (A-16), the substituents L ¹ and L ² are independently fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group and nitro. Group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyanogroup, or one -CH _2- or adjacent. Two or more -CH _2- that are not used independently of -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O -CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, Represents a linear or branched alkyl group with 1 to 20 carbon atoms which may be substituted with -CH = CH-, -CF = CF- or -C≡C- and any hydrogen atom in the alkyl group. May be substituted with a fluorine atom, or represents a group represented by the above general formula (1-c). From the viewpoint of ease of synthesis, the substituents L ¹ and L ² are a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or , Any hydrogen atom may be replaced with a fluorine atom, and one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -O-, -S-, -CO. -, -COO-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- may be substituted with a group having 1 carbon atom. It is preferable to represent a linear or branched alkyl group from 20 to 20 or a group represented by the above general formula (1-c), and a fluorine atom, a chlorine atom, or any hydrogen atom is replaced with a fluorine atom. May be done, and one -CH _2- or two or more non-adjacent -CH ₂ -s are each independently substituted with a group selected from -O-, -COO- or -OCO-. It is more preferable to represent a linear or branched alkyl group having 1 to 12 carbon atoms, and a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted with a fluorine atom from 1 carbon atom. It is more preferable to represent 12 linear or branched alkyl groups or alkoxy groups, and it is particularly preferable to represent a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms. ..

In the above general formulas (A-1) to (A-16), M ¹¹ to M ⁶¹ independently represent the following formula (1-b-MG).

In the formula (1-b-MG), M ^b is from the following formula (M-1) to the formula (M-11).

Represents groups selected from, but these groups may be unsubstituted or substituted with one or more L ^bs . M ^b may be independently unsubstituted or substituted with one or more L ^bs from the viewpoint of availability of raw materials and ease of synthesis, respectively, and may be substituted by the formula (M-1) or the formula (M-2). ) Or an unsubstituted formula (M-3) to represent a group selected from the formula (M-6), which may be substituted or substituted by one or more L ^bs (M-1) or It is more preferable to represent a group selected from the formula (M-2), and it is particularly preferable to represent a group selected from the unsubstituted formula (M-1) or the formula (M-2).

In formula (1-b-MG), G ^b represents a group selected from formula (G-1) to formula (G-6).

In formulas (G-1) to (G-6), R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group is linear or branched. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one -CH _2- or _two or more non-adjacent-CH 2- in the alkyl group may be present. -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, respectively. It may be replaced by -NH-CO- or -C≡C-.
From formula (G-1) to formula (G-6), W ⁸¹ represents a group having at least one aromatic group and having 5 to 30 carbon atoms, wherein the group is unsubstituted or one. It may be replaced by the above L ^b .
W ⁸² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be fluorine. It may be substituted with an atom, and one -CH _2- or _two or more non-adjacent-CH 2- in the alkyl group are independently -O-, -S-, -CO-, respectively. -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH May be replaced by = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, or W ⁸² A group represented by the general formula (1-c)

(In the formula, P ³ represents a polymerizable group, but represents the same as defined in P ¹ and P ² above, and A ⁶ represents -O-, -COO-, -OCO-, and -OCH ₂ . -, -CH ₂ O-, -CH ₂ CH ₂ OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- ,} or a single bond, and Sf ³ is defined by Sf ¹ and Sf ² above. They represent the same thing, q represents 0 or 1, and r represents 0 or 1).

In the formulas (G-1) to (G-6), the aromatic group contained in W ⁸¹ may be an aromatic hydrocarbon group or an aromatic complex group, or may contain both. These aromatic groups may be bonded via a single bond or a linking group (-OCO-, -COO-, -CO-, -O-), or may form a fused ring. Further, W ⁸¹ may contain an acyclic structure and / or a cyclic structure other than the aromatic group in addition to the aromatic group. From the viewpoint of availability of raw materials and ease of synthesis, the aromatic group contained in W ⁸¹ may be unsubstituted or substituted with one or more L ^bs from the following formula (W-1). Equation (W-19)

(In the formula, these groups may have a bond at any position, and may form a group in which two or more aromatic groups selected from these groups are linked by a single bond, Q ¹ Represents -O-, -S-, -NR ^4- (in the formula, ^R4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or -CO-. Among these aromatic groups. -CH = may be independently replaced with -N =, and -CH _2- is independently -O-, -S-, -NR ^4- (in the formula, R ⁴ is a hydrogen atom or carbon. It may be replaced with an alkyl group having 1 to 8 atoms.) Or -CO-, but does not contain an -O-O- bond. The group represented by the formula (W-1) is unsubstituted. Or may be substituted with one or more L ^bs from the following equations (W-1-1) to equations (W-1-8).

(In the formula, these groups may have a bond at any position.) It is preferable to represent a group selected from the above, and the group represented by the formula (W-7) is unsubstituted. Alternatively, it may be substituted by one or more L ^bs from the following equations (W-7-1) to equations (W-7-7).

(In the formula, these groups may have a bond at any position.) It is preferable to represent a group selected from the above, and the group represented by the formula (W-10) is unsubstituted. Alternatively, it may be substituted by one or more L ^bs from the following equations (W-10-1) to equations (W-10-8).

(In the formula, these groups may have a bond at an arbitrary position, and R6 represents a hydrogen atom or an alkyl group having ¹ to 8 carbon atoms.) It is preferable to represent a group selected from. The group represented by the formula (W-11) may be unsubstituted or substituted with one or more L ^bs from the following formula (W-11-1) to the formula (W-11-13). )

(In the formula, these groups may have a bond at an arbitrary position, and R6 represents a hydrogen atom or an alkyl group having ¹ to 8 carbon atoms.) It is preferable to represent a group selected from. The group represented by the formula (W-12) may be unsubstituted or substituted with one or more L ^bs from the following formula (W-12-1) to the formula (W-12-19). )

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but when there are a plurality of R ^6s , they are the same. It may be present or different.) It is preferable to represent a group selected from), and the group represented by the formula (W-13) is unsubstituted or substituted with one or more L ^bs . The following formulas (W-13-1) to formulas (W-13-10) may be used.

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but when there are a plurality of R ^6s , they are the same. It may be present or different.) It is preferable to represent a group selected from), and the group represented by the formula (W-14) is unsubstituted or substituted with one or more L ^bs . The following formulas (W-14-1) to formulas (W-14-4) may be used.

(In the formula, these groups may have a bond at an arbitrary position, and R6 represents a hydrogen atom or an alkyl group having ¹ to 8 carbon atoms.) It is preferable to represent a group selected from. The group represented by the formula (W-15) may be unsubstituted or substituted with one or more L ^bs from the following formula (W-15-1) to the formula (W-15-18). )

(In the formula, these groups may have a bond at an arbitrary position, and R6 represents a hydrogen atom or an alkyl group having ¹ to 8 carbon atoms.) It is preferable to represent a group selected from. The group represented by the formula (W-16) may be unsubstituted or substituted with one or more L ^bs from the following formula (W-16-1) to the formula (W-16-4). )

(In the formula, these groups may have a bond at an arbitrary position, and R6 represents a hydrogen atom or an alkyl group having ¹ to 8 carbon atoms.) It is preferable to represent a group selected from. The group represented by the formula (W-17) may be unsubstituted or substituted with ^one or more L1s from the following formula (W-17-1) to the formula (W-17-6). )

(In the formula, these groups may have a bond at an arbitrary position, and R6 represents a hydrogen atom or an alkyl group having ¹ to 8 carbon atoms.) It is preferable to represent a group selected from. The group represented by the formula (W-18) may be unsubstituted or substituted with one or more L ^bs from the following formula (W-18-1) to the formula (W-18-6).

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but when there are a plurality of R ^6s , they are the same. It may be present or different.) It is preferable to represent a group selected from), and the group represented by the formula (W-19) is unsubstituted or substituted with one or more L ^bs . The following formulas (W-19-1) to formulas (W-19-9) may be used.

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but when there are a plurality of R ^6s , they are the same. It may be present or different.) It is preferable to represent a group selected from. The aromatic group contained in W ⁸¹ may be unsubstituted or substituted with ^one or more L1s, formulas (W-1-1), formulas (W-7-1), formulas (W-). 7-2), formula (W-7-7), formula (W-8), formula (W-10-6), formula (W-10-7), formula (W-10-8), formula ( W-11-8), formula (W-11-9), formula (W-11-10), formula (W-11-11), formula (W-11-12) or formula (W-11-13) ), It is more preferable to represent a group selected from the formulas (W-1-1), formulas (W-7-1), formulas (W-1-1), which may be unsubstituted or substituted with ^one or more L1s. Representing a group selected from W-7-2), formula (W-7-7), formula (W-10-6), formula (W-10-7) or formula (W-10-8). Especially preferable. Further, W ⁸¹ is derived from the following equation (W-a-1) to the equation (W-a-6).

(In the equation, r represents an integer from 0 to 5, s represents an integer from 0 to 4, and t represents an integer from 0 to 3.) It is particularly preferable to represent a group selected from.

W ⁸² has a hydrogen atom or one -CH _2- or two or more non-adjacent -CH _2- independently of -O-, -S-, -CO-, -COO-, -OCO- , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-,- Linear or branched with 1 to 20 carbon atoms which may be substituted by COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Represents an alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or W ⁸² may have the same meaning as W ⁸¹ , and W ⁸¹ and W ⁸² together. May form a ring structure, or W ⁸² is a group represented by the general formula (1-c).

(In the formula, P ³ represents a polymerizable group, but represents the same as defined in P ¹ and P ² above, and A ⁶ represents -O-, -COO-, -OCO-, and -OCH ₂ . -, -CH ₂ O-, -CH ₂ CH ₂ OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- ,} or a single bond, and Sf ³ is defined by Sf ¹ and Sf ² above. They represent the same thing, q represents 0 or 1, and r represents 0 or 1).

In W ⁸² , from the viewpoint of availability of raw materials and ease of synthesis, a hydrogen atom or any hydrogen atom may be replaced with a fluorine atom, and one -CH _2- or two non-adjacent hydrogen atoms may be substituted. The above-CH ₂ -are independently -O-, -CO-, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -CH = CH-,- It preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, which may be substituted by CF = CF- or -C≡C-, and has a hydrogen atom or 1 to 20 carbon atoms. It is more preferable to represent a linear or branched alkyl group, and it is particularly preferable to represent a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms. Further, when W ⁸² has the same meaning as W ⁸¹ , W ⁸² may be the same as or different from W ⁸¹ , but the preferred group is the same as that described for W ⁸¹ . Further, when W ⁸¹ and W ⁸² together form a ring structure, the cyclic group represented by −NW ⁸¹ W ⁸² may be unsubstituted or substituted with one or more L ^bs as follows. Equation (W-b-1) to Equation (W-b-42)

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group, and from the viewpoint of easy availability of raw materials and ease of synthesis, unsubstituted or substituted. Formulas (W-b-20), formulas (W-b-21), formulas (W-b-22), formulas (W-b-23), formulas (W- ^b -23), which may be substituted by one or more Lb. It is particularly preferred to represent a group selected from W-b-24), formula (W-b-25) or formula (W-b-33).

Further, the cyclic group represented by = CW ⁸¹ W ⁸² may be unsubstituted or substituted with one or more L ^bs from the following equations (W-c-1) to the equation (W-c-81). )

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but when a plurality of R ^6s are present, they may be the same or different from each other.) The formula (W-c-11), the formula (W-c-12), which may be unsubstituted or substituted with one or more Ls, is preferable, and from the viewpoint of easy availability of raw materials and ease of synthesis. Formula (W-c-13), formula (W-c-14), formula (W-c-53), formula (W-c-54), formula (W-c-55), formula (W-c) -56), it is particularly preferable to represent a group selected from the formula (W-c-57) or the formula (W-c-78).

W ⁸² is the following group

(In the formula, P ³ represents a polymerizable group, but represents the same as defined in P ¹ and P ² above, and A ⁶ represents -O-, -COO-, -OCO-, and -OCH ₂ . -, -CH ₂ O-, -CH ₂ CH ₂ OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- ,} or a single bond, and Sf ³ is defined by Sf ¹ and Sf ² above. They represent the same thing, q represents 0 or 1, and r represents 0 or 1.)
In the case of, the preferred P ³ is the same as that defined by P ¹ and P ² , the preferred Sf ³ is the same as that defined by Sf ¹ and Sf ² , and the preferred A ⁶ is -O- or It is a single bond.

The total number of π electrons contained in W ⁸¹ and W ⁸² is preferably 4 to 24 from the viewpoint of wavelength dispersion characteristics, storage stability and ease of synthesis.

W ⁸³ and W ⁸⁴ each have a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, and at least one aromatic group and have 5 to 30 carbon atoms. Group, alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms, cycloalkenyl group with 3 to 20 carbon atoms, 1 to 20 carbon atoms Which represents an alkoxy group, an acyloxy group having 2 to 20 carbon atoms, an alkylcarbonyloxy group having 2 to 20 carbon atoms, or the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy. One -CH _2- or two or more non-adjacent -CH _2- in a group, an alkylcarbonyloxy group are independently -O-, -S-, -CO-, -COO-,-, respectively. It may be replaced by OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-, and W ⁸³ is A cyano group, a nitro group, a carboxyl group, one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -O-, -S-, -CO-, -COO-, respectively. 1 carbon atom substituted with -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- Groups selected from 20 alkyl groups, alkenyl groups, acyloxy groups and alkylcarbonyloxy groups are more preferred, with cyano groups, carboxyl groups, one -CH _2- or two or more non-adjacent-CH ₂ groups. -Is a carbon atom independently substituted with -CO-, -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-. A group selected from an alkyl group, an alkenyl group, an acyloxy group, and an alkylcarbonyloxy group having a number of 1 to 20 is particularly preferable, and W ⁸⁴ has a cyano group, a nitro group, a carboxyl group, one -CH _2- or an adjacent group. Not two or more -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO It is selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group and an alkylcarbonyloxy group substituted with -O-, -CO-NH-, -NH-CO- or -C≡C-. Basic More preferably, a cyano group, a carboxyl group, one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -CO-, -COO-, -OCO-, -O-, respectively. Selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group, and an alkylcarbonyloxy group substituted with CO-O-, -CO-NH-, -NH-CO- or -C≡C-. The group selected by the group is particularly preferable.

^Lb is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, or a diisopropylamino. A group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -S-, -CO- , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- may be substituted with 1 carbon atom Represents from 20 linear or branched alkyl groups, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. From the viewpoint of ease of synthesis, L ¹ is a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or any hydrogen atom is fluorine. It may be substituted with an atom, and one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -O-, -S-, -CO-, -COO-,-, respectively. Linear or linear with 1 to 20 carbon atoms which may be substituted with a group selected from OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- It preferably represents a branched alkyl group, where a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted with a fluorine atom, one -CH _2- or two or more non-adjacent-CHs. It is more preferable that _2- represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be independently substituted with a group selected from -O-, -COO- or -OCO-. , Fluorine atom, chlorine atom, or any hydrogen atom may represent a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms which may be substituted with a fluorine atom. It is particularly preferable to represent a chlorine atom or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms.

In the general formulas (1-b-1) to (1-b-5), Z ¹¹ to Z ⁷² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, and -CH, respectively. ₂ CH _2- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-,- OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, It represents -C≡C- or a single bond, but when a plurality of Z ¹¹ to Z ⁷² appear, they may be the same or different. From the viewpoint of availability of raw materials and ease of synthesis, Z ¹¹ to Z ⁷² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, and -O-CO. -O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond is preferable, and Z ¹¹ to Z ⁷² are independently -OCH _2- , respectively. -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF ₂ -, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ --OCO-, -CH = CH-, -C≡C- or It is more preferable to represent a single bond, and Z ¹¹ to Z ⁷² are independently -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH. It is more preferred to represent -CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, respectively. Independently -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or single bond It is particularly preferable to represent it.

In the above general formula (1-b-2), the terminal group R ²¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, or a thioisocyano group. , Or one -CH _2- or two or more non-adjacent -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO. A straight line having 1 to 20 carbon atoms which may be substituted by -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-. Representing a state or branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. From the viewpoint of ease of synthesis, R ²¹ has a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or one -CH _2- or two or more non-adjacent-CH ₂ -independently. It preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with O-, -COO-, -OCO-, -O-CO-O-, and preferably represents a hydrogen atom, a fluorine atom, or chlorine. It is more preferable to represent an atom, a cyano group, or a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms, and it may represent a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms. Especially preferable.

In the above general formulas (1-b-1) to (1-b-5), n11 to n62 each independently represent an integer of 0 to 6, but the characteristics of the compound, the availability of raw materials, and the synthesis thereof. From the viewpoint of ease, it is preferable to represent an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0 or 1.

In the above general formulas (1-b-1) to (1-b-5), j11, j12, j21, j22, j41, j42, j51, j52, j61, and j62 each independently have an integer of 0 to 5. In this way, j11 + j12 represents an integer from 2 to 7, j21 + j22 represents an integer from 2 to 7, j41 + j42 represents an integer from 2 to 7, j51 + j52 represents an integer from 2 to 7, and j61 + j62 represents an integer from 2 to 7. Represents. From the viewpoint of ease of synthesis and storage stability, it is preferable that j11, j21, j22, j41, j42, j51, j52, j61, j62, j71, and j72 each independently represent an integer of 1 to 4. It is more preferable to represent an integer of 3 to 3, and it is particularly preferable to represent 1 or 2. j11 + j12, j21 + j22, j41 + j42, j51 + j52, and j61 + j62 each preferably represent an integer of 2 to 4, and particularly preferably 2 or 3.

Specific examples of the compound represented by the above general formula (1-b-1) are represented by the following general formulas (1-b-1-1) to general formulas (1-b-1-65). Compounds are preferred.

(In the formula, n represents an integer of 1 to 10.) These polymerizable compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the above general formula (1-b-2) are represented by the following general formulas (1-b-2-1) to general formula (1-b-2-17). Compounds are preferred.

These polymerizable compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the above general formula (1-b-3) are represented by the following general formulas (1-b-3-1) to general formulas (1-b-3-29). Compounds are preferred.

(In the formula, n indicates the number of carbon atoms 1 to 10.) These liquid crystal compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the above general formula (1-b-4) are represented by the following general formulas (1-b-4-1) to general formulas (1-b-4-25). Compounds are preferred.

(In the formula, k, l, m and n each independently represent 1 to 10 carbon atoms.) These polymerizable compounds may be used alone or in combination of two or more. You can also do it.

Specific examples of the compound represented by the above general formula (1-b-5) are represented by the following general formulas (1-b-5-1) to general formulas (1-b-5-26). Compounds are preferred.

These liquid crystal compounds may be used alone or in combination of two or more.

At least one type of polymerizable compound is used for the gas separation membrane of the present invention, but from the viewpoint of durability, the polyfunctional polycyclic polymerizable compound represented by the above general formula (1) is used as a gas separation membrane. It is preferably contained in an amount of 10 to 100% by weight, more preferably 15 to 100% by weight, still more preferably 20 to 100% by weight, based on the total content of the compounds in the composition produced when the product is produced. It is particularly preferable to contain it.

In particular, among the polyfunctional polycyclic polymerizable compounds represented by the general formula (1), when a compound having a group represented by the general formula (1-a) is used as the main component as the HD group, That is, when the polyfunctional polycyclic polymerizable compound represented by the general formulas (1-a-1) to (1-a-7) is used as a main component, the general formulas (1-a-1) to (1-a-1) to the above are used. The polyfunctional polycyclic polymerizable compound represented by (1-a-7) is 10 to 100% by weight based on the total content of the compounds in the composition prepared when the gas separation membrane is produced. % Is preferably contained, 15 to 100% by weight is more preferable, and 20 to 100% by weight is particularly preferable.

Further, among the polyfunctional polycyclic polymerizable compounds represented by the general formula (1), when a compound having a group represented by the general formula (1-b) is used as the main component as the HD group. That is, when the polyfunctional polycyclic polymerizable compound represented by the general formulas (1-b-1) to (1-b-5) is used as a main component, the general formulas (1-b-1) to (1-b-1) to the above are used. The polyfunctional polycyclic polymerizable compound represented by (1-b-5) is 30 to 90 weight by weight with respect to the total content of the compounds in the composition prepared when the gas separation membrane is produced. % Is preferably contained, 35 to 90% by weight is more preferable, and 40 to 90% by weight is particularly preferable.

In the gas separation membrane of the present invention, compounds other than the above can also be used.

A compound having two or more polymerizable groups, a hard segment having two ring structures, and a soft segment if necessary (hereinafter, abbreviated as "polyfunctional bicyclic polymerizable compound") used in the present invention. , The compound has two or more polymerizable functional groups, hard segments in which the rings of each other are bonded by a linking group, and the polymerizable functional group is directly bonded to the ring or is bonded to the ring. The soft segments are attached and the polymerizable functional groups are attached via the soft segments.
(Polyfunctional bicyclic polymerizable compound)
A polyfunctional bicyclic polymerizable compound can be used as the polymerizable compound in the composition used when forming the polymer contained in the gas separation membrane of the present invention. The polyfunctional bicyclic polymerizable compound is specifically represented by the general formula (2).

(In the formula, Sf ²¹ and Sf ²² each independently represent a soft segment, but when a plurality of Sf ²¹ and Sf ²² exist, they may be the same or different, and P ²¹ and P ²² are respectively. Although they independently represent polymerizable groups, when a plurality of P ²¹ and P ²² are present, they may be the same or different from each other. HD ² is a hard segment having two ring structures, and n1 and n2 are hard segments. Each independently represents an integer of 0 to 3, but if it is 0, it has a terminal group, but represents n1 + n2 ≧ 2.)
Examples of P ²¹ and P ²² include radically polymerizable ones and cationically polymerizable ones.

As P ¹ and P ² , any polymerizable group may be used as long as it is a heat initiator, a photoinitiator, or one that undergoes a polymerization reaction by heat or active energy rays, but each of them independently has the following formula (P). A polymerizable group selected from -1) to (P-20) is preferable.

(Me represents a methyl group and Et represents an ethyl group.) In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), the formula (P-2), the formula (P-3), Formula (P-4), formula (P-5), formula (P-7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferable. , Formula (P-1), formula (P-2), formula (P-7), formula (P-11) or formula (P-13) is more preferable, and formula (P-1), formula (P-). 2) or the formula (P-3) is more preferable, and the formula (P-1) or the formula (P-2) is particularly preferable.

Examples of the Sf ²¹ and Sf ²² include linear and branched ones.

Sf ²¹ and Sf ²² each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms (one or two or more hydrogen atoms bonded to the alkylene group are independent halogen atoms, respectively. , CN group, alkyl group having 1 to 8 carbon atoms, or alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or _Two or more CHs that are not adjacent to each other are independent of each other _, and oxygen atoms do not directly bond to each other. -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH -Or-may be replaced by -C≡C-.) Is preferable.

When n21 and / or n22 is 0, HD ² has a terminal group, and the terminal groups are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and pentafluorosulfuranyl. A group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -S-,-, respectively. Replaced by CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- It represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be used, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

Examples of the HD ² include rod-shaped, disk-shaped, and bent-shaped ones.

Specifically, HD ² may have two ring structures bonded to each other by a linking group and / or a single bond as described above. Examples of the ring structure include 3- to 8-membered rings, heterocycles, and fused rings, and even if one or two or more hydrogen atoms bonded to each ring are independently substituted with substituents. good.

More specifically, HD ² preferably has a hard segment represented by the general formula (2-a).

(In the formula, A ²¹ and A ²² are independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-Diyl group, pyrimidin-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene -2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b'] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5 -B'] diselenovene-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophen-2, Representing a 7-diyl group or a fluorene-2,7-diyl group, one or more hydrogen atoms attached to the respective rings of A ²¹ and A ²² are independently substituted with the substituent L ^HD2 , respectively. The substituent ^LHD2 may be F, Cl, CF ₃ , OCF ₃ , CN group, nitro group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkanoyl group, and the like. An alkanoyloxy group, a carbamoyl group, a sulfamoyl group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group, an alkenoyloxy group, or a general formula (2-b). Group to be

(In the formula, P ³ represents a polymerizable group, but represents the same as defined in P ¹ and P ² above, and A ⁶ represents -O-, -COO-, -OCO-, and -OCH ₂ . -, -CH ₂ O-, -CH ₂ CH ₂ OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- ,} or a single bond, and Sf ³ is defined by Sf ¹ and Sf ² above. It represents the same thing, q represents 0 or 1, and r represents 0 or 1).

Z ²¹ is -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO-S-, -S. -CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = Represents N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond. ).

As the polyfunctional bicyclic polymerizable compound represented by the general formula (2), more specifically, the compounds represented by the general formulas (2-1) to (2-7) are preferable.

In the above general formulas (2-1) to (2-7), P ²¹¹ to P ²⁷⁶ represent polymerizable groups, but each of them independently has the following formulas (P-1) to formulas (P-20).

It is preferable to represent a group selected from the above, and among these polymerizable groups, from the viewpoint of enhancing the polymerizable property and the storage stability, the formula (P-1), the formula (P-2), the formula (P-7), and the like. The formula (P-12) or the formula (P-13) is preferable, and the formula (P-1), the formula (P-2), the formula (P-7), and the formula (P-12) are more preferable, and the formula (P-12) is more preferable. P-1) or the formula (P-2) is more preferable.

In the general formulas (2-1) to (2-8),-(S ²¹¹ -X ²¹¹ )-to-(S276- ^X276 ) ^{-independently} represent a soft segment or a single bond.

S ²¹¹ to S ²⁷⁶ each independently represent a spacer group or a single bond, but when a plurality of S ²¹¹ to S ²⁷⁶ are present, they may be the same or different. The spacer group represents an alkylene group having 1 to 18 carbon atoms, and one or two or more hydrogen atoms bonded to the alkylene group independently have a halogen atom, a CN group, and a carbon atom number. It may be substituted with an alkyl group of 1 to 8 or an alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or two or more not adjacent to each other. CH ₂ groups are independent of each other _, and oxygen atoms are not directly bonded to each other. It may be replaced by OH)-, -CH (COOH)-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and one CH ₂ existing in the alkylene group. Preferably, an alkylene group having 3 to 12 carbon atoms in which two or more CH ₂ groups that are not adjacent or adjacent to each other may be replaced with —O—.

In the general formulas (2-1) to (2-7), X ²¹¹ to X ²⁷⁶ are independently -O-, -S-, -OCH _2- , -CH ₂ O-, and -CO-, respectively. , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S -, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO -CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -,- OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C It represents ≡ C- or a single bond, but if there are a plurality of X ²¹¹ to X ²⁷⁶ , they may be the same or different. Further, from the viewpoint of easy availability of raw materials and ease of synthesis, when a plurality of raw materials exist, they may be the same or different from each other, and each of them may be independently -O-, -S-, -OCH _2- ,. -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, each independently of -O-, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH _2- It is more preferable to represent OCO- or a single bond, and when a plurality of X ²¹¹ to X ²⁷⁶ are present, they may be the same or different, and they are independently -O-, -COO-, and -OCO. -Or it is particularly preferred to represent a single bond.

In the above general formulas (2-1) to (2-7), each P- (SX)-does not include an -O-O- bond.

In the general formulas (2-1) to (2-7), A ²¹¹ to A ²⁷² are independently 1,4-phenylene group, 1,4-cyclohexylene group and pyridine-2,5-diyl group, respectively. , Pyrimidin-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1 , ³ -Dioxane-2,5-Diyl groups, but these groups may be unsubstituted or substituted with one or more substituents, but are the same when multiple A11 to ^A72 appear. However, they may be different. A ²¹¹ to A ²⁷² are 1,4-phenylene groups, which may be independently substituted or substituted with ^one or ^more substituents L1 and L2, respectively, from the viewpoint of availability of raw materials and ease of synthesis. It is preferable to represent a 1,4-cyclohexylene group or a naphthalene-2,6-diyl, and each of them independently has the following formulas (A-1) to (A-16).

It is more preferable to represent the groups selected from the formulas (A-1), and it is further preferable to represent the groups selected from the formulas (A-1) to the formulas (A-13) independently. It is particularly preferable to represent a group selected from the formula (A-4).

In the general formulas (2-1) to (2-7), Z ²¹¹ to Z ²⁷¹ are independently -O-, -S-, -OCH _2- , -CH ₂ O-, and -CH ₂ . CH _2- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO -NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO -, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-,- Represents C≡C- or a single bond. Z ²¹¹ to Z ²⁷¹ are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, and -O-CO, respectively, from the viewpoint of availability of raw materials and ease of synthesis. -O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond is preferable, and Z ²¹¹ to Z ²⁷¹ are independently -OCH _2- , respectively. -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF ₂ -, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ --OCO-, -CH = CH-, -C≡C- or It is more preferable to represent a single bond, and Z ²¹¹ to Z ²⁷¹ independently represent -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH. It is more preferred to represent -CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, respectively. It is particularly preferred to independently represent -CH ₂ CH _2- , -COO-, -OCO- or a single bond.

In the above general formula (2-2), the terminal group ^R221 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or One -CH _2- or two or more non-adjacent -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S. -, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- may be substituted in a linear or linear manner with 1 to 20 carbon atoms. Although it represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R ³¹ has a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or one -CH _2- or two or more -CH ₂ -not adjacent to each other from the viewpoint of the characteristics of the compound and the ease of synthesis. It preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be independently substituted with —O—, —COO—, —OCO—, —O—CO—O—, preferably a hydrogen atom, It is more preferable to represent a fluorine atom, a chlorine atom, a cyano group, or a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms, and a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms. Is particularly preferable.

In the above general formulas (A-1) to (A-16), the substituents L ¹ and L ² are independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group and a nitro group, respectively. Isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH _2- or adjacent. Not two or more -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with = CH-, -CF = CF- or -C≡C-, and any hydrogen atom in the alkyl group is fluorine. It may be substituted with an atom, or represents a group represented by the above general formula (2-b). From the viewpoint of the properties of the compound and the ease of synthesis, L ² is a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or any of them. The hydrogen atom may be replaced with a fluorine atom, and one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -O-, -S-, -CO-,-, respectively. COO-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- may be substituted with a group having 1 to 20 carbon atoms. It is preferable to represent a group represented by a linear or branched alkyl group, and a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted with a fluorine atom, and one -CH _2- or an adjacent atom may be substituted. Two or more non-CH2- may be independently substituted with a group selected from -O-, -COO- or _-OCO- in a linear or branched manner with 1 to 12 carbon atoms. It is more preferable to represent a state alkyl group, and a fluorine atom, a chlorine atom, or any hydrogen atom may be replaced with a fluorine atom. A linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms may be used. It is more preferable to represent a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms.

In the above general formulas (2-1) to (2-7), n211 to n276 each independently represent an integer of 0 to 6, but from the viewpoint of the characteristics of the compound, the availability of raw materials, and the ease of synthesis. It is preferable to represent an integer from 0 to 4, more preferably to represent an integer from 0 to 2, and even more preferably to represent 0 or 1.

As the compound represented by the general formula (2-1), specifically, a compound represented by the following general formula (2-1-1) to the general formula (2-1-8) is preferable.

(In the formula, a and b each independently represent an integer of 1 to 18. L ¹¹ and L ¹² independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a nitro group, respectively. Cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms. It is shown. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is unsubstituted, or one or two. It may be substituted with one or more halogen atoms.) These compounds may be used alone or in combination of two or more.

As the compound represented by the general formula (2-2), specifically, a compound represented by the following general formula (2-2-1) to the general formula (2-2-6) is preferable.

These compounds may be used alone or in combination of two or more.

As the compound represented by the general formula (2-3), specifically, a compound represented by the following general formula (2-3-1) to the general formula (2-3-4) is preferable.

(In the formula, a, b and c each independently represent an integer of 1 to 18. L ¹¹ and L ¹² independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a nitro. Group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, alkyl group with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms Indicates a group. If these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is unsubstituted or one. Alternatively, they may be substituted with two or more halogen atoms.) These compounds may be used alone or in combination of two or more.

As the compound represented by the general formula (2-4), specifically, a compound represented by the following general formula (2-4-1) to the general formula (2-4-4) is preferable.

(In the formula, a independently represents an integer of 1 to 18. L ¹¹ and L ¹² independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, and a cyano group, respectively. , Isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is unsubstituted, or one or more. These compounds may be used alone or in admixture of two or more.

As the compound represented by the general formula (2-5), specifically, a compound represented by the following general formula (2-5-1) to the general formula (2-5-8) is preferable.

(In the formula, a, b, c and d each independently represent an integer of 1 to 18. L ¹¹ and L ¹² independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, respectively. , Nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, alkyl group with 1 to 6 carbon atoms, 1 to 6 carbon atoms If these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is unsubstituted or substituted. It may be substituted with one or more halogen atoms.) These compounds may be used alone or in admixture of two or more.

As the compound represented by the general formula (2-6), specifically, a compound represented by the following general formula (2-6-1) to the general formula (2-6-3) is preferable.

(In the formula, L ¹¹ and L ¹² are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl. A group, a mercapto group, a methylamino group, a dimethylamino group, a trimethylsilyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are shown. These groups are alkyl groups having 1 to 6 carbon atoms, or In the case of an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group may be unsubstituted or substituted with one or more halogen atoms.) These The compound may be used alone or in combination of two or more.

As the compound represented by the general formula (2-7), specifically, a compound represented by the following general formulas (2-7-1) to the general formula (2-7-8) is preferable.

(In the formula, a, b, c, d, e and f each independently represent an integer of 1 to 18.) These compounds may be used alone or in combination of two or more. You can also do it.
(Monofunctional polycyclic polymerizable compound)
The composition used for constituting the polymer contained in the gas separation membrane of the present invention includes, as a polymerizable compound, one polymerizable group, a hard segment having two or more ring structures, and soft if necessary. A compound having a segment (hereinafter, abbreviated as "monofunctional polycyclic polymerizable compound") can be used. It has the monofunctional polycyclic polymerizable compound, one polymerizable functional group in the compound, and a hard segment in which each ring is bonded to each other by a linking group, and the polymerizable functional group is directly bonded to the ring. Or, the ring and the soft segment are bonded, and the polymerizable functional group is bonded via the soft segment.

The monofunctional polycyclic polymerizable compound of the present invention is specifically represented by the general formula (3).

(In the formula, Sf ³¹ and Sf ³² each independently represent a soft segment, P ³¹ represents a polymerizable group, and HD ³ represents a hard segment having two or more ring structures.)
Examples of the P ³¹ include radically polymerizable ones and cationically polymerizable ones.

As P ³¹ , any polymerizable group may be used as long as it is a heat initiator, a photoinitiator, or one that undergoes a polymerization reaction by heat or active energy rays, but each of them independently has the following formula (P-1). A polymerizable group selected from (P-20) is preferable.

(Me represents a methyl group and Et represents an ethyl group.) In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), the formula (P-2), the formula (P-3), Formula (P-4), formula (P-5), formula (P-7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferable. , Formula (P-1), formula (P-2), formula (P-7), formula (P-11) or formula (P-13) is more preferable, and formula (P-1), formula (P-). 2) or the formula (P-3) is more preferable, and the formula (P-1) or the formula (P-2) is particularly preferable.

The Sf ³¹ represents a single bond or an alkylene group having 1 to 18 carbon atoms (one or two or more hydrogen atoms bonded to the alkylene group are independently halogen atoms, CN groups, and carbon atoms, respectively. It may be substituted with an alkyl group of 1 to 8 or an alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or two or more not adjacent to each other. CH ₂ groups are independent of each other _, and oxygen atoms are not directly bonded to each other. , -OCO-, -OCOO-, -SCO-, -COS-, -CF ₂ O-, -OCF 2-, -CF ₂ S-, _{-SCF 2-} , -CH = CH-, or -C≡C -May be replaced with.) Is preferable.

Sf ³² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an isocyanul group, a thioisosianul group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, a carbamoyl group, a sulfamoyl group, and carbon. Representing an alkenyl group, an alkenyloxy group, an alkenoyl group, or an alkenoyloxy group having 2 to 8 atoms, the group may be substituted with one or more halogen atoms or CN, and 1 present in this group. _Two CH groups or _two or more non-adjacent CH groups are independent of each other, and the oxygen atoms do not directly bond to each other, and -O-, -S-, -NH-, and -N ( It may be replaced by CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-.

As described above, the HD ³ may have two or more ring structures bonded to each other by a linking group and / or a single bond. Examples of the ring structure include 3- to 8-membered rings, heterocycles, and fused rings, and even if one or two or more hydrogen atoms bonded to each ring are independently substituted with substituents. good.

More specifically, a hard segment represented by the general formula (3-a) is preferable.

(In the formula, A ³¹ , A ³² , A ³³ , A ³⁴ , and A ³⁵ are independent, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran, respectively. -2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene -2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 , 4-Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4 , 4a, 9,10a-Octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b'] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b'] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [1] 3,2-b] Represents a selenophen-2,7-diyl group or a fluorene-2,7-diyl group.
One or more F, Cl, CF ₃ , OCF ₃ , CN group, nitro group, alkyl group with 1 to 8 carbon atoms, alkoxy group, alkanoyl group, alkanoyloxy group, carbamoyl group, sulfamoyl group, carbon as substituents It may have an alkenyl group, an alkenyloxy group, an alkenoyl group, or an alkenoyloxy group having 2 to 8 atoms, and Z0, Z1, Z2, Z3, Z4, and Z5 are independently each of -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- , -CONH-} , -NHCO-, an alkyl group may have a halogen atom having 2 to 10 carbon atoms. Or represents a single bond, one or more hydrogen atoms attached to the respective rings of A ³¹ , A ³² , A ³³ , A ³⁴ , and A ³⁵ are each independently substituted with the substituent ^LHD3 . The substituent L ^HD3 may be F, Cl, CF ₃ , OCF ₃ , CN group, nitro group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkanoyl group, alkanoyl. Examples thereof include an oxy group, a carbamoyl group, a sulfamoyl group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group, and an alkenoyloxy group.

A ³¹ , A ³² , A ³³ , A ³⁴ , and A ³⁵ may each independently have one or more hydrogen atoms bonded to the ring substituted with the above-mentioned substituent ^LHD3 1, A group selected from a 4-phenylene group, a 1,4-cyclohexylene group and a 2,6-naphthylene group is preferable, and the 1,4-phenylene group, 1,4-cyclohexylene group and 2,6 are independent of each other. -A group selected from naphthylene groups is more preferred.

Z ³¹ , Z ³² , Z ³³ , and Z ³⁴ are independent of -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO, respectively. -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-,- Represents CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond.
l3, m3 and k3 independently represent 0 or 1, respectively, and represent 1 ≦ l3 + m3 + k3 ≦ 8. ).

The monofunctional polycyclic polymerizable compound represented by the general formula (3) is more preferably the compound represented by the general formula (3-1).

In the above general formula (3-1), P ³¹¹ represents a polymerizable group, and the following formulas (P-1) to formulas (P-20) are used.

It is preferable to represent a group selected from the above, and among these polymerizable groups, from the viewpoint of enhancing the polymerizable property and the storage stability, the formula (P-1), the formula (P-2), the formula (P-7), and the like. The formula (P-12) or the formula (P-13) is preferable, and the formula (P-1), the formula (P-2), the formula (P-7), and the formula (P-12) are more preferable, and the formula (P-12) is more preferable. P-1) or the formula (P-2) is more preferable.

In the general formula (3-1),-(S ³¹¹ -X ³¹¹ )-independently represents a soft segment or a single bond.

In the general formula (3-1), S ³¹¹ represents a spacer group or a single bond, but when a plurality of S ^311s are present, they may be the same or different. The spacer group represents an alkylene group having 1 to 18 carbon atoms, and one or two or more hydrogen atoms bonded to the alkylene group independently have a halogen atom, a CN group, and a carbon atom number. It may be substituted with an alkyl group of 1 to 8 or an alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or two or more not adjacent to each other. CH ₂ groups are independent of each other _, and oxygen atoms are not directly bonded to each other. It may be replaced by OH)-, -CH (COOH)-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and one CH ₂ existing in the alkylene group. Preferably, an alkylene group having 3 to 12 carbon atoms in which two or more CH ₂ groups that are not adjacent or adjacent to each other may be replaced with —O—.

In the general formula (3-1), X ³¹¹ independently have -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-. S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO- , -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but X ³¹¹ If there are a plurality of each, they may be the same or different. Further, from the viewpoint of easy availability of raw materials and ease of synthesis, when a plurality of raw materials exist, they may be the same or different from each other, and each of them may be independently -O-, -S-, -OCH _2- ,. -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, each independently of -O-, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH _2- It is more preferable to represent OCO- or a single bond, and when a plurality of X ^311s are present, they may be the same or different, and they may be independently -O-, -COO-, -OCO- or a single bond. It is particularly preferred to represent a bond.

In the above general formula (3-1), P ³¹¹ − (S ³¹¹ − X ³¹¹ ) − does not include an —O— bond.

In the general formula (3-1), A ³¹¹ to A ³¹² and M ³¹¹ independently have a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, and a pyrimidine-. 2,5-Diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3- Representing a dioxane-2,5-diyl group, these groups may be unsubstituted or substituted with one or more substituents, but are the same when multiple A ³¹¹ and A ³¹² appear. May be different. A ³¹¹ and A ³¹² may be independently substituted or substituted with ^one or ^more substituents L1 and L2, respectively, independently from the viewpoint of availability of raw materials and ease of synthesis, 1,4-phenylene groups. , 1,4-Cyclohexylene group or naphthalene-2,6-diyl, respectively, independently of the following formulas (A-1) to (A-16).

It is more preferable to represent the groups selected from the formulas (A-1), and it is further preferable to represent the groups selected from the formulas (A-1) to the formulas (A-13) independently. It is particularly preferable to represent a group selected from the formula (A-4).

In the general formula (3-1), Z ³¹¹ to Z ³¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-,-, respectively. COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO- , -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-,- SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond .. Z ³¹¹ to Z ³¹² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -O-CO, respectively, from the viewpoint of availability of raw materials and ease of synthesis. -O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond is preferable, and Z ³¹¹ to Z ³¹² are independently -OCH _2- , respectively. -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF ₂ -, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ --OCO-, -CH = CH-, -C≡C- or It is more preferable to represent a single bond, and Z ³¹¹ to Z ³¹² are independently -CH ₂ CH _2- , -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH. It is more preferred to represent -CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond, respectively. It is particularly preferred to independently represent -CH ₂ CH _2- , -COO-, -OCO- or a single bond.

In the general formula (3-1), the terminal group R ³¹¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or One -CH _2- or two or more non-adjacent -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S- , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- may be substituted with 1 to 20 carbon atoms linear or branched. Representing a state alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. R ³¹ has a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or one -CH _2- or two or more -CH ₂ -not adjacent to each other from the viewpoint of the characteristics of the compound and the ease of synthesis. It preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be independently substituted with —O—, —COO—, —OCO—, —O—CO—O—, preferably a hydrogen atom, It is more preferable to represent a fluorine atom, a chlorine atom, a cyano group, or a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms, and a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms. Is particularly preferable.

In the above general formulas (A-1) to (A-16), the substituents L ¹ and L ² are independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group and a nitro group, respectively. Isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH _2- or adjacent. Not two or more -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH Represents a linear or branched alkyl group with 1 to 20 carbon atoms which may be substituted with = CH-, -CF = CF- or -C≡C-, any hydrogen atom in the alkyl group. It may be substituted with a fluorine atom. From the viewpoint of the characteristics of the compound and the ease of synthesis, the substituents L ¹ and L ² are independently a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, and a dimethylamino. A group, a diethylamino group, a diisopropylamino group, or any hydrogen atom may be substituted with a fluorine atom, and one -CH _2- or two or more non-adjacent-CH ₂ -s are independently of each other. A group selected from -O-, -S-, -CO-, -COO-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by the above is preferable, and a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted with a fluorine atom. CH ₂ -or two or more non-adjacent-CH ₂ -may be independently substituted with a group selected from -O-, -COO- or -OCO- with 1 to 12 carbon atoms. It is more preferable to represent a linear or branched alkyl group, and a fluorine atom, a chlorine atom, or any hydrogen atom may be replaced with a fluorine atom. A linear or branched alkyl having 1 to 12 carbon atoms. It is more preferable to represent a group or an alkoxy group, and it is particularly preferable to represent a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms.

In the above general formula (3-1), n31 independently represents an integer of 0 to 6, but represents an integer of 0 to 4 from the viewpoint of the characteristics of the compound, the availability of raw materials, and the ease of synthesis. It is preferable, it is more preferable to represent an integer of 0 to 2, and it is even more preferable to represent 0 or 1.

In the above general formula (3-1), j311 and j312 independently represent integers from 0 to 5, while j311 + j312 represent integers from 2 to 7. From the viewpoint of ease of synthesis and storage stability, j311 and j312 preferably independently represent an integer of 1 to 4, more preferably an integer of 1 to 3, and represent 1 or 2. Especially preferable. j311 + j312 preferably represent an integer of 2 to 4, respectively, and particularly preferably 2 or 3.

As the compound represented by the general formula (3-1), specifically, a compound represented by the following general formula (3-1-1) to the general formula (3-1-47) is preferable.

(In the above formula, h and i each independently represent an integer of 0 to 18, and L ³¹ , L ³² , L ³³ , L ³⁴ and L ³⁵ independently represent a hydrogen atom, a fluorine atom and a chlorine atom, respectively. Bromine atom, iodine atom, nitro group, cyano group, isocyano group, carboxyl group, carbamoyl group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, trimethylsilyl group, alkyl group with 1 to 6 carbon atoms, Indicates an alkoxy group having 1 to 6 carbon atoms. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, the hydrogen atom bonded to the alkyl group or the alkoxy group is unsubstituted. Or may be substituted with one or more halogen atoms.) These compounds may be used alone or in admixture of two or more.

Among the polymerizable liquid crystal compounds that can be optically arranged on one or more axes described in detail above, the polyfunctional polycyclic polymerizable compound represented by the general formula (1) has orientation and curability. The compound represented by the general formula (1-a), particularly the compound represented by the general formula (1-a-1), is particularly preferable because it is preferable in terms of excellent gas separation ability and can exhibit excellent gas separation ability when homeo-oriented. The represented compound is preferred. Further, the compound represented by the general formula (1-b) is preferable from the viewpoint of excellent orientation and gas permeability.

Further, when the compound represented by the general formula (1-a) or the general formula (1-b) is used, the monofunctional polycyclic polymerizable compound represented by the general formula (3-1) is used. Is preferable because it is easy to form a smectic phase and the gas separation ability is good, and particularly when the general formula (1-a-1) and the general formula (3-1) are used in combination. It is preferable because the effect of polymerization is remarkable. Here, when the compound represented by the general formula (1-a) or the general formula (1-b) is used, the monofunctional polycyclic polymerizable property represented by the general formula (3-1) is used. When used in combination with a compound, the mass ratio [(1-a) or (1-b) / (3-1)] is preferably in the range of 20/80 to 90/10.
(Polymer initiator)
A polymerization initiator is used as necessary in the composition used when forming the polymer contained in the gas separation membrane of the present invention. The polymerization initiator is used to polymerize the composition. The photopolymerization initiator used when the polymerization is carried out by light irradiation is not particularly limited, but is known and commonly used to the extent that the molecular arrangement of the compound in the composition containing the polyfunctional polycyclic polymerizable compound is not impaired. Things can be used.

For example, 1-hydroxycyclohexylphenyl ketone "Irgacure 184", 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one "Darocure 1116", 2-methyl-1-[(methylthio) phenyl]. -2-Moliphorinopropane-1 "Irgacure 907", 2,2-dimethoxy-1,2-diphenylethan-1-one "Irgacure 651", 2-benzyl-2-dimethylamino-1- (4-morpho) Renophenyl) -butanone "Irgacure 369"), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholino-phenyl) butane-1-one "Irgacure 379", 2,2-dimethoxy- 1,2-Diphenylethan-1-one, bis (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide "Lucillin TPO", 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide "Irgacure 819" , 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone "Irgacure OXE01"), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) "Irgacure OXE02" (above, manufactured by BASF Co., Ltd. 2,4-diethylthioxanthone (" Kayacure DETX" manufactured by Nippon Kayaku Co., Ltd.) and p. -Mixed with ethyl dimethylaminobenzoate ("Kayacure EPA" manufactured by Nippon Kayaku Co., Ltd.), mixture of isopropylthioxanthone ("CantaCure-ITX" manufactured by Ward Prekinsop) and ethyl p-dimethylaminobenzoate, "Esacure ONE" , "Esacure KIP150", "Esacure KIP160", "Esacure 1001M", "Esacure A198", "Esacure KIP IT", "Esacure KTO46", "Esacure TZT" (manufactured by lamberti Co., Ltd.),
Examples thereof include "Speed Cure BMS", "Speed Cure PBZ", and "Benzophenone" manufactured by LAMBSON. Further, as the photocation initiator, a photoacid generator can be used. Examples of the photoacid generator include a diazodisulfone-based compound, a triphenylsulfonium-based compound, a phenylsulfone-based compound, a sulfonylpyridine-based compound, a triazine-based compound, and a diphenyliodonium-based compound.

The content of the photopolymerization initiator is 0.1 to 10% by mass with respect to the total content of the compounds in the composition prepared when the gas separation membrane containing the polyfunctional polycyclic polymerizable compound is produced. It is preferable, and 1 to 6% by mass is particularly preferable. These can be used alone or in combination of two or more.

Further, as the thermal polymerization initiator used in the thermal polymerization, known and commonly used ones can be used, for example, methylacetate acetate peroxide, cumenhydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl). Peroxydicarbonate, t-butylperoxybenzoate, methylethylketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydro Organic peroxides such as peroxide, dicumyl peroxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2, 2'-Azobisisobutyronitrile, azonitrile compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methyl-N-phenylpropion-amidin) dihydro Azoamidin compounds such as chloride, azoamide compounds such as 2,2'azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'azobis (2,) An alkylazo compound or the like such as 4,4-trimethylpentane) can be used. The content of the thermal polymerization initiator is preferably 0.1 to 10% by mass with respect to the total content of the compounds in the composition produced when the gas separation membrane containing the polyfunctional polycyclic polymerizable compound is produced. 1 to 6% by mass is particularly preferable. These can be used alone or in combination of two or more.
(Organic solvent)
If necessary, an organic solvent is used in the composition used when forming the polymer contained in the gas separation membrane of the present invention. The organic solvent used is not particularly limited, but an organic solvent in which the polyfunctional polycyclic polymerizable compound exhibits good solubility is preferable, and an organic solvent that can be dried at a temperature of 120 ° C. or lower is preferable. Examples of such a solvent include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylen, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, 3-butoxymethyl acetate, ethyl lactate and the like. Ester solvent, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone and other ketone solvents, tetrahydrofuran, 1,2-dimethoxyethane, anisole and other ether solvents, N, N-dimethylformamide, N-methyl-2- Examples thereof include amide solvents such as pyrrolidone, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol monomethyl propyl ether, diethylene glycol monomethyl ether acetate, γ-butyrolactone and chlorobenzene. .. These can be used alone or in combination of two or more, but one of a ketone solvent, an ether solvent, an ester solvent and an aromatic hydrocarbon solvent. It is preferable to use the above from the viewpoint of solution stability.

The ratio of the organic solvent used is particularly limited as long as the coated state is not significantly impaired because the polymerizable composition used for forming the polymer contained in the gas separation film of the present invention is usually applied. However, the content ratio of the total content of the compounds in the composition produced when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound is preferably 0.1 to 99% by mass. It is more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass.

Further, when the polymerizable compound is dissolved in an organic solvent, it is preferable to heat and stir in order to uniformly dissolve the polymerizable compound. The heating temperature during heating and stirring may be appropriately adjusted in consideration of the solubility of the polymerizable compound used in the organic solvent, but is preferably 15 ° C to 130 ° C, more preferably 30 ° C to 110 ° C from the viewpoint of productivity. , 50 ° C to 100 ° C is particularly preferable.
(Additive)
In the composition used for forming the polymer contained in the gas separation membrane of the present invention, a general-purpose additive or the like is used for uniform coating or depending on each purpose. For example, polymerization inhibitors, antioxidants, UV absorbers, leveling agents, orientation control agents, chain transfer agents, infrared absorbers, thixo agents, antistatic agents, fillers, chiral compounds, monomers, other compounds, alignment materials, etc. Additives can be added to the extent that they do not significantly reduce the molecular arrangement.
(Polymerization inhibitor)
The composition used for forming the polymer contained in the gas separation membrane of the present invention may contain a polymerization inhibitor, if necessary. The polymerization inhibitor to be used is not particularly limited, and known and customary ones can be used.

For example, p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol), 2.2. '-Methylenebis (4-ethyl-6-t-butylphenol), 4.4'-thiobis (3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2 , 2'-bi-1-naphthol, and other phenolic compounds, hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone. , 2-Hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone, and other quinone compounds, p-phenylenediamine, 4-aminodiphenylamine, N. et al. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, diphenylamine, 4 .4'-Dicumyl-diphenylamine, 4.4'-dioctyl-diphenylamine and other amine compounds, phenothiazine, distearylthiodipropionate and other thioether compounds, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p. -Nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N, N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitronodimethylamine, p-nitroso-N, N- Diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanol Amin, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholin, N-nitrosomorpho N-phenylhydroxylamine ammonium salt, ditrosobenzene, 2,4.6-tree tert-butylnitronbenzene, N-nitroso-N -Methyl-p-toluene sulfoneamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2 -Sodium naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, etc. Examples thereof include nitroso compounds.

The amount of the polymerization inhibitor added is the composition produced when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound used when forming the polymer contained in the gas separation membrane of the present invention. It is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.0% by mass, based on the total content of the compounds in the mixture.
(Antioxidant)
The composition used when forming the polymer contained in the gas separation membrane of the present invention may contain an antioxidant or the like, if necessary. Examples of such a compound include a hydroquinone derivative, a nitrosoamine-based polymerization inhibitor, a hindered phenol-based antioxidant, and more specifically, tert-butylhydroquinone, "Q-1300" manufactured by Wako Pure Chemical Industries, Ltd., "Q-1301", pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate "IRGANOX1010", thiodiethylenebis [3- (3,5-di-tert-butyl-) 4-Hydroxyphenyl) propionate "IRGANOX1035", octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate "IRGANOX1076", "IRGANOX1135", "IRGANOX1330", 4,6-bis (octyl) Thiomethyl) -o-cresol "IRGANOX1520L", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565" (above, manufactured by BASF Co., Ltd.), ADEKA Co., Ltd. Examples thereof include Adecastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 manufactured by Sumitomo Chemical Co., Ltd., Sumilyzer BHT, Sumilyzer BBM-S, and Sumilyzer GA-80.

The amount of the antioxidant added is the composition prepared when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound used when forming the polymer contained in the gas separation membrane of the present invention. It is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.0% by mass, based on the total content of the compounds in the mixture.
(UV absorber)
The composition used when forming the polymer contained in the gas separation membrane of the present invention may contain an ultraviolet absorber and a light stabilizer, if necessary. The ultraviolet absorber and light stabilizer used are not particularly limited, but those that improve the light resistance of an optically anisotropic substance, an optical film, or the like are preferable.

Examples of the ultraviolet absorber include 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole "Tinubin PS", "Tinubin 109", "TINUVIN 213", "TINUVIN 234", and "TINUVIN". 326 ”,“ TINUVIN 328 ”,“ TINUVIN 329 ”,“ TINUVIN 384-2 ”,“ TINUVIN 571 ”, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-yl) Phenylethyl) Phenol "TINUVIN 900", 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) Phenol "TINUVIN 928", "TINUVIN 1130", "TINUVIN 400", "TINUVIN 405", 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1 , 3,5-Triazine "TINUVIN 460", "Tinubin 479", "TINUVIN 5236" (all manufactured by BASF Co., Ltd.), "Adekastab LA-32", "Adekastab LA-34", "Adekastab LA-36", Examples thereof include "Adekastab LA-31", "Adekastab 1413", and "Adekastab LA-51" (all manufactured by ADEKA Co., Ltd.).

Examples of the light stabilizer include "TINUVIN 123", "TINUVIN 144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 622", "TINUVIN 770", "TINUVIN 765", "TINUVIN 780", "TINUVIN 905". , "TINUVIN 5100", "TINUVIN 5050", "TINUVIN 5060", "TINUVIN 5151", "CHIMASORB 119FL", "CHIMASORB 944FL", "CHIMASORB 944LD" (above, ADEKA CORPORATION), "ADEKA CORPORATION" , "ADEKA STAB LA-57", "ADEKA STAB LA-62", "ADEKA STAB LA-67", "ADEKA STAB LA-63P", "ADEKA STAB LA-68LD", "ADEKA STAB LA-77", "ADEKA STAB LA-82" , "ADEKA STAB LA-87" (above, manufactured by ADEKA CORPORATION) and the like.

The amount of the ultraviolet absorber added is the composition produced when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound used when forming the polymer contained in the gas separation membrane of the present invention. It is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.0% by mass, based on the total content of the compounds in the mixture.
(Surfactant)
The composition used for forming the polymer contained in the gas separation membrane of the present invention may contain a surfactant, if necessary. The surfactant to be used is not particularly limited, but one is preferable because it reduces film thickness unevenness when forming a gas separation film.

Examples of the surfactant include an alkyl carboxylate, an alkyl phosphate, an alkyl sulfonate, a fluoroalkyl carboxylate, a fluoroalkyl phosphate, a fluoroalkyl sulfonate, a polyoxyethylene derivative, and a fluoroalkylethylene oxide derivative. Examples thereof include polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like.

Specifically, "Mega Fuck F-251", "Mega Fuck F-281", "Mega Fuck F-430", "Mega Fuck F-444", "Mega Fuck F-472SF", "Mega Fuck F-" 477 ”,“ Mega Fuck F-510 ”,“ Mega Fuck F-511 ”,“ Mega Fuck F-553 ”,“ Mega Fuck F-554 ”,“ Mega Fuck F-555 ”,“ Mega Fuck F-556 ” , "Mega Fuck F-557", "Mega Fuck F-558", "Mega Fuck F-559", "Mega Fuck F-561", "Mega Fuck F-562", "Mega Fuck F-563", "Mega Fuck F-563""Mega Fuck F-565", "Mega Fuck F-567", "Mega Fuck F-568", "Mega Fuck F-569", "Mega Fuck F-570", "Mega Fuck F-571", "Mega Fuck""R-40","Mega Fuck R-41", "Mega Fuck R-43", "Mega Fuck R-94", "Mega Fuck RS-72-K", "Mega Fuck RS-75", "Mega Fuck" RS-76-E ”,“ Megafuck RS-76-NS ”,“ Megafuck RS-90 ”,“ Megafuck EXP.TF-1367 ”,“ Megafuck EXP.TF1437 ”,“ Megafuck EXP.TF1537 ” , "Mega Fuck EXP.TF-2066" (all manufactured by DIC Corporation),
"Futtergent 100", "Futtergent 110", "Futtergent 150", "Futtergent 150CH", "Futtergent 300", "Futtergent 310", "Futtergent 320", "Futtergent 400SW", "Futtergent" Gent 251 ”,“ Footergent 212M ”,“ Footergent 215M ”,“ Footergent 250 ”,“ Footergent 222F ”,“ Footergent 212D ”,“ FTX-218 ”,“ Footergent 209F ”,“ Footergent 245F ” , "Futagent 208G", "Futagent 240G", "Futagent 212P", "Futagent 220P", "Futagent 228P", "DFX-18", "Futagent 601AD", "Futagent 602A", "Futtergent 650A", "Futergent 750FM", "FTX-730FM", "Futtergent 730FL", "Futtergent 710FS", "Futtergent 710FM", "Futtergent 710FL", "FTX-730LS", "Futter" GENT 730LM ", (all made by Neos Co., Ltd.),
"BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-320", "BYK-322", "BYK" 323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-340 "," BYK-344 "," BYK-370 " , "BYK-375", "BYK-377", "BYK-350", "BYK-352", "BYK-354", "BYK-355", "BYK-356", "BYK-358N", "BYK-361N", "BYK-357", "BYK-390", "BYK-392", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-Silclean3700" (above, BYK Co., Ltd.),
"TEGO Rad2100", "TEGO Rad2200N", "TEGO Rad2250", "TEGO Rad2300", "TEGO Rad2500", "TEGO Flow300", "TEGO Flow370", "TEGO Flow425", "TEGO Flow2F" , "TEGO Glide 100", "TEGO Glide 130", "TEGO Glide 410", "TEGO Glide 415", "TEGO Glide 432", "TEGO Glide 440", "TEGO Glide 450", "TEGO Glide 450", "TEGO Glide 450""GlideB1484","TEGO Glide ZG400", "TEGO Twin4000", "TEGO Twin4100", "TEGO Twin4200", "TEGO Wet240", "TEGO Wet500", "TEGO Wet500", "TEGO Wet510", "TEGO Wet510", "TEGO"・ Made by Industries, Ltd.),
"FC-4430", "FC-4432" (all manufactured by 3M Japan Ltd.),
"Unidyne NS" (all manufactured by Daikin Industries, Ltd.),
"Surflon S-241", "Surflon S-242", "Surflon S-243", "Surflon S-420", "Surflon S-611", "Surflon S-651", "Surflon S-386" (and above) , AGC Seimi Chemical Co., Ltd.),
"DISPALLON OX-880EF", "DISPALLON OX-883", "DISPALLON OX-77EF", "DISPALLON OX-710", "DISPALLON 1922", "DISPALLON 1927", "DISPALLON 1958", "DISPARLON -4""DISPALLONP-420","DISPALLONPD-7","DISPALLON1970","DISPALLON230","DISPALLONLF-1980","DISPALLONLF-1982","DISPALLONLF-1084","DISPALLON LF- , "DISPARLON LHP-90", "DISPARLON LHP-91", "DISPARLON LHP-96", "DISPARLON OX-715", "DISPARLON 1930N", "DISPARLON 1931", "DISPARLON 1933", "DISPARLON""DISPALLON1751N","DISPALLON1761","DISPALLONLS-009","DISPALLONLS-001","DISPALLONLS-050" (all manufactured by Kusumoto Kasei Co., Ltd.),
"PF-151N", "PF-636", "PF-6320", "PF-6620", "PF-6520", "PF-652-NF", "PF-3320" (all manufactured by OMNOVA SOLUTIONS) ),
"Polyflow No.7", "Polyflow No.50E", "Polyflow No.50EHF", "Polyflow No.54N", "Polyflow No.75", "Polyflow No.85", "Polyflow No.90", "Polyflow No.90" Polyflow No. 90D-50 ”,“ Polyflow No. 95 ”,“ Polyflow No. 99C ”,“ Polyflow KL-400K ”,“ Polyflow KL-400HF ”,“ Polyflow KL-401 ”,“ Polyflow KL-402 ”, "Polyflow KL-403", "Polyflow KL-100", "Polyflow LE-604", "Polyflow KL-700", "Floren AC-300", "Floren AC-303", "Floren AC-326F", " Floren AC-530, Floren AC-903, Floren AC-903HF, Floren AC-1160, Floren AC-2000, Floren AC-2300C, Floren AO-82, Floren "AO-98", "Floren AO-108" (all manufactured by Kyoeisha Chemical Co., Ltd.),
"L-7001", "L-7002", "8032ADDITION", "57ADDTIVE", "L-7064", "FZ-2110", "FZ-2105", "67ADDTIVE", "8616ADDTIVE" (above, Toray. Dow Silicone Co., Ltd.) and the like can be mentioned.

The amount of the surfactant added is the composition produced when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound used when forming the polymer contained in the gas separation membrane of the present invention. It is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 0.5% by mass, based on the total content of the compounds in the mixture.

Further, by using the above-mentioned surfactant, the gas separation membrane in the molecular arrangement state shown in FIG. 1, FIG. 4 or FIG. 5 may be obtained as the gas separation membrane of the present invention.
(Orientation control agent)
The composition used when forming the polymer contained in the gas separation membrane of the present invention can contain an orientation control agent in order to control the molecular arrangement state of the polymerizable compound. Examples of the orientation control agent used include those in which the polymerizable compound has a molecular arrangement that is optically one-axis or more and less than three-axis crystals with respect to the substrate. As described above, a surfactant may induce a molecular arrangement of one or more axes, but there is no particular limitation as long as each molecular arrangement state is induced, and a known and commonly used one is used. can do.

As such an orientation control agent, for example, in the case of a gas separation membrane, the polymerizable compound at the air interface has the effect of inducing a molecular arrangement state in the horizontal direction of the membrane, according to the following general formula (8). Examples thereof include compounds having a repeating unit represented by a weight average molecular weight of 100 or more and 1,000,000 or less.

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom in the hydrogen atom is one. It may be substituted with the above halogen atoms.)
In the case of a gas separation membrane, examples of the polymerizable compound at the air interface having the effect of inducing a molecular arrangement state in the vertical direction of the membrane include cellulose nitrate, cellulose acetate, cellulose propionic acid, cellulose butyrate and the like. Be done.
(Chain transfer agent)
The composition used when forming the polymer contained in the gas separation membrane of the present invention may contain a chain transfer agent in order to further improve the adhesion between the obtained gas separation membrane and the substrate. .. Examples of the chain transfer agent include aromatic hydrocarbons, chloroform, carbon tetrachloride, carbon tetrabromide, halogenated hydrocarbons such as bromotrichloromethane, octyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mel, and n. -Mercaptan compounds such as dodecyl mercaptan, t-tetradecyl mercaptan, t-dodecyl mercaptan, hexanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate. Rate, Ethylene Glycol Bisthiopropionate, Trimethylol Propanitris Thiolthioglycolate, Trimethylol Propanthry Tristhiopropionate, Trimethylol Propantris (3-Mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthio Propionate, Tris (2-hydroxyethyl) isocyanurate, trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino)- Thiol compounds such as 4,6-dimercapto-s-triazine, dimethylxanthogen disulfides, diethylxanthogen disulfides, diisopropylxanthogen disulfides, tetramethylthium disulfides, tetraethylthium disulfides, tetrabutylthium disulfides and other sulfide compounds, N, N-dimethylaniline , N, N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, achlorein, allyl alcohol, turpinolene, α-terpinen, γ-terbinen, dipentene, etc., 2,4-diphenyl-4-methyl, etc. -1-Pentene and thiol compounds are more preferable.

Specifically, compounds represented by the following general formulas (9-1) to (9-12) are preferable.

In the formula, ^R95 represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be a straight chain or a branched chain, and one or more methylene groups in the alkyl group are oxygen atoms. , And the sulfur atom may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH = CH-, assuming that the sulfur atoms do not bond directly to each other, and R ⁹⁶ is a carbon atom. Representing the number 2 to 18 alkylene groups, one or more methylene groups in the alkylene group assume that the oxygen atom and the sulfur atom do not directly bond to each other, and the oxygen atom, the sulfur atom, -CO-, and -OCO- , -COO-, or -CH = CH- may be substituted.

The chain transfer agent is preferably added in the step of preparing a polymerizable solution by mixing the composition containing the polyfunctional polycyclic polymerizable compound with an organic solvent and heating and stirring, but it is preferable to add the chain transfer agent to the polymerizable solution thereafter. The polymerization initiator may be added in the step of mixing, or may be added in both steps.

The amount of the chain transfer agent added is used when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound used in the composition used when forming the polymer contained in the gas separation membrane of the present invention. It is preferably 0.5 to 10% by mass, more preferably 1.0 to 5.0% by mass, based on the total content of the compounds in the composition prepared in 1.

Further, in order to adjust the physical properties, a hard segment having two or more non-polymerizable ring structures and a non-polymerizable compound having a soft segment, if necessary, can be added as needed (hard segment and soft). The segments are the same as those defined above). The polymerizable compound having one or less ring structures and having a soft segment is preferably added in the step of mixing the polymerizable compound with an organic solvent and heating and stirring to prepare a polymerizable solution. A hard segment having two or more non-sexual ring structures and, if necessary, a compound having a soft segment and the like may be added in the subsequent step of mixing the polymerization initiator with the polymerizable solution, or both. It may be added in the process. The amount of these compounds added is the above-mentioned at least two or more polymerizable groups, a hard segment having three or more ring structures, and a soft segment if necessary, which are used in the composition used for the gas separation membrane of the present invention. The amount of the non-polymerizable compound added to the composition containing the compound having is the total amount of the compounds in the composition prepared when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound. On the other hand, 20% by mass or less is preferable, 10% by mass or less is more preferable, and 5% by mass or less is even more preferable.
(Infrared absorber)
The composition used for forming the polymer contained in the gas separation membrane of the present invention may contain an infrared absorber, if necessary. The infrared absorber to be used is not particularly limited, and may contain known and commonly used ones as long as the orientation is not disturbed.

Examples of the infrared absorber include cyanine compounds, phthalocyanine compounds, naphthoquinone compounds, dithiol compounds, diimmonium compounds, azo compounds, aluminum salts and the like.

Specifically, diimmonium salt type "NIR-IM1", aluminum salt type "NIR-AM1" (above, manufactured by Nagase Chemtech Co., Ltd.), "Karenzu IR-T", "Karenzu IR-13F" (above). , Showa Denko Co., Ltd.), "YKR-2200", "YKR-2100" (above, Yamamoto Chemicals, Inc.), "IRA908", "IRA931", "IRA955", "IRA1034" (above, INDEC O Co., Ltd.) ) Etc. can be mentioned.
(Antistatic agent)
The composition used for forming the polymer contained in the gas separation membrane of the present invention may contain an antistatic agent, if necessary. The antistatic agent used is not particularly limited and may contain known and commonly used antistatic agents as long as the orientation is not disturbed.

Examples of such an antistatic agent include a polymer compound having at least one kind of sulfonic acid base or a phosphate base in the molecule, a compound having a quaternary ammonium salt, a surfactant having a polymerizable group, and the like.

Of these, surfactants having a polymerizable group are preferable, and for example, among the surfactants having a polymerizable group, "Antox SAD" and "Antox MS-2N" (all of which are Japanese emulsifier stocks) are used as anionic ones. (Manufactured by the company), "Aqualon KH-05", "Aqualon KH-10", "Aqualon KH-0530", "Aqualon KH-1025" (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), "Adecaria Soap SR-10N" , "Adecaria Soap SR-20N" (manufactured by ADEKA Corporation), "Latemuru PD-104" (manufactured by Kao Co., Ltd.), etc.
"Latemuru S-120", "Latemuru S-120A", "Latemuru S-180P", "Latemuru S-180A" (above, manufactured by Kao Corporation), "Eleminor JS-2" (manufactured by Sanyo Chemical Industries, Ltd.), Sulfocuccinate-based, such as
"Aqualon H-2855A", "Aqualon H-3855B", "Aqualon H-3856", "Aqualon HS-05", "Aqualon HS-10", "Aqualon HS-30", "Aqualon HS-1025", " Aqualon BC-05, Aqualon BC-10, Aqualon BC-1025, Aqualon BC-2020 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Adecaria Soap SDX-222, Adecaria Alkyl phenyl ethers or alkyl phenyl esters such as "Soap SDX-232", "Adecaria Soap SDX-259", "Adecaria Soap SE-10N", "Adecaria Soap SE-20N" (above, manufactured by ADEKA CORPORATION), etc. system,
(Meta) acrylate sulfate ester-based products such as "Antox MS-60", "Antox MS-2N" (manufactured by Nippon Embroidery Co., Ltd.), "Eleminor RS-30" (manufactured by Sanyo Kasei Co., Ltd.), " Examples thereof include phosphoric acid esters such as "H-3330P" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and "Adecaria Soap PP-70" (manufactured by ADEKA Corporation).

On the other hand, among the surfactants having a polymerizable group, nonionic ones include, for example, "Antox LMA-20", "Antox LMA-27", "Antox EMH-20", and "Antox LMH-". 20, "Antox SMH-20" (above, manufactured by Nippon Emulsorium Co., Ltd.), "Adecaria Soap ER-10", "Adecaria Soap ER-20", "Adecaria Soap ER-30", (above, stocks Alkyl ethers such as "Latemuru PD-420", "Latemuru PD-430", "Latemuru PD-450" (all manufactured by Kao Corporation), "Aqualon RN-10", "Aqualon RN" -20, "Aqualon RN-50", "Aqualon RN-2025" (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Adecaria Soap NE-10", "Adecaria Soap NE-30", "Adecaria" Alkylphenyl ether type or alkylphenyl ester type such as "Soap NE-40" (above, manufactured by ADEKA Corporation), "RMA-564", "RMA-568", "RMA-1114" (above, Nippon Embroidery Co., Ltd.) (Manufactured) and the like (meth) acrylate sulfate ester system can be mentioned.

Examples of other antistatic agents include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, and n-butoxypolyethylene glycol (meth) acrylate. , Phenoxy polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate, n-butoxypolypropylene glycol (meth) acrylate, Phenoxypolyethylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) ) Examples include acrylate.

The antistatic agent may be used alone or in combination of two or more.

The amount of the antistatic agent added is produced when the gas separation membrane containing the polyfunctional polycyclic polymerizable compound used when forming the polymer contained in the gas separation membrane of the present invention is produced. It is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total content of the compounds in the composition.
(Filler)
The composition used for forming the polymer contained in the gas separation membrane of the present invention may contain a filler as necessary in order to control the gas permeability. The filler to be used is not particularly limited, and may contain a known and commonly used filler as long as the gas selectivity of the obtained gas separation membrane is not deteriorated.

Examples of the filler include alumina, titanium white, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide, glass fiber and other inorganic fillers, metal powder such as silver powder and copper powder, aluminum nitride, and nitride. Thermally conductive fillers such as boron, silicon nitride, gallium nitride, silicon carbide, magnesia (aluminum oxide), silica, crystalline silica (silicon oxide), molten silica (silicon oxide), graphite, carbon fiber including carbon nanofibers, etc. , Silver nanoparticles and the like.

Specifically, as alumina, DAM-70, DAM-45, DAM-07, DAM-05, DAW-45, DAW-05, DAW-03, ASUSP-20 (all manufactured by Denki Kagaku Kogyo Co., Ltd.), AL 43-KT, AL-47-H, AL-47-1, AL-160SG-3, AL-43-BE, AS-30, AS-40, AS-50, AS-400, CB-P02, CB -P05 (all manufactured by Showa Denko Co., Ltd.), A31, A31B, A32, A33F, A41A, A43A, MM-22, MM-26, MM-P, MM-23B, LS-110F, LS-130, LS- 210, LS-242C, LS-250, AHP300 (all manufactured by Nippon Light Metal Co., Ltd.), AA-03, AA-04, AA-05, AA-07, AA-2, AA-5, AA-10, AA -18 (above, manufactured by Sumitomo Chemical Co., Ltd.), G-1, G-10, F-2, F-4, F-6 (above, manufactured by Showa Denko Co., Ltd.), TAF-520, TAF- as titanium white. 500, TAF-1500, TM-1, TA-100C, TA-100CT (all manufactured by Fuji Titanium Industry Co., Ltd.), MT-01, MT-10EX, MT-05, MT-100S, MT-100TV, MT- 100Z, MT-150EX, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-300HD, MT-500SA, MT-600SA, MT-700HD (all manufactured by Teika Co., Ltd.), TTO-51 ( A), TTO-51 (C), TTO-55 (A), TTO-55 (B), TTO-55 (C), TTO-55 (D), TTO-S-1, TTO-S-2, TTO-S-3, TTO-S-4, MPT-136, TTO-V-3 (above, manufactured by Ishihara Sangyo Co., Ltd.), B-309, B-309 (above, manufactured by Tomoe Kogyo Co., Ltd.) as aluminum hydroxide ), BA173, BA103, B703, B1403, BF013, BE033, BX103, BX043 (above, Nippon Light Metal Co., Ltd.), Nano Ace D-1000, Nano Ace D-800, Micro Ace SG-95, Micro Ace P-8, as talc. Micro Ace P-6 (above, manufactured by Nippon Tarku Co., Ltd.), FH104, FH105, FL108, FG106, MG115, FH104S, ML112S (above, manufactured by Fuji Tarku Kogyo Co., Ltd.), Y-1800, TM-10, A as mica. -11, SJ-005 (above, Yama Co., Ltd.) BT-H9DX, HF-9, HF-37N, HF-90D, HF-120D, HT-F (above, Kyoritsu Material Co., Ltd.), BT-100, HPBT series (above, manufactured by Guchimika), barium titanate. Fuji Titanium Industry Co., Ltd.), BT series (Sakai Chemical Industry Co., Ltd.), Pulceram BT (Nippon Chemical Industry Co., Ltd.), FINEX-30, FINEX-30W-LP2, FINEX-50, FINEX-50S as zinc oxide -LP2, XZ-100F (above, Sakai Chemical Industry Co., Ltd.), FZO-50 (manufactured by Ishihara Sangyo Co., Ltd.), MZ-300, MZ-306X, MZY-505S, MZ-506X, MZ-510HPSX (above, Teika Co., Ltd.), CS6SK-406, CS13C-897, CS3PC-455, CS3LCP-256 (above, Nitto Spinning Co., Ltd.), ECS03-615, ECS03-650, EFDE50-01, EFDE50-31 (above) as glass fibers , Central Glass Co., Ltd.), ACS6H-103, ACS6S-750 (above, manufactured by Nippon Electric Glass Co., Ltd.), Spherical silver powder AG3, AG4, flake silver powder FA5, FA2 (above, manufactured by DOWA Hi-Tech Co., Ltd.), SPQ03R, SPN05N, SPN08S, Q03R (above, manufactured by Mitsui Metal Mining Co., Ltd.), AY-6010, AY-6080 (above, manufactured by Tanaka Kikinzoku Co., Ltd.), ASP-100 (above, Aida Chemical Industry Co., Ltd.), Ag coat powder AG / SP (Made by Mitsubishi Materials Electronics Chemical Co., Ltd.), MA-O015K, MA-O02K, MA-O025K (above, manufactured by Mitsui Metal Mining Co., Ltd.), Electrolytic copper powder # 52-C, # 6 (above, JX Nikko) Nisseki Metal Co., Ltd.), 10% Ag Coat Cu-HWQ (Fukuda Metal Foil Powder Industry Co., Ltd.), Copper Powder Type-A, Type-B (above, DOWA Electronics Co., Ltd.), UCP-030 (Sumitomo) Made by Metal Mining Co., Ltd.),
As aluminum nitride, H grade, E grade, HT grade (above, manufactured by Tokuyama Co., Ltd.), TOYAL TecFiller TFS-A05P, TOYAL TecFiller TFZ-A02P (above, manufactured by Toyo Aluminum Co., Ltd.), ALN020BF, ALN050BF, ALN020AF, ALN , ALN020SF (above, manufactured by Tomoe Kogyo Co., Ltd.), FAN-f05, FAN-f30 (above, manufactured by Furukawa Electronics Co., Ltd.), Denkaboron Nightride SGP as boron nitride, Denkaboron Nightride MGP, Denkaboron Nightride GP, Denkaboron Nightride HGP, Denkaboron Nightride SP-2, Denkaboron Nightride SGPS (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), UHP-S1, UHP-1K, UHP-2, UHP-EX (above, Showa Denko) Silicon nitride manufactured by SN-9, SN-9S, SN-9FWS, SN-F1, SN-F2 (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), CF0027, CF00903, CF0018, CF0033 (above, Nippon Frit Co., Ltd.) As silicon carbide, GMF-H type, GMF-H2 type, GMF-LC type (above, Pacific Random Co., Ltd.), HSC1200, HSC1000, HSC059, HSC059I, HSC007 (above, manufactured by Tomoe Kogyo Co., Ltd.), Sisilia (Fuji Silicia Chemical Co., Ltd.), AEROSIL R972, AEROSIL R104, AEROSIL R202, AEROSIL 805, AEROSIL R812, AEROSIL R7200 (above, manufactured by Nippon Aerosil Co., Ltd.), Leosil series (manufactured by Tokuyama Co., Ltd.), crystalline CMC-12, VX-S, VX-SR (above, manufactured by Ryumori Co., Ltd.) as silica (silicon oxide), FB-3SDC, FB-3SDX, SFP-30M, SFP-20M as molten silica (silicon oxide) , SFP-30MHE, SFP-130MC, UFP-30 (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), Excelica series (manufactured by Tokuyama Co., Ltd.), AEROXIDE Alu C, AEROXIDE Alu 65 (above, Japan Aerosil Co., Ltd.) as aluminum oxide Made), Trecamiled Fiber MLD-30, Trecamiled Fiber MLD-30 (above, manufactured by Toray Co., Ltd.), CFMP-30X, CFM as carbon fibers and graphite P-150X (above, manufactured by Nippon Polymer Sangyo Co., Ltd.), XN-100, HC-600 (above, manufactured by Nippon Graphite Fiber Corporation), SWeNT SG65, SWeNT SGi, IsoNanoTubes-M, IsoNanoTubes-S, PureTubes, Pyrograf PR -25-XT-PS, PR-25XT-LHT (all manufactured by Sigma-Aldrich Co., Ltd.), and the like can be mentioned.

The filler may be used alone or in combination of two or more.

The amount of the filler added is a composition prepared when producing a gas separation membrane containing the polyfunctional polycyclic polymerizable compound, which is used when forming a polymer contained in the gas separation membrane of the present invention. It is preferably 0.01 to 80% by weight, more preferably 0.1 to 50% by weight, based on the total content of the compounds in the mixture.
(Chiral compound)
The composition used when forming the polymer contained in the gas separation membrane of the present invention may contain a chiral compound for the purpose of obtaining a spiral molecular arrangement. The chiral compound itself may or may not have a polymerizable group. Further, the direction of the spiral of the chiral compound can be appropriately selected depending on the intended use of the obtained gas separation membrane.

The chiral compound having a polymerizable group is not particularly limited, and known and commonly used ones can be used, but a chiral compound having a large spiral twisting force (HTP) is preferable. The polymerizable group is preferably a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, an acryloyloxy group, a methacryloyloxy group, a glycidyl group or an oxetanyl group, and an acryloyloxy group, a glycidyl group or an oxetanyl group is particularly preferable.

The blending amount of the chiral compound needs to be appropriately adjusted by the spiral-inducing force of the compound, but the polyfunctional polycyclic polymerizable material used when forming the polymer contained in the gas separation membrane of the present invention. It is preferably contained in an amount of 0.5 to 70% by mass, preferably 1 to 40% by mass, based on the total content of the polymerizable compound in the composition produced when the gas separation film containing the compound is produced. It is more preferable, and it is particularly preferable that the content is 2 to 25% by mass.

Specific examples of the chiral compound include compounds represented by the following general formulas (10-1) to (10-4), but the compound is not limited to the following general formulas.

In the above general formulas (10-1) to (10-4), Sp ^5a and Sp ^5b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group is one or more halogens. It may be substituted with an atom, a CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group existing in this group or two or more CHs not adjacent to each other may be substituted. The _two groups are independent of each other _, and the oxygen atoms do not bond directly to each other. It may be replaced by OCO-, -OCOO-, -SCO-, -COS- or -C≡C-.
In the above general formulas (10-1) to (10-4), A1, A2, A3, A4, A5 and A6 are independently 1,4-phenylene group and 1,4-cyclohexylene group, respectively. 1,4-Cyclohexenyl group, tetrahydropyrrane-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2, 2,2) Octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5 -Diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7- Diyl group, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b'] Dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b'] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7- Represents a diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7-diyl group, where n, l and k are independently 0 or Represents 1 and becomes 0 ≦ n + l + k ≦ 3.
In the above general formulas (10-1) to (10-4), m5 represents 0 or 1, and represents 0 or 1.
In the general formulas (10-1) to (10-4), Z0, Z1, Z2, Z3, Z4, Z5 and Z6 are independently of -COO-, -OCO- and -CH ₂ CH ₂ . -, -OCH _2- , -CH ₂ O-, -CH = CH-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ Represents an alkyl group or single bond that may have a halogen atom of OCO-, -COOCH _{2 CH 2-, -OCOCH 2 CH 2- , -CONH-} , -NHCO-, 2-10 carbon atoms.
In the above general formulas (10-1) to (10-4), R ^5a and R ^5b represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 18 carbon atoms, and the alkyl group. May be substituted with one or more halogen atoms or CN, and one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups are independent of each other and oxygen atoms. -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-,- It may be replaced by COS- or -C≡C-, or R ^5a and R ^5b are given by the general formula (10-a).

(In the formula, P ^5a represents a polymerizable functional group, and Sp ^5a has the same meaning as Sp ^1. )
P ^5a represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).

Further specific examples of the chiral compound include compounds represented by the following general formulas (10-5) to (10-38).

In the above general formulas (10-5) to (10-38), m and n each independently represent an integer of 1 to 10, and R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group. , Represents a fluorine atom, but when there are a plurality of R's, they may be the same or different.

Specific examples of the chiral compound having no polymerizable group include cholesterol pelargonate having a cholesteryl group as a chiral group, cholesterol stearate, and BDH having a 2-methylbutyl group as a chiral group. "CB-15", "C-15", "S-1082" manufactured by Merck, "CM-19", "CM-20", "CM" manufactured by Chisso, 1-methylheptyl group as a chiral group. Examples thereof include "S-811" manufactured by Merck Co., Ltd., "CM-21" manufactured by Chisso Co., Ltd., and "CM-22" manufactured by Chisso.

When a chiral compound is added, it depends on the specific use of the gas separation membrane of the present invention, but the value (d) obtained by dividing the thickness (d) of the obtained gas separation membrane by the spiral pitch (P) in the gas separation membrane. It is preferable to add an amount in which / P) is in the range of 0.1 to 100, and even more preferably, an amount in the range of 0.1 to 20.
(monomer)
The composition used for constituting the polymer contained in the gas separation membrane of the present invention may have one or less ring structures, and a polymerizable compound having a soft segment may be added. As such a compound, usually, any compound recognized as a polymerizable monomer or a polymerizable oligomer can be used without particular limitation. When added, it is contained in a composition prepared for producing a gas separation membrane containing the polyfunctional polycyclic polymerizable compound, which is used when forming a polymer contained in the gas separation membrane of the present invention. It is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total content of the compound.

Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 4-Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate Cyclopentenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxydiethylene glycol (meth) Acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) Methyl (meth) acrylate, o-phenylphenol ethoxy (meth) acrylate, dimethylamino (meth) acrylate, diethylamino (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2 , 3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) Acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodeca Fluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2,2-te Trafluoro-1- (trifluoromethyl) ethyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 2- (meth) ) Acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, iropropyl Mono (meth) acrylates such as acrylamide, diethyl acrylamide, hydroxyethyl acrylamide, N-acryloyloxyethyl hexahydrophthalimide, 1,4-butanediol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates, 1 , 9-Nonandiol di (meth) acrylate, neopentyldiol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) ) Acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, glycerindi (meth) acrylate , 2-Hydroxy-3-acroyloxypropyl methacrylate, acrylic acid adduct of 1,6-hexanediol diglycidyl ether, acrylic acid adduct of 1,4-butanediol diglycidyl ether, etc. Tri (meth) acrylates such as propanetri (meth) acrylate, ethoxylated isocyanuric acid tri-acrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, pentaerythritol tetra ( Tetra (meth) acrylates such as meta) acrylates, ditrimethylolpropane tetra (meth) acrylates, dipentaerythritol hexa (meth) acrylates, oligomer-type (meth) acrylates, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl Acrylate, diethylene glycol diglycy Examples thereof include epoxy compounds such as diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, and bisphenol A diglycidyl ether, and maleimide. These can be used alone or in combination of two or more.
(Orientation material)
The composition used for forming the polymer contained in the gas separation membrane of the present invention can contain an orientation material as necessary in order to improve the molecular arrangement state. The orientation material used may be a known and commonly used material as long as it is soluble in a solvent capable of dissolving the polyfunctional polycyclic polymerizable compound used in the composition used for the gas separation membrane of the present invention. , It can be added within a range that does not significantly deteriorate the orientation. Specifically, in the composition produced when producing the gas separation membrane containing the polyfunctional polycyclic polymerizable compound used when constituting the polymer contained in the gas separation membrane of the present invention. With respect to the total content of the compound, 0.05 to 30% by weight is preferable, 0.5 to 15% by weight is more preferable, and 1 to 10% by weight is particularly preferable.

Specifically, the orientation material is polyimide, polyamide, BCB (penzocyclobutene polymer), polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic. Examples of compounds that photoisomerize or photodimerize, such as resins, coumarin compounds, chalcone compounds, cinnamate compounds, flugide compounds, anthraquinone compounds, azo compounds, and arylethene compounds, are materials that are oriented by ultraviolet irradiation or visible light irradiation. (Photo-alignment material) is preferable.

Examples of the photoalignment material include polyimide having a cyclic cycloalkane, total aromatic polyarylate, polyvinyl cinnamate as shown in JP-A-5-232473, polyvinyl ester of paramethoxycinnamic acid, JP-A-6-. Examples thereof include cinnamate derivatives as shown in JP-A-6-289374, maleimide derivatives as shown in JP-A-2002-265541, and the like. Specifically, compounds represented by the following general formulas (12-1) to (12-9) are preferable.

In the above general formulas (12-1) to ⁽ 12-9), R5 is a hydrogen atom, a halogen atom, an alkyl group having 1 to ³ carbon atoms, an alkoxy group, a nitro group, and R6 is a hydrogen atom or carbon. Although an alkyl group having 1 to 10 atoms is shown, the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. One -CH _2- or two or more non-adjacent -CH _2- in the alkyl group are independently -O-, -S-, -CO-, -COO-, -OCO-, respectively. It may be replaced by -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-, and the terminal CH ₃ is It may be substituted with CF ₃ , CCl ₃ , a cyano group, a nitro group, an isocyano group, or a thioisocyano group. n represents 4 to 100000, and m represents an integer of 1 to 10.

In the general formulas (12-1) to (12-9), R ⁷ is a hydrogen atom, a halogen atom, an alkyl halide group, an allyloxy group, a cyano group, a nitro group, an alkyl group, a hydroxyalkyl group and an alkoxy group. , Carboxy group or alkali metal salt thereof, alkoxycarbonyl group, methoxy halide group, hydroxy group, sulfonyloxy group or alkali metal salt thereof, amino group, carbamoyl group, sulfamoyl group or (meth) acryloyl group, (meth) acryloyloxy. Represents a polymerizable functional group selected from the group consisting of a group, a (meth) acryloylamino group, a vinyl group, a vinyloxy group and a maleimide group.
(Manufacturing method of gas separation membrane / laminate)
(Gas separation membrane / laminate)
The gas separation membrane of the present invention shows a polymer of a composition containing the polyfunctional polycyclic polymerizable compound, or a layer portion made of the polymer.

The laminate of the present invention is a polymer in which an alignment film is used as necessary on a substrate having gas permeability, and a polymer of a composition containing the polyfunctional polycyclic polymerizable compound is sequentially laminated. Alternatively, a polymer of a composition containing the polyfunctional polycyclic polymerizable compound is laminated on a substrate, and a group having gas permeability on the polymer via an adhesive, an adhesive tape, or an adhesive. The base material used for forming the polymer after being bonded to the material is peeled off from the polymer. The base material used when forming the polymer of the composition containing the polyfunctional polycyclic polymerizable compound may or may not have gas permeability, but is not particularly limited. , Polyester, polystyrene, polycarbonate such as glass, metal film, acrylate crosslinked product with regular uneven processing, cycloolefin polymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. from the viewpoint of peelability of the polymer. Etc. are preferable.
(Base material with gas permeability)
As the gas-permeable substrate used for the gas separation membrane or the laminate of the present invention, a known and conventional one can be used as long as it is a gas-permeable inorganic membrane or an organic membrane, and there is no particular limitation. Examples of such a base material include films made of organic materials such as plastics, sheets, hollow fiber membranes, porous membranes, and porous membranes made of inorganic materials such as ceramic base materials.

Specifically, when the base material is an organic material, cellulose derivatives such as diacetyl cellulose, triacetyl cellulose, acetate cellulose, nitrocellulose, low density polyethylene, high density polyethylene, polypropylene, polymethylpentene (TPX), butyl rubber and the like can be used. Polyacrylate such as polyolefin, cycloolefin polymer, polycarbonate, PMMA, polyacrylonitrile, polyacetate, aromatic polyimide, polyimide such as aliphatic polyimide, polyamide, polysulfone, polyether sulfone, polyphenylene sulfide, polyphenylene ether, polyarylate, nylon , Polystyrene, or silicone rubber, and the like.

When the base material is an inorganic material, examples thereof include zeolite, silica-based ceramics, silica-based glass, alumina-based ceramics, stainless porous body, titanium porous body, and silver porous body.

Of these, plastic substrates such as polyolefin, polymethylpentene (TPX), cellulose derivatives, polyimide, and polyacrylate are preferable.

The shape of the base material having gas permeability may be a flat plate shape, a cylindrical shape, or a curved surface shape. In the case of a flat base material such as a film or a sheet, even if the base material is an asymmetric type in which one side of the base material is a dense layer and the other side is a porous layer, a symmetrical type in which both sides of the base material are dense layers. However, it may be a symmetrical type in which both sides of the base material are porous layers. In the case of a cylindrical substrate such as a hollow fiber membrane, whether it is an asymmetric type consisting of a dense layer on the outside and a porous layer on the inside, or a symmetrical type in which both the outside and the inside are dense layers, the outside. , It may be a symmetrical type in which both the inside and the inside are porous layers. Further, the base material may be optically transparent or opaque, may be formed by a melting method, may be formed by a solution casting method, or may be unstretched or uniaxially stretched. It may be biaxially stretched.

When the gas separation membrane of the present invention is used as a laminate, the film thickness of the base material having gas permeability is preferably 1 to 100 μm from the viewpoint of gas permeability, productivity, and processability into a module, preferably 4 to 80 μm. More preferably, 10 to 50 μm is particularly preferable.

In order to improve the coatability and adhesiveness of the composition used for forming the polymer contained in the gas separation membrane of the present invention to the gas-permeable substrate, these gas-permeable substrates The surface treatment may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment.
(Orientation processing)
Further, the polymerizable composition is oriented when the solution of the composition used for forming the polymer contained in the gas separation membrane of the present invention is applied and dried on the base material having gas permeability. Or is usually subjected to an alignment treatment, or may be provided with an alignment film. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet-visible light irradiation treatment, ion beam treatment, oblique vapor deposition treatment of SiO ₂ on a substrate, and the like. When an alignment film is used, a known and commonly used alignment film is used. Examples of such an alignment film include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, and coumarin. Examples thereof include compounds such as compounds, chalcone compounds, cinnamate compounds, flugide compounds, anthraquinone compounds, azo compounds and arylethene compounds, and polymers and copolymers of the above compounds. As the compound to be oriented by rubbing, it is preferable that the compound is oriented or the crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds to be subjected to alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
(Application)
The coating method for obtaining the gas separation membrane of the present invention includes an applicator method, a bar coating method, a spin coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, a flexographic coating method, an inkjet method, and a die coating method. , A known and commonly used method such as a cap coating method, a dip coating method, and a slit coating method can be used.

It is preferable that the molecule of the polymerizable compound in the polymerizable composition used for producing the gas separation membrane of the present invention retains a molecular arrangement of one axis or more after coating. Specifically, it is preferable to perform a heat treatment that promotes the molecular arrangement because the molecular arrangement state of one axis or more can be further promoted. As a heat treatment method, for example, the polymerizable composition used for producing the gas separation membrane of the present invention is applied onto a substrate, the composition is made into a liquid state, and then slowly cooled as necessary. It forms a molecular arrangement state with one or more axes. At this time, it is preferable to keep the temperature constant and form a uniform molecular arrangement state. Alternatively, after the polymerizable composition used for producing the gas separation membrane of the present invention is applied onto a substrate, the temperature is set within a temperature range in which each molecule in the composition forms a molecular arrangement state of one axis or more. It may be heat-treated to keep it for a certain period of time. If the heating temperature is too high, the composition may undergo an unfavorable polymerization reaction and deteriorate. Further, if it is cooled too much, each molecule in the composition may undergo phase separation or crystals may precipitate, and the molecular arrangement state may be disturbed.

By performing the heat treatment in this way, it is possible to obtain a homogeneous gas separation membrane having a uniform molecular arrangement state and few defects as compared with a coating method in which the coating method is simply applied.

Specifically, in order to obtain a polymer having no repellent or pinholes of the polymerizable liquid crystal compound by various coating methods, after applying a solution containing the polymerizable liquid crystal compound having a low solid content concentration of 20% by weight or less, the polymer is applied. The temperature within which the polymerizable liquid crystal composition exhibits a liquid crystal phase is 120 ° C. or lower (step 1), and the temperature is equal to or lower than the solvent drying temperature and the polymerizable liquid crystal composition exhibits a liquid crystal phase. A method of orienting the polymer at a temperature within the range of room temperature or higher (step 2) and then irradiating with UV at the same temperature or lower as step 2 (step 3) to obtain a homogeneous polymer having a uniform molecular arrangement and few defects. preferable.
(Polymerization process)
Examples of the method for polymerizing the polymerizable composition used for producing the permeable film having gas selectivity of the present invention include a method of irradiating with active energy rays and a thermal polymerization method, but they do not require heating and do not require heating. Since the reaction proceeds at room temperature, the method of irradiating with active energy rays is preferable, and above all, the method of irradiating with light such as ultraviolet rays is preferable because the operation is simple.

Specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable composition is decomposed by ultraviolet light of 390 nm or less, it may be preferable to carry out the polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and is preferably unpolarized light. The ultraviolet irradiation intensity is preferably in the range of 0.05 kW / m ² to 10 kW / m ² . In particular, the range of 0.2 kW / m ² to 2 kW / m ² is preferable. When the ultraviolet intensity is less than 0.05 kW / m ² , it takes a long time to complete the polymerization. On the other hand, when the intensity exceeds 2 kW / m ² , the molecules in the polymerizable composition tend to be photodecomposed, and a large amount of heat of polymerization is generated to raise the temperature during polymerization, so that the order parameters of the molecules change. As a result, the gas permeability and gas selectivity of the permeable film having gas selectivity after polymerization may be disturbed.

Further, after polymerizing only a specific portion by irradiation with ultraviolet rays using a mask, the molecular arrangement state of the unpolymerized portion is changed by applying an electric field, a magnetic field, a temperature, or the like, and then the unpolymerized portion is polymerized. And, it is also possible to obtain a permeable film having gas selectivity having a plurality of regions having different molecular arrangement directions.

The temperature at the time of irradiation with ultraviolet light is a temperature at which the polymerizable composition used for producing the gas-selective permeable film of the present invention can maintain a molecular arrangement state of one axis or more, and the heat of the polymerizable composition is set. In order to avoid the induction of polymerization, the temperature is preferably 60 ° C. or lower as much as possible.

The permeable film having gas selectivity of the present invention can be used alone as a permeable film having gas selectivity by peeling from the substrate having gas permeability, without peeling from the substrate having gas permeability. It can also be used as it is as a laminated body having gas permeability and gas selectivity. Further, when the permeable film having gas selectivity of the present invention is bonded to a substrate having gas permeability via an adhesive, an adhesive tape, or an adhesive, the permeable film having gas selectivity of the present invention is used. Even if the transparent film having gas selectivity of the present invention is attached to the substrate having gas permeability, the permeable film is attached to the permeable film even if the transparent film is attached after being peeled off from the substrate used for producing the permeable film. It may be peeled off from the base material used in the production. When a pressure-sensitive adhesive, a pressure-sensitive adhesive tape, or an adhesive is used, a known and commonly used pressure-sensitive adhesive, a pressure-sensitive adhesive tape, or an adhesive can be used. When an adhesive tape is used, a substrate-free adhesive tape in which a substrate such as PET or cellulose is not contained in the center of the adhesive tape in order to maintain gas permeability is preferable. When an adhesive is used, either a heat-bonding adhesive or a light-bonding adhesive can be used as long as the gas permeability and gas selectivity of the gas separation membrane of the present invention are not impaired.
(Gas selectivity module)
The gas separation membrane or laminate of the present invention can be modularized and suitably used. Further, the gas separation membrane, laminate, or gas selectivity module of the present invention can be used to obtain a gas separation device having gas separation / recovery and separation / purification ability. The module having gas selectivity is not limited as long as it has the ability to separate gas and liquid, and examples thereof include a spiral type, a hollow fiber type, a bleeds type, and a tubular type (tube type). In the present invention, a spiral type or a hollow fiber type is preferable from the viewpoint of processability and productivity. Specifically, as such a hollow fiber type module, a gas separation membrane is formed in the shape of a hollow fiber, and a plurality of the hollow fibers are arranged in a container, and one of the inside of the hollow fiber and the outside of the hollow fiber is provided. A gas separation module characterized in that one communicates with a mixed gas or dissolved gas supply port and the other communicates with a separated gas discharge port.

Hereinafter, some of the best embodiments of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are based on mass.
(Preparation of Solution (1) Used for Gas Separation Membrane of the Present Invention)
43 parts of the compound represented by the formula (A-1), 43 parts of the compound represented by the formula (A-2), 14 parts of the compound represented by the formula (B-1), and the formula (D-1). 5.0 parts of the compound represented, 0.1 part of the compound represented by the formula (E-1), and 0.05 part of the surfactant Megafuck F-554 (manufactured by DIC Co., Ltd.) are propylene glycol. The gas of the present invention is filtered through a 0.2 μm membrane filter after stirring for 1 hour under the conditions of a stirring speed of 500 rpm and a solution temperature of 70 ° C. using a stirring device having a stirring propeller in 300 parts of monomethyl ether acetate. The solution (1) used for the separation membrane was obtained.
(Preparation of solutions (2) to (15) used for the gas separation membrane of the present invention)
Similar to the preparation of the solution (1) used for the gas separation membrane of the present invention, the formulas (A-1) to (A-11) and the formulas (B-1) to (B-7) shown in Table 1 are prepared. Compounds represented by formulas (C-1) to (C-9), compounds represented by formulas (D-1) to (D-3), formulas (E-1), and surfactants. Using a stirring device having a stirring propeller in the organic solvent represented by the formulas (H-1) to (H-3), the compound represented by the formula (F-1) is used at a stirring speed of 500 rpm and a solution temperature of 500 rpm. After stirring for 1 hour under the condition of 70 ° C., the mixture was filtered through a 0.2 μm membrane filter to obtain solutions (2) to (15) used for the gas separation membrane of the present invention.

Tables 1 and 2 show specific compositions of the solutions (1) to (15) of the present invention.

Irga Cure 907 (D-1)
Irga Cure OXE01 (D-2)
Irga Cure 819 (D-3)
p-Methoxyphenol (E-1)
Mega Fuck F-554 (F-1)
Methyl isobutyl ketone (abbreviation; MIBK) (H-1)
Toluene (abbreviation; TOR) (H-2)
Cyclopentanone (abbreviation; CPN) (H-3)

(Example 1)
(Measurement of phase transition temperature)
The solution (1) was applied onto a glass substrate with a spin coater and then dried at 100 ° C. for 2 minutes to obtain a sample (1) for measuring the phase transition temperature. The sample (1) for measuring the phase transition temperature is the solution (1) from which the solvent has been removed. When the phase transition temperature of this sample (1) was measured using a polarizing microscope, the NI (nematic-isotropic) transition temperature measured under the temperature rising condition was 65 ° C., and the N-I measured under the temperature falling condition. The Sm (nematic-smetic) transition temperature was 30 ° C.
(Preparation of Polymer 1)
A silane coupling-based vertical alignment film formed on a glass substrate was used as a substrate, and the solution (1) was applied onto the substrate with a spin coater and then dried at 60 ° C. for 2 minutes. Then, after leaving it at 25 ° C. for 5 minutes, UV light was irradiated at 25 ° C. using an ultra-high pressure mercury lamp under a nitrogen atmosphere so that the integrated light amount was 1000 mJ / cm ² , and the entire film was free of cissing. Polymer 1 was obtained. The thickness of the polymer 1 functioning as a gas separation membrane was 0.5 μm as measured using DEKTAK XT (manufactured by Bruker Corporation).
(Small-angle X-ray scattering measurement)
Using the beamline BL03XU 1st hatch owned by the Frontier Soft Matter Development Industry-Academia Union in the high-intensity radiation experimental facility SPring8, the measurement mode is oblique incident small angle / wide angle X-ray scattering method (Grazing Incidence Small Angle X-ray). Scattering: GISAXS / Grazing Industry Wide X-ray Scattering: GIWAXS), camera length 2.3 m / 0.14 m, wavelength 0.1 nm, X-ray incident angle 0.12 °, exposure time 1-5 seconds, room temperature The above polymer 1 was measured under the conditions of measurement and scattering angle range 2θ = 0.2 to 25 °. As for the incident direction of the X-rays, the X-rays were incident in the horizontal direction with respect to the X direction, with any one side direction of the glass substrate on which the polymer 1 was formed as the X direction.
The two-dimensional X-ray diffraction scattering image obtained from the GISAXS measurement is shown in FIG. 7, and the scattering / diffraction intensity I on a straight line in the vertical upward direction when viewed from the beam center of the diffraction scattering image is taken with respect to the scattering angle 2θ from the reflection beam center. FIG. 8 shows a one-dimensional scattering spectrum V as the scattering intensity I. From FIG. 7, a strong peak was observed in the y direction from the center of the beam, whereas a strong peak was not observed in the x direction, but the peaks of [1] and [2] were confirmed, and the sample surface was confirmed. It was confirmed that the layer was formed in the horizontal direction.
Further, in FIG. 9, the two-dimensional X-ray diffraction scattering image obtained by GIWAXS is taken as the scattering / diffraction intensity I on a straight line in the horizontal direction when viewed from the beam center of the diffraction scattering image, and the scattering angle 2θ from the reflection beam center is taken. FIG. 10 shows a one-dimensional scattering spectrum H as the scattering intensity I, and FIG. 11 shows a scattering intensity distribution in the azimuth angle direction.
From these characteristics, it was confirmed that the polymer 1 had molecules standing perpendicular to the surface of the film and had a layered structure in the horizontal direction.
From the GIWAXS measurement of the polymer 1, the maximum peak of the scattering angle 2θ in the direction perpendicular to the X direction is 13 °, and the scattering angle 2θ is integrated in the range of 5 ° around the peak, and the azimuth angle of the scattering profile is 5 °. The total value (azimuth angle width) of the azimuths indicating more than half of the integrated value in the range of about 175 ° was 30 °.
(Preparation of laminated body 1)
Sylgard 184 (manufactured by Dow Corning; main agent / curing agent = 10/1 mixed solution) was applied onto a glass substrate with an applicator, cured at 100 ° C. for 30 minutes, and then peeled off from the glass substrate to form 50 micron polydimethyl. A siloxane (PDMS) film was obtained. The polymer 1 that functions as the gas separation membrane obtained above was peeled off from the glass substrate and laminated on the PDMS film to prepare the laminated body 1.
(Measurement of gas permeability and evaluation of separation performance)
Using the laminate 1 obtained by the above method, the gas permeability of CO ₂ and CH ₄ is measured using a gas permeability measuring device (GTR-31A: manufactured by GTR Tech) under the conditions of a pressure of 150 kPa and a temperature of 40 ° C. The permeation coefficient of each gas was obtained.

The permeation flux of each gas was obtained by dividing the obtained permeation coefficient by the film thickness. Next, the permeation flux of the permeation membrane of the example was obtained using the formula (1). Further, the gas separation performance of the permeation membrane was obtained by determining the ratio of the permeation flux of each gas.
Q (permeable membrane) = {Q (laminated body) x Q (base material)} / {Q (base material) -Q (laminated body)} Equation (1)
(In the equation, Q represents the gas permeation flux of each layer.)
The permeation flux of CO ₂ and CH ₄ of the permeation membrane was 1.30 GPU for Q _CO2 (permeate membrane) and 0.06 GPU for Q _{CH 4} (permeate membrane). Separation performance Q _CO2 (permeate membrane) / Q _CH4 (permeate membrane) was 21.7.
(Examples 2 to 17)
(Measurement of phase transition temperature of solutions 2 to 15)
The solution used for producing the gas separation membrane of the present invention was measured under the same conditions as the phase transition temperature measurement of the solution (1) except that the solution was changed to the solutions (2) to (7).
(Preparation of Polymer 2 to Polymer 7)
Under the same conditions as the method for producing the polymer 1 except that the solution used for producing the gas separation membrane of the present invention was changed to the solutions (2) to (7), the molecule was 1 in the direction perpendicular to the membrane surface. Polymers 2 to 7 polymerized in a state of being arranged on the shaft were obtained.
(Preparation of polymer 8)
After applying the solution (8) with a bar coater in order to prepare the gas separation membrane of the present invention on a PET film which is a substrate having a thickness of 50 μm and has been rubbed at an angle of 45 ° with respect to the MD direction of the film. It was dried at 80 ° C. for 2 minutes. Then, after leaving it at room temperature for 2 minutes, it is irradiated with UV light using an ultra-high pressure mercury lamp so that the integrated light amount becomes 500 mJ / cm ² in a nitrogen atmosphere, and the molecules are 1 in the horizontal direction with respect to the film surface. A laminate 8 containing a polymer polymerized in a state of being arranged on the shaft was obtained (FIG. 1).
(Preparation of Polymer 9 to Polymer 15)
The solution (8) used for producing the gas separation membrane of the present invention was changed to the solutions (9) to (15), but under the same conditions as the method for producing the polymer 8, in the horizontal direction with respect to the membrane surface. Polymers 9 to 15 polymerized with the molecules arranged on one axis were obtained.
(Preparation of polymer 16)
The polymer 16 was polymerized under the same conditions as the method for producing the polymer 1 except that the spin coating conditions of the solution (1) were changed, in which the molecules were arranged uniaxially in the direction perpendicular to the film surface.
(Preparation of polymer 17)
The solution used to prepare the gas separation membrane of the present invention was changed to the solution (3), and the spin coating conditions of the solution (3) were changed. On the other hand, a polymer 17 polymerized with the molecules arranged in one axis in the vertical direction was obtained.

Polymers 2 to 7 and polymers 17 to 18 were subjected to oblique incident X-ray scattering measurement under the same conditions as polymer 1. In the polymers 8 to 16, the major axis direction of the molecular arrangement was the X direction, and X-rays were incident in the horizontal direction with respect to the X direction.

The azimuth angle width at which the scattering intensity of the polymers 2 to 18 is at least half the value was calculated by X-ray profile analysis in the same manner as in the polymer 1.

Laminates 2 to 18 were prepared in the same manner as in the laminate 1, and the gas permeability of CO ₂ and CH ₄ was measured and the separation performance was evaluated.
(Comparative Example 1)
Obliquely incident X-ray measurements (GIWAXS) of a 25 micron optically isotropic polymethylmethacrylate (PMMA) film showed a broad halo-like diffraction pattern with no clear molecular arrangement. The permeability coefficients of carbon dioxide and methane of this PMMA film were evaluated using GTR-11A under the same conditions as in Example 1.
Table 3 shows the phase transition temperature, solvent drying temperature, orientation temperature, UV irradiation temperature, and film thickness of Examples 1 to 17. Table 4 shows the total value, gas permeability, and separation performance of the azimuth angles of Examples 1 to 17 and Comparative Example 1.

From Table 4 above, it was found that the gas selective permeability membrane of the present invention has a regular molecular arrangement, and therefore has high permeability and high gas selective performance. On the other hand, since the PMMA film shown in Comparative Example 1 does not have a regular molecular arrangement, a high gas selective permeable membrane could not be obtained.

Further, since the gas selective permeation film of the present invention has high gas selective performance, it can be laminated with a base material having high gas permeation performance to form a laminated body, and high gas selective performance is added to the base material used. It can be a laminated body, and can be used for various gas selection applications and as a gas selective transmission film module.

Claims (12)

A gas separation membrane containing a polymer optically aligned on one or more axes using at least one polymerizable liquid crystal compound, wherein the polymer is a scattering profile obtained by a oblique incident X-ray scattering measurement method. In, the scattering angle 2θ has a maximum peak in the range of 5 to 15 °, the scattering angle 2θ is integrated in the range of 5 ° around the peak, and the integrated value in the range of 5 to 175 ° in the azimuth angle of the scattering profile. A gas separation film characterized in that the width of an azimuth angle indicating a half value or more (the total of two or more of the maximum peaks) is in the range of 30 to 108 °. The gas according to claim 1, wherein the major axis direction of the molecular arrangement having one or more axes of the polymer is horizontal with respect to both sides of the film surface or perpendicular to both sides of the film. Separation membrane. Claim 1 is characterized in that the major axis direction of the molecular arrangement having one or more axes of the polymer is horizontal with respect to both sides of the film surface and is spiral in the thickness direction of the film. The gas separation membrane according to. The first aspect of claim 1, wherein the major axis direction of the molecular arrangement having one or more axes of the polymer is horizontal to one membrane surface and perpendicular to the other membrane surface. Gas separation membrane. The gas separation membrane according to claim 1, wherein the polymerizable liquid crystal compound is a compound having a hard segment having three or more ring structures. The following general formula (1), wherein the polymerizable liquid crystal compound has at least two or more polymerizable groups.

(In the formula, Sf ¹ and Sf ² are independently single-bonded or alkylene groups having 1 to 18 carbon atoms (one or two or more hydrogen atoms bonded to the alkylene group are independently halogen atoms, respectively). , CN group, alkyl group having 1 to 8 carbon atoms, or alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH 2 group or one CH ₂ group present in this group or _Two or more CHs that are not adjacent to each other are independent of each other _, and the oxygen atoms do not directly bond to each other. -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH -Or-may be replaced by C≡C-), but when there are a plurality of Sf ¹ and Sf ² , they may be the same or different, and P ¹ and P ² are Each of them independently represents a polymerizable group, but when a plurality of P ¹ and P ² are present, they may be the same or different, and HD has hard segments having three or more ring structures, n1 and. Although n2 independently represents an integer of 0 to 3, the bond on HD when either n1 or n2 is 0 is bonded to a hydrogen atom, and also represents n1 + n2 ≧ 1.) The gas separation membrane according to any one of claims 1 to 5, which is a compound represented by. As the polymerizable liquid crystal compound, the following general formula (1-a-1)

(In the formula, P ¹¹ and P ¹² represent polymerizable groups, and
S ¹¹ and S ¹² each independently represent a spacer group or a single bond, and the spacer group represents an alkylene group having 1 to 18 carbon atoms, and one or more hydrogens bonded to the alkylene group. Each atom may be independently substituted with a halogen atom, a CN group, an alkyl group having 1 to 8 carbon atoms, or an alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and this group may be substituted. One CH ₂ group existing in the group or two or more CH ₂ groups not adjacent to each other are independent of each other, and oxygen atoms do not directly bond to each other, and -O-, -S-, and -NH. -, -N (CH ₃ )-, -CO-, -CH (OH)-, -CH (COOH)-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C May be replaced by ≡ C-
X ¹¹ and X ¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S- CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S- , -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO- CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO -, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond.
A ¹¹ , A ¹² and M ¹¹ are independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, naphthalene-2, respectively. It represents a 6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group. , These groups may be unsubstituted or substituted with one or more substituents.
Z ¹¹ and Z ¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH- COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = Represents N-, -CH = N-, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond.
n11 and n12 each independently represent an integer of 0 to 6, j11 and j12 each independently represent an integer of 0 to 5, while j11 + j12 represent an integer of 2 to 7. )
And the compound represented by
The following general formula (3-1)

(In the formula, P ³¹¹ represents a polymerizable group and represents
S ³¹¹ and S ³¹² each independently represent a spacer group or a single bond, and the spacer group represents an alkylene group having 1 to 18 carbon atoms, and one or more hydrogens bonded to the alkylene group. Each atom may be independently substituted with a halogen atom, a CN group, an alkyl group having 1 to 8 carbon atoms, or an alkylene group having 1 to 8 carbon atoms having a polymerizable functional group, and this group may be substituted. One CH ₂ group existing in the group or two or more CH ₂ groups not adjacent to each other are independent of each other, and oxygen atoms do not directly bond to each other, and -O-, -S-, and -NH. -, -N (CH ₃ )-, -CO-, -CH (OH)-, -CH (COOH)-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C May be replaced by ≡ C-
X ³¹¹ and X ³¹¹ are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S- CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S- , -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO- CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO -, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond.
A ³¹¹ to A ³¹² and M ³¹¹ are independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, naphthalene-, respectively. 2,6-Diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group As represented, these groups may be unsubstituted or substituted with one or more substituents.
Z ³¹¹ to Z ³¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH- COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = Represents N-, -CH = N-, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond.
The terminal group R ³¹¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one -CH _2- . Or two or more non-adjacent -CH ₂ -s are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-. Any hydrogen atom in the alkyl group may be replaced with a fluorine atom.
n31 independently represents an integer from 0 to 6, respectively.
j311 and j312 independently represent integers from 0 to 5, while j311 + j312 represent integers from 2 to 7. )
The gas separation membrane according to any one of claims 1 to 6, which is used in combination with the compound represented by. The gas separation membrane according to any one of claims 1 to 7, wherein the membrane thickness is 0.005 μm or more and 50 μm or less. Has the ability to separate two or more mixed or dissolved gases selected from hydrogen, helium, methane, carbon monoxide, carbon dioxide, nitrogen, oxygen, ethane, ethylene, propane, propylene, butane, and hydrogen sulfide. The gas separation membrane according to any one of claims 1 to 8. A laminate in which the gas separation membrane according to any one of claims 1 to 9 is laminated on a gas permeable substrate. The gas permeable substrate may be any of a planar film, a porous film, and a hollow fiber membrane selected from polyethylene glycol, polypropylene glycol, polyvinyl acetate, polydimethylsiloxane, polyimide, polyethylene, polypropylene, polymethylpentene, and polyurethane. The laminate according to claim 10. The gas separation membrane according to any one of claims 1 to 9 is formed in the shape of a hollow fiber, and a plurality of the hollow fibers are arranged in a container, and one of the inside of the hollow fiber and the outside of the hollow fiber is mixed. A gas separation module characterized in that it communicates with a gas or dissolved gas supply port and the other with a separated gas discharge port.

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