JP2018167139A - Gas separation membrane - Google Patents

Abstract

To provide a gas separation membrane that has high permeability coefficient of a gas component and a high separation coefficient of a gas component and is excellent in tolerance to a liquid chemical substance, namely, plasticization resistance by condensation component.SOLUTION: A gas separation membrane includes a curable urethane resin and a zeolite.SELECTED DRAWING: None

Description

  The present invention relates to a gas separation membrane, a gas separation method, a gas separation module, and a gas separation device.

  In any industry, the technique of separating compounds from mixtures containing various compounds is very important. A technique for separating a gas component as a separation target has been used for a long time, and examples thereof include a distillation method, a cryogenic separation method, an adsorption separation method, and a membrane separation method. Among these, the membrane separation method is in principle the most energy efficient method, and due to the recent trend of energy saving in recent years, further technological development is expected in the future.

  Gas separation membranes have been commercialized so far in hydrogen separation, carbon dioxide separation, air separation, air dehumidification, separation of volatile organic compounds from air, and the like. In these gas separation membranes, cellulose acetate resin, polyimide resin, silicone resin, thermoplastic urethane resin or the like is used.

Urethane resins have a hard segment and a soft segment, and various developments have been made because the characteristics as gas separation membranes differ greatly depending on the compound used in each segment. However, as with other resins, the trace component contained in the gas component may deteriorate the characteristics as a gas separation membrane, or may be plasticized by a condensed component.
For example, Non-Patent Document 1 and Patent Document 1 disclose a method of suppressing deterioration in characteristics of a gas separation membrane due to a condensed component by using a urethane resin having a three-dimensional structure.

Moreover, as a general characteristic of a gas separation membrane using a resin, as shown in Non-Patent Document 2, the gas permeability coefficient and the separation coefficient are in a trade-off relationship. Therefore, even now, development aimed at improving both the transmission coefficient and the separation coefficient is being carried out.
Non-Patent Documents 3 and 4 include zeolites called ZSM-5, 3A, 4A, and heat for the purpose of improving the gas permeability coefficient and selectivity at the same time as compared with gas separation membranes made only of thermoplastic urethane resin. It has been reported that gas separation membranes containing plastic urethane resins have been studied.

J. et al. Mater. Chem. A 2016, 4, 17431-17439. J. et al. Membr. Sci. 2008, 320, 390-400. J. et al. Nat. GasSci. Technol. 2016, 695-702. Adv. Polym. Technol. 2016, AheadofPrint. (DOI: 10.1002 / adv. 21672)

Special table 2016-536119

  In Non-Patent Document 1, a thermoplastic urethane resin having a functional group (C (= O) Cl) in the side chain is reacted with a diol compound having two hydroxyl groups or a diamine compound having two amino groups. Discloses a gas separation membrane containing a urethane resin having a three-dimensional structure. Non-Patent Document 1 shows that a thermoplastic urethane resin is plasticized by carbon dioxide, which is a condensing component, but plasticization is suppressed by using a urethane resin having a three-dimensional structure. . Furthermore, Non-Patent Document 1 also shows that the urethane resin having a three-dimensional structure has high plasticization resistance because of its high resistance to organic solvents. However, since the urethane resin has a three-dimensional structure, the permeability coefficient of the gas component of the urethane resin is greatly reduced. In addition, the thermoplastic urethane resin in Non-Patent Document 1 is a characteristic that is still far from the UpperBound shown in Non-Patent Document 2, and may increase the gas component permeability coefficient and the gas component separation coefficient. It has been demanded.

  Patent Document 1 discloses a crosslinked rubber which is a gas separation membrane having a three-dimensional structure formed by reacting a compound having a specific structure having four hydroxyl groups with a polyether compound having two isocyanate groups at its ends. A shaped polyurethane-ether membrane is shown. Patent Document 1 discloses the possibility of suppressing the deterioration of the characteristics of the gas separation membrane due to the condensed components by including a three-dimensional structure in the gas separation membrane. Moreover, although patent document 1 does not show what the liquid chemical substance is, it is said that the crosslinked rubber-like polyurethane-ether film has high resistance to the liquid chemical substance. However, the crosslinked rubber-like polyurethane-ether membrane shown in Patent Document 1 is still a characteristic that is different from the UpperBound shown in Non-Patent Document 2, and the gas component permeability coefficient and gas component separation coefficient are more It is required to be high.

  Non-Patent Document 3 discloses a gas separation membrane containing a zeolite called ZSM-5 and a thermoplastic urethane resin composed of diphenylmethane diisocyanate and polyester / polyether. By using ZSM-5, the permeability coefficient of the gas component and the separation coefficient of the gas component are improved, but the characteristics are still far from the UpperBound shown in Non-Patent Document 2, the permeability coefficient of the gas component, and There is a demand for a higher separation factor of gas components. Further, although Non-Patent Document 3 does not describe plasticization by a condensed component, in view of Non-Patent Document 1, there is a possibility that the thermoplastic urethane resin contained in the gas separation membrane is plasticized by the condensed component.

  Non-Patent Document 4 discloses a gas separation membrane containing a thermoplastic urethane / urea composed of zeolite called ZSM-5, 3A, 4A, toluene diisocyanate, poly (propylene glycol), and 1,4-butanediamine. Is disclosed. Even if any zeolite is used, the permeability coefficient of the gas component and the separation coefficient of the gas component are improved, but the characteristics are still far from the UpperBound shown in Non-Patent Document 2, the permeability coefficient of the gas component, Further, there is a demand for a higher separation factor of gas components. Moreover, although there is no description regarding the plasticization by a condensation component in the nonpatent literature 4, if the nonpatent literature 1 is considered, there exists a possibility that the thermoplastic urethane resin contained in a gas separation membrane may be plasticized by a condensation component.

  The present invention has been made in view of the above circumstances, and provides a gas separation membrane that has a high gas component permeability coefficient and gas component separation coefficient, and is excellent in resistance to liquid chemical substances, that is, plasticizing resistance due to condensed components. For the purpose.

As a result of intensive studies on such problems, the inventor of the present invention has a gas separation membrane containing a curable urethane resin and zeolite having a high gas component permeability coefficient and gas component separation coefficient, resistance to liquid chemicals, In other words, the present inventors have found that it has excellent plasticization resistance due to high condensation components, and has completed the present invention.
That is, the present invention is as follows.

[1]
A gas separation membrane comprising a curable urethane resin and zeolite.
[2]
The gas separation membrane according to [1], wherein the zeolite has at least one kind of pores selected from the group consisting of pores composed of oxygen 8-membered rings to oxygen 12-membered rings.
[3]
The gas separation membrane according to [1] or [2], wherein the curable urethane resin has at least one structure selected from the group consisting of a polycarbonate structure, a polyether structure, a polyester structure, and a polycaprolactone structure.
[4]
The curable urethane resin has at least one structure selected from the group consisting of an isocyanurate structure, a biuret structure, an adduct structure, a polynuclear structure, an allophanate structure, and a urea structure, according to any one of [1] to [3]. Gas separation membrane.
[5]
Curable urethane resin
A polyol compound having at least one structure selected from the group consisting of a polycarbonate structure, a polyether structure, a polyester structure, a polycaprolactone structure, and two or more hydroxyl groups;
A polyisocyanate compound having at least one structure selected from the group consisting of an isocyanurate structure, a biuret structure, an adduct structure, a polynuclear structure, an allophanate structure and a urea structure, and three or more isocyanate groups;
The gas separation membrane according to any one of [1] to [4], which is a resin obtained by curing a curable urethane resin composition including
[6]
Curable urethane resin
A polyol compound having at least one structure selected from the group consisting of a polycarbonate structure, a polyether structure, a polyester structure, a polycaprolactone structure, and three or more hydroxyl groups;
Isocyanurate structure, biuret structure, adduct structure, polynuclear structure, allophanate structure, at least one structure selected from the group consisting of urea structures, and a polyisocyanate compound having two or more isocyanate groups, or a diisocyanate compound,
The gas separation membrane according to any one of [1] to [4], which is a resin obtained by curing a curable urethane resin composition including
[7]
A gas separation method comprising a step of bringing a gas mixture comprising two or more gas components into contact with the gas separation membrane according to any one of [1] to [6] and separating the gas mixture.
[8]
The gas mixture is helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, normal butane, isobutane, 1-butene, 2-butene, isobutene, pentane, pentene, cyclopentanediene, hexane. [7] comprising at least two gas components selected from the group consisting of hexene, hexadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene, sulfur hexafluoride, carbon monoxide, nitric oxide, water and hydrogen sulfide. The gas separation method described.
[9]
A module for gas separation including the gas separation membrane according to any one of [1] to [6].
[10]
A gas separation device comprising the gas separation membrane according to any one of [1] to [6] or the gas separation module according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the gas separation membrane with the high permeability | transmittance coefficient of a gas component and the separation factor of a gas component and excellent in the tolerance with respect to a liquid chemical substance, ie, the plasticization tolerance by a condensed component, is provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

<Gas separation membrane>
The gas separation membrane of this embodiment contains a curable urethane resin and zeolite.

(Curable urethane resin)
The curable urethane resin in the present embodiment is a curable urethane resin composition containing a polyol compound having two or more hydroxyl groups and a polyisocyanate compound having three or more isocyanate groups, or a polyol having three or more hydroxyl groups. It is a resin that can be obtained by polymerizing a curable urethane resin composition containing a compound and a polyisocyanate compound having two or more isocyanate groups by heat and / or light.
It should be noted that a three-dimensional structure or a network structure is formed from a curable urethane resin composition by bond formation including urethane bond formation between an isocyanate group and a hydroxyl group by heat and / or light. In the embodiment, it is called polymerization.
The curable urethane resin composition may also contain an isocyanate compound polymerization initiator. An isocyanate compound polymerization initiator is a compound that promotes the formation of a three-dimensional structure or network structure by generating a urethane bond between an isocyanate group and a hydroxyl group by heat and / or light. .

  Examples of the polyisocyanate compound include a diisocyanate compound, a polyfunctional isocyanate compound having an isocyanurate structure, a polyfunctional isocyanate compound having a biuret structure, a polyfunctional isocyanate compound having an adduct structure, a polyfunctional isocyanate compound having a polynuclear structure, and alpha. Examples thereof include polyfunctional isocyanate compounds having an nate structure and polyfunctional isocyanate compounds having a urea structure. These may be used alone or in combination of two or more. As a polyisocyanate compound, a polyfunctional isocyanate compound having an isocyanurate structure, a polyfunctional isocyanate compound having a biuret structure, a polyfunctional isocyanate compound having an adduct structure, a polyfunctional isocyanate compound having a polynuclear structure, a polyfunctional isocyanate having an alphanate structure When at least one of a compound and a polyfunctional isocyanate compound having a urea structure is used, the curable urethane resin in the present embodiment is selected from the group consisting of an isocyanurate structure, a biuret structure, an adduct structure, a polynuclear structure, an allophanate structure, and a urea structure. It has at least one structure selected.

  When a polyfunctional isocyanate compound is used as the polyisocyanate compound, a polyfunctional isocyanate compound having an isocyanurate structure and a polyfunctional isocyanate compound having a biuret structure are preferred. The reason is not clear, but it originates from the isocyanurate structure and biuret structure, and by forming a specific three-dimensional structure, the permeability coefficient of gas components and the separation coefficient of gas components tend to be improved. From the same viewpoint, a polyfunctional isocyanate compound having an isocyanurate structure is more preferable.

(Diisocyanate compound)
The diisocyanate compound is not particularly limited as long as it has two isocyanate groups and is generally used. For example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexa Aliphatic diisocyanates such as methylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer isocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1- Methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate And alicyclic diisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane; xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5- Naphthylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate And an aromatic diisocyanate such as m-tetramethylxylylene diisocyanate; a dimer of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. A diisocyanate compound having an allophanate structure using at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; and an aliphatic group. A diisocyanate compound having a urea structure using at least one diisocyanate selected from the group consisting of diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates And the like.

  The diisocyanate compound can also be obtained by reacting a diisocyanate compound with a diol compound having two hydroxyl groups. Examples of the diol compound having two hydroxyl groups include a non-polymerized diol compound and a polymerized diol compound. The non-polymerized diol compound is a diol compound that does not undergo polymerization history, and the polymerized diol compound is a diol compound obtained by polymerizing monomers.

  The non-polymerized diol compound is not particularly limited as long as it is generally used. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5- Pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3- Dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,4- Chlohexanediol, 1,4-dimethylolcyclohexane, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,9-nonanediol, 1,2 -Nonanediol, 1,10-decanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1 , 3-propanediol, 2,2′-bis (4-hydroxycyclohexyl) -propane, p-xylylenediol, p-tetrachloroxylylenediol, bishydroxymethyltetrahydrofuran, di (2-hydroxyethyl) dimethylhydantoin, Polyethylene glycol, polypropylene glycol, polytetramethyl Glycol, 2,6'-dihydroxyethylhexyl ether, 2,4'-dihydroxyethyl butyl ether, 2,5'-dihydroxyethyl pentyl ether, 2,3'-dihydroxy-2,2'-dimethylethylpropyl ether, thioglycol 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 2,2-bis (4-hydroxy) Phenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2 -Bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5) -Nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy) Phenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9-bis (4-Hydroxyphenyl) fluorene, 9,9-bis 4-hydroxy-2-methylphenyl) fluorene, diol compounds containing a fluorine atom, a bisphenol type diol compounds, and the like. These may be used alone or in combination of two or more.

  The polymerization diol compound is not particularly limited as long as it is generally used, and examples thereof include dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid and the like. Polyester diols obtained by condensation reaction of an acid alone or a mixture with a non-polymerized diol compound alone or a mixture; polycaprolactone diols obtained by ring-opening polymerization of ε-caprolactone using a non-polymerized diol compound alone or a mixture Obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide alone or a mixture thereof to a non-polymerized diol compound and / or a diamine compound such as ethylenediamine alone or a mixture thereof; Polyether diols such as polybutadiene having two hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene; ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, phosgene, etc. Examples thereof include polycarbonate diols obtained by dealcoholization reaction and / or dephenol reaction of a carbonate compound alone or a mixture and a non-polymerized diol compound alone or a mixture; a silicone diol compound and the like. These may be used alone or in combination of two or more.

(Polyfunctional isocyanate compound having an isocyanurate structure)
The polyfunctional isocyanate compound having an isocyanurate structure is a compound having an isocyanurate structure represented by the following formula (1) and having three or more isocyanate groups.

R ₁ , R ₂ , and R ₃ may be the same or different, and are a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, substituted or unsubstituted aromatic carbonization Represents a hydrogen group and may be linked to each other.
When R ₁ , R ₂ and R ₃ are not linked, R ₁ , R ₂ and R ₃ each have at least one isocyanate group.
When any _one of R ₁ and R ₂ , R ₁ and R ₃ , and R ₂ and R ₃ is linked, the compound has at least three isocyanate groups in the formula (1).

Among these, R ₁ , R _2, and R ₃ are each a chain, branched, or cyclic aliphatic having 2 to 20 carbon atoms, each having at least one isocyanate group, because of easy handling and availability. It is preferably a hydrocarbon group and / or a substituted or unsubstituted aromatic hydrocarbon group, more preferably a linear or branched alkyl group having 2 to 20 carbon atoms and having at least one isocyanate group. preferably, - (CH ₂₎ it is further preferred ₆ is NCO structure.

  The polyfunctional isocyanate compound having an isocyanurate structure is not particularly limited as long as it is generally used. Further, the diisocyanate compound described above can also be obtained by (2N + 1) quantification (N is an integer of 1 or more) such as trimerization, pentamerization, and sevenmerization. The (2N + 1) quantification method is not particularly limited as long as it is a general method.

  As a polyfunctional isocyanate compound having an isocyanurate structure, for example, a commercially available product can be used. Specifically, Tosoh Corporation coronate (grade examples: 2030, 2031, 2037, 2050, 2071) and coronate HX, Duranate manufactured by Asahi Kasei Corporation (grade examples; TPA-100, TKA-100, MFA-75B, MHG-60B, TUL-100, TLA-100, TSA-100, TSS-100, TSE-100), Sumika Covestro Urethane Co., Ltd. Sumidur (grade examples: N-3300, N-3800), Death Module (grade example: Z-4470), Mitsui Chemicals Takenate (grade examples: D-121N, D-127N) , D-170N), Burnock made by DIC Corporation Examples: D-800, DN-980, DN-981, DN-902S, DN-990, DN-992), Evonik's VESTANAT T (grade examples: 1890E, 1890L, 1890M, 1890/100), and VESTANAT HT (grade example: 2500E, 2500L, 2500LV, 2500/100) and the like.

(Polyfunctional isocyanate compound having biuret structure)
The polyfunctional isocyanate compound having a biuret structure is a compound represented by the following formula (2).

R ₄ , R ₅ and R ₆ may be the same or different, and are a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon Represents a group and may be linked to each other.
When R ₄ , R ₅ and R ₆ are not linked, R ₄ , R ₅ and R ₆ each have at least one isocyanate group.
When any one of R ₄ and R ₅ , R ₄ and R ₆ and R ₅ and R ₆ is linked, it has at least three isocyanate groups in the formula (2).

Among these, R ₄ , R ₅ , and R ₆ are each a chain, branched or cyclic fat having 2 to 20 carbon atoms each having at least one isocyanate group because of easy handling and availability. It is preferably an aromatic hydrocarbon group and / or a substituted or unsubstituted aromatic hydrocarbon group, and is a chain or branched aliphatic alkyl group having 2 to 20 carbon atoms and having at least one isocyanate group. Are more preferable, and a — (CH ₂ ) ₆ NCO structure is preferable.

  The polyfunctional isocyanate compound having a biuret structure is not particularly limited as long as it is generally used. Alternatively, the diisocyanate compound can be obtained by (2N + 1) quantification (N is an integer of 1 or more) such as trimerization, quinomerization, and 7 merization. The (2N + 1) quantification method is not particularly limited as long as it is a general method.

  Commercially available products can also be used as the polyfunctional isocyanate compound having a biuret structure, and specifically, Death Module (grade example: N-3200) manufactured by Sumika Covestro Urethane Co., Ltd., Duranate manufactured by Asahi Kasei Corporation ( Grade examples: 24A-100, 22A-75P, 21S-75E), Takenate manufactured by Mitsui Chemicals, Inc. (grade example: D-165N), and VESTANAT HB manufactured by Evonik (grade examples: 2640E, 2640MX, 2640LV, 2640/100) ) And the like.

(Polyfunctional isocyanate compound having adduct structure)
The polyfunctional isocyanate compound having an adduct structure can be obtained, for example, by reacting a diisocyanate compound with a polyvalent hydroxyl compound having three or more hydroxyl groups. As the diisocyanate compound, the above-described examples of the diisocyanate compound are suitable. Examples of the polyvalent hydroxyl compound having three or more hydroxyl groups include non-polymerized polyvalent hydroxyl compounds and polymerized polyvalent hydroxyl compounds. The non-polymerized polyhydric hydroxyl compound is a polyhydric hydroxyl compound that does not undergo polymerization, and the polymerized polyhydric hydroxyl compound is a polyhydric hydroxyl compound obtained by polymerizing monomers.

  The non-polymerized polyvalent hydroxyl compound is not particularly limited as long as it is generally used. For example, glycerin, trimethylolpropane, pentaerythritol, diglycerin, dipentaerythritol, D-threitol, L-arabinitol, Ribitol, xylitol, sorbitol, mannitol, galactitol, rhamnitol, arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesource, trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, Examples include raffinose, gentianose, meletitol and stachyose. These may be used alone or in combination of two or more.

  The polymerized polyvalent hydroxyl compound is not particularly limited as long as it is generally used. For example, succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, etc. Polyester hydroxyl group compounds obtained by condensation reaction of a dicarboxylic acid alone or in mixture with a non-polymerized polyhydroxyl compound alone or in a mixture; ε-caprolactone is opened using a non-polymerized polyhydroxyl compound alone or in a mixture Polycaprolactone polyhydric hydroxyl compounds obtained by polymerization; alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, alone or a mixture thereof, non-polymerized polyhydric hydroxyl compounds, and / or ethylenediamine, etc. Polyamine compound alone or Polyether polyhydric hydroxyl compounds obtained by adding to a mixture; Polymer polyhydric hydroxyl compounds obtained by polymerizing polyether polyols with acrylamide or the like; Ethylenically unsaturated bond-containing compounds having a hydroxy group alone or in a mixture Acrylic polyhydric hydroxyl compound which is a copolymer of the above-mentioned polymer, and an ethylenically unsaturated bond-containing compound having a hydroxy group alone or a mixture thereof, and an ethylenically unsaturated bond-containing compound which does not contain a hydroxy group Polyolefin polyhydroxyl compounds such as polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene; ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl Polycarbonate polyhydroxyl compounds obtained by dealcoholization reaction and / or dephenol reaction of carbonate compounds such as nyl carbonate and phosgene alone or in mixture with non-polymerized polyhydroxyl compounds alone or in mixture; fluoroolefin homopolymerization or Fluorine atom-containing polyhydric hydroxyl compounds, which are polyols containing fluorine atoms in the molecule, obtained by copolymerization with vinyls such as cyclovinyl ether, hydroxyalkyl vinyl ether, and monocarboxylic acid vinyl ester; have three or more hydroxyl groups Novolac type, glycidyl ether type, glycol ether type, aliphatic unsaturated compound epoxy type, fatty acid ester epoxy type, polycarboxylic acid ester type, aminoglycidyl type, β-methyl epichloro type, cyclic oxirane type, halogen type Polysiloxane compounds and the like having three or more silanol groups, epoxy resins of resorcinol type. These may be used alone or in combination of two or more.

  The ethylenically unsaturated bond-containing compound having a hydroxy group is not particularly limited as long as it is generally used. For example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate , Hydroxypropyl methacrylate, hydroxybutyl methacrylate and the like. These may be used alone or in combination of two or more.

  The ethylenically unsaturated bond-containing compound not containing a hydroxy group is not particularly limited as long as it is generally used. For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, acrylic acid- n-butyl, isobutyl acrylate, acrylic acid-n-hexyl, cyclohexyl acrylate, acrylate-2-ethylhexyl, lauryl acrylate, benzyl acrylate, phenyl acrylate, and other acrylic esters, methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, isopropyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, methacrylate-n-hexyl, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methacrylate Methacrylic acid esters such as benzyl phosphate and phenyl methacrylate, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, dye Unsaturated amides such as acetone methacrylamide, maleic amide, maleimide, glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, and other vinyl monomers, vinyl trimethoxysilane, vinyl methyl dimethoxy Examples thereof include vinyl monomers having a hydrolyzable silyl group such as silane and γ- (meth) acryloxypropyltrimethoxysilane. These may be used alone or in combination of two or more.

  As a polyfunctional isocyanate compound which has an adduct structure, the compound represented by following formula (3) is mentioned, for example.

R ₇ represents a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group.
R ₈ has at least one isocyanate group and may be the same or different, and is a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, substituted or unsubstituted aromatic Represents a group hydrocarbon group.
n is an integer of 3 or more.

  Among the compounds represented by the formula (3), a compound represented by the following formula (4) is preferable because it is easily available.

R ₉ has at least one isocyanate group and may be the same or different, and is a chain, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, substituted or unsubstituted aromatic Represents a hydrocarbon group.
o is 3.

Among the compounds represented by formula (4), R ₉ is a linear, branched or cyclic aliphatic group having 2 to 20 carbon atoms having at least one isocyanate group because of easy handling and availability. It is preferably a hydrocarbon group and / or a substituted or unsubstituted aromatic hydrocarbon group, and is a chain or branched aliphatic alkyl group having 2 to 20 carbon atoms and having at least one isocyanate group. More preferably, it is a — (CH ₂ ) ₆ NCO structure.

  The polyfunctional isocyanate compound having an adduct structure is not particularly limited as long as it is generally used. It can also be obtained by reacting a compound having three or more hydroxyl groups with the aforementioned diisocyanate compound. The reaction method is not particularly limited as long as it is a general method.

  As a polyfunctional isocyanate compound having an adduct structure, for example, a commercially available product can be used. Specifically, Coronate L manufactured by Tosoh Corporation, Takenate manufactured by Mitsui Chemicals, Inc. (grade examples: D110N, D120N, D140N) DURANATE manufactured by Asahi Kasei Corporation (grade examples: P301-75E, E402-80B, E405-70B, AE700-100), Burnock manufactured by DIC Corporation (grade examples: D-750, DN-950, DN-955), etc. Is mentioned.

(Polyfunctional isocyanate compound having a polynuclear structure)
The polyfunctional isocyanate compound having a polynuclear structure is obtained by converting and isomerizing an amino group into an isocyanate group by phosgenation or the like from a condensation mixture obtained by a condensation reaction of aniline and formalin. A polyfunctional isocyanate compound having a desired condensation degree and having a polynuclear structure can be obtained by changing the raw material composition ratio and the reaction conditions during the condensation.

  As a polyfunctional isocyanate compound which has a polynuclear structure, the compound represented by following formula (5) is mentioned, for example.

  p is an integer of 1 or more.

  As a polyfunctional isocyanate compound having a polynuclear structure, for example, a commercially available product can be used. Specifically, Cosmonate manufactured by Mitsui Chemicals, Inc. (grade example: M-100, M-200), Tosoh Corporation Millionate (grade examples: MR100, MR200, MR400), Lupranate (grade examples: M20S, M11S, M5S) manufactured by BASF INOAC Polyurethanes, PAPI (grade examples: 135, 135C, 27, 2940) manufactured by DOW, and VORANATE (Grade examples: M590, M595) and the like.

  As the polyfunctional isocyanate compound in the present embodiment, a polyfunctional isocyanate compound having an allophanate structure or a polyfunctional isocyanate compound having a urea structure can also be used. These are not particularly limited as long as they are generally used.

  The polyisocyanate compound in the present embodiment also includes a compound having a structure in which an isocyanate group reacts with a heat dissociable blocking agent to form a blocked isocyanate group (hereinafter referred to as block polyisocyanate). The heat dissociable blocking agent is a compound having a property that allows the heat dissociable blocking agent bonded to the isocyanate group to be dissociated by heating to generate an isocyanate group.

  The heat dissociable blocking agent is not particularly limited as long as it is generally used. For example, oximes such as formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketone oxime, cyclohexanone oxime; methanol, ethanol, 2 Alcohols such as propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol; acetanilide, acetic acid amide, ε-caprolactam, δ-valero Acid amides such as lactam and γ-butyrolactam; acid imides such as succinimide and maleic imide; phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol And phenols such as hydroxy and benzoic acid esters; amines such as diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine; dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate Active methylenes such as acetylacetone; imidazoles such as imidazole and 2-methylimidazole; pyrazoles such as pyrazole, 3-methylpyrazole and 3,5-dimethylpyrazole; These may be used alone or in combination of two or more.

  The block polyisocyanate is not particularly limited as long as it is generally used. For example, Coronate manufactured by Tosoh Corporation (grade examples: BI-301, 2507, 2554, 2512, 2513, 2515, 2520), DIC stock Burnock (grade examples: D-500, D-550, DB-980K), Takenate manufactured by Mitsui Chemicals, Inc. (grade examples: WB-700, WB-720, WB-730, WB-920, XWB-72- K55, B-830, B-815, B-846, B-870, B-874, B-882), Sumika manufactured by Sumika Covestro Urethane Co., Ltd. (grade examples: BL-3175, BL-4165, BL) -1100, BL-1265), Death Module (grade example: TPLS-2957, TPLS-2) 62, TPLS-2078, TPLS-2117), desmotherm (grade examples: 2170, 2265), and bihijoule (grade examples: BL5140, BL5235), Elastron (BN-69, BN-77, BN) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -27, BN-04), LuxinHC manufactured by Olin Chemicals (grade examples: 1170, 2170), blocked isocyanate manufactured by Baxenden (grade examples: 7950, 7951, 7960, 7961, 7962, 7990, 7991, 7992, AquaBI200, AquaBI220), Asahi Kasei Corporation Duranate (17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, SBF-70E, E402-B80B, WM 4-L70G), and the like. These may be used alone or in combination of two or more.

  The polyol compound is not particularly limited as long as it is generally used, and examples thereof include the aforementioned compounds such as a non-polymerized diol compound, a polymerized diol compound, a non-polymerized polyvalent hydroxyl compound, and a polymerized polyvalent hydroxyl compound. . These may be used alone or in combination of two or more.

Among polyol compounds, polyester diol is easily available and tends to have a good gas component permeability coefficient and gas component separation coefficient when a gas separation membrane containing a curable urethane resin and zeolite is used. Selected from the group consisting of polycaprolactone diols, polyether diols, polycarbonate diols, polyester polyhydric hydroxyl compounds, polycaprolactone polyhydric hydroxyl compounds, polyether polyhydric hydroxyl compounds, polycarbonate polyhydric hydroxyl compounds It is preferable that it is at least one kind. Therefore, the curable urethane resin in the present embodiment preferably has at least one structure selected from the group consisting of a polycarbonate structure, a polyether structure, a polyester structure, and a polycaprolactone structure.
In addition, when a gas separation membrane containing a curable urethane resin and zeolite is used, the permeability coefficient of the gas component and the separation coefficient of the gas component tend to be improved. Therefore, polyether diols, polycarbonate diols, More preferably, it is at least one selected from the group consisting of polyvalent hydroxyl compounds and polycarbonate polyvalent hydroxyl compounds. The polyol compound is more preferably a polyether diol and / or a polycarbonate diol. Therefore, it is more preferable that the curable urethane resin in the present embodiment has at least one structure selected from the group consisting of a polycarbonate structure and a polyether structure.

  The isocyanate compound polymerization initiator that can be used for the curable urethane resin in the present embodiment is not particularly limited as long as it is generally used. For example, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin. Tin compounds such as dithiodecanoate and bis (2-ethylhexanoic acid) tin; zinc compounds such as zinc 2-ethylhexanoate and zinc naphthenate; titanium 2-ethylhexanoate and titanium diisopropoxybis Titanium compounds such as (2-ethylacetonate); cobalt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate; bismuth compounds such as bismuth 2-ethylhexanoate and bismuth naphthenate; zirconium tetra Acetylacetonate, 2- Chiruhekisan acid zirconyl, zirconium compounds such as naphthenic acid zirconium; and the like. These may be used alone or in combination of two or more.

  In the curable urethane resin composition, the ratio of the amount of hydroxyl group contained in the polyol compound to the amount of isocyanate group and blocked isocyanate group contained in the polyisocyanate and block polyisocyanate (isocyanate group and block contained in the polyisocyanate and block polyisocyanate) The substance amount of isocyanate group / the substance amount of hydroxyl group of the polyol compound is not particularly limited, but is preferably 1 / 1.5 or more, more preferably 1 / 1.2 or more, and 1/1. More preferably, it is 1 or more. When a gas separation membrane containing a curable urethane resin and zeolite is used, it is suppressed that unreacted hydroxyl groups remain, and resistance to liquid chemical substances, that is, plasticization resistance due to condensed components tends to improve. The ratio of the amount of the hydroxyl group is preferably 1 / 1.5 or more, and more preferably 1 / 1.2 or more from the same viewpoint. When a gas separation membrane containing a curable urethane resin and zeolite is used, since the permeability coefficient of the gas component and the separation coefficient of the gas component tend to be improved, the ratio of the hydroxyl group substance amount is 1 / 1.1. More preferably, it is the above.

  In the curable urethane resin composition, the ratio of the amount of hydroxyl group contained in the polyol compound to the amount of isocyanate group and blocked isocyanate group contained in the polyisocyanate and block polyisocyanate (isocyanate group and block contained in the polyisocyanate and block polyisocyanate) The substance amount of the isocyanate group / the substance amount of the hydroxyl group of the polyol compound is not particularly limited, but is preferably 1.5 / 1 or less, more preferably 1.2 / 1 or less, and 1.1. More preferably, it is / 1 or less. When a gas separation membrane containing a curable urethane resin and zeolite is used, it is suppressed that unreacted polyisocyanate and / or block polyisocyanate remains, and resistance to liquid chemicals, that is, plasticization resistance due to condensation components is suppressed. Since it tends to improve, the ratio of the substance amount of the hydroxyl group is preferably 1.5 / 1 or less, and more preferably 1.2 / 1 or less from the same viewpoint. When a gas separation membrane containing a curable urethane resin and zeolite is used, since the permeability coefficient of the gas component and the separation coefficient of the gas component tend to be improved, the ratio of the substance amount of the hydroxyl group is 1.1 / 1. More preferably, it is as follows.

  The amount of the isocyanate compound polymerization initiator contained in the curable urethane resin composition is preferably 0.001 part by mass or more with respect to 100 parts by mass of the curable urethane resin composition, and 0.003 part by mass or more. More preferably, it is more preferably 0.05 parts by mass or more. When a gas separation membrane containing a curable urethane resin and zeolite is used, residual isocyanate groups, blocked isocyanate groups, and hydroxyl groups contained in the curable urethane resin are suppressed, and resistance to liquid chemicals, that is, plasticization by condensation components Since the resistance tends to improve, the amount of the isocyanate compound polymerization initiator is preferably 0.001 part by mass or more, and more preferably 0.003 part by mass or more from the same viewpoint. When a gas separation membrane containing a curable urethane resin and zeolite is used, since the gas component permeability coefficient and the gas component separation coefficient tend to be improved, the amount of the isocyanate compound polymerization initiator is 0.05 mass. More preferably, it is at least part.

  The amount of the isocyanate compound polymerization initiator contained in the curable urethane resin composition is preferably 5 parts by mass or less and more preferably 3 parts by mass or less with respect to 100 parts by mass of the curable urethane resin composition. Preferably, it is 1 part by mass or less. Residue of the isocyanate compound polymerization initiator is suppressed, and when a gas separation membrane containing a curable urethane resin and zeolite is used, the resistance to liquid chemical substances, that is, the plasticization resistance due to the condensation component tends to be improved. The amount of the isocyanate compound polymerization initiator is preferably 5 parts by mass or less. When a gas separation membrane containing a curable urethane resin and zeolite is used, since the gas component permeability coefficient and the gas component separation coefficient tend to improve, the amount of the isocyanate compound polymerization initiator is 3 parts by mass or less. More preferably, it is more preferably 1 part by mass or less from the same viewpoint.

  In this embodiment, a curable urethane resin can be obtained by polymerizing a generally available curable urethane resin composition. A curable urethane resin composition may be used independently and may be used in combination of 2 or more type.

  Specific examples of the curable polyurethane resin composition include high cast (grade number example: 3012W, 3017, 3019, 3030, 3091, 3150, 3155, 3166, 3751, 3095, 3180, 3263, manufactured by Etch & Kay Co., Ltd. 3434, 3479, 3500, 3530, 3550, 3570, 3601, 3603, 3610-60, 3615, 3744), Nissin Resin Co., Ltd. Adapt (example of grade number; RU-10A / B, RU-12A / B, RU-15A / B, RU-17A / B, RU-42AN / B, RU-510AN / B, RU-650AH / B, RU-650AS / B, RU-750A / B, RU-70A / RUS-B, RU-78A / B, RU-80A / B, RU-68A / B, RU-550A / , RU-610A / BH, RU-610A / BS, PU-01A / B, RU-850A / RUG-B, RU-860A / RUG-B, RU870A / RUG-B, RU-880A / RUG-B, RU -890A / RUG-B, RU841A / B, RU630A / B, 60L, 80L, 80P, 90L, RU910A / B, E-No.1, E-No.2, E-No.3), and craft resin ( Grade number example: hobby cast NX), Coronate manufactured by Nippon Polyurethane Industry Co., Ltd. (grade number examples: C-4080, C-4090, C-4095, DC-6912, C-4076, C-40747, C-4048), And coronate nipporan (grade number examples: C-4362 / N-4038, C-4370 / N-4378, C-4370 / -4379), and the like. These may be used alone or in combination of two or more.

(Zeolite)
The zeolite in the present embodiment is a tetrahedral structure of TO ₄ units (T is a central atom) sharing O atoms (oxygen atoms) three-dimensionally to form open regular pores. (In this embodiment, the pore is composed of a pore inlet and a cavity inside the pore). Specific examples of the zeolite include silicates, phosphates, germanates, arsenates and the like described in the data collection of International Zeolite Association (hereinafter referred to as IZA). Zeolites can be classified into oxygen 8-membered rings, oxygen 10-membered rings, oxygen 12-membered rings, and the like, depending on the number of oxygen present in the portion constituting the pore inlet of the zeolite.

  Among these, when a gas separation membrane containing a curable urethane resin and zeolite is used, it tends to have a good gas component permeability coefficient and gas component separation coefficient. It is preferably at least one selected from the group consisting of zeolites having pores composed of: Further, since it is easily available, the zeolite is more preferably at least one selected from the group consisting of zeolites having pores composed of an oxygen 8-membered ring, an oxygen 10-membered ring, and an oxygen 12-membered ring. preferable. When a gas separation membrane containing a curable urethane resin and zeolite is used, since the permeability coefficient of the gas component tends to improve, it has pores composed of an oxygen 8-membered ring and / or an oxygen 12-membered ring. More preferably, it is zeolite. When a gas separation membrane containing a curable urethane resin and zeolite is used, the permeability coefficient of the gas component and the separation coefficient of the gas component tend to improve. Therefore, the zeolite has pores composed of oxygen 8-membered rings. More preferably it is.

  The zeolite in this embodiment should just have the X-ray-diffraction pattern shown by the XZA diffraction pattern obtained by an X-ray-diffraction apparatus by IZA or well-known literature, and a patent. Zeolites in this embodiment also include those in which the heights and height ratios of the X-ray diffraction peaks are different from the heights and height ratios described in IZA or known literatures and patents. It is.

  Zeolite can be specifically exemplified by a code that defines the structure of the zeolite defined by IZA.

(Zeolite with oxygen 8-membered ring)
Examples of the zeolite having an oxygen 8-membered ring include ABW, ACO, AEI, AEN, AFN, AFT, AFV, AFX, APC, APD, ATN, ATT, ATV, AWO, AWW, BIK, BRE, CAS, CDO, CHA, DDR, DFT, EDI, EEI, ERI, ESV, ETL, GIS, IFY, IHW, IRN, ITE, ITW, JBW, JNT, KFI, LEV, LTA, LTJ, MER, MON, MTF, MWF, NSI, OWE, PAU, PHI, RHO, RTE, RTH, RWR, SAS, SAT, SAV, SFW, SIV, THO, UEI, UFI, VNI, YUG, ZON, ANA, JSW, NPT, TSC, AFR, AFS, AFY, BPH, CGF, CSV, EON, ETR, FER, GME, HEU, IF , IWW, LTF, MAZ, MFS, MOR, NAT, OFF, PCR, PSI, RRO, SBE, SFO, STI, STW, SZR, UOS, UOV, VSV, BOZ, -CLO, DFO, LOV, OBW, OSO, PUN, RSN, SBN, SOS, WEI, -WEN etc. are mentioned.

  Among these, it is easy to obtain or synthesize, and when a gas separation membrane containing a curable urethane resin and zeolite is used, the permeability coefficient of the gas component and / or the separation coefficient of the gas component tend to be improved. ABW, ACO, AEI, AEN, AFN, AFT, AFV, AFX, APC, APD, ATN, ATT, ATV, AWO, AWW, BIK, BRE, CAS, CDO, CHA, DDR, DFT, EDI, EEI, ERI, ESV, ETL, GIS, IFY, IHW, IRN, ITE, ITW, JBW, JNT, KFI, LEV, LTA, LTJ, MER, MON, MTF, MWF, NSI, OWE, PAU, PHI, RHO, RTE, RTH, RWR, SAS, SAT, SAV, SFW, SIV, THO, UEI, UFI, VNI, UG, it is preferably ZON.

  When a gas separation membrane containing a curable urethane resin and zeolite is used, the permeability coefficient of the gas component and / or the separation coefficient of the gas component tend to be improved. More than AEI, AFN, AFT, AFX, CHA, DFT, EDI, ERI, GIS, KFI, LTA, LTJ, MER, MWF, PAU, PHI, RHO, SAT, SAV, SFW, SIV, THO, VNI preferable. These zeolites having an eight-membered oxygen ring have pores spread in three dimensions, and it is considered that the zeolite functions more.

When a gas separation membrane containing a curable urethane resin and zeolite is used, since the gas component permeability coefficient and / or the gas component separation coefficient tend to be improved, the zeolite having an oxygen 8-membered ring is AEI, AFT, AFX, CHA, KFI, MWF, PAU, RHO, SAT, SAV, and SFW are more preferable. These zeolites having an oxygen 8-membered ring are considered to function more because the zeolite having an oxygen 8-membered ring has a large cavity.
More preferably, the zeolite having an oxygen 8-membered ring is CHA.

(Zeolite with oxygen 10-membered ring)
Examples of the zeolite having an oxygen 10-membered ring include, for example, AEL, AFO, BOF, EUO, IMF, JRY, LAU, MEL, MFI, * MRE, MTT, MVY, MWW, NES, SFF, SFG, STF, -SVR, TON, TUN, AHT, JST, -PAR, PON, TER, CON, * -EWT, ITG, ITH, * -ITN, ITR, ITT, IWR, MSE, SEW, SFS, * SFV, SOF, USI, UWY, Examples include BOG and DAC.

  Among these, since it is easily available or easy to synthesize, AEL, AFO, EUO, IMF, LAU, MEL, MFI, * MRE, MTT, MWW, NES, SFF, STF, SVR, TON, TUN, * -EWT, ITH, * -ITN, MSE, * SFV are preferred.

  When a gas separation membrane containing a curable urethane resin and zeolite is used, the gas component permeability coefficient and / or the gas component separation coefficient tend to improve. MFI, SVR, TUN, * -EWT, ITH, * -ITN, MSE, * SFV are more preferable. These zeolites having a 10-membered oxygen ring have pores spread in three dimensions, and it is considered that the zeolite functions more.

When a gas separation membrane containing a curable urethane resin and zeolite is used, the permeability coefficient of the gas component and / or the separation factor of the gas component tend to be improved. Therefore, the zeolite having a 10-membered oxygen ring is MEL, MFI. , -SVR, and TUN are more preferable.
More preferably, the zeolite having an oxygen 10-membered ring is MFI.

(Zeolite with oxygen 12-membered ring)
Examples of the zeolite having an oxygen 12-membered ring include AFI, ASV, ATO, ATS, * BEA, BEC, BSV, CAN, CZP, EMT, EZT, FAU, GON, IFR, ISV, IWS, IWV, LTL, and MTW. , NPO, OSI, SAF, SAO, SBT, SFE, SSY, * STO, VET, -RON, RWY, SBS, -IFU, IRR, UTL and the like.

  Among these, AFI, ATO, ATS, * BEA, CAN, EMT, EZT, FAU, GON, IFR, ISV, IWV, LTL, MTW, OSI, SAF, because it is easily available or synthesized. SAO, SFE, * STO, and VET are preferable.

When a gas separation membrane containing a curable urethane resin and zeolite is used, since the permeability coefficient of the gas component and / or the separation coefficient of the gas component tend to be improved, the zeolite having an oxygen 12-membered ring is * BEA EMT, FAU, ISV and SAO are more preferable. These zeolites having an oxygen 12-membered ring have pores spread in three dimensions, and it is considered that the zeolite functions more.
More preferably, the zeolite having an oxygen 12-membered ring is * BEA or FAU.

  As zeolites other than the above-mentioned zeolite, for example, MEI, STT, NAB, * -SSO, JSR, POS, OKO, AET, CFI, SFH, SFN, SSF, DON, IFO, -IRY, VFI, ITV, AFG, AST, DOH, FAR, FRA, GIU, LIO, -LIT, LOS, LTN, MAR, MEP, MSO, MTN, NON, RUT, SGT, SOD, SVV, TOL, UOZ and the like.

  As the zeolite in the present embodiment, a surface-modified zeolite is also included. Here, the surface modification means that the surface modifier is bonded to the zeolite surface by reacting with a compound capable of reacting with the zeolite surface (hereinafter referred to as a surface modifier).

  The surface modifier is not particularly limited as long as it is generally used. For example, silazanes, siloxanes, alkoxysilanes, hydrogen silanes having a Si-H structure in the molecule, Si in the molecule. Examples include chlorosilanes having a -Cl structure. These may be used alone or in combination of two or more. Among these, silazanes and alkoxysilanes are preferably used because compounds having various organic groups are easily available, easy to handle, and highly reactive with the zeolite surface.

  Examples of silazanes include hexamethyldisilazane and hexaethyldisilazane.

  Examples of siloxanes include hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, hexaethyldisiloxane, 3-glycol. Sidoxypropylpentamethyldisiloxane and the like can be mentioned.

  Examples of alkoxysilanes include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetrapropoxy. Silane, tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldiethoxysilane, n-decyltrimethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, Netyltrimethoxysilane, dodecyltrimethoxysilane, n-octadecyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, γ-methacryloxy Propyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxyp Propyltriethoxysilane, N-β (aminoethyl) γ- (aminopropyl) methyldimethoxysilane, N-β (aminoethyl) γ- (aminopropyl) trimethoxysilane, N-β (aminoethyl) γ- ( Aminopropyl) triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane , Trifluoropropyltrimethoxysilane, heptadecatrifluoropropyltrimethoxysilane, n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis (triethoxysilyl) ethane, hexaethoxydisiloxane and the like.

  Examples of hydrogen silanes having a Si—H structure in the molecule include, for example, a compound in which an alkoxy group bonded to silicon contained in the alkoxy silane is substituted with a hydrogen atom, an aliphatic group in a side chain, and / or Examples include compounds in which some side chain groups in the polysiloxane having an aromatic group are substituted with hydrogen atoms.

  Examples of chlorosilanes having a Si—Cl structure in the molecule include compounds in which an alkoxy group bonded to silicon contained in the alkoxysilanes is substituted with a chlorine atom, an aliphatic group in the side chain, and / or an aromatic group. Examples thereof include compounds in which some side chain groups in the polysiloxane having a group are substituted with chlorine atoms.

  The method for surface modification is not particularly limited as long as it is a generally used method. For example, a zeolite containing a zeolite, a surface modifier, and a solvent is prepared, and heated as necessary, thereby allowing the zeolite to be modified. Examples thereof include a method for promoting the reaction between the surface and the surface modifier to modify the surface, and a chemical vapor deposition method.

  When preparing the curable urethane resin composition and the mixture of the curable urethane resin composition and zeolite, a solvent that can be dissolved in the curable urethane resin composition can be used. Examples of the solvent include saturated hydrocarbons such as n-pentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Compounds; aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, naphthalene, tetralin and biphenyl; methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane , Dichloroethylene, trichlorethylene, tetrachloroethylene, dichloropropane, trichloropropane, isopropyl chloride, butyl chloride, hexyl chloride, chlorobenzene, dichlorobenzene Halogenated hydrocarbon compounds such as benzene, trichlorobenzene, chlorotoluene and chloronaphthalene; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, cyclohexanol , Alcohols such as benzyl alcohol, ethylene glycol, propylene glycol, butylene glycol and glycerin, multimers of compounds having two hydroxyl groups of the alcohols, and esterified compounds of the multimers; acrylonitrile, benzonitrile, etc. Nitriles; acetone, methyl acetone, ethyl methyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobuty Ketones such as ketone, methyl hexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone and diisobutyl ketone, cyclohexanone; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, hexyl acetate, octyl acetate, cyclohexyl acetate, Esters such as methyl propionate, ethyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate and benzyl benzoate; diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran , Ethers such as dioxane, nitromethane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, carbon disulfide, and fluorine compounds (For example, 3M Novec, Asahi Glass Co., Ltd. Asahi Klin, etc.); These solvents may be used alone or in combination of two or more.

  When preparing the curable urethane resin composition and the mixture of the curable urethane resin composition and zeolite, the amount of the solvent that can dissolve the curable urethane resin composition is not particularly limited, and the desired handling In order to obtain the properties, it is appropriately selected depending on the process cost when drying the solvent.

  The temperature and time for preparing the curable urethane resin composition and the mixture of the curable urethane resin composition and zeolite are not particularly limited as long as they are generally used, and the composition of the mixture Can be selected as appropriate.

  The atmosphere for preparing the curable urethane resin composition and the mixture of the curable urethane resin composition and the zeolite is generally an atmosphere such as air, nitrogen or argon, the reduced atmosphere, or a vacuum. There is no particular limitation as long as it is an atmosphere.

  The mixing method in preparing the curable urethane resin composition and the mixture of the curable urethane resin composition and zeolite is not particularly limited as long as it is a general method. For example, a stirrer, a stirring blade, Homogenizer, high-pressure homogenizer, ultra-high pressure homogenizer, ultrasonic homogenizer, polytron homogenizer, static mixer, nauter mixer, ribbon blender, intensive mixer, gate mixer, butterfly mixer, universal mixer, dissolver, ultrasonic irradiation, rotation / revolution mixer, Examples include a wet jet mill, a ball mill, and a bead mill. These may be used alone or in combination of two or more methods.

The gas separation membrane of this embodiment can also be produced by heating a mixture in which a curable urethane resin and zeolite are mixed, and the mixture containing the curable urethane resin composition and zeolite is polymerized by heating. At the same time, it can be produced by forming a film. From the viewpoint of ease of processing into a membrane, a method for producing a gas separation membrane is preferably a method in which a mixture containing a curable urethane resin composition and zeolite is polymerized by heating and the membrane is molded.
In this embodiment, the temperature and time for polymerizing the mixture containing the curable urethane resin composition and zeolite by heat are not particularly limited as long as they are generally used, and the composition of the mixture is not limited. Can be selected as appropriate.

  There is a tendency to suppress bond dissociation at high temperatures of urethane bonds contained in curable urethane resins. When gas separation membranes containing curable urethane resins and zeolites are used, they have resistance to liquid chemicals, that is, plasticization resistance due to condensation components. Since it tends to improve, the temperature at the time of polymerization by heat is preferably 200 ° C. or less. When the curable urethane resin composition is polymerized, side reactions are suppressed, and when a gas separation membrane containing a curable urethane resin and zeolite is used, the gas component permeability coefficient and / or the gas component separation coefficient tend to improve. Therefore, the temperature when polymerizing by heat is more preferably 170 ° C. or less, and further preferably 150 ° C. or less.

  When mixing a mixture containing a curable urethane resin composition and zeolite, it tends to be able to suppress moisture mixing. When a gas separation membrane containing a curable urethane resin and zeolite is used, it is resistant to liquid chemicals, that is, condensed. Since the plasticization resistance due to the components tends to be improved, the temperature at the time of polymerization by heat is preferably 0 ° C. or higher. When polymerizing a mixture containing a curable urethane resin composition and zeolite, molecular mobility is improved, and unreacted polyisocyanate and / or block polyisocyanate or polyol is prevented from remaining, and liquid chemistry is suppressed. Since the resistance to the substance, that is, the plasticization resistance due to the condensed component tends to be improved, the temperature at the time of polymerization by heat is more preferably 20 ° C. or more, and further preferably 40 ° C. or more.

  The atmosphere at the time of polymerization is not particularly limited as long as it is a commonly used atmosphere such as an atmosphere of air, nitrogen, argon or the like, the decompressed atmosphere, or a vacuum. From the viewpoint of suppressing the cost when manufacturing the gas separation membrane of the present embodiment, the atmosphere during polymerization is preferably air, nitrogen, reduced pressure air, or reduced pressure nitrogen atmosphere.

  In this embodiment, the light used when polymerizing a mixture of a curable urethane resin composition and zeolite by light indicates ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, infrared rays, electron beams, and the like. The type of light to be used is not particularly limited as long as it is generally used, and can be appropriately selected depending on the composition of the curable resin composition, but preferably ultraviolet rays and near ultraviolet rays are used.

  The light source used when the mixture of the curable urethane resin composition and the zeolite is polymerized by light is not particularly limited. For example, the low pressure mercury lamp, the medium pressure mercury lamp, the high pressure mercury lamp, the ultrahigh pressure Mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, excimer laser, light emitting diode, Various light sources such as a CRT light source, a plasma light source, and an electron beam irradiator can be used.

  The type of light and the irradiation intensity and time when polymerizing a mixture of a curable urethane resin composition and zeolite with light are not particularly limited as long as they are generally used, and each curable property is not limited. It can select suitably by the composition of a resin composition. Moreover, the atmosphere at the time of superposition | polymerization will not be specifically limited if it is an atmosphere generally used, such as air, nitrogen, argon.

  The content of the zeolite in the gas separation membrane of the present embodiment may exceed 0% by mass with respect to the total mass of the curable urethane resin and the zeolite from the viewpoint of physically exhibiting the effects of the present invention. From the viewpoint of obtaining the effect of the present invention, it is preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 30% by mass or more. When the zeolite content is 10% by mass or more, the zeolite functions in the gas separation membrane, and the permeability coefficient of the gas component and / or the separation coefficient of the gas component tend to be improved. Further, when the zeolite content is 10% by mass or more, the permeability coefficient of the gas component of the curable urethane resin present in the vicinity of the zeolite and / or the separation coefficient of the gas component is a gas of the curable urethane resin alone. The component permeability coefficient and the gas component separation coefficient are different from each other, and the situation in which the different states are in contact with each other increases, and the gas component permeability coefficient and / or gas component separation coefficient of the gas separation membrane is improved. There is a possibility. From the same viewpoint, the content of the zeolite is more preferably 30% by mass or more.

The content of the zeolite in the gas separation membrane of the present embodiment may be less than 100% by mass with respect to the total mass of the curable urethane resin and the zeolite from the viewpoint of physically expressing the effects of the present invention. From the viewpoint of substantially obtaining the effect of the present invention, the content is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% by mass or less.
When the zeolite content is 80% by mass or less, the state in which the space between the zeolites is filled with the curable urethane resin increases, and the mechanical strength of the gas separation membrane tends to be improved. Since the separation factor of the gas component of the gas separation membrane tends to be improved, the content of zeolite is more preferably 70% by mass or less. When the zeolite content is 70% by mass or less, the state in which the space between the zeolites is filled with the curable urethane resin is increased, and also in a micro region which is an interface between the curable urethane resin and the zeolite, The situation where curable urethane resin exists increases, and the possibility that the separation factor of the gas component of the gas separation membrane is improved is considered. From the same viewpoint, the content of zeolite is more preferably 65% by mass or less.

Since the film-forming property of the gas separation membrane of this embodiment may be improved, a plasticizer can also be used for the gas separation membrane.
The plasticizer is not particularly limited as long as it is generally used. For example, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, or the number of carbon atoms Phthalate plasticizers such as phthalates of higher alcohols or mixed alcohols of about 10 to 13; di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2 -Aliphatic dibasic acid ester plasticizers such as ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate; tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, tridecyl trimellitate Tate, triisodec Trimellitic acid ester plasticizers such as trimellitate, di-n-octyl-n-decyl trimellrate; tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trixyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, cresyl Diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate , Phosphate esters such as bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate Plasticizer; biphenyltetracarboxylic acid tetraalkylester plasticizer such as 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetraheptyl ester; polyester polymer plasticizer; epoxidized soybean oil, epoxidized linseed oil And epoxy plasticizers such as epoxidized cottonseed oil and liquid epoxy resin; chlorinated fatty acid esters such as chlorinated paraffin and alkyl pentastearate; These may be used alone or in combination of two or more.

  The gas separation membrane of the present embodiment can be selected from various organic resins, inorganic fillers, colorants, leveling agents, lubricants, surfactants, silicone compounds, reactive diluents, non-reactive diluents, oxidizing agents, depending on the purpose. An inhibitor, a light stabilizer and the like can be appropriately contained. In addition, generally used as additives for plastics (plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, crosslinking agents, etc.) It may contain the substances to be made.

  The organic resin is not particularly limited, and examples thereof include an acrylic resin, a polyester resin, and a polyimide resin. These may be used alone or in combination of two or more.

  Examples of the inorganic filler include silicas (fused crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.), silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, Barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon Examples include fibers, and molybdenum disulfide. These may be used alone or in combination of two or more.

  The colorant is not particularly limited as long as it is a substance used for coloring purposes. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, and various organic systems such as azomethine Examples thereof include pigments and inorganic pigments such as titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium vermillion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide, and cobalt green. These colorants may be used alone or in combination of two or more.

  A leveling agent is not specifically limited, For example, the oligomer of molecular weight 4000-12000 formed from acrylates, such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil And titanium-based coupling agents. These may be used alone or in combination of two or more.

  The lubricant is not particularly limited. For example, hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax; higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid; stearyl Higher fatty acid amide based lubricants such as amide, palmitylamide, oleylamide, methylene bisstearamide and ethylene bisstearamide; hydrogenated castor oil, butyl stearate, ethylene glycol monostearate and pentaerythritol (mono-, di-, Higher fatty acid ester lubricants such as tri- or tetra-stearate; alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol and polyglycerol; lauric acid, myristic acid, palmitic acid, Metal soaps which are metal salts such as magnesium, calcium, cadmium, barium, zinc and lead such as arlic acid, arachidic acid, behenic acid, ricinoleic acid and naphthenic acid; and natural waxes such as carnauba wax, candelilla wax, beeswax and montan wax; Etc. These may be used alone or in combination of two or more.

  A surfactant refers to an amphiphilic substance having a hydrophobic group having no affinity for a solvent in a molecule and a philic group (usually a hydrophilic group) having an affinity for a solvent. The kind of surfactant is not specifically limited, For example, a silicon-type surfactant, a fluorine-type surfactant, etc. are mentioned. These may be used alone or in combination of two or more.

  The silicone compound is not particularly limited, and examples thereof include silicone resins, silicone condensates, silicone partial condensates, silicone oils, silane coupling agents, silicone oils, and polysiloxanes. The silicone compound may be modified by introducing an organic group at both ends, one end, or side chain of the silicone compound. The method for modifying the silicone compound is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, Examples include polyether modification, polyether and / or methoxy modification, and diol modification. These may be used alone or in combination of two or more.

  The reactive diluent is not particularly limited. For example, alkyl glycidyl ether, monoglycidyl ether of alkylphenol, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, ethylene glycol diglycidyl ether And propylene glycol diglycidyl ether. These may be used alone or in combination of two or more.

  The non-reactive diluent is not particularly limited, and examples thereof include benzyl alcohol, butyl diglycol and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

  Although antioxidant is not specifically limited, For example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, an amine antioxidant, etc. are mentioned. These may be used alone or in combination. Specific examples of the antioxidant include the following (1) to (4).

(1) Phenol antioxidants: For example, the following alkylphenols, hydroquinones, thioalkyl or thioarylphenols, bisphenols, benzyl compounds, triazines, β- (3,5-di-tert-butyl-4 -Hydroxyphenyl) ester of propionic acid and monohydric or polyhydric alcohol, ester of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and monohydric or polyhydric alcohol, β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and monohydric or polyhydric alcohol ester, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and monohydric or polyhydric alcohol ester , Β- (3,5-di-tert-butyl-4-hydroxyphenyl) propion Amides, and vitamins, and the like.

(1-1) Alkylphenols: 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methyl) Cyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear Nonylphenols having a branched or branched side chain (for example, 2,6-di-nonyl-4-methylphenol), 2,4- Methyl-6- (1′-methylundec-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadec-1′-yl) phenol, 2,4-dimethyl-6- (1 '-Methyltridec-1'-yl) phenol and mixtures thereof, 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate, etc. ;

(1-2) Hydroquinones: 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl -4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate and the like;

(1-3) Thioalkyl or thioarylphenols: 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethyl Phenol, 2,6-di-dodecylthiomethyl-4-nonylphenol, 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4 '-Thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec- Amylphenol), 4,4′-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide and the like;

(1-4) Bisphenols: 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), 2,2 ′ -Methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol) ), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (6-tert) -Butyl-4-isobutylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2, 2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-methylenebis (6-tert- Butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxy) Benzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2) -Methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxypheny L) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3′-tert-butyl-2′-hydroxy-5′-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4 -Hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, and 1,1,5,5-tetra (5-tert) -Butyl-4-hydroxy-2-methylphenyl) pentane and the like;

(1-5) benzyl compounds: 3,5,3 ′, 5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate Tart, dioctadecyl-2,2-bis (3,5-di-tert-butyl-2- Loxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl) -4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl- 4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Phenol and the like;

(1-6) Triazines: 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto -4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-tert -Butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, , 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ) Iso Anurat, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert -Butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and the like;

(1-7) Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols: β- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionic acid and methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl Glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl Hexanediol, Trimethylo Propane esters of mono- or polyhydric alcohols selected from, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

(1-8) Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and mono- or polyhydric alcohols: β- (5-tert-butyl-4-hydroxy-3 -Methylphenyl) propionic acid and methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl Glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl Hexanediol, tri Tyrolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and 3,9-bis [2- {3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane or an ester with a monohydric or polyhydric alcohol ;

(1-9) β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and a monovalent or polyhydric alcohol ester: β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid; Methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, Tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oximide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl Esters with mono- or polyhydric alcohols selected from til-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and the like;

(1-10) Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and monovalent or polyhydric alcohols: 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and monovalent or Polyhydric alcohol, methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene Glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4 -Hydro Esters of mono- or polyhydric alcohols selected from Shimechiru 1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

(1-11) Amide of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid: N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) ) Hexamethylenediamide, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N′-bis (3,5-di-tert-butyl-4) -Hydroxyphenylpropionyl) hydrazide, N, N′-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide and the like;

(1-12) Vitamins: α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof, tocotrienol, ascorbic acid and the like;

(2) Phosphorous antioxidants: The following phosphonates, phosphites, oxaphosphaphenanthrenes and the like can be mentioned.

(2-1) Phosphonates: Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylene diphosphonate, and calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and the like;

(2-2) Phosphites: trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite , Tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4- Hydroxyphenyl) butanediphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-tert-butylphenol ) Diphosphite, Tris (3 5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl)- Bis [4,4′-butylidenebis (3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4′-isopropylidenediphenol-pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4′-isopropylidene Bis (2-tert-butylphenol)] phosphite, phenyl Rudiisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite), tris (1,3-di-stearoyloxyisopropyl) phosphite, and 4,4′-isopropylidenebis (2-tert-butylphenol) -di (Nonylphenyl) phosphite etc .;

(2-3) Oxaphosphaphenanthrenes: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-chloro-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, and 8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

(3) Sulfur-based antioxidants: dialkylthiopropionates such as the following, esters of octylthiopropionic acid and polyhydric alcohol, esters of laurylthiopropionic acid and polyhydric alcohol, and stearyl thiopropionic acid and polyhydric acid Examples include esters with alcohol.

(3-1) Dialkylthiopropionates: dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and the like;
(3-2) Esters of octylthiopropionic acid and polyhydric alcohol: octylthiopropionic acid, polyhydric alcohol selected from glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate, and the like Esters of;
(3-3) Esters of lauryl thiopropionic acid and polyhydric alcohols: Esters of lauryl thiopropionic acid and glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate;
(3-4) An ester of stearyl thiopropionic acid and a polyhydric alcohol: stearyl thiopropionic acid and a polyhydric alcohol selected from glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate, and the like Esters of;

(4) Amine-based antioxidants: N, N′-di-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N, N′-bis (1,4- Dimethylpentyl) -p-phenylenediamine, N, N′-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N′-bis (1-methylheptyl) -p-phenylenediamine, N , N′-dicyclohexyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N, N′-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N′-phenyl-p -Phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-ph Nylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N′-dimethyl-N, N′-di-sec-butyl-p-phenylenediamine , Diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine (for example, P, p'-di-tert-octyldiphenylamine), 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol , Bi (4-methoxyphenyl) -amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N, N, N ′, N '-Tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4 -(1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl- / tert-octyldiphenylamine, mono- and di- -Mixtures of alkylated nonyl diphenylamines, mono- and di-alkylated dodecyl diphenylamines Mixtures, mono- and di-alkylated isopropyl / isohexyldiphenylamine mixtures, mono- and di-alkylated tert-butyldiphenylamine mixtures, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine , Phenothiazines, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ′, N '-Tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidi-4-yl) hexamethylenediamine, bis (2,2,6, 6-tetramethylpiperidi-4-yl) sebacate, 2,2,6,6-tetramethylpiperi Down-4-one, and, 2,2,6,6-tetramethyl-4-ol.

  The light stabilizer is not particularly limited, and examples thereof include UV absorbers such as triazole, benzophenone, ester, acrylate, nickel, triazine, and oxamide, and hindered amine light stabilizers. . These may be used alone or in combination. Specific examples of the antioxidant include the following (1) to (8).

(1) Triazole ultraviolet absorber: 2- (2′-hydroxy-5 ′-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (2′-hydroxy-4′-octyl) Oxyphenyl) benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3′-tert-butyl) -5 ′-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2 -Methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 -(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'- tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2′-methylenebis [4- (1,1,3,3- Tetramethylbutyl) -6-benzotriazol-2-ylphenol], 2- [3′-tert- Chill -5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H- transesterification products of benzotriazole with polyethylene glycol 300 and the like;

(2) Benzophenone ultraviolet absorbers: 4-decyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives, etc .;

(3) Ester ultraviolet absorber: 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di- tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl- 4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and the like;

(4) Acrylate ultraviolet absorber: ethyl-α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl-α- Cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β -Cyanovinyl) -2-methylindoline and the like;

(5) Nickel-based UV absorbers: 1: 1 or 1: 2 complexes with or without additional ligands such as n-butylamine, triethanolamine and N-cyclohexyldiethanolamine (eg, 2,2′- Nickel complex of thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, monoalkyl ester of 4-hydroxy-3,5-di-tert-butylbenzyl phosphate Nickel salts of (eg methyl or ethyl esters), nickel complexes of ketoximes (eg nickel complexes of 2-hydroxy-4-methylphenylundecyl ketoxime), and with or without additional ligands, 1 -Nickel complex of phenyl-4-lauroyl-5-hydroxypyrazole and the like;

(6) Triazine UV absorber: 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3 , 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4- Dimethylphenyl -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5 -Triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3 , 5- Riazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, and 2- {2-hydroxy-4- [3- (2-ethylhexyl-) 1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like;

(7) Oxamide ultraviolet absorber: 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy -5-tert-butyl-2'-ethoxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, a mixture of o- and p-methoxy-disubstituted oxanilide, And mixtures of o- and p-ethoxy-disubstituted oxanilides and the like;

(8) Hindered amine light stabilizer: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl- Condensation product of 4-hydroxypiperidine and succinic acid, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylami Linear or cyclic condensates with 2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2 , 6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) -bis (3,3,5,5-tetra Methylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6) -Pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 , 3,8-Triazas B [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-) Tetramethylpiperidyl) succinate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine A linear or cyclic condensate of

2-Chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) Condensate with ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2 A condensate with bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2, 4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6) -Pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 5- (2 Ethylhexanoyl) -oxymethyl-3,3,5-trimethyl-2-morpholinone, 1- (2-hydroxy-2-methylpropyl) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine 1,3,5-tris (N-cyclohexyl-N- (2,2,6,6-tetramethylpiperazin-3-one-4-yl) amino) -s-triazine, 1,3,5-tris (N-cyclohexyl-N- (1,2,2,6,6-pentamethylpiperazin-3-one-4-yl) amino) -s-triazine, 2,4-bis [(1-cyclohexyloxy-2 , 2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N′-bis (3-aminopropyl) ethylenediamine), 4-hexade A mixture of ruoxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4- Condensate of cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine In addition, a condensate of 4-butylamino-2,2,6,6-tetramethylpiperidine, 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, and N , N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine condensate, N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecyl succin Imide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8- Diaza-4-oxo-spiro [4.5] decane; 5- (2-ethylhexanoyl) oxymethyl-3,3,5-trimethyl-2-morpholinone, 7,7,9,9-tetramethyl-2 The reaction product of cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4,5] decane with epichlorohydrin, 1,1-bis (1,2,2,6, 6-Pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N′-bis-formyl-N, N′-bis (2,2,6,6-tetramethyl-4- Piperidyl) hexamethylenedia Diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetra Methyl-4-piperidyl)] siloxane, and a maleic anhydride α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4- Reaction products with aminopiperidine, etc.

<Gas separation method>
The gas separation membrane of this embodiment can be used for the process which makes the gas mixture which consists of 2 or more types of gas components contact, and isolate | separates the said gas mixture. That is, one of the embodiments is a gas separation method including a step of bringing a gas mixture made of two or more gas components into contact with the gas separation membrane of the embodiment and separating the gas mixture.

  The gas mixture is not particularly limited as long as it is a general gas mixture. For example, helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, normal butane, isobutane, 1-butene 2-butene, isobutene, pentane, pentene, cyclopentanediene, hexane, hexene, hexadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene, sulfur hexafluoride, carbon monoxide, nitrogen monoxide, water, and hydrogen sulfide Examples thereof include a gas mixture containing at least two gas components selected from the group.

  As the gas mixture, since it tends to be excellent in the separation efficiency of the gas mixture, that is, in the economy of the process of separating the gas mixture, the component having a high gas permeability coefficient and the component having a low gas permeability coefficient A mixture is preferred.

  As the gas mixture, by using the gas separation membrane of the present embodiment in practice, there is a possibility that the process becomes more economical, so helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, At least two selected from the group consisting of ethane, ethylene, propane, propylene, normal butane, isobutane, 1-butene, 2-butene, isobutene, sulfur hexafluoride, carbon monoxide, nitrogen monoxide, water, and hydrogen sulfide It is preferable that it is a gas mixture containing these gas components. The gas mixture is more preferably a gas mixture containing at least two gas components selected from the group consisting of helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, and water.

  In the step of separating the gas mixture using the gas separation membrane of the present embodiment, the region to which the gas mixture is supplied out of at least two regions divided by the gas separation membrane is passed through the gas separation membrane. The region containing the gas mixture to be used is defined as the transmission side.

The temperature of the step of separating the gas mixture using the gas separation membrane of the present embodiment is not particularly limited as long as it is a commonly used temperature, and the desired amount of the gas component that permeates the gas separation membrane or the present step It is appropriately selected depending on the temperature of the gas component supplied from the previous step.
Since the amount of the gas component that permeates the gas separation membrane tends to increase and becomes a more economical process, the temperature of the step of separating the gas mixture using the gas separation membrane of the present embodiment is as follows: The temperature is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher.
Since there exists a tendency which can suppress the bond dissociation in the high temperature of the urethane bond contained in curable urethane resin, the temperature of the process of isolate | separating the said gas mixture is 200 degrees C or less using the gas separation membrane of this embodiment. Is preferable, it is more preferable that it is 170 degrees C or less, and it is still more preferable that it is 150 degrees C or less.

The pressure on the supply side may be the same as long as the gas component to be separated is high, or may be used by adjusting the pressure appropriately to a desired pressure. When the gas component to be separated is lower than the pressure used for separation, the pressure can be increased with a compressor or the like. The pressure on the supply side is not particularly limited as long as it is a pressure generally used.
From the viewpoint of practical use, the pressure on the supply side is preferably atmospheric pressure or a pressure larger than atmospheric pressure, more preferably 0.1 MPa or more, and further preferably 0.11 MPa or more. From the same viewpoint, the pressure on the supply side is preferably 20 MPa or less, more preferably 10 MPa or less, and further preferably 8 MPa or less.

The differential pressure that is the difference between the pressure on the supply side and the pressure on the permeate side is not particularly limited as long as it is a differential pressure that is generally used. From the viewpoint of practical use, the differential pressure is preferably 21 MPa or less, more preferably 11 MPa or less, and further preferably 9 MPa or less. From the same viewpoint, the differential pressure is preferably more than 0 MPa, more preferably 0.001 MPa or more, and further preferably 0.01 MPa or more.
The differential pressure is the difference between the partial pressure of the specific gas component contained on the supply side and the partial pressure of the specific gas component contained on the permeation side. In order to obtain a desired differential pressure, the permeate side may be depressurized. Moreover, unless otherwise indicated, the pressure [Pa] in this embodiment points out an absolute pressure.

In the step of separating the gas mixture using the gas separation membrane of the present embodiment, the flow rate of the gas mixture to be supplied is not particularly limited as long as it is a generally used flow rate, but compensates for the decrease in the permeate gas mixture. It is preferable that the flow rate is higher than a certain level. In addition, the gas mixture to be supplied is mixed so that the concentration in the vicinity of the membrane of the gas component having a small permeability coefficient of the gas contained in the gas mixture to be supplied matches the concentration in the whole gas mixture to be supplied. It is more preferable that the flow rate be equal to or higher.
The flow rate depends on the shape of the gas separation membrane, the temperature of the step of separating the gas mixture, the pressure of the supplied gas mixture, the differential pressure, etc., but is usually preferably 0.5 mm / sec or more, preferably 1 mm / sec. More preferably. The upper limit of the flow rate is not particularly limited, and in the step of separating the gas mixture, the flow rate is preferably equal to or less than a flow rate at which desired separation is possible, more preferably 1 m / sec or less, and 0.5 m / sec or less. More preferably.

  In the step of separating the gas mixture, a sweep gas may be used on the permeate side. The method using the sweep gas is a method in which a gas component different from the gas mixture to be supplied is flowed to the permeate side and the gas component on the permeate side is recovered.

  The pressure of the sweep gas is not particularly limited as long as it is a pressure generally used. From the viewpoint of practical use, the pressure is preferably atmospheric pressure or a pressure larger than atmospheric pressure, more preferably 0.09 MPa or more, and further preferably 0.1 MPa or more. From the same viewpoint, the pressure is preferably 20 MPa or less, more preferably 10 MPa or less, and further preferably 8 MPa or less. In some cases, the pressure may be reduced.

  The flow rate of the sweep gas is not particularly limited as long as it is a generally used flow rate. Depending on the shape of the gas separation membrane, the temperature of the process of separating the gas mixture, the pressure, differential pressure, flow rate of the gas mixture supplied, the type of gas component used in the sweep gas, the pressure, etc., the flow rate is usually 0.5 mm. / Sec or more is preferable, and 1 mm / sec or more is more preferable. The upper limit of the flow rate is not particularly limited, and in the step of separating the gas mixture, the flow rate is preferably equal to or less than a flow rate at which desired separation is possible, more preferably 1 m / sec or less, and 0.5 m / sec or less. More preferably.

<Gas separation module>
The gas separation membrane of this embodiment can be suitably used for practical use by using a gas separation module. That is, one of the embodiments is a gas separation module including the gas separation membrane of the embodiment. The gas separation module is a container having at least a gas separation membrane, an introduction port to which a gas mixture is supplied, and an exhaust port from which the gas mixture that permeates the gas separation membrane is discharged. In addition, you may use for the gas separation module the film | membrane in which the gas separation membrane of this embodiment was formed on the porous support body.

  The shape of the gas separation membrane module is not particularly limited as long as it is generally used, and examples thereof include a spiral type, a hollow fiber type, a pleat type, a tubular type, and a plate & frame type.

<Gas separator>
The gas separation membrane of this embodiment and the gas separation module including the gas separation membrane can be used in an apparatus that provides means for separating and recovering or purifying gas components. Examples of the apparatus include those disclosed in JP-A-6-99035 and Ind. Eng. Chem. Res. 2009, 48, 4638-4663. And devices and systems described in JP2007-297605A.

  The gas separation membrane of the present embodiment, the gas separation module including the gas separation membrane, and the gas separation device including the gas separation module include, for example, carbon dioxide, hydrogen, oxygen, nitrogen, water vapor, It can be used as a technique for separating gaseous components such as dissolved gas and organic gas.

  Carbon dioxide separation technology includes landfill gas generated by removal of carbon dioxide from natural gas and landfilling of organic matter such as domestic waste (containing about 60% methane, about 40% carbon dioxide, containing trace amounts of nitrogen and water vapor) And carbon dioxide removal from artificial fermentation gas discharged from an anaerobic fermentation process generated artificially.

  Hydrogen separation technologies include hydrogen recovery in the petroleum refining industry, hydrogen recovery and refining in various reaction processes in the chemical industry (mixtures of hydrogen, carbon monoxide, carbon dioxide, hydrocarbons, etc.), and production of high-purity hydrogen for fuel cells. Etc. Hydrogen production for fuel cells is obtained by a steam reforming reaction of methane, and it is necessary to separate hydrogen from a mixed gas of hydrogen, carbon monoxide, methane, and water.

  In addition, as oxygen separation technology, production of oxygen-enriched gas from air (medical, oxygen-enriched air for combustion, etc.), as nitrogen separation technology, production of nitrogen-enriched gas from air (explosion-proof, antioxidant, etc.) ), Water vapor separation (dehumidification of precision machinery, etc.), dissolved gas separation (deaeration from water and organic liquids), organic gas separation (organic gas separation in the oil refining industry and petrochemical industry, separation of olefin and paraffin), etc. Is mentioned.

  Examples that specifically describe this embodiment will be described below. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.

  The gas separation membrane was evaluated as follows.

<Defect evaluation of gas separation membrane: Defect evaluation>
(Gas component)
Carbon dioxide gas (manufactured by Sumitomo Seika Co., Ltd., purity:> 99.9%, hereinafter referred to as “CO ₂ ”)
Methane gas (Sumitomo Seika Co., Ltd., purity:> 99.9%, hereinafter referred to as “CH ₄ ”)
(Evaluation method)
(1) A test piece of 48 mmφ was attached to a stainless gas line holder (LS-47-HP manufactured by Advantech Co., Ltd.). In this evaluation, hereinafter, through the test piece, the side where the support screen is located is the transmission side, and the opposite side is the supply side. The stainless steel holder was placed in a small high temperature chamber (ST-110 type manufactured by ESPEC) adjusted to 35 ± 0.1 ° C.
(2) CO ₂ was supplied to the supply side to obtain a pressure of about 0.3 MPa and then to atmospheric pressure. The same operation was repeated twice.
(3) After supplying CO ₂ to the supply side to obtain a pressure of 0.3 ± 0.01 MPa, the pressure was kept constant. The flow rate of CO ₂ on the permeate side was measured using a mass flow meter (M series manufactured by ALICAT).
(4) After the supply side was set to atmospheric pressure, CH ₄ was supplied to obtain a pressure of about 0.3 MPa, and then the atmospheric pressure was set. The same operation was repeated twice.
(5) CH ₄ was supplied to the supply side to obtain a pressure of 0.3 ± 0.01 MPa, and then the pressure was kept constant. The flow rate of CH ₄ on the permeate side was measured using a mass flow meter (M series manufactured by ALICAT).
(6) When the value obtained by dividing the flow rate of CO ₂ obtained in (3) by the flow rate of CH ₄ obtained in (5) was 2 or more, it was judged as good (“A”). When it was less than 2, it was judged as rejected ("C"), and subsequent transmission evaluation A, transmission evaluation B, and resistance evaluation were not performed.

<Evaluation of permeability coefficient of single gas component: Permeation evaluation A>
According to JIS K-7126-1 (Plastic-Film and Sheet-Gas Permeability Test Method-Part 1: Appendix 2 (normative) Gas Permeability Test Method by Gas Chromatograph Method), the permeability coefficient of the gas component was evaluated. In addition, the apparatus used, the gas component, test conditions, etc. are shown below.
(apparatus)
Dissolution coefficient / diffusion coefficient assumption device (GTR-30X, manufactured by GTR Tech Co., Ltd.)
(Gas component)
Helium gas (manufactured by Japan Air Liquide Co., Ltd., purity:> 99.995%, hereinafter referred to as “He”)
Hydrogen gas (manufactured by Japan Air Liquide Co., Ltd., purity:> 99.9%, hereinafter referred to as “H ₂ ”)
Carbon dioxide gas (manufactured by Sumitomo Seika Co., Ltd., purity:> 99.9%, hereinafter referred to as “CO ₂ ”)
Oxygen gas (manufactured by Japan Air Liquide Co., Ltd., purity:> 99.5%, hereinafter referred to as “O ₂ ”)
Nitrogen gas (manufactured by Japan Air Liquide Co., Ltd., purity:> 99.999%, hereinafter referred to as “N ₂ ”)
Methane gas (Sumitomo Seika Co., Ltd., purity:> 99.9%, hereinafter referred to as “CH ₄ ”)
(Test conditions)
Test temperature: 35 ± 0.1 ° C
Supply gas component pressure: 0.2 ± 0.01 MPa (gauge pressure)
Transmission area: 15.2 cm ²
Number of specimens: 6
Number of tests: 3 times per specimen (measurement of specimen size and thickness)
Size of test piece: 53mmφ
Thickness of test piece: Thickness using a micrometer (Mitutoyo Co., Ltd., MDH-25M) at a total of 9 points, 1 point at the center of the test piece, a distance of 5 mm above the cross perpendicular to the center, and 8 points of 15 mm. Was measured. When the value 100 times the value obtained by dividing the standard error of the thickness of the obtained test piece by the average value is less than 1, the test piece was used for evaluation.
(Changes in test method)
In the method of JIS K-7126-1, when removing the adsorbed gas before the test, the temperature of the thermostatic chamber in which the film was installed was set to 80 ° C. and held for 8 hours. Then, it cooled to the test temperature and implemented the test. Moreover, when the same test piece was repeatedly tested, the method for removing the adsorbed gas described in JIS K-7126-1 was performed in order to remove the adsorbed gas adsorbed on the film. In addition, the temperature of the thermostat in which the membrane was installed was 80 ° C., held for 8 hours, and then cooled to the test temperature.
(Calculation of transmission coefficient)
The transmission coefficient was calculated according to JIS K-7126-1. Since six tests are performed for each gas component and three tests are performed for each test specimen, a total of 18 transmission coefficients are obtained. The average value of the transmission coefficients of a total of 18 points thus obtained was defined as the transmission coefficient. In this example, the unit of the transmission coefficient was cm ³ · cm / (cm ² · s · cmHg).

<Permeation coefficient evaluation of two or more gas components: Permeation evaluation B>
According to JIS K-7126-2 (Plastic-Film and Sheet-Gas Permeability Test Method-Part 2: Appendix 2 (normative) Test Method by Gas Chromatograph Method), the permeability coefficient of gas components was evaluated. In addition, the apparatus used, the gas component, test conditions, etc. are shown below.
(apparatus)
Flow type gas permeability measuring device (RGP-2000AX, manufactured by Round Science Co., Ltd.)
(Gas component)
Helium gas (manufactured by Japan Air Liquide Co., Ltd., purity:> 99.995%, hereinafter referred to as “He”)
Carbon dioxide gas (manufactured by Sumitomo Seika Co., Ltd., purity:> 99.9%, hereinafter referred to as “CO ₂ ”)
Nitrogen gas (manufactured by Japan Air Liquide Co., Ltd., purity:> 99.999%, hereinafter referred to as “N ₂ ”)
Methane gas (Sumitomo Seika Co., Ltd., purity:> 99.9%, hereinafter referred to as “CH ₄ ”)
(Test conditions)
Test temperature: 50 ± 0.1 ° C
Supply gas component pressure: atmospheric pressure Permeation area: 15.9 cm ²
Number of specimens: 3
Number of tests: 2 times per specimen (measurement of specimen size and thickness)
Size of test piece: 54mmφ
Thickness of test piece: Thickness using a micrometer (Mitutoyo Co., Ltd., MDH-25M) at a total of 9 points, 1 point at the center of the test piece, a distance of 5 mm above the cross perpendicular to the center, and 8 points of 15 mm. Was measured. When the value 100 times the value obtained by dividing the standard error of the thickness of the obtained test piece by the average value is less than 1, the test piece was used for evaluation.
(Changes in test method-1)
In the method of JIS K-7126-2, in order to remove the adsorbed gas adsorbed on the membrane before the test, He was flowed on both sides of the membrane, the temperature of the thermostatic bath was set to 80 ° C., and held for 8 hours. Then, it cooled to the test temperature and implemented the test. When the same test piece was repeatedly tested, in order to remove the adsorbed gas adsorbed on the membrane, He was allowed to flow on both sides of the membrane, and the temperature of the thermostatic bath was set to 80 ° C. and held for 8 hours. Then, it cooled to the test temperature and implemented the test.
(Changes in test method-2)
The composition of the gas component to be supplied was determined by the same method as that for creating the calibration curve described in JIS K-7126-2.
(Calculation of transmission coefficient)
The transmission coefficient was calculated according to JIS K-7126-2. Since the test is performed twice for three test pieces and one test piece for each gas component used, a total of six transmission coefficients can be obtained. The average value of the transmission coefficients of a total of 6 points was used as the transmission coefficient. In this example, the unit of the transmission coefficient was set to cm ³ · cm / (cm ² · s · cmHg) by the conversion described in JIS K-7126-1.

<Calculation of separation factor>
Using the permeability coefficients of the two gas components obtained by permeability evaluation, the separation coefficient was calculated by dividing each of the permeability coefficients.

<Evaluation of resistance to liquid chemicals: Evaluation of resistance>
(1) A 20 mmφ test piece was placed in a 50 mL glass vial, and 40 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was added.
(2) The vial was attached to a rotary shaker (manufactured by ASONE Co., Ltd., RS-2 type) and shaken at 23 ° C. for 24 hours at 150 rpm.
(3) The test piece was taken out from the vial after shaking. When it was able to be taken out while maintaining a circular shape, it was judged as good (“A”). Further, when all the test pieces were dissolved or could not be taken out, the test piece was rejected (“C”).

  The raw materials used in the examples and comparative examples are shown below.

(Polyisocyanate)
(1) Polyisocyanate having an isocyanurate structure (trade name: Duranate TPA-100, manufactured by Asahi Kasei Corporation, NCO content: 23% by mass, hereinafter referred to as “A-1”)
(2) Polyisocyanate having a biuret structure (trade name: Duranate 24A-100, manufactured by Asahi Kasei Corporation, NCO content: 23% by mass, hereinafter referred to as “A-2”)
(3) Polyisocyanate having an adduct structure (trade name: Duranate AE700-100, manufactured by Asahi Kasei Corporation, NCO content: 12% by mass, hereinafter referred to as “A-3”)

(Polyol)
(4) Polycarbonate diol (trade name: DURANOL G4672, manufactured by Asahi Kasei Corporation, hydroxyl value: 54 mgKOH / g, number average molecular weight (Mn): about 2000, hereinafter referred to as “B-1”)
(5) Polyethylene glycol 2000 (manufactured by Wako Pure Chemical Industries, Ltd., hydroxyl value: 56 mgKOH / g, hereinafter referred to as “B-2”)

(Thermoplastic urethane resin)
(6) MDI-polyester / polyether polythene (manufactured by Aldrich, product number: 430218, hereinafter referred to as “C-1”)

(Zeolite)
(7) SAPO-34 (zeolite having an oxygen 8-membered ring having a CHA structure, manufactured by JGC Catalysts & Chemicals, Inc., hereinafter referred to as “D-1”)
(8) ZSM-5 (zeolite having an oxygen 10-membered ring having an MFI structure, manufactured by JGC Catalysts & Chemicals, Inc., hereinafter referred to as “D-2”)
(9) NaY (zeolite having an oxygen 12-membered ring having a FAU structure, HS-320 manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “D-3”)
(10) 4A (zeolite having an oxygen 8-membered ring having an LTA structure, Shiruton M, manufactured by Mizusawa Chemical Co., Ltd., hereinafter referred to as “D-4”)

(solvent)
(11) Chloroform (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade grade, hereinafter referred to as “E-1”)
(12) N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade, hereinafter referred to as “E-2”)

Example 1
A gas separation membrane containing a curable urethane resin and zeolite was produced according to the following procedure.
(1) SAPO-34 was put in a glass container and dried with a vacuum dryer. The conditions of the vacuum dryer were as follows.
Vacuum dryer: Tokyo Rika Instruments Co., Ltd., VOS-451D
Vacuum pump: ULVAC Kiko Co., Ltd., small oil rotary vacuum pump GCD-201X
(1-1) At room temperature, the vacuum valve of the vacuum dryer was fully opened, the temperature was raised to 100 ° C. at a rate of temperature increase of 5 ° C./min, and held for 24 hours.
(1-2) After cooling to room temperature, the vacuum valve was fully closed, the purge valve capable of introducing nitrogen was opened, and the pressure was normal.
(2) According to the composition ratio in Table 1, the polyisocyanate compound, the polyol compound, and the solvent are put in a container and mixed for 10 minutes at 2000 rpm with a rotation / revolution mixer (ARE-500 manufactured by Sinky Co., Ltd.). A resin composition was obtained.
(3) Place the curable urethane resin composition obtained in (2) and the dried SAPO-34 obtained in (1) in a container so that the composition ratios shown in Table 2 are obtained. ARE-500 (manufactured by Shinki Corporation) was mixed at 2000 rpm for 10 minutes to obtain a mixture containing a curable urethane resin composition and zeolite.
(4) The container containing the mixture was placed in an ultrasonic dispersion device (Ultrasonic Processor UTR200, manufactured by Hielscher), and ultrasonically dispersed in an Amplitude 60 for 5 minutes.
(5) The mixture obtained in (4) was put into a polytetrafluoroethylene petri dish, and the solvent was removed and polymerized under the following conditions.
Vacuum dryer: Tokyo Rika Instruments Co., Ltd., VOS-451D
Vacuum pump: ULVAC Kiko Co., Ltd., small oil rotary vacuum pump GCD-201X
(5-1) The polytetrafluoroethylene petri dish containing the mixture obtained in (4) was placed in a vacuum dryer.
(5-2) Adjust the opening degree of the vacuum valve of the vacuum dryer and the purge valve capable of introducing nitrogen at room temperature, reduce the pressure to -0.02 MPa (gauge pressure), and increase the temperature at 5 ° C / min. At 60 ° C. and held for 5 hours.
(5-3) The purge valve was closed, the vacuum valve was fully opened, and held for 3 hours.
(5-4) The temperature was raised to 100 ° C. at 5 ° C./min and held for 3 hours.
(5-5) The temperature was raised to 120 ° C. at 5 ° C./min and held for 3 hours.
(5-6) After cooling to room temperature, the polytetrafluoroethylene petri dish was taken out from the vacuum dryer.
(6) A gas separation membrane containing a curable urethane resin and zeolite was taken out from the polytetraethylene petri dish. In Table 1, the zeolite content (% by mass) contained in the gas separation membrane is obtained by dividing the mass of the zeolite by the sum of the mass of the zeolite, the mass of the polyisocyanate compound, and the mass of the polyol compound. It was described as a value multiplied by 100.

(Examples 2-9)
A gas separation membrane was obtained in the same manner as in Example 1 except that the composition ratios in Table 1 were used.

  Table 2 shows the results of defect evaluation, permeation evaluation A, and resistance evaluation of the gas separation membranes obtained in Examples 1 to 9.

  Table 3 shows typical separation factors of the gas separation membranes obtained in Examples 1 to 9.

(Comparative Example 1)
A gas separation membrane containing a thermoplastic urethane resin and zeolite was produced according to the following procedure.
(1) SAPO-34 was put in a glass container and dried with a vacuum dryer. The conditions of the vacuum dryer were as follows.
Vacuum dryer: Tokyo Rika Instruments Co., Ltd., VOS-451D
Vacuum pump: ULVAC Kiko Co., Ltd., small oil rotary vacuum pump GCD-201X
(1-1) At room temperature, the vacuum valve of the vacuum dryer was fully opened, the temperature was raised to 100 ° C. at a rate of temperature increase of 5 ° C./min, and held for 24 hours.
(1-2) After cooling to room temperature, the vacuum valve was fully closed, the purge valve capable of introducing nitrogen was opened, and the pressure was normal.
(2) An oil bath containing oil and a stirrer was placed on a magnetic stirrer, and the temperature was 65 ° C.
(3) According to the composition ratio in Table 4, the thermoplastic urethane resin and the solvent were placed in a three-necked flask container in a nitrogen atmosphere, and a stir bar was placed, and then placed in the oil bath of (2).
(4) After stirring at 65 ° C. for 6 hours, the mixture was cooled to room temperature.
(5) The SAPO-34 after drying obtained in (1) is placed in a three-necked flask container containing the solution containing the thermoplastic urethane resin obtained in (4) so that the composition ratio in Table 4 is obtained. The mixture was mixed with a rotation / revolution mixer (ARE-500 manufactured by Sinky Corporation) at 2000 rpm for 10 minutes to obtain a mixture containing a thermoplastic urethane resin and zeolite.
(6) The container containing the mixture was placed in an ultrasonic dispersion device (Ultrasonic Processor UTR200, manufactured by Hielscher), and ultrasonically dispersed in an Amplitude 60 for 5 minutes.
(7) The mixture obtained in (6) was put into a polytetrafluoroethylene petri dish, and the solvent was removed and heated under the following conditions.
Vacuum dryer: Tokyo Rika Instruments Co., Ltd., VOS-451D
Vacuum pump: ULVAC Kiko Co., Ltd., small oil rotary vacuum pump GCD-201X
(7-1) The polytetrafluoroethylene petri dish containing the mixture obtained in (6) was placed in a vacuum dryer.
(7-2) Adjust the opening degree of the vacuum valve of the vacuum dryer and the purge valve that can introduce nitrogen at room temperature, reduce the pressure to -0.02 MPa (gauge pressure), and increase the temperature at 5 ° C / min. At 60 ° C. and held for 5 hours.
(7-3) The purge valve was closed, the vacuum valve was fully opened, and held for 3 hours.
(7-4) The temperature was raised to 100 ° C. at 5 ° C./min and held for 24 hours.
(7-6) After cooling to room temperature, the polytetrafluoroethylene petri dish was taken out from the vacuum dryer.
(8) A gas separation membrane containing a thermoplastic urethane resin and zeolite was taken out from the polytetraethylene petri dish. In Table 4, the zeolite content (% by mass) contained in the gas separation membrane was multiplied by 100 by dividing the mass of the zeolite by the sum of the mass of the zeolite and the mass of the thermoplastic urethane resin. Described as a value.

(Comparative Examples 2 to 4)
A gas separation membrane was obtained by the same method as in Comparative Example 1 except that the composition ratios in Table 4 were used.

  Table 5 shows the results of defect evaluation and resistance evaluation of the gas separation membranes obtained in Comparative Examples 1 to 4.

(Comparative Examples 5 to 8)
In Comparative Examples 1 to 4, good results were not obtained in the defect evaluation. Nat. GasSci. Technol. 2016, 695-702. Table 6 shows the composition of the gas separation membrane containing the thermoplastic urethane resin described in 1 and ZEM-5, the permeation coefficient of the gas component shown, and the value read from the separation coefficient.

(Comparative Examples 9-20)
In Comparative Examples 1 to 4, good results were not obtained in the defect evaluation. Polym. Technol. 2016, AheadofPrint. Tables 7 and 8 show the permeability coefficient and separation coefficient of the gas component described in (DOI: 10.1002 / adv. 21672).

  As shown in Tables 1-8, the gas separation membrane containing a curable urethane resin and zeolite according to this example is more permeable to gas components than a gas separation membrane containing a thermoplastic urethane resin and zeolite. It was confirmed that the gas separation membrane had a high coefficient and a high separation factor for gas components, and was excellent in resistance to liquid chemical substances, that is, plasticization resistance due to condensed components.

(Example 10)
A gas separation membrane containing a curable urethane resin and zeolite was produced according to the following procedure.
(1) SAPO-34 was put in a glass container and dried with a vacuum dryer. The conditions of the vacuum dryer were as follows.
Vacuum dryer: Tokyo Rika Instruments Co., Ltd., VOS-451D
Vacuum pump: ULVAC Kiko Co., Ltd., small oil rotary vacuum pump GCD-201X
(1-1) At room temperature, the vacuum valve of the vacuum dryer was fully opened, the temperature was raised to 100 ° C. at a rate of temperature increase of 5 ° C./min, and held for 24 hours.
(1-2) After cooling to room temperature, the vacuum valve was fully closed, the purge valve capable of introducing nitrogen was opened, and the pressure was normal.
(2) Polyisocyanate compound (A-1) 1.5 parts by mass, polyol compound (B-1) 2.9 parts by mass, polyol compound (B-2) 5.6 parts by mass, solvent (E-1) 80 The mass part was put into a container and mixed for 10 minutes at 2000 rpm with a rotation / revolution mixer (ARE-500, manufactured by Shinky Corporation) to obtain a curable urethane resin composition.
(3) 10 parts by mass of SAPO-34 (D-1), 1.5 parts by mass of polyisocyanate compound (A-1), 2.9 parts by mass of polyol compound (B-1), polyol compound (B-2) Put curable urethane resin composition obtained in (2) and SAPO-34 after drying obtained in (1) into a container so that 5.6 parts by mass and solvent (E-1) 80 parts by mass are obtained. The mixture containing curable urethane resin composition and zeolite was obtained by mixing with a rotation / revolution mixer (ARE-500, manufactured by Sinky Corporation) for 10 minutes at 2000 rpm.
(4) The container containing the mixture was placed in an ultrasonic dispersion device (Ultrasonic Processor UTR200, manufactured by Hielscher), and ultrasonically dispersed in an Amplitude 60 for 5 minutes.
(5) The mixture obtained in (4) was put into a polytetrafluoroethylene petri dish, and the solvent was removed and polymerized under the following conditions.
Vacuum dryer: Tokyo Rika Instruments Co., Ltd., VOS-451D
Vacuum pump: ULVAC Kiko Co., Ltd., small oil rotary vacuum pump GCD-201X
(5-1) The polytetrafluoroethylene petri dish containing the mixture obtained in (4) was placed in a vacuum dryer.
(5-2) Adjust the opening degree of the vacuum valve of the vacuum dryer and the purge valve capable of introducing nitrogen at room temperature, reduce the pressure to -0.02 MPa (gauge pressure), and increase the temperature at 5 ° C / min. At 60 ° C. and held for 5 hours.
(5-3) The purge valve was closed, the vacuum valve was fully opened, and held for 3 hours.
(5-4) The temperature was raised to 100 ° C. at 5 ° C./min and held for 3 hours.
(5-5) The temperature was raised to 120 ° C. at 5 ° C./min and held for 3 hours.
(5-6) After cooling to room temperature, the polytetrafluoroethylene petri dish was taken out from the vacuum dryer.
(6) A gas separation membrane containing a curable urethane resin and zeolite was taken out from the polytetraethylene petri dish. The zeolite content (% by mass) contained in the obtained gas separation membrane is a value obtained by multiplying 100 by the value obtained by dividing the mass of the zeolite by the sum of the mass of the zeolite, the mass of the polyisocyanate compound and the mass of the polyol compound. Was calculated to be 50% by mass.

  Tables 9 and 10 show the defect evaluation, permeation evaluation A, resistance evaluation results, and separation factors of the gas separation membrane obtained in Example 10.

  As shown in Table 9 and Table 10, the gas separation membrane according to the present embodiment, which contains a curable urethane resin and zeolite, and when polyether diols and polycarbonate diols are used as the polyol compound, gas It has been confirmed that the gas separation membrane has a high permeability coefficient for components and a high separation coefficient for gas components, and is excellent in resistance to liquid chemical substances, that is, plasticization resistance due to condensed components.

Using the gas separation membrane obtained in Example 10, permeability evaluation B was performed. The composition when a mixed gas of CO ₂ and CH ₄ was used as the supply gas was 10% CO ₂ /90% CH ₄ . The composition when a mixed gas of CO ₂ and N ₂ was used as the supply gas was 10% CO ₂ /90% N ₂ . The obtained results are shown in Table 11.

Using the gas separation membrane obtained in Example 10, permeability evaluation B was performed. 200ppm of moisture (hereinafter, "H ₂ O", that.) A gas mixture of CO ₂ and CH ₄ containing composition when used as a feed gas, in _{10% CO 2/90% CH} 4 / 200ppmH 2 O there were. The composition of the case of using a mixed gas of CO ₂ and N ₂ containing of H ₂ O 200ppm as feed gas _{was 10% CO 2/90% N} 2 / 200ppmH 2 O. Table 12 shows the obtained results. In addition, when performing the permeability evaluation B, according to JIS K7219 (Plastic-film and sheet-how to obtain water vapor permeability (instrument measurement method): Annex C (normative) how to obtain water vapor permeability by gas chromatography) Water permeability (water vapor permeability) was evaluated.

  The gas separation membrane according to the present invention, the gas separation module including the gas separation membrane, and the gas separation device provided with the gas separation module can be obtained by removing carbon dioxide from natural gas, or landfilling organic matter such as domestic waste. Carbon dioxide removal from the generated landfill gas (approximately 60% methane, approximately 40% carbon dioxide, trace amounts of nitrogen and water vapor), carbon dioxide from artificial fermentation gas discharged from an anaerobic fermentation process generated artificially Carbon removal, hydrogen recovery in the petroleum refining industry, hydrogen recovery and purification in various reaction processes in the chemical industry (mixtures of hydrogen, carbon monoxide, carbon dioxide, hydrocarbons, etc.), production of high-purity hydrogen for fuel cells (methane Hydrogen separation from hydrogen, carbon monoxide, methane, and water mixture obtained by steam reforming reaction), production of oxygen-enriched gas from air (medical use, Oxygen-enriched air for baking), production of nitrogen-enriched gas from air (explosion-proof, antioxidant, etc.), steam separation (dehumidification of precision machinery, etc.), dissolved gas separation (water, organic) Degassing from liquid), organic gas separation (organic gas separation in petroleum refining industry, petrochemical industry, separation of olefin and paraffin), etc., it has industrial applicability.

Claims (10)

  A gas separation membrane comprising a curable urethane resin and zeolite.   The gas separation membrane according to claim 1, wherein the zeolite has at least one kind of pores selected from the group consisting of pores composed of oxygen 8-membered rings to oxygen 12-membered rings.   The gas separation membrane according to claim 1 or 2, wherein the curable urethane resin has at least one structure selected from the group consisting of a polycarbonate structure, a polyether structure, a polyester structure, and a polycaprolactone structure.   The curable urethane resin has at least one structure selected from the group consisting of an isocyanurate structure, a biuret structure, an adduct structure, a polynuclear structure, an allophanate structure, and a urea structure, according to any one of claims 1 to 3. Gas separation membrane. Curable urethane resin
A polyol compound having at least one structure selected from the group consisting of a polycarbonate structure, a polyether structure, a polyester structure, a polycaprolactone structure, and two or more hydroxyl groups;
A polyisocyanate compound having at least one structure selected from the group consisting of an isocyanurate structure, a biuret structure, an adduct structure, a polynuclear structure, an allophanate structure and a urea structure, and three or more isocyanate groups;
The gas separation membrane as described in any one of Claims 1-4 which is resin which hardened | cured the curable urethane resin composition containing this. Curable urethane resin
A polyol compound having at least one structure selected from the group consisting of a polycarbonate structure, a polyether structure, a polyester structure, a polycaprolactone structure, and three or more hydroxyl groups;
Isocyanurate structure, biuret structure, adduct structure, polynuclear structure, allophanate structure, at least one structure selected from the group consisting of urea structures, and a polyisocyanate compound having two or more isocyanate groups, or a diisocyanate compound,
The gas separation membrane as described in any one of Claims 1-4 which is resin which hardened | cured the curable urethane resin composition containing this.   A gas separation method comprising: bringing the gas mixture comprising two or more gas components into contact with the gas separation membrane according to any one of claims 1 to 6 and separating the gas mixture.   The gas mixture is helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, normal butane, isobutane, 1-butene, 2-butene, isobutene, pentane, pentene, cyclopentanediene, hexane. And at least two gas components selected from the group consisting of hexene, hexadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene, sulfur hexafluoride, carbon monoxide, nitric oxide, water, and hydrogen sulfide. The gas separation method described.   A gas separation module comprising the gas separation membrane according to claim 1.   A gas separation device comprising the gas separation membrane according to any one of claims 1 to 6 or the gas separation module according to claim 9.