JP5934640B2 - LAMINATE, MANUFACTURING METHOD THEREOF, AND GAS SEPARATION MEMBRANE - Google Patents

Description

  The present invention relates to a laminate, a method for producing the same, and a gas separation membrane. More specifically, hydrogen, helium, carbon monoxide, carbon dioxide, hydrogen sulfide, oxygen, nitrogen, ammonia, sulfur oxides, nitrogen oxides, hydrocarbons such as methane and ethane, unsaturated hydrocarbons such as propylene, tetrafluoro Regarding a laminate that can be used as a novel gas separation membrane that can efficiently separate a specific gas from a gas mixture containing a gas such as a perfluoro compound such as ethane, particularly carbon dioxide is selected from a gas mixture containing carbon dioxide The present invention relates to a laminate that can be used as a gas separation membrane to be separated. Moreover, it is related with the manufacturing method of the laminated body which can be used as said gas separation membrane. The present invention also relates to a gas separation membrane including the laminate, and more particularly to a gas separation membrane capable of separating at least one acidic gas from a gas mixture of acidic gas and non-acidic gas.

  Conventionally, it has been known that a gas component can be separated by a polymer film composed of a polymer material because the polymer material has gas permeability unique to the material. In connection with the problems of global warming in recent years, there is a possibility that carbon dioxide can be separated and recovered with energy saving from large-scale carbon dioxide generation sources such as thermal power plants, cement plants, steelworks blast furnaces, etc. Attention has been focused on separating gas components by a polymer membrane. Natural gas and biogas (biological excrement, organic fertilizer, biodegradable material, sewage, garbage, gas generated by fermentation and anaerobic digestion of energy crops) are mainly mixed gas of methane and carbon dioxide, hydrogen Is generally produced through steam reforming of natural gas and water gas shift, and in the production process, a gas mixture of about 40% of carbon dioxide and about 60% of hydrogen is obtained. If carbon dioxide, which is a low concentration impurity, can be selectively permeated and removed, it can be said that it is economically superior as a separation and purification method, and a membrane separation method has been studied as a means for removing impurities (Patent Document 1, Patent). Reference 2).

  By the way, the gas permeability (permeability coefficient) in the polymer membrane is expressed by the product of the solubility coefficient (solubility) of the gas in the polymer membrane and the diffusion coefficient (diffusivity) (Non-Patent Document 1). Therefore, in order to selectively improve the permeability (permeability coefficient) of carbon dioxide with respect to the separation target gas, the solubility coefficient (solubility) and / or diffusion coefficient (diffusibility) of carbon dioxide in the polymer membrane However, a general polymer membrane has been known to have a trade-off relationship that the permeability decreases when the selectivity is increased.

  Conventionally, a gas separation membrane is a laminate having an asymmetric structure mainly composed of a porous layer that mainly performs a supporting function and a dense layer that mainly performs a separating function, and the dense layer in which gas permeation resistance is generated has a low gas permeation rate. It is used so as not to become thin. Patent Document 3 discloses a composite gas separation in which a porous polyacrylonitrile structure support, a gutter layer containing a crosslinked phenyl-containing polar organopolysiloxane, and an ultrathin selective membrane layer made of a specific fluorine atom-containing polyimide are laminated. A membrane is disclosed. Patent Document 4 discloses a gas composite separation membrane in which an aliphatic porous polyimide support layer and a thin film made of fluorine atom-containing polyimide are laminated.

JP 2007-297605 A JP 2006-297335 A JP-A-6-269650 JP-A-8-52332

Supervised by Kazuyoshi Nagai, CMC Publishing, “Latest Technology of Gas Separation / Permeation / Barrier Membrane”, pages 52-59

  In the composite films described in Patent Documents 3 and 4, it is necessary to stack a uniform thin film on the porous layer. However, as a result of studies by the present inventors, a uniform thin film is formed on the porous layer. It has been found that it is not easy to obtain a high-performance gas separation membrane by the methods shown in these documents. That is, a laminate having high gas separation performance and a large gas permeation flux has not been known.

  The problem to be solved by the present invention is to provide a laminate having high gas separation performance and high gas permeation flux.

  As a result of intensive studies by the inventor in order to solve the above problems, a liquid crystal layer of an ultrathin film in a specific range is used as a dense layer, and a highly gas permeable layer such as an arbitrary porous layer is laminated on the liquid crystal layer. By doing so, it was found that the gas permeation flux can be increased by using an ultrathin dense layer, and further the gas separation performance is improved, and the present invention has been achieved. The gas permeation flux is expressed by gas permeability (permeation coefficient) / film thickness. Although the gas permeability cannot be improved by reducing the film thickness, the permeation flux can be improved. Although the trade-off relationship cannot be overcome, gas permeation flux and high separation selectivity can both be achieved by making the film ultra-thin.

The present invention, which is a specific means for solving the problems to be solved by the present invention, has the following configuration.
[1] A liquid crystal layer having a film thickness of 0.5 nm to 10 nm and a highly gas permeable layer having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the same kind of gas. A laminate comprising:
[2] High gas permeability having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the substrate, the liquid crystal layer having a film thickness of 0.5 nm to 10 nm, and the same kind of gas The laminated body characterized by including a layer in this order.
[3] In the laminate according to [1] or [2], the liquid crystal layer is preferably an optically anisotropic layer formed by fixing the alignment state of the polymerizable liquid crystal compound.
[4] In the laminate according to any one of [1] to [3], it is preferable that the high gas-permeable layer contains a crosslinked polymer.
[5] In the laminate according to [4], the crosslinked polymer is at least one selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polydimethylsiloxane, polyvinylpyrrolidone, polyethyleneimine, polyimide, and polyallylamine. It is preferable to have a repeating unit constituting a seed polymer.
[6] In the laminate according to any one of [1] to [5], the substrate is preferably a polyethylene terephthalate film.
[7] In the laminate according to any one of [1] to [6], the liquid crystal layer preferably has an average roughness Ra of 1 nm or less.
[8] Application of applying a polymerizable liquid crystal composition containing (A) a polymerizable liquid crystal compound, (B) a photopolymerization initiator and (C) an organic solvent on a substrate to a thickness of 0.5 to 10 nm. A step of aligning the polymerizable liquid crystal compound by applying heat, an irradiation step of irradiating the polymerizable liquid crystal composition with active radiation to fix the liquid crystal phase and obtaining a liquid crystal layer, and And a step of laminating a high gas permeable layer having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the same kind of gas, Method.
[9] In the method for manufacturing a laminate according to [8], it is preferable that the substrate is peeled from the laminate including the substrate, the liquid crystal layer, and the highly gas permeable layer in this order.
[10] In the method for producing a laminate according to [8] or [9], the substrate is preferably a polyethylene terephthalate film.
[11] A laminate produced by the method for producing a laminate according to any one of [8] to [10].
[12] A gas separation membrane comprising the laminate according to any one of [1] to [7] and [11].
[13] The gas separation membrane according to [12] is preferably capable of separating at least one kind of acidic gas from a gas mixture of acidic gas and non-acidic gas.

  According to the present invention, it is possible to provide a laminate having high gas separation performance and high gas permeation flux.

FIG. 1 is a schematic cross-sectional view showing an example of the laminate of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the laminate of the present invention.

Below, the laminated body of this invention, the manufacturing method of a laminated body, etc. are demonstrated in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Laminated body, gas separation membrane]
<Configuration>
The laminated body of the present invention has a high gas permeability that has a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with a liquid crystal layer having a film thickness of 0.5 nm to 10 nm with the same kind of gas And a sex layer. The gas separation membrane of the present invention includes the laminate of the present invention.
With such a configuration, it can be used as a high performance gas separation membrane having high gas separation performance and a large gas permeation flux. Although not bound by any theory, by controlling the film thickness of the liquid crystal layer to a level close to the molecular size level, a very dense liquid crystal layer can be obtained by making the molecular arrangement different from that of the thick film. It is thought that it was done.
FIG. 1 shows a schematic cross-sectional view of an example of the laminate of the present invention having such a configuration. The laminate 4 of the present invention has a liquid crystal layer 1 and a high gas permeability layer 2. The liquid crystal layer 1 and the high gas permeable layer 2 are preferably adjacent to each other.
The laminate of the present invention can be used alone as a gas separation membrane. However, the gas separation membrane of the present invention may be the laminate of the present invention, or may include other members known as general configurations of other gas separation membranes in addition to the laminate of the present invention. Also good.

Further, the laminate of the present invention may be an embodiment having a substrate that can be optionally peeled off. Specifically, the laminate of the present invention includes a substrate and a liquid crystal having a film thickness of 0.5 nm to 10 nm. And a high gas permeable layer having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the same kind of gas in this order. Good. The substrate may be non-gas permeable and may not be used as a gas separation membrane in this configuration, but the liquid crystal layer which is an ultra-thin dense layer and the high gas permeable layer (for example, a porous layer) Can be used as a gas separation membrane.
FIG. 2 shows a schematic cross-sectional view of an example of the laminate of the present invention having such a configuration. The laminate 4 of the present invention has the substrate 3, the liquid crystal layer 1, and the high gas permeable layer 2 in this order. The substrate 3 and the liquid crystal layer 1, and the liquid crystal layer 1 and the high gas permeable layer 2 are preferably adjacent to each other.

<Characteristics: Gas separation performance>
The laminate and gas separation membrane of the present invention are preferably gas separation membranes for separating at least one acidic gas from a gas mixture of acidic gas and non-acidic gas.
In the laminate of the present invention, the separation ratio between the acidic gas and the non-acidic gas (permeation flux of acidic gas / permeation flux of non-acidic gas) is preferably 18 or more, and more preferably 20 or more. , 22 or more is particularly preferable. There is no restriction | limiting in particular about the upper limit of the separation ratio of the said acidic gas and non-acidic gas.

Examples of the acid gas include carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxide (SOx), and nitrogen oxide (NOx), and carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxide (SOx), and nitrogen. It is preferably at least one selected from oxides (NOx), more preferably carbon dioxide, hydrogen sulfide or sulfur oxide (SOx), and particularly preferably carbon dioxide.
In the laminate of the present invention, the permeation flux with respect to at least one acid gas selected from the acid gases is preferably 40 GPU or more, more preferably 50 GPU or more, and particularly preferably 100 GPU or more. More preferably, it is 120 GPU or more. Although there is no restriction | limiting in particular about the upper limit of the permeation | transmission flux of the said acidic gas, For example, it can be set to 10,000 GPU or less, and is good also as 5000 GPU or less.
1 GPU = 1 × 10 ⁻⁶ cm ³ (STP) / (s · cm ² · cmHg).

  The non-acid gas is preferably at least one selected from hydrogen, methane, nitrogen, and carbon monoxide, more preferably methane and hydrogen, and particularly preferably methane.

<Application>
(Gas mixture separation method)
The laminate of the present invention is a method for separating at least one acid gas from a mixed gas containing at least one acid gas and at least one non-acid gas, wherein the acid gas is carbon dioxide, hydrogen sulfide, sulfide. At least one selected from carbonyl, sulfur oxide (SOx), and nitrogen oxide (NOx), and the non-acid gas is at least one selected from hydrogen, methane, nitrogen, and carbon monoxide, It can be used in a gas mixture separation method using the laminate of the present invention as a gas separation membrane.

  In the gas separation method using the laminate of the present invention, the components of the gas mixture of the raw material are affected by the raw material production area, application or use environment, and are not particularly defined, but the main component of the gas mixture Is preferably carbon dioxide and methane or carbon dioxide and hydrogen. That is, the proportion of carbon dioxide and methane or carbon dioxide and hydrogen in the gas mixture is preferably 5 to 50%, more preferably 10 to 40% as the proportion of carbon dioxide. When the gas mixture is in the presence of an acidic gas such as carbon dioxide or hydrogen sulfide, the gas separation method using the laminate of the present invention exhibits particularly excellent performance, preferably hydrocarbons such as carbon dioxide and methane, Excellent performance in the separation of carbon dioxide and nitrogen, carbon dioxide and hydrogen.

(Gas separation membrane module / gas separation device)
The laminate of the present invention is preferably a gas separation membrane module using the laminate. Moreover, it can be set as the apparatus which has a means for carrying out separation collection | recovery or separation refinement | purification using the laminated body or gas separation membrane module of this invention.
The laminate of the present invention can be suitably used in a modular form. Examples of modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like. The laminate of the present invention may be applied to a gas separation / recovery device as a membrane / absorption hybrid method used in combination with an absorbing solution as described in JP-A-2007-297605, for example.

  The laminate of the present invention having the above excellent characteristics can be suitably used for a gas separation recovery method and a gas separation purification method.

<Board>
Each layer that can constitute the laminate of the present invention will be described below.
The laminate of the present invention may or may not have a substrate.
The substrate is not particularly limited and may be gas impermeable or gas permeable, but is preferably gas impermeable.
Further, the substrate is preferably a non-porous film having a smooth surface from the viewpoint that the liquid crystal layer can be formed as a uniform ultrathin film on the non-porous film.

(material)
The material used for the substrate is not particularly limited, but is preferably a solid such as a polymer film or glass. Furthermore, an alignment film may be formed on a solid such as a polymer film or glass as necessary.
The polymer film that can be used as the substrate is preferably a non-porous film having a smooth surface. Specifically, polyester such as polyethylene terephthalate film, polybutylene terephthalate, polyethylene naphthalate (PEN); Examples of the film include polycarbonate (PC), polymethyl methacrylate; polyolefin such as polyethylene and polypropylene; polyimide, triacetyl cellulose (TAC), and the like. Among them, in the present invention, the substrate is a polyethylene terephthalate film. It is particularly preferable from the viewpoint that a non-porous film having a smooth surface can be obtained, and as a result, the surface roughness Ra of the liquid crystal layer can be reduced.

<Liquid crystal layer>
The laminate of the present invention has a liquid crystal layer having a thickness of 0.5 nm to 10 nm.

(Film thickness)
The liquid crystal layer has a film thickness of 0.5 to 10 nm, and has a molecular arrangement different from that of the thick film by controlling the film thickness to a molecular size level (several to several tens of thousands). Further high separation selectivity can be obtained. The film thickness of the liquid crystal layer is preferably 0.5 to 8 nm, and more preferably 0.5 to 6 nm. When giving priority to the permeation flux of the acidic gas over the separation ratio, the thickness of the liquid crystal layer is particularly preferably 0.5 to 5 nm.

(Average roughness Ra)
In the laminate of the present invention, the average roughness Ra of the liquid crystal layer is preferably 1 nm or less, more preferably 0.6 nm or less, and particularly preferably 0.5 nm or less.

(material)
Moreover, there is no restriction | limiting in particular as a material of the said liquid-crystal layer, A well-known liquid crystal compound can be used. In the present invention, the ultra-thin liquid crystal layer is preferably an optically anisotropic layer formed by fixing the alignment state of the polymerizable liquid crystal compound from the viewpoint of forming a more uniform dense layer.
The polymerizable liquid crystal compound and other materials that can be preferably used for the liquid crystal layer will be described in the laminate production method of the present invention described later.

<High gas permeability layer>
The laminate of the present invention includes a highly gas permeable layer having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the same kind of gas. The gas permeation flow rate of the high gas permeable layer is more preferably 1.5 times or more of the gas permeation flux of the liquid crystal layer, and more preferably 2 times or more.

(Film thickness)
The high gas permeable layer preferably has a thickness of 0.1 to 1000 μm, more preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

  The thickness ratio between the high gas permeable layer and the liquid crystal layer is not particularly defined, but the liquid crystal layer is preferably as thin as possible as long as it exhibits permeability and separation selectivity. In terms of film thickness, the liquid crystal layer is preferably 0.001 to 5%, more preferably 0.01 to 1%, and more preferably 0.05 to 0.5% with respect to the highly gas permeable layer. It is.

  The high gas permeable layer preferably has a cross-linked structure from the viewpoint of plastic resistance, heat resistance, pressure resistance and mechanical strength imparted when absorbing the target acidic gas, and includes an aldehyde group, an epoxide group, and an isocyanate group. It is preferable to include a polymer having a crosslinked structure derived from a group, a carbodiimide group or an oxazoline group.

(Material: Cross-linked polymer)
There is no restriction | limiting in particular as a material of the said high gas-permeable layer, A well-known porous layer etc. can be used. As a well-known porous layer, the thing as described in Unexamined-Japanese-Patent No. 2011-161387 can be used.
In the laminate of the present invention, the high gas permeability layer preferably contains a crosslinked polymer. The crosslinked polymer is not particularly limited, but at least one selected from at least one polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polydimethylsiloxane, polyvinylpyrrolidone, polyethyleneimine, polyimide and polyallylamine. It preferably has a repeating unit constituting a seed polymer. As a result, there is an effect that a stable crosslinked film can be produced.

(1) Repeating unit constituting polyimide Among them, it is more preferable that the crosslinked polymer has a repeating unit constituting polyimide. As the polyimide, (5,5′-2,2,2-trifluoro-1- (trifluoromethyl) ethylidene-bis-1,3-isobenzofurandion (6FDA) type polyimide can be preferably used. The ones described in JP-A-8-52332 and JP-A-6-269650 can be used more preferably.
The weight average molecular weight of the crosslinked polymer having a repeating unit constituting the polyimide is preferably 5,000 to 5,000,000, more preferably 8,000 to 3,000,000, and particularly preferably 10,000 to 2,000,000.

  When the cross-linked polymer has a repeating unit constituting polyimide, it is also preferable to further have a repeating unit of 1,4-phenylene and a derivative thereof, or a repeating unit of 1,3-phenylene and a derivative thereof. Examples of the repeating unit of 1,4-phenylene and derivatives thereof include 2,3,5,6-trimethyl-1,4-phenylene. Examples of the repeating unit of 1,3-phenylene and derivatives thereof include 5-carboxy-1,3-phenylene.

In the general formula (3), the preferred range of the copolymerization ratio of the repeating units of 1,4-phenylene and its derivatives to the repeating units constituting the polyimide is preferably 50 to 90 mol%, preferably 70 to 90 mol. % Is more preferable.
In the general formula (3), the preferable range of the copolymerization ratio of 1,3-phenylene and its derivative repeating units to the repeating units constituting the polyimide is preferably 10 to 50 mol%, preferably 10 to 30 mol. % Is more preferable.

  When the crosslinked polymer has a repeating unit constituting polyimide, a polymer represented by the following general formula (3) is preferable.

In the general formula (3), the preferable range of the copolymerization ratio X of 2,3,5,6-trimethyl-1,4-phenylene repeating units to the repeating units constituting the polyimide is 50 to 90 mol%. Is preferable, and it is more preferable that it is 70-90 mol%.
In the general formula (3), a preferable range of the copolymerization ratio Y of the 5-carboxy-1,3-phenylene repeating unit to the repeating unit constituting the polyimide is preferably 50 to 90 mol%, and 70 to 90 More preferably, it is mol%.

(2) Crosslinked polymer other than polyimide Crosslinked polymer other than polyimide may be used, and more preferably as a crosslinked polymer other than polyimide, at least one repeating unit represented by the following general formula (I) and the following general formula: It is preferable to include a copolymer (hereinafter sometimes referred to as a crosslinked polymer (A1)) containing (II) or a repeating unit represented by the general formula (III).
General formula (I) represents the repeating unit of polyvinyl alcohol.

  General formula (II) is demonstrated.

(In general formula (II), R ¹ represents a hydrogen atom or a substituent. J ¹ represents —CO—, —COO—, —CONR ² —, —OCO—, a methylene group, a phenylene group, or —C ₆ H. ₄ represents a CO— group, R ² represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W ¹ represents a divalent linking group, and A represents a dissociable group.

In general formula (II), R < ¹ > represents a hydrogen atom or a substituent each independently. As the substituent, any one selected from the substituent group Z shown below can be used.
Substituent group Z:
An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, Iso-propyl, tert-butyl, n-octyl , N-decyl, n-hexadecyl), a cycloalkyl group (preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, such as cyclopropyl, Cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 2 -Butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably An alkynyl group having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl and 3-pentynyl, and an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 carbon atoms). -20, particularly preferably an aryl group having 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc., an amino group (preferably having 0 to 30 carbon atoms, more preferably carbon An amino group having 0 to 20, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino), an alkoxy group (preferably C 1-30, more preferably 1-20, particularly preferably 1-10 carbon atoms. Coxy group, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably carbon number). 6-12 aryloxy groups such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like, and heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably having 1 to 30 carbon atoms). 20, particularly preferably a heterocyclic oxy group having 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like.

An acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl, etc.), alkoxy A carbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl), aryloxy A carbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl), an acyloxy group ( Preferably 2-30 carbons, more preferably 2-20 carbons, especially preferred. Or an acyloxy group having 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon number). 2-10 acylamino groups such as acetylamino and benzoylamino).

An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryl Oxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino group). A sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino), a sulfamoyl group (Preferably 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably a sulfamoyl group having 0 to 12 carbon atoms, for example sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.),

A carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group ( Preferably, it is an arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio.), A heterocyclic thio group (preferably having 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms. A heterocyclic thio group, e.g. pyridylthio, 2-benzoxazolyl thio, and 2-benzthiazolylthio the like.),

A sulfonyl group (preferably a sulfonyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), a sulfinyl group (preferably A sulfinyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, and the like, and a ureido group (preferably 1 carbon atom). -30, more preferably a ureido group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having carbon number) 1 to 30, more preferably a phosphoric acid amide group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms. For example, diethyl phosphoric acid amide, phenylphosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, more preferably fluorine atom). ),

A cyano group, a sulfo group, a carboxyl group, an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, and a heterocyclic group (preferably having a carbon number of 1 to 30, more preferably a heterocyclic group having 1 to 12 carbon atoms) Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl Group, azepinyl group, etc.), a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl, triphenyl, etc. And silyloxy group (preferably having 3 to 3 carbon atoms). 0, more preferably 3 to 30 carbon atoms, particularly preferably a silyloxy group having 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted with any one or more substituents selected from the above substituent group Z.

R ¹ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.

J ¹ represents —CO—, —COO—, —CONR ² —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group. R ² represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, preferably a hydrogen atom, an alkyl group, or an aryl group, and a preferred range thereof is synonymous with a preferred range of the alkyl group and aryl group described for the substituent Z. is there. Among these, as the J ¹ -CO -, - COO- or -OCO- are preferred, -COO- is particularly preferable.

W ¹ represents a divalent linking group. Examples of the divalent linking group include a linear, branched, or cyclic alkylene group (preferably an alkylene group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 4 carbon atoms. , For example, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, decylene, etc.), an alkyleneoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably carbon). An alkyleneoxy group having a number of 1 to 4, for example, methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, octyleneoxy, decyleneoxy, etc.), aralkylene group (preferably carbon An aralkylene group having 7 to 30, more preferably 7 to 13 carbon atoms. For example, benzylidene, cinnamylidene, etc.), an arylene group (preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, such as phenylene, cumenylene, mesitylene, tolylene, xylylene, etc. And the like. These may further have a substituent. Further substituents include alkyl groups, alkylene groups, alkoxy groups, silyl groups, or silyloxy groups, with alkyl groups or silyloxy groups being preferred. Moreover, it is also preferable to have an ether bond in the molecule.

W ¹ is preferably an alkylene group, an alkyleneoxy group, or a silyloxy group.

A represents a dissociable group, preferably a dissociable group having a pKa of 5 or less in water. Specific examples include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, —CONHSO ₂ —R ^9. , —SO ₂ NHCO—R ¹⁰ or SO ₂ NHSO ₂ —R ¹¹ . R ⁹ , R ¹⁰ and R ¹¹ represent a substituent (preferably an alkyl group or an aryl group, more preferably an alkyl group). A is more preferably a carboxyl group, a sulfonic acid group or a phosphoric acid group, still more preferably a carboxyl group or a sulfonic acid group.

  General formula (III) is demonstrated.

(In general formula (III), R ³ represents a hydrogen atom or an alkyl group.)

In the general formula (III), R ³ represents a hydrogen atom or an alkyl group, and in the case of an alkyl group, the preferred range is synonymous with the preferred range described for the alkyl group described in the substituent group Z, and among them, preferred Is a methyl group.

In the laminate of the present invention, the crosslinked polymer preferably contains at least one repeating unit represented by the following general formula (IV), and includes at least one general formula (IV) and at least one general formula ( More preferably, the polymer includes a repeating unit represented by V) (hereinafter sometimes referred to as a crosslinked polymer (A2)).
The crosslinked polymer (A2) has a crosslinked structure in which the repeating units of the general formula (IV) or the repeating units of the general formula (V) are connected to each other by —W ² —Ra.
The general formula (IV) will be described in detail.

(In the general formula (IV), R ⁴ each independently represents a hydrogen atom or a substituent. L ¹ represents an n-valent linking group. N represents a positive integer of 2 or more. J ² represents —CO—. , —COO—, —CONR ⁵ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group, wherein R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. W ² represents a single bond or a divalent linking group, R ^a represents an alkylene glycol residue or a propylene glycol residue, and a plurality of J ² , W ² , R ⁴ and R ^a may be the same or different. Good.)

In general formula (IV), each R ⁴ independently represents a hydrogen atom or a substituent. Examples of the substituent are selected from the groups listed in the substituent group Z. R ⁴ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.

L ¹ represents an n-valent linking group, and specific examples thereof include a structural unit represented by the following (L-1) to (L-35) or a linking group constituted by combining them. Can do.

L ¹ composed of a group selected from the above (L-1) to (L-35) is preferably an alkylene group, an alkyleneoxy group or an arylene group, more preferably an alkylene group or an alkyleneoxy group, More preferably, it has an ether bond in the molecule. For such a crosslinked structure, it is preferable to use a crosslinking agent such as a polyfunctional aldehyde, a polyfunctional epoxide, a polyfunctional isocyanate, or a polyfunctional carbodiimide.

J ² represents —CO—, —COO—, —CONR ⁵ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, preferably a hydrogen atom, an alkyl group, or an aryl group, and a preferred range thereof is synonymous with a preferred range of the alkyl group and aryl group described for the substituent Z. is there. Among these, as the J ² -CO -, - COO- or -OCO- are preferred, -COO- is particularly preferable.

W ² represents a single bond or a divalent linking group. Examples of the divalent linking group include a linear, branched, or cyclic alkylene group (preferably an alkylene group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 4 carbon atoms. , For example, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, decylene, etc.), an alkyleneoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably carbon). An alkyleneoxy group having a number of 1 to 4, for example, methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, octyleneoxy, decyleneoxy, etc.), aralkylene group (preferably carbon An aralkylene group having 7 to 30, more preferably 7 to 13 carbon atoms. For example, benzylidene, cinnamylidene, etc.), an arylene group (preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, such as phenylene, cumenylene, mesitylene, tolylene, xylylene, etc. And the like. These may further have a substituent. The further substituent is preferably a hydroxy group or a halogen atom, more preferably a hydroxy group or a fluorine atom, and particularly preferably a fluorine atom. Further, it preferably has an ether bond in the molecule.
W ² is preferably a single bond, an alkylene group or an alkyleneoxy group, and preferably a single bond.

R ^a represents an alkylene glycol residue or a propylene glycol residue. The molecular weight of the alkylene glycol residue or propylene glycol residue is preferably 500 to 1,000,000, more preferably 500 to 500,000, and still more preferably 1,000 to 300,000.
A plurality of J ² , W ² , R ⁴ and R ^a may be the same or different.

n represents a positive integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and still more preferably 2 to 10.

  The general formula (IV) is preferably formed by polymerizing a compound represented by the following general formula (IVa).

(In the general formula (IVa), R ⁴ each independently represents a hydrogen atom or a substituent. L ¹ represents an n-valent linking group. N represents a positive integer of 2 or more. J ² represents —CO—. , —COO—, —CONR ⁵ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group, wherein R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. W ² represents a single bond or a divalent linking group, R ^a represents an alkylene glycol residue or a propylene glycol residue, and a plurality of J ² , W ² , R ⁴ and R ^a may be the same or different. Good.)

In the general formula ^{(IVa), R 4, J} 2, W 2, R a, L 1 and n, R ⁴ in the general formula ^{(IV), J 2, W} 2, R a, L 1 and n synonymous The preferred range is also the same.

  The general formula (V) will be described in detail.

(In the general formula (V), .J ³ R ⁶ is representing a hydrogen atom or a substituent -CO -, - COO -, - CONR 8 -, - OCO-, a methylene group, a phenylene group, or -C ₆ H ₄ represents a CO— group, R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W ³ represents a single bond or a divalent linking group, and a plurality of J ³ , W ³ , R ^b R ⁶ and R ⁷ may be the same or different, R ^b represents an alkylene glycol residue or a propylene glycol residue, and R ⁷ represents a hydrogen atom, an alkyl group or an aryl group.)

In general formula (V), R ⁶ represents a hydrogen atom or a substituent. Examples of the substituent are selected from the groups listed in the substituent group Z. R ⁶ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.

J ³ represents —CO—, —COO—, —CONR ⁸ —, —OCO—, a methylene group, a phenylene group, or a —C ₆ H ₄ CO— group. R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, preferably a hydrogen atom, an alkyl group, or an aryl group, and a preferred range thereof is synonymous with the preferred range of the alkyl group or aryl group described for the substituent Z. is there. Of these, J ³ -CO -, - COO- or -OCO- are preferred, -COO- is particularly preferable.

W ³ represents a single bond or a divalent linking group. Examples of the divalent linking group include a linear, branched, or cyclic alkylene group (preferably an alkylene group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 4 carbon atoms. , For example, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, decylene, etc.), an alkyleneoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably carbon). An alkyleneoxy group having a number of 1 to 4, for example, methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, octyleneoxy, decyleneoxy, etc.), aralkylene group (preferably carbon An aralkylene group having 7 to 30, more preferably 7 to 13 carbon atoms. For example, benzylidene, cinnamylidene, etc.), an arylene group (preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, such as phenylene, cumenylene, mesitylene, tolylene, xylylene, etc. And the like. These may further have a substituent. The further substituent is preferably a hydroxy group or a halogen atom, more preferably a hydroxy group or a fluorine atom, and particularly preferably a fluorine atom. Further, it preferably has an ether bond in the molecule.

W ³ is preferably a single bond, an alkylene group or an alkyleneoxy group, and preferably a single bond.

R ^b represents an alkylene glycol residue or a propylene glycol residue. The molecular weight of the alkylene glycol residue or propylene glycol residue is preferably 500 to 1,000,000, more preferably 500 to 500,000, and still more preferably 1,000 to 300,000. R ⁷ represents a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group.

  The general formula (V) is preferably formed by polymerizing one compound represented by the following general formula (Va).

(In the general formula (Va), R ⁶ represents a hydrogen atom or a substituent. J ³ represents —CO—, —COO—, —CONR ⁸ —, —OCO—, a methylene group, a phenylene group, or —C ₆ H. ₄ represents a CO— group, R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W ³ represents a single bond or a divalent linking group, R ^b represents an alkylene glycol residue or a propylene glycol residue. And R ⁷ represents a hydrogen atom, an alkyl group or an aryl group.)

In the general formula ^{(Va), R 6, R} 7, R b, J 3 and W ^3, the R ⁶ in the general formula ^{(V), R 7, R} b, have the same meanings as J ³ and W ^3, the The preferable range is also the same.

In the laminate of the present invention, the crosslinked polymer is a polyethylene glycol having a main chain structure represented by the general formula (VI), a polypropylene glycol represented by the general formula (VII) or the general formula (VIII), or the general formula (IX). It is also preferable that the polymer has a repeating unit selected from polydimethylsiloxane represented by formula (1).
When the repeating unit represented by the general formulas (VII) to (IX) is a main chain, the weight ratio in the crosslinked polymer preferably accounts for 30 to 99%, more preferably 40 to 99. %, More preferably 50 to 99%. The molecular weight of the main chain portion is desirably a certain high molecular weight from the viewpoint of imparting film-forming properties due to entanglement of molecular chains, preferably 500 to 1,000,000, more preferably 500 to 500, 000, more preferably 1,000 to 300,000.

[Repeating unit represented by general formula (X)]
It is preferable that the repeating unit represented by the general formula (IV) is a repeating unit represented by the following general formula (X).

(In general formula (X), W ² and W ⁴ each represent a single bond or a divalent linking group. R ⁴ and R ¹² each independently represents ^a hydrogen atom or a substituent. R ^a represents an alkylene glycol residue or Represents a propylene glycol residue, and x and z represent a positive integer of 1 or more.)

In the general formula ^{(X), W 2, R} 4 and R ^a have the same meanings as W ^2, R ⁴ and R ^a in the general formula (IV). W ⁴ is synonymous with W ² . R ¹² has the same meaning as R ⁴ , and its preferred range is also the same. x and z represent a positive integer of 1 or more.

  It is preferable that the compound represented by the general formula (X) is formed by polymerizing a compound represented by the following general formula (Xa).

(In General Formula (Xa), W ² and W ⁴ each represent a single bond or a divalent linking group. R ⁴ and R ¹² each independently represent ^a hydrogen atom or a substituent. R ^a represents an alkylene glycol residue or Represents a propylene glycol residue.)

In the general formula ^{(Xa), R 4, R} 12, W 2, W 4 and R ^a are the same as ^{R 4, R 12, W 2} , W 4 and R ^a in the general formula (X), its The preferable range is also the same.

  The repeating unit represented by the general formula (V) is preferably a repeating unit represented by the following general formula (XI).

(In General Formula (XI), R ⁶ represents a hydrogen atom or a substituent. R ^b represents an alkylene glycol residue or a propylene glycol residue, and R ⁷ represents a hydrogen atom, an alkyl group or an aryl group. R ⁶ , R ^b and R ⁷ may be the same or different.)

In the general formula (XI), R ^6, R ⁷ and R ^b are the same as R ^6, R ⁷ and R ^b in formula (V), it is also the preferred ranges thereof.

  The compound represented by the general formula (XI) is preferably formed by polymerizing a compound represented by the following general formula (XIa).

(In the general formula (XIa), R ⁶ represents a hydrogen atom or a substituent. R ^b represents an alkylene glycol residue or a propylene glycol residue, and R ⁷ represents a hydrogen atom, an alkyl group or an aryl group.)

In the general formula (XIa), R ^6, R ⁷ and R ^b, wherein a R ^6, R ⁷ and R ^b synonymous in the general formula (XI), it is also the preferred ranges thereof

  The copolymer containing the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) or the general formula (III) is, for example, vinyl acetate as a raw material as the general formula (I). As general formula (II) and general formula (III), for example, the following monomers (M-1 to M-20) can be obtained by copolymerization as examples of raw materials, but the present invention is not limited thereto. It is not a thing.

The content of the repeating unit represented by the general formula (I) in the crosslinked polymer (A1) is preferably 10 to 90 mol%, more preferably 20 to the total repeating unit constituting the crosslinked polymer (A1). 80 mol%, particularly preferably 25 to 70 mol%.
The content of the repeating unit represented by the general formula (II) or the general formula (III) in the crosslinked polymer (A1) is preferably 10 to 90 mol% with respect to all the repeating units constituting the crosslinked polymer (A1). More preferably, it is 20-80 mol%, Most preferably, it is 25-70 mol%.
The repeating unit represented by the general formula (II) or the general formula (III) is preferably 10 to 90 mol%, more preferably 20 to 80 mol% based on the repeating unit represented by the general formula (I). Especially preferably, it is 25-70 mol%.

  The repeating units represented by the general formulas (IV) to (V) can be obtained by copolymerizing monomers corresponding to the respective repeating units. Specific examples (example monomers M-21 to M-50) preferable as the monomer are listed below, but the present invention is not limited thereto. Moreover, p, q, and r in a specific example represent arbitrary positive integers.

The content of the repeating unit represented by the general formula (IV) in the crosslinked polymer (A2) is preferably 10 to 90 mol%, more preferably 20 to 20%, based on all repeating units constituting the crosslinked polymer (A2). 80 mol%, particularly preferably 25 to 70 mol%.
The content of the repeating unit represented by the general formula (V) in the crosslinked polymer (A2) is preferably 10 to 90 mol%, more preferably 20 to 20%, based on all repeating units constituting the crosslinked polymer (A2). 80 mol%, particularly preferably 25 to 70 mol%.
The repeating unit represented by the general formula (IV) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, particularly preferably 25 to 25 mol% based on the repeating unit represented by the general formula (V). 70 mol%.

Since the crosslinked polymer that can be used in the laminate of the present invention has a three-dimensional crosslinked structure, the molecular weight is not particularly specified, but the weight average molecular weight as the main chain or side chain excluding the crosslinked structure portion is: The polystyrene conversion value by the GPC method is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
Similarly, the degree of dispersion of the crosslinked polymer is not particularly specified as a whole, but the main chain or side chain is preferably 1 to 5, more preferably 1 to 3. More preferably, it is -2. Within this range, it is possible to achieve better film forming properties and mechanical strength.

A crosslinked polymer may be used individually by 1 type, and may be used in combination of 2 or more types.
The content of the crosslinked polymer is preferably 0.1 to 90% by mass, more preferably 1 to 70% by mass, based on the total solid content in the composition forming the separation active membrane. More preferably, it is -50 mass%.

As each compound for synthesizing the polymer containing the repeating unit of the general formula (II) to the general formula (V), commercially available compounds may be used, or they can be easily synthesized.
The crosslinked polymer may be a copolymer with other monomers. Examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. These known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.
Examples of monomer synthesis methods include, for example, ester synthesis in “5th edition Experimental Science Course 16 Synthesis of Organic Compounds (IV)” edited by The Chemical Society of Japan, Maruzen Co., Ltd. and “5th edition Experimental Science Course 26 Polymer Chemistry”. The monomer handling, purification items, etc. can be referred to.

[Manufacturing method of laminate]
In the method for producing a laminate of the present invention, a polymerizable liquid crystal composition containing (A) a polymerizable liquid crystal compound, (B) a photopolymerization initiator, and (C) an organic solvent on a substrate is 0.5 to 10 nm. A coating step of coating with a film thickness, an alignment step of aligning the polymerizable liquid crystal compound by applying heat, and irradiation to irradiate the polymerizable liquid crystal composition with active radiation to fix the liquid crystal phase and obtain a liquid crystal layer And laminating a high gas permeable layer having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the same type of gas on the liquid crystal layer. Features.
Furthermore, the method for manufacturing a laminate of the present invention uses the substrate, the liquid crystal layer, and the highly gas permeable layer in this order as a gas separation membrane to peel the substrate from the laminate. From the viewpoint of obtaining a laminate of the liquid crystal layer and the highly gas permeable layer.
The laminate of the present invention forms an alignment film on a substrate such as a polymer film or glass as necessary, and (A) a polymerizable liquid crystal compound, (B) a photopolymerization initiator and ( C) A liquid crystal composition coating solution containing an organic solvent is applied, dried, aligned and fixed to form a liquid crystal layer, and further, a polymer coating solution containing a crosslinked polymer containing a solvent described later is applied to the surface. It is more preferable to dry to form a highly gas permeable layer.
The detail of the manufacturing method of the laminated body of this invention is described below.

<Application process of polymerizable liquid crystal composition>
In the method for producing a laminate of the present invention, a polymerizable liquid crystal composition containing (A) a polymerizable liquid crystal compound, (B) a photopolymerization initiator, and (C) an organic solvent on a substrate is 0.5 to 10 nm. A coating process of coating with a film thickness of
As the substrate, those mentioned in the description of the laminate of the present invention can be used. Among them, it is possible to form a liquid crystal layer, which is an ultra-thin dense layer, on a substrate, which is a non-porous film with a smooth surface, and to provide a porous layer that performs a supporting function on the upper layer. Rather than forming a layer, it is preferable to form a liquid crystal layer that is an ultrathin film on a non-porous film from the viewpoint of easily obtaining a uniform ultrathin film.
As for the manufacturing method of the laminated body of this invention, it is more preferable that the said board | substrate is a polyethylene terephthalate film.

  Application of the polymerizable liquid crystal composition to the substrate may be performed by applying a coating liquid that is the polymerizable liquid crystal composition to a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, Die coating method). Alternatively, it may be formed by discharging using an inkjet apparatus.

<Orientation process, irradiation process>
The manufacturing method of the laminated body of this invention includes the aligning process which heats and aligns the said polymeric liquid crystal compound.
Furthermore, the method for producing a laminate of the present invention includes an irradiation step of obtaining a liquid crystal layer by irradiating the polymerizable liquid crystal composition with active radiation to fix a liquid crystal phase.
Details of the alignment step and the irradiation step in the method for producing the liquid crystal layer will be described.
The state in which the liquid crystal phase of the liquid crystal layer is “fixed” is the most typical and preferred mode in which the orientation of the liquid crystal compound contained in the liquid crystal layer is maintained, but is not limited thereto, and specifically Is usually 0 ° C. to 50 ° C., and under harsher conditions, in the temperature range of −30 ° C. to 70 ° C., the optically anisotropic film has no fluidity, and changes in orientation form due to external field or external force. This means a state in which the fixed alignment form can be kept stable without causing the fixing.

  As a method for fixing the alignment state in the present invention, the polymerizable liquid crystal composition is once heated to the liquid crystal phase formation temperature, and then cooled while maintaining the alignment state, whereby the alignment form in the liquid crystal state is obtained. It can be formed by fixing without impairing. Further, the polymerizable liquid crystal composition to which a polymerization initiator is added can be formed by heating and aligning to a liquid crystal phase forming temperature, and then fixing the alignment state of the liquid crystal state by polymerization. It is preferable to carry out by the latter polymerization reaction. In the present invention, when the liquid crystal layer is finally formed, the liquid crystal compound is no longer required to be liquid crystalline as long as the gas permeability is maintained. For example, a low-molecular liquid crystalline compound may have a group that reacts with heat, light, or the like, and as a result, it may be polymerized or cross-linked by reaction with heat, light, or the like to increase the molecular weight and lose liquid crystallinity.

  The polymerizable liquid crystal composition coating liquid can be obtained by mixing a polymerizable nematic liquid crystal compound, a polymerization initiator, and a solvent. One or more liquid crystalline compounds may be used. For example, a polymerizable liquid crystal compound and a non-polymerizable liquid crystal compound can be used in combination. Also, a combination of a low-molecular liquid crystal compound and a high-molecular liquid crystal compound is possible. Further, a horizontal alignment agent, a non-uniformity inhibitor, a repellency inhibitor, a polymerizable monomer and the like may be added in order to improve alignment uniformity, coating suitability and film strength. If necessary, the liquid crystal composition coating liquid may further contain a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, and the like as long as optical performance is not deteriorated.

  A method for producing the polymer layer will be described. The polymer coating solution can be obtained by mixing a crosslinked polymer and a solvent. A polymer layer is formed by applying and drying this.

(Liquid crystal compound)
Examples of the liquid crystal compound include a rod-like liquid crystal compound and a disk-like liquid crystal compound.

  Examples of the rod-like liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. In addition to the above low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used.

  It is more preferable to fix the orientation of the rod-like liquid crystal compound by polymerization, and examples of the polymerizable rod-like liquid crystal compound include those described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, WO 95/22586, 95/24455, 97/97. No. 0600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and Japanese Patent Application No. 2001-64627 These compounds can be used. The polymerizable rod-like liquid crystal compound is preferably a polymerizable rod-like liquid crystal compound represented by the following general formula (1).

Formula ^{(1) Q 1 -L 1 -Cy} 1 -L 2 - (Cy 2 -L 3) n-Cy 3 -L 4 -Q 2
(In General Formula (1), Q ¹ and Q ² are each independently a polymerizable group, L ¹ and L ⁴ are each independently a divalent linking group, and L ² and L ³ are each independently a single group. A bond or a divalent linking group, Cy ¹ , Cy ² and Cy ³ are divalent cyclic groups, and n is 0, 1, 2 or 3.)

Hereinafter, the polymerizable rod-like liquid crystal compound represented by the general formula (1) will be described.
In general formula (1), Q ¹ and Q ² are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

In general formula (1), L ¹ and L ⁴ are each independently a divalent linking group. L ¹ and L ⁴ each independently include —O—, —S—, —CO—, —NR—, —C═N—, a divalent chain group, a divalent cyclic group, and combinations thereof. A divalent linking group selected from the group is preferred. R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. R is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and most preferably a hydrogen atom.

The example of the bivalent coupling group which consists of a combination is shown below. Here, the left side is coupled to Q (Q ¹ or Q ² ), and the right side is coupled to Cy (Cy ¹ or Cy ³ ).

L-1: —CO—O—divalent chain group —O—
L-2: -CO-O-divalent chain group -O-CO-
L-3: —CO—O—divalent chain group —O—CO—O—
L-4: -CO-O-divalent chain group -O-divalent cyclic group-
L-5: -CO-O-divalent chain group -O-divalent cyclic group -CO-O-
L-6: -CO-O-divalent chain group -O-divalent cyclic group -O-CO-
L-7: -CO-O-divalent chain group-O-divalent cyclic group-divalent chain group-
L-8: -CO-O-divalent chain group -O-divalent cyclic group -divalent chain group -CO-O-
L-9: -CO-O-divalent chain group -O-divalent cyclic group -divalent chain group -O-CO-
L-10: —CO—O—divalent chain group—O—CO—divalent cyclic group—
L-11: -CO-O-divalent chain group -O-CO-divalent cyclic group -CO-O-
L-12: -CO-O-divalent chain group -O-CO-divalent cyclic group -O-CO-
L-13: —CO—O—Divalent chain group—O—CO—Divalent cyclic group—Divalent chain group—
L-14: -CO-O-divalent chain group -O-CO-divalent cyclic group -divalent chain group -CO-O-
L-15: -CO-O-divalent chain group-O-CO-divalent cyclic group-divalent chain group-O-CO-
L-16: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—
L-17: -CO-O-divalent chain group -O-CO-O-divalent cyclic group -CO-O-
L-18: -CO-O-divalent chain group -O-CO-O-divalent cyclic group -O-CO-
L-19: —CO—O—Divalent chain group—O—CO—O—Divalent cyclic group—Divalent chain group—
L-20: -CO-O-divalent chain group -O-CO-O-divalent cyclic group -divalent chain group -CO-O-
L-21: -CO-O-divalent chain group -O-CO-O-divalent cyclic group -divalent chain group -O-CO-

The divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group and an alkenylene group are more preferred.
The alkylene group may have a branch. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkenylene group may have a branch. The alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkynylene group may have a branch. The alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent include a halogen atom.
Specific examples of the divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene and the like.

The definition and examples of the divalent cyclic group are the same as those of Cy ¹ , Cy ² and Cy ³ described later.

In the general formula (1), L ^{2 and} L ³ are each independently a single bond or a divalent linking group. L ² and L ³ each independently include —O—, —S—, —CO—, —NR—, —C═N—, a divalent chain group, a divalent cyclic group, and combinations thereof. It is preferably a divalent linking group or a single bond selected from the group. R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom. The divalent chain group and the divalent cyclic group have the same definitions as L ¹ and L ⁴ .
Preferred divalent linking groups as L ² or L ³ include —COO—, —OCO—, —OCOO—, —OCONR—, —COS—, —SCO—, —CONR—, —NRCO—, —CH _2. CH _2- , -C = C-COO-, -C = N-, -C = N-N = C-, and the like.

In the general formula (1), n is 0, 1, 2, or 3. When n is 2 or 3, two L ³ may be the same or different, and two Cy ² may be the same or different. n is preferably 1 or 2, and more preferably 1.

In the general formula (1), Cy ¹ , Cy ² and Cy ³ are each independently a divalent cyclic group.
The ring contained in the cyclic group is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.
The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.
The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
As the cyclic group having a benzene ring, 1,4-phenylene is preferable. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. As the cyclic group having a pyrimidine ring, pyrimidine-2,5-diyl is preferable.
The cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. An alkylthio group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and an alkyl-substituted carbamoyl group having 2 to 6 carbon atoms And an acylamino group having 2 to 6 carbon atoms.

  Examples of the polymerizable rod-like liquid crystal compound represented by the general formula (1) are shown below. The present invention is not limited to these.

  In addition to the polymerizable rod-shaped liquid crystal compound represented by the general formula (1), it is preferable to use at least one compound represented by the following general formula (2) as the rod-shaped liquid crystal compound.

General formula (2)
^{M 1 - (L 1) p} -Cy 1 -L 2 - (Cy 2 -L 3) n-Cy 3 - (L 4) q-M 2
(In General Formula (2), M ¹ and M ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic group, a cyano group, a halogen, —SCN, — CF 3, a nitro group, or Q ¹ is represented, but at least one of M ¹ and M ² represents a group other than Q ¹ .
^{However, Q 1, L 1, L} 2, L 3, L 4, Cy 1, Cy 2, Cy 3 and n have the same meanings as the group represented by the general formula (1). P and q are 0 or 1. )

When M ¹ and M ² do not represent Q ¹ , M ¹ and M ² are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a cyano group, more preferably , An alkyl group having 1 to 4 carbon atoms, or a phenyl group, and p and q are preferably 0.

  Moreover, as a preferable mixing ratio of the compound represented by the general formula (2) in the mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the compound represented by the general formula (2), It is 0.1% -40%, More preferably, it is 1% -30%, More preferably, it is 5% -20%.

  Although the preferable example of a compound represented by General formula (2) below is shown, this invention is not limited to these.

  The discotic liquid crystalline compound is disclosed in various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by The Chemical Society of Japan, Quarterly Chemical Review, No. 22). , Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J. Am. Chem. Soc., Vol. 116, page 2655 (1994)). The polymerization of the discotic liquid crystalline compound is described in JP-A-8-27284. In order to fix the discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline compound. However, when the polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. That is, the photocurable discotic liquid crystalline compound is preferably a compound represented by the following formula (II).

Formula (II)
D (-LP) n
(In the general formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.)
Preferred specific examples of the discotic core (D), the divalent linking group (L), and the polymerizable group (P) in the formula (II) are (D1) described in JP-A No. 2001-4837, respectively. To (D15), (L1) to (L25), and (P1) to (P18), and the contents described in the publication can be preferably used.

((B) Photopolymerization initiator)
The polymerizable liquid crystal composition is preferably a curable composition, and for that purpose, it preferably contains a photopolymerization initiator. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and a polymerization reaction by electron beam irradiation. In order to prevent the support and the like from being deformed or altered by heat. Also, a photopolymerization reaction and a polymerization reaction by electron beam irradiation are preferable.

  Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,221,970), and the like. .

The amount of the photopolymerization initiator used is preferably 0.1 to 20% by mass, more preferably 1 to 8% by mass, based on the liquid crystal composition (solid content in the case of a coating liquid). Light irradiation for the polymerization of the liquid crystal compound is preferably performed using ultraviolet rays. Irradiation energy is preferably ^{10mJ / cm 2 ~50J / cm 2} , further preferably ^{50mJ / cm 2 ~800mJ / cm 2} . In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. Further, since the oxygen concentration in the atmosphere is related to the degree of polymerization, when the desired degree of polymerization is not reached in the air, it is preferable to reduce the oxygen concentration by a method such as nitrogen substitution. A preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and most preferably 3% or less.

  The polymerization reaction rate is preferably 70% or more, and preferably 80% or more from the viewpoint of maintaining the mechanical strength of the optically anisotropic film and suppressing unreacted substances from flowing into the liquid crystal layer. Is more preferable, and it is still more preferable that it is 90% or more. In order to improve the polymerization reaction rate, a method of increasing the irradiation amount of ultraviolet rays to be irradiated and polymerization under a nitrogen atmosphere or heating conditions are effective. Moreover, after superposing | polymerizing once, the method of hold | maintaining at a temperature higher than superposition | polymerization temperature, and pushing a reaction further by thermal polymerization reaction, and the method of irradiating an ultraviolet-ray again can also be used. The polymerization reaction rate can be measured by comparing the absorption intensity of the infrared vibration spectrum of the polymerization reactive bonding group before and after the polymerization.

((C) Organic solvent)
In the manufacturing method of the laminated body of this invention, (C) organic solvent is used as a solvent of the said polymeric liquid crystal composition. There is no restriction | limiting in particular as said organic solvent, A well-known solvent can be used. For example, ketones (acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic Group hydrocarbons (toluene, xylene, trimethylbenzene, etc.), halogenated carbons (dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols ( Ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, di Such as chill acetamide), etc. can be exemplified.
In the manufacturing method of the laminated body of this invention, 1 type, or 2 or more types of organic solvents can be used in the said polymeric liquid crystal composition, and it is preferable to use 2 or more types of organic solvents.

  From the viewpoint of coating film formability and production efficiency, the addition amount of the organic solvent in the polymerizable liquid crystal composition is preferably 50% by mass to 90% by mass, and 40% by mass to 85% by mass. Is more preferable.

(Orientation control agent)
By containing at least one of the fluorine-containing acrylate or the compounds represented by the following general formulas (X1) to (X3) in the liquid crystal composition, the tilt angle of molecules of the liquid crystal compound is reduced at the air interface or A substantially horizontal orientation can be achieved. In this specification, “horizontal alignment” means that the major axis of the liquid crystal molecule is parallel to the film surface, but it is not required to be strictly parallel. An orientation with an inclination angle of less than 20 degrees is meant. When the liquid crystal compound is horizontally aligned in the vicinity of the air interface, alignment defects are less likely to occur, so that the transparency in the visible light region is increased and the reflectance in the infrared region is increased. On the other hand, when the tilt angle of the liquid crystal compound is large, the cholesteric helical axis is deviated from the normal of the film surface, so that the reflectivity is reduced, the fingerprint pattern is generated, haze is increased, and diffractive properties are exhibited. Absent.
Hereinafter, the following general formulas (X1) to (X3) will be described in order.

（一般式（Ｘ１）中、Ｒ¹、Ｒ²及びＲ³は各々独立して、水素原子又は置換基を表し、Ｘ¹、Ｘ²及びＸ³は単結合又は二価の連結基を表す。）

(In the general formula (X1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent, and X ¹ , X ² and X ³ represent a single bond or a divalent linking group. )

In the general formula (X1), the substituents represented by R ^{1 to} R ³ are each preferably a substituted or unsubstituted alkyl group (more preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group), An aryl group (in particular, an aryl group having a fluorine-substituted alkyl group is preferable), a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom.
The divalent linking groups represented by X ¹ , X ² and X ³ are each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NRa— (Ra Is a divalent linking group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO ₂ — and combinations thereof. Is preferred. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, —CO—, —NRa—, —O—, —S— and —SO ₂ —, or the group. It is more preferably a divalent linking group in which at least two groups are combined. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the divalent aromatic group is preferably 6-10.

（一般式（Ｘ２）中、Ｒは置換基を表し、ｍは０〜５の整数を表す。ｍが２以上の整数を表す場合、複数個のＲは同一でも異なっていてもよい。）
一般式（Ｘ２）中、Ｒとして好ましい置換基は、Ｒ¹、Ｒ²及びＲ³で表される置換基の好ましい範囲として挙げてものと同じである。
ｍは、好ましくは１〜３の整数を表し、特に好ましくは２又は３である。

(In general formula (X2), R represents a substituent, m represents an integer of 0 to 5. When m represents an integer of 2 or more, a plurality of R may be the same or different.)
In the general formula (X2), preferable substituents as R are the same as those described as preferable ranges of the substituents represented by R ¹ , R ² and R ³ .
m preferably represents an integer of 1 to 3, particularly preferably 2 or 3.

（一般式（Ｘ３）中、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹は各々独立して、水素原子又は置換基を表す。Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹でそれぞれ表される置換基は、好ましくは一般式（Ｘ１）におけるＲ¹、Ｒ²及びＲ³で表される置換基の好ましいものとして挙げたものである。

(In the general formula (X3), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a substituent. R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably the substituents represented by R ¹ , R ² and R ³ in the general formula (X1).

  As the horizontal alignment agent used in the present invention, the compounds described in Japanese Patent Application No. 2003-331269 (Japanese Patent Laid-Open No. 2005-099258) can be used, and the synthesis method of these compounds is also described in the specification. ing.

  The amount of the compound represented by any one of the general formulas (X1) to (X3) is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the mass of the liquid crystal compound. 0.02 to 1% by mass is particularly preferable. In addition, the compound represented by the said general formula (X1)-(X3) may be used independently, and may use 2 or more types together.

<Process of laminating a high gas permeability layer>
The method for producing a laminate according to the present invention comprises a step of laminating a highly gas permeable layer having a gas permeation flux of 1.0 times or more of the liquid crystal layer on the liquid crystal layer when compared with the same kind of gas. The process of carrying out is included.
There is no restriction | limiting in particular as a method of laminating | stacking the said high gas permeability layer on the said liquid-crystal layer, For example, it can laminate | stack by application | coating.
As a method of forming the high gas permeable layer, it is preferable to apply a crosslinkable polymer-containing composition having the crosslinkable polymer on the liquid crystal layer. Examples of the method for applying the crosslinkable polymer-containing composition to the liquid crystal layer include the methods mentioned as the method for applying the polymerizable liquid crystal composition.
An organic solvent is used as a solvent for the crosslinkable polymer-containing composition. There is no restriction | limiting in particular as said organic solvent, The organic solvent quoted as the organic solvent of the said polymeric liquid crystal composition can be mentioned. In addition, the solvent described in JP2011-161387A can be used.
Other additives may be added to the crosslinkable polymer-containing composition, and as the additive, those described in JP-A No. 2011-161387 can be used.

  The high gas permeable layer is preferably formed by curing the crosslinkable polymer-containing composition. In the case of photocuring, it is preferable to add a known photopolymerization initiator to the crosslinkable polymer-containing composition. In the case of thermosetting, heating at 40 ° C. to 250 ° C. is preferable, and heating at 40 ° C. to 180 ° C. is more preferable. Since the heating time is influenced by the film material used, the concentration, the amount of the initiator or the cross-linking agent added, it is determined by the temperature and time sufficient to form the film, but generally 10 minutes to 24 minutes. Time is preferable, and 1 hour to 12 hours is more preferable. Heating can be performed by using various ovens, hot plates, blowers and the like.

<Step of peeling substrate>
In the laminate manufacturing method of the present invention, it is preferable that the substrate is peeled from the laminate including the substrate, the liquid crystal layer, and the high gas-permeable layer in this order. By this step, it is possible to easily produce the laminate of the present invention that does not include the substrate, includes the liquid crystal layer and the high gas permeable layer, and is suitably used as a gas separation membrane.
A method for peeling the substrate from the laminate including the substrate, the liquid crystal layer, and the highly gas permeable layer in this order is not particularly limited, and for example, peeling using an adhesive tape. it can.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Examples 1-6, Comparative Examples 1-3]
<Liquid crystal layer formation>
FUJIFILM's coating liquids prepared in the formulations of the coating liquids (A) and (B) shown in Tables 1 and 2 below, using a wire bar, so that the dry film thickness after drying is 1 to 4000 nm. On a porous PDMS film (thickness 150 μm) obtained by applying a PDMS emulsion (45% (w / v), manufactured by Toray Dow Corning Silicone) on PET (film thickness 75 μm) or PET non-woven fabric and drying for 16 hours, Application was at room temperature.
After drying at room temperature for 30 seconds, heated in an atmosphere of 125 ° C. for 2 minutes, and then UV-irradiated at 95 ° C. with a fusion D bulb (lamp 90 mW / cm) at an output of 60% for 6 to 12 seconds. Was made.

Coating liquid (A)

Coating liquid (B)

The film thickness of the liquid crystal layer obtained above was measured by FE3000 (Otsuka Electronics) at 200 points (100 mm width) at intervals of 0.5 mm.
Ra of the liquid crystal layer obtained above was similarly calculated from the result of measurement with FE3000 (Otsuka Electronics).
Table 4 below shows the film thickness and Ra measurement results of the liquid crystal layers for producing the laminates of the obtained Examples and Comparative Examples.

<High gas permeable layer formation>
The liquid crystal produced as described above so that the thickness of the dry film after drying the coating liquid prepared in the formulation of the coating liquid (C) shown in Table 3 below is 1.3 to 1.6 μm using a wire bar. On the layer, it apply | coated at room temperature (except the porous PDMS base | substrate of the comparative example 3).
After drying at room temperature for 30 seconds, heating was performed in an atmosphere of 70 ° C. for 120 minutes to produce a high gas permeable layer.

Ｘ＝８０、Ｙ＝２０
重量平均分子量ＭＷ＝９３０００。

X = 80, Y = 20
Weight average molecular weight MW = 93000.

<Peeling the substrate>
It peeled using the adhesive tape from the base material which used the laminated body of the said liquid crystal layer and the high gas-permeable layer as a foundation | substrate (The porous PDMS foundation | substrate of the comparative example 3 did not peel a liquid crystal layer from a foundation | substrate). Thus, the laminated body of each Example and comparative example with which the liquid crystal layer and the high gas-permeable layer were laminated | stacked was produced (however, the porous PDMS base | substrate of the comparative example 3 does not have a high gas-permeable layer).

（Ｑ：各層のガス透過流束を表す。）
得られた結果を下記表４に記載した。 <Evaluation>
(Measurement and calculation of gas permeation performance)
The laminates of Examples and Comparative Examples obtained in the above, by using a GTR-11A (manufactured by GTR Tec), and permeability coefficient of CO ₂ under a pressure of 200 kPa, temperature 40 ° C., the transmission coefficient of CH ₄ Was measured.
The CO ₂ permeation flux and the CH ₄ permeation flux were calculated by dividing the permeation coefficient by the film thickness.
The separation ratio was calculated by dividing the permeate flux of CO _{2 by} the permeate flux of CH ₄ .
In addition, in Reference Examples 4 to 10, the permeation flux of only the liquid crystal layer of Example 1 was calculated and described by the following formula 1.

(Q represents the gas permeation flux of each layer.)
The obtained results are shown in Table 4 below.

From Table 4 above, it was found that the laminate of the present invention is a high-performance gas separation membrane having a good CO ₂ and CH ₄ separation ratio and a large CO ₂ gas permeation flux.
On the other hand, it was found that the laminates of Comparative Examples 1 and 2 in which the film thickness of the liquid crystal layer exceeded the upper limit defined in the present invention had a poor CO ₂ and CH ₄ separation ratio.
Moreover, the laminated body of the comparative example 3 which did not laminate | stack a high gas-permeable layer had the part which is not a film | membrane, and gas-permeation performance and gas separation ratio were unmeasurable.

1 Liquid Crystal Layer 2 High Gas Permeability Layer 3 Substrate 4 Laminate

Claims (9)

And a liquid crystal layer thickness is 0.5 nm to 10 nm, the gas permeation flux with respect to the liquid crystal layer when compared with the same type of gas observed contains a high gas permeable layer is 1.0 times or more,
The laminate, wherein the liquid crystal layer is an optically anisotropic layer formed by fixing the alignment state of the polymerizable liquid crystal compound . A substrate, a liquid crystal layer having a thickness of 0.5 nm to 10 nm, and a highly gas permeable layer having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the same type of gas. this order only contains,
The laminate, wherein the liquid crystal layer is an optically anisotropic layer formed by fixing the alignment state of the polymerizable liquid crystal compound .   The laminate according to claim 2, wherein the substrate is a polyethylene terephthalate film.   The laminate according to any one of claims 1 to 3, wherein the high gas-permeable layer contains a crosslinked polymer.   The crosslinked polymer has a repeating unit constituting at least one polymer selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polydimethylsiloxane, polyvinylpyrrolidone, polyethyleneimine, polyimide and polyallylamine. The laminate according to claim 4. The laminate according to any one of claims 1 to 5 , wherein the average roughness Ra of the liquid crystal layer is 1 nm or less. An application step of applying a polymerizable liquid crystal composition containing (A) a polymerizable liquid crystal compound, (B) a photopolymerization initiator, and (C) an organic solvent on the substrate to a thickness of 0.5 to 10 nm;
An alignment step of aligning the polymerizable liquid crystal compound by applying heat;
An irradiation step of irradiating the polymerizable liquid crystal composition with active radiation to fix a liquid crystal phase to obtain a liquid crystal layer;
On the liquid crystal layer, a step of laminating a high gas permeable layer having a gas permeation flux of 1.0 times or more with respect to the liquid crystal layer when compared with the same kind of gas;
The manufacturing method of the laminated body characterized by including. The method for manufacturing a laminate according to claim 7 , wherein the substrate is peeled from a laminate including the substrate, the liquid crystal layer, and the highly gas permeable layer in this order. The method for producing a laminate according to claim 7 or 8 , wherein the substrate is a polyethylene terephthalate film.

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