JP2015047537A - Polymer functional film and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer functional film where production cost is suppressed to be low by light irradiation at a low exposure amount in a short time and any of homogeneity, water permeability and film resistance is superior in a good balance.SOLUTION: A polymer functional film produced by the photocuring reaction of a composition containing a styrene monomer expressed by general formula (HSM), a styrene crosslinking agent and a photoacid generator, and a production method of the same are provided. In the general formula (HSM), R represents a halogen atom or -N(R)(R)(R)(X); n represents an integer of 1-10; Rto Rrepresents an alkyl group or an aryl group; Rand Ror R, Rand Rmay be bonded to each other to form an aliphatic heterocycle; and Xrepresents an organic or inorganic anion.

Description

  The present invention relates to a polymer functional membrane useful for an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, a gas separation membrane, and the like, and a production method thereof.

As a polymer functional membrane, an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, a gas separation membrane, or the like is known as a membrane having various functions.
For example, ion exchange membranes are used for electrodeionization (EDI), continuous electrodeionization (CEDI), electrodialysis (ED), reverse electrodialysis (EDR), and the like. .
Electrodesalting (EDI) is a water treatment process in which ions are removed from an aqueous liquid using thin films and electrical potentials to achieve ionic transport. Unlike other water purification techniques such as conventional ion exchange, it does not require the use of chemicals such as acid or caustic soda and can be used to produce ultrapure water. Electrodialysis (ED) and reverse electrodialysis (EDR) are electrochemical separation processes that remove ions and the like from water and other fluids.

  Among ion exchange membranes, styrene-based anion exchange membranes are generally obtained by thermally curing a nonionic monomer (for example, chloromethylstyrene) and a nonionic crosslinking agent (for example, divinylbenzene) and further ionizing the ionic anion exchange membrane. Manufactured (for example, see Patent Documents 1 and 2).

JP 2000-212306 A JP 2007-103372 A

According to the studies by the present inventors, in particular, in the methods described in Patent Documents 1 and 2, (i) the two steps (thermosetting and ionization) are slow in reaction, and particularly in thermosetting reactions, they are very long. The manufacturing cost is high because time is required. (Ii) Since the reactivity of the ionization process after film formation depends on the diffusivity of the reaction reagent into the film because the reaction reagent reacts in the cured film that has been thermally cured, it does not diffuse uniformly in the film. The charge density is insufficient or the charge density is distributed. Therefore, an anion exchange membrane obtained by a method generally used so far has a very high membrane resistance. (Iii) The azo initiator, which is frequently used for thermosetting, generates radicals and releases nitrogen gas, so that film defects are easily caused by the nitrogen gas. In addition, if an ionic styrene monomer is used to omit the ionization step, the compatibility with the nonionic crosslinking agent is poor, and the degree of crosslinking becomes non-uniform in conventional thermosetting with an organic peroxide. is there.
Further investigations focused on solving these problems.
On the other hand, as an approach different from the methods described in Patent Documents 1 and 2, the photo radical curing process using an ionic monomer, an ionic crosslinker (charged crosslinker) and a photoradical initiator is also studied by the present inventors. Has found that an ion exchange membrane having a high charge density and a low membrane resistance can be obtained in a short time. However, since this method is subject to oxygen inhibition, it needs to be cured in a short time with a high exposure UV. For this reason, unless the reaction conditions are strictly managed, the required homogeneity of the ion exchange membrane may not be obtained.

  The present invention provides a functional polymer film having a good balance of homogeneity, water permeability and membrane resistance, and a method for producing the same, by suppressing the production cost by light irradiation with a low exposure amount in a short time. Let it be an issue.

  As a result of further research, the inventors of the present invention have made it possible to produce a styrene ion exchange membrane by combining photopolymerization with a monofunctional styrene monomer combined with a styrene crosslinking agent, regardless of whether the monomer is ionic or not. When a photoacid generator is used as an initiator, it is possible to obtain an ion exchange membrane with excellent film homogeneity, high charge density, low membrane resistance, and low water permeability by irradiating light with a low exposure amount for a short time. I found it. The present invention has been completed based on this finding.

That is, the said subject of this invention was solved by the following means.
<1> (A) A polymer function obtained by photocuring a composition containing a styrene monomer represented by the following general formula (HSM), (B) a styrene crosslinking agent, and (C) a photoacid generator. Sex membrane.

[In General Formula (HSM), R represents a halogen atom or —N ⁺ (R ¹ ) (R ² ) (R ³ ) (X ₂ ⁻ ). n represents an integer of 1 to 10. Here, R ^{1 to} R ³ each independently represents a linear or branched alkyl group or aryl group. R ¹ and R ² , or R ¹ , R ² and R ³ may be bonded to each other to form an aliphatic heterocycle. X ₂ ⁻ represents an organic or inorganic anion. ]
<2>-(CH ₂ ) n—R is a group represented by the following general formula (ALX), and after the composition is photocured, a tertiary amine compound that is a quaternary ammonium agent is reacted. The polymer functional film according to <1>.

[In General Formula (ALX), X ₁ represents a halogen atom. n1 is synonymous with n in the general formula (HSM). ]
<3> (B) The functional polymer film according to <1> or <2>, wherein the styrene-based crosslinking agent is represented by the following general formula (CL).

[In General Formula (CL), L ¹ represents an alkylene group or an alkenylene group. Ra, Rb, Rc and Rd each independently represents an alkyl group or an aryl group, and Ra and Rb or / and Rc and Rd may be bonded to each other to form a ring. n3 represents an integer of 1 to 10. X ₃ ⁻ and X ₄ ⁻ each independently represents an organic or inorganic anion. ]
<4> (C) The polymeric functional film according to any one of <1> to <3>, wherein the photoacid generator is represented by the following general formula (PAG1) or (PAG2).

[In General Formula (PAG1) or (PAG2), Ar ^{1 to} Ar ⁵ each independently represents a substituted or unsubstituted aryl group. X ₅ ^- and _{X 6} ^- are each independently represents an organic or inorganic anion. ]
<5> The polymer functional film according to any one of <1> to <4>, wherein the composition further comprises (D) a polymerization initiator represented by the following general formula (AI).

[In General Formula (AI), R ^{5 to} R ⁸ each independently represents an alkyl group, and Y represents ═O or ═N—Ri. Re to Ri each independently represent a hydrogen atom or an alkyl group. Re and Rf, Rg and Rh, Re and Ri, and Rg and Ri may be bonded to each other to form a ring. ]
<6> the total solid content 100 parts by weight of the composition, R is + a halogen atom or ^{-N (R 1) (R 2} ) (R 3) - a styrene-based monomer represented by _{(X 2)} And the polymer functional film in any one of <1> and <3>-<5> whose content of this styrene-type monomer is 1-85 mass parts.
<7> The polymer functional film according to any one of <2> to <6>, wherein the content of the styrene-based crosslinking agent is 10 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the composition. .
<8> The polymer function according to any one of <1> to <7>, wherein the content of (C) the photoacid generator is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the composition. Sex membrane.
<9> The polymer functional film according to any one of <1> to <8>, wherein the composition contains a solvent (E).
<10> (E) The polymer functional film according to <9>, wherein the solvent is water or a water-soluble solvent.
<11> The polymer functional membrane according to any one of <1> to <10>, which has a support.
<12> The polymer functional membrane according to <11>, wherein the support is a synthetic woven fabric or synthetic nonwoven fabric, a sponge film, or a film having fine through holes.
<13> The polymer functional film according to <11> or <12>, wherein the support is a polyolefin.
<14> The polymer functional membrane according to any one of <1> to <13>, wherein the polymer functional membrane is an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, or a gas separation membrane.
<15> (A) A polymer functional film for photocuring a composition containing a styrene monomer represented by the following general formula (HSM), (B) a styrene crosslinking agent, and (C) a photoacid generator Manufacturing method.

[In General Formula (HSM), R represents a halogen atom or —N ⁺ (R ¹ ) (R ² ) (R ³ ) (X ₂ ⁻ ). n represents an integer of 1 to 10. Here, R ^{1 to} R ³ each independently represents a linear or branched alkyl group or aryl group. R ¹ and R ² , or R ¹ , R ² and R ³ may be bonded to each other to form an aliphatic heterocycle. X ₂ ⁻ represents an organic or inorganic anion. ]
<16>-(CH ₂ ) n—R is a group represented by the following general formula (ALX), and after the composition is photocured, a tertiary amine compound that is a quaternary ammonium agent is reacted. <15> The method for producing a functional polymer film according to <15>.

[In General Formula (ALX), X ₁ represents a halogen atom. n1 is synonymous with n in the general formula (HSM). ]
<17> (B) The method for producing a functional polymer film according to <15> or <16>, wherein the styrene-based crosslinking agent is represented by the following general formula (CL).

[In General Formula (CL), L ¹ represents an alkylene group or an alkenylene group. Ra, Rb, Rc and Rd each independently represents an alkyl group or an aryl group, and Ra and Rb or / and Rc and Rd may be bonded to each other to form a ring. n3 represents an integer of 1 to 10. X ₃ ⁻ and X ₄ ⁻ each independently represents an organic or inorganic anion. ]
<18> (C) The method for producing a functional polymer film according to any one of <15> to <18>, wherein the photoacid generator is represented by the following general formula (PAG1) or (PAG2).

[In General Formula (PAG1) or (PAG2), Ar ^{1 to} Ar ⁵ each independently represents a substituted or unsubstituted aryl group. X ₅ ^- and _{X 6} ^- are each independently represents an organic or inorganic anion. ]
<19> The method for producing a functional polymer film according to any one of <15> to <18>, wherein the composition further comprises (D) a polymerization initiator represented by the following general formula (AI).

[In General Formula (AI), R ^{5 to} R ⁸ each independently represents an alkyl group, and Y represents ═O or ═N—Ri. Re to Ri each independently represent a hydrogen atom or an alkyl group. Re and Rf, Rg and Rh, Re and Ri, and Rg and Ri may be bonded to each other to form a ring. ]
<20> The method for producing a functional polymer film according to any one of <15> to <19>, wherein the composition contains (D) a solvent.
<21> (D) The method for producing a functional polymer film according to <20>, wherein the solvent is water or a water-soluble solvent.
<22> The method for producing a functional polymer film according to any one of <15> to <21>, wherein the composition is applied to and / or impregnated on a support and then cured.
<23> The method for producing a functional polymer film according to any one of <15> to <22>, wherein the curing reaction is a curing reaction in which the composition is polymerized by irradiation with energy rays and heating.
<24> The method for producing a functional polymer film according to any one of <15> to <23>, wherein the curing reaction is a curing reaction in which the composition is heated and polymerized after being irradiated with energy rays.

In the present specification, the “hole volume fraction” described later refers to the measurement of the electrical resistance of a polymer functional film (hereinafter sometimes simply referred to as “film”) using five NaCl solutions having different concentrations. , The conductivity of the film when immersed in NaCl solution of each concentration is A (S / cm ² ), the conductivity per unit film thickness of each NaCl concentration solution is B (S / cm ² ), and A is y The value calculated by the following formula (b) when the y intercept when B is the x axis and C is the axis.

      Void volume fraction = (AC) / B (b)

Since the vacancies in the present invention are smaller than the detection limit of a standard scanning electron microscope (SEM) and cannot be detected using a Jeol JSM-6335F field emission SEM having a detection limit of 5 nm, the average vacancy size is It is considered to be less than 5 nm.
In addition, since it is smaller than the detection limit of SEM, it is considered that this vacancy is a gap between atoms. In the present specification, “vacancy” means to include a gap between atoms.
It is considered that the pores are formed by shrinkage at the time of curing the solvent, neutralized water, salt, or composition in the composition when the composition for forming a functional polymer film is cured.

  The pores are void portions having an arbitrary shape existing inside the polymer functional film, and include both independent holes and continuous holes. “Independent holes” refer to holes that are independent of each other, and may be in contact with any surface of the film. On the other hand, “continuous hole” means a hole in which independent holes are formed. The continuous pores may be continuous from any surface of the membrane to other surfaces in the form of passages.

Further, in the present specification, “to” is used in the sense of including numerical values described before and after it as a lower limit value and an upper limit value.
In each general formula, unless otherwise specified, when there are a plurality of groups having the same sign, these may be the same or different from each other, and similarly, when there are repetitions of a plurality of partial structures, These repetitions mean both the same repetition and a mixture of different repetitions within the specified range.
Furthermore, the geometrical isomer which is the substitution mode of the double bond in each general formula is not limited to the E-form or the Z-form unless otherwise specified, even if one of the isomers is described for convenience of display. Or a mixture thereof.

  In addition, when the term “compound” is used at the end in this specification, or when a specific compound is indicated by its name or formula, in addition to the compound itself, a dissociative partial structure in the chemical structural formula If it has, it is used in the meaning including its salt and its ion. Further, in this specification, when the term “group” is added to the end of the description, or when a specific compound is referred to by its name, the group or compound may have an arbitrary substituent. Meaning.

  The polymer functional membrane of the present invention is excellent in uniformity, water permeability, and membrane resistance. Furthermore, according to the method for producing a polymer functional membrane of the present invention, a polymer functional membrane having a good balance of homogeneity, water permeability and membrane resistance can be obtained at a low production cost by short-time energy irradiation or the like. Can be manufactured.

It is a schematic diagram of the flow path of the apparatus for measuring the water permeability of a membrane.

  The polymer functional membrane of the present invention can be used for ion exchange, reverse osmosis, forward osmosis, gas separation and the like. Hereinafter, a preferred embodiment of the present invention will be described by taking as an example the case where the polymer functional membrane has a function as an ion exchange membrane.

The polymer functional membrane of the present invention is preferably an anion exchange membrane.
When it has a support body, the thickness of the film | membrane of this invention is 30-250 micrometers including a support body, 40-200 micrometers is more preferable, 50-150 micrometers is especially preferable.

  The polymer functional membrane of the present invention is preferably 1.5 meq / g or more based on the total dry mass of the membrane or any porous reinforcing material such as a membrane and a porous support when having a support. The ion exchange capacity is preferably 2.0 meq / g or more, particularly preferably 2.5 meq / g or more. The upper limit of the ion exchange capacity is not particularly limited, but is practically 7.0 meq / g or less. Here, meq is milliequivalent.

Film of the present invention is based on the area of the dry film, preferably 45meq / ^{m 2} or more, more preferably 60 meq / ^{m 2} or more, particularly preferably a 75 mEq / ^{m 2} or more charge density. The upper limit of the charge density is not particularly limited, but it is practical that it is 1,750 meq / m ² or less.

Cl polymeric functional film of the present invention (anion exchange membrane) ^- selective permeability to anions, such as, preferably greater than 0.90, more preferably greater than 0.93, greater than 0.95, the theoretical value It is particularly preferable that the value approaches 1.0.

The electrical resistance of the polymer functional film of the present invention (film resistor) is preferably less than 2 [Omega · cm ^2, more preferably less than 1.5 [Omega · cm ^2, less than 1.3Ω · cm ² is particularly preferred. The lower the electrical resistance, the better, and the lowest value in the realizable range is preferable for achieving the effects of the present invention. Although there is no restriction | limiting in particular in the minimum of electrical resistance, it is practical that it is 0.1 ohm * cm < ² > or more.
The swelling ratio (rate of dimensional change due to swelling) of the functional polymer film of the present invention in water is preferably less than 30%, more preferably less than 15%, and particularly preferably less than 8%. The swelling rate can be controlled by selecting curing conditions in the curing stage.

  The electrical resistance, permselectivity and% swelling in water are determined by the method described in Membrane Science, 319, 217-218 (2008), Masayuki Nakagaki, Membrane Experimental Method, pages 193-195 (1984). Can be measured.

The water permeability of the polymer functional membrane of the present invention is preferably 15 × 10 ⁻⁵ ml / m ² / Pa / hr or less, more preferably 10 × 10 ⁻⁵ ml / m ² / Pa / hr or less, and 8 × 10 ⁻⁵ ml / m ² / Pa / hr or less is particularly preferable. Although there is no restriction | limiting in particular in the minimum of a water permeability, it is practical that it is 1 * 10 < ^-5 > ml / m < ² > / Pa / hr or more.

  The mass average molecular weight of the polymer constituting the polymer functional film of the present invention is several hundred thousand or more because three-dimensional crosslinking is formed, and cannot be measured substantially. Generally considered as infinite.

  The polymer functional film of the present invention contains (A) a styrene monomer represented by the general formula (HSM), (B) a styrene crosslinking agent, and (C) a photoacid generator as essential components. Accordingly, it is formed by a curing reaction of a composition containing (D) a polymerization initiator represented by the general formula (AI), (E) a solvent and (F) a polymerization inhibitor.

<(A) Styrenic monomer represented by general formula (HSM)>
The (A) styrenic monomer used in the composition in the present invention is represented by the following general formula (HSM).

In the general formula (HSM), R represents a halogen atom or —N ⁺ (R ¹ ) (R ² ) (R ³ ) (X ₂ ⁻ ). n represents an integer of 1 to 10. Here, R ^{1 to} R ³ each independently represent a linear or branched alkyl group or an aryl group. R ¹ and R ² , or R ¹ , R ² and R ³ may be bonded to each other to form an aliphatic heterocycle. X ₂ ⁻ represents an organic or inorganic anion.

_{Here, - (CH 2) n-} R can be divided into groups represented by the following general formula based on the following formula represented by (ALX) (ALA).

Formula (ALX), in (ALA), _{X 1} represents a halogen ^atom, R 1 to R ³ and _{X 2} ^- is ^R 1 to R in the general formula (HSM) ³ and _{X 2} ^- in the above formula, preferred The range is the same. n1 and n2 are both synonymous with n in the general formula (HSM), and the preferred range is also the same.

In the general formula (ALX), X ₁ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom, more preferably a chlorine atom and a bromine atom, and particularly preferably a chlorine atom. preferable.
As for n in general formula (HMS), n1 in general formula (ALX), and n2 in general formula (ALA), 1 or 2 is preferable, and 1 is particularly preferable.

In general formulas (HMS) and (ALA), the alkyl group in R ^{1 to} R ³ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2. Examples of the alkyl group include methyl, ethyl, isopropyl, n-butyl, and 2-ethylhexyl. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
Aryl group in R ¹ to R ³ has a carbon number of preferably 6 to 12, more preferably 6 to 10, 6 to 8 is more preferred. The aryl group may have a substituent, and examples thereof include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group. The aryl group is preferably a phenyl group.
Of these, R ^{1 to} R ³ are preferably alkyl groups.

The ring formed by combining R ¹ and R ² with each other is preferably a 5- or 6-membered ring, and examples thereof include a pyrrolidine ring, a piperidine ring, a morpholine ring, a thiomorpholine ring, and a piperazine ring.
Examples of the ring formed by combining R ¹ , R ^2, and R ³ with each other include a quinuclidine ring and a triethylenediamine ring (1,4-diazabicyclo [2.2.2] octane ring).

In general formulas (HMS) and (ALA), X ₂ ⁻ represents an organic or inorganic anion, and an inorganic anion is preferred.
Examples of the organic anion include an alkyl sulfonate anion, an aryl sulfonate anion, an alkyl or aryl carboxylate anion, and examples thereof include a methane sulfonate anion, a benzene sulfonate anion, a toluene sulfonate anion, and an acetate anion.
Examples of inorganic anions include halogen anions, sulfate dianions, and phosphate anions, with halogen anions being preferred. Among the halogen anions, a chlorine anion and a bromine anion are preferable, and a chlorine anion is particularly preferable.

  Of the groups represented by the general formula (ALX) or (ALA), the group represented by the general formula (ALX) is preferable.

Hereinafter, in the general formula (HSM), the styrene monomer in the case where — (CH ₂ ) n—R is a group represented by the general formula (ALA) may be referred to as a styrene monomer (SM). Here, although the specific example of a styrene-type monomer (SM) is shown, this invention is not limited to these.

  The styrene monomer (SM) compound can be synthesized by the method described in JP 2000-229917 A or JP 2000-212306 A or a method analogous thereto. Moreover, it is also possible to obtain as a commercial item from Sigma-Aldrich.

  In the polymer functional film of the present embodiment, a combination of two or more styrene monomers (SM) may be used.

  In the present invention, the styrene monomer (SM) content is preferably 1 to 85 parts by mass, more preferably 10 to 80 parts by mass, with respect to 100 parts by mass of the total solid content of the composition for forming a film. -75 mass parts is particularly preferred.

In the general formula (HSM), when — (CH ₂ ) n—R represents a group represented by the general formula (ALX), after the photocuring reaction, a tertiary amine compound which is a quaternary ammonium agent is reacted. The polymer functional membrane is preferably an anion exchange membrane.

In the present specification, the following, in the general formula _{(HSM), - (CH 2} ) if n-R represents a group represented by the formula (ALX), referred to as styrene monomer and styrene monomer (HSM). Here, although the specific example of a styrene-type monomer (HSM) is shown, this invention is not limited to these.

  In the present invention, the styrene monomer (HSM) content is preferably 1 to 95 parts by mass, more preferably 10 to 95 parts by mass, with respect to 100 parts by mass of the total solid content of the composition for forming a film. -95 mass parts is especially preferable.

  Next, although the specific example of the tertiary amine compound which is a quaternary ammonium agent is shown, this invention is not limited to these.

Although there is no restriction | limiting in particular in the reaction conditions at the time of making the tertiary amine compound which is a quaternary ammonium agent react with the film | membrane after hardening, Usually, it reacts by immersing a cured film in a tertiary amine compound solution. The amine compound solution concentration at this time is preferably 0.01 mol / L to 5.00 mol / L, more preferably 0.05 mol / L to 3.00 mol / L, and 0.10 mol / L to 1. 00 mol / L is particularly preferred.
The temperature at which the cured film is immersed in the tertiary amine compound solution is preferably 0 to 100 ° C, more preferably 10 to 80 ° C, and particularly preferably 20 to 60 ° C.
The time for immersing the cured film in the tertiary amine compound solution is preferably 0.5 to 24 hours, more preferably 1 to 18 hours, and particularly preferably 2 to 12 hours.

(B) Styrenic crosslinking agent (B) The styrene crosslinking agent used for the polymer functional film of the present invention is not particularly limited. In the present invention, a general crosslinking agent such as divinylstyrene or a compound represented by the following general formula (CL) is preferably used.

In the general formula (CL), L ¹ represents an alkylene group or an alkenylene group. Ra, Rb, Rc and Rd each independently represents an alkyl group or an aryl group, and Ra and Rb or / and Rc and Rd may be bonded to each other to form a ring. n3 represents an integer of 1 to 10. X ₃ ⁻ and X ₄ ⁻ each independently represents an organic or inorganic anion.

The alkylene group for L ¹ preferably has 2 or 3 carbon atoms, and examples thereof include ethylene and propylene. The alkylene group may have a substituent, and examples of the substituent include an alkyl group.
The alkenylene group in L ¹ preferably has 2 or 3 carbon atoms, more preferably 2, particularly an ethenylene group.
The ring formed by L ¹ is preferably a piperazine ring.
The alkyl group and aryl group in Ra, Rb, Rc and Rd are preferably in the preferred range of the alkyl group and aryl group in R ^{2 to} R ⁴ .

Of these, Ra, Rb, Rc and Rd are preferably alkyl groups, and methyl is particularly preferred.
Ra and Rb, Rc and Rd may be bonded to each other to form a ring, and a triethylenediamine ring (1,4-diazabicyclo [2.2.2] octane ring) is particularly preferable.

n3 is preferably 1 or 2, and 1 is particularly preferable.
X ₃ ^- and _{X 4} ^- is _{X 2} ^- in the above formula, the preferred range is also the same.

  Specific examples of the crosslinking agent represented by the general formula (CL) are shown below, but the present invention is not limited thereto.

  The crosslinking agent represented by the general formula (CL) can be synthesized by the method described in JP-A No. 2000-229917 or a method analogous thereto.

  In the polymer functional film of the present embodiment, (B) two or more kinds of crosslinking agents represented by the general formula (CL) may be used in combination.

  In this invention, 10-100 mass parts is preferable, as for crosslinking agent content represented by the said (B) general formula (CL) with respect to 100 mass parts of total solid of the composition for forming a film | membrane, 15 -90 mass parts is more preferable, and 20-80 mass parts is especially preferable.

  In the composition for forming a film of the present invention, the molar ratio of (A) the styrenic monomer represented by the general formula (HSM) and (B) the crosslinking agent represented by the general formula (CL) is 1 /0.1 to 1/55 is preferable, 1 / 0.14 to 1/55 is more preferable, and 1 / 0.3 to 1/55 is particularly preferable.

In the present invention, the crosslink density of the polymer formed by reacting the styrene monomer represented by (A) the general formula (HSM) and the crosslinker represented by (B) the general formula (CL) is 0.4. ˜2 mmol / g is preferable, 0.5 to 2 mmol / g is more preferable, and 1.0 to 2 mmol / g is particularly preferable.
When the crosslinking density is within the above range, the membrane water content is decreased, the water permeability is decreased, and the membrane resistance is also small.

  The photoacid generator (C) used in the polymer functional film of the present invention is not particularly limited, but a compound represented by the following general formula (PAG1) or general formula (PAG2) is preferable.

In General Formula (PAG1) and General Formula (PAG2), Ar ^{1 to} Ar ⁵ each independently represents a substituted or unsubstituted aryl group. X ₅ ^- and X ₆ ^- represent an organic or inorganic anion. X ₅ ^- and _{X 6} ^- is _{X 2} ^- in the above formula, the preferred range is also the same.
Aryl group for Ar ¹ to Ar ⁵ has a carbon number of preferably 6 to 12, more preferably 6 to 10, 6 to 8 is more preferred. The aryl group may have a substituent, and examples thereof include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group. The aryl group is preferably a phenyl group.

  Hereinafter, although the specific example of a photo-acid generator represented by general formula (PAG1) or general formula (PAG2) is shown, this invention is not limited to these.

  In the composition of the present invention, a photoacid generator represented by the general formula (PAG1) or the general formula (PAG2) and a photoacid generator represented by the following general formula (PAG3) may be used in combination.

In General Formula (PAG3), Ar ⁶ and Ar ⁷ each independently represent a substituted or unsubstituted alkyl group or an aryl group.
The alkyl group in Ar ⁶ and Ar ⁷ preferably has 1 to 10 carbon atoms, preferably 1 to 8 and more preferably 1 to 6. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl and hexyl. These alkyl groups may be linear or cyclic, and in the case of linear, they may be linear or branched. Moreover, you may have a substituent and a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxy group etc. are mentioned.
Aryl group for Ar ⁶ and Ar ⁷ has a carbon number of preferably 6 to 12, more preferably 6 to 10, 6 to 8 is more preferred. The aryl group may have a substituent, and examples thereof include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group. The aryl group is preferably a phenyl group.

  Hereinafter, although the specific example of a photo-acid generator represented by general formula (PAG3) is shown, this invention is not limited to these.

  Moreover, in this invention, the photo-acid generator represented by the following general formula (PAG4) can also be used together with the photo-acid generator represented by general formula (PAG1)-general formula (PAG3).

In General Formula (PAG4), Ar ⁸ and Ar ⁹ each independently represent a substituted or unsubstituted aryl group.
The aryl group in Ar ⁸ and Ar ⁹ preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and still more preferably 4 to 8 carbon atoms. The aryl group may have a substituent, and examples thereof include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group. The aryl group is preferably a phenyl group.

  Hereinafter, although the specific example of the photo-acid generator represented by general formula (PAG4) is shown, this invention is not limited to these.

  In addition, in this invention, the photo-acid generator which has the following structure can also be used.

  In the present invention, the photogenerator content is preferably from 0.1 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the total solid content of the composition for forming a film. 0.5-5 mass parts is especially preferable.

  The composition in the present invention preferably further contains (D) a polymerization initiator represented by the following general formula (AI).

In General Formula (AI), R ^{5 to} R ⁸ each independently represents an alkyl group, and Y represents ═O or ═N—Ri. Re to Ri each independently represent a hydrogen atom or an alkyl group. Re and Rf, Rg and Rh, Re and Ri, and Rg and Ri may be bonded to each other to form a ring.

The alkyl group for R ^{5 to} R ⁸ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably methyl.
Re to Ri are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The ring formed by combining Re and Rf, Rg and Rh, Re and Ri, and Rg and Ri is preferably a 5- or 6-membered ring.
The ring formed by combining Re and Ri and Rg and Ri with each other is preferably an imidazoline ring, and the ring formed by combining Re and Rf and Rg and Rh with each other includes a pyrrolidine ring and a piperidine ring. Piperazine ring, morpholine ring, and thiomorpholine ring are preferable.

  Y is preferably ═N—Ri.

  Specific examples of the polymerization initiator represented by the general formula (AI) are shown below, but the present invention is not limited thereto.

  The polymerization initiator represented by the general formula (AI) can be obtained from Wako Pure Chemical Industries, Ltd., the exemplary compound (AI-1) is VA-061, and the exemplary compound (AI-2) is VA-044. The exemplified compound (AI-3) is VA-046B, the exemplified compound (AI-4) is V-50, the exemplified compound (AI-5) is VA-067, the exemplified compound (AI-6) is VA-057, Compound (AI-7) is commercially available as VA086 (both trade names).

  In the present invention, the polymerization initiator content represented by (D) general formula (AI) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the composition for forming a film. 0.1-10 mass parts is more preferable, and 0.5-5 mass parts is especially preferable.

(E) Solvent The composition for forming the film of the present invention may contain (E) a solvent.
In this invention, 5-60 mass parts is preferable with respect to 100 mass parts of all compositions, and, as for content of the (E) solvent in the said composition, 10-40 mass parts is more preferable.
By setting the content of the solvent within this range, a uniform film can be produced without increasing the viscosity of the composition. In addition, the occurrence of pinholes (fine defect holes) can be suppressed.

(E) As the solvent, a solvent having a solubility in water of 5% by mass or more is preferably used, and a solvent that is freely mixed with water is preferable. For this reason, a solvent selected from water and a water-soluble solvent is preferred. As the water-soluble solvent, alcohol solvents, ether solvents that are aprotic polar solvents, amide solvents, ketone solvents, sulfoxide solvents, sulfone solvents, nitrile solvents, and organic phosphorus solvents are particularly preferable. . Water and alcohol solvents are preferred. Examples of alcohol solvents include methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like. Among alcohol solvents, ethanol, isopropanol, n-butanol, and ethylene glycol are more preferable, and isopropanol is particularly preferable. These can be used alone or in combination of two or more. Water alone or a combination of water and a water-soluble solvent is preferred, and water alone or a combination of water and at least one alcohol solvent is more preferred. In the combined use of water and a water-soluble solvent, 0.1 to 10% of isopropanol is preferable with respect to 100% by mass of water, more preferably 0.5 to 5%, and still more preferably 1.0 to 2.0%.
Examples of aprotic polar solvents include dimethyl sulfoxide, dimethyl imidazolidinone, sulfolane, N-methylpyrrolidone, dimethylformamide, acetonitrile, acetone, dioxane, tetramethylurea, hexamethylphosphorotriamide, pyridine, propionitrile, Preferred examples of the solvent include butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, ethylene glycol diacetate, and γ-butyrolactone. Among them, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone or acetonitrile, and tetrahydrofuran are preferable. preferable. These can be used alone or in combination of two or more.

(F) Polymerization inhibitor The composition for forming a film of the present invention preferably contains a polymerization inhibitor in order to impart stability to the coating solution used to form the film.
As the polymerization inhibitor, a known polymerization inhibitor can be used, and examples thereof include a phenol compound, a hydroquinone compound, an amine compound, and a mercapto compound.
Examples of the phenol compound include hindered phenols (phenols having a t-butyl group in the ortho position, typically 2,6-di-t-butyl-4-methylphenol) and bisphenols. Specific examples of the hydroquinone compound include monomethyl ether hydroquinone. Specific examples of the amine compound include N-nitroso-N-phenylhydroxylamine and N, N-diethylhydroxylamine.
These polymerization inhibitors may be used singly or in combination of two or more.
The content of the polymerization inhibitor is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total solid content in the composition. Part by mass is more preferable.

[Other ingredients]
The composition for forming the film of the present invention may contain a surfactant, a polymer dispersant, an anti-crater agent and the like in addition to the components (A) to (F).

[Surfactant]
Various polymer compounds can be added to the composition for forming the film of the present invention in order to adjust film properties. High molecular compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinyl resins, acrylic resins, rubber resins. Waxes and other natural resins can be used. Two or more of these may be used in combination.
Further, nonionic surfactants, cationic surfactants, organic fluoro compounds, and the like can be added to adjust liquid properties.

  Specific examples of the surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate ester of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl Anionic surfactants such as alkyl carboxylates of sulfonamides, alkyl phosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of acetylene glycol, Nonionic surfactants such as ethylene oxide adducts of glycerin and polyoxyethylene sorbitan fatty acid esters, and other amphoteric interfaces such as alkyl betaines and amide betaines Sexual agents, silicone surface active agent, including a fluorine-based surfactant, can be appropriately selected from surfactants and derivatives thereof are known.

[Polymer dispersant]
The composition for forming the film of the present invention may contain a polymer dispersant.
Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide. Among them, polyvinyl pyrrolidone is also preferably used.

[Anti-crater]
Anti-crater agent is also called surface conditioner, leveling agent or slip agent, and prevents unevenness on the film surface. For example, organic modified polysiloxane (mixture of polyether siloxane and polyether), polyether modified poly Examples thereof include compounds having a structure of siloxane copolymer or silicon-modified copolymer.
Examples of commercially available products include, for example, Tego Glide 432, 110, 110, 130, 406, 410, 411, 415, 420, 435, 440, 450, and the like manufactured by Evonik Industries. 482, A115, B1484, and ZG400 (all are trade names).
The crater inhibitor is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, and still more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the total solid content in the composition.

  In addition to the above, the composition for forming the film of the present invention may contain, for example, a viscosity improver and a preservative, if necessary.

<Support>
Many techniques can be used to provide the membrane of this embodiment having particularly good mechanical strength. For example, a support can be used as the membrane reinforcing material, and a porous support can be preferably used. This porous support can form a part of a membrane by applying and / or impregnating the composition and then curing.
Examples of the porous support as the reinforcing material include a synthetic woven fabric or synthetic nonwoven fabric, a sponge film, a film having fine through holes, and the like. The material forming the porous support of the present invention is, for example, polyolefin (polyethylene, polypropylene, etc.), polyacrylonitrile, polyvinyl chloride, polyester, polyamide and copolymers thereof, or, for example, polysulfone, polyethersulfone, Polyphenylene sulfone, polyphenylene sulfide, polyimide, polyetherimide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, polypropylene, poly (4-methyl-1-pentene), polyvinylidene fluoride, polytetra A porous membrane based on fluoroethylene, polyhexafluoropropylene, polychlorotrifluoroethylene and their copolymers Door can be. Of these, polyolefins are preferred in the present invention.
Commercially available porous supports and reinforcement materials are commercially available from, for example, Japan Vilene, Freudenberg Filtration Technologies (Novatex material) and Separ AG. In an embodiment in which the porous reinforcing material is applied to the curable composition before curing, the porous reinforcing material is capable of passing irradiation of the wavelength used for curing and / or the curable composition is It is preferable that the material can penetrate into the porous reinforcing material so as to be cured in the step (ii) described later.

  The porous support preferably has hydrophilicity. As a method for imparting hydrophilicity to the support, general methods such as corona treatment, ozone treatment, sulfuric acid treatment, and silane coupling agent treatment can be used.

[Method for producing polymer functional film]
Next, the manufacturing method of the polymeric functional film of this embodiment is demonstrated.
The method for producing a polymer functional film of the present invention comprises ((A) a styrene monomer represented by the general formula (HSM), (B) a styrene crosslinking agent, and (C) a photoacid generator. Is cured to form a film.

In the present invention, it is preferable to produce the membrane such that the pore volume fraction of the membrane is preferably 3% or less, more preferably 2% or less, and particularly preferably 1.5% or less.
The pore volume fraction of the membrane can be adjusted by the amount of the crosslinking agent and the solid content concentration.
When the pore volume fraction of the membrane is within the above range, an effect that the moisture content of the membrane is lowered occurs, and salt leakage is suppressed, which is preferable.

The composition preferably further contains (D) a polymerization initiator represented by the general formula (AI).
The composition further contains (E) a solvent, and the content of the solvent is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the total mass of the composition.
Further, the solvent (E) is preferably water or a water-soluble solvent, and is preferably subjected to a curing reaction after the composition is applied to and / or impregnated on a support. Further, the curing reaction is preferably a curing reaction in which the composition is polymerized by irradiation and heating with energy rays. Furthermore, heating is preferably performed on a film formed by energy beam irradiation.
In the present invention, the heating temperature is preferably 40 to 120 ° C, more preferably 60 to 100 ° C, and particularly preferably 75 to 90 ° C. In addition, the heating time when heating after irradiation with energy rays is preferably 1 minute to 12 hours, more preferably 1 minute to 8 hours, and particularly preferably 1 minute to 6 hours.

Hereinafter, an example of the manufacturing method of the polymeric functional film of this invention is demonstrated in detail.
The polymer functional membrane of the present embodiment can be prepared batchwise using a fixed support, but the membrane can also be prepared continuously using a moving support. The support may be in the form of a roll that is continuously rewound. In addition, when preparing a film | membrane by a continuous type, a support body can be mounted on the belt moved continuously, and a film | membrane can be prepared (or combination of these methods). Using such techniques, the composition of the present invention can be applied to the support in a continuous manner or it can be applied in a large batch.
In addition, you may use a temporary support body (it peels a film | membrane from a temporary support body after completion | finish of hardening reaction) until a hardening reaction is completed by immersing a composition in a porous support body separately from a support body.
Such a temporary support does not need to consider material permeation, and may be any material as long as it can be fixed for film formation including a metal plate such as a PET film or an aluminum plate. .
Alternatively, the composition can be immersed in a porous support and cured without using a support other than the porous support.

  The composition can be applied by any suitable method such as curtain coating, extrusion coating, air knife coating, slide coating, nip roll coating, forward roll coating, reverse roll coating, dip coating, kiss coating, rod bar coating or spray coating. It can be applied to the porous support layer. Multi-layer coating can be performed simultaneously or sequentially. For multilayer simultaneous coating, curtain coating, slide coating, slot die coating and extrusion coating are preferred.

  Therefore, in a preferred method, the composition is continuously applied to a moving support, more preferably, a composition application section, an irradiation source for curing the composition, a film collection section, and a support. And a means for moving the body from the composition application section to the irradiation source and the film collection section.

In this production example, (i) a composition for forming a film of the present invention is applied and / or impregnated on a porous support, and (ii) the composition is irradiated with light, and if necessary, further heated. The polymer functional film of the present embodiment is produced through a process of curing reaction and (iii) removing the film from the support if desired.
In (ii), heating may be performed simultaneously with light irradiation, or may be performed on a film formed by light irradiation.

[Energy beam irradiation]
The composition application unit can be placed upstream of the irradiation source, and the irradiation source is placed upstream of the composite film collection station.
In order to have sufficient fluidity when applied with a high-speed coating machine, the viscosity at 35 ° C. of the composition of the present invention is preferably less than 4000 mPa · s, more preferably 1 to 1000 mPa · s, and more preferably 1 to 500 mPa · s. s is most preferred. In the case of slide bead coating, the viscosity at 35 ° C. is preferably 1 to 100 mPa · s.

  With suitable coating techniques, the composition of the invention can be applied to a support moving at a speed in excess of 15 m / min, such as a speed in excess of 20 m / min, or even at a higher speed, for example 60 m. / Min, 120 m / min, or up to 400 m / min.

  Especially when using a support to increase the mechanical strength, before applying the composition of the invention to the surface of the support, the support is used, for example, to improve the wettability and adhesion of the support. , Corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, and the like.

Table in _(CH 2) a styrene-based monomer and having a group n-R is represented by the general formula (ALX) (B) the general formula (CL) - during the curing reaction, the (A) formula (HSM), The resulting crosslinking agent polymerizes to form a polymer. The curing reaction can be carried out by light irradiation and heating under the condition that the curing occurs quickly enough to form a film within 30 seconds.

Curing of the composition of the present invention is initiated within 60 seconds, more preferably within 15 seconds, especially within 5 seconds, and most preferably within 3 seconds after the composition is applied to the support layer.
The curing light irradiation is preferably less than 10 seconds, more preferably less than 5 seconds, particularly preferably less than 3 seconds, and most preferably less than 2 seconds. In the continuous method, irradiation is performed continuously, and the curing reaction time is determined in consideration of the speed at which the composition moves through the irradiation beam.

  When high intensity UV light is used in the curing reaction, a significant amount of heat is generated and cooling air may be applied to the lamp and / or support / film of the light source to prevent overheating. When a significant dose of IR light is irradiated with the UV beam, the UV light is irradiated using an IR reflective quartz plate as a filter.

  It is preferable to use ultraviolet rays for curing. Suitable wavelengths are preferably compatible with the absorption wavelength and wavelength of any photoinitiator included in the composition, for example UV-A (400-320 nm), UV-B (320-280 nm), UV- C (280 to 200 nm).

  Suitable UV sources include mercury arc lamps, carbon arc lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, swirling plasma arc lamps, metal halide lamps, xenon lamps, tungsten lamps, halogen lamps, lasers and UV light emitting diodes. is there. Medium pressure or high pressure mercury vapor type UV lamps are particularly preferred. In addition, additives such as metal halides may be present to modify the emission spectrum of the lamp. Particularly suitable are lamps having an emission maximum between 200 and 450 nm.

The energy output of the irradiation source is preferably 20 to 1000 W / cm, preferably 40 to 500 W / cm, but may be higher or lower as long as a desired exposure dose can be realized. The curing of the film is adjusted according to the exposure intensity. The exposure dose is preferably measured by the High Energy UV Radiometer (UV Power Pack ^™ manufactured by EIT-Instrument Markets) in the UV-A range indicated by the apparatus, and is preferably at least 40 mJ / cm ² or more, more preferably 100 or more. ˜2,000 mJ / cm ² , most preferably 150 to 1,500 mJ / cm ² . The exposure time can be chosen freely but is preferably short, typically less than 2 seconds.

  Multiple light sources may be used to reach the desired dose at high coating speeds. These light sources may have the same or different exposure intensity.

  The polymer functional membrane of this embodiment is mainly intended for use in ion exchange. However, it is considered that the polymer functional membrane of the present invention is not limited to ion exchange and can be suitably used for reverse osmosis and gas separation.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.

[(E) Synthesis of Styrenic Crosslinking Agent]
(Synthesis Example 1)
For a mixed solution of 321 g of chloromethylstyrene (2.10 mol, CMS-P manufactured by Seimi Chemical), 1.30 g of 2,6-di-tert-butyl-4-methylphenol (manufactured by Wako Pure Chemical Industries), and 433 g of acetonitrile, 4-diazabicyclo [2.2.2] octane (1.00 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 80 ° C. for 15 hours.
The resulting crystals were filtered to obtain 405 g (yield 97%) of white crystals of the exemplified compound (CL-1).

(Synthesis Example 2)
For a mixed solution of 458 g of chloromethylstyrene (3.00 mol, CMS-P manufactured by Seimi Chemical), 1.85 g of 2,6-di-tert-butyl-4-methylphenol (manufactured by Wako Pure Chemical Industries), and 1232 g of nitrobenzene, N , N, N ′, N′-tetramethyl-1,3-diaminopropane (130 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was heated and stirred at 80 ° C. for 20 hours.
The resulting crystals were filtered to obtain 218 g (yield 50%) of white crystals of the exemplified compound (CL-8).

In the examples, the following compounds were used.
(A) The styrene monomer represented by the general formula (SM) is exemplified monomer (SM-1) (manufactured by Sigma-Aldrich).
The styrenic monomer represented by the general formula (HSM-1) is chloromethylstyrene (HSM-1-p) (manufactured by Seimi Chemical, trade name: CMS-P), or 4- (4-bromobutyl) styrene (HSM). -8-p) (synthesized according to the method described in Production Example 1 of JP-A-2000-212306)
(B) Styrenic crosslinking agent is divinylbenzene (HCL-1) (product name; divinylbenzene (m-, p-mixture) (including ethylvinylbenzene and diethylbenzene)), a synthesized exemplary compound (CL -1), (CL-8)
(C) The photoacid generator is exemplified compound (PAG1-1) (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: Diphenyliodonium hexafluorophosphate), (PAG2-1) (manufactured by San Apro Co., Ltd., trade name: CPI-100P), or (PAG3-1) (made by Wako Pure Chemical Industries, Ltd., trade name: WPAG-145)
(D) The polymerization initiator represented by the general formula (AI) is exemplified compound (AI-3) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-046B))

(Example 1)
(Creation of anion exchange membrane)
A coating solution of the composition shown in Table 1 below was manually applied to an aluminum plate at a speed of about 5 m / min using a 150 μm wire winding rod, followed by a non-woven fabric (FO-2223 manufactured by Freudenberg). −10, thickness 100 μm) was impregnated with the coating solution. Excess coating solution was removed using a rod around which no wire was wound. The temperature of the coating solution at the time of coating was about 25 ° C. (room temperature). Anion exchange is performed by curing reaction of the coating liquid-impregnated support using a UV exposure machine (Fusion UV Systems, Model Light Hammer 10, D-valve, conveyor speed 9.5 m / min, 60% strength). A membrane was prepared. The exposure amount was 1,000 mJ / cm ² in the UV-A region. The resulting membrane was removed from the aluminum plate and stored in 0.1 M NaCl solution for at least 12 hours.

(Examples 2 to 13, 16 and Comparative Examples 3 and 4)
In the production of the anion exchange membrane of Example 1, the anion exchange membranes of Examples 2 to 10 and 12 and Comparative Examples 3 and 4 were the same as Example 1 except that the composition was changed to the composition described in Table 1 below. Was created respectively.

(Examples 14, 15, 17, 18)
In the preparation of the cation exchange membrane of Example 1, a film was formed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1 below. Subsequently, the membrane obtained by immersion in a 0.5 mol / L trimethylamine hydrochloride aqueous solution (adjusted to pH 12) at 40 ° C. for 6 hours was removed from the aluminum plate, and further stored in a 0.1 M NaCl solution for at least 12 hours.

(Comparative Example 1)
Anion exchange membranes of Comparative Examples 1 to 3 were respectively prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1 below and the polymerization conditions were changed to those shown in Table 2 below.

(Comparative Example 2)
A film was formed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1 below and the polymerization conditions were changed to those shown in Table 2 below. Subsequently, the membrane obtained by immersion in a 0.5 mol / L trimethylamine hydrochloride aqueous solution (adjusted to pH 12) at 40 ° C. for 6 hours was removed from the aluminum plate, and further stored in a 0.1 M NaCl solution for at least 12 hours.

(Comparative Example 5)
An anion exchange membrane was formed according to the method described in Example 1 of JP-A No. 2000-212306.

(Comparative Example 6)
In the preparation of the cation exchange membrane of Example 1, the composition was changed to the composition shown in Table 1 below, and the intensity of the UV exposure machine was changed from “60% intensity” to “100% intensity”. A film was formed in the same manner.

  From the results in Table 2, it can be seen that in Examples 1 to 18 that satisfy the provisions of the present invention, film formation was performed in an extremely short time. On the other hand, the anion exchange membranes of Comparative Examples 1, 2, and 5 that did not satisfy the provisions of the present invention required a long time for membrane formation. Further, Comparative Examples 3 and 4 that did not satisfy the provisions of the present invention could not be cured sufficiently.

  The following items were evaluated for the anion exchange membranes prepared in Examples 1 to 18 and Comparative Examples 1, 2, and 5. The results are shown in Table 3 below.

[Moisture content (%)]
The water content of the membrane was calculated according to the following formula.
{(Membrane weight after 15 hours immersion in 25 ° C. 0.5M NaCl aqueous solution) − (Membrane weight after 15 hours drying in 60 ° C. vacuum oven after immersion)} ÷ (In 25 ° C. 0.5M NaCl aqueous solution) Film mass after 15 hours immersion) x 100

[Electrical resistance of membrane (Ω · cm ² )]
Wipe both sides of the membrane immersed in 0.6 M NaCl aqueous solution for about 2 hours with dry filter paper, and sandwich between two-chamber cell (effective membrane area 1 cm ² , Ag / AgCl reference electrode (made by Metrohm) used as electrode) Both chambers are filled with 100 mL of the same concentration of NaCl, placed in a constant temperature water bath at 25 ° C. and allowed to reach equilibrium, and after the liquid temperature in the cell has reached 25 ° C. correctly, an AC bridge (frequency 1,000 Hz) ) To measure the electrical resistance r _{1. The} measured NaCl concentrations were 0.6M, 0.7M, 1.5M, 3.5M, and 4.5M, and measured in order from the low concentration solution. The electrical resistance r ₂ between the _two electrodes was measured using only a 0.6 M NaCl aqueous solution, and the electrical resistance r of the film was determined as r ₁ -r ₂ .

  In Table 3 below, “electrical resistance of the membrane” is abbreviated as “membrane resistance”.

[Water permeability (mL / m ² / Pa / hr)]
The water permeability of the membrane was measured by an apparatus having a flow path 10 shown in FIG. In FIG. 1, reference numeral 1 represents a membrane, and reference numerals 3 and 4 represent flow paths for a feed solution (pure water) and a draw solution (4M NaCl), respectively. The arrow 2 indicates the flow of water separated from the feed solution.
400 mL of the feed solution and 400 mL of the draw solution were brought into contact with each other through the membrane (membrane contact area 18 cm ² ), and each solution was flowed at a flow rate of 0.11 cm / sec in the direction of the arrow 5 with a peristaltic pump. The rate at which the water in the feed solution penetrates the draw solution through the membrane was analyzed by measuring the mass of the feed solution and the draw solution in real time, and the water permeability was determined.

[Pinhole test]
The film for measurement was coated with 1.5 nm thick Pt, and SEM measurement was performed under the following conditions.

Acceleration voltage: 2 kV
Working distance: 4mm
Aperture: 4
Magnification: × 100,000 times Field tilt: 3 °

  From the SEM image, pinhole evaluation was performed from the following viewpoints.

A: Defects and pinholes were not observed.
B: One or two defects and pinholes were observed.
C: Three or more defects and pinholes were observed.

  From the results of Table 3, the anion exchange membranes of Examples 1 to 18 that satisfy the provisions of the present invention show that the product of the membrane resistance and the water permeability both show a low value and are high-performance anion exchange membranes. I understand. In contrast, the anion exchange membranes of Comparative Examples 1, 2, and 5 that do not satisfy the provisions of the present invention have particularly high membrane resistance, and the product of membrane resistance and water permeability showed a large value. From this, it can be said that the anion exchange membrane according to the present invention has a sufficient advantage.

  Further, in a hydroxy ion conductive membrane for an alkaline fuel cell, the power generation efficiency is lowered due to the high water permeability (water permeability). As described above, the ion exchange membrane of the present invention has a product of membrane resistance and water permeability lower than that of conventional ion exchange membranes, and can be suitably used as an ion conductive membrane for fuel cell applications.

DESCRIPTION OF SYMBOLS 1 Membrane 2 The arrow which shows that the water in a feed solution osmose | permeates a draw solution through a film | membrane 3 The flow path of a feed solution 4 The flow path of a draw solution 10 The flow direction of a liquid 10 The flow path of a water permeability measuring apparatus

Claims (24)

(A) A polymer functional film obtained by photocuring a composition containing a styrene monomer represented by the following general formula (HSM), (B) a styrene crosslinker, and (C) a photoacid generator.

[In General Formula (HSM), R represents a halogen atom or —N ⁺ (R ¹ ) (R ² ) (R ³ ) (X ₂ ⁻ ). n represents an integer of 1 to 10. Here, R ^{1 to} R ³ each independently represents a linear or branched alkyl group or aryl group. R ¹ and R ² , or R ¹ , R ² and R ³ may be bonded to each other to form an aliphatic heterocycle. X ₂ ⁻ represents an organic or inorganic anion. ] The — (CH ₂ ) n—R is a group represented by the following general formula (ALX), and the composition is subjected to a photocuring reaction, followed by reaction with a tertiary amine compound that is a quaternary ammonium agent. The polymer functional film according to claim 1.

[In General Formula (ALX), X ₁ represents a halogen atom. n1 has the same meaning as n in the general formula (HSM). ] The polymer functional film according to claim 1 or 2, wherein the (B) styrenic crosslinking agent is represented by the following general formula (CL).

[In General Formula (CL), L ¹ represents an alkylene group or an alkenylene group. Ra, Rb, Rc and Rd each independently represents an alkyl group or an aryl group, and Ra and Rb or / and Rc and Rd may be bonded to each other to form a ring. n3 represents an integer of 1 to 10. X ₃ ⁻ and X ₄ ⁻ each independently represents an organic or inorganic anion. ] The polymer functional film according to any one of claims 1 to 3, wherein the (C) photoacid generator is represented by the following general formula (PAG1) or (PAG2).

[In General Formula (PAG1) or (PAG2), Ar ^{1 to} Ar ⁵ each independently represents a substituted or unsubstituted aryl group. X ₅ ^- and _{X 6} ^- are each independently represents an organic or inorganic anion. ] The polymer functional film according to any one of claims 1 to 4, wherein the composition further comprises (D) a polymerization initiator represented by the following general formula (AI).

[In General Formula (AI), R ^{5 to} R ⁸ each independently represents an alkyl group, and Y represents ═O or ═N—Ri. Re to Ri each independently represent a hydrogen atom or an alkyl group. Re and Rf, Rg and Rh, Re and Ri, and Rg and Ri may be bonded to each other to form a ring. ] A styrene-based monomer represented by, ^- the total solid content 100 parts by weight of the composition, wherein R is a halogen atom or ^{-N + (R 1) (R} 2) (R 3) (X 2) And content of this styrene-type monomer is 1-85 mass parts, The polymeric functional film of any one of Claim 1, 3-5.   The polymer functional film according to any one of claims 2 to 6, wherein the content of the (B) styrene-based crosslinking agent is 10 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the composition.   The polymer functionality according to any one of claims 1 to 7, wherein the content of the (C) photoacid generator is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the composition. film.   The polymeric functional film of any one of Claims 1-8 in which the said composition contains (E) solvent.   The polymer functional film according to claim 9, wherein the solvent (E) is water or a water-soluble solvent.   The polymeric functional film of any one of Claims 1-10 which has a support body.   The polymer functional membrane according to claim 11, wherein the support is a synthetic woven fabric or synthetic nonwoven fabric, a sponge-like film, or a film having fine through holes.   The polymer functional film according to claim 11 or 12, wherein the support is a polyolefin.   The polymer functional membrane according to any one of claims 1 to 13, wherein the polymer functional membrane is an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, or a gas separation membrane. (A) A method for producing a polymer functional film, wherein a composition containing a styrene monomer represented by the following general formula (HSM), (B) a styrene crosslinking agent, and (C) a photoacid generator is photocured. .

[In General Formula (HSM), R represents a halogen atom or —N ⁺ (R ¹ ) (R ² ) (R ³ ) (X ₂ ⁻ ). n represents an integer of 1 to 10. Here, R ^{1 to} R ³ each independently represents a linear or branched alkyl group or aryl group. R ¹ and R ² , or R ¹ , R ² and R ³ may be bonded to each other to form an aliphatic heterocycle. X ₂ ⁻ represents an organic or inorganic anion. ] The - (CH 2) _n-R is a group represented by the following general formula (ALX), after the composition was allowed to photocuring reaction, wherein the reaction of the tertiary amine compound is a quaternary ammonium agent Item 16. A method for producing a functional polymer membrane according to Item 15.

[In General Formula (ALX), X ₁ represents a halogen atom. n1 has the same meaning as n in the general formula (HSM). ] The method for producing a functional polymer film according to claim 15 or 16, wherein the (B) styrene-based crosslinking agent is represented by the following general formula (CL).

[In General Formula (CL), L ¹ represents an alkylene group or an alkenylene group. Ra, Rb, Rc and Rd each independently represents an alkyl group or an aryl group, and Ra and Rb or / and Rc and Rd may be bonded to each other to form a ring. n3 represents an integer of 1 to 10. X ₃ ⁻ and X ₄ ⁻ each independently represents an organic or inorganic anion. ] The method for producing a polymer functional film according to any one of claims 15 to 18, wherein the (C) photoacid generator is represented by the following general formula (PAG1) or (PAG2).

[In General Formula (PAG1) or (PAG2), Ar ^{1 to} Ar ⁵ each independently represents a substituted or unsubstituted aryl group. X ₅ ^- and _{X 6} ^- are each independently represents an organic or inorganic anion. ] The method for producing a polymer functional film according to any one of claims 15 to 18, wherein the composition further comprises (D) a polymerization initiator represented by the following general formula (AI).

[In General Formula (AI), R ^{5 to} R ⁸ each independently represents an alkyl group, and Y represents ═O or ═N—Ri. Re to Ri each independently represent a hydrogen atom or an alkyl group. Re and Rf, Rg and Rh, Re and Ri, and Rg and Ri may be bonded to each other to form a ring. ]   The method for producing a functional polymer film according to any one of claims 15 to 19, wherein the composition contains (D) a solvent.   The method for producing a functional polymer film according to claim 20, wherein the solvent (D) is water or a water-soluble solvent.   The method for producing a functional polymer film according to any one of claims 15 to 21, wherein the composition is applied and / or impregnated on a support and then cured.   The method for producing a polymer functional film according to any one of claims 15 to 22, wherein the curing reaction is a curing reaction in which the composition is polymerized by irradiation with energy rays and heating.   The method for producing a polymeric functional film according to any one of claims 15 to 23, wherein the curing reaction is a curing reaction in which the composition is heated and polymerized after irradiation with energy rays.

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