WO2015030072A1

WO2015030072A1 - Polymer functional film and method for producing same

Info

Publication number: WO2015030072A1
Application number: PCT/JP2014/072474
Authority: WO
Inventors: 啓祐小玉; 和臣井上
Original assignee: 富士フイルム株式会社
Priority date: 2013-08-30
Filing date: 2014-08-27
Publication date: 2015-03-05
Also published as: JP2015047537A

Abstract

A polymer functional film which is obtained by photocuring a composition that contains a styrene monomer represented by general formula (HSM), a styrene crosslinking agent and a photoacid generator; and a method for producing the polymer functional film. In general formula (HSM), R represents a halogen atom or -N⁺(R¹)(R²)(R³)(X₁ ^-); n represents an integer of 1-10; each of R¹-R³ represents an alkyl group or an aryl group; R¹ and R², or R¹, R² and R³ may combine together to form an aliphatic heterocyclic ring; and X₁ ^- represents an organic or inorganic anion.)

Description

Polymer functional membrane and method for producing the same

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 or the like, and a method for producing the same.

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 can be used for electrodeionization (EDI), continuous electrodeionization (CEDI), electrodialysis (ED), electrodialysis reversal (EDR) and reverse. Used for electrodialysis (RED: Reverse Electrodialysis) 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 polarity-changing 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 (see, for example, 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) The reactivity of the ionization process after film formation depends on the diffusibility of the reaction reagent into the film because the reaction reagent reacts in the heat-cured film. Otherwise, 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-based initiator frequently used for thermosetting generates radicals and releases nitrogen gas, so that film defects are easily caused by nitrogen gas. In addition, if an ionic styrene monomer is used in order to omit the ionization step, the compatibility with the nonionic crosslinking agent is poor, and the degree of cross-linking becomes non-uniform in conventional heat curing with organic peroxides. There is.
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 film 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 polymer functional film obtained by photocuring a composition containing a styrene monomer represented by the following general formula (HSM), a styrene crosslinking agent, and a photoacid generator.

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

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} ^- is independently represents an organic or inorganic anion.
<4> 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 the 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 contains a polymerization initiator represented by the following general formula (AI).

In the 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> A styrene monomer in which R is represented by a halogen atom or —N ⁺ (R ¹ ) (R ² ) (R ³ ) (X ₂ ⁻ ) with respect to 100 parts by mass of the total solid content of the composition, The functional polymer film according to any one of <1> and <3> to <5>, wherein the content of the styrene monomer is 1 to 85 parts by mass.
<7> The polymer functional film according to any one of <2> to <6>, wherein the content of the styrenic 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 functionality according to any one of <1> to <7>, wherein the content of 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 film.
<9> The polymer functional film according to any one of <1> to <8>, wherein the composition contains a solvent.
<10> The polymer functional film according to <9>, wherein the solvent is water or a water-soluble solvent.
<11> The polymer functional film 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 method for producing a functional polymer film, wherein a composition containing a styrene monomer represented by the following general formula (HSM), a styrene crosslinking agent, and a photoacid generator is photocured.

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 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 ) nR is a group represented by the following general formula (ALX), and the composition is photocured and then reacted with a tertiary amine compound which is a quaternary ammonium agent. <15> The method for producing a functional polymer film according to <15>.

In the general formula (ALX), X ₁ represents a halogen atom. n1 is synonymous with n in the general formula (HSM).
<17> 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 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} ^- is independently represents an organic or inorganic anion.
<18> 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 the 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 contains a polymerization initiator represented by the following general formula (AI).

In the 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 a solvent.
<21> 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 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 irradiation 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 voids 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, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In each general formula, if there are a plurality of groups having the same symbol unless otherwise specified, they may be the same or different from each other. Further, when there are repetitions of a plurality of partial structures, these repetitions may be the same as each other, or may be a mixture of different repetitions as long as they are 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.

Further, in this specification, when the term “compound” is added at the end, or when a specific compound is indicated by its name or formula, it has a dissociative partial structure in its chemical structural formula in addition to the compound itself. If it is, 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.

The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings as appropriate.

FIG. 1 is a schematic view of a flow path of an 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 taking as an example the case where the polymer functional membrane of the present invention has a function as an ion exchange membrane.

The polymer functional membrane of the present invention is preferably an anion exchange membrane.
In the case of having a support, the thickness of the membrane of the present invention is preferably 30 to 250 μm, more preferably 40 to 200 μm, particularly preferably 50 to 150 μm, including the support.

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, the permselectivity and the swelling ratio 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. The lower limit of the water permeability is not particularly limited, but 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 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.

Here, — (CH ₂ ) n—R can be divided into a group represented by the following general formula (ALX) and a group represented by the following general formula (ALA).

Formula (ALX), in (ALA), _{X 1} represents a halogen ^atom, R 1 ~ ^{R 3} and _{X 2} ^- is ^R 1 ~ in the general formula (HSM) ^{R 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 such a substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
The aryl group in R ¹ to R ³ preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably 6 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.
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 the 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), a 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. It can also be obtained as a commercial product from Sigma-Aldrich.

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

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 parts by mass 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, hereinafter, in the general formula (HSM), when — (CH ₂ ) n—R represents a group represented by the formula (ALX), the styrene monomer is referred to as a 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 parts by mass are particularly preferred.

Next, specific examples of a tertiary amine compound that is a quaternary ammonium agent will be shown, but the present invention is not limited thereto.

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 more preferably 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} ^- is 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 such a 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 the present invention, the content of the crosslinking agent represented by (B) the general formula (CL) is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the composition for forming a film, 90 parts by mass is more preferable, and 20 to 80 parts by mass is particularly 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 preferred, 0.5˜2 mmol / g is more preferred, and 1.0˜2 mmol / g is particularly preferred.
When the crosslinking density is within such a 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 the general formulas (PAG1) and (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.
The aryl group in Ar ¹ to Ar ⁵ preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably 6 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, a hydroxy group, an alkylthio group, and an arylthio group. The aryl group is preferably a phenyl group.

Hereinafter, although the specific example of the 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) can 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 for Ar ⁶ and Ar ⁷ preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, and cyclohexyl. These alkyl groups may be chain-like or cyclic (that is, cycloalkyl group), and in the case of a chain-like, 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.
The aryl group in Ar ⁶ and Ar ⁷ preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably 6 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 (PAG3) is shown, this invention is not limited to these.

In the present invention, the photoacid generator represented by the following general formula (PAG4) can be used alone or in combination with the photoacid generator represented by the general formula (PAG1) to the general formula (PAG3).

In General Formula (PAG4), Ar ⁸ and Ar ⁹ each independently represent a substituted or unsubstituted aryl group or heteroaryl group.
The number of carbon atoms of the aryl group in Ar ⁸ and Ar ⁹ is preferably 4 to 12, more preferably 4 to 10, and still more preferably 4 to 8. 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. The heteroaryl group in Ar ⁸ and Ar ⁹ preferably has 2 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. The heterocycle of the heteroaryl group preferably has a 5- or 6-membered feeling, and the ring-constituting heteroatoms are preferably oxygen atoms, sulfur atoms, and nitrogen atoms. The heteroaryl group may be substituted with a substituent, and examples thereof include an alkyl group, a halogen-substituted alkyl group, an aryl group, and an alkoxy group. Examples of the heterocycle of the heteroaryl group include a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring.

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

In addition, in the present invention, a photoacid generator having the following structure can also be used.

In the present invention, the photogenerating agent content is preferably 0.1 to 20 parts by weight, more preferably 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 to 5 parts by mass is particularly preferable.

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

In the 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 content of the polymerization initiator represented by the 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 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is particularly preferable.

(E) Solvent The composition for forming the film of the present invention may contain (E) a solvent.
In the present invention, the content of the solvent (E) in the composition is preferably 5 to 60 parts by mass and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the total composition.
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% by mass of isopropanol is preferable with respect to 100% by mass of water, more preferably 0.5 to 5% by mass, and even more preferably 1.0 to 2.0% by mass. preferable.
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, a mercapto compound, and a nitroxyl radical compound.
Examples of the phenol compound include hindered phenol (phenol having a t-butyl group at the ortho position, typically 2,6-di-t-butyl-4-methylphenol) and bisphenol. Specific examples of the hydroquinone compound include monomethyl ether hydroquinone. Specific examples of the amine compound include N-nitroso-N-phenylhydroxylamine, N, N-diethylhydroxylamine and the like. Specific examples of the nitroxyl radical compound include 4-hydroxy TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical) and the like.
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 weight, more preferably 0.01 to 1 part by weight, and more preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the total solid content in the composition. Part is more preferable.

[Other ingredients]
The composition for forming a 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 boundaries such as alkyl betaines and amide betaines Active 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 weight, more preferably 0 to 5 parts by weight, and even more preferably 1 to 2 parts by weight with respect to 100 parts by weight 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 constitute a part of the membrane by applying and / or impregnating the composition for forming the membrane and then performing a curing reaction.
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 Those that can penetrate into the porous reinforcing material are preferred so as to be cured in the step (ii) described later.

It is preferable that the porous support 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 composition containing a styrene monomer represented by the general formula (HSM), (B) a styrene crosslinking agent, and (C) a photoacid generator. A photo-curing reaction is performed 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 such a range, an effect that the moisture content of the membrane is lowered occurs, and salt leakage is suppressed, which is preferable.

The composition for forming a film preferably further contains (D) a polymerization initiator represented by the general formula (AI).
The composition for forming a film 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.
In addition, 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. Furthermore, the curing reaction is preferably a curing reaction in which the composition is polymerized by irradiation with energy rays and heating. 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. 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 in a batch manner by fixing the support, but the membrane can also be prepared in a continuous manner by moving the 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). If such a technique is used, the said composition of this invention can be apply | coated to a support body by a continuous type. Moreover, a batch process can be enlarged on a large scale by combining specific processes into batch processes.
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, when a polymer functional film is produced continuously, it is preferably produced by a production unit comprising at least a composition application part for continuously applying the above composition while moving the support. And a production unit comprising a radiation source for curing the composition, a film collection part, and means for moving the support from the composition application part to the radiation source and the film collection part. preferable.

In this production example, (i) a composition for forming a film of the present invention is applied to and / or impregnated on a porous support, and (ii) the composition is irradiated with light, and if necessary, further cured by heating. The polymer functional membrane of this embodiment is produced through a process of reacting and (iii) removing the membrane from the support as 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]
Since the functional polymer film is manufactured in the order of coating, light irradiation, and composite film collection, the composition application part is placed at a position upstream from the irradiation source in the arrangement of these facilities, and the irradiation source is the composite film. Located upstream of the collection station.
In order to have sufficient fluidity when applied with a high-speed coating machine, the viscosity of the composition of the present invention at 35 ° C. 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.

Using high speed coating techniques, the compositions of the present invention can be applied at speeds exceeding 15 m / min, such as speeds exceeding 20 m / min, such as 60 m / min, 120 m / min and even up to 400 m / min. But it can be applied.

In particular, when using a support to increase the mechanical strength, support that has been subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, etc. in order to improve the wettability and adhesion of the surface of the support. It is preferable to use the body.

In the curing reaction, (A) in the general formula (HSM),-(CH ₂ ) n-R is represented by the styrenic monomer having a group represented by the general formula (ALX) and (B) the general formula (CL). The cross-linking agent is polymerized to form a polymer (film). The curing reaction time for forming the film is preferably 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, 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, since the irradiation is continuously performed, the curing reaction time is determined in consideration of the speed at which the composition moves through the irradiation beam.

When a high intensity UV light is used for the curing reaction, a considerable amount of heat is generated, so that cooling air may be applied to the lamp of the light source and / or the support / film in order 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. The irradiation wavelength is preferably a wavelength that can be absorbed by the photoinitiator (photoacid generator, photopolymerization initiator) contained in the composition. For this reason, the irradiation wavelength is preferably the same wavelength as the absorption wavelength of the photoinitiator or a wavelength overlapping with the absorption wavelength. Examples thereof include UV-A (400 to 320 nm), UV-B (320 to 280 nm), and UV-C (280 to 200 nm).

Examples of 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 ultraviolet light-emitting diodes. It is done. Medium pressure or high pressure mercury vapor type UV lamps are particularly preferred. In addition, additives such as metal halides may be added to the lamp to modify the lamp's emission spectrum. A lamp having an emission maximum at 200 to 450 nm is particularly suitable.

The energy output of the irradiation source is preferably 20 to 1000 W / cm, more preferably 40 to 500 W / cm. However, it 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 40 mJ / cm ² or more when measured in the UV-A range indicated by the apparatus using a high energy UV radiometer (UV Power Pack ^™ manufactured by EIT-Instrument Markets), and is preferably 100 to 2,000 mJ / cm ^2. cm ² is more preferable, and 150 to 1,500 mJ / cm ² is most preferable. The exposure time can be chosen freely but is preferably short, typically less than 2 seconds.

When performing high-speed coating, a plurality of light sources may be used to reach a desired dose. These light sources may have the same or different exposure intensity.

The polymer functional membrane of the present invention is mainly intended to be used in particular by 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.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

[(B) Synthesis of Styrenic Crosslinking Agent]
(Synthesis Example 1)
In 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, Ltd.), and 433 g of acetonitrile On the other hand, 1,4-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 exemplary compound (CL-1).

(Synthesis Example 2)
To 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, Ltd.), and 1232 g of nitrobenzene On the other hand, 130 g (1.00 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of N, N, N ′, N′-tetramethyl-1,3-diaminopropane was added and stirred with heating 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) (trade name; CMS-P, manufactured by Seimi Chemical), or 4- (4-bromobutyl) styrene (HSM). -8-p) (synthesized according to the method described in Production Example 1 of JP-A-2000-212306)
(B) Styrene-based crosslinking agent is divinylbenzene (HCL-1) (trade name; divinylbenzene (m-, p-mixture) (including ethylvinylbenzene and diethylbenzene)) manufactured by Tokyo Chemical Industry Co., Ltd. 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) (Wako Pure Chemical Industries, Ltd., trade name: WPAG-145)
(D) The polymerization initiator represented by formula (AI) is exemplified compound (AI-3) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-046B))
The polymerization initiator Darocur (registered trademark) 1173 (trade name: manufactured by BASF Japan Ltd.) is a polymerization initiator different from the polymerization initiator represented by the general formula (AI).

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). By using a UV exposure machine (Fusion UV Systems, Model Light Hammer 10, D-valve, conveyor speed 9.5 m / min, 60% strength), the coating liquid-impregnated support is subjected to a curing reaction, thereby anion exchange 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)
Anion exchange membranes of Examples 2 to 13, 16 and Comparative Examples 3 and 4 were prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1 below in the preparation of the anion exchange membrane of Example 1. Was created respectively.

(Examples 14, 15, 17, 18)
In the production of the anion 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 described 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)
An anion exchange membrane of Comparative Example 1 was 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 anion exchange membrane of Example 1, the composition was changed to the composition described 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.
In Table 1, a portion where no number is described means that it is not contained.

From the results in Table 2, it can be seen that in Examples 1 to 18 that satisfy the provisions of the present invention, the film could be formed in an extremely short time. On the other hand, the anion exchange membranes of Comparative Examples 1, 2, and 5 (thermosetting) that did not satisfy the provisions of the present invention required a long time for film formation. Further, Comparative Examples 3, 4, and 6 (ultraviolet ray curing) that do not satisfy the provisions of the present invention could not be sufficiently cured, and in particular, Comparative Example 4 did not substantially undergo a curing reaction.

The following items were evaluated for the anion exchange membranes prepared in Examples 1 to 18 and Comparative Examples 1 to 6. 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 electric resistance r ₂ between the _two electrodes was measured using only a 0.6 M NaCl aqueous solution, and the electric resistance r of the film was determined as r ₁ -r ₂ .

In Table 3 below, “membrane electrical resistance” 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 in Table 3, the anion exchange membranes of Examples 1 to 18 that satisfy the provisions of the present invention have low values of product of membrane resistance and water permeability (5.0 × 10 −5 ^to 7.7 × 10 ^{− 5} ), which indicates that the membrane is a high performance anion exchange membrane. In contrast, the anion exchange membranes of Comparative Examples 1 to 3, 5, and 6 that do not satisfy the provisions of the present invention have particularly large membrane resistance, and the product of membrane resistance and water permeability is 1.0 × 10 ⁻⁴ to 1 .4 × 10 ⁻⁴ , both showing large values. From this, it can be said that the anion exchange membrane according to the present invention has a sufficient advantage.

Moreover, in the hydroxy ion conductive membrane for alkaline fuel cells, the power generation efficiency decreases 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 that is lower than that of conventional ion exchange membranes and can be suitably used as an ion conductive membrane for fuel cell applications.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2013-179802 filed in Japan on August 30, 2013, which is hereby incorporated herein by reference. Capture as part.

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

Claims

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

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 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 the 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, wherein the styrene-based crosslinking agent is represented by the following general formula (CL).

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 - is independently represents an organic or inorganic anion.
The polymer functional film according to any one of claims 1 to 3, wherein the photoacid generator is represented by the following general formula (PAG1) or (PAG2).

In the 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 contains a polymerization initiator represented by the following general formula (AI).

In the 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) 6. The polymeric functional film according to claim 1, wherein the content of the styrene monomer is 1 to 85 parts by mass.
The polymer functional film according to any one of claims 2 to 6, wherein the content of the styrenic 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 functional film according to any one of claims 1 to 7, wherein the content of 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.
The polymer functional film according to any one of claims 1 to 8, wherein the composition contains a solvent.
The polymer functional film according to claim 9, wherein the solvent is water or a water-soluble solvent.
The polymer functional film according to any one of claims 1 to 10, which has a support.
The polymer functional membrane according to claim 11, wherein the support is a synthetic woven fabric or synthetic nonwoven fabric, a sponge 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 method for producing a functional polymer film, wherein a composition containing a styrene monomer represented by the following general formula (HSM), a styrene crosslinking agent and a photoacid generator is photocured.

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 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.
Claims wherein the — (CH 2 ) n—R is a group represented by the following general formula (ALX), and the composition is photocured and then reacted with a tertiary amine compound which is a quaternary ammonium agent. Item 16. A method for producing a functional polymer membrane according to Item 15.

In the 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 styrene-based crosslinking agent is represented by the following general formula (CL).

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 - is independently represents an organic or inorganic anion.
The method for producing a functional polymer film according to any one of claims 15 to 18, wherein the photoacid generator is represented by the following general formula (PAG1) or (PAG2).

In the 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 functional polymer film according to any one of claims 15 to 18, wherein the composition further contains a polymerization initiator represented by the following general formula (AI).

In the 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 a solvent.
The method for producing a functional polymer film according to claim 20, wherein the solvent 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 to and / or impregnated on a support and then cured.
The method for producing a functional polymer 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 functional polymer 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.