JP6118284B2 - Method for producing polymer functional membrane - Google Patents

Description

  The present invention relates to a method for producing a polymer functional film.

As membranes having various functions as polymer functional membranes, ion exchange membranes, reverse osmosis membranes, forward osmosis membranes, gas separation membranes, and the like are known.
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.

  As the ion exchange membrane, a polymer functional membrane having a film thickness of about 30 μm to about 150 μm is usually the mainstream. There are two types of ion exchange membranes, mainly anion exchange membranes with cationic groups such as quaternary ammonium in the polymer and cation exchange membranes with anionic groups such as sulfonates. Research is actively conducted (see, for example, Patent Documents 1 to 3).

International Publication No. 2013/011273 Pamphlet International Publication No. 2010/110333 Pamphlet Special table 2013-514419 gazette

In the case of a polymer functional membrane such as an ion exchange membrane, when the ion exchange membrane is thin, performance due to wear such as deterioration due to alkali or cleaning is lowered. For this reason, an ion exchange membrane with a large film thickness is desired.
However, according to the study by the present inventors, it has been found that, depending on the type of polymer constituting the film, even if the film is thickened, deterioration due to alkali and deterioration in performance due to wear such as washing are not necessarily improved sufficiently. .
Therefore, an object of the present invention is to provide a method for producing a polymer functional film having a thick polymer functional film and excellent durability.

As a result of analyzing the above-mentioned causes in the film thickness of the ion exchange membrane, the present inventors have found that the degree of cross-linking differs in the thickness direction of the ion exchange membrane and is irradiated with ultraviolet rays, particularly when polymerized and cured with ultraviolet rays. It turned out that the cross-linking is insufficient in the part far from.
Based on the results of this analysis, as a result of various studies on methods for uniformly polymerizing and curing the entire film without increasing the amount of irradiation light, the composition for forming a polymer functional film has a maximum absorption wavelength in different wavelength regions. It has been found that when the polymerization and curing reaction is performed using the two types of photopolymerization initiators, the entire film can be uniformly cured even if the film thickness is increased. The present invention has been completed based on this finding.

<1> A method for producing a functional polymer film by polymerizing and curing a composition containing at least a monomer and a photopolymerization initiator,
The film thickness of the polymer functional film is greater than 500 μm and 1,000 μm or less,
At least one of the monomers is a styrene monomer or an acrylamide monomer having a quaternary ammonium group or a sulfo group or a salt thereof,
As the photopolymerization initiator, at least one photopolymerization initiator having (I-1) maximum absorption wavelength of 300 nm to less than 350 nm and at least one (I-2) maximum absorption wavelength of 350 nm to 420 nm. Use a combination of polymerization initiators ,
The photopolymerization initiator (I-1) is a photopolymerization initiator represented by the following general formula (PI-1), and the photopolymerization initiator (I-2) is represented by the following general formula (PI-2). producing how the polymer functional film is a photopolymerization initiator represented.

In the general formula (PI-1), R ^P1 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, a pyrrolidino group, a piperidino group, a morpholino group, a thiomorpholino group or a dialkylamino group, R ^P2 and R ^P3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. Here, R ^P2 and R ^P3 may be bonded to each other to form a ring. x represents an integer of 1 or more. R ^P4 represents a hydrogen atom or an x-valent substituent or linking group.

In general formula (PI-2), R ^P5 , R ^P6 and R ^P7 each independently represents an alkyl group or an aryl group, and l and m each independently represents 0 or 1.
< 2 > Of the total solid content of the composition of 100% by mass, the total amount of the photopolymerization initiator is 0.01 to 10% by mass, and the photopolymerization initiator (I-) with respect to the photopolymerization initiator (I-1). The method for producing a functional polymer film according to <1 >, wherein the mass ratio of 2) is 5 to 50 mass%.
< 3 > The method for producing a polymer functional film according to <1> or < 2>, wherein the film thickness of the polymer functional film is greater than 500 μm and 800 μm or less.
< 4 > The method for producing a polymer functional film according to any one of <1> to < 3 >, wherein the film thickness of the polymer functional film is greater than 500 μm and 700 μm or less.
< 5 > The styrene monomer having a quaternary ammonium group is a compound represented by the following general formula (SM) or (SXL), and the acrylamide monomer having a quaternary ammonium group is represented by the following general formula (AM-1). ) Or (AXL-1) is a compound represented by any one of <1> to < 4 >.

In the general formula (SM), R ^{1 to} R ³ each independently represents an 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. n1 represents an integer of 1 to 3. X ₁ ⁻ represents an organic or inorganic anion.

In General Formula (SXL), L ¹ and L ² each independently represent an alkylene group or an alkenylene group. R ^d and R ^e each independently represents an alkyl group or an aryl group, and R ^d and R ^e may be bonded to each other to form a ring. n2 represents an integer of 1 to 3. X ₂ ^- and _{X 3} ^- each independently represents an organic or inorganic anion.

In General Formula (AM-1), R ⁴ represents a hydrogen atom or an alkyl group, and R ^{5 to} R ⁷ each independently represents an alkyl group or an aryl group. Z ¹ represents -NRa-. Here, Ra represents a hydrogen atom or an alkyl group. L ³ represents an alkylene group, and X ₄ ⁻ represents a halogen ion or an aliphatic or aromatic carboxylate ion.

In General Formula (AXL-1), R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group, and R ^{10 to} R ¹³ each independently represent an alkyl group or an aryl group. Z ² and Z ³ each independently represent —NRb—. Here, Rb represents a hydrogen atom or an alkyl group. L ⁴ and L ⁵ each independently represent an alkylene group, and R ^X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined. X ₅ ^- and X ₆ ^- represents a halogen ion or an aliphatic or aromatic carboxylate ion independently.
< 6 > The acrylamide monomer having a sulfo group or a salt thereof is a compound represented by any one of the following general formulas (AM-2) or (AXL-2), and any one of <1> to < 5 > The manufacturing method of the polymeric functional film of description.

In General Formula (AM-2), R ¹⁴ represents a hydrogen atom or an alkyl group. M ₁ ⁺ represents a hydrogen ion or an alkali metal ion.

In General Formula (AXL-2), R ¹⁵ represents a hydrogen atom or an alkyl group, and Z ⁴ represents —NRf—. Here, Rf represents a hydrogen atom or an alkyl group. M ₂ ⁺ represents a hydrogen ion or an alkali metal ion.
< 7 > The composition contains a compound represented by the general formula (AM-1) and a compound represented by the general formula (AXL-1) or the following general formula (CL) in combination, or the general formula ( < 5 > The manufacturing method of the polymeric functional film as described in < 5 > which contains combining the compound represented by SM), and the compound represented by general formula (SXL).

In General Formula (CL), R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or an alkyl group. Y ¹ and Y ² each independently represent —O— or —N (Rc) —. Here, Rc represents a hydrogen atom or an alkyl group. L ⁶ represents a p1 + 1-valent linking group having 1 or more carbon atoms. p1 represents an integer of 1 or more.
<8> composition comprises a compound represented by the general formula (AM-2), the general formula in combination with (AXL-2) or a compound represented by the following general formula (CL) according to <6> A method for producing a polymer functional membrane.

In General Formula (CL), R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or an alkyl group. Y ¹ and Y ² each independently represent —O— or —N (Rc) —. Here, Rc represents a hydrogen atom or an alkyl group. L ⁶ represents a p1 + 1-valent linking group having 1 or more carbon atoms. p1 represents an integer of 1 or more.

  In the present specification, the “film thickness of the polymer functional film” refers to the thickness after being immersed in a 0.01 M NaCl aqueous solution at a temperature of 25 ° C. for 12 hours.

In the present specification, “to” is used in the sense of including the numerical values described before and after the lower limit value and the 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.

  According to the present invention, it is possible to provide a method for producing a polymer functional film having a high polymer functional film having a large thickness, the entire film being uniformly cured, and excellent durability.

The flow path of the apparatus for measuring the water permeability of a film | membrane is typically represented.

<< Composition for forming polymer functional film >>
In the method for producing a polymer functional film of the present invention (in this specification, the polymer functional film may be simply referred to as “film”), a composition containing at least a monomer and a photopolymerization initiator is polymerized and cured. At this time, as the photopolymerization initiator, at least one (I-1) maximum absorption wavelength is 300 nm or more and less than 350 nm and at least one (I-2) maximum absorption wavelength is 350 nm or more and 420 nm or less. A certain photopolymerization initiator is used in combination.
First, a photopolymerization initiator will be described as a material contained in a composition for forming a polymer functional film (hereinafter also referred to as “film forming composition”).

<Photopolymerization initiator>
The photopolymerization initiator (I-1) having a maximum absorption wavelength of 300 nm or more and less than 350 nm and (I-2) a photopolymerization initiator having a maximum absorption wavelength of 350 nm or more and 420 nm or less used in the present invention have a maximum absorption wavelength. However, in the present invention, (I-1) a photopolymerization initiator having a maximum absorption wavelength of 300 nm or more and less than 350 nm is represented by the following general formula: A photopolymerization initiator represented by (PI-1) is used, and (I-2) a photopolymerization initiator having a maximum absorption wavelength of 350 nm or more and 420 nm or less is represented by the general formula (PI-2) described later. A photoinitiator is used .

[(I-1) Photopolymerization initiator having maximum absorption wavelength of 300 nm or more and less than 350 nm]
The photopolymerization initiator (I-1) having a maximum absorption wavelength of 300 nm or more and less than 350 nm is preferably a photopolymerization initiator represented by the following general formula (PI-1).

In the general formula (PI-1), R ^P1 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, a pyrrolidino group, a piperidino group, a morpholino group, a thiomorpholino group or a dialkylamino group, R ^P2 and R ^P3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. Here, R ^P2 and R ^P3 may be bonded to each other to form a ring. x represents an integer of 1 or more. R ^P4 represents a hydrogen atom or an x-valent substituent or linking group.

1-12 are preferable, as for carbon number of the alkyl group in R ^{< P1>} , R ^<P2> and R ^<P3 >, 1-8 are more preferable, 1-4 are more preferable, for example, methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl , Dodecyl.

2-12 are preferable, as for carbon number of the alkenyl group in R ^{< P1>} , R ^<P2> and R ^<P3 >, 2-8 are more preferable, and 2-4 are more preferable, for example, vinyl, allyl, 1-propenyl, 2-butenyl, 2 -Pentenyl.

R number of carbon atoms of the aryl group in ^P1 is preferably 6 to 12, more preferably 6 to 10, for example, phenyl, naphthyl.
The aryl group is preferably a phenyl group which may have a substituent.

R ^P1 carbon number of dialkylamino groups in preferably 2 to 12, more preferably 2 to 10, for example, dimethylamino, methylethylamino, diethylamino, and di (n- butylamino is.

R ^P2 and ^R number of carbon atoms of the alkoxy group in the ^P3 preferably 1 to 12, more preferably 1 to 8, more preferably 1 to 4, for example, methoxy, ethoxy, isopropoxy, n- butoxy, 2-ethylhexyloxy, Dodecyloxy is mentioned.

R ^P2 and the number of carbon atoms of the aryloxy group in ^{R P3} is preferably 6 to 12, more preferably 6 to 10, e.g., phenoxy, include naphthoxy.

R ^P2 and ^{R P3} number of carbon atoms of the alkylthio group in preferably 1 to 12, more preferably 1 to 8, more preferably 1 to 4, for example, cyclohexylthio methylthio, ethylthio, isopropylthio, n- butylthio, 2- ethylhexyl , Dodecylthio.

6-12 are preferable and, as for carbon number of the arylthio group in R ^{< P2>} and R ^<P3 >, 6-10 are more preferable, for example, phenylthio and naphthylthio are mentioned.

Each group of R ^P1 , R ^P2 and R ^P3 may be further substituted with a substituent, and examples of the substituent include those described in the substituent group α described later.
Among the substituent group α, an alkyl group, an alkenyl group, an aryl group, a heterocyclic amino group (preferably pyrrolidino, piperidino, morpholino, thiomorpholino are preferred), an amino group (—NH ₂ ), an alkylamino group, a dialkylamino group An arylamino group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfo group or a salt thereof, or a carboxy group or a salt thereof is preferable.

  For example, a substituted alkyl group is preferably a hydroxyalkyl group, a pyrrolidinoalkyl group, a piperidinoalkyl group, a morpholinoalkyl group, a thiomorpholinoalkyl group, an aminoalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group or an arylaminoalkyl group. . For substituted aryl groups, hydroxy substituted aryl groups, pyrrolidino substituted aryl groups, piperidino substituted aryl groups, morpholino substituted aryl groups, thiomorpholino substituted aryl groups, amino substituted aryl groups, alkylamino substituted aryl groups, dialkylamino substituted aryl groups, arylamino substituted Aryl groups are preferred.

  The same applies to substituted alkenyl groups, substituted alkoxy groups, substituted aryl groups, substituted alkylthio groups, and substituted arylthio groups.

  Among these, a hydroxyalkyl group, a dialkylaminoalkyl group, a morpholinoalkyl group, a hydroxyalkoxy group, and a morpholino-substituted aryl group are preferable.

R ^P1 is preferably a hydroxy group, a pyrrolidino group, a piperidino group, a morpholino group, a thiomorpholino group or a dialkylamino group, and R ^P2 and R ^P3 are preferably an alkyl group, an aryl group, an alkoxy group and an alkylthio group, and R ^P2 and R ^P3 Are preferably bonded to form a cyclohexane ring.

  x is preferably an integer of 1 to 3, and more preferably 1 or 2.

R ^P4 represents a hydrogen atom or an x-valent substituent or linking group. When x is 1, it is a hydrogen atom or a substituent (monovalent substituent), and when x is 2, an alkylene group or an arylene A group, —O—, —S—, —SO ₂ —, —N (Rx) —, —C (═O) — or a divalent linking group in combination of these is preferred. Here, Rx represents a hydrogen atom or a substituent.
Examples of the trivalent or higher valent linking group include the groups exemplified as L ⁶ in the general formula (CL) described later.

Examples of the substituent (monovalent substituent) include those described in Substituent Group α described later, and include an alkyl group, an alkenyl group, an aryl group, and a heterocyclic amino group (especially pyrrolidino, piperidino, morpholino, thiomorpholino). Preferable), amino group (—NH ₂ ), alkylamino group, dialkylamino group, arylamino group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfo group or salt thereof, carboxy group Or its salt is preferable.

The alkylene group in the divalent linking group is preferably an alkylene group having 1 to 12 carbon atoms, and examples include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, and tetramethylene. The arylene group is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include phenylene and naphthylene, and a phenylene group which may have a substituent is preferable.
These alkylene groups and arylene groups may be further substituted with a substituent, and examples of the substituent include those described in the substituent group α described later.
Among the substituent group α, an alkyl group, an alkenyl group, an aryl group, a heterocyclic amino group (preferably pyrrolidino, piperidino, morpholino, thiomorpholino are preferred), an amino group (—NH ₂ ), an alkylamino group, a dialkylamino group An arylamino group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfo group or a salt thereof, or a carboxy group or a salt thereof is preferable.

R ^P4, when x is 1, a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic amino group (particularly pyrrolidino, piperidino, morpholino, thiomorpholino), amino _(-NH 2), alkyl An amino group, dialkylamino group, arylamino group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfo group or salt thereof, carboxy group or salt thereof are preferred.
In particular, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic amino group, an alkoxy group (an alkoxy group substituted with a hydroxy group is also preferable) and an alkylthio group are particularly preferable.

^RP4 is preferably an alkylene group when x is 2, and preferably a methylene group which may have a substituent. As the substituent, an alkyl group is preferable.

The ring formed by combining R ^P2 and R ^P3 with each other is preferably a 5- or 6-membered ring, and more preferably a cyclopentane ring or a cyclohexane ring.

  Specific examples of the photopolymerization initiator represented by the general formula (PI-1) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (PI-1) can be obtained from BASF Japan Ltd.

[(I-2) Photopolymerization initiator having a maximum absorption wavelength of 350 nm to 420 nm]

  The photopolymerization initiator having a maximum absorption wavelength of 350 nm to 420 nm is preferably a photopolymerization initiator represented by the following general formula (PI-2).

In general formula (PI-2), R ^P5 , R ^P6 and R ^P7 each independently represents an alkyl group or an aryl group, and l and m each independently represents 0 or 1.

The alkyl group in R ^{P5 to} R ^P7 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 and even more preferably 1 to 8. Examples of the alkyl group include methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl, and 2,4,4-trimethylpentyl. The alkyl group may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described below.

6-12 are preferable, as for the aryl group in R ^{< P5} > -R < ^P7 >, 6-10 are more preferable, and 6-8 are more preferable. 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 aryl group in R ^{P5 to} R ^P7 is preferably a phenyl group having substituents at the 2-position, 2-position and 6-position, 2-position, 4-position and 6-position, and the substituent is the substituent group α described later. An alkyl group and an alkoxy group are preferred.
The aryl group in R ^{P5 to} R ^P7 is preferably phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, or 2,4,6-trimethoxyphenyl.

  Although the specific example of a photoinitiator represented by general formula (PI-2) below is shown, this invention is not limited to these.

In the present invention, out of 100% by mass of the total solid content of the film-forming composition, the total amount of the photopolymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and 0.01% -3 mass% is particularly preferred.
5-50 mass% is preferable, as for the mass ratio of the photoinitiator (I-2) with respect to a photoinitiator (I-1), 5-40 mass% is more preferable, and 5-30 mass% is especially preferable.

<Monomer having an ion exchange group>
The composition for forming a polymer functional film contains a monomer having an ion exchange group. In the present invention, a styrene monomer having a quaternary ammonium group, a sulfo group or a salt thereof as an ion exchange group, or An acrylamide monomer having a quaternary ammonium group, a sulfo group or a salt thereof as an ion exchange group is used.

[Styrene monomer having a quaternary ammonium group, a sulfo group or a salt thereof as an ion exchange group]
In the present invention, the styrenic monomer having a quaternary ammonium group or a sulfo group or a salt thereof as an ion exchange group may be an ethylenically unsaturated group even if it is a monofunctional monomer having only one ethylenically unsaturated group. It may be a polyfunctional monomer having two or more.

(Monofunctional styrene monomer)
The monofunctional styrenic monomer is not particularly limited as long as it is a monofunctional monomer having a quaternary ammonium group or a sulfo group or a salt thereof and a styrene structure as an ion exchange group, but a monofunctional styrene monomer having a quaternary ammonium group and a styrene structure. The monomer represented by the following general formula (SM) is preferable.

In the general formula (SM), R ^{1 to} R ³ each independently represents an 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. n1 represents an integer of 1 to 3. X ₁ ⁻ represents an organic or inorganic anion.

Alkyl group in R ¹ to R ³ has a carbon number of 1 to 8, more preferably 1 to 4, 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 any substituent selected from the substituent group α described below.
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).

n1 is preferably 1 or 2, and 1 is particularly preferable.
X ₁ ⁻ represents an organic or inorganic anion, and is preferably an inorganic anion.
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.

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

  The compound represented by the general formula (SM) 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 film forming composition of the present invention, two or more compounds represented by the general formula (SM) may be used in combination.

(Multifunctional styrene monomer)
The polyfunctional monomer having an ion exchange group is also referred to as a cross-linking agent (charged crosslinker) having an ion exchange group, and the polyfunctional styrenic monomer used in the present invention is a quaternary ammonium group, a sulfo group or a salt thereof. The polyfunctional monomer having a styrene structure is not particularly limited, but a polyfunctional monomer having a quaternary ammonium group and a styrene structure is preferable, and a compound represented by the following general formula (SXL) is particularly preferable.

In General Formula (SXL), L ¹ and L ² each independently represent an alkylene group or an alkenylene group. R ^d and R ^e each independently represents an alkyl group or an aryl group, and R ^d and R ^e may be bonded to each other to form a ring. n2 represents an integer of 1 to 3. X ₂ ^- and _{X 3} ^- each independently represents an organic or inorganic anion.

The alkylene group for L ¹ and L ² 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 any substituent selected from the substituent group α described below.
The alkenylene group in L ¹ and L ² preferably has 2 or 3 carbon atoms, more preferably 2, and an ethenylene group is particularly preferable.
The ring formed by L ¹ and L ² is preferably a piperazine ring.
The alkyl group and aryl group in R ^d and R ^e are preferably in the preferred range of the alkyl group and aryl group in R ^{1 to} R ³ in the general formula (SM).

Of these, R ^d and R ^e are preferably alkyl groups, and methyl is particularly preferred.
R ^d and R ^e 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.

n2 is preferably 1 or 2, and 1 is particularly preferable.
X ₂ ^- and _{X 3} ^- is _{X 1} in the general formula (SM) ^- an synonymous, and preferred ranges are also the same.

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

  The compound represented by the general formula (SXL) can be synthesized by the method described in JP-A-2000-229917 or a method analogous thereto.

[Acrylamide monomer having a quaternary ammonium group, a sulfo group or a salt thereof as an ion exchange group]
(Monofunctional acrylamide monomer)
The monofunctional acrylamide monomer is not particularly limited as long as it is a monofunctional monomer having a quaternary ammonium group or a sulfo group or a salt thereof and an acrylamide structure as an ion exchange group, but a monofunctional acrylamide monomer having a quaternary ammonium group as an ion exchange group. The functional acrylamide monomer is preferably a compound represented by the following general formula (AM-1).
On the other hand, the monofunctional acrylamide monomer having a sulfo group or a salt thereof as an ion exchange group is preferably a compound represented by the following general formula (AM-2).

<Monofunctional acrylamide monomer having a quaternary ammonium group as an ion exchange group>
The acrylamide monomer having a quaternary ammonium group as an ion exchange group is not particularly limited as long as it is a monofunctional monomer having a quaternary ammonium group and an acrylamide structure, but the compound represented by the following general formula (AM-1) is preferable.

In General Formula (AM-1), R ⁴ represents a hydrogen atom or an alkyl group, and R ^{5 to} R ⁷ each independently represents an alkyl group or an aryl group. Z ¹ represents -NRa-. Here, Ra represents a hydrogen atom or an alkyl group. L ³ represents an alkylene group, and X ₄ ⁻ represents a halogen ion or an aliphatic or aromatic carboxylate ion.

The alkyl group in R ⁴ and Ra is a linear or branched alkyl group, preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1.
R ⁴ is preferably a hydrogen atom or methyl, and most preferably a hydrogen atom.
Ra is preferably a hydrogen atom among a hydrogen atom and an alkyl group.

The alkyl group in R ⁴ and Ra may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described later.

The alkyl group in R ^{5 to} R ⁷ is a linear or branched alkyl group, preferably having 1 to 9 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1.
Aryl group in R ⁵ to R ⁷ has a carbon number of 6 to 12, more preferably 6 to 9, 6 is particularly preferred.
R ^{5 to} R ⁷ are preferably an alkyl group.
The alkyl group and aryl group in R ^{5 to} R ⁷ may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described later.

The alkylene group in L ³ is a linear or branched alkylene group, preferably having 1 to 9 carbon atoms, more preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 or 3. The alkylene group may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described below.

Examples of the halogen ion in X ₄ ⁻ include a chlorine ion, a bromine ion, and an iodine ion.
X ₄ ^- aliphatic or aromatic carboxylate ion in the formate ions, acetate ions, propionate ions, butanoate ion, benzoate ion and the like.
The aliphatic or aromatic carboxylate ion in X ₄ ⁻ is preferably an aliphatic carboxylate ion, particularly preferably an acetate ion.
X ₄ ⁻ is preferably a chlorine ion, a bromine ion, an iodine ion, or an acetate ion.

  Although the specific example of a compound represented by general formula (AM-1) below is given, this invention is not limited to these.

(Multifunctional acrylamide monomer)
The polyfunctional acrylamide monomer having an ion exchange group is not particularly limited as long as it is a polyfunctional monomer having a quaternary ammonium group or a sulfo group or a salt thereof and an acrylamide structure. The functional monomer is preferably a compound represented by the following general formula (AXL-1), and the polyfunctional monomer having a sulfo group or a salt thereof and an acrylamide structure is represented by the following general formula (AXL-2). Compounds are preferred.

<Polyfunctional acrylamide monomer having a quaternary ammonium group as an ion exchange group>
The polyfunctional acrylamide monomer having a quaternary ammonium group as an ion exchange group is not particularly limited as long as it is a polyfunctional monomer having a quaternary ammonium group and an acrylamide structure, but is represented by the general formula (AXL-1). Are preferred.

R ⁸ and R ⁹ in General Formula (AXL-1) have the same meaning as R ⁴ in General Formula (AM-1), and the preferred ranges are also the same. R < ¹⁰ > -R < ¹³ > in general formula (AXL-1) is synonymous with R < ⁵ > in general formula (AM-1), respectively, and its preferable range is also the same. Z ² and Z ³ in the general formula (AXL-1) have the same meanings as Z ¹ in the general formula (AM-1), respectively, and the preferred ranges are also the same. L ⁴ and L ⁵ in General Formula (AXL-1) have the same definitions as L ³ in General Formula (AM-1), respectively, and the preferred ranges are also the same. X ₅ ^- and _{X 6} ^- are each _{X 4} in the general formula (AM-1) ^- has the same meaning as, the preferred range is also the same.

In General Formula (AXL-1), R ^X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, or a divalent linking group in which these are combined.
The alkylene group represents a linear or branched alkylene group, preferably having 1 to 9 carbon atoms, the alkenylene group or alkynylene group is a linear or branched alkenylene group or alkynylene group, and preferably having 2 to 9 carbon atoms. .
The arylene group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and particularly preferably 6 carbon atoms.

As the divalent linking group in which an alkylene group, alkenylene group, alkynylene group, arylene group, and -O- are combined, the number of combinations of these groups is preferably 2 to 4. For example, the two combinations include a combination of an alkylene group and —O—, a combination of an alkylene group and an arylene group, a combination of an arylene group and an arylene group, and the like.
Each group in R ^X may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described later.
As a group in which these are combined, -alkylene-phenylene-alkylene- is preferable.
Specific examples of the polyfunctional monomer represented by the general formula (AXL-1) are shown below, but the present invention is not limited thereto.

<Monofunctional acrylamide monomer having sulfo group or salt thereof as ion exchange group>
The monofunctional acrylamide monomer having a sulfo group or a salt thereof as an ion exchange group is not particularly limited as long as it is a monofunctional monomer having a sulfo group or a salt thereof and an acrylamide structure, but the following general formula (AM-2) The compounds represented are preferred.

In general formula (AM-2), R < ¹⁴ > is synonymous with R < ⁴ > in the said general formula (AM-1), and its preferable range is also the same.

In General Formula (AM-2), M ₁ ⁺ represents a hydrogen ion or an alkali metal ion. Examples of alkali metal ions include lithium ions, potassium ions, and sodium ions, which are preferable.
M ₁ ⁺ is preferably a hydrogen ion, lithium ion, potassium ion, or sodium ion, more preferably a hydrogen ion or sodium ion, and even more preferably a sodium ion.
Within the above preferred ranges, the desired curability, pH resistance, mechanical strength and flexibility are excellent.

  Although the specific example of the monofunctional monomer represented with general formula (AM-2) below is given, this invention is not limited to these.

  These monomers can be synthesized by the method described in US Pat. No. 4,034,001 or a method analogous thereto.

<Polyfunctional acrylamide monomer having sulfo group or salt thereof as ion exchange group>
The polyfunctional acrylamide monomer having a sulfo group or a salt thereof as an ion exchange group is not particularly limited as long as it is a polyfunctional monomer having a sulfo group or a salt thereof and an acrylamide structure, but the following general formula (AXL-2) The compounds represented are preferred.

R ¹⁵ and M ₂ ⁺ in the general formula (AXL-2) have the same meanings as R ¹⁴ and M ₁ ⁺ in the general formula (AM-2), respectively, and preferred ranges thereof are also the same. Z ⁴ has the same meaning as Z ¹ in formula (AM-1), and the preferred range is also the same.

  Specific examples of the compound represented by the general formula (AXL-2) are shown below, but the present invention is not limited thereto.

  These compounds can be synthesized by the method shown in the examples described later or a method analogous thereto.

<Monomer not having ion exchange group>
The composition for forming a polymer functional film contains a monomer having an ion exchange group. In the present invention, a styrene monomer having a quaternary ammonium group, a sulfo group or a salt thereof as an ion exchange group, or An acrylamide monomer having a quaternary ammonium group or a sulfo group or a salt thereof is used as the ion exchange group, but in addition to these, a monomer having no ion exchange group may be further included.
The monomer having no ion exchange group may be a monofunctional monomer or a polyfunctional monomer. Alternatively, both a monofunctional monomer and a polyfunctional monomer may be included.
In the present invention, a compound represented by the following general formula (CL) is preferable.

In General Formula (CL), R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or an alkyl group. Y ¹ and Y ² each independently represent —O— or —N (Rc) —. Here, Rc represents a hydrogen atom or an alkyl group. L ⁶ represents a p1 + 1-valent linking group having 1 or more carbon atoms. p1 represents an integer of 1 or more.

The alkyl group in R ¹⁶ , R ¹⁷ and Rc may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described later.

The alkyl group in R ¹⁶ and R ¹⁷ is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, isopropyl, n-butyl, isobutyl, and t-butyl.
R ¹⁶ and R ¹⁷ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Y ¹ and Y ² represent —O— or —N (Rc) —, preferably —N (Rc) —, and those in which both Y ¹ and Y ² are —N (Rc) — preferable.
Here, the alkyl group in Rc is preferably an alkyl group having 1 to 4 carbon atoms.
Rc is particularly preferably a hydrogen atom.

L ⁶ represents a p1 + 1-valent linking group having 1 or more carbon atoms. Here, although p1 represents an integer greater than or equal to 1, 1-5 are preferable, 1-3 are more preferable, and 1 is especially preferable.
The linking group in L ⁶ is preferably such that the atoms bonded to Y ¹ and Y ² are both carbon atoms.

When p1 is 1, for example, a linear, branched or cyclic alkylene group (preferably an alkylene group having 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 4 carbon atoms, , Ethylene, propylene, butylene, pentylene, hexylene, octylene, decylene, etc. In the case of a cyclic alkylene group, that is, a cycloalkylene group, the minimum carbon number is preferably 3, and cyclopentylene, cyclohexylene And-(alkyleneoxy) _t -alkylene group (where t represents an integer of 1 or more, preferably 1 to 50, more preferably 1 to 20, still more preferably 1 to 10.) Preferably it is C2-C30, More preferably, it is C2-C12, More preferably, it is C2-C4 alkylene. .

Examples thereof include ethyleneoxyethylene, propyleneoxypropylene, butyleneoxybutylene, pentyleneoxypentylene, hexyleneoxyhexylene, octyleneoxyoctylene, decyleneoxyethylene, polyethyleneoxyethylene, and polypropyleneoxypropylene. ), An aralkylene group (preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 13 carbon atoms, such as benzylidene and cinnamylidene), an arylene group (preferably having 6 to 30 carbon atoms and more). An arylene group having 6 to 15 carbon atoms is preferred, and examples thereof include phenylene, cumenylene, mesitylene, tolylene, xylylene, etc.), -alkylene-E-alkylene group (where E is -S-, -SO). —, —SO ₂ —, —S—S—, —C (═O) —, —N (R ^L1 ) —, phenylene, cycloalkylene, alkylene, a divalent hetero group, and a group in which these groups are combined. .R ^L1 representing the represents a hydrogen atom, an alkyl group or an aryl group), -. arylene -E- arylene group (wherein, E is as defined above. , (Wherein, E is as defined above.) Arylene -E- alkylene group and the like.
Here, the divalent heterocyclic group in E is preferably the following divalent heterocyclic group.
Each of these rings may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described later.
Among them, 1,4-diazabicyclo [2.2.2] octane ring (diazabicyclo [2.2.2] octane-1,4-diyl), 1,4-piperazine ring (piperazi-1,4-diyl) Is preferred.

When p1 is 3 or more, the linking group represented by L ⁶ is preferably the following linking group.

  W represents an alkyl group, a hydroxy group or an amino group, m represents an integer of 2 or more, and a1 to a6 each independently represents an integer of 0 or more.

m is preferably 2 or 3.
a1 to a6 are preferably 0 to 20, and more preferably 0 to 10.

Each group in L ⁶ may have a substituent, and examples of the substituent include any substituent selected from the substituent group α described later.

  Although the specific example of a compound represented by general formula (CL) below is shown, this invention is not limited to these.

  These compounds are commercially available from Kojin Co., Ltd., Kyowa Hakko Chemical Co., Ltd., Fluka Co., Ltd., aldrich Co., Ltd., and Toa Gosei Co., Ltd., and can be easily synthesized by known methods.

  In the film forming composition of the present invention, two or more compounds represented by the general formula (CL) may be used in combination.

  In the present invention, the content of the compound represented by any one of the general formulas (SM), (AM-1), and (AM-2) in 100% by mass of the total solid content of the film-forming composition is 0 to 85 mass% is preferable, 0-80 mass% is more preferable, and 0-75 mass% is especially preferable.

  In the present invention, the content of the compound represented by the general formula (SXL), (AXL-1) or (AXL-2) is 10 to 95 parts by mass with respect to 100 parts by mass of the total solid content of the film-forming composition. Is preferable, 30-90 mass parts is more preferable, and 35-85 mass parts is especially preferable.

  In the present invention, the content of the compound represented by the general formula (CL) is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, out of 100% by mass of the total solid content of the film-forming composition. 15-30 mass% is especially preferable.

In the present invention, the compound represented by the general formula (AM-1) is preferably used in combination with the compound represented by the general formula (AXL-1) or the general formula (CL).
Moreover, it is preferable to use the compound represented by the said general formula (SM) in combination with the compound represented by the said general formula (SXL).
On the other hand, the compound represented by the general formula (AM-2) is preferably used in combination with the compound represented by the general formula (AXL-2) or the general formula (CL).

Here, the substituent group α will be described.
The substituent group α is a group of substituents composed of the following substituents.

(Substituent group α)
As the substituent group α, an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, and t-butyl. , N-octyl, 2-ethylhexyl, n-decyl, n-hexadecyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms). Group, for example, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms). For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably An alkynyl group having 2 to 30 primes, more preferably 2 to 20 carbons, particularly preferably 2 to 10 carbons, and examples thereof include propargyl and 3-pentynyl, and aryl groups (preferably 6 to 6 carbons). 30, more preferably an aryl group having 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), amino group (amino group, alkyl group) An amino group and an arylamino group, preferably an amino group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, Diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), alkoxy groups (preferably An alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like. Group (preferably an aryloxy group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like. And a heterocyclic oxy group (preferably a heterocyclic oxy group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, Quinolyloxy, etc.)

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

An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryl Oxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino group). , Alkyl or arylsulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino). Sulfamoyl group (sulfamoyl group) An alkyl or aryl sulfamoyl group, preferably a sulfamoyl group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, Dimethylsulfamoyl, phenylsulfamoyl, etc.),

A carbamoyl group (including a carbamoyl group, an alkyl or arylcarbamoyl group, preferably a carbamoyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl , Diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio etc.), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio). A heterocyclic thio group (preferably having 2 to 3 carbon atoms) More preferably a heterocyclic thio group having 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like. ),

An alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl). An alkyl or arylsulfinyl group (preferably an alkyl or arylsulfinyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc. Ureido group (preferably a ureido group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, and phenylureido. ), Phosphoric acid amide groups (preferably carbon A phosphoric acid amide group having 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide)), hydroxy group, mercapto A group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, more preferably a fluorine atom),

A cyano group, a sulfo group, a carboxyl group, an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, and a heterocyclic group (preferably having a carbon number of 1 to 30, more preferably a heterocyclic group having 1 to 12 carbon atoms) A ring group, and the ring-constituting hetero atom is preferably, for example, a nitrogen atom, an oxygen atom, or a sulfur atom. Specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl , Benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Trimethylsilyl, triphenylsilyl, etc.), silyloxy groups (preferably Ku 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably a silyloxy group having 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like.

These substituents may be further substituted with any one or more substituents selected from the above substituent group α.
In the present invention, when one structural site has a plurality of substituents, these substituents are connected to each other to form a ring, or condensed with a part or all of the above structural sites to form an aromatic group. A ring or an unsaturated heterocyclic ring may be formed.

<Other ingredients>
The composition for forming a polymer functional film of the present invention may further contain a solvent, a polymerization inhibitor and the like, if necessary.

(solvent)
The film-forming composition in the present invention may contain a solvent.
In the present invention, the content of the solvent in the film-forming 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 film-forming composition.
By setting the content of the solvent within this range, a uniform film can be produced without increasing the viscosity of the film-forming composition. In addition, the occurrence of pinholes (fine defect holes) can be suppressed.

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 in 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, isopropanol is preferably 0.1 to 50%, more preferably 10 to 45%, and still more preferably 15 to 40% with respect to 100% by mass of water.
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.

(Polymerization inhibitor)
The film-forming composition in the present invention also preferably contains a polymerization inhibitor in order to impart stability to the coating solution when forming a film.
As a polymerization inhibitor, a well-known polymerization inhibitor can be used, and a phenol compound, a hydroquinone compound, an amine compound, a mercapto compound, etc. are mentioned.
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. Specific examples of the aliphatic heterocyclic compound include 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl.
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 with respect to 100 parts by mass of the total solid content in the film-forming composition, and 0.01 to 0.5 parts by mass is more preferable.

(Surfactant)
Various polymer compounds may be added to the film-forming composition in the present invention in order to adjust film physical 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 film-forming composition in 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.

(Alkali metal compound)
The film-forming composition in the present invention may contain an alkali metal compound in order to improve the solubility of the monomer, particularly the compound represented by the general formula (CL) having no ionic group. As the alkali metal compound, lithium, sodium, potassium hydroxide salt, chloride salt, nitrate salt and the like are preferable. Among them, lithium compounds are more preferable, and specific examples thereof include lithium hydroxide, lithium chloride, lithium bromide, lithium nitrate, lithium iodide, lithium chlorate, lithium thiocyanate, lithium perchlorate, lithium tetrafluoro Examples thereof include borate, lithium hexafluorophosphate, and lithium hexafluoroarsenate.
Here, the alkali metal compound is also preferably used for neutralizing the film-forming composition and the film-forming composition solution mixture.
These alkali metal compounds may be hydrates. Moreover, it can be used individually by 1 type or in combination of 2 or more types.
0.1-30 mass parts is preferable with respect to 100 mass parts of total solid content in the film forming composition, and the addition amount in the case of adding an alkali metal compound is more preferably 1-30 mass parts, More preferred is 25 parts by weight.

(Anti-crater agent)
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 film-forming composition.

  In addition to the above, the film-forming composition in 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 the present invention 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 membrane-forming composition and then carrying out a polymerization 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.
When the porous support and the reinforcing material are subjected to a photopolymerization curing reaction, it is required not to block the wavelength region of the irradiation light, that is, to pass the irradiation of the wavelength used for the polymerization curing. This need not be considered in the case of curing. Moreover, it is preferable that the porous reinforcing material can be penetrated by the film-forming composition.

  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 invention is demonstrated.
In the method for producing a functional polymer film of the present invention, the film-forming composition of the present invention is polymerized and cured to form a film. 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 invention can be prepared in a batch system using a fixed support (batch system), but it can be prepared in a continuous system using a moving support (continuous system). ). The support may be in the form of a roll that is continuously rewound. In the case of the continuous method, a support is placed on a belt that is continuously moved, and a process of continuously applying a coating liquid that is a film forming composition and polymerizing and curing to form a film is continuously performed. Can do. However, only one of the coating process and the film forming process may be performed continuously.
Separately from the support, a temporary support (the film is peeled off from the temporary support after the completion of the polymerization and curing reaction) is used until the film-forming composition is immersed in the porous support and the polymerization and curing reaction is completed. Also good.
Such a temporary support does not need to consider material permeation, and includes any metal plate such as a polyethylene terephthalate (PET) film or an aluminum plate that can be fixed for film formation. It does n’t matter.
Alternatively, the film-forming composition can be immersed in a porous support and polymerized and cured without using a support other than the porous support.

  The film-forming composition can be applied by various methods, 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 or immersed in a porous support. Multiple layers can be applied simultaneously or sequentially. For simultaneous multi-layer application, curtain coating, slide coating, slot die coating and extrusion coating are preferred.

  The production of the polymer functional film in a continuous manner is carried out by continuously applying the film-forming composition to the moving support, more preferably, the film-forming composition application part and the film-forming composition. An irradiation source for polymerizing and curing the product, a film collecting unit for collecting the formed film, and a means for moving the support from the film forming composition application unit to the irradiation source and the film collecting unit Manufactured by a manufacturing unit.

In this production example, (i) the film-forming composition of the present invention is applied to and / or impregnated on a porous support, and (ii) the film-forming composition is irradiated with light, and if necessary, further heated. The polymer functional film of the present invention is produced through a process of polymerizing and curing, 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. Furthermore, the above (ii) may be a polymerization curing reaction by heating, but a polymerization curing reaction by light irradiation is preferred.

[Energy beam irradiation]
In the manufacturing unit, the film-forming composition application unit is provided at a position upstream of the irradiation source, and the irradiation source is positioned at an upstream position of the collection unit.
In order to have sufficient fluidity when applied with a high-speed coater, the viscosity at 35 ° C. of the film-forming composition in the present invention is preferably less than 4,000 mPa · s, and preferably 1 to 1,000 mPa · s. 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.

  In the high-speed coating machine, the coating liquid that is the film forming composition in the present invention can be applied to the moving support at a speed exceeding 15 m / min, and can also be applied at a speed exceeding 400 m / min. .

  In particular, when a support is used to increase the mechanical strength, before applying the film-forming composition of the present invention to the surface of the support, the support is improved, for example, the wettability and adhesion of the support. Therefore, it may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, and the like.

The polymerization and curing of the film-forming composition in the present invention is preferably performed within 60 seconds, more preferably within 15 seconds, particularly preferably within 5 seconds, and most preferably after coating or impregnating the film-forming composition on a support. Start within 3 seconds.
The light irradiation for polymerization curing 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 continuously performed, and the polymerization curing reaction time is determined in consideration of the speed at which the film-forming composition moves through the irradiation beam.

  When high intensity ultraviolet rays (UV light) are used in the polymerization curing reaction, a considerable amount of heat is generated, and therefore the lamp of the light source and / or the support / film is cooled with cooling air or the like to prevent overheating. Is preferred. When a significant dose of infrared (IR light) is irradiated with the UV beam, the UV light is irradiated using an IR reflective quartz plate as a filter.

  The energy rays are preferably ultraviolet rays. The irradiation wavelength is preferably matched with the absorption wavelength of any photopolymerization initiator included in the film-forming composition, for example, UV-A (400 to 320 nm), UV-B (320 to 280 nm). , UV-C (280-200 nm).

  Ultraviolet sources are mercury arc lamps, carbon arc lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, swirling flow plasma arc lamps, metal halide lamps, xenon lamps, tungsten lamps, halogen lamps, lasers and ultraviolet light emitting diodes. 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 polymerization hardening of the film is adjusted according to the exposure strength. 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 and most preferably less than 2 seconds.

  When the application speed is high, a plurality of light sources may be used to obtain a necessary exposure dose. In this case, the plurality of light sources may have the same or different exposure intensity.

  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.

<Thickness>
The polymer functional membrane of the present invention is preferably an ion exchange membrane.
The thickness of the film of the present invention is the film thickness including the support when it has a support, and is greater than 500 μm and 1,000 μm or less.
In the present invention, the thickness of the film is preferably 510 to 990 μm, more preferably 530 to 980 μm, further preferably 530 to 900 μm, and particularly preferably 530 to 700 μm.

<Ion exchange capacity>
The polymer functional membrane of the present invention is based on the total dry mass of any porous reinforcing material such as a membrane, or a membrane and a porous support when having a support, and 2.0 meq / g to 7.0 meq / g, preferably 2.5 meq / g to 7.0 meq / g, more preferably 3.0 meq / g to 7.0 meq / g.

<Charge density>
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.

<Selective permeability>
The selective permeability of anions such as Cl 2 ⁻ of the polymer functional membrane (anion exchange membrane) of the present invention is preferably more than 0.90, more preferably more than 0.93, more than 0.95, It is particularly preferable that the value approaches 1.0.
On the other hand, in the polymer functional membrane (cation exchange membrane) of the present invention, the selective permeability of cations such as Na ⁺ is preferably more than 0.9, more preferably more than 0.93, and particularly preferably 0.8. Greater than 95, most preferably greater than 0.96.

<Electrical resistance>
The electrical resistance of the polymer functional film of the present invention (film resistor) is preferably less than 2.8Ω · cm ^2, more preferably less than 2.0Ω · cm ^2, less than 1.8Ω · 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. There is no particular limitation on the lower limit of the electrical resistance, but it is practical that it is 0.1 Ω · cm ² or more.

<Swelling rate>
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 polymerization curing conditions in the polymerization curing stage.

<Measurement of electrical resistance, selective permeability and swelling ratio in water>
Electrical resistance, permselectivity and% swelling in water are described, for example, in Membrane Science, 319, 217-218 (2008), Masayuki Nakagaki, Membrane Experimental Method, pages 193-195 (1984). It can be measured by the method.

<Water permeability>
The water permeability of the polymer functional membrane of the present invention is preferably 3 × 10 ⁻⁵ ml / m ² / Pa / hr or less, more preferably 2.5 × 10 ⁻⁵ ml / m ² / Pa / hr or less, 2 × 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, Although it is so preferable that it is low, it is practical that it is 1 * 10 < ^-5 > ml / m < ² > / Pa / hr or more.
Furthermore, it is better that the change rate of the water permeability is small with respect to stimulation such as alkali immersion and friction, and the fluctuation range of the change rate is preferably 2 × 10 ⁻⁵ ml / m ² / Pa / hr or less, and 1.5 × 10 ⁻⁵ ml / m ² / Pa / hr or less is more preferable, and 1 × 10 ⁻⁵ ml / m ² / Pa / hr or less is particularly preferable.

<Mass average molecular weight>
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 membrane of the present invention is mainly intended for use in particular 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.
(Synthesis of multifunctional monomer)

(Synthesis of Exemplary Compound AXL-1-3)
It was synthesized by the following synthesis scheme.

  313 g of N- [3- (dimethylaminopropyl) acrylamide] with respect to a mixed solution of 175 g of paradichloroxylene (1.00 mol, manufactured by Tokyo Chemical Industry), 1220 g of acetonitrile, 244 g of methanol, and 1 g of t-butyl hydroperoxide (produced by Tokyo Chemical Industry) (2.00 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred with heating at 50 ° C. for 2 hours. Subsequently, 1220 g of acetone was added and stirred at room temperature for 1 hour, and the resulting crystals were filtered to obtain 450 g (yield 92%) of white crystals of the exemplary compound AXL-1-3.

(Synthesis of Exemplified Compound AXL-1-4)
It was synthesized by the following synthesis scheme.

  For a mixed solution of 1,3-dibromopropane 80.8 g (0.40 mol, Wako Pure Chemical Industries), methoxyphenol 0.617 g (Wako Pure Chemical Industries), acetonitrile 309 ml, methanol 103 ml, N- [3- (dimethyl Amino) propyl] acrylamide 125 g (0.80 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 50 ° C. for 7 hours. Subsequently, 2.2 L of acetone was added, and the supernatant was removed by decantation. Then, 0.1 g of methoxyphenol and 30 g of water were added, and the mixture was concentrated at 35 ° C. and 40 mmHg for 30 minutes, whereby exemplary compound AXL-1-4 188 g (water content 19%, yield 74%) was obtained.

(Synthesis of Exemplified Compound SXL-1)
For a mixed solution of 321 g of chloromethylstyrene (2.10 mol, CMS-P manufactured by Seimi Chemical Co., Ltd.), 1.30 g of 2,6-di-t-butyl-4-methylphenol (manufactured by Wako Pure Chemical Industries), and 433 g of acetonitrile, 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 SXL-1.

(Synthesis of Exemplary Compound AXL-2-1)
It was synthesized by the following synthesis scheme.

  To a 5 L three-necked flask, 288.29 g (3.43 mol) of sodium hydrogen carbonate (product number: 195-01303, manufactured by Wako Pure Chemical Industries, Ltd.) and 1,343 mL of ion-exchanged water were added and stirred at room temperature. 4,4′-benzidine-2,2′-disulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product number: B0395), 268.6 g (0.78 mol) was added little by little. After stirring at room temperature for 30 minutes, the mixture was cooled under ice cooling and stirring was continued. 138.7 mL (1.53 mol) of acryloyl chloride (manufactured by Wako Pure Chemical Industries, product number: 013-12485) was added dropwise little by little to keep the system at 10 ° C. or lower while stirring under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice cooling and then for 3 hours at room temperature. To the reaction mixture, 2,686 mL of isopropyl alcohol was added little by little, and the resulting insoluble material was removed by filtration. The obtained filtrate was transferred to a 30 L stainless steel bucket, and 10,744 mL of isopropyl alcohol was added little by little while stirring at room temperature. The obtained crystals were filtered, and then washed with 1,074 mL of a mixed solution of isopropyl alcohol: water (5: 1) to obtain 339 g (yield: 87%) of the target compound AXL-2-1. . The water content of the compound AXL-2-1 measured by the Karl Fischer method was 15.8% by mass.

¹ H-NMR (300 MHz, DMSO-d6) δ · = 10.3 (s, 2H), 8.09 (d, J = 2.4 Hz, 2H), 7.71 (dd, J = 2.4, 8.4 Hz, 2H), 7.16 (d, J = 8.4 Hz, 2H), 7.71 (dd, J = 2.4, 8.4 Hz, 2H)

Example 1
(Creation of ion exchange membrane)
A coating solution of the composition (unit: g) 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 nonwoven fabric (tapyrus P030UA-00X, 500 μm thick) 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 9.0 m / min, 100% strength), the coating liquid-impregnated support is polymerized and cured to cause anion. An exchange membrane was prepared. The exposure amount was 1,000 mJ / cm ² in the UV-A region. The exposure time was 3.5 seconds. 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 10, Comparative Examples 1 and 2)
In the production of the ion exchange membrane of Example 1, the ion exchange membranes of Examples 2 to 10 and Comparative Examples 1 and 2 were the same as in Example 1 except that the composition was changed to the composition described in Table 1 below. Each of the film thicknesses shown in Table 3 was prepared.

  Below, the absorption region where the maximum absorption wavelength of the used photopolymerization initiator is located is summarized in Table 2 below.

[Description of Abbreviations in Table 1]
IPA: isopropyl alcohol MEHQ: monomethyl ether hydroquinone Genrad 16: trade name, DMAPAA-Q: dimethylaminopropylacrylamide methyl chloride quaternary salt, manufactured by Rahn AG
(3-acrylamidopropyltrimethylammonium chloride)
VBTMAC: Exemplified compound SM-1, vinylbenzyltrimethylammonium chloride (trade name: (vinylbenzyl) trimethylammonium chloride, manufactured by Sigma-Aldrich)
AMPS: AMPS: 2-acrylamido-2-methylpropanesulfonic acid MBA: methylenebisacrylamide (manufactured by Tokyo Chemical Industry)
Darocur 1173: trade name, Irgacure 184 manufactured by Ciba Specialty Chemicals, Inc .: trade name, Irgacure 500 manufactured by BASF Japan, Inc. Irgacure 819: trade name, BASF Japan Inc. Irgacure 1700: product Name, BASF Japan made LUCIRIN TPO: Product name, BASF Japan made Tego Glide 432: Product name, made by Evonil Industries

  About the ion exchange membrane created in Examples 1-10 and Comparative Examples 1 and 2, the water permeability before and after alkali immersion and before and after the friction test was evaluated. The results are shown in Table 3 below.

[Alkaline immersion]
300 mL of a phosphate buffer solution having a pH of 13 was prepared at room temperature, and the membrane was immersed in this phosphate buffer solution for 24 hours while being heated to 50 ° C.

[Friction test]
In the friction test, the film was placed on a hard and flat material surface, a sandpaper (# 400) was placed in parallel, and the film was slid back and forth 15 times in the front-rear direction with a 150 g weight placed on the sandpaper.

[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. Moreover, the arrow of a code | symbol 2 shows the flow of the water isolate | 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.
Tables 3 and 4 show values multiplied by 10 ⁵ . For example, the water permeability before immersion in alkali of Example 1 was 2.1 × 10 ⁻⁵ mL / m ² / Pa / hr, which was indicated as 2.1.

[Measurement method of film thickness]
After immersing in a 0.01 M NaCl aqueous solution at a temperature of 25 ° C. for 12 hours, the membrane was taken out and wiped off with water on the surface, and then measured with a micrometer.
The film thickness in the following Table 3 is a film thickness before each test of alkali immersion and friction test.

As is clear from the results in Table 3, Examples 1 to 10 using two types of photopolymerization initiators having film thicknesses that satisfy the provisions of the present invention and have maximum absorption wavelengths in different wavelength regions are shown after each test. The water permeability did not increase by 2 (mL / m ² / Pa / hr) or more. On the other hand, although the film thickness satisfies the provisions of the present invention, Comparative Examples 1 and 2 using only one kind of photopolymerization initiator have a water permeability of 2 (mL / m ² / Pa / hr) after each test. More than that. This shows that the polymer functional film of the present invention is excellent in durability.

  Next, anion exchange membranes having the film thicknesses shown in Table 4 below were prepared in the same manner as in Example 1, and the water permeability before and after the alkali immersion and before and after the friction test was evaluated. The results are shown in Table 4 below.

Test No. 1 and No. As is clear from the comparison of the results of Test No. 2, the test No. 1 satisfying the lower limit of the film thickness of the present invention is shown. No. 2 shows that the water permeability before and after the alkali soaking and before and after the friction test are both test Nos. It can be seen that it was lower than 1. On the other hand, test no. 5 and test no. As is clear from the comparison of the test No. 6, the test No. 1 satisfying the upper limit of the film thickness of the present invention. No. 5 shows that the water permeability before and after the alkali immersion and before and after the friction test are both test Nos. It turns out that it was low compared with 6.
As a result, it can be seen that the functional polymer film obtained by the production method of the present invention is excellent in durability even when the film thickness is large.

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 (8)

A method for producing a functional polymer film comprising polymerizing and curing a composition containing at least a monomer and a photopolymerization initiator,
The film thickness of the functional polymer film is greater than 500 μm and 1,000 μm or less,
At least one of the monomers is a styrene monomer or an acrylamide monomer having a quaternary ammonium group, a sulfo group or a salt thereof,
As the photopolymerization initiator, at least one (I-1) maximum absorption wavelength is 300 nm or more and less than 350 nm and at least one (I-2) maximum absorption wavelength is 350 nm or more and 420 nm or less. Use a combination of photopolymerization initiators ,
The photopolymerization initiator (I-1) is a photopolymerization initiator represented by the following general formula (PI-1), and the photopolymerization initiator (I-2) is represented by the following general formula (PI-2). The manufacturing method of the polymeric functional film which is a photoinitiator represented by this .

In the general formula (PI-1), R ^P1 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, a pyrrolidino group, a piperidino group, a morpholino group, a thiomorpholino group or a dialkylamino group, R ^P2 and R ^P3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. Here, R ^P2 and R ^P3 may be bonded to each other to form a ring. x represents an integer of 1 or more. R ^P4 represents a hydrogen atom or an x-valent substituent or linking group.

In general formula (PI-2), R ^P5 , R ^P6 and R ^P7 each independently represents an alkyl group or an aryl group, and l and m each independently represents 0 or 1. Of the total solid content of 100% by mass of the composition, the total amount of the photopolymerization initiator is 0.01 to 10% by mass, and the photopolymerization initiator (I−) relative to the photopolymerization initiator (I-1) The method for producing a functional polymer film according to claim 1, wherein the mass ratio of 2) is 5 to 50 mass%. The method for producing a polymer functional film according to claim 1 or 2 , wherein a film thickness of the polymer functional film is greater than 500 µm and 800 µm or less. The thickness of the polymer functional membrane, method for producing a polymer functional film according to any one of claims 1 to 3 or less larger than 500 [mu] m 700 .mu.m. The styrene monomer having the quaternary ammonium group is a compound represented by the following general formula (SM) or (SXL), and the acrylamide monomer having the quaternary ammonium group is represented by the following general formula (AM-1) Or it is a compound represented by (AXL-1), The manufacturing method of the polymeric functional film of any one of Claims 1-4 .

In the general formula (SM), R ^{1 to} R ³ each independently represents an 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. n1 represents an integer of 1 to 3. X ₁ ⁻ represents an organic or inorganic anion.

In General Formula (SXL), L ¹ and L ² each independently represent an alkylene group or an alkenylene group. R ^d and R ^e each independently represents an alkyl group or an aryl group, and R ^d and R ^e may be bonded to each other to form a ring. n2 represents an integer of 1 to 3. X ₂ ^- and _{X 3} ^- each independently represents an organic or inorganic anion.

In General Formula (AM-1), R ⁴ represents a hydrogen atom or an alkyl group, and R ^{5 to} R ⁷ each independently represents an alkyl group or an aryl group. Z ¹ represents -NRa-. Here, Ra represents a hydrogen atom or an alkyl group. L ³ represents an alkylene group, and X ₄ ⁻ represents a halogen ion or an aliphatic or aromatic carboxylate ion.

In General Formula (AXL-1), R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group, and R ^{10 to} R ¹³ each independently represent an alkyl group or an aryl group. Z ² and Z ³ each independently represent —NRb—. Here, Rb represents a hydrogen atom or an alkyl group. L ⁴ and L ⁵ each independently represent an alkylene group, and R ^X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined. X ₅ ^- and X ₆ ^- represents a halogen ion or an aliphatic or aromatic carboxylate ion independently. Acrylamide monomer having a sulfo group or a salt thereof, as claimed in any one of claims 1 to 5 which is a compound represented by any one of the following formulas (AM-2) or (AXL-2) A method for producing a polymer functional membrane.

In General Formula (AM-2), R ¹⁴ represents a hydrogen atom or an alkyl group. M ₁ ⁺ represents a hydrogen ion or an alkali metal ion.

In General Formula (AXL-2), R ¹⁵ represents a hydrogen atom or an alkyl group, and Z ⁴ represents —NRf—. Here, Rf represents a hydrogen atom or an alkyl group. M ₂ ⁺ represents a hydrogen ion or an alkali metal ion. The composition contains a combination of the compound represented by the general formula (AM-1) and the compound represented by the general formula (AXL-1) or the following general formula (CL), or the general formula The method for producing a polymer functional film according to claim 5 , comprising a combination of the compound represented by (SM) and the compound represented by the general formula (SXL).

In General Formula (CL), R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or an alkyl group. Y ¹ and Y ² each independently represent —O— or —N (Rc) —. Here, Rc represents a hydrogen atom or an alkyl group. L ⁶ represents a p1 + 1-valent linking group having 1 or more carbon atoms. p1 represents an integer of 1 or more. The said composition contains the compound represented by the said general formula (AM-2), and the compound represented by the said general formula (AXL-2) or the following general formula (CL) of Claim 6 characterized by the above-mentioned. A method for producing a polymer functional membrane.

In General Formula (CL), R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or an alkyl group. Y ¹ and Y ² each independently represent —O— or —N (Rc) —. Here, Rc represents a hydrogen atom or an alkyl group. L ⁶ represents a p1 + 1-valent linking group having 1 or more carbon atoms. p1 represents an integer of 1 or more.

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