WO2017038276A1 - Photocurable composition, cured material, member, and device - Google Patents

Photocurable composition, cured material, member, and device Download PDF

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Publication number
WO2017038276A1
WO2017038276A1 PCT/JP2016/071044 JP2016071044W WO2017038276A1 WO 2017038276 A1 WO2017038276 A1 WO 2017038276A1 JP 2016071044 W JP2016071044 W JP 2016071044W WO 2017038276 A1 WO2017038276 A1 WO 2017038276A1
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group
photocurable composition
composition according
cured product
present
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PCT/JP2016/071044
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French (fr)
Japanese (ja)
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裕介 飯塚
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen

Definitions

  • the present invention relates to a photocurable composition, a cured product, a member, and an apparatus.
  • ion exchange membranes 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.
  • 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 ion exchange membranes and electrical potentials to achieve ion 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.
  • conventional ion exchange membranes those described in Patent Documents 1 to 3 are known
  • the problem to be solved by the present invention is a photocurable composition capable of obtaining a cured product having low water permeability and excellent pH resistance, a cured product formed by curing the photocurable composition, and It is providing the member and apparatus provided with the said hardened
  • ⁇ 1> a photocurable composition comprising a quaternary ammonium salt structure, an acrylamide group, an ionic crosslinking monomer having a polymerizable group other than an acrylamide group, and a photopolymerization initiator
  • ⁇ 2> The photocurable composition according to ⁇ 1>, wherein the photocurable composition has an aromatic ring density of 1.5 mmol / g or more and a charge density of 3 mmol / g or more.
  • a 1 and B 1 each independently represent a divalent linking group
  • R 1 and R 2 each independently represent an alkyl group
  • X 1 ⁇ represents Cl ⁇ , Br ⁇ , I ⁇ .
  • Or represents CH 3 COO — .
  • ⁇ 5> The photocurable composition according to ⁇ 1> or ⁇ 2>, wherein the polymerizable group other than the acrylamide group is a methacrylamide group
  • ⁇ 6> The photocurable composition according to ⁇ 1>, ⁇ 2> or ⁇ 5>, wherein the ionic crosslinking monomer includes a compound represented by the following formula 2.
  • a 2 , A 3 and B 2 each independently represent a divalent linking group
  • R 3 to R 6 each independently represents an alkyl group
  • R 7 represents an alkyl group
  • X 2 - and X 3- each independently, Cl -, Br -, I - or CH 3 COO - represents a.
  • ⁇ 7> The photocurable composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a solvent, ⁇ 8>
  • ⁇ 9> A cured product formed by curing the photocurable composition according to any one of ⁇ 1> to ⁇ 8>, ⁇ 10>
  • ⁇ 11> a member comprising a cured product formed by curing the photocurable composition according to any one of ⁇ 1> to ⁇ 8>
  • ⁇ 12> An apparatus comprising a cured product formed by curing the photocurable composition according to any one of ⁇ 1> to ⁇ 8>.
  • a photocurable composition capable of obtaining a cured product having low water permeability and excellent pH resistance, a cured product formed by curing the photocurable composition, and the cured product. It was possible to provide a member and a device including the above.
  • the contents of the present invention will be described in detail.
  • the description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the geometrical isomer that is the substitution pattern of the double bond in each formula may be either E-form or Z-form, unless otherwise specified, even if one of the isomers is described for the convenience of display. Or a mixture thereof.
  • the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
  • “(meth) acrylate” represents acrylate and methacrylate
  • “(meth) acryl” represents acryl and methacryl
  • (meth) acryloyl” represents acryloyl and methacryloyl
  • (meth) ) Acrylamide refers to acrylamide and methacrylamide.
  • the “acrylic resin” is a homopolymer or copolymer of a compound selected from the group consisting of a (meth) acrylate compound and a (meth) acrylamide compound. It is assumed that the resin is copolymerized by 50% by mass or more.
  • “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the photocurable composition of the present invention (hereinafter also simply referred to as “composition”) includes an ionic crosslinking monomer having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than the acrylamide group, and And a photopolymerization initiator.
  • the photocurable composition of the present invention is preferably a photocurable composition for ion exchange membranes, proton conducting membranes, reverse osmosis membranes, forward osmosis membranes, polymer electrolytes or water-absorbing resins, and ion exchange membranes. It is more preferable that it is a photocurable composition.
  • an anion exchange membrane is preferable.
  • the “photocurability” in the present invention is not particularly limited as long as a solid or gel-like material can be formed by irradiation with actinic rays.
  • the “active light” is not particularly limited as long as it is an energy ray that can give energy capable of generating an initiation species from a photopolymerization initiator described later by irradiation, and is broadly ⁇ -ray, ⁇ Including X-rays, X-rays, ultraviolet rays (UV), visible rays, electron beams, and the like. Among these, light containing at least ultraviolet rays is preferable.
  • the ionic crosslinking monomer having an acrylamide group used in the photocuring application described in Patent Document 3 cannot be said to have sufficient pH resistance of the cured product.
  • a monomer having a styryl group or a methacrylamide group is conceivable.
  • the ionic crosslinking monomer which has a styryl group is described in patent document 1 or 2, as patent document 3 pointed out, it was a subject to satisfy
  • the inventor of the present invention has a low water permeability and excellent pH resistance by using an ionic crosslinking monomer having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than the acrylamide group. It has been found that a photocurable composition capable of forming a cured product is obtained.
  • the physical property value and each component of the photocurable composition of the present invention will be described.
  • the aromatic ring density of the photocurable composition is preferably 1 mmol / g or more, more preferably 1.5 mmol / g or more, still more preferably 2 mmol / g or more, and 2 to 4 mmol / g. It is particularly preferred that When it is in the above range, the water permeability of the obtained cured product is more excellent, and the membrane resistance is reduced.
  • Aromatic ring density of photocurable composition n a ⁇ w a / m a + n b ⁇ w b / m b
  • the charge density of the photocurable composition is preferably 1 mmol / g or more, more preferably 3 mmol / g or more, still more preferably 3.5 mmol / g or more, and 3.5 to 10 mmol / g. Particularly preferred is g. When it is in the above range, the film resistance of the obtained cured product becomes small.
  • the charge density of the photocurable composition is obtained by the following formula.
  • Charge density of the photocurable composition l a ⁇ w a / m a + l b ⁇ w b / m b
  • the photocurable composition of the present invention contains an ionic crosslinking monomer (hereinafter also referred to as “specific monomer”) having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than the acrylamide group.
  • the quaternary ammonium salt structure in the specific monomer is preferably a quaternary tetraalkylammonium salt structure.
  • a polymerizable group such as the acrylamide group or an aromatic ring may be bonded to the alkyl group bonded to the nitrogen atom in the quaternary tetraalkylammonium salt structure.
  • the quaternary ammonium salt structure preferably has at least two straight chain or branched alkyl groups directly bonded to the nitrogen atom, and is a straight chain having 1 to 8 carbon atoms directly bonded to the nitrogen atom or It preferably has at least two branched alkyl groups, and particularly preferably has at least two methyl groups directly bonded to a nitrogen atom.
  • the number of quaternary ammonium salt structures in the specific monomer may be 1 or more, preferably 1 to 4, more preferably 1 or 2, from the viewpoint of water permeability of the cured product obtained. Is particularly preferably 1.
  • the counter anion in the quaternary ammonium salt structure in the specific monomer is not particularly limited as long as it is an anion that neutralizes the charge, and may be a monovalent anion or a polyvalent anion. preferably there, Cl -, Br -, I - or CH 3 COO - more preferably, Cl - or Br - is more preferably, Cl - and particularly preferably.
  • the nitrogen atom of the quaternary ammonium salt structure in the specific monomer and the nitrogen atom of the acrylamide group are preferably bonded via 2 to 8 atoms in between. More preferably, they are bonded, and it is particularly preferable that they are bonded via 3 to 5 atoms.
  • the above intervening atoms are preferably carbon atoms.
  • the number of acrylamide groups in the specific monomer may be one or more, but is preferably 1 to 4, more preferably 1 or 2, from the viewpoint of water permeability and pH resistance of the obtained cured product. 1 is particularly preferred.
  • the polymerizable group other than the acrylamide group in the specific monomer is preferably an ethylenically unsaturated group, and more preferably a styryl group or a methacrylamide group. Further, the polymerizable group other than the acrylamide group in the specific monomer is particularly preferably a styryl group from the viewpoint of water permeability, and particularly preferably a methacrylamide group from the viewpoint of synthesis.
  • the number of polymerizable groups other than the acrylamide group in the specific monomer may be 1 or more, but is preferably 1 to 4 from the viewpoint of water permeability and pH resistance of the obtained cured product, and is 1 or 2. More preferably, 1 is particularly preferable.
  • the specific monomer preferably has the same number of acrylamide groups and polymerizable groups other than acrylamide groups, and particularly preferably has one acrylamide group and one polymerizable group other than the acrylamide group. It is excellent in the film resistance of the hardened
  • the specific monomer preferably includes a compound represented by the formula 1, and the polymerizable group other than the acrylamide group is an ⁇ -alkyl such as a methacrylamide group.
  • it is preferable to include the compound represented by Formula 2.
  • a 1 and B 1 each independently represent a divalent linking group
  • R 1 and R 2 each independently represent an alkyl group
  • X 1 ⁇ represents Cl ⁇ , Br ⁇ , I ⁇ .
  • Or represents CH 3 COO — .
  • a 2 , A 3 and B 2 each independently represent a divalent linking group
  • R 3 to R 6 each independently represents an alkyl group
  • R 7 represents an alkyl group
  • X 2 - and X 3- each independently, Cl -, Br -, I - or CH 3 COO - represents a.
  • the divalent linking group in A 1 of Formula 1 is an alkylene group, or one or more alkylene groups, and one or more linking groups selected from the group consisting of an arylene group, —O—, and —NR 8. It is preferably a combined group, more preferably an alkylene group.
  • R 8 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
  • the number of carbon atoms of the divalent linking group in A 1 is preferably 1-20, more preferably 2-20, still more preferably 3-8, and particularly preferably 3. preferable.
  • the divalent linking group in B 1 of Formula 1 is an alkylene group, or one or more alkylene groups, and one or more linking groups selected from the group consisting of an arylene group, —O—, and —NR 9. It is preferably a combined group, more preferably an alkylene group, and particularly preferably a methylene group.
  • R 9 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
  • the carbon number of the divalent linking group in B 1 is preferably 1 to 20, more preferably 1 to 8, still more preferably 1 to 4, and particularly preferably 1. preferable.
  • R 1 and R 2 in Formula 1 each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
  • the divalent linking groups in A 2 and A 3 of Formula 2 are each independently selected from the group consisting of an alkylene group, or one or more alkylene groups, an arylene group, —O—, and —NR 10.
  • a group obtained by combining the above linking groups is preferable, and an alkylene group is more preferable.
  • R 10 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
  • the carbon number of the divalent linking group in A 2 and A 3 is each independently preferably 1 to 20, more preferably 2 to 20, still more preferably 3 to 8, 3 is particularly preferred.
  • a 2 and A 3 in Formula 2 are preferably the same group.
  • the divalent linking group in B 2 of Formula 2 is an alkylene group, or one or more alkylene groups, and one or more linking groups selected from the group consisting of an arylene group, —O—, and —NR 11. It is preferably a combined group, more preferably an alkylene-arylene-alkylene group, still more preferably —CH 2 —C 6 H 4 —CH 2 —, —CH 2 —pC 6 H Particularly preferred is 4- CH 2 —.
  • R 11 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
  • the carbon number of the divalent linking group in B 2 is preferably 1 to 20, more preferably 2 to 20, further preferably 8 to 20, and particularly preferably 8. preferable.
  • R 3 to R 6 in Formula 2 each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
  • R 7 in Formula 2 represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
  • X 2 ⁇ and X 3 ⁇ in Formula 2 each independently represent Cl ⁇ , Br ⁇ , I ⁇ or CH 3 COO ⁇ , preferably Cl ⁇ or Br ⁇ , and more preferably Cl ⁇ . .
  • Preferred examples of the compound represented by Formula 1 or Formula 2 include the following compounds, but the present invention is not limited thereto.
  • the photocurable composition of the present invention may contain one specific monomer or two or more specific monomers.
  • the specific monomer is preferably contained in an amount of 5 to 80% by mass, more preferably 10 to 70% by mass, more preferably 10 to 60% by mass based on the total mass of the composition. More preferably, it is contained, particularly preferably 30 to 60% by mass.
  • the photocurable composition of the present invention preferably contains the specific monomer in an amount of 5 to 95 parts by mass, more preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total solid content of the composition. 30 to 90 parts by mass is more preferable, and 50 to 85 parts by mass is particularly preferable.
  • the total solid content of a photocurable composition means the component remove
  • the method for synthesizing the specific monomer is not particularly limited, and can be synthesized using a known method. Further, at the time of preparing the photocurable composition of the present invention, for example, a specific monomer may be separately synthesized and isolated, and the obtained specific monomer may be used. You may synthesize
  • the photocurable composition of the present invention contains a photopolymerization initiator. Therefore, the photocurable composition can be cured by a photopolymerization reaction.
  • the photopolymerization reaction may be simply referred to as “polymerization reaction” or “curing reaction”.
  • the photopolymerization initiator that can be used in the present invention is a compound that can initiate and accelerate a polymerization reaction of a polymerizable compound such as a compound having an ethylenically unsaturated group by actinic rays.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • a water-soluble photoinitiator is preferable.
  • the fact that the photopolymerization initiator is water-soluble means that it dissolves in distilled water at 0.1% by mass or more at 25 ° C.
  • the water-soluble photopolymerization initiator is more preferably dissolved by 1% by mass or more in distilled water at 25 ° C., particularly preferably 3% by mass or more.
  • aromatic ketone compounds As photopolymerization initiators, aromatic ketone compounds, acylphosphine compounds, aromatic onium salt compounds, oxime ester compounds, organic peroxide compounds, thio compounds, hexaarylbiimidazole compounds, borate compounds, azinium compounds, metallocene compounds, activity Examples thereof include ester compounds, compounds having a carbon halogen bond, and alkylamine compounds. Of these, aromatic ketone compounds or acylphosphine compounds are preferred, and compounds represented by the following formula PPI-1 or PPI-2 are more preferred.
  • R P1 and R P2 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group
  • R P3 represents an alkyl group, an alkoxy group, or an aryloxy group
  • L represents an integer of 0 to 5
  • R P4 represents an alkyl group, an aryl group, an alkylthio group or an arylthio group
  • R P5 represents an alkyl group, an aryl group, an alkylthio group, an arylthio group or an acyl group
  • R P6 Represents an alkyl group or an aryl group.
  • R P1 and R P2 or R P4 and R P5 may be bonded to each other to form a ring.
  • R P1 and R P2 are each independently preferably an alkyl group, an alkoxy group or an aryloxy group, more preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
  • An alkyl group is more preferable, and a methyl group is particularly preferable.
  • the ring formed by combining R P1 and R P2 with each other is preferably a 5- or 6-membered ring, and more preferably a cyclopentane ring or a cyclohexane ring.
  • R P3 is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the alkyl group, alkoxy group and aryloxy group may have a substituent.
  • the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
  • the aryl group as the substituent is preferably a phenyl group.
  • R P3 is more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydroxyethyl group.
  • the bonding position of RP3 on the aromatic ring is not particularly limited, and may be any position other than the position where the carbonyl group is bonded.
  • L represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 0 or 1.
  • the alkyl group in R P4 to R P6 is preferably an alkyl group having 1 to 8 carbon atoms
  • the aryl group in R P4 to R P6 is preferably an aryl group having 6 to 16 carbon atoms, and the aryl group has a substituent. You may have. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
  • the alkylthio group or arylthio group in R P4 and R P5 is preferably an alkylthio group having 1 to 12 carbon atoms or an arylthio group having 6 to 12 carbon atoms.
  • the acyl group in R P5 is preferably an alkylcarbonyl group or an arylcarbonyl group, more preferably an alkylcarbonyl group having 2 to 12 carbon atoms or an arylcarbonyl group having 7 to 17 carbon atoms.
  • R P5 is more preferably an arylcarbonyl group, particularly preferably a phenylcarbonyl group which may have a substituent.
  • the acyl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
  • RP6 is preferably an aryl group, more preferably a phenyl group which may have a substituent.
  • a compound represented by the formula PPI-1 is particularly preferred over a compound represented by the formula PPI-2.
  • Specific examples of the compound represented by Formula PPI-1 or Formula PPI-2 are shown below, but the present invention is not limited thereto.
  • the photocurable composition of the present invention may contain one photopolymerization initiator alone, or two or more photopolymerization initiators.
  • the content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the composition. More preferred is 0.5 to 5 parts by mass.
  • the photocurable composition of the present invention may contain a monomer other than the specific monomer (also referred to as “other monomer”). Although there is no restriction
  • the photocurable composition of the present invention preferably contains an ionic monofunctional monomer as the other monomer. As the ionic monofunctional monomer, a compound represented by the following formula IA is preferable.
  • R CA1 represents a hydrogen atom or an alkyl group
  • R CA2 to R CA4 each independently represents an alkyl group or an aryl group
  • two or more of R CA2 to R CA4 are bonded to each other to form a ring.
  • Z CA1 represents —O— or —N (R Ca ) —
  • R Ca represents a hydrogen atom or an alkyl group
  • L CA1 represents an alkylene group
  • X CA1 ⁇ represents a halide ion or Represents an aliphatic or aromatic carboxylate ion.
  • the alkyl group in R CA2 to R CA4 and R Ca is preferably a linear or branched alkyl group, and the carbon number thereof is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4. 1 or 2 is particularly preferable, and 1 is most preferable.
  • the carbon number of the aryl group in R CA2 to R CA4 is preferably 6 to 16, more preferably 6 to 12, and still more preferably 6 to 10. For example, a phenyl group and a naphthyl group are mentioned.
  • the ring formed by combining two or more of R CA2 to R CA4 with each other is preferably a 5- or 6-membered monocyclic or bridged ring, and preferably has 4 to 16 carbon atoms, preferably 4 to 10 carbon atoms. More preferred. Examples include pyrrolidine ring, piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, indole ring, and quinuclidine ring.
  • L CA1 preferably has 1 to 10 carbon atoms, more preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and most preferably 3.
  • Halide ions in X CA1 is fluoride ion, chloride ion, bromide ion, and iodide ion.
  • the carbon number of the aliphatic carboxylate ion in XCA1 is preferably 1 to 20, more preferably 2 to 10, still more preferably 2 to 5, particularly preferably 2 or 3, and most preferably 2.
  • the aliphatic carboxylic acid in the aliphatic carboxylate ion may be either a carboxylic acid in which a carboxyl group is bonded to a saturated hydrocarbon or a carboxylic acid in which a carboxyl group is bonded to an unsaturated hydrocarbon, but the saturated hydrocarbon has a carboxyl group.
  • a bound carboxylic acid is preferred.
  • the aromatic carboxylate ion in XCA1 is preferably an arylcarboxylate ion or a heteroarylcarboxylate ion.
  • the heteroaryl group in the heteroaryl sulfonate ion is preferably a 5- or 6-membered ring, and the hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.
  • the aromatic carboxylate ion has preferably 1 to 17 carbon atoms, more preferably 2 to 13 carbon atoms, and still more preferably 6 to 11 carbon atoms.
  • benzoate ion, naphthalenecarboxylate ion, nicotinate ion, and isonicotinic acid ion can be mentioned.
  • R CA1 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • R CA2 to R CA4 are preferably each independently a methyl group or an ethyl group.
  • Z CA1 is preferably —N (R Ca ) —.
  • R Ca is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • X CA1- is preferably Cl ⁇ , Br ⁇ , I ⁇ or CH 3 COO — .
  • the photocurable composition of the present invention includes, as other monomers, a group consisting of an ionic monofunctional monomer, a compound having one or more acrylamide groups, a compound having one or more methacrylamide groups, and a compound having one or more styryl groups. It is preferable that no monomer other than the compound selected from the above is included. As other monomers, an ionic monofunctional monomer, a compound having one or more acrylamide groups, a compound having one or more methacrylamide groups, and one styryl group More preferably, no monomer other than the compound selected from the group consisting of the compounds is included.
  • Examples of the compound having one or more acrylamide groups and the compound having one or more methacrylamide groups include 3-dimethylaminopropyl (meth) acrylamide and polymerizable groups at both ends of the compound represented by the above formula 2.
  • a compound in which both are acrylamide groups or a methacrylamide group in both are preferred.
  • Other monomers may be contained alone or in combination of two or more.
  • the content of other monomers in the composition is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and more preferably 10 to 40% by mass with respect to the total mass of the composition. More preferably.
  • the photocurable composition of the present invention may contain a solvent.
  • the solvent may be included singly or in combination of two or more.
  • the content of the solvent in the composition is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and more preferably 10 to 45% by mass with respect to the total mass of the composition. Further preferred is 20 to 40% by mass.
  • the water permeability of the cured product obtained is excellent, the film resistance is reduced, and the handleability is also excellent.
  • the curing (polymerization) reaction proceeds uniformly and smoothly.
  • the porous support is impregnated with the photocurable composition of the present invention, the impregnation proceeds smoothly.
  • the solvent water or a mixed liquid of a solvent having a solubility in water and water of 5% by mass or more is preferably used. Moreover, as said solvent, the solvent mixed freely with water is preferable. For this reason, the solvent selected from water and a water-soluble solvent is preferable.
  • 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.
  • alcohol solvent examples include methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like. These can be used alone or in combination of two or more.
  • aprotic polar solvent examples include dimethyl sulfoxide, dimethylimidazolidinone, sulfolane, N-methylpyrrolidone, dimethylformamide, acetonitrile, acetone, dioxane, tetramethylurea, hexamethylphosphoramide, hexamethylphosphorotriamide, Pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, ethylene glycol diacetate, ⁇ -butyrolactone and the like are mentioned as preferred solvents.
  • dimethyl sulfoxide N-methylpyrrolidone, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone or acetonitrile, and tetrahydrofuran are preferred. These can be used alone or in combination of two or more.
  • the solvent preferably includes water, more preferably water or a mixed solvent of water and an alcohol solvent, and particularly preferably a mixed solvent of water and an alcohol solvent.
  • a mixed solvent of water and an alcohol solvent a mixed solvent of water and isopropanol is particularly preferable.
  • the photocurable composition of the present invention may contain a polymerization inhibitor.
  • 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.
  • the phenol compound include hindered phenols (phenols having a t-butyl group at the ortho position, typically 2,6-di-t-butyl-4-methylphenol) and bisphenols.
  • Specific examples of the hydroquinone compound include monomethyl ether hydroquinone.
  • the amine compound include N-nitroso-N-phenylhydroxylamine and N, N-diethylhydroxylamine.
  • polymerization inhibitors may be used alone 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 photocurable composition. More preferably, the content is 0.01 to 0.5 parts by mass.
  • the photocurable composition of the present invention preferably contains a catalyst from the viewpoint of improving the solubility of the polymerizable compound used and / or improving the polymerization rate.
  • Preferred examples of the catalyst include alkali metal compounds.
  • the alkali metal compound lithium, sodium, potassium hydroxide salt, chloride salt, nitrate salt and the like are preferable. Among these, lithium compounds are more preferable.
  • the lithium compound examples include lithium hydroxide, lithium chloride, lithium bromide, lithium nitrate, lithium iodide, lithium chlorate, lithium thiocyanate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, And lithium hexafluoroarsenate.
  • the alkali metal compound is also preferably used for neutralizing the photocurable composition. These alkali metal compounds may be hydrates.
  • a catalyst can be used individually by 1 type or in combination of 2 or more types. The addition amount of the catalyst is preferably 0.1 to 35 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photocurable composition.
  • the photocurable composition of the present invention may contain known additives other than those described above as necessary.
  • surfactants for example, surfactants, viscosity improvers, polymer compounds, polymer dispersants, crater prevention
  • An agent for example, a plasticizer, a viscosity adjusting agent, an antioxidant, and / or a preservative may be contained.
  • various polymer compounds can be added in order to adjust film physical properties.
  • High molecular compounds include acrylic resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, vinyl resin, rubbers, waxes, and other natural resins. Etc. can be used. Moreover, these may be used individually by 1 type, or may use 2 or more types together.
  • the photocurable composition of the present invention may contain a polymer dispersant. Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide.
  • An anti-crater agent is also referred to as a surface tension adjusting agent, surface adjusting agent, leveling agent or slip agent, and is an additive for obtaining a uniform film surface.
  • organic modified polysiloxane polyether siloxane and polyether And a compound having a structure of a polyether-modified polysiloxane copolymer and a silicone-modified copolymer.
  • examples of commercially available products include, for example, Tego Glide 432, 110, 130, 406, 410, 411, 415, 420, 435, 440, 450, 482, and 480 manufactured by Evonik Industries. 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 of the photocurable composition.
  • the photocurable composition of the present invention contains a surfactant such as a nonionic surfactant, a cationic surfactant, or an organic fluoro compound in order to adjust the liquid properties of the coating liquid when forming a film. It may be.
  • a surfactant such as a nonionic surfactant, a cationic surfactant, or an organic fluoro compound in order to adjust the liquid properties of the coating liquid when forming a film. It may be.
  • 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-based surfactants, including such as a fluorine-based fluor
  • the cured product of the present invention is a cured product formed by curing the photocurable composition of the present invention.
  • the use of the cured product of the present invention is not particularly limited and can be used for various applications. Since the cured product of the present invention has a quaternary ammonium salt structure, an ion exchange resin (preferably anion exchange resin) is used. It also functions as a resin.
  • the cured product of the present invention can be suitably used for an ion exchange membrane (preferably an anion exchange membrane), a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte, or a water absorbent resin.
  • the shape of the cured product of the present invention is not particularly limited and may take a desired shape.
  • a polymer functional membrane such as an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane and a forward osmosis membrane, or a solid
  • the polymer electrolyte used in a polymer electrolyte fuel cell or the like is preferably in the form of a film, and the water absorbent resin is preferably in the form of a film, a sphere, or a bead.
  • the thickness of the polymer functional membrane such as an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane and a forward osmosis membrane is preferably 30 to 1,000 ⁇ m including the support when it has a support described later. 50 to 500 ⁇ m is more preferable, and 50 to 400 ⁇ m is still more preferable.
  • the support is preferably a porous support.
  • the porous support as a material for reinforcing the cured product is preferably a resin porous support, and has, for example, a nonwoven fabric such as a synthetic woven fabric or a synthetic nonwoven fabric, a sponge-like film, or fine through-holes.
  • a film is mentioned.
  • the film is preferably a film having at least a part of the cured product of the present invention inside the porous support.
  • membrane is a film
  • porous supports include, for example, polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyester, polyamide and copolymers thereof, or, for example, polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylenesulfide, polyimide, polyether. Imide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, polypropylene, poly (4-methyl-1-pentene), polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polychlorotrifluoroethylene And porous membranes formed using these copolymers.
  • porous supports are commercially available from, for example, Mitsubishi Paper Industries Co., Ltd., Nippon Kogyo Paper Industry Co., Ltd., Asahi Kasei Fibers Co., Ltd., Japan Vilene Co., Ltd., Tapils Co., Ltd., and Freudenberg Filtration Technologies.
  • the porous support when performing the polymerization reaction by energy ray irradiation, is required not to block the wavelength region of the energy ray, that is, to pass the irradiation of the wavelength used for the polymerization reaction.
  • the porous support is preferably a support through which the photocurable composition of the present invention can penetrate.
  • the porous support preferably has hydrophilicity.
  • general methods such as corona treatment, plasma treatment, fluorine gas treatment, ozone treatment, sulfuric acid treatment, and silane coupling agent treatment can be used.
  • the porous support that can be used in the present invention is preferably a nonwoven fabric, and more preferably a nonwoven fabric made of a composite fiber of polyethylene and polypropylene.
  • the fiber diameter of the composite fiber is preferably 0.5 to 15 ⁇ m, more preferably 1 to 13 ⁇ m, and particularly preferably 2 to 10 ⁇ m.
  • the thickness of the porous support that can be used in the present invention is preferably 20 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and particularly preferably 40 to 120 ⁇ m.
  • the photocurable composition of the present invention may be applied onto a substrate and photopolymerized, or obtained after photocuring the photocurable composition of the present invention in an arbitrary shape to obtain a cured product.
  • the cured product may be further processed into a desired shape.
  • the film can be suitably produced by impregnating or applying the photocurable composition of the present invention to the porous support and photopolymerizing it.
  • the film may be formed using a temporary support (attached to one or both surfaces of the porous support and peeled off from the film after completion of the curing reaction).
  • a temporary support attached to one or both surfaces of the porous support and peeled off from the film after completion of the curing reaction.
  • the cured product of the present invention particularly when the cured product of the present invention is formed into a film, it can be prepared in a batch system using a fixed support, or using a moving support. It can also be prepared in a continuous manner (continuous manner).
  • the temporary support does not need to consider material permeation.
  • any temporary support can be used as long as it can be fixed for film formation, including a metal plate such as an aluminum plate. It does n’t matter.
  • the photocurable composition of the present invention can be applied in various ways, 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 spraying.
  • the porous support can be applied or impregnated. Multiple layers can be applied simultaneously or sequentially.
  • curtain coating, slide coating, slot die coating and extrusion coating are preferred.
  • the production of the film obtained by curing the photocurable composition of the present invention in a continuous system is preferably performed by continuously applying the photocurable composition of the present invention to a moving support.
  • an application part for applying the photocurable composition of the present invention, an irradiation source for curing the photocurable composition of the present invention, a film winding part for collecting the formed film, and a support More preferably, it is manufactured by a manufacturing unit including means for moving from the application part to the irradiation source and the film winding part.
  • Examples of the method for producing a film obtained by curing the photocurable composition of the present invention include a step of applying or impregnating a porous support with the photocurable composition of the present invention, and a photocurable composition coated or impregnated. It is preferable that the method includes a step of polymerizing the product by light irradiation, and if necessary, further heating.
  • the application unit is provided at a position upstream of the irradiation source, and the irradiation source is positioned upstream of the collection unit.
  • the viscosity at 35 ° C. of the photocurable composition of the present invention is preferably less than 4,000 mPa ⁇ s, preferably 1 to 1,000 mPa ⁇ s in order to have sufficient fluidity when applied with a high-speed coater. More preferably, 1 to 500 mPa.s. s is more preferable. In the case of slide bead coating, the viscosity at 35 ° C. is preferably 1 to 100 mPa ⁇ s.
  • the photocurable composition of the present invention can be applied to a moving support at a speed exceeding 15 m / min, and can also be applied at a speed exceeding 20 m / min.
  • the support is treated with, for example, the wettability and adhesion of the support.
  • it may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment and the like.
  • the polymerization reaction of the photocurable composition of the present invention is preferably performed within 60 seconds, more preferably within 15 seconds, and particularly preferably within 5 seconds by applying or impregnating the photocurable composition of the present invention to a support. Most preferably, it starts within 3 seconds.
  • the light irradiation for 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.
  • irradiation is continuously performed, and the polymerization reaction time is determined in consideration of the speed at which the photocurable composition of the present invention moves through the irradiation beam.
  • UV light ultraviolet ray
  • the lamp of the light source and / or the support / film may be cooled with cooling air or the like.
  • IR light infrared
  • the UV light is irradiated using an IR reflective quartz plate as a filter.
  • the energy ray is preferably ultraviolet light.
  • the irradiation wavelength is preferably the same as the absorption wavelength of any photopolymerization initiator contained in the photocurable composition of the present invention. For example, UV-A (400 to 320 nm), UV-B (320 ⁇ 280 nm) and UV-C (280 ⁇ 200 nm).
  • UV sources are mercury arc lamp, carbon arc lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, swirling plasma arc lamp, metal halide lamp, xenon lamp, tungsten lamp, halogen lamp, laser and ultraviolet light emitting diode.
  • Medium pressure or high pressure mercury vapor type ultraviolet light emitting lamps are preferred.
  • additives such as metal halides may be present to modify the emission spectrum of the lamp.
  • a lamp having an emission maximum at 200 to 450 nm is particularly suitable.
  • the energy output of the irradiation source is preferably 20 to 1,000 W / cm, more preferably 40 to 500 W / cm, but it can be higher or lower if the desired exposure dose can be achieved. I do not care.
  • the degree of cure of the film can be adjusted by the exposure strength.
  • the exposure dose is preferably at least 40 mJ / cm 2 or more, more preferably 100 mJ / cm 2 or more, as measured in the UV-A range indicated by the apparatus with a High Energy UV Radiometer (UV Power Pack TM manufactured by EIT-Instrument Markets). ⁇ 2,000 mJ / cm 2 , particularly 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.
  • a plurality of light sources may be used to obtain a necessary exposure dose.
  • the plurality of light sources may have the same or different exposure intensity.
  • cured material of this invention may include arbitrary well-known processes other than the said process as needed.
  • the member of this invention is a member provided with the hardened
  • the apparatus of this invention is an apparatus provided with the hardened
  • the apparatus of the present invention is not particularly limited as long as it includes a cured product formed by curing the photocurable composition of the present invention.
  • a water treatment apparatus, a desalting apparatus, a pure water production apparatus, a concentration apparatus examples thereof include a device, a dialysis device, a purification device, and a combustion battery.
  • the member of the present invention is not particularly limited as long as it is provided with a cured product formed by curing the photocurable composition of the present invention, and examples thereof include a component member and a water absorbing material in the above apparatus.
  • Example 1 Synthesis of Compound M-1 (Synthesis of Ionic Crosslinking Monomer)> Compound M-1 was synthesized according to the following synthesis scheme.
  • ⁇ Preparation of photocurable composition> The obtained aqueous solution of Compound M-1 was returned to room temperature (25 ° C.), and then 32 parts of (3-acrylamidopropyl) trimethylammonium chloride 75% by weight aqueous solution (0.12 mol, Tokyo Chemical Industry Co., Ltd.) Product), 6.0 parts 2-propanol and 1.0 part Darocur 1173 (photopolymerization initiator, trade name, manufactured by Ciba Specialty Chemicals) A curable composition was obtained.
  • ⁇ Preparation of ion exchange membrane> The prepared photocurable composition was manually applied to an aluminum plate at a speed of about 5 m / min using a 150 ⁇ m wire winding rod, followed by a nonwoven fabric (manufactured by Freudenberg, FO-2226-14, below) Also referred to as “support”) was impregnated with a photocurable composition. Subsequently, the excess photocurable composition on an aluminum plate was removed using the rod which has not wound the wire.
  • the photocurable composition-impregnated support obtained as described above was subjected to 0 It was exposed for 47 seconds and cured by a polymerization reaction at a reaction time of 0.8 seconds to obtain a membrane (anion exchange membrane).
  • the obtained membrane was removed from the aluminum plate and stored in a 0.1 M NaCl aqueous solution for at least 12 hours to produce an ion exchange membrane.
  • the electric resistance r 1 of the ion exchange membrane was measured with an AC bridge (frequency: 1,000 Hz), and the NaCl concentration was measured under the conditions of 0.5M, 0.7M, 1.5M, 3.5M, or 4.5M. Then, the membrane was removed from the two-chamber cell, and the electrical resistance r2 was measured when only the 0.5 M NaCl aqueous solution was present between the two electrodes. the r It was determined by -r 2.
  • the membrane was immersed in an aqueous hydrochloric acid solution having a pH of 1 and an aqueous sodium hydroxide solution having a pH of 14, respectively, and kept at 40 ° C. for 3 hours.
  • the ratio (retention rate (%)) of the water permeability of the film after immersion to the water permeability of the film before immersion was calculated. Even if immersed in any one of a pH 1 aqueous hydrochloric acid solution and a pH 14 sodium hydroxide aqueous solution, the case where the retention rate of the water permeability of the membrane before and after immersion is 90% or more is “good”. The case where the retention rate was less than 90% was evaluated as “bad”.
  • Example 2 to 7 and Comparative Examples 1 and 2 In Examples 2 to 7 and Comparative Examples 1 and 2, a photocurable composition was prepared in the same manner as in Example 1 except that the compositions shown in Table 1 were changed. Similarly, an ion exchange membrane was produced. In Examples 3 to 7, the compounds (DCX or DBX) described in the other column were used in place of 4- (chloromethyl) styrene in Example 1. In Comparative Example 1, a crosslinking monomer (DVB) was used instead of (3-acrylamidopropyl) trimethylammonium chloride in Example 1. In the synthesis of the ionic crosslinking monomers of Examples 3 to 6, acrylamide and methacrylamide or methacrylate were used in combination.
  • DMAPA acrylamide
  • DMAPMA methacrylamide
  • DEAEMA methacrylate
  • DCX or DBX xylene
  • a diacrylamide compound in which two molecules of acrylamide are bonded to one molecule of xylene an acrylamide-methacrylamide or methacrylate compound in which one molecule of acrylamide and one molecule of methacrylamide or methacrylate are bonded to one molecule of xylene
  • xylene Dimethacrylamides in which two molecules of methacrylamide were bonded to one molecule were sequentially formed at a molar ratio of approximately 1: 2: 1.
  • Example 7 7% by mass of 25% by mass of DEAEMA remained unreacted without reacting with DBX in the aqueous solution of the ionic crosslinking monomer corresponding to the aqueous solution of Compound M-1 in Example 1. It was confirmed that In Example 7, it was confirmed that diacrylamide, acrylamide-methacrylate, and dimethacrylate were formed as ionic crosslinking monomers.
  • Table 1 The evaluation results are summarized in Table 1.
  • DMAPA N- [3- (dimethylamino) propyl] acrylamide, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound VBC: 4- (chloromethyl) styrene 25.7, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DMAPMA: N- [3- (dimethylamino) propyl] methacrylamide, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DMAEMA: 2- (dimethylamino) ethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DEAEMA: 2- ( Diethylamino) ethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DVB: divinylbenzene (m-, p-mixture), manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DMAPAAQ: 3-acrylamidopropyltrimethylammonium chloride (m-, p-mixture), manufactured by Tokyo Chemical Industry Co
  • Irgacure 2959 Photopolymerization initiator, manufactured by BASF, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, the following compound IPA: isopropyl alcohol, Wako Pure Chemical Industries, Ltd.
  • Membrane 2 Arrow indicating the flow of water separated from the feed solution 3: Feed solution channel 4: Draw solution channel 5: Liquid traveling direction 10: Channel

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Abstract

A cured material of a photocurable composition according to the present invention including a photopolymeriziation initiator and an ionic cross-linked monomer having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than an acrylamide group is formed by curing the photocurable composition, and the member or device according to the present invention is provided with the cured material formed by curing the photocurable composition.

Description

光硬化性組成物、硬化物、部材、及び、装置Photocurable composition, cured product, member, and apparatus
　本発明は、光硬化性組成物、硬化物、部材、及び、装置に関する。 The present invention relates to a photocurable composition, a cured product, a member, and an apparatus.
　高分子機能性膜としての各種の機能を有する膜として、イオン交換膜、逆浸透膜、正浸透膜又はガス分離膜等が知られている。
　例えば、イオン交換膜は、電気脱塩（ＥＤＩ：Ｅｌｅｃｔｒｏｄｅｉｏｎｉｚａｔｉｏｎ）、連続的な電気脱塩（ＣＥＤＩ：Ｃｏｎｔｉｎｕｏｕｓ　Ｅｌｅｃｔｒｏｄｅｉｏｎｉｚａｔｉｏｎ）、電気透析（ＥＤ：Ｅｌｅｃｔｒｏｄｉａｌｙｓｉｓ）、逆電気透析（ＥＤＲ：Ｅｌｅｃｔｒｏｄｉａｌｙｓｉｓ　ｒｅｖｅｒｓａｌ）等に用いられる。
　電気脱塩（ＥＤＩ）は、イオン輸送を達成するためにイオン交換膜と電位を使用して、水性液体からイオンが取り除かれる水処理プロセスである。従来のイオン交換のような他の浄水技術と異なり、酸又は苛性ソーダのような化学薬品の使用を要求せず、超純水を生産するために使用することができる。電気透析（ＥＤ）及び逆電気透析（ＥＤＲ）は、水及び他の流体からイオン等を取り除く電気化学の分離プロセスである。
　従来のイオン交換膜としては、特許文献１～３に記載のものが知られている。 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 ion exchange membranes and electrical potentials to achieve ion 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 conventional ion exchange membranes, those described in Patent Documents 1 to 3 are known.
米国特許出願公開第２０１２／０１６５４１９号明細書US Patent Application Publication No. 2012/0165419 米国特許第５１１８７１７号明細書US Pat. No. 5,118,717 特開２０１５－４７５３８号公報JP 2015-47538 A
　本発明が解決しようとする課題は、透水率が低く、ｐＨ耐性に優れた硬化物を得ることができる光硬化性組成物、上記光硬化性組成物を硬化して形成される硬化物、並びに、上記硬化物を備えた部材及び装置を提供することである。 The problem to be solved by the present invention is a photocurable composition capable of obtaining a cured product having low water permeability and excellent pH resistance, a cured product formed by curing the photocurable composition, and It is providing the member and apparatus provided with the said hardened | cured material.
　本発明の上記課題は、以下の＜１＞、＜９＞、＜１１＞又は＜１２＞に記載の手段により解決された。好ましい実施態様である＜２＞～＜８＞及び＜１０＞と共に以下に記載する。
　＜１＞第四級アンモニウム塩構造と、アクリルアミド基と、アクリルアミド基以外の重合性基とを有するイオン性架橋モノマー、及び、光重合開始剤を含む光硬化性組成物、
　＜２＞上記光硬化性組成物の芳香環密度が１．５ｍｍｏｌ／ｇ以上であり、かつ、電荷密度が３ｍｍｏｌ／ｇ以上である、＜１＞に記載の光硬化性組成物、
　＜３＞上記アクリルアミド基以外の重合性基が、スチリル基である、＜１＞又は＜２＞に記載の光硬化性組成物、
　＜４＞上記イオン性架橋モノマーが、下記式１で表される化合物を含む、＜１＞～＜３＞のいずれか１つに記載の光硬化性組成物、 The above-described problems of the present invention have been solved by the means described in <1>, <9>, <11> or <12> below. It is described below together with <2> to <8> and <10> which are preferred embodiments.
<1> a photocurable composition comprising a quaternary ammonium salt structure, an acrylamide group, an ionic crosslinking monomer having a polymerizable group other than an acrylamide group, and a photopolymerization initiator,
<2> The photocurable composition according to <1>, wherein the photocurable composition has an aromatic ring density of 1.5 mmol / g or more and a charge density of 3 mmol / g or more.
<3> The photocurable composition according to <1> or <2>, wherein the polymerizable group other than the acrylamide group is a styryl group,
<4> The photocurable composition according to any one of <1> to <3>, wherein the ionic crosslinking monomer includes a compound represented by the following formula 1:
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式１中、Ａ１及びＢ１はそれぞれ独立に、二価の連結基を表し、Ｒ１及びＲ２はそれぞれ独立に、アルキル基を表し、Ｘ１－は、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表す。 In Formula 1, A 1 and B 1 each independently represent a divalent linking group, R 1 and R 2 each independently represent an alkyl group, and X 1− represents Cl − , Br − , I −. Or represents CH 3 COO — .
　＜５＞上記アクリルアミド基以外の重合性基が、メタクリルアミド基である、＜１＞又は＜２＞に記載の光硬化性組成物、
　＜６＞上記イオン性架橋モノマーが、下記式２で表される化合物を含む、＜１＞、＜２＞又は＜５＞に記載の光硬化性組成物、 <5> The photocurable composition according to <1> or <2>, wherein the polymerizable group other than the acrylamide group is a methacrylamide group,
<6> The photocurable composition according to <1>, <2> or <5>, wherein the ionic crosslinking monomer includes a compound represented by the following formula 2.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式２中、Ａ２、Ａ３及びＢ２はそれぞれ独立に、二価の連結基を表し、Ｒ３～Ｒ６はそれぞれ独立に、アルキル基を表し、Ｒ７はアルキル基を表し、Ｘ２－及びＸ３－はそれぞれ独立に、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表す。 In Formula 2, A 2 , A 3 and B 2 each independently represent a divalent linking group, R 3 to R 6 each independently represents an alkyl group, R 7 represents an alkyl group, and X 2 - and X 3- each independently, Cl -, Br -, I - or CH 3 COO - represents a.
　＜７＞溶媒を更に含む、＜１＞～＜６＞のいずれか１つに記載の光硬化性組成物、
　＜８＞上記溶媒が、水を含む、＜７＞に記載の光硬化性組成物、
　＜９＞＜１＞～＜８＞のいずれか１つに記載の光硬化性組成物を硬化して形成される硬化物、
　＜１０＞上記硬化物が、イオン交換膜、プロトン伝導膜、逆浸透膜、正浸透膜、高分子電解質又は吸水性樹脂である、＜９＞に記載の硬化物、
　＜１１＞＜１＞～＜８＞のいずれか１つに記載の光硬化性組成物を硬化して形成された硬化物を備える部材、
　＜１２＞＜１＞～＜８＞のいずれか１つに記載の光硬化性組成物を硬化して形成された硬化物を備える装置。 <7> The photocurable composition according to any one of <1> to <6>, further comprising a solvent,
<8> The photocurable composition according to <7>, wherein the solvent contains water,
<9> A cured product formed by curing the photocurable composition according to any one of <1> to <8>,
<10> The cured product according to <9>, wherein the cured product is an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte, or a water absorbent resin.
<11> a member comprising a cured product formed by curing the photocurable composition according to any one of <1> to <8>,
<12> An apparatus comprising a cured product formed by curing the photocurable composition according to any one of <1> to <8>.
　本発明によれば、透水率が低く、ｐＨ耐性に優れた硬化物を得ることができる光硬化性組成物、上記光硬化性組成物を硬化して形成される硬化物、並びに、上記硬化物を備えた部材及び装置を提供することができた。 According to the present invention, a photocurable composition capable of obtaining a cured product having low water permeability and excellent pH resistance, a cured product formed by curing the photocurable composition, and the cured product. It was possible to provide a member and a device including the above.
膜の透水率を測定するための装置の流路の模式図である。It is a schematic diagram of the flow path of the apparatus for measuring the water permeability of a membrane.
　以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されない。なお、本明細書において「～」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
　本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有する基をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　更に、各式における二重結合の置換様式である幾何異性体は、表示の都合上、異性体の一方を記載したとしても、特段の断りがない限り、Ｅ体であってもＺ体であっても、これらの混合物であっても構わない。
　また、本明細書における化学構造式は、水素原子を省略した簡略構造式で記載する場合もある。
　なお、本明細書中において、“（メタ）アクリレート”はアクリレート及びメタクリレートを表し、“（メタ）アクリル”はアクリル及びメタクリルを表し、“（メタ）アクリロイル”はアクリロイル及びメタクリロイルを表し、”（メタ）アクリルアミド”はアクリルアミド及びメタクリルアミドを表す。また、“アクリル樹脂”は、（メタ）アクリレート化合物及び（メタ）アクリルアミド化合物よりなる群から選ばれた化合物の単独重合体又は共重合体であり、共重合体の場合は、上記化合物を樹脂全体の５０質量％以上共重合した樹脂であるものとする。
　また、本発明において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　また、本発明において、２以上の好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the notation of group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Furthermore, the geometrical isomer that is the substitution pattern of the double bond in each formula may be either E-form or Z-form, unless otherwise specified, even if one of the isomers is described for the convenience of display. Or a mixture thereof.
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In this specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, “(meth) acryloyl” represents acryloyl and methacryloyl, “(meth) ) Acrylamide "refers to acrylamide and methacrylamide. The “acrylic resin” is a homopolymer or copolymer of a compound selected from the group consisting of a (meth) acrylate compound and a (meth) acrylamide compound. It is assumed that the resin is copolymerized by 50% by mass or more.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.
（光硬化性組成物）
　本発明の光硬化性組成物（以下、単に「組成物」ともいう。）は、第四級アンモニウム塩構造と、アクリルアミド基と、アクリルアミド基以外の重合性基とを有するイオン性架橋モノマー、及び、光重合開始剤を含む。
　本発明の光硬化性組成物は、イオン交換膜、プロトン伝導膜、逆浸透膜、正浸透膜、高分子電解質又は吸水性樹脂用の、光硬化性組成物であることが好ましく、イオン交換膜用光硬化性組成物であることがより好ましい。また、イオン交換膜としては、アニオン交換膜が好ましい。
　なお、本発明における「光硬化性」とは、活性光線の照射により固体又はゲル状のものを形成可能であれば、特に制限はない。
　また、「活性光線」とは、その照射により後述する光重合開始剤より開始種を発生させることができるエネルギーを付与することができるエネルギー線であれば、特に制限はなく、広くα線、γ線、Ｘ線、紫外線（ＵＶ）、可視光線、電子線などを包含するものである。これらの中でも、紫外線を少なくとも含む光が好ましい。 (Photocurable composition)
The photocurable composition of the present invention (hereinafter also simply referred to as “composition”) includes an ionic crosslinking monomer having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than the acrylamide group, and And a photopolymerization initiator.
The photocurable composition of the present invention is preferably a photocurable composition for ion exchange membranes, proton conducting membranes, reverse osmosis membranes, forward osmosis membranes, polymer electrolytes or water-absorbing resins, and ion exchange membranes. It is more preferable that it is a photocurable composition. Moreover, as an ion exchange membrane, an anion exchange membrane is preferable.
The “photocurability” in the present invention is not particularly limited as long as a solid or gel-like material can be formed by irradiation with actinic rays.
In addition, the “active light” is not particularly limited as long as it is an energy ray that can give energy capable of generating an initiation species from a photopolymerization initiator described later by irradiation, and is broadly α-ray, γ Including X-rays, X-rays, ultraviolet rays (UV), visible rays, electron beams, and the like. Among these, light containing at least ultraviolet rays is preferable.
　特許文献３に記載された光硬化用途で用いられるアクリルアミド基を有するイオン性架橋モノマーは、硬化物のｐＨ耐性が十分とは言えなかった。他のイオン性架橋モノマーの例として、スチリル基又はメタクリルアミド基を有するモノマーが考えられるが、本発明者が検討したところ、ｐＨ耐性と光硬化性との両立が困難であった。
　また、スチリル基を有するイオン性架橋モノマーが、特許文献１又は２に記載されるが、特許文献３において指摘されているように、光硬化性を満たすことが課題であった。
　本発明者は鋭意検討した結果、第四級アンモニウム塩構造と、アクリルアミド基と、アクリルアミド基以外の重合性基とを有するイオン性架橋モノマーを用いることにより、透水率が低く、ｐＨ耐性に優れた硬化物を形成しうる光硬化性組成物が得られることを見出した。
　以下、本発明の光硬化性組成物の物性値及び各成分について説明する。 The ionic crosslinking monomer having an acrylamide group used in the photocuring application described in Patent Document 3 cannot be said to have sufficient pH resistance of the cured product. As another example of the ionic crosslinking monomer, a monomer having a styryl group or a methacrylamide group is conceivable. However, when the present inventor examined, it was difficult to achieve both pH resistance and photocurability.
Moreover, although the ionic crosslinking monomer which has a styryl group is described in patent document 1 or 2, as patent document 3 pointed out, it was a subject to satisfy | fill photocurability.
As a result of intensive studies, the inventor of the present invention has a low water permeability and excellent pH resistance by using an ionic crosslinking monomer having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than the acrylamide group. It has been found that a photocurable composition capable of forming a cured product is obtained.
Hereinafter, the physical property value and each component of the photocurable composition of the present invention will be described.
＜光硬化性組成物の芳香環密度＞
　光硬化性組成物の芳香環密度は、１ｍｍｏｌ／ｇ以上であることが好ましく、１．５ｍｍｏｌ／ｇ以上であることがより好ましく、２ｍｍｏｌ／ｇ以上であることが更に好ましく、２～４ｍｍｏｌ／ｇであることが特に好ましい。上記範囲であると、得られる硬化物の透水率がより優れ、膜抵抗が小さくなる。
　光硬化性組成物の芳香環密度の算出方法は、モノマーＡ中の芳香環数をｎａとし、モノマーＡの分子量をｍａとし、全モノマー成分中に占めるモノマーＡの質量分率をｗａとして、モノマーＡとモノマーＢとの２成分系の場合、光硬化性組成物の芳香環密度は、下記式で求められる。
　　　光硬化性組成物の芳香環密度＝ｎａ×ｗａ／ｍａ＋ｎｂ×ｗｂ／ｍｂ <Aromatic ring density of photocurable composition>
The aromatic ring density of the photocurable composition is preferably 1 mmol / g or more, more preferably 1.5 mmol / g or more, still more preferably 2 mmol / g or more, and 2 to 4 mmol / g. It is particularly preferred that When it is in the above range, the water permeability of the obtained cured product is more excellent, and the membrane resistance is reduced.
The method of calculating the aromatic ring density of the photocurable composition, the number of aromatic rings in the monomer A and n a, the molecular weight of the monomer A and m a, the mass fraction of the monomers A in the total monomer components w a In the case of a two-component system of monomer A and monomer B, the aromatic ring density of the photocurable composition is obtained by the following formula.
Aromatic ring density of photocurable composition = n a × w a / m a + n b × w b / m b
＜光硬化性組成物の電荷密度＞
　光硬化性組成物の電荷密度は、１ｍｍｏｌ／ｇ以上であることが好ましく、３ｍｍｏｌ／ｇ以上であることがより好ましく、３．５ｍｍｏｌ／ｇ以上であることが更に好ましく、３．５～１０ｍｍｏｌ／ｇであることが特に好ましい。上記範囲であると、得られる硬化物の膜抵抗が小さくなる。
　光硬化性組成物の電荷密度の算出方法は、モノマーＡ中の４級アミンの数をｌａとし、モノマーＡの分子量をｍａとし、全モノマー成分中に占めるモノマーＡの重量分率をｗａとして、モノマーＡとモノマーＢとの２成分系の場合、光硬化性組成物の電荷密度は、下記式で求められる。
　　　光硬化性組成物の電荷密度＝ｌａ×ｗａ／ｍａ＋ｌｂ×ｗｂ／ｍｂ <Charge density of the photocurable composition>
The charge density of the photocurable composition is preferably 1 mmol / g or more, more preferably 3 mmol / g or more, still more preferably 3.5 mmol / g or more, and 3.5 to 10 mmol / g. Particularly preferred is g. When it is in the above range, the film resistance of the obtained cured product becomes small.
The method of calculating the charge density of the photocurable composition, the number of quaternary amine in the monomer A and l a, the molecular weight of the monomer A and m a, the weight fraction of monomer A in the total monomer components w In the case of a two-component system of monomer A and monomer B as a, the charge density of the photocurable composition is obtained by the following formula.
Charge density of the photocurable composition = l a × w a / m a + l b × w b / m b
＜第四級アンモニウム塩構造と、アクリルアミド基と、アクリルアミド基以外の重合性基とを有するイオン性架橋モノマー＞
　本発明の光硬化性組成物は、第四級アンモニウム塩構造と、アクリルアミド基と、アクリルアミド基以外の重合性基とを有するイオン性架橋モノマー（以下、「特定モノマー」ともいう。）を含む。
　特定モノマーにおける第四級アンモニウム塩構造は、第四級テトラアルキルアンモニウム塩構造であることが好ましい。なお、第四級テトラアルキルアンモニウム塩構造における窒素原子に結合したアルキル基には、上記アクリルアミド基等の重合性基や芳香環が結合していてもよい。
　また、上記第四級アンモニウム塩構造は、窒素原子に直接結合した直鎖又は分岐アルキル基を少なくとも２つ有していることが好ましく、窒素原子に直接結合した炭素数１～８の直鎖又は分岐アルキル基を少なくとも２つ有していることが好ましく、窒素原子に直接結合したメチル基を少なくとも２つ有していることが特に好ましい。
　特定モノマーにおける第四級アンモニウム塩構造の数は、１以上であればよいが、１～４であることが好ましく、１又は２であることがより好ましく、得られる硬化物の透水率の観点からは、１であることが特に好ましい。
　特定モノマーにおける第四級アンモニウム塩構造における対アニオンは、電荷を中和するアニオンであれば特に制限はなく、一価アニオンであっても、多価アニオンであってもよいが、一価アニオンであることが好ましく、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－であることがより好ましく、Ｃｌ－又はＢｒ－であることが更に好ましく、Ｃｌ－であることが特に好ましい。
　また、特定モノマーにおける第四級アンモニウム塩構造の窒素原子と、アクリルアミド基の窒素原子とは、２～８原子を間に介して結合していることが好ましく、３～８原子を間に介して結合していることがより好ましく、３～５原子を間に介して結合していることが特に好ましい。間に介する上記原子は、炭素原子であることが好ましい。 <Ionic crosslinking monomer having quaternary ammonium salt structure, acrylamide group, and polymerizable group other than acrylamide group>
The photocurable composition of the present invention contains an ionic crosslinking monomer (hereinafter also referred to as “specific monomer”) having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than the acrylamide group.
The quaternary ammonium salt structure in the specific monomer is preferably a quaternary tetraalkylammonium salt structure. A polymerizable group such as the acrylamide group or an aromatic ring may be bonded to the alkyl group bonded to the nitrogen atom in the quaternary tetraalkylammonium salt structure.
The quaternary ammonium salt structure preferably has at least two straight chain or branched alkyl groups directly bonded to the nitrogen atom, and is a straight chain having 1 to 8 carbon atoms directly bonded to the nitrogen atom or It preferably has at least two branched alkyl groups, and particularly preferably has at least two methyl groups directly bonded to a nitrogen atom.
The number of quaternary ammonium salt structures in the specific monomer may be 1 or more, preferably 1 to 4, more preferably 1 or 2, from the viewpoint of water permeability of the cured product obtained. Is particularly preferably 1.
The counter anion in the quaternary ammonium salt structure in the specific monomer is not particularly limited as long as it is an anion that neutralizes the charge, and may be a monovalent anion or a polyvalent anion. preferably there, Cl -, Br -, I - or CH 3 COO - more preferably, Cl - or Br - is more preferably, Cl - and particularly preferably.
In addition, the nitrogen atom of the quaternary ammonium salt structure in the specific monomer and the nitrogen atom of the acrylamide group are preferably bonded via 2 to 8 atoms in between. More preferably, they are bonded, and it is particularly preferable that they are bonded via 3 to 5 atoms. The above intervening atoms are preferably carbon atoms.
　特定モノマーにおけるアクリルアミド基の数は、１以上であればよいが、得られる硬化物の透水率及びｐＨ耐性の観点から、１～４であることが好ましく、１又は２であることがより好ましく、１であることが特に好ましい。
　特定モノマーにおけるアクリルアミド基以外の重合性基としては、エチレン性不飽和基であることが好ましく、スチリル基又はメタクリルアミド基であることがより好ましい。
　また、特定モノマーにおけるアクリルアミド基以外の重合性基としては、透水率の観点から、スチリル基であることが特に好ましく、また、合成上の観点からは、メタクリルアミド基であることが特に好ましい。
　特定モノマーにおけるアクリルアミド基以外の重合性基の数は、１以上であればよいが、得られる硬化物の透水率及びｐＨ耐性の観点から、１～４であることが好ましく、１又は２であることがより好ましく、１であることが特に好ましい。
　また、特定モノマーは、アクリルアミド基と、アクリルアミド基以外の重合性基とを同数有することが好ましく、アクリルアミド基を１つと、アクリルアミド基以外の重合性基を１つ有することが特に好ましい。上記態様であると、得られる硬化物の膜抵抗に優れ、また、得られる硬化物の透水率及びｐＨ耐性により優れる。 The number of acrylamide groups in the specific monomer may be one or more, but is preferably 1 to 4, more preferably 1 or 2, from the viewpoint of water permeability and pH resistance of the obtained cured product. 1 is particularly preferred.
The polymerizable group other than the acrylamide group in the specific monomer is preferably an ethylenically unsaturated group, and more preferably a styryl group or a methacrylamide group.
Further, the polymerizable group other than the acrylamide group in the specific monomer is particularly preferably a styryl group from the viewpoint of water permeability, and particularly preferably a methacrylamide group from the viewpoint of synthesis.
The number of polymerizable groups other than the acrylamide group in the specific monomer may be 1 or more, but is preferably 1 to 4 from the viewpoint of water permeability and pH resistance of the obtained cured product, and is 1 or 2. More preferably, 1 is particularly preferable.
The specific monomer preferably has the same number of acrylamide groups and polymerizable groups other than acrylamide groups, and particularly preferably has one acrylamide group and one polymerizable group other than the acrylamide group. It is excellent in the film resistance of the hardened | cured material obtained as it is the said aspect, and it is excellent by the water permeability and pH tolerance of the hardened | cured material obtained.
　特定モノマーとしては、アクリルアミド基以外の重合性基がスチリル基である場合、式１で表される化合物を含むことが好ましく、また、アクリルアミド基以外の重合性基がメタクリルアミド基等のα－アルキルアクリルアミド基である場合、式２で表される化合物を含むことが好ましい。 When the polymerizable group other than the acrylamide group is a styryl group, the specific monomer preferably includes a compound represented by the formula 1, and the polymerizable group other than the acrylamide group is an α-alkyl such as a methacrylamide group. When it is an acrylamide group, it is preferable to include the compound represented by Formula 2.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式１中、Ａ１及びＢ１はそれぞれ独立に、二価の連結基を表し、Ｒ１及びＲ２はそれぞれ独立に、アルキル基を表し、Ｘ１－は、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表す。 In Formula 1, A 1 and B 1 each independently represent a divalent linking group, R 1 and R 2 each independently represent an alkyl group, and X 1− represents Cl − , Br − , I −. Or represents CH 3 COO — .
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式２中、Ａ２、Ａ３及びＢ２はそれぞれ独立に、二価の連結基を表し、Ｒ３～Ｒ６はそれぞれ独立に、アルキル基を表し、Ｒ７はアルキル基を表し、Ｘ２－及びＸ３－はそれぞれ独立に、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表す。 In Formula 2, A 2 , A 3 and B 2 each independently represent a divalent linking group, R 3 to R 6 each independently represents an alkyl group, R 7 represents an alkyl group, and X 2 - and X 3- each independently, Cl -, Br -, I - or CH 3 COO - represents a.
　式１のＡ１における二価の連結基は、アルキレン基、又は、１つ以上のアルキレン基と、アリーレン基、－Ｏ－及び－ＮＲ８よりなる群から選ばれた１以上の連結基とを組み合わせた基であることが好ましく、アルキレン基であることがより好ましい。Ｒ８は、アルキル基又はアリール基を表し、炭素数１～８のアルキル基であることが好ましく、メチル基であることがより好ましい。
　また、Ａ１における二価の連結基の炭素数は、１～２０であることが好ましく、２～２０であることがより好ましく、３～８であることが更に好ましく、３であることが特に好ましい。
　式１のＢ１における二価の連結基は、アルキレン基、又は、１つ以上のアルキレン基と、アリーレン基、－Ｏ－及び－ＮＲ９よりなる群から選ばれた１以上の連結基とを組み合わせた基であることが好ましく、アルキレン基であることがより好ましく、メチレン基であることが特に好ましい。Ｒ９は、アルキル基又はアリール基を表し、炭素数１～８のアルキル基であることが好ましく、メチル基であることがより好ましい。
　また、Ｂ１における二価の連結基の炭素数は、１～２０であることが好ましく、１～８であることがより好ましく、１～４であることが更に好ましく、１であることが特に好ましい。 The divalent linking group in A 1 of Formula 1 is an alkylene group, or one or more alkylene groups, and one or more linking groups selected from the group consisting of an arylene group, —O—, and —NR 8. It is preferably a combined group, more preferably an alkylene group. R 8 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
The number of carbon atoms of the divalent linking group in A 1 is preferably 1-20, more preferably 2-20, still more preferably 3-8, and particularly preferably 3. preferable.
The divalent linking group in B 1 of Formula 1 is an alkylene group, or one or more alkylene groups, and one or more linking groups selected from the group consisting of an arylene group, —O—, and —NR 9. It is preferably a combined group, more preferably an alkylene group, and particularly preferably a methylene group. R 9 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
In addition, the carbon number of the divalent linking group in B 1 is preferably 1 to 20, more preferably 1 to 8, still more preferably 1 to 4, and particularly preferably 1. preferable.
　式１におけるＲ１及びＲ２はそれぞれ独立に、アルキル基を表し、炭素数１～８のアルキル基であることが好ましく、メチル基であることがより好ましい。
　式１におけるＸ１－は、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表し、Ｃｌ－又はＢｒ－であることが好ましく、Ｃｌ－であることがより好ましい。 R 1 and R 2 in Formula 1 each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
X 1- in Formula 1, Cl -, Br -, I - or CH 3 COO - represents, Cl - or Br - is preferably, Cl - is more preferable.
　式２のＡ２及びＡ３における二価の連結基はそれぞれ独立に、アルキレン基、又は、１つ以上のアルキレン基と、アリーレン基、－Ｏ－及び－ＮＲ１０よりなる群から選ばれた１以上の連結基とを組み合わせた基であることが好ましく、アルキレン基であることがより好ましい。Ｒ１０は、アルキル基又はアリール基を表し、炭素数１～８のアルキル基であることが好ましく、メチル基であることがより好ましい。
　また、Ａ２及びＡ３における二価の連結基の炭素数はそれぞれ独立に、１～２０であることが好ましく、２～２０であることがより好ましく、３～８であることが更に好ましく、３であることが特に好ましい。
　更に、式２におけるＡ２及びＡ３は、同じ基であることが好ましい。
　式２のＢ２における二価の連結基は、アルキレン基、又は、１つ以上のアルキレン基と、アリーレン基、－Ｏ－及び－ＮＲ１１よりなる群から選ばれた１以上の連結基とを組み合わせた基であることが好ましく、アルキレン－アリーレン－アルキレン基であることがより好ましく、－ＣＨ２－Ｃ６Ｈ４－ＣＨ２－であることが更に好ましく、－ＣＨ２－ｐ－Ｃ６Ｈ４－ＣＨ２－であることが特に好ましい。Ｒ１１は、アルキル基又はアリール基を表し、炭素数１～８のアルキル基であることが好ましく、メチル基であることがより好ましい。
　また、Ｂ２における二価の連結基の炭素数は、１～２０であることが好ましく、２～２０であることがより好ましく、８～２０であることが更に好ましく、８であることが特に好ましい。 The divalent linking groups in A 2 and A 3 of Formula 2 are each independently selected from the group consisting of an alkylene group, or one or more alkylene groups, an arylene group, —O—, and —NR 10. A group obtained by combining the above linking groups is preferable, and an alkylene group is more preferable. R 10 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
In addition, the carbon number of the divalent linking group in A 2 and A 3 is each independently preferably 1 to 20, more preferably 2 to 20, still more preferably 3 to 8, 3 is particularly preferred.
Furthermore, A 2 and A 3 in Formula 2 are preferably the same group.
The divalent linking group in B 2 of Formula 2 is an alkylene group, or one or more alkylene groups, and one or more linking groups selected from the group consisting of an arylene group, —O—, and —NR 11. It is preferably a combined group, more preferably an alkylene-arylene-alkylene group, still more preferably —CH 2 —C 6 H 4 —CH 2 —, —CH 2 —pC 6 H Particularly preferred is 4- CH 2 —. R 11 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
Further, the carbon number of the divalent linking group in B 2 is preferably 1 to 20, more preferably 2 to 20, further preferably 8 to 20, and particularly preferably 8. preferable.
　式２におけるＲ３～Ｒ６はそれぞれ独立に、アルキル基を表し、炭素数１～８のアルキル基であることが好ましく、メチル基であることがより好ましい。
　式２におけるＲ７は、アルキル基を表し、炭素数１～８のアルキル基であることが好ましく、メチル基であることがより好ましい。
　式２におけるＸ２－及びＸ３－はそれぞれ独立に、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表し、Ｃｌ－又はＢｒ－であることが好ましく、Ｃｌ－であることがより好ましい。 R 3 to R 6 in Formula 2 each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
R 7 in Formula 2 represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
X 2− and X 3− in Formula 2 each independently represent Cl − , Br − , I − or CH 3 COO − , preferably Cl − or Br − , and more preferably Cl −. .
　式１又は式２で表される化合物としては、下記に示す化合物が好ましく挙げられるが、本発明はこれらに限定されない。 Preferred examples of the compound represented by Formula 1 or Formula 2 include the following compounds, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　本発明の光硬化性組成物は、特定モノマーを１種単独で含有していてもよく、２種以上を含有していてもよい。
　本発明の光硬化性組成物は、特定モノマーを、組成物の全質量に対し、５～８０質量％含有することが好ましく、１０～７０質量％含有することがより好ましく、１０～６０質量％含有することが更に好ましく、３０～６０質量％含有することが特に好ましい。
　また、本発明の光硬化性組成物は、特定モノマーを、組成物の全固形分１００質量部に対し、５～９５質量部含有することが好ましく、１０～９０質量部含有することがより好ましく、３０～９０質量部含有することが更に好ましく、５０～８５質量部含有することが特に好ましい。
　なお、光硬化性組成物の全固形分とは、光硬化性組成物から溶媒などの揮発成分を除いた成分を意味する。 The photocurable composition of the present invention may contain one specific monomer or two or more specific monomers.
In the photocurable composition of the present invention, the specific monomer is preferably contained in an amount of 5 to 80% by mass, more preferably 10 to 70% by mass, more preferably 10 to 60% by mass based on the total mass of the composition. More preferably, it is contained, particularly preferably 30 to 60% by mass.
In addition, the photocurable composition of the present invention preferably contains the specific monomer in an amount of 5 to 95 parts by mass, more preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total solid content of the composition. 30 to 90 parts by mass is more preferable, and 50 to 85 parts by mass is particularly preferable.
In addition, the total solid content of a photocurable composition means the component remove | excluding volatile components, such as a solvent, from a photocurable composition.
　特定モノマーの合成方法は、特に制限はなく、公知の方法を用いて合成することができる。
　また、本発明の光硬化性組成物の調製時において、例えば、特定モノマーを別途合成し単離して、得られた特定モノマーを用いてもよいし、特定モノマーの原料を混合して特定モノマーを合成し、特定モノマーを含む混合物をそのまま用いて、光硬化性組成物を調製してもよい。 The method for synthesizing the specific monomer is not particularly limited, and can be synthesized using a known method.
Further, at the time of preparing the photocurable composition of the present invention, for example, a specific monomer may be separately synthesized and isolated, and the obtained specific monomer may be used. You may synthesize | combine and prepare a photocurable composition using the mixture containing a specific monomer as it is.
＜光重合開始剤＞
　本発明の光硬化性組成物は、光重合開始剤を含む。したがって、光硬化性組成物を光重合反応により硬化することができる。本明細書において、以下、光重合反応を単に「重合反応」または「硬化反応」ということがある。
　本発明に用いることができる光重合開始剤は、活性光線により、エチレン性不飽和基を有する化合物等の重合性化合物の重合反応を開始可能であり、促進可能な化合物である。
　光重合開始剤としては、光ラジカル重合開始剤であることが好ましい。
　また、光重合開始剤としては、水溶性の光重合開始剤が好ましい。
　ここで、光重合開始剤が水溶性であることは、２５℃において蒸留水に０．１質量％以上溶解することを意味する。水溶性の光重合開始剤は、２５℃において蒸留水に１質量％以上溶解することが更に好ましく、３質量％以上溶解することが特に好ましい。
　光重合開始剤としては、芳香族ケトン化合物、アシルホスフィン化合物、芳香族オニウム塩化合物、オキシムエステル化合物、有機過酸化化合物、チオ化合物、ヘキサアリールビイミダゾール化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、及び、アルキルアミン化合物等が挙げられる。
　中でも、芳香族ケトン化合物、又は、アシルホスフィン化合物が好ましく挙げられ、下記式ＰＰＩ－１又は式ＰＰＩ－２で表される化合物がより好ましく挙げられる。 <Photopolymerization initiator>
The photocurable composition of the present invention contains a photopolymerization initiator. Therefore, the photocurable composition can be cured by a photopolymerization reaction. In the present specification, hereinafter, the photopolymerization reaction may be simply referred to as “polymerization reaction” or “curing reaction”.
The photopolymerization initiator that can be used in the present invention is a compound that can initiate and accelerate a polymerization reaction of a polymerizable compound such as a compound having an ethylenically unsaturated group by actinic rays.
The photopolymerization initiator is preferably a radical photopolymerization initiator.
Moreover, as a photoinitiator, a water-soluble photoinitiator is preferable.
Here, the fact that the photopolymerization initiator is water-soluble means that it dissolves in distilled water at 0.1% by mass or more at 25 ° C. The water-soluble photopolymerization initiator is more preferably dissolved by 1% by mass or more in distilled water at 25 ° C., particularly preferably 3% by mass or more.
As photopolymerization initiators, aromatic ketone compounds, acylphosphine compounds, aromatic onium salt compounds, oxime ester compounds, organic peroxide compounds, thio compounds, hexaarylbiimidazole compounds, borate compounds, azinium compounds, metallocene compounds, activity Examples thereof include ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Of these, aromatic ketone compounds or acylphosphine compounds are preferred, and compounds represented by the following formula PPI-1 or PPI-2 are more preferred.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式ＰＰＩ－１及び式ＰＰＩ－２において、ＲＰ１及びＲＰ２はそれぞれ独立に、水素原子、アルキル基、アルコキシ基又はアリールオキシ基を表し、ＲＰ３はアルキル基、アルコキシ基又はアリールオキシ基を表し、Ｌは０～５の整数を表し、ＲＰ４はアルキル基、アリール基、アルキルチオ基又はアリールチオ基を表し、ＲＰ５はアルキル基、アリール基、アルキルチオ基、アリールチオ基又はアシル基を表し、ＲＰ６はアルキル基又はアリール基を表す。ここで、ＲＰ１とＲＰ２、又は、ＲＰ４とＲＰ５が互いに結合して環を形成してもよい。 In the formulas PPI-1 and PPI-2, R P1 and R P2 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and R P3 represents an alkyl group, an alkoxy group, or an aryloxy group , L represents an integer of 0 to 5, R P4 represents an alkyl group, an aryl group, an alkylthio group or an arylthio group, R P5 represents an alkyl group, an aryl group, an alkylthio group, an arylthio group or an acyl group, and R P6 Represents an alkyl group or an aryl group. Here, R P1 and R P2 or R P4 and R P5 may be bonded to each other to form a ring.
　ＲＰ１及びＲＰ２はそれぞれ独立に、アルキル基、アルコキシ基又はアリールオキシ基が好ましく、炭素数１～８のアルキル基、炭素数１～８のアルコキシ基、炭素数６～１０のアリール基がより好ましく、アルキル基が更に好ましく、メチル基が特に好ましい。
　ＲＰ１及びＲＰ２が互いに結合して形成する環は、５又は６員環が好ましく、シクロペンタン環又はシクロヘキサン環がより好ましい。
　ＲＰ３は炭素数１～１８のアルキル基、炭素数１～１０のアルコキシ基又は炭素数６～１２のアリール基が好ましく、アルキル基、アルコキシ基、アリールオキシ基は置換基を有してもよい。上記置換基としては、ハロゲン原子、アルキル基、アリール基、アルコキシ基、ヒドロキシ基等が挙げられる。
　上記置換基としての上記アリール基は、フェニル基が好ましい。
　ＲＰ３は、炭素数１～４のアルキル基であることがより好ましく、ヒドロキシエチル基が特に好ましい。
　また、芳香環上のＲＰ３の結合位置は、特に制限はなく、カルボニル基が結合している位置以外であればよい。
　Ｌは、０～５の整数を表し、０～３の整数が好ましく、０又は１がより好ましい。 R P1 and R P2 are each independently preferably an alkyl group, an alkoxy group or an aryloxy group, more preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. An alkyl group is more preferable, and a methyl group is particularly preferable.
The ring formed by combining R P1 and R P2 with each other is preferably a 5- or 6-membered ring, and more preferably a cyclopentane ring or a cyclohexane ring.
R P3 is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the alkyl group, alkoxy group and aryloxy group may have a substituent. . Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
The aryl group as the substituent is preferably a phenyl group.
R P3 is more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydroxyethyl group.
Further, the bonding position of RP3 on the aromatic ring is not particularly limited, and may be any position other than the position where the carbonyl group is bonded.
L represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 0 or 1.
　ＲＰ４～ＲＰ６におけるアルキル基は、炭素数１～８のアルキル基が好ましく、また、ＲＰ４～ＲＰ６におけるアリール基は、炭素数６～１６のアリール基が好ましく、アリール基は置換基を有してもよい。上記置換基としては、ハロゲン原子、アルキル基、アリール基、アルコキシ基、ヒドロキシ基等が挙げられる。
　ＲＰ４及びＲＰ５におけるアルキルチオ基又はアリールチオ基は、炭素数１～１２のアルキルチオ基又は炭素数６～１２のアリールチオ基が好ましい。
　ＲＰ５におけるアシル基は、アルキルカルボニル基又はアリールカルボニル基が好ましく、炭素数２～１２のアルキルカルボニル基又は炭素数７～１７のアリールカルボニル基がより好ましい。
　ＲＰ５は、アリールカルボニル基であることが更に好ましく、置換基を有してもよいフェニルカルボニル基が特に好ましい。アシル基は置換基を有してもよく、上記置換基としては、ハロゲン原子、アルキル基、アリール基、アルコキシ基、ヒドロキシ基等が挙げられる。
　ＲＰ６は、アリール基であることが好ましく、置換基を有してもよいフェニル基であることがより好ましい。 The alkyl group in R P4 to R P6 is preferably an alkyl group having 1 to 8 carbon atoms, and the aryl group in R P4 to R P6 is preferably an aryl group having 6 to 16 carbon atoms, and the aryl group has a substituent. You may have. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
The alkylthio group or arylthio group in R P4 and R P5 is preferably an alkylthio group having 1 to 12 carbon atoms or an arylthio group having 6 to 12 carbon atoms.
The acyl group in R P5 is preferably an alkylcarbonyl group or an arylcarbonyl group, more preferably an alkylcarbonyl group having 2 to 12 carbon atoms or an arylcarbonyl group having 7 to 17 carbon atoms.
R P5 is more preferably an arylcarbonyl group, particularly preferably a phenylcarbonyl group which may have a substituent. The acyl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
RP6 is preferably an aryl group, more preferably a phenyl group which may have a substituent.
　光重合開始剤としては、式ＰＰＩ－２で表される化合物よりも、式ＰＰＩ－１で表される化合物が特に好ましい。
　以下に、式ＰＰＩ－１又は式ＰＰＩ－２で表される化合物の具体例を示すが、本発明はこれらに限定されない。 As the photopolymerization initiator, a compound represented by the formula PPI-1 is particularly preferred over a compound represented by the formula PPI-2.
Specific examples of the compound represented by Formula PPI-1 or Formula PPI-2 are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　本発明の光硬化性組成物は、光重合開始剤を１種単独で含有していてもよく、２種以上を含有していてもよい。
　本発明の光硬化性組成物において、光重合開始剤の含有量は、組成物中の全固形分１００質量部に対し、０．１～２０質量部が好ましく、０．１～１０質量部がより好ましく、０．５～５質量部が特に好ましい。 The photocurable composition of the present invention may contain one photopolymerization initiator alone, or two or more photopolymerization initiators.
In the photocurable composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the composition. More preferred is 0.5 to 5 parts by mass.
＜その他のモノマー＞
　本発明の光硬化性組成物は、特定モノマー以外のモノマー（「その他のモノマー」ともいう。）を含んでいてもよい。
　その他のモノマーとしては、特に制限はないが、エチレン性不飽和化合物であることが好ましい。
　本発明の光硬化性組成物は、その他のモノマーとして、イオン性単官能モノマーを含むことが好ましい。
　イオン性単官能モノマーとしては、下記式ＩＡで表される化合物が好ましい。 <Other monomers>
The photocurable composition of the present invention may contain a monomer other than the specific monomer (also referred to as “other monomer”).
Although there is no restriction | limiting in particular as another monomer, It is preferable that it is an ethylenically unsaturated compound.
The photocurable composition of the present invention preferably contains an ionic monofunctional monomer as the other monomer.
As the ionic monofunctional monomer, a compound represented by the following formula IA is preferable.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式ＩＡ中、ＲＣＡ１は水素原子又はアルキル基を表し、ＲＣＡ２～ＲＣＡ４はそれぞれ独立に、アルキル基又はアリール基を表し、ＲＣＡ２～ＲＣＡ４のうち２つ以上が互いに結合して環を形成してもよく、ＺＣＡ１は－Ｏ－又は－Ｎ（ＲＣａ）－を表し、ＲＣａは水素原子又はアルキル基を表し、ＬＣＡ１はアルキレン基を表し、ＸＣＡ１－はハロゲン化物イオン又は脂肪族若しくは芳香族カルボン酸イオンを表す。 In Formula IA, R CA1 represents a hydrogen atom or an alkyl group, R CA2 to R CA4 each independently represents an alkyl group or an aryl group, and two or more of R CA2 to R CA4 are bonded to each other to form a ring. Z CA1 represents —O— or —N (R Ca ) —, R Ca represents a hydrogen atom or an alkyl group, L CA1 represents an alkylene group, and X CA1− represents a halide ion or Represents an aliphatic or aromatic carboxylate ion.
　ＲＣＡ２～ＲＣＡ４及びＲＣａにおけるアルキル基は、直鎖又は分岐のアルキル基であることが好ましく、その炭素数は、１～１０が好ましく、１～６がより好ましく、１～４が更に好ましく、１又は２が特に好ましく、１が最も好ましい。
　ＲＣＡ２～ＲＣＡ４におけるアリール基の炭素数は、６～１６が好ましく、６～１２がより好ましく、６～１０が更に好ましい。例えば、フェニル基、ナフチル基が挙げられる。
　ＲＣＡ２～ＲＣＡ４のうち２つ以上が互いに結合して形成する環としては、５又は６員環の単環若しくは架橋環が好ましく、その炭素数は、４～１６が好ましく、４～１０がより好ましい。例えば、ピロリジン環、ピペラジン環、ピペリジン環、モルホリン環、チオモルホリン環、インドール環、キヌクリジン環が挙げられる。 The alkyl group in R CA2 to R CA4 and R Ca is preferably a linear or branched alkyl group, and the carbon number thereof is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4. 1 or 2 is particularly preferable, and 1 is most preferable.
The carbon number of the aryl group in R CA2 to R CA4 is preferably 6 to 16, more preferably 6 to 12, and still more preferably 6 to 10. For example, a phenyl group and a naphthyl group are mentioned.
The ring formed by combining two or more of R CA2 to R CA4 with each other is preferably a 5- or 6-membered monocyclic or bridged ring, and preferably has 4 to 16 carbon atoms, preferably 4 to 10 carbon atoms. More preferred. Examples include pyrrolidine ring, piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, indole ring, and quinuclidine ring.
　ＬＣＡ１の炭素数は、１～１０が好ましく、２～１０がより好ましく、２～６が更に好ましく、２～４が更に特に好ましく、３が最も好ましい。
　ＸＣＡ１におけるハロゲン化物イオンは、フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオンが挙げられる。
　ＸＣＡ１における脂肪族カルボン酸イオンの炭素数は、１～２０が好ましく、２～１０がより好ましく、２～５が更に好ましく、２又は３が特に好ましく、２が最も好ましい。
　上記脂肪族カルボン酸イオンにおける脂肪族カルボン酸は、飽和炭化水素にカルボキシル基が結合したカルボン酸、不飽和炭化水素にカルボキシル基が結合したカルボン酸のいずれでもよいが、飽和炭化水素にカルボキシル基が結合したカルボン酸が好ましい。
　ＸＣＡ１における芳香族カルボン酸イオンは、アリールカルボン酸イオン及びヘテロアリールカルボン酸イオンが好ましい。ここで、ヘテロアリールスルホン酸イオンにおけるヘテロアリール基は、５又は６員環が好ましく、ヘテロ環を構成するヘテロ原子は、窒素原子、酸素原子又は硫黄原子が好ましく、窒素原子がより好ましい。芳香族カルボン酸イオンの炭素数は、１～１７が好ましく、２～１３がより好ましく、６～１１が更に好ましい。例えば、安息香酸イオン、ナフタレンカルボン酸イオン、ニコチン酸イオン、イソニコチン酸イオンが挙げられる。 L CA1 preferably has 1 to 10 carbon atoms, more preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and most preferably 3.
Halide ions in X CA1 is fluoride ion, chloride ion, bromide ion, and iodide ion.
The carbon number of the aliphatic carboxylate ion in XCA1 is preferably 1 to 20, more preferably 2 to 10, still more preferably 2 to 5, particularly preferably 2 or 3, and most preferably 2.
The aliphatic carboxylic acid in the aliphatic carboxylate ion may be either a carboxylic acid in which a carboxyl group is bonded to a saturated hydrocarbon or a carboxylic acid in which a carboxyl group is bonded to an unsaturated hydrocarbon, but the saturated hydrocarbon has a carboxyl group. A bound carboxylic acid is preferred.
The aromatic carboxylate ion in XCA1 is preferably an arylcarboxylate ion or a heteroarylcarboxylate ion. Here, the heteroaryl group in the heteroaryl sulfonate ion is preferably a 5- or 6-membered ring, and the hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom. The aromatic carboxylate ion has preferably 1 to 17 carbon atoms, more preferably 2 to 13 carbon atoms, and still more preferably 6 to 11 carbon atoms. For example, benzoate ion, naphthalenecarboxylate ion, nicotinate ion, and isonicotinic acid ion can be mentioned.
　ＲＣＡ１は、水素原子又はメチル基であることが好ましく、水素原子であることがより好ましい。
　ＲＣＡ２～ＲＣＡ４はそれぞれ独立に、メチル基又はエチル基であることが好ましい。
　ＺＣＡ１は、－Ｎ（ＲＣａ）－であることが好ましい。
　ＲＣａは、水素原子又はメチル基であることが好ましく、水素原子であることがより好ましい。
　ＸＣＡ１－は、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－であることが好ましい。 R CA1 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
R CA2 to R CA4 are preferably each independently a methyl group or an ethyl group.
Z CA1 is preferably —N (R Ca ) —.
R Ca is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
X CA1- is preferably Cl − , Br − , I − or CH 3 COO — .
　本発明の光硬化性組成物は、その他のモノマーとして、イオン性単官能モノマー、アクリルアミド基を１以上有する化合物、メタクリルアミド基を１以上有する化合物、及び、スチリル基を１以上有する化合物よりなる群から選ばれた化合物以外のモノマーを含まないことが好ましく、その他のモノマーとして、イオン性単官能モノマー、アクリルアミド基を１以上有する化合物、メタクリルアミド基を１以上有する化合物、及び、スチリル基を１つ有する化合物よりなる群から選ばれた化合物以外のモノマーを含まないことがより好ましい。
　アクリルアミド基を１以上有する化合物、及び、メタクリルアミド基を１以上有する化合物としては、例えば、３－ジメチルアミノプロピル（メタ）アクリルアミド、及び、上記式２で表される化合物の両端の重合性基が両方ともアクリルアミド基である化合物又は両方ともメタクリルアミド基が好ましく挙げられる。 The photocurable composition of the present invention includes, as other monomers, a group consisting of an ionic monofunctional monomer, a compound having one or more acrylamide groups, a compound having one or more methacrylamide groups, and a compound having one or more styryl groups. It is preferable that no monomer other than the compound selected from the above is included. As other monomers, an ionic monofunctional monomer, a compound having one or more acrylamide groups, a compound having one or more methacrylamide groups, and one styryl group More preferably, no monomer other than the compound selected from the group consisting of the compounds is included.
Examples of the compound having one or more acrylamide groups and the compound having one or more methacrylamide groups include 3-dimethylaminopropyl (meth) acrylamide and polymerizable groups at both ends of the compound represented by the above formula 2. A compound in which both are acrylamide groups or a methacrylamide group in both are preferred.
　その他のモノマーは、１種単独で含んでいても、２種以上を含んでいてもよい。
　組成物中のその他のモノマーの含有量は、組成物の全質量に対し、１～７０質量％であることが好ましく、５～６０質量％であることがより好ましく、１０～４０質量％であることが更に好ましい。 Other monomers may be contained alone or in combination of two or more.
The content of other monomers in the composition is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and more preferably 10 to 40% by mass with respect to the total mass of the composition. More preferably.
＜溶媒＞
　本発明の光硬化性組成物は、溶媒を含んでいてもよい。
　溶媒は、１種単独で含んでいてもよく、２種以上を含んでいてもよい。
　組成物中の溶媒の含有量は、組成物の全質量に対し、１～６０質量％であることが好ましく、５～５０質量％であることがより好ましく、１０～４５質量％であることが更に好ましく、２０～４０質量％であることが特に好ましい。上記範囲であると、得られる硬化物の透水率により優れ、膜抵抗が小さくなり、また、取り扱い性にも優れる。
　溶媒を含むことで、硬化（重合）反応が、均一にしかもスムーズに進行する。また、多孔質支持体へ本発明の光硬化性組成物を含浸させる場合に含浸がスムーズに進行する。 <Solvent>
The photocurable composition of the present invention may contain a solvent.
The solvent may be included singly or in combination of two or more.
The content of the solvent in the composition is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and more preferably 10 to 45% by mass with respect to the total mass of the composition. Further preferred is 20 to 40% by mass. Within the above range, the water permeability of the cured product obtained is excellent, the film resistance is reduced, and the handleability is also excellent.
By including the solvent, the curing (polymerization) reaction proceeds uniformly and smoothly. In addition, when the porous support is impregnated with the photocurable composition of the present invention, the impregnation proceeds smoothly.
　溶媒は、水、又は、水と水に対する溶解度が５質量％以上の溶媒の混合液が好ましく用いられる。また、上記溶媒としては、水に対して自由に混合する溶媒が好ましい。このため、水及び水溶性溶媒から選択される溶媒が好ましい。
　水溶性溶媒としては、特に、アルコール系溶媒、非プロトン性極性溶媒であるエーテル系溶媒、アミド系溶媒、ケトン系溶媒、スルホキシド系溶媒、スルホン系溶媒、ニトリル系溶媒、有機リン系溶媒が好ましい。
　アルコール系溶媒としては、例えばメタノール、エタノール、イソプロパノール、ｎ－ブタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコールなどが挙げられる。これらは１種類単独又は２種類以上を併用して用いることができる。
　また、非プロトン性極性溶媒としては、ジメチルスルホキシド、ジメチルイミダゾリジノン、スルホラン、Ｎ－メチルピロリドン、ジメチルホルムアミド、アセトニトリル、アセトン、ジオキサン、テトラメチル尿素、ヘキサメチルホスホルアミド、ヘキサメチルホスホロトリアミド、ピリジン、プロピオニトリル、ブタノン、シクロヘキサノン、テトラヒドロフラン、テトラヒドロピラン、エチレングリコールジアセテート、γ－ブチロラクトン等が好ましい溶媒として挙げられる。中でも、ジメチルスルホキシド、Ｎ－メチルピロリドン、ジメチルホルムアミド、ジメチルイミダゾリジノン、スルホラン、アセトンまたはアセトニトリル、テトラヒドロフランが好ましい。これらは１種類単独又は２種類以上を併用して用いることができる。 As the solvent, water or a mixed liquid of a solvent having a solubility in water and water of 5% by mass or more is preferably used. Moreover, as said solvent, the solvent mixed freely with water is preferable. For this reason, the solvent selected from water and a water-soluble solvent is preferable.
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.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like. These can be used alone or in combination of two or more.
Examples of the aprotic polar solvent include dimethyl sulfoxide, dimethylimidazolidinone, sulfolane, N-methylpyrrolidone, dimethylformamide, acetonitrile, acetone, dioxane, tetramethylurea, hexamethylphosphoramide, hexamethylphosphorotriamide, Pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, ethylene glycol diacetate, γ-butyrolactone and the like are mentioned as preferred solvents. Of these, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone or acetonitrile, and tetrahydrofuran are preferred. These can be used alone or in combination of two or more.
　中でも、溶媒としては、水を含むことが好ましく、水、又は、水及びアルコール系溶媒の混合溶媒であることがより好ましく、水及びアルコール系溶媒の混合溶媒であることが特に好ましい。
　水及びアルコール系溶媒の混合溶媒としては、水及びイソプロパノールの混合溶媒が特に好ましい。
　また、水及びアルコール系溶媒の混合溶媒の混合比は、質量比で、水：アルコール系溶媒＝２０：１～３：１であることが好ましく、水：アルコール系溶媒＝１０：１～４：１であることがより好ましい。 Among them, the solvent preferably includes water, more preferably water or a mixed solvent of water and an alcohol solvent, and particularly preferably a mixed solvent of water and an alcohol solvent.
As a mixed solvent of water and an alcohol solvent, a mixed solvent of water and isopropanol is particularly preferable.
Further, the mixing ratio of the mixed solvent of water and alcohol solvent is preferably water: alcohol solvent = 20: 1 to 3: 1 in terms of mass ratio, and water: alcohol solvent = 10: 1 to 4: 1 is more preferable.
＜重合禁止剤＞
　本発明の光硬化性組成物は、重合禁止剤を含んでいてもよい。
　重合禁止剤としては、公知の重合禁止剤が使用でき、フェノール化合物、ハイドロキノン化合物、アミン化合物、メルカプト化合物などが挙げられる。
　フェノール化合物としては、ヒンダードフェノール（オルト位にｔ－ブチル基を有するフェノールで、代表的には、２，６－ジ－ｔ－ブチル－４－メチルフェノールが挙げられる。）、ビスフェノールが挙げられる。ハイドロキノン化合物の具体例としては、モノメチルエーテルハイドロキノンが挙げられる。また、アミン化合物の具体例としては、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミン、Ｎ，Ｎ－ジエチルヒドロキシルアミン等が挙げられる。
　なお、これらの重合禁止剤は、１種単独でも、２種以上を組み合わせて使用してもよい。
　重合禁止剤の含有量は、光硬化性組成物中の全固形分１００質量部に対し、０．０１～５質量部であることが好ましく、０．０１～１質量部であることがより好ましく、０．０１～０．５質量部であることが更に好ましい。 <Polymerization inhibitor>
The photocurable composition of the present invention may contain a polymerization inhibitor.
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 at 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.
In addition, these polymerization inhibitors may be used alone 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 photocurable composition. More preferably, the content is 0.01 to 0.5 parts by mass.
＜触媒＞
　本発明の光硬化性組成物は、使用する重合性化合物の溶解性の向上及び／又は重合速度の向上等の観点から、触媒を含有することが好ましい。
　触媒としては、アルカリ金属化合物が好ましく挙げられる。
　アルカリ金属化合物としては、リチウム、ナトリウム、カリウムの水酸化物塩、塩化物塩、硝酸塩等が好ましい。中でも、リチウム化合物がより好ましい。
　リチウム化合物の具体例としては、水酸化リチウム、塩化リチウム、臭化リチウム、硝酸リチウム、ヨウ化リチウム、リチウム塩素酸塩、チオシアン酸リチウム、過塩素酸リチウム、リチウムテトラフルオロボレート、リチウムヘキサフルオロホスフェート、及び、リチウムヘキサフルオロアルセナートが挙げられる。
　また、上記アルカリ金属化合物は、光硬化性組成物を中和するために使用することも好ましい。
　これらのアルカリ金属化合物は、水和物であってもよい。
　また、触媒は、１種単独又は２種以上を組み合わせて用いることができる。
　触媒の添加量は、光硬化性組成物の全固形分１００質量部に対し、０．１～３５質量部が好ましく、１～３０質量部がより好ましく、５～３０質量部が更に好ましい。 <Catalyst>
The photocurable composition of the present invention preferably contains a catalyst from the viewpoint of improving the solubility of the polymerizable compound used and / or improving the polymerization rate.
Preferred examples of the catalyst include alkali metal compounds.
As the alkali metal compound, lithium, sodium, potassium hydroxide salt, chloride salt, nitrate salt and the like are preferable. Among these, lithium compounds are more preferable.
Specific examples of the lithium compound include lithium hydroxide, lithium chloride, lithium bromide, lithium nitrate, lithium iodide, lithium chlorate, lithium thiocyanate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, And lithium hexafluoroarsenate.
The alkali metal compound is also preferably used for neutralizing the photocurable composition.
These alkali metal compounds may be hydrates.
Moreover, a catalyst can be used individually by 1 type or in combination of 2 or more types.
The addition amount of the catalyst is preferably 0.1 to 35 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photocurable composition.
　本発明の光硬化性組成物は、必要に応じ、上述した以外の公知の添加剤を含んでいてもよく、例えば、界面活性剤、粘度向上剤、高分子化合物、高分子分散剤、クレーター防止剤、可塑剤、粘度調製剤、酸化防止剤、及び／又は、防腐剤等を含有してもよい。 The photocurable composition of the present invention may contain known additives other than those described above as necessary. For example, surfactants, viscosity improvers, polymer compounds, polymer dispersants, crater prevention An agent, a plasticizer, a viscosity adjusting agent, an antioxidant, and / or a preservative may be contained.
　本発明の光硬化性組成物は、膜物性を調整するため、各種高分子化合物を添加することもできる。
　高分子化合物としては、アクリル樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ポリカーボネート樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、シェラック、ビニル樹脂、ゴム類、ワックス類、その他の天然樹脂等が使用できる。また、これらは、１種単独で使用しても、２種以上を併用してもよい。
　また、本発明の光硬化性組成物は、高分子分散剤を含んでいてもよい。
　高分子分散剤として、具体的にはポリビニルピロリドン、ポリビニルアルコール、ポリビニルメチルエーテル、ポリエチレンオキシド、ポリエチレングリコール、ポリプロピレングリコール、ポリアクリルアミド等が挙げられる。 In the photocurable composition of the present invention, various polymer compounds can be added in order to adjust film physical properties.
High molecular compounds include acrylic resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, vinyl resin, rubbers, waxes, and other natural resins. Etc. can be used. Moreover, these may be used individually by 1 type, or may use 2 or more types together.
Moreover, the photocurable composition of the present invention may contain a polymer dispersant.
Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide.
　クレーター防止剤とは、表面張力調整剤、表面調整剤、レベリング剤又はスリップ剤とも称し、面一な膜表面を得るための添加剤であり、例えば、有機変性ポリシロキサン（ポリエーテルシロキサンとポリエーテルの混合物）、ポリエーテル変性ポリシロキサンコポリマー、シリコーン変性コポリマーの構造の化合物が挙げられる。
　市販品としては、例えば、Ｅｖｏｎｉｋ　ｉｎｄｕｓｔｒｉｅｓ社製のＴｅｇｏ Ｇｌｉｄｅ ４３２、同１１０、同１３０、同４０６、同４１０、同４１１、同４１５、同４２０、同４３５、同４４０、同４５０、同４８２、同Ａ１１５、同Ｂ１４８４、同ＺＧ４００（いずれも商品名）が挙げられる。
　クレーター防止剤は、光硬化性組成物の全固形分１００質量部に対し、０～１０質量部が好ましく、０～５質量部がより好ましく、１～２質量部が更に好ましい。 An anti-crater agent is also referred to as a surface tension adjusting agent, surface adjusting agent, leveling agent or slip agent, and is an additive for obtaining a uniform film surface. For example, organic modified polysiloxane (polyether siloxane and polyether And a compound having a structure of a polyether-modified polysiloxane copolymer and a silicone-modified copolymer.
Examples of commercially available products include, for example, Tego Glide 432, 110, 130, 406, 410, 411, 415, 420, 435, 440, 450, 482, and 480 manufactured by Evonik Industries. 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 of the photocurable composition.
　本発明の光硬化性組成物は、膜を形成する際の塗布液の液物性調整のために、ノニオン性界面活性剤、カチオン性界面活性剤や、有機フルオロ化合物などの界面活性剤を含有していてもよい。
　界面活性剤の具体例としては、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、高級脂肪酸塩、高級脂肪酸エステルのスルホン酸塩、高級アルコールエーテルの硫酸エステル塩、高級アルコールエーテルのスルホン酸塩、高級アルキルスルホンアミドのアルキルカルボン酸塩、アルキルリン酸塩などのアニオン界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、アセチレングリコールのエチレンオキサイド付加物、グリセリンのエチレンオキサイド付加物、ポリオキシエチレンソルビタン脂肪酸エステルなどの非イオン性界面活性剤、また、この他にもアルキルベタインやアミドベタインなどの両性界面活性剤、シリコーン系界面活性剤、フッ素系界面活性剤などを含めて、従来公知である界面活性剤及びその誘導体から適宜選ぶことができる。
　界面活性剤の含有量は、光硬化性組成物の全固形分１００質量部に対し、０．０００１～５質量部が好ましく、０．００１～２質量部がより好ましく、０．０１～１質量部が更に好ましい。 The photocurable composition of the present invention contains a surfactant such as a nonionic surfactant, a cationic surfactant, or an organic fluoro compound in order to adjust the liquid properties of the coating liquid when forming a film. It may be.
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-based surfactants, including such as a fluorine-based surfactant, can be appropriately selected from surfactants and derivatives thereof are known.
The content of the surfactant is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 2 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the total solid content of the photocurable composition. Part is more preferred.
（硬化物）
　本発明の硬化物は、本発明の光硬化性組成物を硬化して形成される硬化物である。
　本発明の硬化物の用途は、特に制限はなく、種々の用途に用いることができ、また、本発明の硬化物は、第四級アンモニウム塩構造を有するため、イオン交換樹脂（好ましくはアニオン交換樹脂）としても機能する。
　例えば、本発明の硬化物は、イオン交換膜（好ましくはアニオン交換膜）、プロトン伝導膜、逆浸透膜、正浸透膜、高分子電解質又は吸水性樹脂に好適に用いることができる。
　本発明の硬化物の形状は、特に制限はなく、所望の形状をとりうるが、例えば、イオン交換膜、プロトン伝導膜、逆浸透膜及び正浸透膜等の高分子機能性膜、又は、固体高分子電解質型燃料電池等に用いる高分子電解質の用途では、膜状であることが好ましく、また、吸水性樹脂の用途では、膜状や球状、ビーズ状等であることが好ましい。
　イオン交換膜、プロトン伝導膜、逆浸透膜及び正浸透膜等の上記高分子機能性膜の厚さは、後述する支持体を有する場合は支持体を含めて、３０～１，０００μｍが好ましく、５０～５００μｍがより好ましく、５０～４００μｍが更に好ましい。 (Cured product)
The cured product of the present invention is a cured product formed by curing the photocurable composition of the present invention.
The use of the cured product of the present invention is not particularly limited and can be used for various applications. Since the cured product of the present invention has a quaternary ammonium salt structure, an ion exchange resin (preferably anion exchange resin) is used. It also functions as a resin.
For example, the cured product of the present invention can be suitably used for an ion exchange membrane (preferably an anion exchange membrane), a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte, or a water absorbent resin.
The shape of the cured product of the present invention is not particularly limited and may take a desired shape. For example, a polymer functional membrane such as an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane and a forward osmosis membrane, or a solid The polymer electrolyte used in a polymer electrolyte fuel cell or the like is preferably in the form of a film, and the water absorbent resin is preferably in the form of a film, a sphere, or a bead.
The thickness of the polymer functional membrane such as an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane and a forward osmosis membrane is preferably 30 to 1,000 μm including the support when it has a support described later. 50 to 500 μm is more preferable, and 50 to 400 μm is still more preferable.
＜支持体＞
　本発明の硬化物を上記イオン交換膜等の膜として形成する用途においては、支持体上、及び／又は、支持体内部に本発明の硬化物を形成してもよい。上記支持体は、多孔質支持体であることが好ましい。
　硬化物を補強する材料としての多孔質支持体は、樹脂製多孔質支持体であることが好ましく、例えば、合成織布、合成不織布等の不織布、スポンジ状フィルム、又は、微細な貫通孔を有するフィルムが挙げられる。
　多孔質支持体を用いる場合、上記膜は、本発明の硬化物の少なくとも一部を多孔質支持体の内部に有する膜であることが好ましい。
　また、上記膜は、多孔質支持体の表面及び／又は内部に本発明の硬化物を有する膜であることが好ましい。 <Support>
In the use which forms hardened | cured material of this invention as films | membranes, such as said ion exchange membrane, you may form the hardened | cured material of this invention on a support body and / or inside a support body. The support is preferably a porous support.
The porous support as a material for reinforcing the cured product is preferably a resin porous support, and has, for example, a nonwoven fabric such as a synthetic woven fabric or a synthetic nonwoven fabric, a sponge-like film, or fine through-holes. A film is mentioned.
In the case of using a porous support, the film is preferably a film having at least a part of the cured product of the present invention inside the porous support.
Moreover, it is preferable that the said film | membrane is a film | membrane which has the hardened | cured material of this invention in the surface and / or inside of a porous support body.
　多孔質支持体の例としては、例えば、ポリエチレン、ポリプロピレン、ポリアクリロニトリル、ポリ塩化ビニル、ポリエステル、ポリアミド及びそれらのコポリマー、あるいは、例えば、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルホン、ポリフェニレンスルフィド、ポリイミド、ポリエーテルイミド、ポリアミド、ポリアミドイミド、ポリアクリロニトリル、ポリカーボネート、ポリアクリレート、酢酸セルロース、ポリプロピレン、ポリ（４－メチル－１－ペンテン）、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、ポリクロロトリフルオロエチレン及びそれらのコポリマーを用いて形成された多孔質膜が挙げられる。
　市販の多孔質支持体は、例えば、三菱製紙（株）、ニッポン高度紙工業（株）、旭化成せんい（株）、日本バイリーン（株）、タピルス社、Ｆｒｅｕｄｅｎｂｅｒｇ　Ｆｉｌｔｒａｔｉｏｎ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社から市販されている。
　なお、多孔質支持体は、エネルギー線照射による重合反応を行う場合、エネルギー線の波長領域を遮らないこと、すなわち、重合反応に用いられる波長の照射を通過させることが要求される。 Examples of porous supports include, for example, polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyester, polyamide and copolymers thereof, or, for example, polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylenesulfide, polyimide, polyether. Imide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, polypropylene, poly (4-methyl-1-pentene), polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polychlorotrifluoroethylene And porous membranes formed using these copolymers.
Commercially available porous supports are commercially available from, for example, Mitsubishi Paper Industries Co., Ltd., Nippon Kogyo Paper Industry Co., Ltd., Asahi Kasei Fibers Co., Ltd., Japan Vilene Co., Ltd., Tapils Co., Ltd., and Freudenberg Filtration Technologies.
In addition, when performing the polymerization reaction by energy ray irradiation, the porous support is required not to block the wavelength region of the energy ray, that is, to pass the irradiation of the wavelength used for the polymerization reaction.
　多孔質支持体は、本発明の光硬化性組成物が浸透可能な支持体であることが好ましい。
　また、多孔質支持体は、親水性を有することが好ましい。支持体に親水性を付与するには、コロナ処理、プラズマ処理、フッ素ガス処理、オゾン処理、硫酸処理、シランカップリング剤処理などの一般的な方法を使用することができる。 The porous support is preferably a support through which the photocurable composition of the present invention can penetrate.
The porous support preferably has hydrophilicity. In order to impart hydrophilicity to the support, general methods such as corona treatment, plasma treatment, fluorine gas treatment, ozone treatment, sulfuric acid treatment, and silane coupling agent treatment can be used.
　本発明に用いることができる多孔質支持体は、不織布が好ましく、不織布の中でも、ポリエチレンとポリプロピレンとの複合繊維からなる不織布がより好ましい。また、この複合繊維の繊維径は、０．５～１５μｍが好ましく、１～１３μｍがより好ましく、２～１０μｍが特に好ましい。
　本発明に用いることができる多孔質支持体の厚さは、２０～２００μｍが好ましく、３０～１５０μｍがより好ましく、４０～１２０μｍが特に好ましい。 The porous support that can be used in the present invention is preferably a nonwoven fabric, and more preferably a nonwoven fabric made of a composite fiber of polyethylene and polypropylene. The fiber diameter of the composite fiber is preferably 0.5 to 15 μm, more preferably 1 to 13 μm, and particularly preferably 2 to 10 μm.
The thickness of the porous support that can be used in the present invention is preferably 20 to 200 μm, more preferably 30 to 150 μm, and particularly preferably 40 to 120 μm.
　本発明の硬化物の製造方法は、特に制限はなく、公知の方法を用いることができる。
　例えば、基板上に本発明の光硬化性組成物を塗布し、光重合してもよいし、任意の形状で本発明の光硬化性組成物を光硬化し硬化物を得た後、得られた硬化物を更に所望の形状へ加工してもよい。
　また、例えば、多孔質支持体を用いる場合は、多孔質支持体に本発明の光硬化性組成物を含浸又は塗布して光重合し、膜を好適に製造することができる。また、仮支持体（多孔質支持体の一方又は両方の面に貼り付け、硬化反応終了後、膜から剥がされる。）を用いて膜を形成してもよい。
　また、本発明の硬化物、特に膜状に本発明の硬化物を形成する場合は、固定された支持体を用いてバッチ式（バッチ方式）で調製することも、移動する支持体を用いて連続式（連続方式）で調製することもできる。
　なお、仮支持体を使用する場合、この仮支持体は、物質透過を考慮する必要がなく、例えば、アルミ板等の金属板を含め、膜形成のために固定できるものであれば、どのようなものでも構わない。 There is no restriction | limiting in particular in the manufacturing method of the hardened | cured material of this invention, A well-known method can be used.
For example, the photocurable composition of the present invention may be applied onto a substrate and photopolymerized, or obtained after photocuring the photocurable composition of the present invention in an arbitrary shape to obtain a cured product. The cured product may be further processed into a desired shape.
For example, when a porous support is used, the film can be suitably produced by impregnating or applying the photocurable composition of the present invention to the porous support and photopolymerizing it. Alternatively, the film may be formed using a temporary support (attached to one or both surfaces of the porous support and peeled off from the film after completion of the curing reaction).
In addition, when the cured product of the present invention, particularly when the cured product of the present invention is formed into a film, it can be prepared in a batch system using a fixed support, or using a moving support. It can also be prepared in a continuous manner (continuous manner).
In the case of using a temporary support, the temporary support does not need to consider material permeation. For example, any temporary support can be used as long as it can be fixed for film formation, including a metal plate such as an aluminum plate. It does n’t matter.
　本発明の光硬化性組成物は、種々の方法、例えば、カーテンコーティング、押し出しコーティング、エアナイフコーティング、スライドコーティング、ニップロールコーティング、フォワードロールコーティング、リバースロールコーティング、浸漬コーティング、キスコーティング、ロッドバーコーティング若しくは噴霧コーティングにより、多孔質支持体に塗布又は含浸することができる。複数の層の塗布は、同時又は連続して行うことができる。同時重層塗布するには、カーテンコーティング、スライドコーティング、スロットダイコーティング及び押し出しコーティングが好ましい。 The photocurable composition of the present invention can be applied in various ways, 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 spraying. By coating, the porous support can be applied or impregnated. 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.
　本発明の光硬化性組成物を硬化させた膜の連続方式での製造は、本発明の光硬化性組成物を、移動している支持体に連続的に塗布して製造することが好ましい。また、本発明の光硬化性組成物を塗布する塗布部と、本発明の光硬化性組成物を硬化するための照射源と、形成された膜を収集する膜巻取り部と、支持体を上記塗布部から上記照射源及び上記膜巻取り部に移動させるための手段とを含む製造ユニットにより製造することがより好ましい。 The production of the film obtained by curing the photocurable composition of the present invention in a continuous system is preferably performed by continuously applying the photocurable composition of the present invention to a moving support. Further, an application part for applying the photocurable composition of the present invention, an irradiation source for curing the photocurable composition of the present invention, a film winding part for collecting the formed film, and a support More preferably, it is manufactured by a manufacturing unit including means for moving from the application part to the irradiation source and the film winding part.
　本発明の光硬化性組成物を硬化させた膜の製造方法としては、本発明の光硬化性組成物を多孔質支持体に塗布又は含浸する工程、並びに、塗布又は含浸させた光硬化性組成物を光照射、必要に応じて、これに加えて更に加熱により重合反応させる工程を含む方法であることが好ましい。 Examples of the method for producing a film obtained by curing the photocurable composition of the present invention include a step of applying or impregnating a porous support with the photocurable composition of the present invention, and a photocurable composition coated or impregnated. It is preferable that the method includes a step of polymerizing the product by light irradiation, and if necessary, further heating.
　製造ユニットでは、上記塗布部は照射源に対し上流の位置に設け、照射源は収集部に対し上流の位置に置かれる。
　高速塗布機で塗布する際に十分な流動性を有するために、本発明の光硬化性組成物の３５℃での粘度は、４，０００ｍＰａ・ｓ未満が好ましく、１～１，０００ｍＰａ・ｓがより好ましく、１～５００ｍＰａ．ｓが更に好ましい。スライドビードコーティングの場合に３５℃での粘度は、１～１００ｍＰａ・ｓが好ましい。
　高速塗布機では、本発明の光硬化性組成物を、１５ｍ／分を超える速度で、移動する支持体に塗布することができ、２０ｍ／分を超える速度で塗布することもできる。
　特に機械的強度を高めるために支持体を使用する場合、本発明の光硬化性組成物を支持体の表面に塗布する前に、この支持体を、例えば、支持体の湿潤性及び付着力を改善するために、コロナ放電処理、グロー放電処理、火炎処理、紫外線照射処理などに付してもよい。 In the manufacturing unit, the application unit is provided at a position upstream of the irradiation source, and the irradiation source is positioned upstream of the collection unit.
The viscosity at 35 ° C. of the photocurable composition of the present invention is preferably less than 4,000 mPa · s, preferably 1 to 1,000 mPa · s in order to have sufficient fluidity when applied with a high-speed coater. More preferably, 1 to 500 mPa.s. s is more preferable. In the case of slide bead coating, the viscosity at 35 ° C. is preferably 1 to 100 mPa · s.
In a high-speed coating machine, the photocurable composition of the present invention can be applied to a moving support at a speed exceeding 15 m / min, and can also be applied at a speed exceeding 20 m / min.
In particular, when a support is used to increase the mechanical strength, before applying the photocurable composition of the present invention to the surface of the support, the support is treated with, for example, the wettability and adhesion of the support. In order to improve, it may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment and the like.
　本発明の光硬化性組成物の重合反応は、本発明の光硬化性組成物を支持体に塗布又は含浸して、好ましくは６０秒以内、より好ましくは１５秒以内、特に好ましくは５秒以内、最も好ましくは３秒以内に開始する。
　硬化するための光照射は、好ましくは１０秒未満、より好ましくは５秒未満、特に好ましくは３秒未満、最も好ましくは２秒未満である。連続法では照射を連続的に行い、本発明の光硬化性組成物が照射ビームを通過して移動する速度を考慮して、重合反応時間を決める。
　強度の高い紫外線（ＵＶ光）を重合反応に用いる場合、かなりの量の熱が発生するため、過熱を防ぐために、光源のランプ及び／又は支持体／膜を冷却用空気などで冷却することが好ましい。著しい線量の赤外線（ＩＲ光）がＵＶビームと一緒に照射される場合、ＩＲ反射性石英プレートをフィルターにしてＵＶ光を照射する。
　エネルギー線は、紫外線が好ましい。照射波長は、本発明の光硬化性組成物中に含まれる任意の光重合開始剤の吸収波長と波長が適合することが好ましく、例えば、ＵＶ－Ａ（４００～３２０ｎｍ）、ＵＶ－Ｂ（３２０～２８０ｎｍ）、ＵＶ－Ｃ（２８０～２００ｎｍ）が挙げられる。 The polymerization reaction of the photocurable composition of the present invention is preferably performed within 60 seconds, more preferably within 15 seconds, and particularly preferably within 5 seconds by applying or impregnating the photocurable composition of the present invention to a support. Most preferably, it starts within 3 seconds.
The light irradiation for 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 reaction time is determined in consideration of the speed at which the photocurable composition of the present invention moves through the irradiation beam.
When a high-intensity ultraviolet ray (UV light) is used for the polymerization reaction, a considerable amount of heat is generated. Therefore, in order to prevent overheating, the lamp of the light source and / or the support / film may be cooled with cooling air or the like. preferable. 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 ray is preferably ultraviolet light. The irradiation wavelength is preferably the same as the absorption wavelength of any photopolymerization initiator contained in the photocurable composition of the present invention. For example, UV-A (400 to 320 nm), UV-B (320 ˜280 nm) and UV-C (280˜200 nm).
　紫外線源は、水銀アーク灯、炭素アーク灯、低圧水銀灯、中圧水銀灯、高圧水銀灯、旋回流プラズマアーク灯、金属ハロゲン化物灯、キセノン灯、タングステン灯、ハロゲン灯、レーザー及び紫外線発光ダイオードである。中圧又は高圧水銀蒸気タイプの紫外線発光ランプが好ましい。これに加えて、ランプの発光スペクトルを改変するために、金属ハロゲン化物などの添加剤が存在していてもよい。２００～４５０ｎｍに発光極大を有するランプがとりわけ適している。 UV sources are mercury arc lamp, carbon arc lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, swirling plasma arc lamp, metal halide lamp, xenon lamp, tungsten lamp, halogen lamp, laser and ultraviolet light emitting diode. Medium pressure or high pressure mercury vapor type ultraviolet light emitting lamps are preferred. In addition, additives such as metal halides may be present to modify the emission spectrum of the lamp. A lamp having an emission maximum at 200 to 450 nm is particularly suitable.
　照射源のエネルギー出力は、好ましくは２０～１，０００Ｗ／ｃｍ、より好ましくは４０～５００Ｗ／ｃｍであるが、所望の暴露線量を実現することができるならば、これより高くても低くても構わない。暴露強度により、膜の硬化度を調整することができる。暴露線量は、Ｈｉｇｈ　Ｅｎｅｒｇｙ　ＵＶ　Ｒａｄｉｏｍｅｔｅｒ（ＥＩＴ－Ｉｎｓｔｒｕｍｅｎｔ　Ｍａｒｋｅｔｓ社製のＵＶ　Ｐｏｗｅｒ　ＰｕｃｋＴＭ）により、装置で示されたＵＶ－Ａ範囲で測定して、好ましくは少なくとも４０ｍＪ／ｃｍ２以上、より好ましくは１００～２，０００ｍＪ／ｃｍ２、特に好ましくは１５０～１，５００ｍＪ／ｃｍ２である。暴露時間は自由に選ぶことができるが、短いことが好ましく、最も好ましくは２秒未満である。 The energy output of the irradiation source is preferably 20 to 1,000 W / cm, more preferably 40 to 500 W / cm, but it can be higher or lower if the desired exposure dose can be achieved. I do not care. The degree of cure of the film can be adjusted by the exposure strength. The exposure dose is preferably at least 40 mJ / cm 2 or more, more preferably 100 mJ / cm 2 or more, as measured in the UV-A range indicated by the apparatus with a High Energy UV Radiometer (UV Power Pack ™ manufactured by EIT-Instrument Markets). ˜2,000 mJ / cm 2 , particularly 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.
　なお、塗布速度が速い場合、必要な暴露線量を得るために、複数の光源を使用しても構わない。この場合、複数の光源は暴露強度が同じでも異なってもよい。
　また、本発明の硬化物の製造方法は、必要に応じて、上記工程以外に、任意の公知の工程を含んでいてもよい。 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.
Moreover, the manufacturing method of the hardened | cured material of this invention may include arbitrary well-known processes other than the said process as needed.
（部材、及び、装置）
　本発明の部材は、本発明の光硬化性組成物を硬化して形成された硬化物を備える部材である。
　また、本発明の装置は、本発明の光硬化性組成物を硬化して形成された硬化物を備える装置である。
　本発明の装置としては、本発明の光硬化性組成物を硬化して形成された硬化物を備えていれば特に制限はなく、例えば、水処理装置、脱塩装置、純水製造装置、濃縮装置、透析装置、精製装置、及び、燃焼電池等が挙げられる。
　本発明の部材としては、本発明の光硬化性組成物を硬化して形成された硬化物を備えていれば特に制限はないが、上記装置における構成部材や吸水材等が挙げられる。具体的には、例えば、一対の電極間に本発明の光硬化性組成物を硬化して形成されたアニオン交換膜とカチオン交換膜とが交互に配置されたモジュール、本発明の光硬化性組成物を硬化して形成された吸水性樹脂を含む吸水材、燃料電池における両電極、本発明の光硬化性組成物を硬化して形成された膜及びセパレーターを備えるセル、並びに、上記セルを積層したスタック等が挙げられる。 (Members and devices)
The member of this invention is a member provided with the hardened | cured material formed by hardening | curing the photocurable composition of this invention.
Moreover, the apparatus of this invention is an apparatus provided with the hardened | cured material formed by hardening | curing the photocurable composition of this invention.
The apparatus of the present invention is not particularly limited as long as it includes a cured product formed by curing the photocurable composition of the present invention. For example, a water treatment apparatus, a desalting apparatus, a pure water production apparatus, a concentration apparatus Examples thereof include a device, a dialysis device, a purification device, and a combustion battery.
The member of the present invention is not particularly limited as long as it is provided with a cured product formed by curing the photocurable composition of the present invention, and examples thereof include a component member and a water absorbing material in the above apparatus. Specifically, for example, a module in which an anion exchange membrane and a cation exchange membrane are alternately formed between a pair of electrodes formed by curing the photocurable composition of the present invention, the photocurable composition of the present invention. A water-absorbing material containing a water-absorbing resin formed by curing a product, both electrodes in a fuel cell, a cell comprising a film and a separator formed by curing the photo-curable composition of the present invention, and a stack of the cells Stacks.
　以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されない。なお、特に断りのない限り、「部」、「％」は質量基準である。
　なお、光硬化性組成物における芳香環密度及び電荷密度は、上述した算出方法により算出した。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
The aromatic ring density and the charge density in the photocurable composition were calculated by the calculation method described above.
（実施例１）
＜化合物Ｍ－１の合成（イオン性架橋モノマーの合成）＞
　以下の合成スキームで化合物Ｍ－１を合成した。 Example 1
<Synthesis of Compound M-1 (Synthesis of Ionic Crosslinking Monomer)>
Compound M-1 was synthesized according to the following synthesis scheme.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　Ｎ－［３－（ジメチルアミノ）プロピル］アクリルアミド２５．７部（０．１７ｍｏｌ当量、東京化成工業（株）製）及び水１５．８部の混合液を４０℃に加熱して、そこへ４－（クロロメチル）スチレン２５．７部（０．１７ｍｏｌ当量、東京化成工業（株）製）を滴下して加えた。混合液を６０℃まで昇温して６時間撹拌し、化合物Ｍ－１の水溶液を得た。 A mixed solution of 25.7 parts of N- [3- (dimethylamino) propyl] acrylamide (0.17 mol equivalent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 15.8 parts of water was heated to 40 ° C. 25.7 parts of (chloromethyl) styrene (0.17 mol equivalent, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. The mixture was heated to 60 ° C. and stirred for 6 hours to obtain an aqueous solution of Compound M-1.
＜光硬化性組成物の調製＞
　得られた化合物Ｍ－１の水溶液を室温（２５℃）に戻した後、そこへ、３２部の（３－アクリルアミドプロピル）トリメチルアンモニウムクロリド７５質量％水溶液（０．１２ｍｏｌ、東京化成工業（株）製）と、６．０部の２－プロパノールと、１．０部のＤａｒｏｃｕｒ　１１７３（光重合開始剤、商品名、チバ・スペシャルティ・ケミカルズ社製）とを加えて、撹拌し、均一溶液の光硬化性組成物を得た。 <Preparation of photocurable composition>
The obtained aqueous solution of Compound M-1 was returned to room temperature (25 ° C.), and then 32 parts of (3-acrylamidopropyl) trimethylammonium chloride 75% by weight aqueous solution (0.12 mol, Tokyo Chemical Industry Co., Ltd.) Product), 6.0 parts 2-propanol and 1.0 part Darocur 1173 (photopolymerization initiator, trade name, manufactured by Ciba Specialty Chemicals) A curable composition was obtained.
＜イオン交換膜の作製＞
　調製した光硬化性組成物をアルミ板に、１５０μｍのワイヤ巻き棒を用いて、手動で約５ｍ／分の速さで塗布し、続いて、不織布（Ｆｒｅｕｄｅｎｂｅｒｇ社製、ＦＯ－２２２６－１４、以下「支持体」ともいう。）に光硬化性組成物を含浸させた。次いで、ワイヤを巻いていないロッドを用いてアルミ板上の余分な光硬化性組成物を除去した。ＵＶ露光機（Ｆｕｓｉｏｎ　ＵＶ　Ｓｙｓｔｅｍｓ社製、型式Ｌｉｇｈｔ　Ｈａｍｍｅｒ　ＬＨ６、Ｄ－バルブ、速度１５ｍ／分、１００％強度）を用いて、上記のようにして得た光硬化性組成物含浸支持体に、０．４７秒間露光し、反応時間０．８秒で、重合反応させることにより硬化させて、膜（アニオン交換膜）を得た。得られた膜を、アルミ板から取り外し、０．１Ｍ　ＮａＣｌ水溶液中で少なくとも１２時間保存し、イオン交換膜を作製した。 <Preparation of ion exchange membrane>
The prepared photocurable composition 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 (manufactured by Freudenberg, FO-2226-14, below) Also referred to as “support”) was impregnated with a photocurable composition. Subsequently, the excess photocurable composition on an aluminum plate was removed using the rod which has not wound the wire. Using a UV exposure machine (manufactured by Fusion UV Systems, Model Light Hammer LH6, D-bulb, speed 15 m / min, 100% strength), the photocurable composition-impregnated support obtained as described above was subjected to 0 It was exposed for 47 seconds and cured by a polymerization reaction at a reaction time of 0.8 seconds to obtain a membrane (anion exchange membrane). The obtained membrane was removed from the aluminum plate and stored in a 0.1 M NaCl aqueous solution for at least 12 hours to produce an ion exchange membrane.
＜イオン交換膜の評価＞
－膜の電気抵抗（Ω・ｃｍ２）－
　２時間、０．５Ｍ　ＮａＣｌ水溶液中に浸漬した膜の両面を乾燥ろ紙で拭い、２室型セル（有効膜面積１ｃｍ２、電極にはＡｇ／ＡｇＣｌ参照電極（Ｍｅｔｒｏｈｍ社製）に挟んだ。両室に同一濃度の　ＮａＣｌ水溶液を１００ｍＬ満たし、２５℃の恒温水槽中に２室型セルを置いて平衡に達するまで放置した。セル中の液温が正しく２５℃になったことを確認したのち、交流ブリッジ（周波数１，０００Ｈｚ）によりイオン交換膜の電気抵抗ｒ１を測定した。ＮａＣｌ濃度は、０．５Ｍ、０．７Ｍ、１．５Ｍ、３．５Ｍ、または、４．５Ｍの条件で測定し、低濃度のＮａＣｌ水溶液から順番に測定した。次に２室型セルから膜を取り除き、両極間が０．５Ｍ　ＮａＣｌ水溶液のみである場合の電気抵抗ｒ２を測定した。膜の電気抵抗ｒをｒ１－ｒ２により求めた。 <Evaluation of ion exchange membrane>
-Electrical resistance of membrane (Ω · cm 2 )-
Both sides of the membrane immersed in 0.5 M NaCl aqueous solution for 2 hours were wiped with dry filter paper, and sandwiched between two-chamber cells (effective membrane area 1 cm 2 , Ag / AgCl reference electrode (made by Metrohm) for the electrode). The room was filled with 100 mL of NaCl solution of the same concentration, placed in a constant temperature water bath at 25 ° C. and left to reach equilibrium.After confirming that the liquid temperature in the cell was correctly 25 ° C., The electric resistance r 1 of the ion exchange membrane was measured with an AC bridge (frequency: 1,000 Hz), and the NaCl concentration was measured under the conditions of 0.5M, 0.7M, 1.5M, 3.5M, or 4.5M. Then, the membrane was removed from the two-chamber cell, and the electrical resistance r2 was measured when only the 0.5 M NaCl aqueous solution was present between the two electrodes. the r It was determined by -r 2.
－透水率（ｍＬ／（ｍ２・Ｐａ・ｈｒ））－
　図１に示す流路１０を有する装置を用いて膜の透水率を測定した。　フィード溶液（純水）４００ｍＬとドロー溶液（３Ｍ　ＮａＣｌ水溶液）４００ｍＬとを、膜１を介して接触させ（膜接触面積１８ｃｍ２）、各液を、ペリスタポンプを用いて流路１０中の液体の進行方向５の向きに流速０．１１ｃｍ／秒で流した。フィード溶液中の純水が膜を介してドロー溶液に浸透する速度を、フィード溶液とドロー溶液の質量をリアルタイムで測定することによって解析し、透水率を求めた。 -Water permeability (mL / (m 2 · Pa · hr))-
The water permeability of the membrane was measured using an apparatus having the flow channel 10 shown in FIG. 400 mL of the feed solution (pure water) and 400 mL of the draw solution (3M NaCl aqueous solution) are brought into contact with each other through the membrane 1 (membrane contact area 18 cm 2 ), and each liquid proceeds with the liquid in the channel 10 using a peristaltic pump. It flowed in the direction of direction 5 at a flow rate of 0.11 cm / sec. The rate at which pure water in the feed solution permeates the draw solution through the membrane was analyzed by measuring the mass of the feed solution and the draw solution in real time to obtain the water permeability.
－ｐＨ耐性－
　ｐＨ１の塩酸水溶液とｐＨ１４の水酸化ナトリウム水溶液に、それぞれ、膜を浸漬し、４０℃で３時間保持した。浸漬前の膜の透水率に対する浸漬後の膜の透水率の割合（保持率（％））を算出した。
　ｐＨ１の塩酸水溶液及びｐＨ１４の水酸化ナトリウム水溶液のいずれの液に浸漬しても、浸漬前後における膜の透水率の保持率が９０％以上の場合を「良」、いずれかの液での膜の保持率が９０％未満の場合を「不良」と評価した。 -PH tolerance-
The membrane was immersed in an aqueous hydrochloric acid solution having a pH of 1 and an aqueous sodium hydroxide solution having a pH of 14, respectively, and kept at 40 ° C. for 3 hours. The ratio (retention rate (%)) of the water permeability of the film after immersion to the water permeability of the film before immersion was calculated.
Even if immersed in any one of a pH 1 aqueous hydrochloric acid solution and a pH 14 sodium hydroxide aqueous solution, the case where the retention rate of the water permeability of the membrane before and after immersion is 90% or more is “good”. The case where the retention rate was less than 90% was evaluated as “bad”.
　以上の評価結果を表１に示す。 The above evaluation results are shown in Table 1.
（実施例２～７、並びに、比較例１及び２）
　実施例２～７、並びに、比較例１及び２は、表１に記載の組成に変更した以外は、実施例１と同様の方法で光硬化性組成物を調製し、次いで、実施例１と同様にしてイオン交換膜を作製した。
　なお、実施例３～７は、実施例１における４－（クロロメチル）スチレンの代わりにその他欄に記載の化合物（ＤＣＸまたはＤＢＸ）を、使用した。また、比較例１は、実施例１における（３－アクリルアミドプロピル）トリメチルアンモニウムクロリドの代わりに架橋モノマー（ＤＶＢ）を使用した。
　また、実施例３～６のイオン性架橋モノマーの合成においては、アクリルアミドと、メタクリルアミド又はメタクリレートとを併用した。スチレンの代わりに用いたキシレン（ＤＣＸ又はＤＢＸ）に対する、アクリルアミド（ＤＭＡＰＡ）、メタクリルアミド（ＤＭＡＰＭＡ）又はメタクリレート（ＤＥＡＥＭＡ）の反応性は、それぞれ、ほとんど差がなかった。具体的には、キシレン１分子に対してアクリルアミドが２分子結合したジアクリルアミド体、キシレン１分子に対してアクリルアミドと、メタクリルアミド又はメタクリレートとが１分子ずつ結合したアクリルアミド－メタクリルアミド又はメタクリレート体、キシレン１分子に対してメタクリルアミドが２分子結合したジメタクリルアミド体が、順にほぼ１：２：１のモル比で生成していた。
　また、実施例７においては、実施例１における化合物Ｍ－１の水溶液に対応するイオン性架橋モノマーの水溶液中に、ＤＥＡＥＭＡ２５質量％のうち７質量％がＤＢＸと反応せず未反応のまま残留していることが確認された。また、実施例７において、イオン性架橋モノマーとして、ジアクリルアミド体、アクリルアミド－メタクリレート体、及び、ジメタクリレート体が生成していることを確認した。
　評価結果をまとめて表１に示す。 (Examples 2 to 7 and Comparative Examples 1 and 2)
In Examples 2 to 7 and Comparative Examples 1 and 2, a photocurable composition was prepared in the same manner as in Example 1 except that the compositions shown in Table 1 were changed. Similarly, an ion exchange membrane was produced.
In Examples 3 to 7, the compounds (DCX or DBX) described in the other column were used in place of 4- (chloromethyl) styrene in Example 1. In Comparative Example 1, a crosslinking monomer (DVB) was used instead of (3-acrylamidopropyl) trimethylammonium chloride in Example 1.
In the synthesis of the ionic crosslinking monomers of Examples 3 to 6, acrylamide and methacrylamide or methacrylate were used in combination. The reactivity of acrylamide (DMAPA), methacrylamide (DMAPMA) or methacrylate (DEAEMA) to xylene (DCX or DBX) used instead of styrene was almost the same. Specifically, a diacrylamide compound in which two molecules of acrylamide are bonded to one molecule of xylene, an acrylamide-methacrylamide or methacrylate compound in which one molecule of acrylamide and one molecule of methacrylamide or methacrylate are bonded to one molecule of xylene, xylene Dimethacrylamides in which two molecules of methacrylamide were bonded to one molecule were sequentially formed at a molar ratio of approximately 1: 2: 1.
In Example 7, 7% by mass of 25% by mass of DEAEMA remained unreacted without reacting with DBX in the aqueous solution of the ionic crosslinking monomer corresponding to the aqueous solution of Compound M-1 in Example 1. It was confirmed that In Example 7, it was confirmed that diacrylamide, acrylamide-methacrylate, and dimethacrylate were formed as ionic crosslinking monomers.
The evaluation results are summarized in Table 1.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　表１に記載された略号の詳細を以下に示す。
　ＤＭＡＰＡ：Ｎ－［３－（ジメチルアミノ）プロピル］アクリルアミド、東京化成工業（株）製、下記化合物
　ＶＢＣ：４－（クロロメチル）スチレン２５．７、東京化成工業（株）製、下記化合物
　ＤＭＡＰＭＡ：Ｎ－［３－（ジメチルアミノ）プロピル］メタクリルアミド、東京化成工業（株）製、下記化合物
　ＤＭＡＥＭＡ：２－（ジメチルアミノ）エチルメタクリレート、東京化成工業（株）製、下記化合物
　ＤＥＡＥＭＡ：２－（ジエチルアミノ）エチルメタクリレート、東京化成工業（株）製、下記化合物
　ＤＶＢ：ジビニルベンゼン（ｍ－，ｐ－混合物）、東京化成工業（株）製、下記化合物
　ＤＭＡＰＡＡＱ：３－アクリルアミドプロピルトリメチルアンモニウムクロリド（ジメチルアミノプロピルアクリルアミド塩化メチル第四級塩）、Ａｌｄｒｉｃｈ社製、下記化合物
　ＭＡＰＴＡＣ：３－メタクリルアミドプロピルトリメチルアンモニウムクロリド（ジメチルアミノプロピルメタクリルアミド塩化メチル第四級塩）、Ａｌｄｒｉｃｈ社製、下記化合物
　ＤＣＸ：α，α’－ジクロロ－ｐ－キシレン、東京化成工業（株）製、下記化合物
　ＤＢＸ：α，α’－ジブロモ－ｐ－キシレン、東京化成工業（株）製、下記化合物
　Ｄａｒｏｃｕｒ　１１７３：光重合開始剤、チバ・スペシャリティ・ケミカルズ社製、下記化合物
　Ｉｒｇａｃｕｒｅ２９５９：光重合開始剤、ＢＡＳＦ社製、１－［４－（２－ヒドロキシエトキシ）フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、下記化合物
　ＩＰＡ：イソプロピルアルコール、和光純薬工業（株）製 Details of the abbreviations described in Table 1 are shown below.
DMAPA: N- [3- (dimethylamino) propyl] acrylamide, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound VBC: 4- (chloromethyl) styrene 25.7, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DMAPMA: N- [3- (dimethylamino) propyl] methacrylamide, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DMAEMA: 2- (dimethylamino) ethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DEAEMA: 2- ( Diethylamino) ethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DVB: divinylbenzene (m-, p-mixture), manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DMAPAAQ: 3-acrylamidopropyltrimethylammonium chloride (dimethylamino) Propylacrylamide methyl chloride quaternary ), Manufactured by Aldrich, the following compound MAPTAC: 3-methacrylamideamidopropyltrimethylammonium chloride (dimethylaminopropyl methacrylamide methyl chloride quaternary salt), manufactured by Aldrich, the following compound DCX: α, α′-dichloro-p-xylene Manufactured by Tokyo Chemical Industry Co., Ltd., the following compound DBX: α, α′-dibromo-p-xylene, manufactured by Tokyo Chemical Industry Co., Ltd., the following compound Darocur 1173: photopolymerization initiator, manufactured by Ciba Specialty Chemicals, Inc. The following compound Irgacure 2959: Photopolymerization initiator, manufactured by BASF, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, the following compound IPA: isopropyl alcohol, Wako Pure Chemical Industries, Ltd.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
１：膜
２：フィード溶液から分離された水の流れを示す矢印
３：フィード溶液の流路
４：ドロー溶液の流路
５：液体の進行方向
１０：流路 1: Membrane 2: Arrow indicating the flow of water separated from the feed solution 3: Feed solution channel 4: Draw solution channel 5: Liquid traveling direction 10: Channel

Claims (12)

  1. 　第四級アンモニウム塩構造と、アクリルアミド基と、アクリルアミド基以外の重合性基とを有するイオン性架橋モノマー、及び、
    　光重合開始剤を含む、　光硬化性組成物。     An ionic crosslinking monomer having a quaternary ammonium salt structure, an acrylamide group, and a polymerizable group other than the acrylamide group; and
    A photocurable composition comprising a photopolymerization initiator.
  2. 　前記光硬化性組成物の芳香環密度が１．５ｍｍｏｌ／ｇ以上であり、かつ、電荷密度が３ｍｍｏｌ／ｇ以上である、請求項１に記載の光硬化性組成物。 The photocurable composition according to claim 1, wherein the photocurable composition has an aromatic ring density of 1.5 mmol / g or more and a charge density of 3 mmol / g or more.
  3. 　前記アクリルアミド基以外の重合性基が、スチリル基である、請求項１又は２に記載の光硬化性組成物。 The photocurable composition according to claim 1 or 2, wherein the polymerizable group other than the acrylamide group is a styryl group.
  4. 　前記イオン性架橋モノマーが、下記式１で表される化合物を含む、請求項１～３のいずれか１項に記載の光硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
    　式１中、Ａ１及びＢ１はそれぞれ独立に、二価の連結基を表し、Ｒ１及びＲ２はそれぞれ独立に、アルキル基を表し、Ｘ１－は、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表す。     The photocurable composition according to any one of claims 1 to 3, wherein the ionic crosslinking monomer contains a compound represented by the following formula 1.
    Figure JPOXMLDOC01-appb-C000001
    In Formula 1, A 1 and B 1 each independently represent a divalent linking group, R 1 and R 2 each independently represent an alkyl group, and X 1− represents Cl − , Br − , I −. Or represents CH 3 COO — .
  5. 　前記アクリルアミド基以外の重合性基が、メタクリルアミド基である、請求項１又は２に記載の光硬化性組成物。 The photocurable composition according to claim 1 or 2, wherein the polymerizable group other than the acrylamide group is a methacrylamide group.
  6. 　前記イオン性架橋モノマーが、下記式２で表される化合物を含む、請求項１、２又は５に記載の光硬化性組成物。
    Figure JPOXMLDOC01-appb-C000002
    　式２中、Ａ２、Ａ３及びＢ２はそれぞれ独立に、二価の連結基を表し、Ｒ３～Ｒ６はそれぞれ独立に、アルキル基を表し、Ｒ７はアルキル基を表し、Ｘ２－及びＸ３－はそれぞれ独立に、Ｃｌ－、Ｂｒ－、Ｉ－又はＣＨ３ＣＯＯ－を表す。     The photocurable composition according to claim 1, 2 or 5, wherein the ionic crosslinking monomer contains a compound represented by the following formula 2.
    Figure JPOXMLDOC01-appb-C000002
    In Formula 2, A 2 , A 3 and B 2 each independently represent a divalent linking group, R 3 to R 6 each independently represents an alkyl group, R 7 represents an alkyl group, and X 2 - and X 3- each independently, Cl -, Br -, I - or CH 3 COO - represents a.
  7. 　溶媒を更に含む、請求項１～６のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 6, further comprising a solvent.
  8. 　前記溶媒が、水を含む、請求項７に記載の光硬化性組成物。 The photocurable composition according to claim 7, wherein the solvent contains water.
  9. 　請求項１～８のいずれか１項に記載の光硬化性組成物を硬化して形成される硬化物。 A cured product formed by curing the photocurable composition according to any one of claims 1 to 8.
  10. 　前記硬化物が、イオン交換膜、プロトン伝導膜、逆浸透膜、正浸透膜、高分子電解質又は吸水性樹脂である、請求項９に記載の硬化物。 10. The cured product according to claim 9, wherein the cured product is an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte, or a water absorbent resin.
  11. 　請求項１～８のいずれか１項に記載の光硬化性組成物を硬化して形成された硬化物を備える部材。 A member comprising a cured product formed by curing the photocurable composition according to any one of claims 1 to 8.
  12. 　請求項１～８のいずれか１項に記載の光硬化性組成物を硬化して形成された硬化物を備える装置。 An apparatus comprising a cured product formed by curing the photocurable composition according to any one of claims 1 to 8.
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