WO2024058031A1 - Actinic-ray-curable resin composition, cured object, and multilayered object - Google Patents

Actinic-ray-curable resin composition, cured object, and multilayered object Download PDF

Info

Publication number
WO2024058031A1
WO2024058031A1 PCT/JP2023/032578 JP2023032578W WO2024058031A1 WO 2024058031 A1 WO2024058031 A1 WO 2024058031A1 JP 2023032578 W JP2023032578 W JP 2023032578W WO 2024058031 A1 WO2024058031 A1 WO 2024058031A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
meth
acrylate
examples
curable resin
Prior art date
Application number
PCT/JP2023/032578
Other languages
French (fr)
Japanese (ja)
Inventor
春久 冨樫
雄一 岡本
康平 松村
雄基 橋本
Original Assignee
荒川化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 荒川化学工業株式会社 filed Critical 荒川化学工業株式会社
Publication of WO2024058031A1 publication Critical patent/WO2024058031A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present disclosure relates to an active energy ray-curable resin composition, a cured product, and a laminate.
  • the problem to be solved by the present invention is to provide an active energy ray-curable composition for producing a cured product with good antistatic properties.
  • the present disclosure provides the following items.
  • An active energy ray-curable resin composition The active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a phosphoric acid ester and/or salt, The anion of the salt includes a polyoxyalkylene structure, When the active energy ray curable resin composition contains a phosphoric acid ester, the acid value of the active energy ray curable resin composition is 400 mgKOH/g to 600 mgKOH/g. Active energy ray curable resin composition.
  • (Item 3) A cured product of the active energy ray-curable resin composition according to any one of the above items.
  • (Item 4) A laminate containing the cured product described in the above items.
  • (Item A1) An active energy ray-curable resin composition,
  • the active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a phosphoric acid ester,
  • the active energy ray curable resin composition has an acid value of 400 mgKOH/g to 600 mgKOH/g.
  • the quaternary ammonium salt-containing polymer includes a structural unit (1), a structural unit (2), and a structural unit (3),
  • the structural unit (1) is derived from a quaternary ammonium salt-containing monomer
  • the structural unit (2) is derived from the following compound ⁇ , A-B-(C) n -D (A represents a (meth)acryloyloxy group.
  • B represents a single bond or an alkylene group.
  • D represents a hydroxyl group, an alkoxy group, or an alkyl group.
  • the structural unit (3) is derived from alkyl (meth)acrylate, The active energy ray-curable resin composition described in the above item.
  • Curable resin composition (Item A5) A cured product of the active energy ray-curable resin composition according to any one of the above items. (Item A6) A laminate containing the cured product described in the above items. (Item B1) An active energy ray-curable resin composition, The active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a salt, the anion of the salt includes a polyoxyalkylene structure; Active energy ray curable resin composition. (Item B2) The active energy ray-curable resin composition described in the above item, which contains urethane poly(meth)acrylate. (Item B3) A cured product of the active energy ray-curable resin composition according to any one of the above items. (Item B4) A laminate containing the cured product described in the above items.
  • numerical ranges for each physical property value, content, etc. may be set as appropriate (for example, by selecting from the values listed in each item below).
  • the numerical value ⁇ is exemplified by A3, A2, A1 (A3>A2>A1)
  • the range of the numerical value ⁇ is, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more.
  • A2 or more greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3 , greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, etc.
  • ⁇ amount (A/B) means the ⁇ amount ( ⁇ ) of A relative to B100 ⁇ .
  • ⁇ include mass %, mol %, parts by mass, and the like.
  • amount of ⁇ include content, amount used, and the like.
  • ⁇ amount include mass % content.
  • ⁇ ratio (A/B) means the ⁇ ratio calculated by the formula "A ⁇ B". Examples of the ⁇ ratio include mass ratio and molar ratio.
  • Nonvolatile content means the total mass of components other than organic solvent and water.
  • the non-volatile content of the object A is the total mass of components remaining after heating 1 g of the object A at 105° C. and reaching a constant weight.
  • (Meth)acrylic means “at least one selected from the group consisting of acrylic and methacrylic.”
  • (Meth)acrylate means “at least one selected from the group consisting of acrylate and methacrylate.”
  • (Meth)acryloyl means “at least one selected from the group consisting of acryloyl and methacryloyl.”
  • C means "carbon number".
  • C1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms.
  • C6 alkyl group means an alkyl group having 6 carbon atoms.
  • the present disclosure provides an active energy ray-curable resin composition
  • the active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a phosphoric acid ester and/or salt,
  • the anion of the salt includes a polyoxyalkylene structure
  • the acid value of the active energy ray curable resin composition is 400 mgKOH/g to 600 mgKOH/g.
  • the present invention relates to an active energy ray-curable resin composition.
  • quaternary ammonium salt-containing polymer polymer>
  • the quaternary ammonium salt-containing polymers may be used alone or in combination of two or more.
  • the quaternary ammonium salt-containing polymer includes a structural unit (1), a structural unit (2), and a structural unit (3)
  • the structural unit (1) is derived from a quaternary ammonium salt-containing monomer
  • the structural unit (2) is derived from the following compound ⁇ , A-B-(C) n -D (A represents a (meth)acryloyloxy group.
  • B represents a single bond or an alkylene group.
  • D represents a hydroxyl group, an alkoxy group, or an alkyl group.
  • n represents an integer of 1 or more.
  • the structural unit (3) is derived from alkyl (meth)acrylate.
  • the quaternary ammonium salt-containing monomers may be used alone or in combination of two or more.
  • Examples of the C1-4 alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group.
  • Examples of the C1-3 alkylene group include a methylene group, an ethylene group, a propylene group, and an isopropylene group.
  • Examples of X n- include halogen ions and sulfur-containing ions.
  • halogen ions include fluoride ions, chloride ions, bromide ions, and iodide ions.
  • sulfur-containing ions examples include sulfate ions, sulfite ions, C 2 H 5 SO 4 - , R S1 -(OR S2 ) s -OSO 3 - , and the like.
  • R S1 represents an alkyl group or an aryl group.
  • R S2 represents an alkylene group.
  • s represents an integer greater than or equal to 1
  • R S1 is preferably an alkyl group, more preferably a C1-4 alkyl group.
  • R S2 is a C2-3 alkylene group.
  • X n- preferably includes chloride ion, R S1 -(OR S2 ) s -OSO 3 - .
  • n examples include 1, 2, etc. In one embodiment, n preferably includes 1.
  • Examples of the quaternary ammonium salt-containing monomer (excluding anion) include trimethyl-2-(meth)acryloyloxyethylammonium, (3-(meth)acryloylaminopropyl)trimethylammonium, and the like.
  • the mass% content is, for example, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass. Examples include %. In one embodiment, the content is preferably 25% by mass to 70% by mass, more preferably 35% by mass to 60% by mass.
  • the mol% content (constituent unit (1)/all polymer structural units) is 84 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, Examples include 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 21 mol%, 20 mol%, 15 mol%, and 14 mol%.
  • the content is preferably 14 mol% to 84 mol%, more preferably 21 mol% to 80 mol%.
  • Compound ⁇ may be used alone or in combination of two or more.
  • Compound ⁇ is represented by the following formula.
  • A-B-(C) n -D (A represents a (meth)acryloyloxy group.
  • B represents a single bond or an alkylene group.
  • D represents a hydroxyl group, an alkoxy group, or an alkyl group.
  • n represents an integer of 1 or more.
  • examples of the alkyl group include a C1-4 alkyl group.
  • examples of the alkoxy group include a C1-18 alkoxy group.
  • C1-18 alkoxy groups include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-octoxy group, Examples include 2-ethylhexytoxy group, n-decatoxy group, 2-ethyloctoxy group, n-lauroxy group, n-stearoxy group and the like.
  • a lactone ring-opening polyadduct can be produced by ring-opening polyaddition using a hydroxyl group-containing vinyl monomer and a lactone.
  • the hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more.
  • Examples of the hydroxyl group-containing vinyl monomer include hydroxyl group-containing (meth)acrylate, hydroxyl group-containing vinyl monomer, and the like.
  • hydroxyl group-containing (meth)acrylates examples include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyethyl (meth)acrylamide.
  • hydroxyl group-containing vinyl ether examples include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxydiethylene glycol vinyl ether, and the like.
  • lactones may be used alone or in combination of two or more.
  • examples of the lactone include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
  • weight average molecular weight examples include 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,999, 3,000, 2,000, and 1,000.
  • the weight average molecular weight is preferably from 1,000 to 10,000, more preferably from 1,000 to less than 4,000.
  • the weight average molecular weight (lactone ring-opening polyadduct) can be measured under the following conditions. Measuring equipment: Product name "HLC-8220GPC", manufactured by Tosoh Co., Ltd. Column: Product name "TSKgel SuperHZ-M", manufactured by Tosoh Corporation Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL/min Sample concentration: 0.5% Standard material: Polystyrene (Standard polystyrene kit PStQuick A, B, C manufactured by Tosoh Corporation)
  • a catalyst may optionally be used during the ring-opening polyaddition.
  • the catalyst include mineral acids, alkali metals, alkyl metal compounds, metal alkoxides, and tin compounds.
  • mineral acids examples include sulfuric acid and phosphoric acid.
  • alkali metals examples include lithium, sodium, potassium, and the like.
  • alkyl metal compounds examples include n-butyllithium, s-butyllithium, and t-butyllithium.
  • metal alkoxide examples include titanium tetrabutoxide.
  • tin compound examples include dibutyltin dilaurate, dibutyltin dioctate, dibutyltin mercaptide, tin octylate, and the like.
  • the amount used in parts by mass is preferably 0.01 parts by mass to 10 parts by mass.
  • polyalkylene-containing materials examples include hydroxypolyalkylene glycol mono(meth)acrylate, alkoxypolyalkylene glycol mono(meth)acrylate, and the like.
  • hydroxypolyalkylene glycol mono(meth)acrylate examples include hydroxypolyethylene glycol mono(meth)acrylate, hydroxypolypropylene glycol mono(meth)acrylate, and the like.
  • Alkoxypolyalkylene glycol mono(meth)acrylates include, for example, methoxypolyalkylene glycol mono(meth)acrylate, ethoxypolyalkylene glycol mono(meth)acrylate, propoxypolyalkylene glycol mono(meth)acrylate, butoxypolyalkylene glycol mono(meth)acrylate, and butoxypolyalkylene glycol mono(meth)acrylate.
  • polyalkylene-containing materials include, for example, Blenmar PME-100, PME-200, PME-400, PME-1000, PME-4000, 50POEP-800B, PLE-200, PLE-1300, PSE-1300 (and above). , manufactured by NOF Corporation), Light Ester BC, 130MA, and 041MA (manufactured by Kyoeisha Chemical Co., Ltd.).
  • the mass% content is, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass. Examples include %. In one embodiment, the content is preferably 25% by mass to 60% by mass, more preferably 30% by mass to 55% by mass.
  • the mole% content (constituent unit (2)/total polymer constituent units) is, for example, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 15 mole %, 10 mol%, 9 mol%, 5 mol%, 2 mol%, 1 mol%, 0.5 mol%, etc.
  • the content is preferably 0.5 mol% to 50 mol%, more preferably 1 mol% to 40 mol%.
  • Alkyl (meth)acrylates may be used alone or in combination of two or more.
  • alkyl (meth)acrylates examples include linear alkyl (meth)acrylates, branched alkyl (meth)acrylates, and cycloalkyl (meth)acrylates.
  • Straight chain alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl Examples include (meth)acrylate.
  • Branched alkyl (meth)acrylates include, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 1-methylbutyl (meth)acrylate, 2-methylbutyl ( meth)acrylate, 3-methylbutyl(meth)acrylate, 1-ethylpropyl(meth)acrylate, 1,1-dimethylpropyl(meth)acrylate, 1,2-dimethylpropyl(meth)acrylate, 2,2-dimethylpropyl( Examples include meth)acrylate.
  • cycloalkyl (meth)acrylate examples include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate.
  • the alkyl (meth)acrylate is preferably a branched alkyl (meth)acrylate, more preferably a C3-5 branched alkyl (meth)acrylate.
  • the mass% content (constituent unit (3)/total polymer constituent units) is, for example, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass. %, 10% by mass, 5% by mass, etc. In one embodiment, the content is preferably 5% by mass to 50% by mass.
  • the mole% content (constituent unit (3)/total polymer constituent units) is, for example, 80 mole%, 75 mole%, 70 mole%, 65 mole%, 60 mole%, 55 mole%, 50 mole%, 45 mole %, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, etc. In one embodiment, the content is preferably 10 mol% to 80 mol%.
  • the polymer may optionally contain structural unit (4).
  • Structure (4) means “a structural unit derived from other monomers.”
  • Othermonomers mean monomers other than the quaternary ammonium salt-containing monomer, compound ⁇ , and alkyl (meth)acrylate. Other monomers may be used alone or in combination of two or more.
  • Examples of other monomers include aromatic ring structure-containing vinyl monomers.
  • aromatic ring structure-containing vinyl monomer examples include styrene, ⁇ -methylstyrene, and 4-methylstyrene.
  • Examples of the mass% content include less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, and 0% by mass.
  • mol% content examples include less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, and 0 mol%.
  • the mass% content (constituent unit (4)/any one of structural units (1) to (3)) is, for example, less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 Examples include mass %.
  • the mol% content (constituent unit (4)/any one of structural units (1) to (3)) is, for example, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, 0 Examples include mol%.
  • weight average molecular weight (polymer) examples include 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, and 180,000. In one embodiment, the weight average molecular weight is preferably 180,000 to 500,000.
  • Examples of the number average molecular weight (polymer) (Mn) include 200,000, 175,000, 150,000, 125,000, 100,000, and 50,000. In one embodiment, the number average molecular weight is preferably 50,000 to 200,000.
  • Molecular weight distribution (polymer) is, for example, 5.0, 4.9, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.9, 1.8 etc. are mentioned. In one embodiment, the molecular weight distribution is preferably 1.8 to 5.0.
  • the weight average molecular weight and number average molecular weight (polymer) can be measured under the following conditions. Measuring equipment: Product name "HLC-8320GPC", manufactured by Tosoh Corporation Column: Product name “TSKgel G6000PW XL -CP", “TSKgel G3000PW XL -CP", manufactured by Tosoh Corporation Developing solvent: 0.1M NaNO 3 and 0.1M acetic acid aqueous solution flow rate: 0.5mL/min Sample concentration: 0.5g/L Standard material: Polyethylene oxide (TSKgel Standard Polyethylene Oxide SE-Kit manufactured by Tosoh Corporation)
  • Examples of the manufacturing method (polymer) include radical polymerization.
  • radical polymerization initiators may be used alone or in combination of two or more.
  • examples of the radical polymerization initiator include inorganic peroxides, organic peroxides, and azo compounds.
  • inorganic peroxides examples include hydrogen peroxide, ammonium persulfate, potassium persulfate, and the like.
  • organic peroxides examples include benzoyl peroxide, dicumyl peroxide, and lauryl peroxide.
  • azo compounds examples include 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutyrate.
  • the amount used is preferably about 0.01 to 10 parts by mass.
  • a chain transfer agent may optionally be used during polymer production. Chain transfer agents may be used alone or in combination of two or more. Examples of chain transfer agents include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and ⁇ -methylstyrene dimer.
  • the amount used (chain transfer agent/total monomer components) is preferably about 0 to 10 parts by mass.
  • reaction solvent examples include the following organic solvents.
  • the reaction time is preferably 2 to 12 hours.
  • the polymerization temperature is preferably 70 to 130°C.
  • the mass% content (quaternary ammonium salt-containing polymer/active energy ray-curable resin composition nonvolatile content) is, for example, 20 mass%, 19 mass%, 17 mass%, 15 mass%, 13 mass%, 11 mass%. , 10% by mass, 9% by mass, 7% by mass, 5% by mass, 3% by mass, and the like. In one embodiment, the content is preferably 3% by mass to 20% by mass.
  • the composition may optionally include a phosphate ester.
  • Phosphoric esters may be used alone or in combination of two or more.
  • the phosphoric acid ester is represented by the following formula.
  • X represents a hydrogen atom, a metal atom, or an ammonium ion. (Represents a group.)
  • substituents examples include a (meth)acryloyloxy group and an alkoxy group.
  • metal atoms examples include alkali metal atoms and alkaline earth metal atoms.
  • Examples of the phosphoric acid monoester include (meth)acryloyloxyalkyl phosphate, (poly)alkyleneoxyalkyl phosphate, and the like.
  • Examples of the (meth)acryloyloxyalkyl phosphate include (meth)acryloyloxyethyl phosphate, (meth)acryloyloxypropyl phosphate, and (meth)acryloyloxybutyl phosphate.
  • Examples of the (poly)alkyleneoxyalkyl phosphate include ethyleneoxybutyl phosphate and decyl phosphate (ethylene oxydecyl).
  • phosphate esters include, for example, Light Ester P-1M, P-2M (Kyoeisha Kagaku Co., Ltd.), MP-4, MP-8 (Daihachi Kagaku Co., Ltd.), and the like.
  • Acid value is, for example, 600mgKOH/g, 590mgKOH/g, 580mgKOH/g, 570mgKOH/g, 560mgKOH/g, 550mgKOH/g, 540mgKOH/g, 530mgKOH/g, 520mgKOH/g, 510mgKOH/g , 500mgKOH/g, 490mgKOH/g, 480mgKOH/g, 470mgKOH/g, 460mgKOH/g, 450mgKOH/g, 440mgKOH/g, 430mgKOH/g, 420mgKOH/g, 410mgKOH/g, 400mgKOH/g, etc. Can be mentioned.
  • the acid value is preferably 400 mgKOH/g to 600 mgKOH/g.
  • the mass% content (phosphoric acid ester/active energy ray-curable resin composition nonvolatile content) is, for example, 12 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 3 mass%, 1 mass%. %, 0.9% by mass, 0.5% by mass, 0.3% by mass, 0% by mass, and the like. In one embodiment, the content is preferably 0% by mass to 12% by mass, more preferably 0.3% by mass to 12% by mass.
  • the nonvolatile mass ratio (phosphoric acid ester/polymer containing quaternary ammonium salt) is, for example, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0, etc. can be mentioned.
  • the nonvolatile mass ratio (phosphoric acid ester/quaternary ammonium salt-containing polymer) is preferably 0 to 0.7, more preferably 0.1 to 0.7. , more preferably 0.1 to 0.6. More preferable reasons include, for example, HAZE improvement.
  • composition may optionally include a salt. Salts may be used alone or in combination of two or more.
  • Salt means a compound consisting only of an anion and a cation.
  • Anions include polyoxyalkylene structures.
  • Polyoxyalkylene structure means a structure in which two or more oxyalkylene structures (-O-C n H 2n -) are consecutive.
  • polyoxyalkylene structure examples include a polyoxyethylene structure and a polyoxypropylene structure.
  • the polyoxyalkylene modification number is preferably 2 to 25, more preferably 5 to 20.
  • anion examples include a sulfate ion containing a polyoxyalkylene structure, a phosphate ion containing a polyoxyalkylene structure, and the like.
  • the anion is represented by the following formula.
  • R a1 - (OR a2 ) n -OXO 3 - R a1 represents an alkyl group (eg, C1-6 alkyl group) or an unsaturated group-containing group;
  • R a2 represents an alkylene group (eg, ethylene group, propylene group);
  • n represents an integer of 2 or more.
  • X represents S or P.
  • Examples of the unsaturated group-containing group include the following groups.
  • R b1 represents an alkyl group.
  • Y represents a single bond or an oxygen atom.
  • R b2 to R b4 each independently represent a hydrogen atom or a methyl group.
  • R c1 to R c3 each independently represent a hydrogen atom or a methyl group.
  • R c4 to R c7 each independently represent a hydrogen atom or a methyl group. represents.
  • cation examples include ammonium ions (NH 4 + ), quaternary ammonium salt-containing monomers, and metal ions.
  • Examples of the quaternary ammonium salt-containing monomer include the above-mentioned monomers.
  • metal ions examples include alkali metal ions.
  • alkali metal ions examples include lithium ions, sodium ions, potassium ions, and the like.
  • Examples of the salt (anion-cation) include alkyl polyethylene sulfate ion-ammonium ion, alkyl polyethylene sulfate ion-trimethyl-2-(meth)acryloyloxyethylammonium, alkyl polyethylene sulfate ion-(3-(meth)acryloylaminopropyl) Trimethyl ammonium, alkyl polyethylene sulfate ion - sodium ion, alkyl polyethylene phosphate ion - ammonium ion, alkyl polyethylene phosphate ion - trimethyl-2-(meth)acryloyloxyethylammonium, alkyl polyethylene phosphate ion - (3-(meth) acryloylaminopropyl) trimethylammonium, alkyl polyethylene phosphate ion - sodium ion, (In the formula, n1 to n5 each independently represent an integer of 2 or more
  • polyoxyalkylene structure-containing sulfates include, for example, Aminoion RE3000MF (manufactured by Nippon Nyukazai Co., Ltd.), ADEKA SOAP SR-10, SR-20 (manufactured by ADEKA Co., Ltd.), Aqualon KH-05, KH- 10, AR-10, AR-20 (manufactured by Dai-ichi Kogyo Co., Ltd.), and the like.
  • phosphates containing polyoxyalkylene structures include, for example, Disparon PW-36 (manufactured by Kusumoto Kasei Co., Ltd.).
  • the mass % content (salt/active energy ray curable resin composition nonvolatile content) is, for example, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, Examples include 15% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, and 0% by mass.
  • the content is preferably 0% by mass to 50% by mass, more preferably 1% by mass to 50% by mass.
  • the mass part content is, for example, 1667 parts by mass, 1500 parts by mass, 1000 parts by mass, 500 parts by mass, 200 parts by mass, 100 parts by mass, 75 parts by mass, 50 parts by mass, Examples include 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 5 parts by mass, and 0 parts by mass.
  • the content is preferably from 0 parts by mass to 1667 parts by mass, more preferably from 5 parts by mass to 1667 parts by mass, and even more preferably from 5 parts by mass to 75 parts by mass. parts, and particularly preferably from 5 parts by weight to 50 parts by weight. Further preferable reasons, particularly preferable reasons include, for example, improvement in HAZE.
  • the composition may optionally include poly(meth)acrylate.
  • Poly(meth)acrylates may be used alone or in combination of two or more.
  • Poly(meth)acrylate means a compound having two or more (meth)acryloyl groups.
  • poly(meth)acrylate examples include (poly)pentaerythritol poly(meth)acrylate, urethane poly(meth)acrylate, and the like.
  • ((Poly)pentaerythritol poly(meth)acrylate examples include pentaerythritol poly(meth)acrylate, polypentaerythritol poly(meth)acrylate, and the like.
  • pentaerythritol poly(meth)acrylate examples include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.
  • Polypentaerythritol poly(meth)acrylates include, for example, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.
  • Erythritol hexa(meth)acrylate tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate Acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and the like.
  • urethane poly(meth)acrylate examples include reactants of a group of compounds including hydroxyl group-containing poly(meth)acrylate and polyisocyanate.
  • hydroxyl group-containing poly(meth)acrylate examples include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and (poly)glycerin poly(meth)acrylate.
  • Polyisocyanates may be used alone or in combination of two or more.
  • polyisocyanates examples include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biuret, isocyanurate, allophanate, and adduct forms.
  • linear aliphatic polyisocyanates examples include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like. Can be mentioned.
  • branched aliphatic polyisocyanates examples include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.
  • alicyclic polyisocyanate examples include monocyclic alicyclic polyisocyanate, crosslinked alicyclic polyisocyanate, and fused ring alicyclic polyisocyanate.
  • Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, Examples include dicyclohexylmethane diisocyanate.
  • crosslinked cyclic alicyclic polyisocyanate examples include tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.
  • condensed ring alicyclic polyisocyanate examples include bicyclodecylene diisocyanate.
  • aromatic polyisocyanates examples include monocyclic aromatic polyisocyanates, condensed ring aromatic polyisocyanates, and the like.
  • Monocyclic aromatic polyisocyanates include, for example, dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, Examples include 4,4'-dibenzylisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and the like.
  • dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate
  • tetraalkyldiphenylmethane diisocyanates such as 4,4
  • Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthylene diisocyanate.
  • the urethane poly(meth)acrylate preferably includes a urethane poly(meth)acrylate having (poly)pentaerythritol poly(meth)acrylate as a constituent unit.
  • the mass% content (poly(meth)acrylate/active energy ray-curable resin composition nonvolatile content) is, for example, 97% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass% %, 5% by mass, 1% by mass, 0% by mass, etc.
  • the content is preferably 0% by mass to 97% by mass.
  • the active energy ray-curable composition may optionally include a photopolymerization initiator.
  • the photopolymerization initiators may be used alone or in combination of two or more.
  • photopolymerization initiator examples include ⁇ -hydroxydimethylacetophenone group-containing photopolymerization initiator, ⁇ -hydroxycycloalkylphenone, ⁇ -aminoalkylphenone, benzyl dimethyl ketal, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, Examples include unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, oxime ester, and the like.
  • the ⁇ -hydroxydimethylacetophenone group-containing photoinitiator is, for example, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, non, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, and the like.
  • Examples of ⁇ -hydroxycycloalkylphenones include 1-hydroxycyclohexylphenyl ketone.
  • ⁇ -aminoalkylphenones examples include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.
  • Examples of the benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethan-1-one.
  • Unsubstituted or substituted alkylphenones include, for example, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl -2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2 -isonitrosopropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.
  • unsubstituted or substituted benzyl examples include benzyl and p-anisyl.
  • Unsubstituted or substituted benzophenones include, for example, benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, Examples include 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and methyl 2-benzoylbenzoate.
  • acylphosphine oxide examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
  • substituted thioxanthone examples include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
  • Oxime esters are, for example, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (i.e. 2-((benzoyloxy)imino)-1-(4-( phenylthio)phenyl)octan-1-one); Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (i.e. 1-(((1-(9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethane-1-one) and the like.
  • the mass% content (photopolymerization initiator/active energy ray-curable resin composition nonvolatile content) is, for example, 15% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass. Examples include mass%, 3% by mass, and 1% by mass. In one embodiment, the content is preferably 0% by mass to 15% by mass, more preferably 1% by mass to 15% by mass.
  • the active energy radiation curable composition may optionally include a leveling agent.
  • Leveling agents may be used alone or in combination of two or more.
  • leveling agent examples include silicone leveling agents and fluorine leveling agents.
  • the mass % content (leveling agent/active energy ray curable resin composition nonvolatile content) is, for example, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass % , 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 10% by mass.
  • the active energy ray-curable composition may optionally include an organic solvent.
  • Organic solvents may be used alone or in combination of two or more.
  • organic solvents examples include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, and amide solvents.
  • ketone solvent examples include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.
  • aromatic solvents examples include toluene and xylene.
  • alcohol solvent examples include methanol, ethanol, n-propanol, isopropanol, butanol, and the like.
  • glycol solvent examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and the like.
  • Glycol ether solvents include, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl Examples include ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, and the like.
  • ester solvent examples include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and the like.
  • Examples of petroleum solvents include Solvesso #100 (manufactured by Exxon) and Solvesso #150 (manufactured by Exxon).
  • haloalkane solvent examples include chloroform.
  • Examples of the amide solvent include dimethylformamide.
  • the mass parts content is, for example, 1900 parts by mass, 1750 parts by mass, 1500 parts by mass, 1250 parts by mass, 1000 parts by mass, 500 parts by mass, 100 parts by mass. , 75 parts by mass, 50 parts by mass, 25 parts by mass, 10 parts by mass, 0 parts by mass, and the like.
  • the content is preferably 0 parts by mass to 1900 parts by mass, more preferably 10 parts by mass to 1000 parts by mass.
  • the active energy ray-curable resin composition may optionally contain agents (additives) other than "a quaternary ammonium salt-containing polymer, a phosphate ester, (poly)(meth)acrylate, a photopolymerization initiator, a leveling agent, and an organic solvent.” ) may be included.
  • additives include antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifoaming agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.
  • the mass % content is, for example, less than 10 mass %, less than 5 mass %, less than 1 mass %, less than 0.1 mass %, 0 Examples include less than .01% by mass, 0% by mass, and the like.
  • the parts by weight content (any one of additive/quaternary ammonium salt-containing polymer, phosphoric acid ester, (poly)(meth)acrylate, photoinitiator, and organic solvent) is, for example, Examples include less than 5% by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 part by mass.
  • the active energy ray-curable resin composition contains a quaternary ammonium salt-containing polymer, a phosphoric acid ester, and optionally (poly)(meth)acrylate, a photopolymerization initiator, a leveling agent, an organic solvent, and an additive. It can be manufactured by mixing.
  • dispersing/mixing means examples include an emulsifying disperser, an ultrasonic dispersing device, and the like.
  • the acid value is, for example, 600mgKOH/g, 590mgKOH/g, 580mgKOH/g, 570mgKOH/g, 560mgKOH/g, 550mgKOH/g, 540mgKOH/g, 530mgKOH/g, 520mgKOH/g.
  • the acid value is preferably 0 mgKOH/g to 600 mgKOH/g, more preferably 400 mgKOH/g to 600 mgKOH/g.
  • Acid value can be measured under the following conditions. The following conditions are based on JIS K-0070.
  • Reagent A 0.5 mol/ dm potassium hydroxide ethanol solution
  • (1) Weigh 1 g of a sample containing no inorganic acid into a 300 mL Erlenmeyer flask.
  • the cured product of the composition also has good transmittance.
  • a highly polar resin urethane (meth)acrylate, etc.
  • the cured product of the above-mentioned composition has good surface properties and also has good liquid compatibility of the above-mentioned composition.
  • less polar solvents such as methyl isobutyl ketone may be used.
  • usage forms include antistatic agents, coating agents, and the like.
  • the present disclosure relates to a cured product of the active energy ray-curable resin composition.
  • Examples of the curing conditions include the following conditions.
  • the present disclosure relates to a laminate containing the above-mentioned cured product.
  • the method for producing a laminate includes a step of coating the composition on at least one side of a base material (coating step), a step of forming a cured material layer by irradiating active energy rays ( active energy ray curing process).
  • the base material examples include polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS film, AS film, norbornene resin. Film, cyclic olefin film, polyvinyl alcohol film and the like.
  • the thickness (base material) is preferably 10 ⁇ m to 2000 ⁇ m.
  • the thickness (cured material layer) is preferably 0.1 ⁇ m to 20 ⁇ m.
  • Coating process Coating methods include, for example, bar coater coating, wire bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coat coating, offset printing, flexo printing, screen printing, etc. can be mentioned.
  • active energy ray curing process examples include ultraviolet rays and electron beams.
  • Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.
  • the curing conditions are preferably the following conditions.
  • the curing conditions are preferably the following conditions. Acceleration voltage: 10kV to 300kV Conveying speed: 5m/min ⁇ 50m/min
  • Synthesis example 1 130 parts of hydroxyethyl methacrylate, 1140 parts of ⁇ -caprolactone and 1.3 parts of tin octylate were added to a reaction apparatus equipped with a stirring device and a cooling tube, the temperature was raised to 150°C, the temperature was kept for 6 hours, and then cooled. A ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone having a weight average molecular weight of about 2,750 was obtained.
  • the weight average molecular weight of the above ring-opening polyadduct was determined using a commercially available molecular weight analyzer (main product name: "HLC-8220GPC", manufactured by Tosoh Corporation; column product name: “TSKgel SuperHZ-M”, manufactured by Tosoh Corporation). Using, developing solvent: tetrahydrofuran flow rate: 0.35 mL/min sample concentration: 0.5% Standard material: Polystyrene (Standard polystyrene kit PStQuick A, B, C manufactured by Tosoh Corporation) This value was obtained by measuring under the following conditions.
  • AMBN 2,2'-azobis(methylbutyronitrile)
  • PGM 2,2'-azobis(methylbutyronitrile)
  • Example 1-1 Active energy ray-curable resin composition 5 parts of the polymer of Production Example 1 and 0.2 parts of 2-methacryloyloxyethyl phosphate (trade name "Light Ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd.). 5 parts, 89.5 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-9550W”), a photopolymerization initiator (manufactured by IGM Resins).
  • NK Ester A-9550W a photopolymerization initiator
  • Example 1-1 Unless otherwise specified, the following examples were carried out in the same manner as Example 1-1, except for the changes shown in the table.
  • P-1M 2-methacryloyloxyethyl phosphate, manufactured by Kyoeisha Chemical Co., Ltd.
  • P-2M Di(2-methacryloyloxyethyl) phosphate, manufactured by Kyoeisha Chemical Co., Ltd.
  • Acid value The acid value was measured under the following conditions.
  • Reagent A 0.5 mol/ dm potassium hydroxide ethanol solution
  • 100 mL of reagent B and a phenolphthalein indicator were added to the Erlenmeyer flask, and the flask was sufficiently shaken until the sample was completely dissolved.
  • Example 2-1 Active energy ray-curable resin composition 25 parts of the polymer of Production Example 1 and 1 part of salt (Aminoion RE3000MF, manufactured by Nippon Nyukazai Co., Ltd.) were heated at 60°C for 1 hour, and then placed in a shaker. and mixed to obtain a polymer composition. Next, 5 parts of a photopolymerization initiator (Omnirad 2959, manufactured by IGM Resins B.V.), the above polymer composition, 70.5 parts of propylene glycol monomethyl ether, and 215.5 parts of methyl isobutyl ketone were mixed in a shaker. Then, 125 parts of poly(meth)acrylate A and 1.5 parts of a leveling agent (Ftergent 602A) were added and mixed using a shaker to produce an active energy ray-curable resin composition.
  • a photopolymerization initiator Omnirad 2959, manufactured by IGM Resins B.V.
  • Example 2-1 Unless otherwise specified, the following examples were carried out in the same manner as Example 2-1 except for the changes shown in the table.
  • the active energy ray-curable resin composition was applied onto a polyethylene terephthalate film (Lumirror 100 manufactured by Toray Industries, Inc., film thickness: 100 ⁇ m) using a #11 bar coater so that the thickness of the cured material layer was 5 ⁇ m. The coating was applied at 80° C. for 1 minute. Next, a laminate containing a cured product was obtained using an ultraviolet curing device (product name: UBT-080-7A/BM, manufactured by Multiply Co., Ltd., high pressure mercury lamp 200 mJ/cm 2 ).
  • an ultraviolet curing device product name: UBT-080-7A/BM, manufactured by Multiply Co., Ltd., high pressure mercury lamp 200 mJ/cm 2 ).
  • Liquid compatibility Evaluated based on the following criteria. Other evaluations could not be made for the examples in which the liquid compatibility was rated as x. ⁇ : Completely dissolved. ⁇ : Partially dissolved or not dissolved.
  • the salt/quaternary ammonium salt-containing polymer ratio was calculated based on the following formula.
  • Salt/quaternary ammonium salt-containing polymer ratio [(A ⁇ a)/(B ⁇ b)] ⁇ 100
  • RE3000MF Aminoion RE3000MF (polyoxyalkylene structure-containing sulfate, non-volatile content 50%, manufactured by Nippon Nyukazai Co., Ltd.)
  • SR-20 ADEKA SOAP SR-20 (polyoxyalkylene structure-containing sulfate, non-volatile content 100%, manufactured by ADEKA Co., Ltd.)
  • PW-36 Disparon PW-36 (phosphate containing polyoxyalkylene structure, non-volatile content 50%, manufactured by Kusumoto Kasei Co
  • P-1M Light ester P-1M, 2-methacryloyloxyethyl phosphate, 100% nonvolatile content, manufactured by Kyoeisha Chemical Co., Ltd.
  • Poly(meth)acrylate A Reaction product of biuret hexamethylene diisocyanate and pentaerythritol triacrylate (urethane acrylate), non-volatile content 80%
  • Poly(meth)acrylate B Reaction product of hexamethylene diisocyanate nurate and pentaerythritol triacrylate (urethane acrylate), non-volatile content 80%
  • Poly(meth)acrylate C Product name "SC-2152", reaction product of hexamethylene diisocyanate nurate and dipentaerythritol pentaacrylate (urethane acrylate), manufactured by MIWON, non-volatile content 100% Omnirad2959, manufactured by IGM Resins B.V., non-volatile content 100% FT602A

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

An actinic-ray-curable resin composition comprising: a polymer containing a quaternary ammonium salt; and a phosphoric acid ester and/or a salt, the anion of the salt including a polyoxyalkylene structure. The actinic-ray-curable resin composition, when containing the phosphoric acid ester, has an acid value of 400-600 mgKOH/g.

Description

活性エネルギー線硬化性樹脂組成物、硬化物及び積層物Active energy ray-curable resin compositions, cured products and laminates
　本開示は、活性エネルギー線硬化性樹脂組成物、硬化物及び積層物に関する。 The present disclosure relates to an active energy ray-curable resin composition, a cured product, and a laminate.
　活性エネルギー線硬化性樹脂組成物をフラットパネルディスプレイ用途に用いる場合、ディスプレイの組立や作動中の静電気に起因したトラブルを防止したり、高精細画像を実現したりするために、良好な帯電防止性が要求される。 When using active energy ray-curable resin compositions for flat panel display applications, good antistatic properties are required to prevent troubles caused by static electricity during display assembly and operation, and to realize high-definition images. is required.
特開２０１９－１１２６３０号公報Japanese Patent Application Publication No. 2019-112630
　本発明が解決しようとする課題は、帯電防止性が良好な硬化物を製造するための活性エネルギー線硬化性組成物を提供することとする。 The problem to be solved by the present invention is to provide an active energy ray-curable composition for producing a cured product with good antistatic properties.
　本発明者らは、特定の成分を用いることにより、上記課題が解決されることを見出した。 The present inventors have discovered that the above problems can be solved by using specific components.
　本開示により以下の項目が提供される。
（項目１）
活性エネルギー線硬化性樹脂組成物であって、
前記活性エネルギー線硬化性樹脂組成物は、４級アンモニウム塩含有ポリマー並びにリン酸エステル及び／又は塩を含み、
前記塩のアニオンはポリオキシアルキレン構造を含み、
前記活性エネルギー線硬化性樹脂組成物がリン酸エステルを含む場合、前記活性エネルギー線硬化性樹脂組成物の酸価は、４００ｍｇＫＯＨ／ｇ～６００ｍｇＫＯＨ／ｇである、
活性エネルギー線硬化性樹脂組成物。
（項目２）
ウレタンポリ（メタ）アクリレートを含む、上記項目に記載の活性エネルギー線硬化性樹脂組成物。
（項目３）
上記項目のいずれか１項に記載の活性エネルギー線硬化性樹脂組成物の硬化物。
（項目４）
上記項目に記載の硬化物を含む、積層物。
（項目Ａ１）
活性エネルギー線硬化性樹脂組成物であって、
前記活性エネルギー線硬化性樹脂組成物は４級アンモニウム塩含有ポリマー及びリン酸エステルを含み、
前記活性エネルギー線硬化性樹脂組成物の酸価は４００ｍｇＫＯＨ／ｇ～６００ｍｇＫＯＨ／ｇである、活性エネルギー線硬化性樹脂組成物。
（項目Ａ２）
前記４級アンモニウム塩含有ポリマーは構成単位（１）、構成単位（２）及び構成単位（３）を含み、
前記構成単位（１）は４級アンモニウム塩含有モノマーに由来し、
前記構成単位（２）は下記化合物αに由来し、
Ａ－Ｂ－（Ｃ）ｎ－Ｄ
（Ａは（メタ）アクリロイルオキシ基を表す。Ｂは単結合又はアルキレン基を表す。Ｃは－Ｏ－Ｃ（＝Ｏ）ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－又はオキシアルキレン基を表す。Ｄは水酸基、アルコキシ基又はアルキル基を表す。ｎは１以上の整数を表す。）
前記構成単位（３）はアルキル（メタ）アクリレートに由来する、
上記項目に記載の活性エネルギー線硬化性樹脂組成物。
（項目Ａ３）
不揮発分質量比（前記リン酸エステル／前記４級アンモニウム塩含有ポリマー）が０．１～０．７である、上記項目のいずれか１項に記載の活性エネルギー線硬化性樹脂組成物。
（項目Ａ４）
（ポリ）ペンタエリスリトールポリ（メタ）アクリレート及び／又は（ポリ）ペンタエリスリトールポリ（メタ）アクリレートを構成単位に有するウレタンポリ（メタ）アクリレートを含む、上記項目のいずれか１項に記載の活性エネルギー線硬化性樹脂組成物。
（項目Ａ５）
上記項目のいずれか１項に記載の活性エネルギー線硬化性樹脂組成物の硬化物。
（項目Ａ６）
上記項目に記載の硬化物を含む、積層物。
（項目Ｂ１）
活性エネルギー線硬化性樹脂組成物であって、
前記活性エネルギー線硬化性樹脂組成物は４級アンモニウム塩含有ポリマー及び塩を含み、
前記塩のアニオンはポリオキシアルキレン構造を含む、
活性エネルギー線硬化性樹脂組成物。
（項目Ｂ２）
ウレタンポリ（メタ）アクリレートを含む、上記項目に記載の活性エネルギー線硬化性樹脂組成物。
（項目Ｂ３）
上記項目のいずれか１項に記載の活性エネルギー線硬化性樹脂組成物の硬化物。
（項目Ｂ４）
上記項目に記載の硬化物を含む、積層物。 The present disclosure provides the following items.
(Item 1)
An active energy ray-curable resin composition,
The active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a phosphoric acid ester and/or salt,
The anion of the salt includes a polyoxyalkylene structure,
When the active energy ray curable resin composition contains a phosphoric acid ester, the acid value of the active energy ray curable resin composition is 400 mgKOH/g to 600 mgKOH/g.
Active energy ray curable resin composition.
(Item 2)
The active energy ray-curable resin composition described in the above item, which contains urethane poly(meth)acrylate.
(Item 3)
A cured product of the active energy ray-curable resin composition according to any one of the above items.
(Item 4)
A laminate containing the cured product described in the above items.
(Item A1)
An active energy ray-curable resin composition,
The active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a phosphoric acid ester,
The active energy ray curable resin composition has an acid value of 400 mgKOH/g to 600 mgKOH/g.
(Item A2)
The quaternary ammonium salt-containing polymer includes a structural unit (1), a structural unit (2), and a structural unit (3),
The structural unit (1) is derived from a quaternary ammonium salt-containing monomer,
The structural unit (2) is derived from the following compound α,
A-B-(C) n -D
(A represents a (meth)acryloyloxy group. B represents a single bond or an alkylene group. C represents -OC(=O)CH 2 CH 2 CH 2 CH 2 CH 2 - or an oxyalkylene group. D represents a hydroxyl group, an alkoxy group, or an alkyl group. n represents an integer of 1 or more.)
The structural unit (3) is derived from alkyl (meth)acrylate,
The active energy ray-curable resin composition described in the above item.
(Item A3)
The active energy ray-curable resin composition according to any one of the above items, wherein the nonvolatile mass ratio (the phosphoric acid ester/the quaternary ammonium salt-containing polymer) is 0.1 to 0.7.
(Item A4)
The active energy ray according to any one of the above items, which contains a urethane poly(meth)acrylate having (poly)pentaerythritol poly(meth)acrylate and/or (poly)pentaerythritol poly(meth)acrylate as a constituent unit. Curable resin composition.
(Item A5)
A cured product of the active energy ray-curable resin composition according to any one of the above items.
(Item A6)
A laminate containing the cured product described in the above items.
(Item B1)
An active energy ray-curable resin composition,
The active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a salt,
the anion of the salt includes a polyoxyalkylene structure;
Active energy ray curable resin composition.
(Item B2)
The active energy ray-curable resin composition described in the above item, which contains urethane poly(meth)acrylate.
(Item B3)
A cured product of the active energy ray-curable resin composition according to any one of the above items.
(Item B4)
A laminate containing the cured product described in the above items.
　本開示において、上述した１又は複数の特徴は、明示された組み合わせに加え、さらに組み合わせて提供され得る。 In the present disclosure, one or more of the features described above may be provided in further combinations in addition to the specified combinations.
　本開示の活性エネルギー線硬化性組成物を用いることにより、帯電防止性が良好である硬化物を製造できる。 By using the active energy ray-curable composition of the present disclosure, a cured product with good antistatic properties can be produced.
　本開示の全体にわたり、各物性値、含有量等の数値の範囲は、適宜（例えば下記の各項目に記載の値から選択して）設定され得る。具体的には、数値αの例示がＡ３、Ａ２、Ａ１（Ａ３＞Ａ２＞Ａ１とする）である場合、数値αの範囲は、例えば、Ａ３以下、Ａ２以下、Ａ３未満、Ａ２未満、Ａ１以上、Ａ２以上、Ａ１より大きい、Ａ２より大きい、Ａ１～Ａ２（Ａ１以上Ａ２以下）、Ａ１～Ａ３、Ａ２～Ａ３、Ａ１以上Ａ３未満、Ａ１以上Ａ２未満、Ａ２以上Ａ３未満、Ａ１より大きくＡ３未満、Ａ１より大きくＡ２未満、Ａ２より大きくＡ３未満、Ａ１より大きくＡ３以下、Ａ１より大きくＡ２以下、Ａ２より大きくＡ３以下等が挙げられる。 Throughout the present disclosure, numerical ranges for each physical property value, content, etc. may be set as appropriate (for example, by selecting from the values listed in each item below). Specifically, when the numerical value α is exemplified by A3, A2, A1 (A3>A2>A1), the range of the numerical value α is, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more. , A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3 , greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, etc.
　本発明が解決しようとする課題が解決される限り、成分、条件、数値等は、明細書の記載に限定されない。 Components, conditions, numerical values, etc. are not limited to those described in the specification as long as the problems to be solved by the present invention are solved.
　「αβ量（Ａ／Ｂ）」は、Ｂ１００αに対するＡのβ量（α）を意味する。αは、例えば、質量％、モル％、質量部等が挙げられる。β量は、例えば、含有量、使用量等が挙げられる。αβ量は、例えば、質量％含有量等が挙げられる。 "αβ amount (A/B)" means the β amount (α) of A relative to B100α. Examples of α include mass %, mol %, parts by mass, and the like. Examples of the amount of β include content, amount used, and the like. Examples of the αβ amount include mass % content.
　「γ比（Ａ／Ｂ）」は、式「Ａ÷Ｂ」により算出されるγ比を意味する。γ比は、例えば、質量比、モル比等が挙げられる。 "γ ratio (A/B)" means the γ ratio calculated by the formula "A÷B". Examples of the γ ratio include mass ratio and molar ratio.
　「不揮発分」は、有機溶剤及び水以外の成分の合計質量を意味する。１つの実施形態において、対象物Ａの不揮発分は、対象物Ａ　１ｇを１０５℃で加熱して恒量に達した時点で残存した成分の合計質量とする。 "Nonvolatile content" means the total mass of components other than organic solvent and water. In one embodiment, the non-volatile content of the object A is the total mass of components remaining after heating 1 g of the object A at 105° C. and reaching a constant weight.
　「（メタ）アクリル」は、「アクリル及びメタクリルからなる群より選択される少なくとも１つ」を意味する。「（メタ）アクリレート」は、「アクリレート及びメタクリレートからなる群より選択される少なくとも１つ」を意味する。「（メタ）アクリロイル」は、「アクリロイル及びメタクリロイルからなる群より選択される少なくとも１つ」を意味する。 "(Meth)acrylic" means "at least one selected from the group consisting of acrylic and methacrylic." "(Meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate." "(Meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl."
　「Ｃ・・・」は、「炭素数・・・の」を意味する。例えば、「Ｃ１～６アルキル基」は、炭素数１～６のアルキル基を意味する。「Ｃ６アルキル基」は、炭素数６のアルキル基を意味する。 "C..." means "carbon number...". For example, "C1-6 alkyl group" means an alkyl group having 1 to 6 carbon atoms. "C6 alkyl group" means an alkyl group having 6 carbon atoms.
［活性エネルギー線硬化性樹脂組成物：組成物］
　本開示は、活性エネルギー線硬化性樹脂組成物であって、
前記活性エネルギー線硬化性樹脂組成物は、４級アンモニウム塩含有ポリマー並びにリン酸エステル及び／又は塩を含み、
前記塩のアニオンはポリオキシアルキレン構造を含み、
前記活性エネルギー線硬化性樹脂組成物がリン酸エステルを含む場合、前記活性エネルギー線硬化性樹脂組成物の酸価は、４００ｍｇＫＯＨ／ｇ～６００ｍｇＫＯＨ／ｇである、
活性エネルギー線硬化性樹脂組成物に関する。 [Active energy ray-curable resin composition: composition]
The present disclosure provides an active energy ray-curable resin composition,
The active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a phosphoric acid ester and/or salt,
The anion of the salt includes a polyoxyalkylene structure,
When the active energy ray curable resin composition contains a phosphoric acid ester, the acid value of the active energy ray curable resin composition is 400 mgKOH/g to 600 mgKOH/g.
The present invention relates to an active energy ray-curable resin composition.
＜４級アンモニウム塩含有ポリマー：ポリマー＞
　４級アンモニウム塩含有ポリマーは、単独又は２種以上で使用され得る。 <Quaternary ammonium salt-containing polymer: polymer>
The quaternary ammonium salt-containing polymers may be used alone or in combination of two or more.
　１つの実施形態において、前記４級アンモニウム塩含有ポリマーは構成単位（１）、構成単位（２）及び構成単位（３）を含み、
前記構成単位（１）は４級アンモニウム塩含有モノマーに由来し、
前記構成単位（２）は下記化合物αに由来し、
Ａ－Ｂ－（Ｃ）ｎ－Ｄ
（Ａは（メタ）アクリロイルオキシ基を表す。Ｂは単結合又はアルキレン基を表す。Ｃは－Ｏ－Ｃ（＝Ｏ）ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－又はオキシアルキレン基を表す。Ｄは水酸基、アルコキシ基又はアルキル基を表す。ｎは１以上の整数を表す。）
前記構成単位（３）はアルキル（メタ）アクリレートに由来する。 In one embodiment, the quaternary ammonium salt-containing polymer includes a structural unit (1), a structural unit (2), and a structural unit (3),
The structural unit (1) is derived from a quaternary ammonium salt-containing monomer,
The structural unit (2) is derived from the following compound α,
A-B-(C) n -D
(A represents a (meth)acryloyloxy group. B represents a single bond or an alkylene group. C represents -OC(=O)CH 2 CH 2 CH 2 CH 2 CH 2 - or an oxyalkylene group. D represents a hydroxyl group, an alkoxy group, or an alkyl group. n represents an integer of 1 or more.)
The structural unit (3) is derived from alkyl (meth)acrylate.
（構成単位（１））
　４級アンモニウム塩含有モノマーは、単独又は２種以上で使用され得る。 (Constituent unit (1))
The quaternary ammonium salt-containing monomers may be used alone or in combination of two or more.
　４級アンモニウム塩含有モノマーは、下記式で表わされる（メタ）アクリレート等が挙げられる。
[ＣＨ２＝Ｃ（Ｒ１）－Ｃ（＝Ｏ）－Ａ－Ｂ－Ｎ＋（Ｒ２）（Ｒ３）（Ｒ４）]ｎ・Ｘｎ－
（式中、Ｒ１はＨ又はＣＨ３を表す。Ｒ２～Ｒ４はそれぞれ独立してＣ１～４アルキル基を表す。ＡはＯ又はＮＨを表す。ＢはＣ１～３アルキレン基を表す。Ｘ－はアニオンを表す。ｎは１以上の整数を表す。） Examples of the quaternary ammonium salt-containing monomer include (meth)acrylate represented by the following formula.
[CH 2 =C(R 1 )-C(=O)-AB-N + (R 2 )(R 3 )(R 4 )] n・X n-
(In the formula, R 1 represents H or CH 3. R 2 to R 4 each independently represent a C1-4 alkyl group. A represents O or NH. B represents a C1-3 alkylene group. X - represents an anion. n represents an integer of 1 or more.)
　Ｃ１～４アルキル基は、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基等が挙げられる。 Examples of the C1-4 alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group.
　Ｃ１～３アルキレン基は、例えば、メチレン基、エチレン基、プロピレン基、イソプロピレン基等が挙げられる。 Examples of the C1-3 alkylene group include a methylene group, an ethylene group, a propylene group, and an isopropylene group.
　Ｘｎ－は、例えば、ハロゲンイオン、硫黄含有イオン等が挙げられる。 Examples of X n- include halogen ions and sulfur-containing ions.
　ハロゲンイオンは、例えば、フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン等が挙げられる。 Examples of halogen ions include fluoride ions, chloride ions, bromide ions, and iodide ions.
　硫黄含有イオンは、例えば、硫酸イオン、亜硫酸イオン、Ｃ２Ｈ５ＳＯ４ －、ＲＳ１－（ＯＲＳ２）ｓ－ＯＳＯ３ －等が挙げられる。ＲＳ１はアルキル基、アリール基を表す。ＲＳ２はアルキレン基を表す。ｓは１以上の整数を表す Examples of the sulfur-containing ions include sulfate ions, sulfite ions, C 2 H 5 SO 4 - , R S1 -(OR S2 ) s -OSO 3 - , and the like. R S1 represents an alkyl group or an aryl group. R S2 represents an alkylene group. s represents an integer greater than or equal to 1
　ＲＳ１は、好ましくは、アルキル基が挙げられ、より好ましくは、Ｃ１～４アルキル基が挙げられる。ＲＳ２は、好ましくは、Ｃ２～３アルキレン基が挙げられる。 R S1 is preferably an alkyl group, more preferably a C1-4 alkyl group. Preferably, R S2 is a C2-3 alkylene group.
　１つの実施形態において、Ｘｎ－は、好ましくは、塩化物イオン、ＲＳ１－（ＯＲＳ２）ｓ－ＯＳＯ３ －が挙げられる。 In one embodiment, X n- preferably includes chloride ion, R S1 -(OR S2 ) s -OSO 3 - .
　ｎは、例えば、１、２等が挙げられる。１つの実施形態において、ｎは、好ましくは、１が挙げられる。 Examples of n include 1, 2, etc. In one embodiment, n preferably includes 1.
　４級アンモニウム塩含有モノマー（アニオン除く）は、例えば、トリメチル－２－（メタ）アクリロイルオキシエチルアンモニウム、（３－（メタ）アクリロイルアミノプロピル）トリメチルアンモニウム等が挙げられる。 Examples of the quaternary ammonium salt-containing monomer (excluding anion) include trimethyl-2-(meth)acryloyloxyethylammonium, (3-(meth)acryloylaminopropyl)trimethylammonium, and the like.
　市販品（４級アンモニウム塩含有モノマー）は、例えば、共栄社化学（株）製「ライトエステルＤＱ－１００」、興人（株）製「ＤＭＡＥＡ－Ｑ」、日本乳化剤（株）製「アミノイオンＲＥ３０００ＭＦ」等が挙げられる。 Commercially available products (monomers containing quaternary ammonium salts) include, for example, "Light Ester DQ-100" manufactured by Kyoeisha Kagaku Co., Ltd., "DMAEA-Q" manufactured by Kojin Co., Ltd., and "Amino Ion RE3000MF manufactured by Nippon Nyukazai Co., Ltd." ” etc.
　質量％含有量（構成単位（１）／ポリマー全構成単位）は、例えば、７０質量％、６５質量％、６０質量％、５５質量％、５０質量％、４５質量％、４０質量％、３５質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、２５質量％～７０質量％が挙げられ、より好ましくは３５質量％～６０質量％が挙げられる。 The mass% content (constituent unit (1)/total polymer constituent units) is, for example, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass. Examples include %. In one embodiment, the content is preferably 25% by mass to 70% by mass, more preferably 35% by mass to 60% by mass.
　モル％含有量（構成単位（１）／ポリマー全構成単位）は、８４モル％、８０モル％、７５モル％、７０モル％、６５モル％、６０モル％、５５モル％、５０モル％、４５モル％、４０モル％、３５モル％、３０モル％、２５モル％、２１モル％、２０モル％、１５モル％、１４モル％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、１４モル％～８４モル％が挙げられ、より好ましくは２１モル％～８０モル％が挙げられる。 The mol% content (constituent unit (1)/all polymer structural units) is 84 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, Examples include 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 21 mol%, 20 mol%, 15 mol%, and 14 mol%. In one embodiment, the content is preferably 14 mol% to 84 mol%, more preferably 21 mol% to 80 mol%.
（構成単位（２））
　化合物αは、単独又は２種以上で使用され得る。 (Constituent unit (2))
Compound α may be used alone or in combination of two or more.
　化合物αは、下記式で表される。
Ａ－Ｂ－（Ｃ）ｎ－Ｄ
（Ａは（メタ）アクリロイルオキシ基を表す。Ｂは単結合又はアルキレン基を表す。Ｃは－Ｏ－Ｃ（＝Ｏ）ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－又はオキシアルキレン基を表す。Ｄは水酸基、アルコキシ基又はアルキル基を表す。ｎは１以上の整数を表す。） Compound α is represented by the following formula.
A-B-(C) n -D
(A represents a (meth)acryloyloxy group. B represents a single bond or an alkylene group. C represents -OC(=O)CH 2 CH 2 CH 2 CH 2 CH 2 - or an oxyalkylene group. D represents a hydroxyl group, an alkoxy group, or an alkyl group. n represents an integer of 1 or more.)
　化合物αは、例えば、ラクトン開環重付加物（Ｃ：－Ｏ－Ｃ（＝Ｏ）ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－）、ポリアルキレン含有物（Ｃ：オキシアルキレン基）等が挙げられる。 Examples of the compound α include lactone ring-opening polyadducts (C: -O-C(=O)CH 2 CH 2 CH 2 CH 2 CH 2 -), polyalkylene-containing compounds (C: oxyalkylene group), etc. It will be done.
　化合物αにおいて、アルキル基は、例えば、Ｃ１～４アルキル基等が挙げられる。 In the compound α, examples of the alkyl group include a C1-4 alkyl group.
　化合物αにおいて、アルコキシ基は、例えば、Ｃ１～１８アルコキシ基等が挙げられる。 In compound α, examples of the alkoxy group include a C1-18 alkoxy group.
　Ｃ１～１８アルコキシ基は、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｉ－ブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｎ-オクトキシ基、２－エチルヘキシトキシ基、ｎ-デカトキシ基、２－エチルオクトキシ基、ｎ-ラウロキシ基、ｎ-ステアロキシ基等が挙げられる。 C1-18 alkoxy groups include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-octoxy group, Examples include 2-ethylhexytoxy group, n-decatoxy group, 2-ethyloctoxy group, n-lauroxy group, n-stearoxy group and the like.
<ラクトン開環重付加物>
　ラクトン開環重付加物は、水酸基含有ビニルモノマーとラクトンとを用いて、開環重付加させることにより製造され得る。 <Lactone ring-opening polyadduct>
A lactone ring-opening polyadduct can be produced by ring-opening polyaddition using a hydroxyl group-containing vinyl monomer and a lactone.
　水酸基含有ビニルモノマーは、単独又は２種以上で使用され得る。水酸基含有ビニルモノマーは、例えば、水酸基含有（メタ）アクリレート、水酸基含有ビニルモノマー等が挙げられる。 The hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more. Examples of the hydroxyl group-containing vinyl monomer include hydroxyl group-containing (meth)acrylate, hydroxyl group-containing vinyl monomer, and the like.
　水酸基含有（メタ）アクリレートは、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリルアミド等が挙げられる。 Examples of hydroxyl group-containing (meth)acrylates include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyethyl (meth)acrylamide.
　水酸基含有ビニルエーテルは、例えば、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、ヒドロキシジエチレングリコールビニルエーテル等が挙げられる。 Examples of the hydroxyl group-containing vinyl ether include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxydiethylene glycol vinyl ether, and the like.
　ラクトンは、単独又は２種以上で使用され得る。ラクトンは、例えば、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン、β－メチル－δ－バレロラクトン、ε－カプロラクトン等が挙げられる。 The lactones may be used alone or in combination of two or more. Examples of the lactone include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone.
　重量平均分子量（ラクトン開環重付加物）は、例えば、１００００、９０００、８０００、７０００、６０００、５０００、４０００、３９９９、３０００、２０００、１０００等が挙げられる。１つの実施形態において、上記重量平均分子量は、好ましくは、１０００～１００００が挙げられ、より好ましくは、１０００以上４０００未満が挙げられる。 Examples of the weight average molecular weight (lactone ring-opening polyadduct) include 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,999, 3,000, 2,000, and 1,000. In one embodiment, the weight average molecular weight is preferably from 1,000 to 10,000, more preferably from 1,000 to less than 4,000.
　重量平均分子量（ラクトン開環重付加物）は、下記条件で測定され得る。測定機器：製品名「ＨＬＣ－８２２０ＧＰＣ」、東ソー（株）製カラム　：製品名「ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ－Ｍ」、東ソー（株）製展開溶媒：テトラヒドロフラン流速　　：０．３５ｍＬ／ｍｉｎ試料濃度：０．５％
標準物質：ポリスチレン（標準ポリスチレンキット　ＰＳｔＱｕｉｃｋＡ、Ｂ、Ｃ 東ソー（株）製） The weight average molecular weight (lactone ring-opening polyadduct) can be measured under the following conditions. Measuring equipment: Product name "HLC-8220GPC", manufactured by Tosoh Co., Ltd. Column: Product name "TSKgel SuperHZ-M", manufactured by Tosoh Corporation Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL/min Sample concentration: 0.5%
Standard material: Polystyrene (Standard polystyrene kit PStQuick A, B, C manufactured by Tosoh Corporation)
　開環重付加の際、触媒が任意で使用され得る。触媒は、例えば、鉱酸、アルカリ金属、アルキル金属化合物、金属アルコキシド、スズ化合物等が挙げられる。 A catalyst may optionally be used during the ring-opening polyaddition. Examples of the catalyst include mineral acids, alkali metals, alkyl metal compounds, metal alkoxides, and tin compounds.
　鉱酸は、例えば、硫酸、リン酸等が挙げられる。 Examples of mineral acids include sulfuric acid and phosphoric acid.
　アルカリ金属は、例えば、リチウム、ナトリウム、カリウム等が挙げられる。 Examples of alkali metals include lithium, sodium, potassium, and the like.
　アルキル金属化合物は、例えば、ｎ－ブチルリチウム、ｓ－ブチルリチウム、ｔ－ブチルリチウム等が挙げられる。 Examples of the alkyl metal compounds include n-butyllithium, s-butyllithium, and t-butyllithium.
　金属アルコキシドは、例えば、チタンテトラブトキシド等が挙げられる。 Examples of the metal alkoxide include titanium tetrabutoxide.
　スズ化合物は、例えば、ジブチルスズジラウレート、ジブチルスズジオクテート、ジブチルスズメルカプチド、オクチル酸スズ等が挙げられる。 Examples of the tin compound include dibutyltin dilaurate, dibutyltin dioctate, dibutyltin mercaptide, tin octylate, and the like.
　１つの実施形態において、質量部使用量（触媒／水酸基含有ビニルモノマー及びラクトン）は、好ましくは、０．０１質量部～１０質量部が挙げられる。 In one embodiment, the amount used in parts by mass (catalyst/hydroxyl group-containing vinyl monomer and lactone) is preferably 0.01 parts by mass to 10 parts by mass.
<ポリアルキレン含有物>
　ポリアルキレン含有物は、例えば、ヒドロキシポリアルキレングリコールモノ（メタ）アクリレート、アルコキシポリアルキレングリコールモノ（メタ）アクリレート等が挙げられる。 <Polyalkylene-containing materials>
Examples of the polyalkylene-containing material include hydroxypolyalkylene glycol mono(meth)acrylate, alkoxypolyalkylene glycol mono(meth)acrylate, and the like.
　ヒドロキシポリアルキレングリコールモノ（メタ）アクリレートは、例えば、ヒドロキシポリエチレングリコールモノ（メタ）アクリレート、ヒドロキシポリプロピレングリコールモノ（メタ）アクリレート等が挙げられる。 Examples of the hydroxypolyalkylene glycol mono(meth)acrylate include hydroxypolyethylene glycol mono(meth)acrylate, hydroxypolypropylene glycol mono(meth)acrylate, and the like.
　アルコキシポリアルキレングリコールモノ（メタ）アクリレートは、例えば、メトキシポリアルキレングリコールモノ（メタ）アクリレート、エトキシポリアルキレングリコールモノ（メタ）アクリレート、プロポキシポリアルキレングリコールモノ（メタ）アクリレート、ブトキシポリアルキレングリコールモノ（メタ）アクリレート、アルコキシポリエチレングリコールモノ（メタ）アクリレート、アルコキシポリプロピレングリコールモノ（メタ）アクリレート、メトキシポリエチレングリコールモノ（メタ）アクリレート、メトキシポリプロピレングリコールモノ（メタ）アクリレート、エトキシポリエチレングリコールモノ（メタ）アクリレート、エトキシポリプロピレングリコールモノ（メタ）アクリレート、プロポキシポリエチレングリコールモノ（メタ）アクリレート、プロポキシポリプロピレングリコールモノ（メタ）アクリレート、ブトキシポリエチレングリコールモノ（メタ）アクリレート、ブトキシポリプロピレングリコールモノ（メタ）アクリレート等が挙げられる。 Alkoxypolyalkylene glycol mono(meth)acrylates include, for example, methoxypolyalkylene glycol mono(meth)acrylate, ethoxypolyalkylene glycol mono(meth)acrylate, propoxypolyalkylene glycol mono(meth)acrylate, butoxypolyalkylene glycol mono(meth)acrylate, and butoxypolyalkylene glycol mono(meth)acrylate. ) acrylate, alkoxypolyethylene glycol mono(meth)acrylate, alkoxypolypropylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, methoxypolypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol mono(meth)acrylate, ethoxypolypropylene Examples include glycol mono(meth)acrylate, propoxypolyethylene glycol mono(meth)acrylate, propoxypolypropylene glycol mono(meth)acrylate, butoxypolyethylene glycol mono(meth)acrylate, butoxypolypropylene glycol mono(meth)acrylate, and the like.
　市販品（ポリアルキレン含有物）は、例えば、ブレンマーＰＭＥ－１００、ＰＭＥ－２００、ＰＭＥ－４００、ＰＭＥ－１０００、ＰＭＥ－４０００、５０ＰＯＥＰ－８００Ｂ、ＰＬＥ－２００、ＰＬＥ－１３００、ＰＳＥ－１３００（以上、日油（株）製）、ライトエステルＢＣ、１３０ＭＡ、０４１ＭＡ（共栄社化学（株）製）等が挙げられる。 Commercial products (polyalkylene-containing materials) include, for example, Blenmar PME-100, PME-200, PME-400, PME-1000, PME-4000, 50POEP-800B, PLE-200, PLE-1300, PSE-1300 (and above). , manufactured by NOF Corporation), Light Ester BC, 130MA, and 041MA (manufactured by Kyoeisha Chemical Co., Ltd.).
　質量％含有量（構成単位（２）／ポリマー全構成単位）は、例えば、６０質量％、５５質量％、５０質量％、４５質量％、４０質量％、３５質量％、３０質量％、２５質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、２５質量％～６０質量％が挙げられ、より好ましくは、３０質量％～５５質量％が挙げられる。 The mass% content (constituent unit (2)/total polymer constituent units) is, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass. Examples include %. In one embodiment, the content is preferably 25% by mass to 60% by mass, more preferably 30% by mass to 55% by mass.
　モル％含有量（構成単位（２）／ポリマー全構成単位）は、例えば、５０モル％、４５モル％、４０モル％、３５モル％、３０モル％、２５モル％、２０モル％、１５モル％、１０モル％、９モル％、５モル％、２モル％、１モル％、０．５モル％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０．５モル％～５０モル％が挙げられ、より好ましくは、１モル％～４０モル％が挙げられる。 The mole% content (constituent unit (2)/total polymer constituent units) is, for example, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 15 mole %, 10 mol%, 9 mol%, 5 mol%, 2 mol%, 1 mol%, 0.5 mol%, etc. In one embodiment, the content is preferably 0.5 mol% to 50 mol%, more preferably 1 mol% to 40 mol%.
（構成単位（３））
　アルキル（メタ）アクリレートは、単独又は２種以上で使用され得る。 (Constituent unit (3))
Alkyl (meth)acrylates may be used alone or in combination of two or more.
　アルキル（メタ）アクリレートは、例えば、直鎖アルキル（メタ）アクリレート、分岐アルキル（メタ）アクリレート、シクロアルキル（メタ）アクリレート等が挙げられる。 Examples of alkyl (meth)acrylates include linear alkyl (meth)acrylates, branched alkyl (meth)acrylates, and cycloalkyl (meth)acrylates.
　直鎖アルキル（メタ）アクリレートは、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート等が挙げられる。 Straight chain alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl Examples include (meth)acrylate.
　分岐アルキル（メタ）アクリレートは、例えば、イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、１－メチルブチル（メタ）アクリレート、２－メチルブチル（メタ）アクリレート、３－メチルブチル（メタ）アクリレート、１－エチルプロピル（メタ）アクリレート、１，１－ジメチルプロピル（メタ）アクリレート、１，２－ジメチルプロピル（メタ）アクリレート、２，２－ジメチルプロピル（メタ）アクリレート等が挙げられる。 Branched alkyl (meth)acrylates include, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 1-methylbutyl (meth)acrylate, 2-methylbutyl ( meth)acrylate, 3-methylbutyl(meth)acrylate, 1-ethylpropyl(meth)acrylate, 1,1-dimethylpropyl(meth)acrylate, 1,2-dimethylpropyl(meth)acrylate, 2,2-dimethylpropyl( Examples include meth)acrylate.
　シクロアルキル（メタ）アクリレートは、例えば、シクロプロピル（メタ）アクリレート、シクロブチル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等が挙げられる。 Examples of the cycloalkyl (meth)acrylate include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate.
　１つの実施形態において、アルキル（メタ）アクリレートは、好ましくは、分岐アルキル（メタ）アクリレートが挙げられ、より好ましくは、Ｃ３～５分岐アルキル（メタ）アクリレートが挙げられる。 In one embodiment, the alkyl (meth)acrylate is preferably a branched alkyl (meth)acrylate, more preferably a C3-5 branched alkyl (meth)acrylate.
　質量％含有量（構成単位（３）／ポリマー全構成単位）は、例えば、５０質量％、４５質量％、４０質量％、３５質量％、３０質量％、２５質量％、２０質量％、１５質量％、１０質量％、５質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、５質量％～５０質量％が挙げられる。 The mass% content (constituent unit (3)/total polymer constituent units) is, for example, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass. %, 10% by mass, 5% by mass, etc. In one embodiment, the content is preferably 5% by mass to 50% by mass.
　モル％含有量（構成単位（３）／ポリマー全構成単位）は、例えば、８０モル％、７５モル％、７０モル％、６５モル％、６０モル％、５５モル％、５０モル％、４５モル％、４０モル％、３５モル％、３０モル％、２５モル％、２０モル％、１５モル％、１０モル％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、１０モル％～８０モル％が挙げられる。 The mole% content (constituent unit (3)/total polymer constituent units) is, for example, 80 mole%, 75 mole%, 70 mole%, 65 mole%, 60 mole%, 55 mole%, 50 mole%, 45 mole %, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, etc. In one embodiment, the content is preferably 10 mol% to 80 mol%.
（構成単位（４）：その他の構成単位）
　上記ポリマーは、任意で、構成単位（４）を含み得る。「構成単位（４）」は、「その他モノマーに由来する構成単位」を意味する。「その他モノマー」は、４級アンモニウム塩含有モノマー、化合物α、アルキル（メタ）アクリレート以外のモノマーを意味する。その他モノマーは、単独又は２種以上で使用され得る。 (Component unit (4): Other component units)
The polymer may optionally contain structural unit (4). "Structural unit (4)" means "a structural unit derived from other monomers.""Othermonomers" mean monomers other than the quaternary ammonium salt-containing monomer, compound α, and alkyl (meth)acrylate. Other monomers may be used alone or in combination of two or more.
　その他のモノマーは、例えば、芳香環構造含有ビニルモノマー等が挙げられる。 Examples of other monomers include aromatic ring structure-containing vinyl monomers.
　芳香環構造含有ビニルモノマーは、例えば、スチレン、α－メチルスチレン、４－メチルスチレン等が挙げられる。 Examples of the aromatic ring structure-containing vinyl monomer include styrene, α-methylstyrene, and 4-methylstyrene.
　質量％含有量（構成単位（４）／ポリマー全構成単位）は、例えば、１質量％未満、０．１質量％未満、０．０１質量％未満、０質量％等が挙げられる。 Examples of the mass% content (constituent unit (4)/total polymer structural units) include less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, and 0% by mass.
　モル％含有量（構成単位（４）／ポリマー全構成単位）は、例えば、１モル％未満、０．１モル％未満、０．０１モル％未満、０モル％等が挙げられる。 Examples of the mol% content (constituent unit (4)/total polymer structural units) include less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, and 0 mol%.
　質量％含有量（構成単位（４）／構成単位（１）～（３）のいずれか１つ）は、例えば、１質量％未満、０．１質量％未満、０．０１質量％未満、０質量％等が挙げられる。 The mass% content (constituent unit (4)/any one of structural units (1) to (3)) is, for example, less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 Examples include mass %.
　モル％含有量（構成単位（４）／構成単位（１）～（３）のいずれか１つ）は、例えば、１モル％未満、０．１モル％未満、０．０１モル％未満、０モル％等が挙げられる。 The mol% content (constituent unit (4)/any one of structural units (1) to (3)) is, for example, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, 0 Examples include mol%.
＜物性（ポリマー）＞
　重量平均分子量（ポリマー）（Ｍｗ）は、例えば、５０００００，４５００００、４０００００、３５００００、３０００００、２５００００、２０００００、１８００００等が挙げられる。１つの実施形態において、上記重量平均分子量は、好ましくは、１８００００～５０００００が挙げられる。 <Physical properties (polymer)>
Examples of the weight average molecular weight (polymer) (Mw) include 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, and 180,000. In one embodiment, the weight average molecular weight is preferably 180,000 to 500,000.
　数平均分子量（ポリマー）（Ｍｎ）は、例えば、２０００００、１７５０００、１５００００、１２５０００、１０００００、５００００等が挙げられる。１つの実施形態において、上記数平均分子量は、好ましくは、５００００～２０００００が挙げられる。 Examples of the number average molecular weight (polymer) (Mn) include 200,000, 175,000, 150,000, 125,000, 100,000, and 50,000. In one embodiment, the number average molecular weight is preferably 50,000 to 200,000.
　分子量分布（ポリマー）（Ｍｗ／Ｍｎ）は、例えば、５．０、４．９、４．５、４．０、３．５、３．０、２．５、２．０、１．９、１．８等が挙げられる。１つの実施形態において、上記分子量分布は、好ましくは、１．８～５．０が挙げられる。 Molecular weight distribution (polymer) (Mw/Mn) is, for example, 5.0, 4.9, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.9, 1.8 etc. are mentioned. In one embodiment, the molecular weight distribution is preferably 1.8 to 5.0.
　重量平均分子量、数平均分子量（ポリマー）は、下記条件で測定され得る。
測定機器：製品名「ＨＬＣ－８３２０ＧＰＣ」、東ソー（株）製
カラム　：製品名「ＴＳＫｇｅｌ　Ｇ６０００ＰＷＸＬ－ＣＰ」、「ＴＳＫｇｅｌ　Ｇ３０００ＰＷＸＬ－ＣＰ」、東ソー（株）製
展開溶媒：０．１Ｍ　ＮａＮＯ３及び０．１Ｍ　酢酸水溶液
流速　　：０．５ｍＬ／ｍｉｎ
試料濃度：０．５ｇ／Ｌ
標準物質：ポリエチレンオキサイド（ＴＳＫｇｅｌ標準ポリエチレンオキサイド　ＳＥ－キット　東ソー（株）製） The weight average molecular weight and number average molecular weight (polymer) can be measured under the following conditions.
Measuring equipment: Product name "HLC-8320GPC", manufactured by Tosoh Corporation Column: Product name "TSKgel G6000PW XL -CP", "TSKgel G3000PW XL -CP", manufactured by Tosoh Corporation Developing solvent: 0.1M NaNO 3 and 0.1M acetic acid aqueous solution flow rate: 0.5mL/min
Sample concentration: 0.5g/L
Standard material: Polyethylene oxide (TSKgel Standard Polyethylene Oxide SE-Kit manufactured by Tosoh Corporation)
＜製造方法（ポリマー）＞
　製造方法（ポリマー）は、例えば、ラジカル重合等が挙げられる。 <Manufacturing method (polymer)>
Examples of the manufacturing method (polymer) include radical polymerization.
　ラジカル重合開始剤は、単独又は２種以上で使用され得る。ラジカル重合開始剤は、例えば、無機過酸化物、有機過酸化物、アゾ系化合物等が挙げられる。 The radical polymerization initiators may be used alone or in combination of two or more. Examples of the radical polymerization initiator include inorganic peroxides, organic peroxides, and azo compounds.
　無機過酸化物は、例えば、過酸化水素、過硫酸アンモニウム、過硫酸カリウム等が挙げられる。 Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate, potassium persulfate, and the like.
　有機過酸化物は、例えば、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウリルパーオキサイド等が挙げられる。 Examples of organic peroxides include benzoyl peroxide, dicumyl peroxide, and lauryl peroxide.
　アゾ系化合物は、例えば、２，２’－アゾビスイソブチロニトリル、ジメチル－２，２’－アゾビスイソブチレート等が挙げられる。 Examples of the azo compounds include 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutyrate.
　使用量（ラジカル重合開始剤／全モノマー成分）は、好ましくは、０．０１～１０質量部程度が挙げられる。 The amount used (radical polymerization initiator/total monomer components) is preferably about 0.01 to 10 parts by mass.
　ポリマー製造の際、連鎖移動剤が、任意で使用され得る。連鎖移動剤は、単独又は２種以上で使用され得る。連鎖移動剤は、例えば、ラウリルメルカプタン、ドデシルメルカプタン、２－メルカプトベンゾチアゾール、ブロモトリクロロメタン、α－メチルスチレンダイマー等が挙げられる。 A chain transfer agent may optionally be used during polymer production. Chain transfer agents may be used alone or in combination of two or more. Examples of chain transfer agents include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and α-methylstyrene dimer.
　使用量（連鎖移動剤／全モノマー成分）は、好ましくは、０～１０質量部程度が挙げられる。 The amount used (chain transfer agent/total monomer components) is preferably about 0 to 10 parts by mass.
　溶液重合の場合、反応溶媒は、例えば、下記有機溶媒等が挙げられる。 In the case of solution polymerization, examples of the reaction solvent include the following organic solvents.
　反応時間は、好ましくは、２～１２時間が挙げられる。 The reaction time is preferably 2 to 12 hours.
　重合温度は、好ましくは、７０～１３０℃が挙げられる。 The polymerization temperature is preferably 70 to 130°C.
　質量％含有量（４級アンモニウム塩含有ポリマー／活性エネルギー線硬化性樹脂組成物不揮発分）は、例えば、２０質量％、１９質量％、１７質量％、１５質量％、１３質量％、１１質量％、１０質量％、９質量％、７質量％、５質量％、３質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、３質量％～２０質量％が挙げられる。 The mass% content (quaternary ammonium salt-containing polymer/active energy ray-curable resin composition nonvolatile content) is, for example, 20 mass%, 19 mass%, 17 mass%, 15 mass%, 13 mass%, 11 mass%. , 10% by mass, 9% by mass, 7% by mass, 5% by mass, 3% by mass, and the like. In one embodiment, the content is preferably 3% by mass to 20% by mass.
＜リン酸エステル＞
　１つの実施形態において、上記組成物は、任意で、リン酸エステルを含み得る。リン酸エステルは、単独又は２種以上で使用され得る。 <Phosphoric acid ester>
In one embodiment, the composition may optionally include a phosphate ester. Phosphoric esters may be used alone or in combination of two or more.
　１つの実施形態において、リン酸エステルは、下記式で表される。
（ＲＰ）ｍ－Ｐ（＝Ｏ）（ＯＸ）３－ｍ
（式中、ｍは１、２又は３を表す。Ｘは水素原子、金属原子又はアンモニウムイオンを表す。ＲＰは、置換又は非置換のアルキル基、置換又は非置換のアリール基、ポリアルキレンアルキル基を表す。） In one embodiment, the phosphoric acid ester is represented by the following formula.
(R P ) m -P(=O)(OX) 3-m
(In the formula, m represents 1, 2, or 3. X represents a hydrogen atom, a metal atom, or an ammonium ion. (Represents a group.)
　置換基は、例えば、（メタ）アクリロイルオキシ基、アルコキシ基等が挙げられる。 Examples of the substituent include a (meth)acryloyloxy group and an alkoxy group.
　金属原子は、例えば、アルカリ金属原子、アルカリ土類金属原子等が挙げられる。 Examples of metal atoms include alkali metal atoms and alkaline earth metal atoms.
　リン酸モノエステルは、例えば、リン酸（メタ）アクリロイルオキシアルキル、リン酸（ポリ）アルキレンオキシアルキル等が挙げられる。 Examples of the phosphoric acid monoester include (meth)acryloyloxyalkyl phosphate, (poly)alkyleneoxyalkyl phosphate, and the like.
　リン酸（メタ）アクリロイルオキシアルキルは、例えば、リン酸（メタ）アクリロイルオキシエチル、リン酸（メタ）アクリロイルオキシプロピル、リン酸（メタ）アクリロイルオキシブチル等が挙げられる。 Examples of the (meth)acryloyloxyalkyl phosphate include (meth)acryloyloxyethyl phosphate, (meth)acryloyloxypropyl phosphate, and (meth)acryloyloxybutyl phosphate.
　リン酸（ポリ）アルキレンオキシアルキルは、例えば、リン酸エチレンオキシブチル、リン酸デシル（エチレンオキシデシル）等が挙げられる。 Examples of the (poly)alkyleneoxyalkyl phosphate include ethyleneoxybutyl phosphate and decyl phosphate (ethylene oxydecyl).
　市販品（リン酸エステル）は、例えば、ライトエステルＰ－１Ｍ、Ｐ－２Ｍ（共栄社化学（株））、ＭＰ－４、ＭＰ－８（大八化学（株）製）等が挙げられる。 Commercially available products (phosphate esters) include, for example, Light Ester P-1M, P-2M (Kyoeisha Kagaku Co., Ltd.), MP-4, MP-8 (Daihachi Kagaku Co., Ltd.), and the like.
　酸価（リン酸エステル）は、例えば、６００ｍｇＫＯＨ／ｇ、５９０ｍｇＫＯＨ／ｇ、５８０ｍｇＫＯＨ／ｇ、５７０ｍｇＫＯＨ／ｇ、５６０ｍｇＫＯＨ／ｇ、５５０ｍｇＫＯＨ／ｇ、５４０ｍｇＫＯＨ／ｇ、５３０ｍｇＫＯＨ／ｇ、５２０ｍｇＫＯＨ／ｇ、５１０ｍｇＫＯＨ／ｇ、５００ｍｇＫＯＨ／ｇ、４９０ｍｇＫＯＨ／ｇ、４８０ｍｇＫＯＨ／ｇ、４７０ｍｇＫＯＨ／ｇ、４６０ｍｇＫＯＨ／ｇ、４５０ｍｇＫＯＨ／ｇ、４４０ｍｇＫＯＨ／ｇ、４３０ｍｇＫＯＨ／ｇ、４２０ｍｇＫＯＨ／ｇ、４１０ｍｇＫＯＨ／ｇ、４００ｍｇＫＯＨ／ｇ等が挙げられる。１つの実施形態において、上記酸価は、好ましくは、４００ｍｇＫＯＨ／ｇ～６００ｍｇＫＯＨ／ｇが挙げられる。 Acid value (phosphate ester) is, for example, 600mgKOH/g, 590mgKOH/g, 580mgKOH/g, 570mgKOH/g, 560mgKOH/g, 550mgKOH/g, 540mgKOH/g, 530mgKOH/g, 520mgKOH/g, 510mgKOH/g , 500mgKOH/g, 490mgKOH/g, 480mgKOH/g, 470mgKOH/g, 460mgKOH/g, 450mgKOH/g, 440mgKOH/g, 430mgKOH/g, 420mgKOH/g, 410mgKOH/g, 400mgKOH/g, etc. Can be mentioned. In one embodiment, the acid value is preferably 400 mgKOH/g to 600 mgKOH/g.
　質量％含有量（リン酸エステル／活性エネルギー線硬化性樹脂組成物不揮発分）は、例えば、１２質量％、１０質量％、９質量％、７質量％、５質量％、３質量％、１質量％、０．９質量％、０．５質量％、０．３質量％、０質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０質量％～１２質量％が挙げられ、より好ましくは、０．３質量％～１２質量％が挙げられる。 The mass% content (phosphoric acid ester/active energy ray-curable resin composition nonvolatile content) is, for example, 12 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 3 mass%, 1 mass%. %, 0.9% by mass, 0.5% by mass, 0.3% by mass, 0% by mass, and the like. In one embodiment, the content is preferably 0% by mass to 12% by mass, more preferably 0.3% by mass to 12% by mass.
　不揮発分質量比（リン酸エステル／４級アンモニウム塩含有ポリマー）は、例えば、０．７、０．６、０．５、０．４、０．３、０．２、０．１、０等が挙げられる。１つの実施形態において、不揮発分質量比（リン酸エステル／４級アンモニウム塩含有ポリマー）は、好ましくは、０～０．７が挙げられ、より好ましくは、０．１～０．７が挙げられ、さらに好ましくは、０．１～０．６が挙げられる。さらに好ましい理由は、例えば、ＨＡＺＥ改善等が挙げられる。 The nonvolatile mass ratio (phosphoric acid ester/polymer containing quaternary ammonium salt) is, for example, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0, etc. can be mentioned. In one embodiment, the nonvolatile mass ratio (phosphoric acid ester/quaternary ammonium salt-containing polymer) is preferably 0 to 0.7, more preferably 0.1 to 0.7. , more preferably 0.1 to 0.6. More preferable reasons include, for example, HAZE improvement.
＜塩：ポリアルキレン構造含有塩＞
　１つの実施形態において、上記組成物は、任意で、塩を含み得る。塩は、単独又は２種以上で使用され得る。 <Salt: Salt containing polyalkylene structure>
In one embodiment, the composition may optionally include a salt. Salts may be used alone or in combination of two or more.
　「塩」は、アニオンとカチオンのみからなる化合物を意味する。 "Salt" means a compound consisting only of an anion and a cation.
（アニオン）
　アニオンは、ポリオキシアルキレン構造を含む。 (anion)
Anions include polyoxyalkylene structures.
　「ポリオキシアルキレン構造」は、オキシアルキレン構造（－Ｏ－ＣｎＨ２ｎ－）が２個以上連続している構造を意味する。 "Polyoxyalkylene structure" means a structure in which two or more oxyalkylene structures (-O-C n H 2n -) are consecutive.
　ポリオキシアルキレン構造は、例えば、ポリオキシエチレン構造、ポリオキシプロピレン構造等が挙げられる。 Examples of the polyoxyalkylene structure include a polyoxyethylene structure and a polyoxypropylene structure.
　１つの実施形態において、ポリオキシアルキレン変性数は、好ましくは、２～２５が挙げられ、より好ましくは、５～２０が挙げられる。 In one embodiment, the polyoxyalkylene modification number is preferably 2 to 25, more preferably 5 to 20.
　アニオンは、例えば、ポリオキシアルキレン構造含有硫酸イオン、ポリオキシアルキレン構造含有リン酸イオン等が挙げられる。 Examples of the anion include a sulfate ion containing a polyoxyalkylene structure, a phosphate ion containing a polyoxyalkylene structure, and the like.
　１つの実施形態において、アニオンは、下記式で表される。
Ｒａ１－（ＯＲａ２）ｎ－ＯＸＯ３ －
（Ｒａ１はアルキル基（例えば、Ｃ１～６アルキル基）又は不飽和基含有基を表す。Ｒａ２はアルキレン基（例えば、エチレン基、プロピレン基）を表す。ｎは２以上の整数を表す。ＸはＳ又はＰを表す。） In one embodiment, the anion is represented by the following formula.
R a1 - (OR a2 ) n -OXO 3 -
(R a1 represents an alkyl group (eg, C1-6 alkyl group) or an unsaturated group-containing group; R a2 represents an alkylene group (eg, ethylene group, propylene group); n represents an integer of 2 or more. (X represents S or P.)
　不飽和基含有基は、例えば、下記基等が挙げられる。
（Ｒｂ１は、アルキル基を表す。Ｙは単結合又は酸素原子を表す。Ｒｂ２～Ｒｂ４はそれぞれ独立して、水素原子又はメチル基を表す。）
（Ｒｃ１～Ｒｃ３はそれぞれ独立して、水素原子又はメチル基を表す。Ｒｃ４～Ｒｃ７はそれぞれ独立して、水素原子又は
を表す。） Examples of the unsaturated group-containing group include the following groups.
(R b1 represents an alkyl group. Y represents a single bond or an oxygen atom. R b2 to R b4 each independently represent a hydrogen atom or a methyl group.)
(R c1 to R c3 each independently represent a hydrogen atom or a methyl group. R c4 to R c7 each independently represent a hydrogen atom or a methyl group.
represents. )
（カチオン）
　カチオンは、例えば、アンモニウムイオン（ＮＨ４ ＋）、４級アンモニウム塩含有モノマー、金属イオン等が挙げられる。 (cation)
Examples of cations include ammonium ions (NH 4 + ), quaternary ammonium salt-containing monomers, and metal ions.
　４級アンモニウム塩含有モノマーは、例えば、上述のモノマー等が挙げられる。 Examples of the quaternary ammonium salt-containing monomer include the above-mentioned monomers.
　金属イオンは、例えば、アルカリ金属イオン等が挙げられる。 Examples of metal ions include alkali metal ions.
　アルカリ金属イオンは、例えば、リチウムイオン、ナトリウムイオン、カリウムイオン等が挙げられる。 Examples of the alkali metal ions include lithium ions, sodium ions, potassium ions, and the like.
　塩（アニオン－カチオン）は、例えば、アルキルポリエチレン硫酸イオン－アンモニウムイオン、アルキルポリエチレン硫酸イオン－トリメチル－２－（メタ）アクリロイルオキシエチルアンモニウム、アルキルポリエチレン硫酸イオン－（３－（メタ）アクリロイルアミノプロピル）トリメチルアンモニウム、アルキルポリエチレン硫酸イオン－ナトリウムイオン、アルキルポリエチレンリン酸イオン－アンモニウムイオン、アルキルポリエチレンリン酸イオン－トリメチル－２－（メタ）アクリロイルオキシエチルアンモニウム、アルキルポリエチレンリン酸イオン－（３－（メタ）アクリロイルアミノプロピル）トリメチルアンモニウム、アルキルポリエチレンリン酸イオン－ナトリウムイオン、
（式中、ｎ１～ｎ５は、それぞれ独立して、２以上の整数（例えば、２～２５、５～２０等）を表す。）
等が挙げられる。 Examples of the salt (anion-cation) include alkyl polyethylene sulfate ion-ammonium ion, alkyl polyethylene sulfate ion-trimethyl-2-(meth)acryloyloxyethylammonium, alkyl polyethylene sulfate ion-(3-(meth)acryloylaminopropyl) Trimethyl ammonium, alkyl polyethylene sulfate ion - sodium ion, alkyl polyethylene phosphate ion - ammonium ion, alkyl polyethylene phosphate ion - trimethyl-2-(meth)acryloyloxyethylammonium, alkyl polyethylene phosphate ion - (3-(meth) acryloylaminopropyl) trimethylammonium, alkyl polyethylene phosphate ion - sodium ion,
(In the formula, n1 to n5 each independently represent an integer of 2 or more (for example, 2 to 25, 5 to 20, etc.)
etc.
　市販品（ポリオキシアルキレン構造含有硫酸塩）は、例えば、アミノイオンＲＥ３０００ＭＦ（日本乳化剤（株）製）、アデカソープＳＲ－１０、ＳＲ－２０（（株）ＡＤＥＫＡ製）、アクアロンＫＨ－０５、ＫＨ－１０、ＡＲ－１０、ＡＲ－２０（第一工業（株）製）等が挙げられる。 Commercial products (polyoxyalkylene structure-containing sulfates) include, for example, Aminoion RE3000MF (manufactured by Nippon Nyukazai Co., Ltd.), ADEKA SOAP SR-10, SR-20 (manufactured by ADEKA Co., Ltd.), Aqualon KH-05, KH- 10, AR-10, AR-20 (manufactured by Dai-ichi Kogyo Co., Ltd.), and the like.
　市販品（ポリオキシアルキレン構造含有リン酸塩）は、例えば、ディスパロンＰＷ－３６（楠本化成（株）製）等が挙げられる。 Commercially available products (phosphates containing polyoxyalkylene structures) include, for example, Disparon PW-36 (manufactured by Kusumoto Kasei Co., Ltd.).
　質量％含有量（塩／活性エネルギー線硬化性樹脂組成物不揮発分）は、例えば、５０質量％、４５質量％、４０質量％、３５質量％、３０質量％、２５質量％、２０質量％、１５質量％、１０質量％、５質量％、２質量％、１質量％、０質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０質量％～５０質量％が挙げられ、より好ましくは、１質量％～５０質量％が挙げられる。 The mass % content (salt/active energy ray curable resin composition nonvolatile content) is, for example, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, Examples include 15% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the content is preferably 0% by mass to 50% by mass, more preferably 1% by mass to 50% by mass.
　質量部含有量（塩／４級アンモニウム塩含有ポリマー）は、例えば、１６６７質量部、１５００質量部、１０００質量部、５００質量部、２００質量部、１００質量部、７５質量部、５０質量部、２５質量部、２０質量部、１５質量部、１０質量部、５質量部、０質量部等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０質量部から１６６７質量部が挙げられ、より好ましくは、５質量部～１６６７質量部が挙げられ、さらに好ましくは、５質量部～７５質量部が挙げられ、特に好ましくは、５質量部～５０質量部が挙げられる。さらに好ましい理由、特に好ましい理由は、例えば、ＨＡＺＥの改善等が挙げられる。 The mass part content (salt/quaternary ammonium salt-containing polymer) is, for example, 1667 parts by mass, 1500 parts by mass, 1000 parts by mass, 500 parts by mass, 200 parts by mass, 100 parts by mass, 75 parts by mass, 50 parts by mass, Examples include 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 5 parts by mass, and 0 parts by mass. In one embodiment, the content is preferably from 0 parts by mass to 1667 parts by mass, more preferably from 5 parts by mass to 1667 parts by mass, and even more preferably from 5 parts by mass to 75 parts by mass. parts, and particularly preferably from 5 parts by weight to 50 parts by weight. Further preferable reasons, particularly preferable reasons include, for example, improvement in HAZE.
＜ポリ（メタ）アクリレート＞
　１つの実施形態において、上記組成物は、任意で、ポリ（メタ）アクリレートを含み得る。ポリ（メタ）アクリレートは、単独又は２種以上で使用され得る。 <Poly(meth)acrylate>
In one embodiment, the composition may optionally include poly(meth)acrylate. Poly(meth)acrylates may be used alone or in combination of two or more.
　「ポリ（メタ）アクリレート」は、２個以上（メタ）アクリロイル基を有する化合物を意味する。 "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.
　ポリ（メタ）アクリレートは、例えば、（ポリ）ペンタエリスリトールポリ（メタ）アクリレート、ウレタンポリ（メタ）アクリレート等が挙げられる。 Examples of the poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, urethane poly(meth)acrylate, and the like.
（（ポリ）ペンタエリスリトールポリ（メタ）アクリレート）
　（ポリ）ペンタエリスリトールポリ（メタ）アクリレートは、例えば、ペンタエリスリトールポリ（メタ）アクリレート、ポリペンタエリスリトールポリ（メタ）アクリレート等が挙げられる。 ((Poly)pentaerythritol poly(meth)acrylate)
Examples of the (poly)pentaerythritol poly(meth)acrylate include pentaerythritol poly(meth)acrylate, polypentaerythritol poly(meth)acrylate, and the like.
　ペンタエリスリトールポリ（メタ）アクリレートは、例えば、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等が挙げられる。 Examples of pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.
　ポリペンタエリスリトールポリ（メタ）アクリレートは、例えば、ジペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールジ（メタ）アクリレート、トリペンタエリスリトールトリ（メタ）アクリレート、トリペンタエリスリトールテトラ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート等が挙げられる。 Polypentaerythritol poly(meth)acrylates include, for example, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Erythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate Acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and the like.
（ウレタンポリ（メタ）アクリレート）
　ウレタンポリ（メタ）アクリレートは、例えば、水酸基含有ポリ（メタ）アクリレート及びポリイソシアネートを含む化合物群の反応物等が挙げられる。 (Urethane poly(meth)acrylate)
Examples of the urethane poly(meth)acrylate include reactants of a group of compounds including hydroxyl group-containing poly(meth)acrylate and polyisocyanate.
<水酸基含有ポリ（メタ）アクリレート>
　水酸基含有ポリ（メタ）アクリレートは、例えば、（ポリ）ペンタエリスリトールポリ（メタ）アクリレート、（ポリ）トリメチロールプロパンポリ（メタ）アクリレート、（ポリ）グリセリンポリ（メタ）アクリレート等が挙げられる。 <Hydroxy group-containing poly(meth)acrylate>
Examples of the hydroxyl group-containing poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and (poly)glycerin poly(meth)acrylate.
　ポリイソシアネートは、単独又は２種以上で使用され得る。 Polyisocyanates may be used alone or in combination of two or more.
<ポリイソシアネート>
　「ポリイソシアネート」は、２個以上のイソシアネート基（－Ｎ＝Ｃ＝Ｏ）を有する化合物を意味する。 <Polyisocyanate>
"Polyisocyanate" means a compound having two or more isocyanate groups (-N=C=O).
　ポリイソシアネートは、例えば、直鎖脂肪族ポリイソシアネート、分岐脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート並びにこれらのビウレット体、イソシアヌレート体、アロファネート体、アダクト体等が挙げられる。 Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biuret, isocyanurate, allophanate, and adduct forms.
　直鎖脂肪族ポリイソシアネートは、例えば、メチレンジイソシアネート、ジメチレンジイソシアネート、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ヘプタメチレンジイソシアネート、オクタメチレンジイソシアネート、ノナメチレンジイソシアネート、デカメチレンジイソシアネート等が挙げられる。 Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like. Can be mentioned.
　分岐脂肪族ポリイソシアネートは、例えば、ジエチルペンチレンジイソシアネート、トリメチルブチレンジイソシアネート、トリメチルペンチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等が挙げられる。 Examples of branched aliphatic polyisocyanates include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.
　脂環族ポリイソシアネートは、例えば、単環脂環族ポリイソシアネート、架橋環脂環族ポリイソシアネート、縮合環脂環族ポリイソシアネート等が挙げられる。 Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, crosslinked alicyclic polyisocyanate, and fused ring alicyclic polyisocyanate.
　単環脂環族ポリイソシアネートは、例えば、水添キシレンジイソシアネート、イソホロンジイソシアネート、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、シクロヘプチレンジイソシアネート、シクロデシレンジイソシアネート、３，５，５－トリメチルシクロヘキシレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート等が挙げられる。 Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, Examples include dicyclohexylmethane diisocyanate.
　架橋環脂環族ポリイソシアネートは、例えば、トリシクロデシレンジイソシアネート、アダマンタンジイソシアネート、ノルボルネンジイソシアネート等が挙げられる。 Examples of the crosslinked cyclic alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.
　縮合環脂環族ポリイソシアネートは、例えば、ビシクロデシレンジイソシアネート等が挙げられる。 Examples of the condensed ring alicyclic polyisocyanate include bicyclodecylene diisocyanate.
　芳香族ポリイソシアネートは、例えば、単環芳香族ポリイソシアネート、縮合環芳香族ポリイソシアネート等が挙げられる。 Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates, condensed ring aromatic polyisocyanates, and the like.
　単環芳香族ポリイソシアネートは、例えば、４，４’－ジフェニルジメチルメタンジイソシアネート等のジアルキルジフェニルメタンジイソシアネート、４，４’－ジフェニルテトラメチルメタンジイソシアネート等のテトラアルキルジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、４，４’－ジベンジルイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ｍ－テトラメチルキシリレンジイソシアネート等が挙げられる。 Monocyclic aromatic polyisocyanates include, for example, dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, Examples include 4,4'-dibenzylisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and the like.
　縮合環芳香族ポリイソシアネートは、１，５－ナフチレンジイソシアネート等が挙げられる。 Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthylene diisocyanate.
　１つの実施形態において、ウレタンポリ（メタ）アクリレートは、好ましくは、（ポリ）ペンタエリスリトールポリ（メタ）アクリレートを構成単位に有するウレタンポリ（メタ）アクリレートが挙げられる。 In one embodiment, the urethane poly(meth)acrylate preferably includes a urethane poly(meth)acrylate having (poly)pentaerythritol poly(meth)acrylate as a constituent unit.
　質量％含有量（ポリ（メタ）アクリレート／活性エネルギー線硬化性樹脂組成物不揮発分）は、例えば、９７質量％、９５質量％、９０質量％、８５質量％、８０質量％、７５質量％、７０質量％、６５質量％、６０質量％、５５質量％、５０質量％、４５質量％、４０質量％、３５質量％、３０質量％、２５質量％、２０質量％、１５質量％、１０質量％、５質量％、１質量％、０質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０質量％～９７質量％が挙げられる。 The mass% content (poly(meth)acrylate/active energy ray-curable resin composition nonvolatile content) is, for example, 97% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass% %, 5% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 97% by mass.
＜光重合開始剤＞
　１つの実施形態において、活性エネルギー線硬化性組成物は、任意で、光重合開始剤を含み得る。光重合開始剤は、単独又は２種以上で使用され得る。 <Photopolymerization initiator>
In one embodiment, the active energy ray-curable composition may optionally include a photopolymerization initiator. The photopolymerization initiators may be used alone or in combination of two or more.
　光重合開始剤は、例えば、α－ヒドロキシジメチルアセトフェノン基含有光重合開始剤、α－ヒドロキシシクロアルキルフェノン、α－アミノアルキルフェノン、ベンジルジメチルケタール、無置換又は置換アルキルフェノン、無置換又は置換ベンジル、無置換又は置換ベンゾフェノン、アシルホスフィンオキシド、置換チオキサントン、オキシムエステル等が挙げられる。 Examples of the photopolymerization initiator include α-hydroxydimethylacetophenone group-containing photopolymerization initiator, α-hydroxycycloalkylphenone, α-aminoalkylphenone, benzyl dimethyl ketal, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, Examples include unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, oxime ester, and the like.
　α－ヒドロキシジメチルアセトフェノン基含有光重合開始剤は、例えば、２－ヒドロキシ－２－メチル－１－フェニルプロパノン、１－［４－（２－ヒドロキシエトキシル）－フェニル］－２－ヒドロキシ－メチルプロパノン、２－ヒドロキシ－１－（４－（４－（２－ヒドロキシ－２－メチルプロピオニル）ベンジル）フェニル）－２－メチルプロパン－１－オン等が挙げられる。 The α-hydroxydimethylacetophenone group-containing photoinitiator is, for example, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, non, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, and the like.
　α－ヒドロキシシクロアルキルフェノンは、例えば、１－ヒドロキシシクロヘキシルフェニルケトン等が挙げられる。 Examples of α-hydroxycycloalkylphenones include 1-hydroxycyclohexylphenyl ketone.
　α－アミノアルキルフェノンは、例えば、２－メチル－１－（４－メチルチオフェニル）－２－モルホリノプロパン－１－オン等が挙げられる。 Examples of α-aminoalkylphenones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.
　ベンジルジメチルケタールは、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等が挙げられる。 Examples of the benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethan-1-one.
　無置換又は置換アルキルフェノンは、例えば、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾインエチルエーテル、アセトフェノン、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－フェニル－２－（ｐ－トルエンスルホニルオキシ）アセトフェノン、ベンゾイン、２－ベンジル－２－（ジメチルアミノ）－４’－モルホリノブチロフェノン、２－メチル－４’－（メチルチオ）－２－モルホリノプロピオフェノン、２－イソニトロソプロピオフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等が挙げられる。 Unsubstituted or substituted alkylphenones include, for example, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl -2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2 -isonitrosopropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.
　無置換又は置換ベンジルは、例えば、ベンジル、ｐ－アニシル等が挙げられる。 Examples of unsubstituted or substituted benzyl include benzyl and p-anisyl.
　無置換又は置換ベンゾフェノンは、例えば、ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ジクロロベンゾフェノン、１，４－ジベンゾイルベンゼン、２－ベンゾイル安息香酸、４－ベンゾイル安息香酸、２－ベンゾイル安息香酸メチル等が挙げられる。 Unsubstituted or substituted benzophenones include, for example, benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, Examples include 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and methyl 2-benzoylbenzoate.
　アシルホスフィンオキシドは、例えば、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキシド等が挙げられる。 Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
　置換チオキサントンは、例えば、２－クロロチオキサントン、２－イソプロピルチオキサントン、２，４－ジエチルチオキサントン等が挙げられる。 Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
　オキシムエステルは、例えば、１．２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］（すなわち２－（（ベンゾイルオキシ）イミノ）－１－（４－（フェニルチオ）フェニル）オクタン－１－オン）；
エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）（すなわち１－（（（１－（９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル）エチリデン）アミノ）オキシ）エタン－１－オン）等が挙げられる。 Oxime esters are, for example, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (i.e. 2-((benzoyloxy)imino)-1-(4-( phenylthio)phenyl)octan-1-one);
Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (i.e. 1-(((1-(9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethane-1-one) and the like.
　電子線硬化をする場合、光重合開始剤は必要ではない。 When performing electron beam curing, a photopolymerization initiator is not required.
　質量％含有量（光重合開始剤／活性エネルギー線硬化性樹脂組成物不揮発分）は、例えば、１５質量％、１３質量％、１１質量％、１０質量％、９質量％、７質量％、５質量％、３質量％、１質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０質量％～１５質量％が挙げられ、より好ましくは、１質量％～１５質量％が挙げられる。 The mass% content (photopolymerization initiator/active energy ray-curable resin composition nonvolatile content) is, for example, 15% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass. Examples include mass%, 3% by mass, and 1% by mass. In one embodiment, the content is preferably 0% by mass to 15% by mass, more preferably 1% by mass to 15% by mass.
＜レベリング剤＞
　１つの実施形態において、活性エネルギー線硬化性組成物は、任意でレベリング剤を含み得る。レベリング剤は、単独又は２種以上で使用され得る。 <Leveling agent>
In one embodiment, the active energy radiation curable composition may optionally include a leveling agent. Leveling agents may be used alone or in combination of two or more.
　レベリング剤は、シリコーンレベリング剤、フッ素レベリング剤等が挙げられる。 Examples of the leveling agent include silicone leveling agents and fluorine leveling agents.
　質量％含有量（レベリング剤／活性エネルギー線硬化性樹脂組成物不揮発分）は、例えば、１０質量％、９質量％、７質量％、５質量％、４質量％、２質量％、１質量％、０質量％等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０質量％～１０質量％が挙げられる。 The mass % content (leveling agent/active energy ray curable resin composition nonvolatile content) is, for example, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass % , 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 10% by mass.
＜有機溶媒＞
　１つの実施形態において、活性エネルギー線硬化性組成物は、任意で有機溶媒を含み得る。有機溶媒は、単独又は２種以上で使用され得る。 <Organic solvent>
In one embodiment, the active energy ray-curable composition may optionally include an organic solvent. Organic solvents may be used alone or in combination of two or more.
　有機溶媒は、例えば、ケトン溶媒、芳香族溶媒、アルコール溶媒、グリコール溶媒、グリコールエーテル溶媒、エステル溶媒、石油系溶媒、ハロアルカン溶媒、アミド溶媒等が挙げられる。 Examples of organic solvents include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, and amide solvents.
　ケトン溶媒は、例えば、メチルエチルケトン、アセチルアセトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン等が挙げられる。 Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.
　芳香族溶媒は、例えば、トルエン、キシレン等が挙げられる。 Examples of aromatic solvents include toluene and xylene.
　アルコール溶媒は、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ブタノール等が挙げられる。 Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol, and the like.
　グリコール溶媒は、例えば、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、トリエチレングリコール、トリプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等が挙げられる。 Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and the like.
　グリコールエーテル溶媒は、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ－ｎ－プロピルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノ－ｎ－ブチルエーテル、エチレングリコールモノイソブチルエーテル、エチレングリコールモノ－ｔ－ブチルエーテル等が挙げられる。 Glycol ether solvents include, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl Examples include ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, and the like.
　エステル溶媒は、例えば、酢酸エチル、酢酸ブチル、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。 Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and the like.
　石油系溶媒は、例えば、ソルベッソ＃１００（エクソン社製）、ソルベッソ＃１５０（エクソン社製）等が挙げられる。 Examples of petroleum solvents include Solvesso #100 (manufactured by Exxon) and Solvesso #150 (manufactured by Exxon).
　ハロアルカン溶媒は、例えば、クロロホルム等が挙げられる。 Examples of the haloalkane solvent include chloroform.
　アミド溶媒は、例えば、ジメチルホルムアミド等が挙げられる。 Examples of the amide solvent include dimethylformamide.
　質量部含有量（有機溶媒／活性エネルギー線硬化性樹脂組成物不揮発分）は、例えば、１９００質量部、１７５０質量部、１５００質量部、１２５０質量部、１０００質量部、５００質量部、１００質量部、７５質量部、５０質量部、２５質量部、１０質量部、０質量部等が挙げられる。１つの実施形態において、上記含有量は、好ましくは、０質量部～１９００質量部が挙げられ、より好ましくは、１０質量部～１０００質量部が挙げられる。 The mass parts content (organic solvent/active energy ray curable resin composition nonvolatile content) is, for example, 1900 parts by mass, 1750 parts by mass, 1500 parts by mass, 1250 parts by mass, 1000 parts by mass, 500 parts by mass, 100 parts by mass. , 75 parts by mass, 50 parts by mass, 25 parts by mass, 10 parts by mass, 0 parts by mass, and the like. In one embodiment, the content is preferably 0 parts by mass to 1900 parts by mass, more preferably 10 parts by mass to 1000 parts by mass.
＜添加剤＞
　活性エネルギー線硬化性樹脂組成物は、任意で、「４級アンモニウム塩含有ポリマー、リン酸エステル、（ポリ）（メタ）アクリレート、光重合開始剤、レベリング剤、有機溶媒」以外の剤（添加剤）を含み得る。 <Additives>
The active energy ray-curable resin composition may optionally contain agents (additives) other than "a quaternary ammonium salt-containing polymer, a phosphate ester, (poly)(meth)acrylate, a photopolymerization initiator, a leveling agent, and an organic solvent." ) may be included.
　添加剤は、例えば、酸化防止剤、紫外線吸収剤、光安定剤、消泡剤、表面調整剤、防汚染剤、顔料、金属酸化物微粒子分散体、有機微粒子分散体等が挙げられる。 Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifoaming agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.
　１つの実施形態において、質量％含有量（添加剤／活性エネルギー線硬化性樹脂組成物）は、例えば、１０質量％未満、５質量％未満、１質量％未満、０．１質量％未満、０．０１質量％未満、０質量％等が挙げられる。 In one embodiment, the mass % content (additive/active energy ray curable resin composition) is, for example, less than 10 mass %, less than 5 mass %, less than 1 mass %, less than 0.1 mass %, 0 Examples include less than .01% by mass, 0% by mass, and the like.
　１つの実施形態において、質量部含有量（添加剤／４級アンモニウム塩含有ポリマー、リン酸エステル、（ポリ）（メタ）アクリレート、光重合開始剤、有機溶媒のいずれか１つ）は、例えば、５質量％未満、１質量部未満、０．１質量部未満、０．０１質量部未満、０質量部等が挙げられる。 In one embodiment, the parts by weight content (any one of additive/quaternary ammonium salt-containing polymer, phosphoric acid ester, (poly)(meth)acrylate, photoinitiator, and organic solvent) is, for example, Examples include less than 5% by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 part by mass.
　活性エネルギー線硬化性樹脂組成物は、４級アンモニウム塩含有ポリマー及びリン酸エステル並びに必要に応じて（ポリ）（メタ）アクリレート、光重合開始剤、レベリング剤、有機溶媒及び添加剤が、分散・混合されることにより製造され得る。 The active energy ray-curable resin composition contains a quaternary ammonium salt-containing polymer, a phosphoric acid ester, and optionally (poly)(meth)acrylate, a photopolymerization initiator, a leveling agent, an organic solvent, and an additive. It can be manufactured by mixing.
　分散・混合手段は、例えば、乳化分散機、超音波分散装置等が挙げられる。 Examples of the dispersing/mixing means include an emulsifying disperser, an ultrasonic dispersing device, and the like.
　酸価（活性エネルギー線硬化性樹脂組成物）は、例えば、６００ｍｇＫＯＨ／ｇ、５９０ｍｇＫＯＨ／ｇ、５８０ｍｇＫＯＨ／ｇ、５７０ｍｇＫＯＨ／ｇ、５６０ｍｇＫＯＨ／ｇ、５５０ｍｇＫＯＨ／ｇ、５４０ｍｇＫＯＨ／ｇ、５３０ｍｇＫＯＨ／ｇ、５２０ｍｇＫＯＨ／ｇ、５１０ｍｇＫＯＨ／ｇ、５００ｍｇＫＯＨ／ｇ、４９０ｍｇＫＯＨ／ｇ、４８０ｍｇＫＯＨ／ｇ、４７０ｍｇＫＯＨ／ｇ、４６０ｍｇＫＯＨ／ｇ、４５０ｍｇＫＯＨ／ｇ、４４０ｍｇＫＯＨ／ｇ、４３０ｍｇＫＯＨ／ｇ、４２０ｍｇＫＯＨ／ｇ、４１０ｍｇＫＯＨ／ｇ、４００ｍｇＫＯＨ／ｇ、２００ｍｇＫＯＨ／ｇ、１００ｍｇＫＯＨ／ｇ、５０ｍｇＫＯＨ／ｇ、２５ｍｇＫＯＨ／ｇ、１０ｍｇＫＯＨ／ｇ、０ｍｇＫＯＨ／ｇ等が挙げられる。１つの実施形態において、上記酸価は、好ましくは、０ｍｇＫＯＨ／ｇ～６００ｍｇＫＯＨ／ｇが挙げられ、より好ましくは、４００ｍｇＫＯＨ／ｇ～６００ｍｇＫＯＨ／ｇが挙げられる。 The acid value (active energy ray curable resin composition) is, for example, 600mgKOH/g, 590mgKOH/g, 580mgKOH/g, 570mgKOH/g, 560mgKOH/g, 550mgKOH/g, 540mgKOH/g, 530mgKOH/g, 520mgKOH/g. g, 510mgKOH/g, 500mgKOH/g, 490mgKOH/g, 480mgKOH/g, 470mgKOH/g, 460mgKOH/g, 450mgKOH/g, 440mgKOH/g, 430mgKOH/g, 420mgKOH/g, 410mgKOH/g, 400mgKOH/g, Examples include 200mgKOH/g, 100mgKOH/g, 50mgKOH/g, 25mgKOH/g, 10mgKOH/g, and 0mgKOH/g. In one embodiment, the acid value is preferably 0 mgKOH/g to 600 mgKOH/g, more preferably 400 mgKOH/g to 600 mgKOH/g.
　酸価は、下記条件で測定され得る。下記条件は、ＪＩＳ　Ｋ－００７０に基づいている。
試薬Ａ：０．５ｍｏｌ／ｄｍ３水酸化カリウムエタノール溶液
試薬Ｂ：トルエンエタノール溶液（体積比：トルエン／エタノール＝１／１）を使用直前にフェノールフタレイン指示薬を用い、試薬Ａで中和しておく
（１）３００ｍＬ三角フラスコに、無機酸が混入していない試料を１ｇはかりとる。
（２）当該三角フラスコに、試薬Ｂ　１００ｍＬ及びフェノールフタレイン指示薬を数的加え、試料が完全に溶けるまで十分に振る。固体試料の場合、水浴上で加温して溶かす。
（３）室温の試料溶液を試薬Ａで滴定し、フェノールフタレイン指示薬の微紅色が３０秒続いたときを中和の終点と定める。
（４）下記式に基づいて、酸価を算出する。
酸価＝（２８．０５×Ａ×ｆ）／Ｓ
Ａ：試薬Ａの滴定使用量（ｍＬ）
ｆ：試薬Ａのファクター
Ｓ：試料採取量（ｇ）
（５）試薬の色が濃い場合、（２）において、飽和食塩水２０ｍＬを加え、（３）において、食塩水層の着色が３０秒消失しないときを終点とする。 Acid value can be measured under the following conditions. The following conditions are based on JIS K-0070.
Reagent A: 0.5 mol/ dm potassium hydroxide ethanol solution Reagent B: Toluene ethanol solution (volume ratio: toluene/ethanol = 1/1) was neutralized with reagent A using a phenolphthalein indicator immediately before use. (1) Weigh 1 g of a sample containing no inorganic acid into a 300 mL Erlenmeyer flask.
(2) Add 100 mL of reagent B and phenolphthalein indicator to the Erlenmeyer flask, and shake thoroughly until the sample is completely dissolved. For solid samples, melt by heating on a water bath.
(3) Titrate the sample solution at room temperature with Reagent A, and determine the end point of neutralization when the phenolphthalein indicator remains slightly red for 30 seconds.
(4) Calculate the acid value based on the following formula.
Acid value=(28.05×A×f)/S
A: Titration usage amount of reagent A (mL)
f: Factor S of reagent A: Amount of sample collected (g)
(5) If the color of the reagent is dark, add 20 mL of saturated saline in (2), and determine the end point when the coloring of the saline layer does not disappear for 30 seconds in (3).
　上記組成物がリン酸エステルを含む場合、上記組成物の硬化物は、透過率も良好となる。また、リン酸エステル含有組成物では、高極性樹脂（ウレタン（メタ）アクリレート等）が使用され得る。 When the composition contains a phosphate ester, the cured product of the composition also has good transmittance. Further, in the phosphate ester-containing composition, a highly polar resin (urethane (meth)acrylate, etc.) may be used.
　上記組成物が塩を含む場合、上記組成物の硬化物は、面性も良好となり、上記組成物の液相溶性も良好となる。また、塩含有組成物では、低極性溶媒（メチルイソブチルケトン等）が使用され得る。 When the above-mentioned composition contains a salt, the cured product of the above-mentioned composition has good surface properties and also has good liquid compatibility of the above-mentioned composition. Also, in salt-containing compositions, less polar solvents (such as methyl isobutyl ketone) may be used.
　使用形態（活性エネルギー線硬化性組成物）は、例えば、帯電防止剤、コーティング剤等が挙げられる。 Examples of usage forms (active energy ray-curable compositions) include antistatic agents, coating agents, and the like.
［硬化物］
　本開示は、上記活性エネルギー線硬化性樹脂組成物の硬化物に関する。 [Cured product]
The present disclosure relates to a cured product of the active energy ray-curable resin composition.
　硬化条件は、例えば、下記条件等が挙げられる。 Examples of the curing conditions include the following conditions.
［積層物］
　本開示は、上記硬化物を含む、積層物に関する。 [Laminated product]
The present disclosure relates to a laminate containing the above-mentioned cured product.
　上記積層物は各種公知の方法で製造される。１つの実施形態において、積層物の製造方法は、上記組成物を基材の少なくとも片面に塗工する工程（塗工工程）、活性エネルギー線を照射することにより、硬化物層を形成する工程（活性エネルギー線硬化工程）を含む。 The above laminate is manufactured by various known methods. In one embodiment, the method for producing a laminate includes a step of coating the composition on at least one side of a base material (coating step), a step of forming a cured material layer by irradiating active energy rays ( active energy ray curing process).
　基材は、例えば、ポリカーボネートフィルム、アクリルフィルム（ポリメチルメタクリレートフィルム等）、ポリスチレンフィルム、ポリエステルフィルム、ポリオレフィンフィルム、エポキシ樹脂フィルム、メラミン樹脂フィルム、トリアセチルセルロースフィルム、ＡＢＳフィルム、ＡＳフィルム、ノルボルネン系樹脂フィルム、環状オレフィンフィルム、ポリビニルアルコールフィルム等が挙げられる。 Examples of the base material include polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS film, AS film, norbornene resin. Film, cyclic olefin film, polyvinyl alcohol film and the like.
　１つの実施形態において、厚み（基材）は、好ましくは、１０μｍ～２０００μｍ等が挙げられる。 In one embodiment, the thickness (base material) is preferably 10 μm to 2000 μm.
　１つの実施形態において、厚み（硬化物層）は、好ましくは、０．１μｍ～２０μｍ等が挙げられる。 In one embodiment, the thickness (cured material layer) is preferably 0.1 μm to 20 μm.
（塗工工程）
　塗工方法は、例えば、バーコーター塗工、ワイヤーバー塗工、メイヤーバー塗工、エアナイフ塗工、グラビア塗工、リバースグラビア塗工、フローコート塗工、オフセット印刷、フレキソ印刷、スクリーン印刷法等が挙げられる。 (Coating process)
Coating methods include, for example, bar coater coating, wire bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coat coating, offset printing, flexo printing, screen printing, etc. can be mentioned.
（活性エネルギー線硬化工程）
　活性エネルギー線は、例えば、紫外線、電子線等が挙げられる。 (Active energy ray curing process)
Examples of active energy rays include ultraviolet rays and electron beams.
　紫外線光源は、例えば、キセノンランプ、高圧水銀灯、メタルハライドランプ等が挙げられる。 Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.
　高圧水銀灯を使用する場合、硬化条件は、好ましくは、下記条件等が挙げられる。
ランプ出力：２５Ｗ／ｃｍ～１６０Ｗ／ｃｍ 
　ＵＶ照度：１０ｍＷ／ｃｍ２～８００ｍＷ／ｃｍ２
　積算光量：２５ｍＪ／ｃｍ２～２０００ｍＪ／ｃｍ２
　搬送速度：１ｍ／分～５０ｍ／分 When using a high-pressure mercury lamp, the curing conditions are preferably the following conditions.
Lamp output: 25W/cm ~ 160W/cm
UV illuminance: 10mW/cm 2 ~ 800mW/cm 2
Integrated light amount: 25mJ/cm 2 ~2000mJ/cm 2
Conveying speed: 1m/min ~ 50m/min
　電子線を使用する場合、硬化条件は、好ましくは、下記条件等が挙げられる。
加速電圧：１０ｋＶ～３００ｋＶ
搬送速度：５ｍ／分～５０ｍ／分 When using an electron beam, the curing conditions are preferably the following conditions.
Acceleration voltage: 10kV to 300kV
Conveying speed: 5m/min ~ 50m/min
　以下、実施例及び比較例を通じて本発明を具体的に説明する。但し、上述の説明及び以下の実施例は、本発明を限定する目的で記載されていない。本発明は、特許請求の範囲のみにより限定される。以下特に説明がない限り、部、％等の数値は質量基準である。 Hereinafter, the present invention will be specifically explained through Examples and Comparative Examples. However, the above description and the following examples are not intended to limit the invention. The invention is limited only by the claims that follow. Below, unless otherwise specified, numerical values such as parts and % are based on mass.
合成例１
　撹拌装置、冷却管を備えた反応装置に、ヒドロキシエチルメタクリレート１３０部、ε－カプロラクトン１１４０部及びオクチル酸スズ１．３部を加え、１５０℃まで昇温し、６時間保温した後に冷却して、重量平均分子量が約２７５０である水酸基含有ビニルモノマーとラクトンとの開環重付加物を得た。 Synthesis example 1
130 parts of hydroxyethyl methacrylate, 1140 parts of ε-caprolactone and 1.3 parts of tin octylate were added to a reaction apparatus equipped with a stirring device and a cooling tube, the temperature was raised to 150°C, the temperature was kept for 6 hours, and then cooled. A ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone having a weight average molecular weight of about 2,750 was obtained.
　上記開環重付加物の重量平均分子量は、市販の分子量測定機（本体製品名「ＨＬＣ－８２２０ＧＰＣ」、東ソー（株）製；カラム製品名「ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ－Ｍ」、東ソー（株）製）を用いて、展開溶剤：テトラヒドロフラン流速：０．３５ｍＬ／ｍｉｎ試料濃度：０．５％
標準物質：ポリスチレン（標準ポリスチレンキット　ＰＳｔＱｕｉｃｋＡ、Ｂ、Ｃ 東ソー（株）製）
という条件で測定したことにより得た値である。 The weight average molecular weight of the above ring-opening polyadduct was determined using a commercially available molecular weight analyzer (main product name: "HLC-8220GPC", manufactured by Tosoh Corporation; column product name: "TSKgel SuperHZ-M", manufactured by Tosoh Corporation). Using, developing solvent: tetrahydrofuran flow rate: 0.35 mL/min sample concentration: 0.5%
Standard material: Polystyrene (Standard polystyrene kit PStQuick A, B, C manufactured by Tosoh Corporation)
This value was obtained by measuring under the following conditions.
製造例１　４級アンモニウム塩含有ポリマー
　合成例１と同様の反応装置に、メタクリロイルオキシエチルトリメチルアンモニウムクロリド（ＤＭＣ）（以下、（ａ１－１）成分という。）１００部、（ａ２－１）成分８０部、ｔｅｒｔ－ブチルメタアクリレート（ｔＢＭＡ）（以下、（ａ３－１）成分という。）２０部及びプロピレングリコールモノメチルエーテル（以下、ＰＧＭという。）８００部を加え、８０℃まで昇温した。次いで２，２’－アゾビス（メチルブチロニトリル）（以下、ＡＭＢＮという。）８部及びＰＧＭ３２部を加え、重合反応を開始、８５℃で６時間保温した後に冷却し、４級アンモニウム塩含有ポリマーの溶液（不揮発分２０％）を得た。 Production Example 1 Quaternary ammonium salt-containing polymer In a reaction apparatus similar to Synthesis Example 1, 100 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) (hereinafter referred to as component (a1-1)) and 80 parts of component (a2-1) were added. 20 parts of tert-butyl methacrylate (tBMA) (hereinafter referred to as component (a3-1)) and 800 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) were added, and the temperature was raised to 80°C. Next, 8 parts of 2,2'-azobis(methylbutyronitrile) (hereinafter referred to as AMBN) and 32 parts of PGM were added to start the polymerization reaction, kept at 85°C for 6 hours, and then cooled to form a quaternary ammonium salt-containing polymer. A solution (nonvolatile content 20%) was obtained.
製造例２
　製造例１の（ａ２－１）成分をブレンマー５０ＰＯＥＰ－８００Ｂ（日油（株）製）に代えた以外は同様の操作により、４級アンモニウム塩含有ポリマーの溶液（不揮発分２０％）を得た。 Manufacturing example 2
A solution (non-volatile content: 20%) of a quaternary ammonium salt-containing polymer was obtained by the same operation except that component (a2-1) in Production Example 1 was replaced with Blenmar 50POEP-800B (manufactured by NOF Corporation). .
実施例１－１　活性エネルギー線硬化性樹脂組成物
　製造例１のポリマーを５部、２－メタクリロイルオキシエチルリン酸エステル（共栄社化学（株）製　商品名「ライトエステルＰ－１Ｍ」）を０．５部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（新中村化学工業（株）製　商品名「ＮＫエステルＡ－９５５０Ｗ」）を８９．５部、光重合開始剤（ＩＧＭ　Ｒｅｓｉｎｓ社製、商品名「Ｏｍｎｉｒａｄ１８４」）を５部いずれも不揮発分割合で混合し、更に有機溶剤としてメチルエチルケトンを５０．０部、ＰＧＭを５０．０部加えて活性エネルギー線硬化性樹脂組成物を製造した。 Example 1-1 Active energy ray-curable resin composition 5 parts of the polymer of Production Example 1 and 0.2 parts of 2-methacryloyloxyethyl phosphate (trade name "Light Ester P-1M" manufactured by Kyoeisha Chemical Co., Ltd.). 5 parts, 89.5 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-9550W"), a photopolymerization initiator (manufactured by IGM Resins). , trade name "Omnirad 184") were mixed in a non-volatile content ratio, and 50.0 parts of methyl ethyl ketone and 50.0 parts of PGM were added as organic solvents to produce an active energy ray-curable resin composition.
　特段言及がない限り、下記例は、表のように変更した以外は、実施例１－１と同様にして行った。 Unless otherwise specified, the following examples were carried out in the same manner as Example 1-1, except for the changes shown in the table.
＜略称の説明＞
Ｐ－１Ｍ：リン酸２－メタクリロイルオキシエチル、共栄社化学（株）製　商品名「ライトエステルＰ－１Ｍ」
Ｐ－２Ｍ：リン酸ジ（２－メタクリロイルオキシエチル）、共栄社化学（株）製　商品名「ライトエステルＰ－２Ｍ」
 
９５５０Ｗ：ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物、新中村化学工業（株）製、商品名「ＮＫエステルＡ－９５５０Ｗ」
Ａ－ＴＭＭ－３：ペンタエリスリトールトリアクリレート、新中村化学工業（株）製、製品名「Ａ－ＴＭＭ－３」
Ｖ＃８０２：トリペンタエリスリトールポリ（メタ）アクリレート、大阪有機化学工業（株）製、製品名「ビスコート＃８０２」
ＵＡ：ウレタンアクリレート（イソホロンジイソシアネートとペンタエリスリトールトリアクリレートとの反応物） <Explanation of abbreviations>
P-1M: 2-methacryloyloxyethyl phosphate, manufactured by Kyoeisha Chemical Co., Ltd. Product name: "Light Ester P-1M"
P-2M: Di(2-methacryloyloxyethyl) phosphate, manufactured by Kyoeisha Chemical Co., Ltd. Product name: “Light Ester P-2M”

9550W: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-9550W"
A-TMM-3: Pentaerythritol triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "A-TMM-3"
V#802: Tripentaerythritol poly(meth)acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., product name "Viscoat #802"
UA: Urethane acrylate (reaction product of isophorone diisocyanate and pentaerythritol triacrylate)
酸価
　酸価は、下記条件で測定した。
　試薬Ａ：０．５ｍｏｌ／ｄｍ３水酸化カリウムエタノール溶液
試薬Ｂ：トルエンエタノール溶液（体積比：トルエン／エタノール＝１／１）を使用直前にフェノールフタレイン指示薬を用い、試薬Ａで中和しておいた。
（１）３００ｍＬ三角フラスコに、無機酸が混入していない試料を１ｇはかりとった。
（２）当該三角フラスコに、試薬Ｂ　１００ｍＬ及びフェノールフタレイン指示薬を数的加え、試料が完全に溶けるまで十分に振った。
（３）室温の試料溶液を試薬Ａで滴定し、フェノールフタレイン指示薬の微紅色が３０秒続いたときを中和の終点と定めた。
（４）下記式に基づいて、酸価を算出した。
酸価＝（２８．０５×Ａ×ｆ）／Ｓ
Ａ：試薬Ａの滴定使用量（ｍＬ）
ｆ：試薬Ａのファクター
Ｓ：試料採取量（ｇ） Acid value The acid value was measured under the following conditions.
Reagent A: 0.5 mol/ dm potassium hydroxide ethanol solution Reagent B: Toluene ethanol solution (volume ratio: toluene/ethanol = 1/1) was neutralized with reagent A using a phenolphthalein indicator immediately before use. Oita.
(1) 1 g of a sample containing no inorganic acid was weighed into a 300 mL Erlenmeyer flask.
(2) 100 mL of reagent B and a phenolphthalein indicator were added to the Erlenmeyer flask, and the flask was sufficiently shaken until the sample was completely dissolved.
(3) A sample solution at room temperature was titrated with Reagent A, and the end point of neutralization was determined when the phenolphthalein indicator remained slightly red for 30 seconds.
(4) The acid value was calculated based on the following formula.
Acid value=(28.05×A×f)/S
A: Titration usage amount of reagent A (mL)
f: Factor S of reagent A: Amount of sample collected (g)
積層物の製造
　トリアセチルセルロースフィルム（富士フィルム（株）製　ＦＴ　ＴＤ６０ＵＬ、膜厚：６０μｍ）上に、各活性エネルギー線硬化性樹脂組成物を、硬化物層の膜厚が５μｍとなるように＃１１バーコーターにて塗布し、８０℃で１分間乾燥させた。次いで、紫外線硬化装置（製品名：ＵＢＴ－０８０－７Ａ／ＢＭ、（株）マルチプライ製、高圧水銀灯６００ｍＪ／ｃｍ２）を使用し、硬化物を含む積層物を得た。 Manufacture of laminate Each active energy ray-curable resin composition was placed on a triacetyl cellulose film (Fuji Film Co., Ltd. FT TD60UL, film thickness: 60 μm) so that the thickness of the cured material layer was 5 μm. It was coated using a No. 11 bar coater and dried at 80° C. for 1 minute. Next, a laminate containing a cured product was obtained using an ultraviolet curing device (product name: UBT-080-7A/BM, manufactured by Multiply Co., Ltd., high pressure mercury lamp 600 mJ/cm 2 ).
表面抵抗値
　積層物の製造直後の表面抵抗を、市販抵抗率計（三菱化学（株）製、製品名「ハイレスタＭＣＰ－ＨＴ－４５０」）を用い、ＪＩＳ　Ｋ　６９１１に準じ、印加電圧５００Ｖで測定した。
　「ＯＶＥＲ」は、測定範囲超過を意味する。
　なお、比較例１－３は、活性エネルギー線硬化性組成物中に沈殿物が発生した。そのため、比較例１－３は、評価できなかった。 Surface resistance value The surface resistance of the laminate immediately after manufacture was measured using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Corporation, product name "Hiresta MCP-HT-450") at an applied voltage of 500 V in accordance with JIS K 6911. did.
"OVER" means exceeding the measurement range.
In Comparative Example 1-3, precipitates were generated in the active energy ray curable composition. Therefore, Comparative Example 1-3 could not be evaluated.
評価例　透過率
　ＪＩＳ　Ｋ　７３６１－１（１９９７）の規格に準拠し、ヘーズメーター（製品名「ＨＺ－Ｖ３」、スガ試験機（株）製）を用いて積層物の全光線透過率を測定した。
　透過率が低い場合、塗膜が濁っているか又は着色している。 Evaluation example Transmittance The total light transmittance of the laminate was measured using a haze meter (product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.) in accordance with the standard of JIS K 7361-1 (1997). .
If the transmittance is low, the coating is cloudy or colored.
評価例　ＨＡＺＥ
　ＪＩＳ　Ｋ　７３６１－１（１９９７）に準拠し、ヘーズメーター（製品名「ＨＺ－Ｖ３」、スガ試験機（株）製）を用いて積層物のＨＡＺＥを測定した。 Evaluation example HAZE
The HAZE of the laminate was measured in accordance with JIS K 7361-1 (1997) using a haze meter (product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.).
実施例２－１　活性エネルギー線硬化性樹脂組成物
　製造例１のポリマーを２５部、塩（アミノイオンＲＥ３０００ＭＦ、日本乳化剤（株）製）を１部６０℃で１時間加温した後、振盪機で混合し、ポリマー組成物を得た。
　次に、光重合開始剤（Ｏｍｎｉｒａｄ２９５９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ.Ｖ.社製）５部、上記ポリマー組成物、プロピレングリコールモノメチルエーテル７０．５部、メチルイソブチルケトン２１５．５部を振盪機で混合した。
　そして、ポリ（メタ）アクリレートＡ　１２５部、レベリング剤（フタージェント６０２Ａ）１．５部を加え、振盪機で混合して、活性エネルギー線硬化性樹脂組成物を製造した。 Example 2-1 Active energy ray-curable resin composition 25 parts of the polymer of Production Example 1 and 1 part of salt (Aminoion RE3000MF, manufactured by Nippon Nyukazai Co., Ltd.) were heated at 60°C for 1 hour, and then placed in a shaker. and mixed to obtain a polymer composition.
Next, 5 parts of a photopolymerization initiator (Omnirad 2959, manufactured by IGM Resins B.V.), the above polymer composition, 70.5 parts of propylene glycol monomethyl ether, and 215.5 parts of methyl isobutyl ketone were mixed in a shaker.
Then, 125 parts of poly(meth)acrylate A and 1.5 parts of a leveling agent (Ftergent 602A) were added and mixed using a shaker to produce an active energy ray-curable resin composition.
　特段言及がない限り、下記例は、表のように変更した以外は、実施例２－１と同様にして行った。 Unless otherwise specified, the following examples were carried out in the same manner as Example 2-1 except for the changes shown in the table.
積層物の製造
　ポリエチレンテレフタレートフィルム（東レ（株）製　ルミラー１００、膜厚：１００μｍ）上に、活性エネルギー線硬化性樹脂組成物を、硬化物層の膜厚が５μｍとなるように＃１１バーコーターにて塗布し、８０℃で１分間乾燥させた。次いで、紫外線硬化装置（製品名：ＵＢＴ－０８０－７Ａ／ＢＭ、（株）マルチプライ製、高圧水銀灯２００ｍＪ／ｃｍ２）を使用し、硬化物を含む積層物を得た。 Manufacture of laminate The active energy ray-curable resin composition was applied onto a polyethylene terephthalate film (Lumirror 100 manufactured by Toray Industries, Inc., film thickness: 100 μm) using a #11 bar coater so that the thickness of the cured material layer was 5 μm. The coating was applied at 80° C. for 1 minute. Next, a laminate containing a cured product was obtained using an ultraviolet curing device (product name: UBT-080-7A/BM, manufactured by Multiply Co., Ltd., high pressure mercury lamp 200 mJ/cm 2 ).
液相溶性
　下記基準で評価した。液相溶性が×となった例について、他の評価はできなかった。
○・・・完全に溶解した。
×・・・一部溶解又は溶解せず。 Liquid compatibility Evaluated based on the following criteria. Other evaluations could not be made for the examples in which the liquid compatibility was rated as x.
○: Completely dissolved.
×: Partially dissolved or not dissolved.
表面抵抗値
　積層物の製造直後の表面抵抗を、市販抵抗率計（三菱化学（株）製、製品名「ハイレスタＭＣＰ－ＨＴ－４５０」）を用い、ＪＩＳ　Ｋ　６９１１に準じ、印加電圧５００Ｖで測定した。 Surface resistance value The surface resistance of the laminate immediately after manufacture was measured using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Corporation, product name "Hiresta MCP-HT-450") at an applied voltage of 500 V in accordance with JIS K 6911. did.
　下記式に基づいて、塩／４級アンモニウム塩含有ポリマー比率を算出した。
塩／４級アンモニウム塩含有ポリマー比率　＝［（Ａ×ａ）／（Ｂ×ｂ）］×１００
Ａ：塩の配合比
ａ：塩の不揮発分
Ｂ：４級アンモニウム塩含有ポリマーの配合比
ｂ：４級アンモニウム塩含有ポリマーの不揮発分 The salt/quaternary ammonium salt-containing polymer ratio was calculated based on the following formula.
Salt/quaternary ammonium salt-containing polymer ratio = [(A×a)/(B×b)]×100
A: Blending ratio of salt a: Non-volatile content of salt B: Blending ratio of quaternary ammonium salt-containing polymer b: Non-volatile content of quaternary ammonium salt-containing polymer
＜略称の説明＞
製造例１：不揮発分２０％
１ＳＸ－１０５５Ｆ：４級アンモニウム塩含有ポリマー、不揮発分４０％、大成ファインケミカル（株）製）
 
ＲＥ３０００ＭＦ：アミノイオンＲＥ３０００ＭＦ（ポリオキシアルキレン構造含有硫酸塩、不揮発分５０％、日本乳化剤（株）製）
ＳＲ－２０：アデカソープＳＲ－２０（ポリオキシアルキレン構造含有硫酸塩、不揮発分１００％、（株）ＡＤＥＫＡ製）
ＫＨ－１０：アクアロンＫＨ－１０（ポリオキシアルキレン構造含有硫酸塩、不揮発分１００％、第一工業（株）製）
ＰＷ－３６：ディスパロンＰＷ－３６（ポリオキシアルキレン構造含有リン酸塩、不揮発分５０％、楠本化成（株）製）
 
脂肪酸アマイドＳ：ステアリン酸アマイド、不揮発分１００％、花王ケミカル（株）製
Ｐ－１Ｍ：ライトエステルＰ－１Ｍ、リン酸２－メタクリロイルオキシエチル、不揮発分１００％、共栄社化学（株）製
 
ポリ（メタ）アクリレートＡ：ヘキサメチレンジイソシアネートのビウレット体とペンタエリスリトールトリアクリレートの反応物（ウレタンアクリレート）、不揮発分８０％
ポリ（メタ）アクリレートＢ：ヘキサメチレンジイソシアネートのヌレート体とペンタエリスリトールトリアクリレートの反応物（ウレタンアクリレート）、不揮発分８０％
ポリ（メタ）アクリレートＣ：製品名「ＳＣ－２１５２」、ヘキサメチレンジイソシアネートのヌレート体とジペンタエリスリトールペンタアクリレートとの反応物（ウレタンアクリレート）、ＭＩＷＯＮ製、不揮発分１００％
 
Ｏｍｎｉｒａｄ２９５９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ.Ｖ.社製、不揮発分１００％
 
ＦＴ６０２Ａ：フタージェント６０２Ａ、ラジカル重合性基と分岐フルオロ脂肪族炭化水素基とを有するフッ素系レベリング剤、（株）ネオス製
 
ＭＩＢＫ：メチルイソブチルケト
ＰＧＭＥ：プロピレングリコールモノメチルエーテル <Explanation of abbreviations>
Production example 1: Non-volatile content 20%
1SX-1055F: Quaternary ammonium salt-containing polymer, non-volatile content 40%, manufactured by Taisei Fine Chemical Co., Ltd.)

RE3000MF: Aminoion RE3000MF (polyoxyalkylene structure-containing sulfate, non-volatile content 50%, manufactured by Nippon Nyukazai Co., Ltd.)
SR-20: ADEKA SOAP SR-20 (polyoxyalkylene structure-containing sulfate, non-volatile content 100%, manufactured by ADEKA Co., Ltd.)
KH-10: Aqualon KH-10 (polyoxyalkylene structure-containing sulfate, non-volatile content 100%, manufactured by Dai-ichi Kogyo Co., Ltd.)
PW-36: Disparon PW-36 (phosphate containing polyoxyalkylene structure, non-volatile content 50%, manufactured by Kusumoto Kasei Co., Ltd.)

Fatty acid amide S: Stearamide, 100% nonvolatile content, manufactured by Kao Chemical Co., Ltd. P-1M: Light ester P-1M, 2-methacryloyloxyethyl phosphate, 100% nonvolatile content, manufactured by Kyoeisha Chemical Co., Ltd.
Poly(meth)acrylate A: Reaction product of biuret hexamethylene diisocyanate and pentaerythritol triacrylate (urethane acrylate), non-volatile content 80%
Poly(meth)acrylate B: Reaction product of hexamethylene diisocyanate nurate and pentaerythritol triacrylate (urethane acrylate), non-volatile content 80%
Poly(meth)acrylate C: Product name "SC-2152", reaction product of hexamethylene diisocyanate nurate and dipentaerythritol pentaacrylate (urethane acrylate), manufactured by MIWON, non-volatile content 100%

Omnirad2959, manufactured by IGM Resins B.V., non-volatile content 100%

FT602A: Ftergent 602A, fluorine-based leveling agent having a radically polymerizable group and a branched fluoroaliphatic hydrocarbon group, manufactured by Neos Co., Ltd.
MIBK: Methyl isobutyl keto PGME: Propylene glycol monomethyl ether
評価例　面性
　下記基準で評価した。
○・・・透明で凹凸がない。
×・・・透明だが凹凸がある又は不透明である。 Evaluation example Surface quality Evaluated using the following criteria.
○...Transparent with no unevenness.
×...Transparent but uneven or opaque.
評価例　ＨＡＺＥ
　ＪＩＳ　Ｋ　７３６１－１（１９９７）に準拠し、ヘーズメーター（製品名「ＨＺ－Ｖ３」、スガ試験機（株）製）を用いて積層物のＨＡＺＥを測定した。 Evaluation example HAZE
The HAZE of the laminate was measured in accordance with JIS K 7361-1 (1997) using a haze meter (product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.).
   

Claims (4)

  1. 活性エネルギー線硬化性樹脂組成物であって、
    前記活性エネルギー線硬化性樹脂組成物は、４級アンモニウム塩含有ポリマー並びにリン酸エステル及び／又は塩を含み、
    前記塩のアニオンはポリオキシアルキレン構造を含み、
    前記活性エネルギー線硬化性樹脂組成物がリン酸エステルを含む場合、前記活性エネルギー線硬化性樹脂組成物の酸価は、４００ｍｇＫＯＨ／ｇ～６００ｍｇＫＯＨ／ｇである、
    活性エネルギー線硬化性樹脂組成物。     An active energy ray-curable resin composition,
    The active energy ray-curable resin composition includes a quaternary ammonium salt-containing polymer and a phosphoric acid ester and/or salt,
    The anion of the salt includes a polyoxyalkylene structure,
    When the active energy ray curable resin composition contains a phosphoric acid ester, the acid value of the active energy ray curable resin composition is 400 mgKOH/g to 600 mgKOH/g.
    Active energy ray curable resin composition.
  2. ウレタンポリ（メタ）アクリレートを含む、請求項１に記載の活性エネルギー線硬化性樹脂組成物。 The active energy ray-curable resin composition according to claim 1, comprising urethane poly(meth)acrylate.
  3. 請求項１又は２に記載の活性エネルギー線硬化性樹脂組成物の硬化物。 A cured product of the active energy ray-curable resin composition according to claim 1 or 2.
  4. 請求項３に記載の硬化物を含む、積層物。 A laminate comprising the cured product according to claim 3.
PCT/JP2023/032578 2022-09-12 2023-09-06 Actinic-ray-curable resin composition, cured object, and multilayered object WO2024058031A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2022144792 2022-09-12
JP2022-144792 2022-09-12
JP2022-144793 2022-09-12
JP2022144793 2022-09-12

Publications (1)

Publication Number Publication Date
WO2024058031A1 true WO2024058031A1 (en) 2024-03-21

Family

ID=90274887

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/032578 WO2024058031A1 (en) 2022-09-12 2023-09-06 Actinic-ray-curable resin composition, cured object, and multilayered object

Country Status (1)

Country Link
WO (1) WO2024058031A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012054071A (en) * 2010-08-31 2012-03-15 Sekisui Chem Co Ltd Lithium ion conductive material, lithium ion conductive electrolyte membrane, lithium ion conductive electrolyte membrane-electrode assembly and lithium ion polymer battery
JP2012097243A (en) * 2009-12-16 2012-05-24 Kao Corp Resin modifier
JP2019073616A (en) * 2017-10-16 2019-05-16 Dic株式会社 Active energy ray-curable composition and film using the same
JP2021147615A (en) * 2020-03-16 2021-09-27 荒川化学工業株式会社 Active energy ray-curable resin composition, cured film, and film
JP2022058240A (en) * 2020-09-30 2022-04-11 荒川化学工業株式会社 Active energy ray-curable resin composition and laminate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012097243A (en) * 2009-12-16 2012-05-24 Kao Corp Resin modifier
JP2012054071A (en) * 2010-08-31 2012-03-15 Sekisui Chem Co Ltd Lithium ion conductive material, lithium ion conductive electrolyte membrane, lithium ion conductive electrolyte membrane-electrode assembly and lithium ion polymer battery
JP2019073616A (en) * 2017-10-16 2019-05-16 Dic株式会社 Active energy ray-curable composition and film using the same
JP2021147615A (en) * 2020-03-16 2021-09-27 荒川化学工業株式会社 Active energy ray-curable resin composition, cured film, and film
JP2022058240A (en) * 2020-09-30 2022-04-11 荒川化学工業株式会社 Active energy ray-curable resin composition and laminate

Similar Documents

Publication Publication Date Title
US9182665B2 (en) White curable composition for printed circuit board, cured coating film using the same, and printed circuit board
JP5858278B2 (en) Active energy ray-curable resin composition, method for producing active energy ray-curable resin composition, paint, coating film, and film
KR101598162B1 (en) Active energy ray-curable resin composition, manufacturing method for active energy ray-curable resin composition, coating material, coating film, and film
EP3778657A1 (en) Curable composition, cured product of same, and electronic component comprising said cured product
KR102185318B1 (en) An antistatic agent for active energy-ray curable resin composition, an active energy-ray curable composition, a cured film and an antistatic treated optical film
WO2019189186A1 (en) Curable composition for inkjet printing, cured product of same, and electronic component having said cured product
JP2012031297A (en) Antistatic agent for active energy ray-curable type resin composition, active energy ray-curable type composition, cured coating film, and antistatic-treated optical film
JP2008248069A (en) Active energy ray-curable resin composition for hard-coating use
KR20180127456A (en) Curable composition for inkjet, cured product and printed wiring board
JP6186032B1 (en) Coating agent and coating film
JP2020084055A (en) Active energy ray-curable ink and laminate
TW201329628A (en) Active energy ray-curable composition for molding optical film, optical film, polarizer protecting film and polarizing plate
TWI791642B (en) Active energy ray curable composition, cured product and film using same
JP4806965B2 (en) Method for forming antistatic coating
WO2024058031A1 (en) Actinic-ray-curable resin composition, cured object, and multilayered object
TWI702240B (en) Urethane (meth)acrylate resin and laminated film
WO2020203791A1 (en) Photosensitive black resin composition, cured article produced from same, and display device equipped with shielding layer comprising cured article
KR102181205B1 (en) Fluorinated urethane (meth)acrylate, curable composition, and antireflective film
JP2019178270A (en) Curable composition, cured product of the same and electronic component having cured product
JP2008137190A (en) Antireflection laminate
JP6911420B2 (en) Active energy ray-polymerizable composition
WO2019107026A1 (en) Fluorine-containing active energy ray-curable resin, liquid repellent agent, resin composition containing same, and cured film
JP7321444B2 (en) UV curable coating composition, cured film, article provided with cured film
TWI796371B (en) Active energy ray curable composition, cured product and film using same
JP2023057930A (en) Radically polymerizable polymer and photosensitive composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23865386

Country of ref document: EP

Kind code of ref document: A1