WO2018163837A1 - Active energy ray curable composition, cured product, and film - Google Patents
Active energy ray curable composition, cured product, and film Download PDFInfo
- Publication number
- WO2018163837A1 WO2018163837A1 PCT/JP2018/006389 JP2018006389W WO2018163837A1 WO 2018163837 A1 WO2018163837 A1 WO 2018163837A1 JP 2018006389 W JP2018006389 W JP 2018006389W WO 2018163837 A1 WO2018163837 A1 WO 2018163837A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- energy ray
- active energy
- mass
- Prior art date
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- QNTJKRDAWNRWRV-UHFFFAOYSA-M methyl sulfate;trimethyl(propyl)azanium Chemical compound COS([O-])(=O)=O.CCC[N+](C)(C)C QNTJKRDAWNRWRV-UHFFFAOYSA-M 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 1
- IWDANOJGJIFBEL-UHFFFAOYSA-N spiro[3.4]octane Chemical group C1CCC21CCCC2 IWDANOJGJIFBEL-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- FCGQIZKUTMUWDC-UHFFFAOYSA-M trimethyl(propyl)azanium;bromide Chemical compound [Br-].CCC[N+](C)(C)C FCGQIZKUTMUWDC-UHFFFAOYSA-M 0.000 description 1
- NRWCNEBHECBWRJ-UHFFFAOYSA-M trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)C NRWCNEBHECBWRJ-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- 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
-
- 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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Definitions
- the present invention relates to an active energy ray-curable composition, a cured product thereof, and a film.
- Antireflective (LR) films used on the surface of flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), plasma displays (PDPs), etc. have a large refractive index difference on the film substrate
- FPD flat panel displays
- LCDs liquid crystal displays
- OLEDs organic EL displays
- PDPs plasma displays
- LR refractive index difference
- This is realized by a multilayer structure in which two layers are formed (base material / high refractive index layer / low refractive index layer).
- base material high refractive index layer / low refractive index layer
- Each of these layers is required to have high scratch resistance in order to prevent scratches in the production process of the antireflection film, and also to have high antistatic properties in order to prevent contamination and blocking of the film.
- an antireflection film is an optical film, each layer is also required to have high transparency.
- the problem to be solved by the present invention is an active energy ray capable of forming a hard coat layer having excellent antistatic properties and having excellent water resistance that does not become cloudy even when water is mixed and does not cause poor appearance. It is to provide a curable composition.
- the present invention comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide.
- An active energy ray-curable composition is provided.
- this invention provides the cured
- the active energy ray-curable composition of the present invention is excellent in continuous productivity by providing a composition having water resistance that is not easily clouded even when water is mixed during coating, and excellent in the film surface after curing.
- a hard coat layer having antistatic properties can be formed.
- the film which has a hard-coat layer which consists of a cured coating film of the active energy ray curable composition of this invention is flat panel displays, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP) ( It can be suitably used as an optical film used for FPD). Furthermore, since it has excellent antistatic properties when used in these applications, adhesion of dust and the like can be suppressed. Furthermore, when this film is used for a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.
- LCD liquid crystal display
- OLED organic electroluminescent display
- PDP plasma display
- the active energy ray-curable composition of the present invention comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. It contains.
- Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1), urethane (meth) acrylate (A2), and a high refractive index polymerizable monomer having a refractive index of 1.55 or more.
- Examples thereof include body (A3), epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. These may be used alone or in combination of two or more.
- a polyfunctional (meth) acrylate (A1) is obtained from the viewpoint that a more excellent scratch resistance, hard coat property, water resistance, and transparency of a cured coating film can be obtained.
- a combination of (meth) acrylate (A1) and urethane (meth) acrylate (A2) or a combination of polyfunctional (meth) acrylate (A1) and high refractive index polymerizable monomer (A3) is more preferable.
- (meth) acrylate refers to one or both of acrylate and methacrylate
- (meth) acryloyl refers to one or both of acryloyl and methacryloyl.
- the polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acryloyl groups in one molecule.
- Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol.
- polyfunctional (meth) acrylates (A1) can be used alone or in combination of two or more.
- these polyfunctional (meth) acrylates (A1) since the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention is improved, dipentaerythritol hexa (meth) acrylate, di It is preferable to use at least one compound selected from the group consisting of pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Is more preferable.
- urethane (meth) acrylate (A2) a reaction product of polyisocyanate (a2-1) and (meth) acrylate (a2-2) having a hydroxyl group can be used.
- polyisocyanate (a2-1) examples include aliphatic polyisocyanates and aromatic polyisocyanates. Since the coloring of the cured coating film of the active energy ray-curable composition of the present invention can be reduced, Isocyanates are preferred.
- the aliphatic polyisocyanate is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon.
- Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanato).
- cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane.
- a trimerized product obtained by trimming the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate.
- these aliphatic polyisocyanates can be used alone or in combination of two or more.
- aliphatic polyisocyanates in order to improve the scratch resistance of the coating film, it is preferable to use one or more selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate, and more preferably isophorone diisocyanate.
- the (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryloyl group.
- Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
- Divalent compounds such as acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate Mono (meth) acrylate of alcohol; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meta) Mono- or di (meth) acrylate of trivalent alcohol such as acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups Mono- and di (meth) acrylates having hydroxyl groups modified with
- the urethane (meth) acrylate (A2) since it can improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention, it has four or more (meth) acryloyl groups in one molecule. Those are preferred. Since the urethane (meth) acrylate (A2) has four or more (meth) acryloyl groups in one molecule, the (meth) acrylate (a2-2) has 2 (meth) acryloyl groups. Those having at least two are preferred.
- Examples of such (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, Glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipenta Examples include erythritol penta (meth) acrylate.
- (meth) acrylates (a2-2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates.
- these (meth) acrylates (a2-2) since scratch resistance can be further improved, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) Acrylates are preferred, and pentaerythritol tetra (meth) acrylate is more preferred.
- the reaction of the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate
- urethanization catalyst examples include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
- the high-refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more is sufficient if it has a high refractive index of 1.55 or more before curing.
- Preferable examples include 6 to 6 aromatic polymerizable monomers and fluorene polymerizable monomers.
- polymerizable monomer (A) examples include compounds represented by the following general formula (1): phenylbenzyl such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having a group; (meth) acrylate compound having a phenylphenol group such as phenylphenol EO acrylate; propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, oxyethylene group Examples thereof include bisphenol compounds having 2 to 4 (meth) acryloyl groups such as bisphenol A di (meth) acrylate having an oxyethylene group and bisphenol A tri (meth) acrylate having an oxyethylene group.
- phenylbenzyl such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having
- These polymerizable monomers (A) can be used alone or in combination of two or more.
- a compound represented by the following general formula (1) which has a phenylbenzyl group, can be obtained because a high refractive index can be easily controlled even when a specific organic solvent described later is used ( It is preferable to use one or more monomers selected from the group consisting of a meth) acrylate compound and a bisphenol compound having 2 to 4 (meth) acryloyl groups.
- polymerizable monomer (A3) Commercially available products that can be used as the polymerizable monomer (A3) include “OGSOL EA-0200”, “OGSOL EA-0300”, “OGSOL GA-5060P” manufactured by Osaka Gas Chemical Co., Ltd .; DIC Corporation “UNIDIC EKZ-948”, “UNIDIC EQS-1179” manufactured by Shin-Nakamura Chemical Co., Ltd., “MIRAMER HR6042” manufactured by MIWON, etc. These polymerizable monomers (A) can be used alone or in combination of two or more.
- R 1 and R 2 each represent a hydrogen group or a methyl group, and m and n each represent an integer of 0 to 5.
- the resin (B) has an alicyclic structure and a quaternary ammonium salt.
- Examples of the method for producing the resin (B) include the polymerizable monomer (b1) having an alicyclic structure and the polymerizable monomer (b2) having a quaternary ammonium salt as essential components. Examples thereof include a method of copolymerizing the monomer (b1) and the polymerizable monomer (b2) with a copolymerizable polymerizable monomer (b3).
- the polymerizable monomer (b1) is a polymerizable monomer having an alicyclic structure.
- the alicyclic structure include a monocyclic alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring; a bicycloundecane ring, a decahydro ring Naphthalene (decalin) ring, tricyclo [5.2.1.0 2,6 ] decane ring, bicyclo [4.3.0] nonane ring, tricyclo [5.3.1.1] dodecane ring, tricyclo [5.
- polymerizable monomer (c1) examples include cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples include dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate.
- polymerizable monomers (b1) can be used alone or in combination of two or more.
- Examples of the polymerizable monomer (b2) include those in which the counter anion such as 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride and 3-[(meth) acryloyloxy] propyltrimethylammonium chloride is chloride; Counter anions such as 2-[(meth) acryloyloxy] ethyltrimethylammonium bromide, 3-[(meth) acryloyloxy] propyltrimethylammonium bromide and the like, wherein 2-[(meth) acryloyloxy] ethyltrimethylammonium methylphenyl Sulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammonium methylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylammonium methyl Phenylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylam
- Examples of the polymerizable monomer (b3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n- Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Alkyl (meth) acrylates such as dodecyl (meth) acrylate; methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethyleneglycol / polypropyleneglycol mono (meth) acrylate, lauroxypoly
- the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, mono (meth) acrylate of polyalkylene glycol is preferable, and methoxypolyethylene Glycol mono (meth) acrylate is more preferred.
- the (meth) acrylate which has a fluorinated alkyl group is also preferable from the effect that the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the number average molecular weight of the polyalkylene glycol is preferably in the range of 200 to 8,000, more preferably in the range of 300 to 6,000, still more preferably in the range of 400 to 4,000, and 400 to 2 Those in the range of 1,000 are particularly preferred.
- the ratio of the polymerizable monomer (b1) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
- the range of mass% is preferable, the range of 10 to 50 mass% is more preferable, and the range of 12 to 45 mass% is more preferable.
- the ratio of the polymerizable monomer (b2) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
- the range of ⁇ 90% by mass is preferred, the range of 40 ⁇ 80% by mass is more preferred, and the range of 45 ⁇ 70% by mass is more preferred.
- the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the ratio of the poly (alkylene glycol) mono (meth) acrylate in the total amount of the raw material of the resin (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and 20 to 40% by mass. The range of is more preferable.
- the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the ratio of the (meth) acrylate having a fluorinated alkyl group in the total amount of the raw material of the resin (B) is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass. The range of 1 to 5% by mass is more preferable.
- the weight average molecular weight of the resin (B) is preferably in the range of 1,000 to 100,000 because the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the range of ⁇ 50,000 is more preferred, and the range of 3,000 ⁇ 30,000 is more preferred.
- the weight average molecular weight in this invention is the value in polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the compounding amount of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, it is based on 100 parts by mass of the active energy ray-curable compound (A).
- the range of 0.1 to 30 parts by mass is preferable, the range of 0.3 to 20 parts by mass is more preferable, the range of 0.5 to 10 parts by mass is more preferable, and the range of 0.7 to 7 parts by mass is particularly preferable. preferable.
- the organic solvent (C) must contain dimethylacetamide in order to obtain excellent water resistance.
- Dimethylacetamide has good compatibility with the resin (B) and has a relatively high boiling point. Therefore, even if water is mixed in, dimethylacetamide is completely mixed and has high polymer solubility, so both hydrophilic and hydrophobic components are mixed. Even in the case of evaporation, since it evaporates in the drying step, problems such as whitening can be suppressed, and excellent water resistance can be obtained.
- the content of the dimethylacetamide is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A) from the standpoint that even better water resistance is obtained.
- the range of 7 to 150 parts by mass is more preferable.
- the content of the dimethylacetamide is preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 7% by mass in the organic solvent (C) from the viewpoint of obtaining further excellent water resistance. More preferred is 99% by mass or less.
- organic solvent (C) in addition to the dimethylacetamide, for example, a hydrophobic solvent and a hydrophilic solvent other than the dimethylacetamide can be used.
- hydrophobic solvent examples include diethyl ether, benzene, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, xylene, n-butanol, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, chloroform, propylene glycol.
- examples thereof include monomethyl ether acetate.
- solvents may be used alone or in combination of two or more.
- the hydrophobic solvent the coating stability of the active energy ray-curable composition is further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained.
- hydrophilic solvent examples include acetone, methanol, ethanol, n-propanol, isopropyl alcohol, diacetone alcohol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dioxolane, tetrahydrofuran, tetrahydropyran, dimethylformamide, and the like. . These solvents may be used alone or in combination of two or more. As the hydrophilic solvent, the coating stability of the active energy ray-curable composition is further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained.
- the hydrophilic solvent refers to a solvent having a solubility in water of 10 g / 100 ml or more, and a solvent other than the dimethylacetamide is a hydrophobic solvent.
- the solubility of the organic solvent in water accounts for the solubility in 100 ml of water (25 ° C.).
- the coating stability of the active energy ray-curable composition can be further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained.
- dimethylacetamide in combination with other hydrophilic solvents, or in combination with dimethylacetamide, other hydrophilic solvents and hydrophobic solvents.
- the amount of the hydrophilic solvent used in combination with dimethylacetamide and the other hydrophilic solvent is 100 parts by mass of the active energy ray-curable compound (A).
- the range is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass.
- the amount of the hydrophilic solvent used is the active energy ray-curable compound (A).
- the range of 0.1 to 40 parts by mass with respect to 100 parts by mass is preferable, and the range of 3 to 25 parts by mass is more preferable.
- the amount of the hydrophobic solvent used is the active energy ray-curable compound (A).
- the range of 10 to 95 parts by mass is preferable with respect to 100 parts by mass, and the range of 30 to 93 parts by mass is more preferable.
- the blending amount of the organic solvent (C) in the active energy ray-curable composition of the present invention is preferably an amount that provides a viscosity suitable for a coating method described later.
- the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after coating on a substrate.
- the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve curability.
- a photosensitizer (E) can be further added to improve curability.
- Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo ⁇ 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone ⁇ , benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzo Benzoin compounds such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-
- Examples of the photosensitizer (E) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuro And sulfur compounds such as nitro-p-toluenesulfonate.
- tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine
- urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuro
- sulfur compounds such as nitro-p-toluenesulfonate.
- the usage-amount of said photoinitiator (D) and photosensitizer (E) is 100 mass parts of said active energy ray-curable compounds (A) in the active energy ray-curable composition of the present invention.
- Each is preferably 0.05 to 20 parts by mass, more preferably 0.5 to 10% by mass.
- a polymerization inhibitor as a compound other than the above components (A) to (E), a polymerization inhibitor, a surface conditioner, and an antistatic agent can be used depending on applications and required properties. Addition of antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, UV absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, silica beads, organic beads, etc. Agents: Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.
- the film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of a film substrate, and then irradiating the active energy ray to form a cured coating film. is there.
- the material of the film base used in the film of the present invention is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polypropylene, polyethylene, polymethylpentene-1 Polyolefin resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate and other cellulose resins; poly Acrylic resins such as methyl methacrylate; polyvinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-acetic acid Nyl copolymer; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyimide resin
- the film substrate may be in the form of a film or a sheet, and the thickness is preferably in the range of 20 to 500 ⁇ m.
- the thickness is preferably in the range of 20 to 200 ⁇ m, more preferably in the range of 30 to 150 ⁇ m, and still more preferably in the range of 40 to 130 ⁇ m.
- Examples of the method for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and dip coating. , Spinner coating, brush coating, solid coating by silk screen, wire bar coating, flow coating and the like.
- the drying conditions are not particularly limited as long as the organic solvent (C) is volatilized. Usually, the drying is performed at a temperature of 50 to 100 ° C. and for a time of 0.5 to 10 minutes. It is preferable to do.
- the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- ultraviolet rays examples of devices that emit ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Examples thereof include a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, sunlight, and an LED lamp.
- the film thickness of the cured coating film when forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate is sufficient for the hardness of the cured coating film and curing of the coating film. Since the curling of the film due to shrinkage can be suppressed, the range of 1 to 30 ⁇ m is preferable, the range of 3 to 15 ⁇ m is more preferable, and the range of 4 to 10 ⁇ m is more preferable.
- the weight average molecular weight of the resin (B-1) obtained above was measured by the gel permeation chromatography (GPC) method under the following conditions.
- Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- Example 1 50 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as “DPHA”), urethane acrylate (reaction product of pentaerythritol tetraacrylate and isophorone diisocyanate, solid content 100 mass%, hereinafter abbreviated as “UA1”) 50 Parts by weight, 2.2 parts by weight of a 45% by weight solution of the resin (C-1) obtained in Production Example 1 (1 part by weight as the resin (C-1)), photopolymerization initiator (BASF Japan Ltd.
- DPHA dipentaerythritol hexaacrylate
- UUA1 urethane acrylate
- U1 solid content 100 mass%
- Irgacure 184 ; 1-hydroxycyclohexyl phenyl ketone, hereinafter abbreviated as” Irg184
- DMAC dimethylacetamide
- PGME 8.5 parts by mass of ethanol
- An energy ray curable composition (1) was obtained.
- Example 2 50 parts by mass of DPHA, 50 parts by mass of UA1, 6.6 parts by mass of a 45% by mass resin (C-1) solution obtained in Production Example 1 (3 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part by mass, 36 parts by mass of DMAC, 54 parts by mass of dimethyl carbonate (hereinafter abbreviated as “DMC”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol are mixed to obtain an activity.
- An energy ray-curable composition (2) was obtained.
- Example 3 50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45% by mass resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part, DMAC 10 parts by mass, methyl ethyl ketone (hereinafter abbreviated as “MEK”) 30 parts by mass and DMC 60 parts by mass were uniformly mixed to obtain an active energy ray-curable composition (3).
- MEK methyl ethyl ketone
- Example 4 70 parts by mass of DPHA, 30 parts by mass of “MIRAMER HR6042” (refractive index: 1.618, hereinafter abbreviated as “HR6042”) manufactured by MIWON, 45% by mass solution of the resin (C-1) obtained in Production Example 1 6.6 parts by mass (3 parts by mass as resin (C-1)), 5 parts by mass of Irg184, and 100 parts by mass of DMAC were uniformly mixed to obtain an active energy ray-curable composition (4).
- MIRAMER HR6042 reffractive index: 1.618, hereinafter abbreviated as “HR6042”
- Comparative Example 2 An active energy ray-curable composition (R2) was obtained in the same manner as in Comparative Example 1 except that MEK was changed to DMC.
- Comparative Example 3 Comparative Example, except that 100 parts by mass of MEK was changed to 90 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol.
- MIBK methyl isobutyl ketone
- R3 active energy ray-curable composition
- the active energy ray-curable composition was applied to a 60 ⁇ m-thick triacetylcellulose (TAC) film (manufactured by Fuji Film Co., Ltd.) with a bar coater so as to have a film thickness of 5 ⁇ m, and then at 60 ° C. for 1.5 minutes. After drying, irradiation was performed with an integrated light quantity of 3 kJ / m 2 using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) in an air atmosphere, and a TAC film having a cured coating film was obtained as an evaluation sample. .
- TAC triacetylcellulose
- Comparative Examples 1 to 3 were embodiments in which dimethylacetamide was used as the organic solvent (C), but all had poor water resistance. Further, in Comparative Example 3, the surface resistance value exceeded 10 13 and it was confirmed that the antistatic property was inferior.
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Abstract
The present invention provides an active energy ray curable composition characterized by comprising an active energy ray curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. Also provided are a cured product of the active energy ray curable composition and a film having a cured coating. The content of the dimethylacetamide is preferably in a range of 5 to 200 parts by mass relative to 100 parts by mass of the active energy ray curable compound (A). The present invention addresses the problem of providing an active energy ray curable composition which is not susceptible to whitening, gelation, and sedimentation and is therefore highly suited for continuous production due to the good water resistance of the coating liquid against moisture in the air and condensation and which is capable of forming a hard coat layer having excellent antistatic properties.
Description
本発明は、活性エネルギー線硬化性組成物、その硬化物、及びフィルムに関する。
The present invention relates to an active energy ray-curable composition, a cured product thereof, and a film.
液晶ディスプレイ（ＬＣＤ）、有機ＥＬディスプレイ（ＯＬＥＤ）、プラズマディスプレイ（ＰＤＰ）等のフラットパネルディスプレイ（ＦＰＤ）表面に用いられている反射防止（ＬＲ）フィルムは、フィルム基材上に屈折率差の大きい２つの層を形成した多層構成（基材／高屈率層／低屈率層）により実現している。これらの各層は、反射防止フィルムの製造過程での傷付き防止のため、高い耐擦傷性が要求されるとともに、フィルムの汚染防止やブロッキング防止のため、高い帯電防止性も要求される。また、反射防止フィルムは光学フィルムであるため、各層には高い透明性も要求される。
Antireflective (LR) films used on the surface of flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), plasma displays (PDPs), etc. have a large refractive index difference on the film substrate This is realized by a multilayer structure in which two layers are formed (base material / high refractive index layer / low refractive index layer). Each of these layers is required to have high scratch resistance in order to prevent scratches in the production process of the antireflection film, and also to have high antistatic properties in order to prevent contamination and blocking of the film. Moreover, since an antireflection film is an optical film, each layer is also required to have high transparency.
上記の要求される特性のうち、帯電防止性を付与する手法として、４級アンモニウム塩を有する樹脂を配合した材料を用いることが提案されている（例えば、特許文献１～３を参照。）。しかしながら、４級アンモニウム塩は、親水性が高く、疎水性である活性エネルギー線硬化性組成物とは相溶性が悪く、塗膜が白化し外観不良となる問題があった。
Among the above required properties, it has been proposed to use a material containing a resin having a quaternary ammonium salt as a method for imparting antistatic properties (see, for example, Patent Documents 1 to 3). However, the quaternary ammonium salt has high hydrophilicity and poor compatibility with the hydrophobic active energy ray-curable composition, and there is a problem that the coating film becomes white and the appearance is poor.
本発明が解決しようとする課題は、優れた帯電防止性を有し、かつ、水が混入しても白濁せず外観不良を起こさない優れた耐水性を有するハードコート層を形成できる活性エネルギー線硬化性組成物を提供することである。
The problem to be solved by the present invention is an active energy ray capable of forming a hard coat layer having excellent antistatic properties and having excellent water resistance that does not become cloudy even when water is mixed and does not cause poor appearance. It is to provide a curable composition.
本発明は、活性エネルギー線硬化性化合物（Ａ）と、脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ）と、ジメチルアセトアミドを含有する有機溶剤（Ｃ）とを含有することを特徴とする活性エネルギー線硬化性組成物を提供するものである。また、本発明は前記活性エネルギー線硬化性組成物の硬化物、及び、硬化塗膜を有するフィルムを提供するものである。
The present invention comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. An active energy ray-curable composition is provided. Moreover, this invention provides the cured | curing material of the said active energy ray curable composition, and the film which has a cured coating film.
本発明の活性エネルギー線硬化性組成物は、塗工時に水が混入しても白濁し難い耐水性を有する組成を提供することで連続生産性に優れ、且つ、硬化後、フィルム表面に優れた帯電防止性を有するハードコート層を形成することができる。
The active energy ray-curable composition of the present invention is excellent in continuous productivity by providing a composition having water resistance that is not easily clouded even when water is mixed during coating, and excellent in the film surface after curing. A hard coat layer having antistatic properties can be formed.
また、本発明の活性エネルギー線硬化性組成物の硬化塗膜からなるハードコート層を有するフィルムは、液晶ディスプレイ（ＬＣＤ）、有機ＥＬディスプレイ（ＯＬＥＤ）、プラズマディスプレイ（ＰＤＰ）等のフラットパネルディスプレイ（ＦＰＤ）に用いる光学フィルムとして好適に用いることができる。さらに、これらの用途に用いる際にも優れた帯電防止性があることから、埃等の付着を抑制できる。さらに、このフィルムを液晶ディスプレイ等に用いた場合、発生した静電気によるディスプレイの誤動作も防止できる。
Moreover, the film which has a hard-coat layer which consists of a cured coating film of the active energy ray curable composition of this invention is flat panel displays, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP) ( It can be suitably used as an optical film used for FPD). Furthermore, since it has excellent antistatic properties when used in these applications, adhesion of dust and the like can be suppressed. Furthermore, when this film is used for a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.
本発明の活性エネルギー線硬化性組成物は、活性エネルギー線硬化性化合物（Ａ）と、脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ）と、ジメチルアセトアミドを含有する有機溶剤（Ｃ）とを含有するものである。
The active energy ray-curable composition of the present invention comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. It contains.
前記活性エネルギー線硬化性化合物（Ａ）としては、例えば、多官能（メタ）アクリレート（Ａ１）、ウレタン（メタ）アクリレート（Ａ２）、屈折率が１．５５以上である高屈折率重合性単量体（Ａ３）、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート等が挙げられる。これらは、単独で用いても２種以上を併用してもよい。前記活性エネルギー線硬化性化合物（Ａ）としては、より一層優れた硬化塗膜の耐擦傷性、ハードコート性、耐水性、及び透明性が得られる点から、多官能（メタ）アクリレート（Ａ１）、ウレタン（メタ）アクリレート（Ａ２）、及び、屈折率が１．５５以上である高屈折率重合性単量体（Ａ３）からなる群より選ばれる１種以上を用いることが好ましく、多官能（メタ）アクリレート（Ａ１）とウレタン（メタ）アクリレート（Ａ２）との組合せ、又は、多官能（メタ）アクリレート（Ａ１）と高屈折率重合性単量体（Ａ３）との組合せがより好ましい。
Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1), urethane (meth) acrylate (A2), and a high refractive index polymerizable monomer having a refractive index of 1.55 or more. Examples thereof include body (A3), epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. These may be used alone or in combination of two or more. As the active energy ray curable compound (A), a polyfunctional (meth) acrylate (A1) is obtained from the viewpoint that a more excellent scratch resistance, hard coat property, water resistance, and transparency of a cured coating film can be obtained. It is preferable to use at least one selected from the group consisting of urethane (meth) acrylate (A2) and a high refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more. A combination of (meth) acrylate (A1) and urethane (meth) acrylate (A2) or a combination of polyfunctional (meth) acrylate (A1) and high refractive index polymerizable monomer (A3) is more preferable.
なお、本発明において、「（メタ）アクリレート」とは、アクリレートとメタクリレートの一方又は両方をいい、「（メタ）アクリロイル」とは、アクリロイルとメタクリロイルの一方又は両方をいう。
In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “(meth) acryloyl” refers to one or both of acryloyl and methacryloyl.
前記多官能（メタ）アクリレート（Ａ１）は、１分子中に２つ以上の（メタ）アクリロイル基を有する化合物である。この多官能（メタ）アクリレート（ａ１）の具体例としては、１，４－ブタンジオールジ（メタ）アクリレート、３－メチル－１，５－ペンタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、２－メチル－１，８－オクタンジオールジ（メタ）アクリレート、２－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等の２価アルコールのジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートのジ（メタ）アクリレート、ネオペンチルグリコール１モルに４モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、ビスフェノールＡ１モルに２モルのエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、トリス（２－（メタ）アクリロイルオキシエチル）イソシアヌレート、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、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）アクリレート等が挙げられる。これらの多官能（メタ）アクリレート（Ａ１）は、１種で用いることも２種以上併用することもできる。また、これらの多官能（メタ）アクリレート（Ａ１）の中でも、本発明の活性エネルギー線硬化性組成物の硬化塗膜の耐擦傷性が向上することから、ジペンタエリスリトールヘキサ（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、ペンタエリスリトールテトラ（メタ）アクリレート、及び、ペンタエリスリトールトリ（メタ）アクリレートからなる群より選ばれる１種以上の化合物を用いることが好ましく、ジペンタエリスリトールヘキサ（メタ）アクリレートがより好ましい。
The polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acryloyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, etc. Di (meth) acrylate of dihydric alcohol, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 moles per mole of neopentyl glycol Di (meth) acrylate of diol obtained by adding ethylene oxide or propylene oxide as described above, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane Tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditri Tyrolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These polyfunctional (meth) acrylates (A1) can be used alone or in combination of two or more. Among these polyfunctional (meth) acrylates (A1), since the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention is improved, dipentaerythritol hexa (meth) acrylate, di It is preferable to use at least one compound selected from the group consisting of pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Is more preferable.
前記ウレタン（メタ）アクリレート（Ａ２）は、ポリイソシアネート（ａ２－１）と水酸基を有する（メタ）アクリレート（ａ２－２）との反応物等を用いることができる。
As the urethane (meth) acrylate (A2), a reaction product of polyisocyanate (a2-1) and (meth) acrylate (a2-2) having a hydroxyl group can be used.
前記ポリイソシアネート（ａ２－１）としては、脂肪族ポリイソシアネートと芳香族ポリイソシアネートとが挙げられるが、本発明の活性エネルギー線硬化性組成物の硬化塗膜の着色を低減できることから、脂肪族ポリイソシアネートが好ましい。
Examples of the polyisocyanate (a2-1) include aliphatic polyisocyanates and aromatic polyisocyanates. Since the coloring of the cured coating film of the active energy ray-curable composition of the present invention can be reduced, Isocyanates are preferred.
前記脂肪族ポリイソシアネートは、イソシアネート基を除く部位が脂肪族炭化水素から構成される化合物である。この脂肪族ポリイソシアネートの具体例としては、ヘキサメチレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等の脂肪族ポリイソシアネート；ノルボルナンジイソシアネート、イソホロンジイソシアネート、メチレンビス（４－シクロヘキシルイソシアネート）、１，３－ビス（イソシアナトメチル）シクロヘキサン、２－メチル－１，３－ジイソシアナトシクロヘキサン、２－メチル－１，５－ジイソシアナトシクロヘキサン等の脂環式ポリイソシアネートなどが挙げられる。また、前記脂肪族ポリイソシアネート又は脂環式ポリイソシアネートを３量化した３量化物も前記脂肪族ポリイソシアネートとして用いることができる。また、これらの脂肪族ポリイソシアネートは、１種で用いることも２種以上併用することもできる。
The aliphatic polyisocyanate is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon. Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanato). And cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane. A trimerized product obtained by trimming the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate. Moreover, these aliphatic polyisocyanates can be used alone or in combination of two or more.
前記脂肪族ポリイソシアネートの中でも塗膜の耐擦傷性を向上させるには、ヘキサメチレンジイソシアネート、ノルボルナンジイソシアネート、及びイソホロンジイソシアネートからなる群より選ばれる１種以上を用いることが好ましく、イソホロンジイソシアネートがより好ましい。
Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, it is preferable to use one or more selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate, and more preferably isophorone diisocyanate.
前記（メタ）アクリレート（ａ２－２）は、水酸基と（メタ）アクリロイル基とを有する化合物である。この（メタ）アクリレート（ａ２－２）の具体例としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、１，５－ペンタンジオールモノ（メタ）アクリレート、１，６－ヘキサンジオールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールモノ（メタ）アクリレート等の２価アルコールのモノ（メタ）アクリレート；トリメチロールプロパンジ（メタ）アクリレート、エチレンオキサイド（ＥＯ）変性トリメチロールプロパン（メタ）アクリレート、プロピレンオキサイド（ＰＯ）変性トリメチロールプロパンジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ビス（２－（メタ）アクリロイルオキシエチル）ヒドロキシエチルイソシアヌレート等の３価のアルコールのモノ又はジ（メタ）アクリレート、あるいは、これらのアルコール性水酸基の一部をε－カプロラクトンで変性した水酸基を有するモノ及びジ（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、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の１官能の水酸基と３官能以上の（メタ）アクリロイル基を有する化合物、あるいは、該化合物をさらにε－カプロラクトンで変性した水酸基を有する多官能（メタ）アクリレート；ジプロピレングリコールモノ（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等のオキシアルキレン鎖を有する（メタ）アクリレート；ポリエチレングリコール－ポリプロピレングリコールモノ（メタ）アクリレート、ポリオキシブチレン－ポリオキシプロピレンモノ（メタ）アクリレート等のブロック構造のオキシアルキレン鎖を有する（メタ）アクリレート；ポリ（エチレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート等のランダム構造のオキシアルキレン鎖を有する（メタ）アクリレートなどが挙げられる。これらの（メタ）アクリレート（ａ２－２）は、１種で用いることも２種以上併用することもできる。
The (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryloyl group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Divalent compounds such as acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate Mono (meth) acrylate of alcohol; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meta) Mono- or di (meth) acrylate of trivalent alcohol such as acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups Mono- and di (meth) acrylates having hydroxyl groups modified with ε-caprolactone; monofunctional hydroxyl groups such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 3 A compound having a functional (meth) acryloyl group or a polyfunctional (meth) acrylate having a hydroxyl group in which the compound is further modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene group (Meth) acrylates having an oxyalkylene chain such as coal mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc .; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-poly (Meth) acrylate having an oxyalkylene chain having a block structure such as oxypropylene mono (meth) acrylate; poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) And (meth) acrylate having an oxyalkylene chain having a random structure such as acrylate. These (meth) acrylates (a2-2) can be used alone or in combination of two or more.
前記ウレタン（メタ）アクリレート（Ａ２）の中でも、本発明の活性エネルギー線硬化性組成物の硬化塗膜の耐擦傷性を向上できるため、１分子中に４つ以上の（メタ）アクリロイル基を有するものが好ましい。前記ウレタン（メタ）アクリレート（Ａ２）を１分子中に４つ以上の（メタ）アクリロイル基を有するものとするため、前記（メタ）アクリレート（ａ２－２）としては、（メタ）アクリロイル基は２つ以上有するものが好ましい。このような（メタ）アクリレート（ａ２－２）としては、例えば、トリメチロールプロパンジ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ビス（２－（メタ）アクリロイルオキシエチル）ヒドロキシエチルイソシアヌレート、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、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられる。これらの（メタ）アクリレート（ａ２－２）は、前記脂肪族ポリイソシアネートの１種に対して、１種を用いることも２種以上併用することもできる。また、これらの（メタ）アクリレート（ａ２－２）の中でも、耐擦傷性をより一層向上できるため、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、及びジペンタエリスリトールペンタ（メタ）アクリレートが好ましく、ペンタエリスリトールテトラ（メタ）アクリレートがより好ましい。
Among the urethane (meth) acrylate (A2), since it can improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention, it has four or more (meth) acryloyl groups in one molecule. Those are preferred. Since the urethane (meth) acrylate (A2) has four or more (meth) acryloyl groups in one molecule, the (meth) acrylate (a2-2) has 2 (meth) acryloyl groups. Those having at least two are preferred. Examples of such (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, Glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipenta Examples include erythritol penta (meth) acrylate. These (meth) acrylates (a2-2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates. Among these (meth) acrylates (a2-2), since scratch resistance can be further improved, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) Acrylates are preferred, and pentaerythritol tetra (meth) acrylate is more preferred.
前記ポリイソシアネート（ａ２－１）と前記（メタ）アクリレート（ａ２－２）との反応は、常法のウレタン化反応により行うことができる。また、ウレタン化反応の進行を促進するために、ウレタン化触媒の存在下でウレタン化反応を行うことが好ましい。前記ウレタン化触媒としては、例えば、ピリジン、ピロール、トリエチルアミン、ジエチルアミン、ジブチルアミン等のアミン化合物；トリフェニルホスフィン、トリエチルホスフィン等のリン化合物；ジブチル錫ジラウレート、オクチル錫トリラウレート、オクチル錫ジアセテート、ジブチル錫ジアセテート、オクチル酸錫等の有機錫化合物、オクチル酸亜鉛等の有機亜鉛化合物などが挙げられる。
The reaction of the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate | stimulate progress of a urethanation reaction, it is preferable to perform a urethanation reaction in presence of a urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
前記屈折率が１．５５以上である高屈折率重合性単量体（Ａ３）は、硬化前の屈折率が１．５５以上の高屈折率のものであればよく、例えば、芳香環を２～６個有する芳香族系重合性単量体、フルオレン系重合性単量体等が好ましく挙げられる。また、前記重合性単量体（Ａ）の具体例としては、下記一般式（１）で表される化合物；ｏ－フェニルベンジル（メタ）アクリレート、ｐ－フェニルベンジル（メタ）アクリレート等のフェニルベンジル基を有する（メタ）アクリレート化合物；フェニルフェノールＥＯアクリレート等のフェニルフェノール基を有する（メタ）アクリレート化合物；プロポキシ化ビスフェノールＡジ（メタ）アクリレート、エトキシ化ビスフェノールＡジ（メタ）アクリレート、オキシエチレン基を有するビスフェノールＡジ（メタ）アクリレート、オキシエチレン基を有するビスフェノールＡトリ（メタ）アクリレート等の（メタ）アクリロイル基を２～４個の範囲で有するビスフェノール化合物などが挙げられる。これらの重合性単量体（Ａ）は、１種で用いることも２種以上併用することもできる。これらの中でも、後述する特定の有機溶剤を使用しても屈折率を制御しやすく高い屈折率を得ることができる点から、下記一般式（１）で表される化合物、フェニルベンジル基を有する（メタ）アクリレート化合物、及び、（メタ）アクリロイル基を２～４個の範囲で有するビスフェノール化合物からなる群より選ばれる１種以上の単量体を用いることが好ましい。前記重合性単量体（Ａ３）として用いることのできる市販品としては、大阪ガスケミカル株式会社製の「ＯＧＳＯＬ ＥＡ－０２００」、「ＯＧＳＯＬ ＥＡ－０３００」、「ＯＧＳＯＬ ＧＡ－５０６０Ｐ」；ＤＩＣ株式会社製の「ＵＮＩＤＩＣ ＥＫＺ－９４８」、「ＵＮＩＤＩＣ ＥＱＳ－１１７９」；新中村化学工業株式会社製の「Ａ－ＢＰＥＦ」、ＭＩＷＯＮ社製「ＭＩＲＡＭＥＲ ＨＲ６０４２」等が挙げられる。これらの重合性単量体（Ａ）は、１種で用いることも２種以上併用することもできる。
The high-refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more is sufficient if it has a high refractive index of 1.55 or more before curing. Preferable examples include 6 to 6 aromatic polymerizable monomers and fluorene polymerizable monomers. Specific examples of the polymerizable monomer (A) include compounds represented by the following general formula (1): phenylbenzyl such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having a group; (meth) acrylate compound having a phenylphenol group such as phenylphenol EO acrylate; propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, oxyethylene group Examples thereof include bisphenol compounds having 2 to 4 (meth) acryloyl groups such as bisphenol A di (meth) acrylate having an oxyethylene group and bisphenol A tri (meth) acrylate having an oxyethylene group. These polymerizable monomers (A) can be used alone or in combination of two or more. Among these, a compound represented by the following general formula (1), which has a phenylbenzyl group, can be obtained because a high refractive index can be easily controlled even when a specific organic solvent described later is used ( It is preferable to use one or more monomers selected from the group consisting of a meth) acrylate compound and a bisphenol compound having 2 to 4 (meth) acryloyl groups. Commercially available products that can be used as the polymerizable monomer (A3) include “OGSOL EA-0200”, “OGSOL EA-0300”, “OGSOL GA-5060P” manufactured by Osaka Gas Chemical Co., Ltd .; DIC Corporation “UNIDIC EKZ-948”, “UNIDIC EQS-1179” manufactured by Shin-Nakamura Chemical Co., Ltd., “MIRAMER HR6042” manufactured by MIWON, etc. These polymerizable monomers (A) can be used alone or in combination of two or more.
前記樹脂（Ｂ）は、脂環構造及び４級アンモニウム塩を有するものである。
The resin (B) has an alicyclic structure and a quaternary ammonium salt.
前記樹脂（Ｂ）の製造方法としては、例えば、脂環構造を有する重合性単量体（ｂ１）及び４級アンモニウム塩を有する重合性単量体（ｂ２）を必須成分として、前記重合性単量体（ｂ１）及び前記重合性単量体（ｂ２）と、共重合可能な重合性単量体（ｂ３）とを共重合する方法が挙げられる。
Examples of the method for producing the resin (B) include the polymerizable monomer (b1) having an alicyclic structure and the polymerizable monomer (b2) having a quaternary ammonium salt as essential components. Examples thereof include a method of copolymerizing the monomer (b1) and the polymerizable monomer (b2) with a copolymerizable polymerizable monomer (b3).
前記重合性単量体（ｂ１）は、脂環構造を有する重合性単量体である。前記脂環構造としては、例えば、シクロプロパン環、シクロブタン環、シクロペンタン環、シクロヘキサン環、シクロヘプタン環、シクロオクタン環、シクロノナン環、シクロデカン環等の単環脂環構造；ビシクロウンデカン環、デカヒドロナフタレン（デカリン）環、トリシクロ［５．２．１．０２，６］デカン環、ビシクロ［４．３．０］ノナン環、トリシクロ［５．３．１．１］ドデカン環、トリシクロ［５．３．１．１］ドデカン環、スピロ［３．４］オクタン環等の多環脂環構造などが挙げられる。また、前記重合性単量体（ｃ１）の具体例としては、シクロヘキシル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられる。これらの重合性単量体（ｂ１）は、１種で用いることも２種以上併用することもできる。
The polymerizable monomer (b1) is a polymerizable monomer having an alicyclic structure. Examples of the alicyclic structure include a monocyclic alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring; a bicycloundecane ring, a decahydro ring Naphthalene (decalin) ring, tricyclo [5.2.1.0 2,6 ] decane ring, bicyclo [4.3.0] nonane ring, tricyclo [5.3.1.1] dodecane ring, tricyclo [5. 3.1.1] Polycyclic alicyclic structures such as dodecane ring and spiro [3.4] octane ring. Specific examples of the polymerizable monomer (c1) include cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples include dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate. These polymerizable monomers (b1) can be used alone or in combination of two or more.
前記重合性単量体（ｂ２）としては、例えば、２－［（メタ）アクリロイルオキシ］エチルトリメチルアンモニウムクロライド、３－［（メタ）アクリロイルオキシ］プロピルトリメチルアンモニウムクロライド等のカウンターアニオンがクロライドのもの；２－［（メタ）アクリロイルオキシ］エチルトリメチルアンモニウムブロマイド、３－［（メタ）アクリロイルオキシ］プロピルトリメチルアンモニウムブロマイド等のカウンターアニオンがブロマイドのもの；２－［（メタ）アクリロイルオキシ］エチルトリメチルアンモニウムメチルフェニルスルホネート、２－［（メタ）アクリロイルオキシ］エチルトリメチルアンモニウムメチルスルホネート、３－［（メタ）アクリロイルオキシ］プロピルトリメチルアンモニウムメチルフェニルスルホネート、３－［（メタ）アクリロイルオキシ］プロピルトリメチルアンモニウムメチルスルホネート、２－［（メタ）アクリロイルオキシ］エチルトリメチルアンモニウムメチルスルフェート、３－［（メタ）アクリロイルオキシ］プロピルトリメチルアンモニウムメチルスルフェート等のカウンターアニオンが非ハロゲン系のものなどが挙げられる。これらの重合性単量体（ｂ２）は、１種で用いることも２種以上併用することもできる。
Examples of the polymerizable monomer (b2) include those in which the counter anion such as 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride and 3-[(meth) acryloyloxy] propyltrimethylammonium chloride is chloride; Counter anions such as 2-[(meth) acryloyloxy] ethyltrimethylammonium bromide, 3-[(meth) acryloyloxy] propyltrimethylammonium bromide and the like, wherein 2-[(meth) acryloyloxy] ethyltrimethylammonium methylphenyl Sulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammonium methylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylammonium methyl Phenylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylammonium methylsulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammonium methylsulfate, 3-[(meth) acryloyloxy] propyltrimethylammonium methylsulfate, etc. These counter anions are non-halogen type. These polymerizable monomers (b2) can be used alone or in combination of two or more.
前記重合性単量体（ｂ３）としては、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、イソブチル（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、ｎ－ヘプチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート等のアルキル（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、オクトキシポリエチレングリコール・ポリプロピレングリコールモノ（メタ）アクリレート、ラウロキシポリエチレングリコールモノ（メタ）アクリレート、ステアロキシポリエチレングリコールモノ（メタ）アクリレート、フェノキシポリエチレングリコールモノ（メタ）アクリレート、フェノキシポリエチレングリコール・ポリプロピレングリコールモノ（メタ）アクリレート、ノニルフェノキシポリプロピレングリコールモノ（メタ）アクリレート、ノニルフェノキシポリ（エチレングリコール・プロピレングリコール）モノ（メタ）アクリレート等のポリアルキレングリコールのモノ（メタ）アクリレート；２－パーフルオロヘキシルエチル（メタ）アクリレート等のフッ素化アルキル基を有する（メタ）アクリレートなどが挙げられる。これらの重合性単量体（ｂ３）は、１種で用いることも２種以上併用することもできる。
Examples of the polymerizable monomer (b3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n- Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Alkyl (meth) acrylates such as dodecyl (meth) acrylate; methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethyleneglycol / polypropyleneglycol mono (meth) acrylate, lauroxypolyethyleneglycol (Meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol / polypropylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol mono (meth) acrylate, nonylphenoxy poly ( Examples thereof include mono (meth) acrylates of polyalkylene glycols such as ethylene glycol / propylene glycol) mono (meth) acrylate; (meth) acrylates having a fluorinated alkyl group such as 2-perfluorohexylethyl (meth) acrylate. These polymerizable monomers (b3) can be used alone or in combination of two or more.
前記重合性単量体（ｂ３）の中でも、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できることから、ポリアルキレングリコールのモノ（メタ）アクリレートが好ましく、メトキシポリエチレングリコールモノ（メタ）アクリレートがより好ましい。また、フッ素化アルキル基を有する（メタ）アクリレートも本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できる効果があることから好ましい。
Among the polymerizable monomers (b3), since the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, mono (meth) acrylate of polyalkylene glycol is preferable, and methoxypolyethylene Glycol mono (meth) acrylate is more preferred. Moreover, the (meth) acrylate which has a fluorinated alkyl group is also preferable from the effect that the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
前記ポリアルキレングリコールのモノ（メタ）アクリレートの中でも、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をさらに向上できることから、前記ポリアルキレングリコールのモノ（メタ）アクリレートの原料となるポリアルキレングリコールの数平均分子量が２００～８，０００の範囲のものが好ましく、３００～６，０００の範囲のものがより好ましく、４００～４，０００の範囲のものがさらに好ましく、４００～２，０００の範囲のものが特に好ましい。
Among the poly (alkylene glycol) mono (meth) acrylates, since the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, The number average molecular weight of the polyalkylene glycol is preferably in the range of 200 to 8,000, more preferably in the range of 300 to 6,000, still more preferably in the range of 400 to 4,000, and 400 to 2 Those in the range of 1,000 are particularly preferred.
前記樹脂（Ｂ）の原料全量中の前記重合性単量体（ｂ１）の比率は、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できることから、５～４０質量％の範囲が好ましく、１０～５０質量％の範囲がより好ましく、１２～４５質量％の範囲がさらに好ましい。
The ratio of the polymerizable monomer (b1) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention. The range of mass% is preferable, the range of 10 to 50 mass% is more preferable, and the range of 12 to 45 mass% is more preferable.
また、前記樹脂（Ｂ）の原料全量中の前記重合性単量体（ｂ２）の比率は、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できることから、３０～９０質量％の範囲が好ましく、４０～８０質量％の範囲がより好ましく、４５～７０質量％の範囲がより好ましい。
Further, the ratio of the polymerizable monomer (b2) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention. The range of ˜90% by mass is preferred, the range of 40˜80% by mass is more preferred, and the range of 45˜70% by mass is more preferred.
さらに、前記重合性単量体（ｂ３）として前記ポリアルキレングリコールのモノ（メタ）アクリレートを用いる場合は、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できることから、前記樹脂（Ｂ）の原料全量中のポリアルキレングリコールのモノ（メタ）アクリレートの比率は、５～６０質量％の範囲が好ましく、１０～５０質量％の範囲がより好ましく、２０～４０質量％の範囲がさらに好ましい。
Furthermore, when the poly (alkylene glycol) mono (meth) acrylate is used as the polymerizable monomer (b3), the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved. The ratio of the poly (alkylene glycol) mono (meth) acrylate in the total amount of the raw material of the resin (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and 20 to 40% by mass. The range of is more preferable.
また、前記重合性単量体（ｂ３）として前記フッ素化アルキル基を有する（メタ）アクリレートを用いる場合は、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できることから、前記樹脂（Ｂ）の原料全量中のフッ素化アルキル基を有する（メタ）アクリレートの比率は、０．１～２０質量％の範囲が好ましく、０．５～１０質量％の範囲がより好ましく、１～５質量％の範囲がさらに好ましい。
When the (meth) acrylate having the fluorinated alkyl group is used as the polymerizable monomer (b3), the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved. From the above, the ratio of the (meth) acrylate having a fluorinated alkyl group in the total amount of the raw material of the resin (B) is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass. The range of 1 to 5% by mass is more preferable.
前記樹脂（Ｂ）の重量平均分子量は、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できることから、１，０００～１００，０００の範囲が好ましく、２，０００～５０，０００の範囲がより好ましく、３，０００～３０，０００の範囲がさらに好ましい。なお、本発明における重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定したポリスチレン換算での値である。
The weight average molecular weight of the resin (B) is preferably in the range of 1,000 to 100,000 because the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved. The range of ˜50,000 is more preferred, and the range of 3,000˜30,000 is more preferred. In addition, the weight average molecular weight in this invention is the value in polystyrene conversion measured by the gel permeation chromatography (GPC) method.
前記樹脂（Ｂ）の配合量は、本発明の活性エネルギー線硬化性組成物の硬化塗膜の帯電防止性をより向上できることから、前記活性エネルギー線硬化性化合物（Ａ）１００質量部に対して、０．１～３０質量部の範囲が好ましく、０．３～２０質量部の範囲がより好ましく、０．５～１０質量部の範囲がさらに好ましく、０．７～７質量部の範囲が特に好ましい。
Since the compounding amount of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, it is based on 100 parts by mass of the active energy ray-curable compound (A). The range of 0.1 to 30 parts by mass is preferable, the range of 0.3 to 20 parts by mass is more preferable, the range of 0.5 to 10 parts by mass is more preferable, and the range of 0.7 to 7 parts by mass is particularly preferable. preferable.
前記有機溶剤（Ｃ）としては、優れた耐水性を得る上で、ジメチルアセトアミドを含有することが必須である。ジメチルアセトアミドは、前記樹脂（Ｂ）との相性が良く、沸点も比較的高いことから水が混入しても完全混合するうえ、高分子溶解性も高いため、親水性・疎水性両成分が混在している場合でも乾燥工程にて蒸発するため、白化等の問題を抑制でき、優れた耐水性を得ることができる。
The organic solvent (C) must contain dimethylacetamide in order to obtain excellent water resistance. Dimethylacetamide has good compatibility with the resin (B) and has a relatively high boiling point. Therefore, even if water is mixed in, dimethylacetamide is completely mixed and has high polymer solubility, so both hydrophilic and hydrophobic components are mixed. Even in the case of evaporation, since it evaporates in the drying step, problems such as whitening can be suppressed, and excellent water resistance can be obtained.
前記ジメチルアセトアミドの含有量としては、より一層優れた耐水性が得られる点から、前記活性エネルギー線硬化性化合物（Ａ）１００質量部に対して、５～２００質量部の範囲であることが好ましく、７～１５０質量部の範囲がより好ましい。
The content of the dimethylacetamide is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A) from the standpoint that even better water resistance is obtained. The range of 7 to 150 parts by mass is more preferable.
また、前記ジメチルアセトアミドの含有量としては、より一層優れた耐水性が得られる点から、有機溶剤（Ｃ）中３質量％以上であることが好ましく、５質量％以上がより好ましく、７質量％以上９９質量％以下が更に好ましい。
Further, the content of the dimethylacetamide is preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 7% by mass in the organic solvent (C) from the viewpoint of obtaining further excellent water resistance. More preferred is 99% by mass or less.
前記有機溶剤（Ｃ）としては、前記ジメチルアセトアミド以外にも、例えば、疎水性溶剤、前記ジメチルアセトアミド以外の親水性溶剤を用いることができる。
As the organic solvent (C), in addition to the dimethylacetamide, for example, a hydrophobic solvent and a hydrophilic solvent other than the dimethylacetamide can be used.
前記疎水性溶剤としては、例えば、ジエチルエーテル、ベンゼン、トルエン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、キシレン、ｎ－ブタノール、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、クロロホルム、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。これらの溶剤は単独で用いても２種以上を併用してもよい。前記疎水性溶剤としては、活性エネルギー線硬化性組成物の塗工安定性がより一層向上し、硬化塗膜にヒビが入るのを防止でき、より一層優れた塗膜外観を得ることができる点から、ジメチルカーボネート、メチルエチルケトン、及び、メチルイソブチルケトンからなる群より選ばれる１種以上を用いることが好ましく、ジメチルカーボネート、及び／又は、メチルエチルケトンがより好ましい。
Examples of the hydrophobic solvent include diethyl ether, benzene, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, xylene, n-butanol, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, chloroform, propylene glycol. Examples thereof include monomethyl ether acetate. These solvents may be used alone or in combination of two or more. As the hydrophobic solvent, the coating stability of the active energy ray-curable composition is further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained. Therefore, it is preferable to use one or more selected from the group consisting of dimethyl carbonate, methyl ethyl ketone, and methyl isobutyl ketone, and dimethyl carbonate and / or methyl ethyl ketone is more preferable.
前記親水性溶剤としては、例えば、アセトン、メタノール、エタノール、ｎ－プロパノール、イソプロピルアルコール、ダイアセトンアルコール、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ジオキソラン、テトラヒドロフラン、テトラヒドロピラン、ジメチルホルムアミド等が挙げられる。これらの溶剤は単独で用いても２種以上を併用してもよい。前記親水性溶剤としては、活性エネルギー線硬化性組成物の塗工安定性がより一層向上し、硬化塗膜にヒビが入るのを防止でき、より一層優れた塗膜外観を得ることができる点から、メタノール、エタノール、ｎ－プロパノール、及び、プロピレングリコールモノメチルエーテルからなる群より選ばれる１種以上を用いることが好ましく、メタノールとプロピレングリコールモノメチルエーテルとの併用、又は、メタノール、エタノール、ｎ－プロパノール、及び、プロピレングリコールモノメチルエーテルとを組合せ用いることがより好ましい。
Examples of the hydrophilic solvent include acetone, methanol, ethanol, n-propanol, isopropyl alcohol, diacetone alcohol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dioxolane, tetrahydrofuran, tetrahydropyran, dimethylformamide, and the like. . These solvents may be used alone or in combination of two or more. As the hydrophilic solvent, the coating stability of the active energy ray-curable composition is further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained. It is preferable to use at least one selected from the group consisting of methanol, ethanol, n-propanol, and propylene glycol monomethyl ether, or a combination of methanol and propylene glycol monomethyl ether, or methanol, ethanol, n-propanol More preferably, propylene glycol monomethyl ether is used in combination.
なお、本発明において、前記親水性溶剤とは、水への溶解度が１０ｇ／１００ｍｌ以上である溶剤を示し、これと前記ジメチルアセトアミド以外のものが疎水性溶剤となる。なお、有機溶剤の水への溶解度は、１００ｍｌの水（２５℃）への溶解度を占めす。
In the present invention, the hydrophilic solvent refers to a solvent having a solubility in water of 10 g / 100 ml or more, and a solvent other than the dimethylacetamide is a hydrophobic solvent. The solubility of the organic solvent in water accounts for the solubility in 100 ml of water (25 ° C.).
前記有機溶剤（Ｃ）としては、活性エネルギー線硬化性組成物の塗工安定性がより一層向上し、硬化塗膜にヒビが入るのを防止でき、より一層優れた塗膜外観を得ることができる点から、ジメチルアセトアミドとそれ以外の親水性溶剤との併用、又は、ジメチルアセトアミドとそれ以外の親水性溶剤と疎水性溶剤とを組合せ用いることが好ましい。
As the organic solvent (C), the coating stability of the active energy ray-curable composition can be further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained. From the standpoint, it is preferable to use dimethylacetamide in combination with other hydrophilic solvents, or in combination with dimethylacetamide, other hydrophilic solvents and hydrophobic solvents.
前記有機溶剤（Ｃ）として、ジメチルアセトアミドとそれ以外の親水性溶剤とを併用する場合の前記親水性溶剤の使用量としては、前記活性エネルギー線硬化性化合物（Ａ）１００質量部に対して、０．１～５０質量部の範囲であることが好ましく、１～３０質量部の範囲がより好ましい。
As the organic solvent (C), the amount of the hydrophilic solvent used in combination with dimethylacetamide and the other hydrophilic solvent is 100 parts by mass of the active energy ray-curable compound (A). The range is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass.
前記有機溶剤（Ｃ）として、ジメチルアセトアミドとそれ以外の親水性溶剤と疎水性溶剤とを組合せを用いる場合には、前記親水性溶剤の使用量としては、前記活性エネルギー線硬化性化合物（Ａ）１００質量部に対して、０．１～４０質量部の範囲が好ましく、３～２５質量部の範囲がより好ましく、前記疎水性溶剤の使用量としては、前記活性エネルギー線硬化性化合物（Ａ）１００質量部に対して、１０～９５質量部の範囲が好ましく、３０～９３質量部の範囲がより好ましい。
When a combination of dimethylacetamide, other hydrophilic solvent and hydrophobic solvent is used as the organic solvent (C), the amount of the hydrophilic solvent used is the active energy ray-curable compound (A). The range of 0.1 to 40 parts by mass with respect to 100 parts by mass is preferable, and the range of 3 to 25 parts by mass is more preferable. The amount of the hydrophobic solvent used is the active energy ray-curable compound (A). The range of 10 to 95 parts by mass is preferable with respect to 100 parts by mass, and the range of 30 to 93 parts by mass is more preferable.
本発明の活性エネルギー線硬化性組成物中の前記有機溶剤（Ｃ）の配合量は、後述する塗工方法に適した粘度になる量とすることが好ましい。
The blending amount of the organic solvent (C) in the active energy ray-curable composition of the present invention is preferably an amount that provides a viscosity suitable for a coating method described later.
また、本発明の活性エネルギー線硬化性組成物は、基材に塗工後、活性エネルギー線を照射することで硬化塗膜とすることができる。この活性エネルギー線とは、紫外線、電子線、α線、β線、γ線等の電離放射線をいう。活性エネルギー線として紫外線を照射して硬化塗膜とする場合には、本発明の活性エネルギー線硬化性組成物中に光重合開始剤（Ｄ）を添加し、硬化性を向上することが好ましい。また、必要であればさらに光増感剤（Ｅ）を添加して、硬化性を向上することもできる。一方、電子線、α線、β線、γ線等の電離放射線を用いる場合には、光重合開始剤（Ｄ）や光増感剤（Ｅ）を用いなくても速やかに硬化するので、特に光重合開始剤（Ｄ）や光増感剤（Ｅ）を添加する必要はない。
Moreover, the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after coating on a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve curability. Further, if necessary, a photosensitizer (E) can be further added to improve curability. On the other hand, in the case of using ionizing radiation such as electron beam, α ray, β ray, γ ray, etc., since it cures quickly without using a photopolymerization initiator (D) or photosensitizer (E), It is not necessary to add a photopolymerization initiator (D) or a photosensitizer (E).
前記光重合開始剤（Ｄ）としては、例えば、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、オリゴ｛２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン｝、ベンジルジメチルケタール、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－２－モルホリノ（４－チオメチルフェニル）プロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン等のアセトフェノン系化合物；ベンゾイン、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等のベンゾイン系化合物；２，４，６－トリメチルベンゾイン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のアシルホスフィンオキシド系化合物；ベンジル（ジベンゾイル）、メチルフェニルグリオキシエステル、オキシフェニル酢酸２－（２－ヒドロキシエトキシ）エチルエステル、オキシフェニル酢酸２－（２－オキソ－２－フェニルアセトキシエトキシ）エチルエステル等のベンジル系化合物；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル－４－フェニルベンゾフェノン、４，４’－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチル－ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－メチルベンゾフェノン等のベンゾフェノン系化合物；２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン等のチオキサントン系化合物；ミヒラ－ケトン、４，４’－ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系化合物；１０－ブチル－２－クロロアクリドン、２－エチルアンスラキノン、９，１０－フェナンスレンキノン、カンファーキノン、１－［４－（４－ベンゾイルフェニルサルファニル）フェニル］－２－メチル－２－（４－メチルフェニルサルフォニル）プロパン－１－オン等が挙げられる。これらの光重合開始剤（Ｄ）は、１種で用いることも、２種以上併用することもできる。
Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone}, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzo Benzoin compounds such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl (dibenzoyl), methyl Benzyl compounds such as phenylglyoxyester, oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester; benzophenone, o-benzoylbenzoic acid Methyl-4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ′ Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone; 2-isopropylthioxanthone Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; aminobenzophenone compounds such as Michler's ketone and 4,4′-diethylaminobenzophenone; 10-butyl-2 -Chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenyl) Sulphonyl ) Propan-1-one and the like. These photopolymerization initiators (D) can be used alone or in combination of two or more.
また、前記光増感剤（Ｅ）としては、例えば、ジエタノールアミン、Ｎ－メチルジエタノールアミン、トリブチルアミン等の３級アミン化合物、ｏ－トリルチオ尿素等の尿素化合物、ナトリウムジエチルジチオホスフェート、ｓ－ベンジルイソチウロニウム－ｐ－トルエンスルホネート等の硫黄化合物などが挙げられる。
Examples of the photosensitizer (E) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuro And sulfur compounds such as nitro-p-toluenesulfonate.
上記の光重合開始剤（Ｄ）及び光増感剤（Ｅ）の使用量は、本発明の活性エネルギー線硬化性組成物中の前記活性エネルギー線硬化性化合物（Ａ）１００質量部に対し、各々０．０５～２０質量部が好ましく、０．５～１０質量％がより好ましい。
The usage-amount of said photoinitiator (D) and photosensitizer (E) is 100 mass parts of said active energy ray-curable compounds (A) in the active energy ray-curable composition of the present invention. Each is preferably 0.05 to 20 parts by mass, more preferably 0.5 to 10% by mass.
本発明の活性エネルギー線硬化性組成物には、上記の成分（Ａ）～（Ｅ）以外のその他の配合物として、用途、要求特性に応じて、重合禁止剤、表面調整剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、レベリング剤、有機顔料、無機顔料、顔料分散剤、シリカビーズ、有機ビーズ等の添加剤；酸化ケイ素、酸化アルミニウム、酸化チタン、ジルコニア、五酸化アンチモン等の無機充填剤などを配合することができる。これらその他の配合物は、１種で用いることも２種以上併用することもできる。
In the active energy ray-curable composition of the present invention, as a compound other than the above components (A) to (E), a polymerization inhibitor, a surface conditioner, and an antistatic agent can be used depending on applications and required properties. Addition of antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, UV absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, silica beads, organic beads, etc. Agents: Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.
本発明のフィルムは、フィルム基材の少なくとも１面に、本発明の活性エネルギー線硬化性組成物を塗工し、その後活性エネルギー線を照射して硬化塗膜とすることで得られたものである。
The film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of a film substrate, and then irradiating the active energy ray to form a cured coating film. is there.
本発明のフィルムで用いる前記フィルム基材の材質としては、透明性の高い樹脂が好ましく、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂；ポリプロピレン、ポリエチレン、ポリメチルペンテン－１等のポリオレフィン系樹脂；セルロースアセテート（ジアセチルセルロース、トリアセチルセルロース等）、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルロースアセテートプロピオネートブチレート、セルロースアセテートフタレート、硝酸セルロース等のセルロース系樹脂；ポリメチルメタクリレート等のアクリル系樹脂；ポリ塩化ビニル、ポリ塩化ビニリデン等の塩化ビニル系樹脂；ポリビニルアルコール；エチレン－酢酸ビニル共重合体；ポリスチレン；ポリアミド；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルエーテルケトン；ポリイミド、ポリエーテルイミド等のポリイミド系樹脂；ノルボルネン系樹脂（例えば、日本ゼオン株式会社製「ゼオノア」）、変性ノルボルネン系樹脂（例えば、ＪＳＲ株式会社製「アートン」）、環状オレフィン共重合体（例えば、三井化学株式会社製「アペル」）などが挙げられる。さらに、これらの樹脂からなる基材を２種以上貼り合わせたものを用いても構わない。
The material of the film base used in the film of the present invention is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polypropylene, polyethylene, polymethylpentene-1 Polyolefin resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate and other cellulose resins; poly Acrylic resins such as methyl methacrylate; polyvinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-acetic acid Nyl copolymer; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyimide resin such as polyimide and polyetherimide; norbornene resin (for example, “ZEONOR” manufactured by ZEON Corporation), modified Examples include norbornene resins (for example, “Arton” manufactured by JSR Corporation), cyclic olefin copolymers (for example, “Appel” manufactured by Mitsui Chemicals, Inc.), and the like. Furthermore, you may use what bonded together 2 or more types of base materials which consist of these resin.
また、前記フィルム基材は、フィルム状でもシート状でもよく、その厚さは、２０～５００μｍの範囲が好ましい。また、フィルム状の基材フィルムを用いる場合には、その厚さは、２０～２００μｍの範囲が好ましく、３０～１５０μｍの範囲がより好ましく、４０～１３０μｍの範囲がさらに好ましい。フィルム基材の厚さを当該範囲とすることで、フィルムの片面に、本発明の活性エネルギー線硬化性組成物によりハードコート層を設けた場合にもカールを抑制しやすくなる。
The film substrate may be in the form of a film or a sheet, and the thickness is preferably in the range of 20 to 500 μm. When a film-like base film is used, the thickness is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, and still more preferably in the range of 40 to 130 μm. By setting the thickness of the film base in the above range, curling can be easily suppressed even when a hard coat layer is provided on one side of the film with the active energy ray-curable composition of the present invention.
前記フィルム基材に本発明の活性エネルギー線硬化性組成物を塗工する方法としては、例えば、ダイコート、マイクログラビアコート、グラビアコート、ロールコート、コンマコート、エアナイフコート、キスコート、スプレーコート、ディップコート、スピンナーコート、刷毛塗り、シルクスクリーンによるベタコート、ワイヤーバーコート、フローコート等が挙げられる。
Examples of the method for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and dip coating. , Spinner coating, brush coating, solid coating by silk screen, wire bar coating, flow coating and the like.
また、本発明の活性エネルギー線硬化性組成物を前記基材フィルムへ塗工した後、活性エネルギー線を照射する前に、有機溶媒（Ｃ）を揮発させることが好ましい。加熱乾燥の条件としては、有機溶剤（Ｃ）が揮発する条件であれば、特に限定しないが、通常は、温度５０～１００℃の範囲で、時間は０．５～１０分の範囲で加熱乾燥することが好ましい。
In addition, it is preferable to volatilize the organic solvent (C) after applying the active energy ray-curable composition of the present invention to the substrate film and before irradiating the active energy ray. The drying conditions are not particularly limited as long as the organic solvent (C) is volatilized. Usually, the drying is performed at a temperature of 50 to 100 ° C. and for a time of 0.5 to 10 minutes. It is preferable to do.
本発明の活性エネルギー線硬化性組成物を硬化させる活性エネルギー線としては、上記の通り、紫外線、電子線、α線、β線、γ線等の電離放射線である。ここで、活性エネルギー線として紫外線を用いる場合、その紫外線を照射する装置としては、例えば、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、無電極ランプ（フュージョンランプ）、ケミカルランプ、ブラックライトランプ、水銀－キセノンランプ、ショートアーク灯、ヘリウム・カドミニウムレーザー、アルゴンレーザー、太陽光、ＬＥＤランプ等が挙げられる。
As described above, the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Here, when ultraviolet rays are used as the active energy rays, examples of devices that emit ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Examples thereof include a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, sunlight, and an LED lamp.
前記フィルム基材上に本発明の活性エネルギー線硬化性組成物の硬化塗膜を形成する際の硬化塗膜の膜厚は、硬化塗膜の硬さを充分なものとし、かつ塗膜の硬化収縮によるフィルムのカールを抑制できることから、１～３０μｍの範囲が好ましいが、３～１５μｍの範囲がより好ましく、４～１０μｍの範囲がさらに好ましい。
The film thickness of the cured coating film when forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate is sufficient for the hardness of the cured coating film and curing of the coating film. Since the curling of the film due to shrinkage can be suppressed, the range of 1 to 30 μm is preferable, the range of 3 to 15 μm is more preferable, and the range of 4 to 10 μm is more preferable.
以下に実施例により本発明をより具体的に説明する。
Hereinafter, the present invention will be described more specifically with reference to examples.
（製造例１：脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ－１）の製造）
攪拌装置、還流冷却管及び窒素導入管を備えたフラスコ中に、窒素ガスを導入して、フラスコ内の空気を窒素ガスで置換した。その後、フラスコに２－（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ライド５４．７質量部、シクロヘキシルメタクリレート１９．９質量部、メトキシポリエチレングリコールメタクリレート（日油株式会社製「ブレンマー ＰＭＥ－１０００」；繰り返し単位数ｎ≒２３、分子量１，０００）２４．９質量部、メタクリル酸０．５質量部、メタノール５０質量部及びＰＧＭＥ１０質量部を加えた。次いで、重合開始剤（アゾビスイソブチロニトリル）０．１質量部をプロピレングリコールモノメチルエーテル（以下「ＰＧＭＥ」と略記する。）２．４質量部で溶解した溶液を３０分かけて滴下した後、６５℃で３時間反応させた。次いで、メタノールを加えて希釈し、脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ－１）の４５質量％溶液を得た。得られた樹脂（Ｂ－１）の重量平均分子量は１万であった。 (Production Example 1: Production of resin (B-1) having alicyclic structure and quaternary ammonium salt)
Nitrogen gas was introduced into a flask equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, and the air in the flask was replaced with nitrogen gas. Thereafter, 54.7 parts by weight of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 19.9 parts by weight of cyclohexyl methacrylate, methoxypolyethylene glycol methacrylate (“Blemmer PME-1000” manufactured by NOF Corporation); 23, molecular weight 1,000) 24.9 parts by mass, methacrylic acid 0.5 parts by mass, methanol 50 parts by mass and PGME 10 parts by mass were added. Next, a solution obtained by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of propylene glycol monomethyl ether (hereinafter abbreviated as “PGME”) was dropped over 30 minutes. , Reacted at 65 ° C. for 3 hours. Next, methanol was added for dilution to obtain a 45% by mass solution of a resin (B-1) having an alicyclic structure and a quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-1) was 10,000.
攪拌装置、還流冷却管及び窒素導入管を備えたフラスコ中に、窒素ガスを導入して、フラスコ内の空気を窒素ガスで置換した。その後、フラスコに２－（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ライド５４．７質量部、シクロヘキシルメタクリレート１９．９質量部、メトキシポリエチレングリコールメタクリレート（日油株式会社製「ブレンマー ＰＭＥ－１０００」；繰り返し単位数ｎ≒２３、分子量１，０００）２４．９質量部、メタクリル酸０．５質量部、メタノール５０質量部及びＰＧＭＥ１０質量部を加えた。次いで、重合開始剤（アゾビスイソブチロニトリル）０．１質量部をプロピレングリコールモノメチルエーテル（以下「ＰＧＭＥ」と略記する。）２．４質量部で溶解した溶液を３０分かけて滴下した後、６５℃で３時間反応させた。次いで、メタノールを加えて希釈し、脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ－１）の４５質量％溶液を得た。得られた樹脂（Ｂ－１）の重量平均分子量は１万であった。 (Production Example 1: Production of resin (B-1) having alicyclic structure and quaternary ammonium salt)
Nitrogen gas was introduced into a flask equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, and the air in the flask was replaced with nitrogen gas. Thereafter, 54.7 parts by weight of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 19.9 parts by weight of cyclohexyl methacrylate, methoxypolyethylene glycol methacrylate (“Blemmer PME-1000” manufactured by NOF Corporation); 23, molecular weight 1,000) 24.9 parts by mass, methacrylic acid 0.5 parts by mass, methanol 50 parts by mass and PGME 10 parts by mass were added. Next, a solution obtained by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of propylene glycol monomethyl ether (hereinafter abbreviated as “PGME”) was dropped over 30 minutes. , Reacted at 65 ° C. for 3 hours. Next, methanol was added for dilution to obtain a 45% by mass solution of a resin (B-1) having an alicyclic structure and a quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-1) was 10,000.
上記で得られた樹脂（Ｂ－１）の重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した。
The weight average molecular weight of the resin (B-1) obtained above was measured by the gel permeation chromatography (GPC) method under the following conditions.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」 (Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」 (Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
（実施例１）
ジペンタエリスリトールヘキサアクリレート（以下「ＤＰＨＡ」と略記する。）５０質量部、ウレタンアクリレート（ペンタエリスリトールテトラアクリレートとイソホロンジイソシアネートとの反応物、固形分１００質量％、以下「ＵＡ１」と略記する。）５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液２．２質量部（樹脂（Ｃ－１）として１質量部）、光重合開始剤（ＢＡＳＦジャパン株式会社「イルガキュア １８４」；１－ヒドロキシシクロヘキシルフェニルケトン、以下「Ｉｒｇ１８４」と略記する。）５質量部、ジメチルアセトアミド（以下「ＤＭＡＣ」と略記する。）８５質量部、ＰＧＭＥ５質量部、エタノール８．５質量部、メタノール０．５質量部、ｎ－プロパノール１質量部を均一に混合して、活性エネルギー線硬化性組成物（１）を得た。 Example 1
50 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as “DPHA”), urethane acrylate (reaction product of pentaerythritol tetraacrylate and isophorone diisocyanate, solid content 100 mass%, hereinafter abbreviated as “UA1”) 50 Parts by weight, 2.2 parts by weight of a 45% by weight solution of the resin (C-1) obtained in Production Example 1 (1 part by weight as the resin (C-1)), photopolymerization initiator (BASF Japan Ltd. “Irgacure 184 "; 1-hydroxycyclohexyl phenyl ketone, hereinafter abbreviated as" Irg184 ") 5 parts by mass, 85 parts by mass of dimethylacetamide (hereinafter abbreviated as" DMAC "), 5 parts by mass of PGME, 8.5 parts by mass of ethanol, Mix 0.5 parts by mass of methanol and 1 part by mass of n-propanol to obtain an active solution. An energy ray curable composition (1) was obtained.
ジペンタエリスリトールヘキサアクリレート（以下「ＤＰＨＡ」と略記する。）５０質量部、ウレタンアクリレート（ペンタエリスリトールテトラアクリレートとイソホロンジイソシアネートとの反応物、固形分１００質量％、以下「ＵＡ１」と略記する。）５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液２．２質量部（樹脂（Ｃ－１）として１質量部）、光重合開始剤（ＢＡＳＦジャパン株式会社「イルガキュア １８４」；１－ヒドロキシシクロヘキシルフェニルケトン、以下「Ｉｒｇ１８４」と略記する。）５質量部、ジメチルアセトアミド（以下「ＤＭＡＣ」と略記する。）８５質量部、ＰＧＭＥ５質量部、エタノール８．５質量部、メタノール０．５質量部、ｎ－プロパノール１質量部を均一に混合して、活性エネルギー線硬化性組成物（１）を得た。 Example 1
50 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as “DPHA”), urethane acrylate (reaction product of pentaerythritol tetraacrylate and isophorone diisocyanate, solid content 100 mass%, hereinafter abbreviated as “UA1”) 50 Parts by weight, 2.2 parts by weight of a 45% by weight solution of the resin (C-1) obtained in Production Example 1 (1 part by weight as the resin (C-1)), photopolymerization initiator (BASF Japan Ltd. “Irgacure 184 "; 1-hydroxycyclohexyl phenyl ketone, hereinafter abbreviated as" Irg184 ") 5 parts by mass, 85 parts by mass of dimethylacetamide (hereinafter abbreviated as" DMAC "), 5 parts by mass of PGME, 8.5 parts by mass of ethanol, Mix 0.5 parts by mass of methanol and 1 part by mass of n-propanol to obtain an active solution. An energy ray curable composition (1) was obtained.
（実施例２）
ＤＰＨＡ５０質量部、ＵＡ１を５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液６．６質量部（樹脂（Ｃ－１）として３質量部）、Ｉｒｇ１８４を５質量部、ＤＭＡＣ３６質量部、ジメチルカーボネート（以下「ＤＭＣ」と略記する。）５４質量部、エタノール８．５質量部、メタノール０．５質量部、ｎ－プロパノール１質量部を均一に混合して、活性エネルギー線硬化性組成物（２）を得た。 (Example 2)
50 parts by mass of DPHA, 50 parts by mass of UA1, 6.6 parts by mass of a 45% by mass resin (C-1) solution obtained in Production Example 1 (3 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part by mass, 36 parts by mass of DMAC, 54 parts by mass of dimethyl carbonate (hereinafter abbreviated as “DMC”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol are mixed to obtain an activity. An energy ray-curable composition (2) was obtained.
ＤＰＨＡ５０質量部、ＵＡ１を５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液６．６質量部（樹脂（Ｃ－１）として３質量部）、Ｉｒｇ１８４を５質量部、ＤＭＡＣ３６質量部、ジメチルカーボネート（以下「ＤＭＣ」と略記する。）５４質量部、エタノール８．５質量部、メタノール０．５質量部、ｎ－プロパノール１質量部を均一に混合して、活性エネルギー線硬化性組成物（２）を得た。 (Example 2)
50 parts by mass of DPHA, 50 parts by mass of UA1, 6.6 parts by mass of a 45% by mass resin (C-1) solution obtained in Production Example 1 (3 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part by mass, 36 parts by mass of DMAC, 54 parts by mass of dimethyl carbonate (hereinafter abbreviated as “DMC”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol are mixed to obtain an activity. An energy ray-curable composition (2) was obtained.
（実施例３）
ＤＰＨＡ５０質量部、ＵＡ１を５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液１１．１質量部（樹脂（Ｃ－１）として５質量部）、Ｉｒｇ１８４を５質量部、ＤＭＡＣ１０質量部、メチルエチルケトン（以下「ＭＥＫ」と略記する。）３０質量部、ＤＭＣ６０質量部を均一に混合して、活性エネルギー線硬化性組成物（３）を得た。 (Example 3)
50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45% by mass resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part, DMAC 10 parts by mass, methyl ethyl ketone (hereinafter abbreviated as “MEK”) 30 parts by mass and DMC 60 parts by mass were uniformly mixed to obtain an active energy ray-curable composition (3).
ＤＰＨＡ５０質量部、ＵＡ１を５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液１１．１質量部（樹脂（Ｃ－１）として５質量部）、Ｉｒｇ１８４を５質量部、ＤＭＡＣ１０質量部、メチルエチルケトン（以下「ＭＥＫ」と略記する。）３０質量部、ＤＭＣ６０質量部を均一に混合して、活性エネルギー線硬化性組成物（３）を得た。 (Example 3)
50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45% by mass resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part, DMAC 10 parts by mass, methyl ethyl ketone (hereinafter abbreviated as “MEK”) 30 parts by mass and DMC 60 parts by mass were uniformly mixed to obtain an active energy ray-curable composition (3).
（実施例４）
ＤＰＨＡ７０質量部、ＭＩＷＯＮ社製「ＭＩＲＡＭＥＲ ＨＲ６０４２」（屈折率：１．６１８、以下「ＨＲ６０４２」と略記する。）３０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液６．６質量部（樹脂（Ｃ－１）として３質量部）、Ｉｒｇ１８４を５質量部、ＤＭＡＣ１００質量部を均一に混合して、活性エネルギー線硬化性組成物（４）を得た。 Example 4
70 parts by mass of DPHA, 30 parts by mass of “MIRAMER HR6042” (refractive index: 1.618, hereinafter abbreviated as “HR6042”) manufactured by MIWON, 45% by mass solution of the resin (C-1) obtained in Production Example 1 6.6 parts by mass (3 parts by mass as resin (C-1)), 5 parts by mass of Irg184, and 100 parts by mass of DMAC were uniformly mixed to obtain an active energy ray-curable composition (4).
ＤＰＨＡ７０質量部、ＭＩＷＯＮ社製「ＭＩＲＡＭＥＲ ＨＲ６０４２」（屈折率：１．６１８、以下「ＨＲ６０４２」と略記する。）３０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液６．６質量部（樹脂（Ｃ－１）として３質量部）、Ｉｒｇ１８４を５質量部、ＤＭＡＣ１００質量部を均一に混合して、活性エネルギー線硬化性組成物（４）を得た。 Example 4
70 parts by mass of DPHA, 30 parts by mass of “MIRAMER HR6042” (refractive index: 1.618, hereinafter abbreviated as “HR6042”) manufactured by MIWON, 45% by mass solution of the resin (C-1) obtained in Production Example 1 6.6 parts by mass (3 parts by mass as resin (C-1)), 5 parts by mass of Irg184, and 100 parts by mass of DMAC were uniformly mixed to obtain an active energy ray-curable composition (4).
（比較例１）
ＤＰＨＡ５０質量部、ＵＡ１を５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液１１．１質量部（樹脂（Ｃ－１）として５質量部）、Ｉｒｇ１８４を５質量部、ＭＥＫ１００質量部を均一に混合して、活性エネルギー線硬化性組成物（Ｒ１）を得た。 (Comparative Example 1)
50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45% by mass resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part and 100 parts by mass of MEK were uniformly mixed to obtain an active energy ray-curable composition (R1).
ＤＰＨＡ５０質量部、ＵＡ１を５０質量部、製造例１で得られた樹脂（Ｃ－１）の４５質量％溶液１１．１質量部（樹脂（Ｃ－１）として５質量部）、Ｉｒｇ１８４を５質量部、ＭＥＫ１００質量部を均一に混合して、活性エネルギー線硬化性組成物（Ｒ１）を得た。 (Comparative Example 1)
50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45% by mass resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part and 100 parts by mass of MEK were uniformly mixed to obtain an active energy ray-curable composition (R1).
（比較例２）
ＭＥＫをＤＭＣに変更した以外は、比較例１と同様にして活性エネルギー線硬化性組成物（Ｒ２）を得た。 (Comparative Example 2)
An active energy ray-curable composition (R2) was obtained in the same manner as in Comparative Example 1 except that MEK was changed to DMC.
ＭＥＫをＤＭＣに変更した以外は、比較例１と同様にして活性エネルギー線硬化性組成物（Ｒ２）を得た。 (Comparative Example 2)
An active energy ray-curable composition (R2) was obtained in the same manner as in Comparative Example 1 except that MEK was changed to DMC.
（比較例３）
ＭＥＫ１００質量部を、メチルイソブチルケトン（以下「ＭＩＢＫ」と略記する。）９０質量部、エタノール８．５質量部、メタノール０．５質量部、ｎ－プロパノール１質量部に変更した以外は、比較例１と同様にして活性エネルギー線硬化性組成物（Ｒ３）を得た。 (Comparative Example 3)
Comparative Example, except that 100 parts by mass of MEK was changed to 90 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol. In the same manner as in Example 1, an active energy ray-curable composition (R3) was obtained.
ＭＥＫ１００質量部を、メチルイソブチルケトン（以下「ＭＩＢＫ」と略記する。）９０質量部、エタノール８．５質量部、メタノール０．５質量部、ｎ－プロパノール１質量部に変更した以外は、比較例１と同様にして活性エネルギー線硬化性組成物（Ｒ３）を得た。 (Comparative Example 3)
Comparative Example, except that 100 parts by mass of MEK was changed to 90 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol. In the same manner as in Example 1, an active energy ray-curable composition (R3) was obtained.
上記の実施例１～４及び比較例１～３で得られた活性エネルギー線硬化性組成物（１）～（４）、（Ｒ１）～（Ｒ３）を用いて、下記の試験、測定を行った。
Using the active energy ray-curable compositions (1) to (4) and (R1) to (R3) obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the following tests and measurements were performed. It was.
［評価用サンプルの作製］
活性エネルギー線硬化性組成物を、厚さ６０μｍのトリアセチルセルロース（ＴＡＣ）フィルム（富士フイルム株式会社製）に、バーコーターで膜厚５μｍとなるように塗工し、６０℃で１．５分間乾燥した後、空気雰囲気下で紫外線照射装置（アイグラフィックス株式会社製、高圧水銀ランプ）を用いて積算光量３ｋＪ／ｍ２で照射し、硬化塗膜を有するＴＡＣフィルムを評価用サンプルとして得た。 [Preparation of sample for evaluation]
The active energy ray-curable composition was applied to a 60 μm-thick triacetylcellulose (TAC) film (manufactured by Fuji Film Co., Ltd.) with a bar coater so as to have a film thickness of 5 μm, and then at 60 ° C. for 1.5 minutes. After drying, irradiation was performed with an integrated light quantity of 3 kJ / m 2 using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) in an air atmosphere, and a TAC film having a cured coating film was obtained as an evaluation sample. .
活性エネルギー線硬化性組成物を、厚さ６０μｍのトリアセチルセルロース（ＴＡＣ）フィルム（富士フイルム株式会社製）に、バーコーターで膜厚５μｍとなるように塗工し、６０℃で１．５分間乾燥した後、空気雰囲気下で紫外線照射装置（アイグラフィックス株式会社製、高圧水銀ランプ）を用いて積算光量３ｋＪ／ｍ２で照射し、硬化塗膜を有するＴＡＣフィルムを評価用サンプルとして得た。 [Preparation of sample for evaluation]
The active energy ray-curable composition was applied to a 60 μm-thick triacetylcellulose (TAC) film (manufactured by Fuji Film Co., Ltd.) with a bar coater so as to have a film thickness of 5 μm, and then at 60 ° C. for 1.5 minutes. After drying, irradiation was performed with an integrated light quantity of 3 kJ / m 2 using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) in an air atmosphere, and a TAC film having a cured coating film was obtained as an evaluation sample. .
［表面抵抗値の測定（帯電防止性の評価）］
上記で得られた評価用サンプルの硬化塗膜の表面について、ＪＩＳ試験方法Ｋ６９１１－１９９５に準拠して、高抵抗率計（株式会社三菱化学アナリテック製「ハイレスタ－ＵＰ ＭＣＰ－ＨＴ４５０」）を用いて、印加電圧５００Ｖ、測定時間１０秒で表面抵抗値を測定した。 [Measurement of surface resistance (evaluation of antistatic properties)]
For the surface of the cured coating film of the evaluation sample obtained above, a high resistivity meter (“HIRESTA-UP MCP-HT450” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used in accordance with JIS test method K6911-1995. The surface resistance value was measured at an applied voltage of 500 V and a measurement time of 10 seconds.
上記で得られた評価用サンプルの硬化塗膜の表面について、ＪＩＳ試験方法Ｋ６９１１－１９９５に準拠して、高抵抗率計（株式会社三菱化学アナリテック製「ハイレスタ－ＵＰ ＭＣＰ－ＨＴ４５０」）を用いて、印加電圧５００Ｖ、測定時間１０秒で表面抵抗値を測定した。 [Measurement of surface resistance (evaluation of antistatic properties)]
For the surface of the cured coating film of the evaluation sample obtained above, a high resistivity meter (“HIRESTA-UP MCP-HT450” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used in accordance with JIS test method K6911-1995. The surface resistance value was measured at an applied voltage of 500 V and a measurement time of 10 seconds.
［耐水性の評価方法］
活性エネルギー線硬化性組成物にそれぞれ精製水１質量％及び２質量％添加して均一に混合後、外観を目視評価し以下の様に判別した。
「○」：透明液状で沈殿無し
「△」：やや白濁
「×」：白濁若しくは、ゲル化または、沈殿等発生 [Evaluation method of water resistance]
After adding 1% by mass and 2% by mass of purified water to the active energy ray-curable composition and mixing them uniformly, the appearance was visually evaluated and determined as follows.
“○”: Transparent liquid with no precipitation “△”: Slightly cloudy “×”: Cloudy, gelled or precipitated
活性エネルギー線硬化性組成物にそれぞれ精製水１質量％及び２質量％添加して均一に混合後、外観を目視評価し以下の様に判別した。
「○」：透明液状で沈殿無し
「△」：やや白濁
「×」：白濁若しくは、ゲル化または、沈殿等発生 [Evaluation method of water resistance]
After adding 1% by mass and 2% by mass of purified water to the active energy ray-curable composition and mixing them uniformly, the appearance was visually evaluated and determined as follows.
“○”: Transparent liquid with no precipitation “△”: Slightly cloudy “×”: Cloudy, gelled or precipitated
［全光線透過率の測定］
上記で得られた評価用サンプルについて、日本電色株式会社製「Ｈａｚｅ Ｍｅｔｅｒ（型番ＮＤＨ２０００）」を用いて全光線透過率を測定した。 [Measurement of total light transmittance]
About the sample for evaluation obtained above, the total light transmittance was measured using "Haze Meter (model number NDH2000)" by Nippon Denshoku Co., Ltd.
上記で得られた評価用サンプルについて、日本電色株式会社製「Ｈａｚｅ Ｍｅｔｅｒ（型番ＮＤＨ２０００）」を用いて全光線透過率を測定した。 [Measurement of total light transmittance]
About the sample for evaluation obtained above, the total light transmittance was measured using "Haze Meter (model number NDH2000)" by Nippon Denshoku Co., Ltd.
表１に示した評価結果から、実施例１～４の本発明の活性エネルギー線硬化性組成物の硬化塗膜は、帯電防止性が高く、かつ、優れた耐水性を有することが確認できた。
From the evaluation results shown in Table 1, it was confirmed that the cured coating films of the active energy ray-curable compositions of the present invention of Examples 1 to 4 had high antistatic properties and excellent water resistance. .
一方、比較例１～３は、有機溶剤（Ｃ）として、ジメチルアセトアミドを用いた態様であるが、いずれも耐水性が不良であった。また、比較例３は、表面抵抗値が１０の１３乗を超えており、帯電防止性に劣ることも確認された。
On the other hand, Comparative Examples 1 to 3 were embodiments in which dimethylacetamide was used as the organic solvent (C), but all had poor water resistance. Further, in Comparative Example 3, the surface resistance value exceeded 10 13 and it was confirmed that the antistatic property was inferior.
Claims (7)
- 活性エネルギー線硬化性化合物（Ａ）と、脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ）と、ジメチルアセトアミドを含む有機溶剤（Ｃ）とを含有することを特徴とする活性エネルギー線硬化性組成物。 An active energy ray-curable compound comprising an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. Composition.
- 前記ジメチルアセトアミドの含有量が、前記活性エネルギー線硬化性化合物（Ａ）１００質量部に対して、５～２００質量部の範囲である請求項１記載の活性エネルギー線硬化性組成物。 The active energy ray-curable composition according to claim 1, wherein the dimethylacetamide content is in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A).
- 前記活性エネルギー線硬化性化合物（Ａ）が、多官能（メタ）アクリレート（Ａ１）、ウレタン（メタ）アクリレート（Ａ２）、及び、屈折率が１．５５以上である高屈折率重合性単量体（Ａ３）からなる群より選ばれる１種以上である請求項１又は２記載の活性エネルギー線硬化性組成物。 The active energy ray-curable compound (A) is a polyfunctional (meth) acrylate (A1), urethane (meth) acrylate (A2), and a high refractive index polymerizable monomer having a refractive index of 1.55 or more. The active energy ray-curable composition according to claim 1 or 2, which is one or more selected from the group consisting of (A3).
- 前記樹脂（Ｂ）が、原料として脂環構造を有する重合性単量体（ｂ１）を５～４０質量％用いた重合体である請求項１～３のいずれか１項記載の活性エネルギー線硬化性組成物。 The active energy ray-curable resin according to any one of claims 1 to 3, wherein the resin (B) is a polymer using 5 to 40% by mass of a polymerizable monomer (b1) having an alicyclic structure as a raw material. Sex composition.
- 前記樹脂（Ｂ）の配合量が、活性エネルギー線硬化性化合物（Ａ）１００質量部に対して、０．１～３０質量部の範囲である請求項１～４のいずれか１項記載の活性エネルギー線硬化性組成物。 The activity according to any one of claims 1 to 4, wherein the amount of the resin (B) is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A). Energy ray curable composition.
- 請求項１～５のいずれか１記載の活性エネルギー線硬化性組成物により形成されたことを特徴とする硬化物。 A cured product formed from the active energy ray-curable composition according to any one of claims 1 to 5.
- 請求項１～５のいずれか１記載の活性エネルギー線硬化性組成物の硬化塗膜を有することを特徴とするフィルム。 A film having a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 5.
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