WO2018003294A1 - Active-energy-beam-curable composition and film using same - Google Patents
Active-energy-beam-curable composition and film using same Download PDFInfo
- Publication number
- WO2018003294A1 WO2018003294A1 PCT/JP2017/017496 JP2017017496W WO2018003294A1 WO 2018003294 A1 WO2018003294 A1 WO 2018003294A1 JP 2017017496 W JP2017017496 W JP 2017017496W WO 2018003294 A1 WO2018003294 A1 WO 2018003294A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- mass
- active energy
- curable composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
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- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 145
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
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- 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
- 239000012788 optical film Substances 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
- 229920002454 poly(glycidyl methacrylate) polymer 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
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 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
- 238000002360 preparation method Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012958 reprocessing 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
- 239000007787 solid Substances 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
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 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
- 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
- 238000009966 trimming Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Definitions
- the present invention relates to an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties on a film surface by coating and curing the film surface, and a film using the same.
- Various resin films include scratch prevention films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), decorative films (sheets) for interior and exterior of automobiles, It is used for various applications such as low reflection film for windows and heat ray cut film.
- FPD flat panel displays
- LCD liquid crystal displays
- OLED organic EL displays
- PDP plasma displays
- decorative films sheets for interior and exterior of automobiles
- a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this.
- a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this.
- the outline of the process of providing a hard coat layer is sent out from a film roll wound in a roll shape to a coating machine, a hard coat agent is applied, cured by ultraviolet irradiation to form a hard coat layer, and again It is wound up into a roll.
- a method of adding an antistatic agent to the hard coat agent is generally performed.
- a method of blending a compound having a polyoxyethylene chain and a quaternary ammonium salt into a hard coat agent as an antistatic agent has been proposed (for example, see Patent Document 1).
- the hard coat agent containing these antistatic agents does not have sufficient antistatic performance. Therefore, there has been a demand for an active energy ray-curable composition that can form a hard coat layer having better antistatic properties.
- the problem to be solved by the present invention is to provide an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties and a film using the same.
- the present inventors have obtained excellent antistatic properties by blending a resin having an alicyclic structure and a quaternary ammonium salt into an active energy ray-curable composition.
- the present inventors have found that a hard coat layer having can be formed and completed the present invention.
- 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).
- a curable composition and a film using the same are provided.
- the active energy ray-curable composition of the present invention can form a hard coat layer having excellent antistatic properties by coating and curing on the film surface. Therefore, the cured coating film of the active energy ray-curable composition of the present invention can suppress the generation of static electricity on the film surface. Therefore, functions such as sticking prevention and adhesion of dust due to static electricity can be imparted to various films. Therefore, the film having a cured coating film of the active energy ray-curable composition of the present invention is environmentally friendly, and troubles such as sticking and adhesion of dust, etc. when winding up into a roll or unwinding from the roll. Therefore, a film excellent in subsequent handling can be provided.
- 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 contains an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C). is there.
- Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2). These can be used alone or in combination of two or more.
- (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 Pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.
- the urethane (meth) acrylate (A2) is obtained by reacting polyisocyanate (a2-1) with (meth) acrylate (a2-2) having a hydroxyl group.
- 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, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, isophorone Diisocyanate is preferred.
- 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, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned.
- (meth) acrylates (a2-2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates.
- pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.
- 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.
- active energy ray-curable compound (A) other than said polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2) epoxy (meth) acrylate, polyester (meth) An acrylate, a polyether (meth) acrylate, etc. can be used.
- the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate and the like and esterifying it.
- polyester (meth) acrylate (meth) acrylic acid is made to react and esterify with the polyester which the both terminal obtained by polycondensation of polyhydric carboxylic acid and polyhydric alcohol is a hydroxyl group, for example. Or a product obtained by reacting (meth) acrylic acid with ester obtained by adding an alkylene oxide to a polyvalent carboxylic acid.
- polyether (meth) acrylate what was obtained by reacting (meth) acrylic acid with polyether polyol and esterifying is mentioned, for example.
- 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 (b1) 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 composition (A).
- the range of 0.1 to 30 parts by mass is preferable, the range of 0.5 to 20 parts by mass is more preferable, the range of 1 to 10 parts by mass is more preferable, and the range of 1.5 to 7 parts by mass is particularly preferable .
- the organic solvent (C) can be used without particular limitation as long as it can dissolve other components in the active energy ray-curable composition of the present invention. Further, 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 dispersion term ( ⁇ D) in the Hansen solubility parameter is in the range of 15.5 to 16.1 MPa 0.5 . It is preferable that the polarization term ( ⁇ P) is in the range of 6.3 to 10.4 MPa 0.5 and the hydrogen bond term ( ⁇ H) is in the range of 5.1 to 11.6 MPa 0.5 .
- Hansen solubility parameters For the definition and calculation of Hansen solubility parameters, please refer to Charles M. Hansen, “Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007)”. Further, by using the computer software “Hansen Solubility Parameters in Practice (HSPiP)”, the Hansen solubility parameter can be estimated from the chemical structure of an organic solvent whose parameter value is not described in the literature. In the present invention, the value is used for an organic solvent whose parameter value is described in the literature, and the parameter value estimated using HSPiP version 4.1.06 is used for the organic solvent whose parameter value is not described in the literature. Use.
- the organic solvent (C) can be used as a single organic solvent or as a mixed solvent in combination of two or more organic solvents.
- the value which carried out the weighted average of three parameters of the Hansen solubility parameter of each organic solvent can be used in the said range.
- 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 a photosensitizer (E) is with respect to 100 mass parts of said active energy ray curable compositions (A) in the active energy ray curable composition of this invention.
- 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 active energy ray-curable composition of the present invention contains an organic solvent
- the organic solvent In order to volatilize and to segregate the resin (B) on the coating film surface, it is preferable to heat or dry at room temperature.
- the conditions for heat drying are not particularly limited as long as the organic solvent volatilizes. Usually, the heat drying is performed at a temperature in the range of 50 to 100 ° C. and for a time in the range of 0.5 to 10 minutes. preferable.
- 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.
- methanol was added for dilution to obtain a 45% by mass solution of a resin (B-2) having an alicyclic structure and a quaternary ammonium salt.
- the weight average molecular weight of the obtained resin (B-2) was 10,000.
- the obtained resin (B′-1) had a weight average molecular weight of 10,000.
- the obtained resin (B′-2) had a weight average molecular weight of 10,000.
- the weight average molecular weights of the resins (B-1), (B-2), (B′-1) and (B′-2) obtained above were determined by gel permeation chromatography (GPC) method. The measurement was performed 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 Polyfunctional acrylate mixture (mixture of dipentaerythritol hexaacrylate 64% by mass, dipentaerythritol pentaacrylate 17% by mass, dipentaerythritol tetraacrylate 19% by mass; hereinafter, abbreviated as “polyfunctional acrylate (A1)”) 100 11 parts by mass (5 parts by mass as the resin (B-2)), a photopolymerization initiator (BASF Japan Ltd.
- “Irgacure 184” ; 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone), 60 parts by mass of methyl ethyl ketone (hereinafter abbreviated as” MEK ”) and 40 parts by mass of PGME are uniformly mixed to cure active energy rays having a nonvolatile content of 50% by mass. Sex composition (1) was obtained.
- Example 2 to 4 Active energy ray-curable compositions (2) to (7) were obtained in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were changed.
- 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 at an irradiation light amount 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
- the cured coating films of the active energy ray-curable compositions of the present invention of Examples 1 to 4 have a surface resistance value of the order of 10 9 and high antistatic properties. It could be confirmed.
- Comparative Examples 1 to 5 are examples using a resin having no alicyclic structure and having a quaternary ammonium salt. These surface resistance values 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-beam-curable composition that makes it possible to form a hard coat layer that has excellent antistatic properties; and a film that uses the active-energy-beam-curable composition. The present invention uses an active-energy-beam-curable composition that is characterized by containing: an active-energy-beam-curable compound (A); a resin (B) that has an alicyclic structure and includes a quaternary ammonium salt; and an organic solvent (C). The raw material of the resin (B) that has an alicyclic structure and includes a quaternary ammonium salt is a polymer that uses 5-40 mass% of a polymerizable monomer that has an alicyclic structure. The organic solvent (C) has a dispersion (δD) Hansen solubility parameter of 15.5-16.1 MPa0.5, a polarity (δP) Hansen solubility parameter of 6.3-10.4 MPa0.5, and a hydrogen bonding (δH) Hansen solubility parameter of 5.1-11.6 MPa0.5.
Description
本発明は、フィルムの表面に塗工、硬化させることにより、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できる活性エネルギー線硬化性組成物及びそれを用いたフィルムに関する。
The present invention relates to an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties on a film surface by coating and curing the film surface, and a film using the same.
各種樹脂フィルムは、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）表面の傷付き防止用フィルム、自動車の内外装用加飾フィルム（シート）、窓向けの低反射フィルムや熱線カットフィルムなど各種用途に用いられている。しかしながら、樹脂フィルム表面は柔らかく耐擦傷性が低いため、これを補う目的で、ＵＶ硬化性組成物等からなるハードコート剤をフィルム表面に塗工、硬化させハードコート層をフィルム表面に設けることが一般的に行われている。ハードコート層を設ける工程を概略すると、ロール状に巻いてあるフィルム原反から塗工機へ送り出され、ハードコート剤が塗工され、紫外線照射により硬化してハードコート層を形成した後、再度ロール状に巻き取られる。
Various resin films include scratch prevention films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), decorative films (sheets) for interior and exterior of automobiles, It is used for various applications such as low reflection film for windows and heat ray cut film. However, since the resin film surface is soft and has low scratch resistance, a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this. Generally done. The outline of the process of providing a hard coat layer is sent out from a film roll wound in a roll shape to a coating machine, a hard coat agent is applied, cured by ultraviolet irradiation to form a hard coat layer, and again It is wound up into a roll.
この巻き取り工程でフィルム同士の摩擦によりフィルム表面に静電気が発生するため、再加工時にフィルムをロールから繰り出した際にフィルム同士が張り付いてしまう問題や静電気によりフィルム表面に埃等が付着しやすくなる問題があった。また、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りディスプレイが誤動作する問題もあった。
In this winding process, static electricity is generated on the film surface due to the friction between the films. Therefore, when the film is unwound from the roll during reprocessing, the film surface sticks to the film surface, and dust tends to adhere to the film surface due to static electricity. There was a problem. Further, when this film is used for a liquid crystal display or the like, there is a problem that the display malfunctions due to generated static electricity.
このフィルム表面での静電気の発生を抑制するため、ハードコート剤に帯電防止剤を配合する手法が一般的に行われている。例えば、ポリオキシエチレン鎖と４級アンモニウム塩とを有する化合物を帯電防止剤としてハードコート剤に配合する方法が提案されている（例えば、特許文献１参照。）。
In order to suppress the generation of static electricity on the film surface, a method of adding an antistatic agent to the hard coat agent is generally performed. For example, a method of blending a compound having a polyoxyethylene chain and a quaternary ammonium salt into a hard coat agent as an antistatic agent has been proposed (for example, see Patent Document 1).
また、４級アンモニウム塩を有する重合性単量体を原料とした２種の共重合体を帯電防止剤としてハードコート剤に配合する方法が提案されている（例えば、特許文献２参照。）。
In addition, a method has been proposed in which two types of copolymers using a polymerizable monomer having a quaternary ammonium salt as a raw material are blended as an antistatic agent into a hard coat agent (for example, see Patent Document 2).
しかしながら、これらの帯電防止剤を配合したハードコート剤は、帯電防止性能が十分ではなかった。そこで、より優れた帯電防止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が求められていた。
However, the hard coat agent containing these antistatic agents does not have sufficient antistatic performance. Therefore, there has been a demand for an active energy ray-curable composition that can form a hard coat layer having better antistatic properties.
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及びそれを用いたフィルムを提供することである。
The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties and a film using the same.
本発明者等は、上記の課題を解決するため鋭意研究した結果、活性エネルギー線硬化性組成物に、脂環構造及び４級アンモニウム塩を有する樹脂等を配合することにより、優れた帯電防止性を有するハードコート層を形成できることを見出し、本発明を完成させた。
As a result of intensive studies to solve the above problems, the present inventors have obtained excellent antistatic properties by blending a resin having an alicyclic structure and a quaternary ammonium salt into an active energy ray-curable composition. The present inventors have found that a hard coat layer having can be formed and completed the present invention.
すなわち、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、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及びそれを用いたフィルムを提供するものである。
That is, 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). A curable composition and a film using the same are provided.
本発明の活性エネルギー線硬化性組成物は、フィルム表面に塗工、硬化することで、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。したがって、本発明の活性エネルギー線硬化性組成物の硬化塗膜は、フィルム表面に静電気を発生することを抑制できる。よって、各種フィルムに、張り付き防止、静電気による埃等の付着防止等の機能を付与できる。したがって、本発明の活性エネルギー線硬化性組成物の硬化塗膜を有するフィルムは、環境対応のものとなり、ロール状に巻き取る際、ロールから繰り出す際にも、張り付き、埃等の付着などのトラブルも回避できるため、その後のハンドリングに優れたフィルムを提供することができる。
The active energy ray-curable composition of the present invention can form a hard coat layer having excellent antistatic properties by coating and curing on the film surface. Therefore, the cured coating film of the active energy ray-curable composition of the present invention can suppress the generation of static electricity on the film surface. Therefore, functions such as sticking prevention and adhesion of dust due to static electricity can be imparted to various films. Therefore, the film having a cured coating film of the active energy ray-curable composition of the present invention is environmentally friendly, and troubles such as sticking and adhesion of dust, etc. when winding up into a roll or unwinding from the roll. Therefore, a film excellent in subsequent handling can be provided.
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、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 contains an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C). is there.
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）等が挙げられる。これらは、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 active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2). These can be used alone or in combination of two or more.
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、ペンタエリスリトールトリ（メタ）アクリレートが好ましい。
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 Pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.
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）とを反応させて得られたものである。
The urethane (meth) acrylate (A2) is obtained by reacting polyisocyanate (a2-1) with (meth) acrylate (a2-2) having a hydroxyl group.
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、脂肪族ポリイソシアネートの中でも、直鎖脂肪族炭化水素のジイソシアネートであるヘキサメチレンジイソシアネート、脂環式ジイソシアネートである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が好ましい。
Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, isophorone Diisocyanate is preferred.
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、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、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ペンタ（メタ）アクリレートは、耐擦傷性を向上できるため好ましい。
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, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned. 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), pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.
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.
また、必要に応じて、上記の多官能（メタ）アクリレート（Ａ１）、ウレタン（メタ）アクリレート（Ａ２）以外の活性エネルギー線硬化性化合物（Ａ）として、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）アクリレート等を用いることができる。前記エポキシ（メタ）アクリレートとしては、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリグリシジルメタクリレート等に、（メタ）アクリル酸を反応しエステル化することにより得られるものが挙げられる。また、前記ポリエステル（メタ）アクリレートとしては、例えば、多価カルボン酸と多価アルコールを重縮合して得られた両末端が水酸基であるポリエステルに、（メタ）アクリル酸を反応しエステル化することにより得られたもの、あるいは、多価カルボン酸にアルキレンオキシドを付加したものに（メタ）アクリル酸を反応しエステル化することにより得られたものが挙げられる。さらに、前記ポリエーテル（メタ）アクリレートとしては、例えば、ポリエーテルポリオールに（メタ）アクリル酸を反応しエステル化することにより得られたものが挙げられる。
Moreover, as needed, as active energy ray-curable compound (A) other than said polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2), epoxy (meth) acrylate, polyester (meth) An acrylate, a polyether (meth) acrylate, etc. can be used. Examples of the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate and the like and esterifying it. Moreover, as said polyester (meth) acrylate, (meth) acrylic acid is made to react and esterify with the polyester which the both terminal obtained by polycondensation of polyhydric carboxylic acid and polyhydric alcohol is a hydroxyl group, for example. Or a product obtained by reacting (meth) acrylic acid with ester obtained by adding an alkylene oxide to a polyvalent carboxylic acid. Furthermore, as said polyether (meth) acrylate, what was obtained by reacting (meth) acrylic acid with polyether polyol and esterifying is mentioned, for example.
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（ｂ１）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 (b1) 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 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、５～５５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組成物（Ａ）１００質量部に対して、０．１～３０質量部の範囲が好ましく、０．５～２０質量部の範囲がより好ましく、１～１０質量部の範囲がさらに好ましく、１．５～７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 composition (A). The range of 0.1 to 30 parts by mass is preferable, the range of 0.5 to 20 parts by mass is more preferable, the range of 1 to 10 parts by mass is more preferable, and the range of 1.5 to 7 parts by mass is particularly preferable .
前記有機溶剤（Ｃ）は、本発明の活性エネルギー線硬化性組成物中の他の成分を溶解できるものであれば特に制限なく用いることができる。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の帯電防止性をより向上できることから、ハンセン溶解度パラメータでの分散項（δＤ）が１５．５～１６．１ＭＰａ０．５の範囲であり、分極項（δＰ）が６．３～１０．４ＭＰａ０．５の範囲であり、水素結合項（δＨ）が５．１～１１．６ＭＰａ０．５の範囲であるものが好ましい。
The organic solvent (C) can be used without particular limitation as long as it can dissolve other components in the active energy ray-curable composition of the present invention. Further, 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 dispersion term (δD) in the Hansen solubility parameter is in the range of 15.5 to 16.1 MPa 0.5 . It is preferable that the polarization term (δP) is in the range of 6.3 to 10.4 MPa 0.5 and the hydrogen bond term (δH) is in the range of 5.1 to 11.6 MPa 0.5 .
なお、ハンセン溶解度パラメータの定義と計算は、Ｃｈａｒｌｅｓ Ｍ．Ｈａｎｓｅｎ著「Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒｓ；Ａ Ｕｓｅｒｓ Ｈａｎｄｂｏｏｋ（ＣＲＣ Ｐｒｅｓｓ，２００７）」に記載されている。また、コンピュータソフトウェア「Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒｓ ｉｎ Ｐｒａｃｔｉｃｅ（ＨＳＰｉＰ）」を用いることにより、文献にパラメータ値の記載がない有機溶剤に関しても、その化学構造からハンセン溶解度パラメータを推算することができる。本発明では、文献にパラメータ値の記載がある有機溶剤については、その値を用い、文献にパラメータ値の記載がない有機溶剤に関しては、ＨＳＰｉＰバージョン４．１．０６を用いて推算したパラメータ値を用いる。
For the definition and calculation of Hansen solubility parameters, please refer to Charles M. Hansen, “Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007)”. Further, by using the computer software “Hansen Solubility Parameters in Practice (HSPiP)”, the Hansen solubility parameter can be estimated from the chemical structure of an organic solvent whose parameter value is not described in the literature. In the present invention, the value is used for an organic solvent whose parameter value is described in the literature, and the parameter value estimated using HSPiP version 4.1.06 is used for the organic solvent whose parameter value is not described in the literature. Use.
前記有機溶剤（Ｃ）は、１種の有機溶剤で用いることも２種以上の有機溶剤を併用して混合溶剤として用いることもできる。２種以上併用する場合は、それぞれの有機溶剤のハンセン溶解度パラメータの３つのパラメータを加重平均した値が、上記の範囲内となる組み合わせで用いることができる。
The organic solvent (C) can be used as a single organic solvent or as a mixed solvent in combination of two or more organic solvents. When using 2 or more types together, the value which carried out the weighted average of three parameters of the Hansen solubility parameter of each organic solvent can be used in the said range.
２種以上の有機溶剤を併用して、前記有機溶剤（Ｃ）として用いる場合、そのハンセン溶解度パラメータの範囲に調整する方法としては、例えば、エタノール（δＤ＝１５．８ＭＰａ０．５、δＰ＝８．８ＭＰａ０．５、δＨ＝１９．４ＭＰａ０．５）等のアルコール溶剤と、メチルエチルケトン（δＤ＝１６．０ＭＰａ０．５、δＰ＝９．０ＭＰａ０．５、δＨ＝５．１ＭＰａ０．５）等のケトン溶剤との組み合わせが挙げられ、前記ケトン系溶剤と酢酸メチル（δＤ＝１５．５ＭＰａ０．５、δＰ＝７．２ＭＰａ０．５、δＨ＝７．６ＭＰａ０．５）等のエステル溶剤との組み合わせも挙げられる。また、このアルコール溶剤とケトン溶剤との組み合わせに加え、さらにダイアセトンアルコール（δＤ＝１５．８ＭＰａ０．５、δＰ＝８．２ＭＰａ０．５、δＨ＝１０．８ＭＰａ０．５）、アセチルアセトン（δＤ＝１６．１ＭＰａ０．５、δＰ＝１０．０ＭＰａ０．５、δＨ＝６．２ＭＰａ０．５）、ジメチルカルビトール（δＤ＝１５．７ＭＰａ０．５、δＰ＝６．１ＭＰａ０．５、δＨ＝６．５ＭＰａ０．５）、プロピレングリコールモノメチルエーテルアセテート（δＤ＝１５．６ＭＰａ０．５、δＰ＝５．６ＭＰａ０．５、δＨ＝９．８ＭＰａ０．５）等の沸点１００～１８０℃の高沸点溶剤を前記有機溶剤（Ｃ）中に３～４０質量％含有させることにより、塗工安定性が向上でき、硬化塗膜にヒビが入るのを防止し、塗膜外観を優れたものとすることができることから好ましい。
When two or more organic solvents are used in combination as the organic solvent (C), a method for adjusting the Hansen solubility parameter range is, for example, ethanol (δD = 15.8 MPa 0.5 , δP = 8 .8MPa 0.5, δH = 19.4MPa 0.5) and an alcohol solvent such as methyl ethyl ketone (δD = 16.0MPa 0.5, δP = 9.0MPa 0.5, δH = 5.1MPa 0.5) It includes a combination of a ketone solvent etc., the ketone-based solvent and methyl acetate (δD = 15.5MPa 0.5, δP = 7.2MPa 0.5, δH = 7.6MPa 0.5) ester solvents such as A combination with is also mentioned. In addition to combination with the alcohol solvent and a ketone solvent, further diacetone alcohol (δD = 15.8MPa 0.5, δP = 8.2MPa 0.5, δH = 10.8MPa 0.5), acetylacetone ([delta] D = 16.1MPa 0.5, δP = 10.0MPa 0.5 , δH = 6.2MPa 0.5), dimethyl carbitol (δD = 15.7MPa 0.5, δP = 6.1MPa 0.5, δH = 6.5 MPa 0.5), propylene glycol monomethyl ether acetate (δD = 15.6MPa 0.5, δP = 5.6MPa 0.5, δH = 9.8MPa 0.5) or the like having a boiling point of 100 ~ 180 ° C. of By containing 3 to 40% by mass of the high boiling point solvent in the organic solvent (C), the coating stability can be improved, and the cured coating film can be prevented from cracking, It preferred because it can be provided with excellent Makugaikan.
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-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組成物（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 a photosensitizer (E) is with respect to 100 mass parts of said active energy ray curable compositions (A) in the active energy ray curable composition of this invention. Are preferably 0.05 to 20 parts by mass, and 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中に有機溶媒を含む場合は、活性エネルギー線硬化性組成物を基材フィルムへの塗工した後、活性エネルギー線を照射する前に、有機溶媒を揮発させ、また、前記樹脂（Ｂ）を塗膜表面に偏析させるために、加熱又は室温乾燥することが好ましい。加熱乾燥の条件としては、有機溶剤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, when the active energy ray-curable composition of the present invention contains an organic solvent, after applying the active energy ray-curable composition to the substrate film, before irradiating the active energy ray, the organic solvent In order to volatilize and to segregate the resin (B) on the coating film surface, it is preferable to heat or dry at room temperature. The conditions for heat drying are not particularly limited as long as the organic solvent volatilizes. Usually, the heat drying is performed at a temperature in the range of 50 to 100 ° C. and for a time in the range of 0.5 to 10 minutes. preferable.
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：ウレタンアクリレート（Ａ２－１）の合成）
攪拌機、ガス導入管、冷却管、及び温度計を備えたフラスコに、酢酸ブチル５５．５質量部、ＩＰＤＩ２２２質量部、ｐ－メトキシフェノール０．５質量部、ジブチル錫ジアセテート０．５質量部を仕込み、７０℃に昇温した後、ビス（２－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（以下、「ＢＡＨＩＣ」という。）／トリス（２－アクリロイルオキシエチル）イソシアヌレート（以下、「ＴＡＩＣ」という。）混合物（質量比５６／４４の混合物）の不揮発分８０質量％の酢酸ブチル溶液８２３．６質量部を１時間かけて滴下し、滴下終了後７０℃で３時間反応させた。その後、ＰＥ３Ａ／ＰＥ４Ａ混合物（質量比７５／２５の混合物）の不揮発分８０質量％の酢酸ブチル溶液４９６．６質量部を１時間かけて滴下し、滴下終了後７０℃で３時間反応させ、さらにイソシアネート基を示す２２５０ｃｍ－１の赤外線吸収スペクトルが消失するまで反応を行い、ウレタンアクリレート（Ａ２－１）／ＴＡＩＣ／ＰＥ４Ａの混合物（質量比６９／２３／８の混合物、不揮発分８０質量％の酢酸ブチル溶液）を得た。なお、ウレタンアクリレート（Ａ２－１）の分子量は８８９であった。 (Production Example 1: Synthesis of urethane acrylate (A2-1))
A flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer was charged with 55.5 parts by mass of butyl acetate, 222 parts by mass of IPDI, 0.5 parts by mass of p-methoxyphenol, and 0.5 parts by mass of dibutyltin diacetate. After charging and heating to 70 ° C., bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate (hereinafter referred to as “BAHIC”) / tris (2-acryloyloxyethyl) isocyanurate (hereinafter referred to as “TAIC”). ) 823.6 parts by mass of a butyl acetate solution having a nonvolatile content of 80% by mass of the mixture (mixture having a mass ratio of 56/44) was added dropwise over 1 hour, and reacted at 70 ° C. for 3 hours after completion of the addition. Thereafter, 496.6 parts by mass of a butyl acetate solution having a non-volatile content of 80% by mass of a PE3A / PE4A mixture (a mixture having a mass ratio of 75/25) was added dropwise over 1 hour, and reacted at 70 ° C. for 3 hours after completion of the addition. The reaction is continued until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappears, and a mixture of urethane acrylate (A2-1) / TAIC / PE4A (a mixture of mass ratio 69/23/8, acetic acid having a nonvolatile content of 80% by mass) Butyl solution) was obtained. The molecular weight of urethane acrylate (A2-1) was 889.
攪拌機、ガス導入管、冷却管、及び温度計を備えたフラスコに、酢酸ブチル５５．５質量部、ＩＰＤＩ２２２質量部、ｐ－メトキシフェノール０．５質量部、ジブチル錫ジアセテート０．５質量部を仕込み、７０℃に昇温した後、ビス（２－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（以下、「ＢＡＨＩＣ」という。）／トリス（２－アクリロイルオキシエチル）イソシアヌレート（以下、「ＴＡＩＣ」という。）混合物（質量比５６／４４の混合物）の不揮発分８０質量％の酢酸ブチル溶液８２３．６質量部を１時間かけて滴下し、滴下終了後７０℃で３時間反応させた。その後、ＰＥ３Ａ／ＰＥ４Ａ混合物（質量比７５／２５の混合物）の不揮発分８０質量％の酢酸ブチル溶液４９６．６質量部を１時間かけて滴下し、滴下終了後７０℃で３時間反応させ、さらにイソシアネート基を示す２２５０ｃｍ－１の赤外線吸収スペクトルが消失するまで反応を行い、ウレタンアクリレート（Ａ２－１）／ＴＡＩＣ／ＰＥ４Ａの混合物（質量比６９／２３／８の混合物、不揮発分８０質量％の酢酸ブチル溶液）を得た。なお、ウレタンアクリレート（Ａ２－１）の分子量は８８９であった。 (Production Example 1: Synthesis of urethane acrylate (A2-1))
A flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer was charged with 55.5 parts by mass of butyl acetate, 222 parts by mass of IPDI, 0.5 parts by mass of p-methoxyphenol, and 0.5 parts by mass of dibutyltin diacetate. After charging and heating to 70 ° C., bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate (hereinafter referred to as “BAHIC”) / tris (2-acryloyloxyethyl) isocyanurate (hereinafter referred to as “TAIC”). ) 823.6 parts by mass of a butyl acetate solution having a nonvolatile content of 80% by mass of the mixture (mixture having a mass ratio of 56/44) was added dropwise over 1 hour, and reacted at 70 ° C. for 3 hours after completion of the addition. Thereafter, 496.6 parts by mass of a butyl acetate solution having a non-volatile content of 80% by mass of a PE3A / PE4A mixture (a mixture having a mass ratio of 75/25) was added dropwise over 1 hour, and reacted at 70 ° C. for 3 hours after completion of the addition. The reaction is continued until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappears, and a mixture of urethane acrylate (A2-1) / TAIC / PE4A (a mixture of mass ratio 69/23/8, acetic acid having a nonvolatile content of 80% by mass) Butyl solution) was obtained. The molecular weight of urethane acrylate (A2-1) was 889.
（製造例２：ウレタンアクリレート（Ａ２－２）の合成）
攪拌機、ガス導入管、冷却管、及び温度計を備えたフラスコに、酢酸ブチル５５．５質量部、イソホロンジイソシアネート（以下、「ＩＰＤＩ」という。）２２２質量部、ｐ－メトキシフェノール０．５質量部、ジブチル錫ジアセテート０．５質量部を仕込み、７０℃に昇温した後、ペンタエリスリトールトリアクリレート（以下、「ＰＥ３Ａ」という。）／ペンタエリスリトールテトラアクリレート（以下、「ＰＥ４Ａ」という。）混合物（質量比７５／２５の混合物）の８０質量％酢酸ブチル溶液９９３．４質量部を１時間かけて滴下した。滴下終了後、７０℃で３時間反応させ、さらにイソシアネート基を示す２２５０ｃｍ－１の赤外線吸収スペクトルが消失するまで反応を行い、ウレタンアクリレート（Ａ２－２）／ＰＥ４Ａ混合物（質量比８０／２０の混合物、不揮発分８０質量％の酢酸ブチル溶液）を得た。なお、ウレタンアクリレート（Ａ２－２）の分子量は８１８であった。 (Production Example 2: Synthesis of urethane acrylate (A2-2))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 55.5 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate (hereinafter referred to as “IPDI”), 0.5 parts by mass of p-methoxyphenol Then, 0.5 parts by mass of dibutyltin diacetate was charged and the temperature was raised to 70 ° C., and then a pentaerythritol triacrylate (hereinafter referred to as “PE3A”) / pentaerythritol tetraacrylate (hereinafter referred to as “PE4A”) mixture ( 993.4 parts by mass of 80% by mass butyl acetate solution of 75/25 mass ratio) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappeared, and a urethane acrylate (A2-2) / PE4A mixture (a mixture having a mass ratio of 80/20) Thus, a butyl acetate solution having a nonvolatile content of 80% by mass was obtained. The molecular weight of urethane acrylate (A2-2) was 818.
攪拌機、ガス導入管、冷却管、及び温度計を備えたフラスコに、酢酸ブチル５５．５質量部、イソホロンジイソシアネート（以下、「ＩＰＤＩ」という。）２２２質量部、ｐ－メトキシフェノール０．５質量部、ジブチル錫ジアセテート０．５質量部を仕込み、７０℃に昇温した後、ペンタエリスリトールトリアクリレート（以下、「ＰＥ３Ａ」という。）／ペンタエリスリトールテトラアクリレート（以下、「ＰＥ４Ａ」という。）混合物（質量比７５／２５の混合物）の８０質量％酢酸ブチル溶液９９３．４質量部を１時間かけて滴下した。滴下終了後、７０℃で３時間反応させ、さらにイソシアネート基を示す２２５０ｃｍ－１の赤外線吸収スペクトルが消失するまで反応を行い、ウレタンアクリレート（Ａ２－２）／ＰＥ４Ａ混合物（質量比８０／２０の混合物、不揮発分８０質量％の酢酸ブチル溶液）を得た。なお、ウレタンアクリレート（Ａ２－２）の分子量は８１８であった。 (Production Example 2: Synthesis of urethane acrylate (A2-2))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 55.5 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate (hereinafter referred to as “IPDI”), 0.5 parts by mass of p-methoxyphenol Then, 0.5 parts by mass of dibutyltin diacetate was charged and the temperature was raised to 70 ° C., and then a pentaerythritol triacrylate (hereinafter referred to as “PE3A”) / pentaerythritol tetraacrylate (hereinafter referred to as “PE4A”) mixture ( 993.4 parts by mass of 80% by mass butyl acetate solution of 75/25 mass ratio) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappeared, and a urethane acrylate (A2-2) / PE4A mixture (a mixture having a mass ratio of 80/20) Thus, a butyl acetate solution having a nonvolatile content of 80% by mass was obtained. The molecular weight of urethane acrylate (A2-2) was 818.
（製造例３：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５３．７質量部、シクロヘキシルメタクリレート２９．３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）１４.６質量部、２－パーフルオロヘキシルエチルアクリレート１．９質量部、メタクリル酸０．５質量部、メタノール５０質量部及びプロピレングリコールモノメチルエーテル１０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 3: 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, 53.7 parts by mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 29.3 parts by mass of cyclohexyl methacrylate, methoxypolyethylene glycol methacrylate (“Blemmer PME-1000” manufactured by NOF Corporation); 23, molecular weight 1,000) 14.6 parts by mass, 1.9 parts by mass of 2-perfluorohexylethyl acrylate, 0.5 parts by mass of methacrylic acid, 50 parts by mass of methanol and 10 parts by mass of propylene glycol monomethyl ether. Next, a solution in which 0.1 part by mass of a polymerization initiator (azobisisobutyronitrile) was dissolved in 2.4 parts by mass of propylene glycol monomethyl ether was dropped over 30 minutes, and then 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５３．７質量部、シクロヘキシルメタクリレート２９．３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）１４.６質量部、２－パーフルオロヘキシルエチルアクリレート１．９質量部、メタクリル酸０．５質量部、メタノール５０質量部及びプロピレングリコールモノメチルエーテル１０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 3: 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, 53.7 parts by mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 29.3 parts by mass of cyclohexyl methacrylate, methoxypolyethylene glycol methacrylate (“Blemmer PME-1000” manufactured by NOF Corporation); 23, molecular weight 1,000) 14.6 parts by mass, 1.9 parts by mass of 2-perfluorohexylethyl acrylate, 0.5 parts by mass of methacrylic acid, 50 parts by mass of methanol and 10 parts by mass of propylene glycol monomethyl ether. Next, a solution in which 0.1 part by mass of a polymerization initiator (azobisisobutyronitrile) was dissolved in 2.4 parts by mass of propylene glycol monomethyl ether was dropped over 30 minutes, and then 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.
（製造例４：脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ－２）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ＰＧＭＥ２．４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－２）の４５質量％溶液を得た。得られた樹脂（Ｂ－２）の重量平均分子量は１万であった。 (Production Example 4: Production of resin (B-2) 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 mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 19.9 parts by mass 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 prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then reacted at 65 ° C. for 3 hours. Next, methanol was added for dilution to obtain a 45% by mass solution of a resin (B-2) having an alicyclic structure and a quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-2) 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ＰＧＭＥ２．４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－２）の４５質量％溶液を得た。得られた樹脂（Ｂ－２）の重量平均分子量は１万であった。 (Production Example 4: Production of resin (B-2) 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 mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 19.9 parts by mass 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 prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then reacted at 65 ° C. for 3 hours. Next, methanol was added for dilution to obtain a 45% by mass solution of a resin (B-2) having an alicyclic structure and a quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-2) was 10,000.
（製造例５：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５４．０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）４４．１質量部、２－パーフルオロヘキシルエチルアクリレート１．９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ＰＧＭＥ２．４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 5: 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, 54.0 parts by mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, methoxypolyethylene glycol methacrylate (“Blenmer PME-1000” manufactured by NOF Corporation; number of repeating units n≈23, molecular weight 1,000) 44 0.1 part by mass, 1.9 parts by mass of 2-perfluorohexylethyl acrylate, 50 parts by mass of methanol and 10 parts by mass of PGME were added. Next, a solution prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then 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 obtained resin (B′-1) had a weight average molecular weight of 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５４．０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）４４．１質量部、２－パーフルオロヘキシルエチルアクリレート１．９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ＰＧＭＥ２．４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 5: 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, 54.0 parts by mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, methoxypolyethylene glycol methacrylate (“Blenmer PME-1000” manufactured by NOF Corporation; number of repeating units n≈23, molecular weight 1,000) 44 0.1 part by mass, 1.9 parts by mass of 2-perfluorohexylethyl acrylate, 50 parts by mass of methanol and 10 parts by mass of PGME were added. Next, a solution prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then 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 obtained resin (B′-1) had a weight average molecular weight of 10,000.
（製造例６：脂環構造及び４級アンモニウム塩を有する樹脂（Ｂ’－２）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、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）４４．８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ＰＧＭＥ２．４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’－２）の４５質量％溶液を得た。得られた樹脂（Ｂ’－２）の重量平均分子量は１万であった。 (Production Example 6: Production of resin (B′-2) 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 mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, methoxypolyethyleneglycol methacrylate (“Blenmer PME-1000” manufactured by NOF Corporation; number of repeating units n≈23, molecular weight 1,000) 44 .8 parts by mass, 0.5 parts by mass of methacrylic acid, 50 parts by mass of methanol and 10 parts by mass of PGME were added. Next, a solution prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then reacted at 65 ° C. for 3 hours. Next, methanol was added for dilution to obtain a 45% by mass solution of a resin (B′-2) having an alicyclic structure and a quaternary ammonium salt. The obtained resin (B′-2) had a weight average molecular weight of 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、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）４４．８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ＰＧＭＥ２．４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’－２）の４５質量％溶液を得た。得られた樹脂（Ｂ’－２）の重量平均分子量は１万であった。 (Production Example 6: Production of resin (B′-2) 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 mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, methoxypolyethyleneglycol methacrylate (“Blenmer PME-1000” manufactured by NOF Corporation; number of repeating units n≈23, molecular weight 1,000) 44 .8 parts by mass, 0.5 parts by mass of methacrylic acid, 50 parts by mass of methanol and 10 parts by mass of PGME were added. Next, a solution prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then reacted at 65 ° C. for 3 hours. Next, methanol was added for dilution to obtain a 45% by mass solution of a resin (B′-2) having an alicyclic structure and a quaternary ammonium salt. The obtained resin (B′-2) had a weight average molecular weight of 10,000.
上記で得られた樹脂（Ｂ－１）、（Ｂ－２）、（Ｂ’－１）及び（Ｂ’－２）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 weights of the resins (B-1), (B-2), (B′-1) and (B′-2) obtained above were determined by gel permeation chromatography (GPC) method. The measurement was performed 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）
多官能アクリレート混合物（ジペンタエリスリトールヘキサアクリレート６４質量％、ジペンタエリスリトールペンタアクリレート１７質量％、ジペンタエリスリトールテトラアクリレート１９質量％の混合物；以下、「多官能アクリレート（Ａ１）」と略記する。）１００質量部、製造例４で得られた樹脂（Ｂ－２）の４５質量％溶液１１．１１質量部（樹脂（Ｂ－２）として５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）５質量部、メチルエチルケトン（以下、「ＭＥＫ」と略記する。）６０質量部及びＰＧＭＥ４０質量部を均一に混合して、不揮発分５０質量％の活性エネルギー線硬化性組成物（１）を得た。 Example 1
Polyfunctional acrylate mixture (mixture of dipentaerythritol hexaacrylate 64% by mass, dipentaerythritol pentaacrylate 17% by mass, dipentaerythritol tetraacrylate 19% by mass; hereinafter, abbreviated as “polyfunctional acrylate (A1)”) 100 11 parts by mass (5 parts by mass as the resin (B-2)), a photopolymerization initiator (BASF Japan Ltd. “Irgacure 184 "; 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone), 60 parts by mass of methyl ethyl ketone (hereinafter abbreviated as" MEK ") and 40 parts by mass of PGME are uniformly mixed to cure active energy rays having a nonvolatile content of 50% by mass. Sex composition (1) was obtained.
多官能アクリレート混合物（ジペンタエリスリトールヘキサアクリレート６４質量％、ジペンタエリスリトールペンタアクリレート１７質量％、ジペンタエリスリトールテトラアクリレート１９質量％の混合物；以下、「多官能アクリレート（Ａ１）」と略記する。）１００質量部、製造例４で得られた樹脂（Ｂ－２）の４５質量％溶液１１．１１質量部（樹脂（Ｂ－２）として５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）５質量部、メチルエチルケトン（以下、「ＭＥＫ」と略記する。）６０質量部及びＰＧＭＥ４０質量部を均一に混合して、不揮発分５０質量％の活性エネルギー線硬化性組成物（１）を得た。 Example 1
Polyfunctional acrylate mixture (mixture of dipentaerythritol hexaacrylate 64% by mass, dipentaerythritol pentaacrylate 17% by mass, dipentaerythritol tetraacrylate 19% by mass; hereinafter, abbreviated as “polyfunctional acrylate (A1)”) 100 11 parts by mass (5 parts by mass as the resin (B-2)), a photopolymerization initiator (BASF Japan Ltd. “Irgacure 184 "; 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone), 60 parts by mass of methyl ethyl ketone (hereinafter abbreviated as" MEK ") and 40 parts by mass of PGME are uniformly mixed to cure active energy rays having a nonvolatile content of 50% by mass. Sex composition (1) was obtained.
（実施例２～４）
表１～２に示した組成に変更した以外は実施例１と同様に行い、活性エネルギー線硬化性組成物（２）～（７）を得た。 (Examples 2 to 4)
Active energy ray-curable compositions (2) to (7) were obtained in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were changed.
表１～２に示した組成に変更した以外は実施例１と同様に行い、活性エネルギー線硬化性組成物（２）～（７）を得た。 (Examples 2 to 4)
Active energy ray-curable compositions (2) to (7) were obtained in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were changed.
（比較例１～５）
表２～３に示した組成に変更した以外は実施例１と同様に行い、活性エネルギー線硬化性組成物（Ｒ１）～（Ｒ５）を得た。 (Comparative Examples 1 to 5)
Active energy ray-curable compositions (R1) to (R5) were obtained in the same manner as in Example 1 except that the compositions shown in Tables 2 to 3 were changed.
表２～３に示した組成に変更した以外は実施例１と同様に行い、活性エネルギー線硬化性組成物（Ｒ１）～（Ｒ５）を得た。 (Comparative Examples 1 to 5)
Active energy ray-curable compositions (R1) to (R5) were obtained in the same manner as in Example 1 except that the compositions shown in Tables 2 to 3 were changed.
上記の実施例１～４及び比較例１～５で得られた活性エネルギー線硬化性組成物（１）～（４）、（Ｒ１）～（Ｒ５）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 (R5) obtained in Examples 1 to 4 and Comparative Examples 1 to 5, 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）を用いて照射光量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 at an irradiation light amount 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）を用いて照射光量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 at an irradiation light amount 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. .
［鉛筆硬さの測定］
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Ｋ５６００－５－４：１９９９に準拠して、鉛筆硬さを測定した。 [Measurement of pencil hardness]
With respect to the surface of the cured coating film of the evaluation sample obtained above, the pencil hardness was measured in accordance with JIS test method K5600-5-4: 1999.
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Ｋ５６００－５－４：１９９９に準拠して、鉛筆硬さを測定した。 [Measurement of pencil hardness]
With respect to the surface of the cured coating film of the evaluation sample obtained above, the pencil hardness was measured in accordance with JIS test method K5600-5-4: 1999.
［耐擦傷性の評価］
上記で得られた評価用フィルムの硬化塗膜の表面について、クロックメーター形摩擦試験機（株式会社東洋精機製作所製「平面摩擦試験機」、測定条件：直径２５ｍｍ円形摩擦子、スチールウール＃００００、荷重５００ｇ、１０往復）を用いて試験を行い、試験後の硬化塗膜表面の傷の有無を目視で確認し、下記の基準により耐擦傷性を評価した。
◎：傷がない。
○：傷の数が１～２本である。
△：傷の数が３～１０本である。
×：傷の数が１０本を超える。 [Evaluation of scratch resistance]
About the surface of the cured coating film of the film for evaluation obtained above, a clock meter type friction tester (“Plane Friction Tester” manufactured by Toyo Seiki Seisakusho Co., Ltd.), measurement conditions: 25 mm diameter circular friction piece, steel wool # 0000, A test was performed using a load of 500 g, 10 reciprocations), and the presence or absence of scratches on the surface of the cured coating film after the test was visually confirmed. The scratch resistance was evaluated according to the following criteria.
A: There is no scratch.
○: The number of scratches is 1-2.
Δ: The number of scratches is 3-10.
X: The number of scratches exceeds 10.
上記で得られた評価用フィルムの硬化塗膜の表面について、クロックメーター形摩擦試験機（株式会社東洋精機製作所製「平面摩擦試験機」、測定条件：直径２５ｍｍ円形摩擦子、スチールウール＃００００、荷重５００ｇ、１０往復）を用いて試験を行い、試験後の硬化塗膜表面の傷の有無を目視で確認し、下記の基準により耐擦傷性を評価した。
◎：傷がない。
○：傷の数が１～２本である。
△：傷の数が３～１０本である。
×：傷の数が１０本を超える。 [Evaluation of scratch resistance]
About the surface of the cured coating film of the film for evaluation obtained above, a clock meter type friction tester (“Plane Friction Tester” manufactured by Toyo Seiki Seisakusho Co., Ltd.), measurement conditions: 25 mm diameter circular friction piece, steel wool # 0000, A test was performed using a load of 500 g, 10 reciprocations), and the presence or absence of scratches on the surface of the cured coating film after the test was visually confirmed. The scratch resistance was evaluated according to the following criteria.
A: There is no scratch.
○: The number of scratches is 1-2.
Δ: The number of scratches is 3-10.
X: The number of scratches exceeds 10.
［ヘーズの測定（透明性の評価）］
上記で得られた評価用サンプルについて、ＪＩＳ試験方法Ｋ７１３６：２０００に準拠して、ヘーズメーター（日本電色工業株式会社製「ＮＤＨ２０００」）を用いてヘーズ値を測定した。 [Measurement of haze (evaluation of transparency)]
About the sample for evaluation obtained above, based on JIS test method K7136: 2000, haze value was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. "NDH2000").
上記で得られた評価用サンプルについて、ＪＩＳ試験方法Ｋ７１３６：２０００に準拠して、ヘーズメーター（日本電色工業株式会社製「ＮＤＨ２０００」）を用いてヘーズ値を測定した。 [Measurement of haze (evaluation of transparency)]
About the sample for evaluation obtained above, based on JIS test method K7136: 2000, haze value was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. "NDH2000").
［屈折率の測定］
上記で得られた評価用サンプルについて、ＪＩＳ試験方法Ｋ７１４２：２０１４のＡ法に準拠して、アッベ屈折率計（株式会社アタゴ製「ＤＲ－Ｍ２」）を用いて屈折率を測定した。 [Measurement of refractive index]
The refractive index of the sample for evaluation obtained above was measured using an Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.) in accordance with method A of JIS test method K7142: 2014.
上記で得られた評価用サンプルについて、ＪＩＳ試験方法Ｋ７１４２：２０１４のＡ法に準拠して、アッベ屈折率計（株式会社アタゴ製「ＤＲ－Ｍ２」）を用いて屈折率を測定した。 [Measurement of refractive index]
The refractive index of the sample for evaluation obtained above was measured using an Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.) in accordance with method A of JIS test method K7142: 2014.
［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.
上記で測定した結果を表１～３に示す。
The results measured above are shown in Tables 1-3.
表１～２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、表面抵抗値が１０の９乗オーダーで帯電防止性も高いことが確認できた。
From the evaluation results shown in Tables 1 and 2, the cured coating films of the active energy ray-curable compositions of the present invention of Examples 1 to 4 have a surface resistance value of the order of 10 9 and high antistatic properties. It could be confirmed.
一方、比較例１～５は、脂環構造を有さず、４級アンモニウム塩を有する樹脂を用いた例である。これらの表面抵抗値は１０の１３乗を超えており、帯電防止性に劣ることが確認できた。
On the other hand, Comparative Examples 1 to 5 are examples using a resin having no alicyclic structure and having a quaternary ammonium salt. These surface resistance values exceeded 10 13, and it was confirmed that the antistatic property was inferior.
Claims (6)
- 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、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 composition 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).
- 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を５～４０質量％用いた重合体である請求項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 resin (B) is a polymer using 5 to 40% by mass of a polymerizable monomer having an alicyclic structure as a raw material.
- 前記有機溶剤（Ｃ）が、ハンセン溶解度パラメータでの分散項（δＤ）が１５．５～１６．１ＭＰａ０．５の範囲であり、分極項（δＰ）が６．３～１０．４ＭＰａ０．５の範囲であり、水素結合項（δＨ）が５．１～１１．６ＭＰａ０．５の範囲であるものである請求項１又は２記載の活性エネルギー線硬化性組成物。 The organic solvent (C) has a dispersion term (δD) in the range of 15.5 to 16.1 MPa 0.5 with a Hansen solubility parameter and a polarization term (δP) of 6.3 to 10.4 MPa 0.5. The active energy ray-curable composition according to claim 1 or 2, wherein the hydrogen bond term (δH) is in the range of 5.1 to 11.6 MPa 0.5 .
- 前記樹脂（Ｂ）の配合量が、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、０．１～３０質量部の範囲である請求項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 blending 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). An active energy ray-curable composition.
- 請求項１～４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物。 A cured product of the active energy ray-curable composition according to any one of claims 1 to 4.
- 請求項１～４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 4.
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| JP2007269993A (en) * | 2006-03-31 | 2007-10-18 | Toppan Printing Co Ltd | Glare-proof antistatic hard coat resin composition and glare-proof antistatic hard coat film formed body coated with the same |
| JP2007092073A (en) * | 2006-11-06 | 2007-04-12 | Toppan Printing Co Ltd | Glare-proof antistatic hard coating resin composition, and hard coating film and hard coating film-formed product |
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