JP2022097848A - Active energy ray-curable hard-coating agent, hard coat layer and laminate - Google Patents
Active energy ray-curable hard-coating agent, hard coat layer and laminate Download PDFInfo
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- JP2022097848A JP2022097848A JP2020211044A JP2020211044A JP2022097848A JP 2022097848 A JP2022097848 A JP 2022097848A JP 2020211044 A JP2020211044 A JP 2020211044A JP 2020211044 A JP2020211044 A JP 2020211044A JP 2022097848 A JP2022097848 A JP 2022097848A
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- Prior art keywords
- hard coat
- active energy
- energy ray
- compound
- meth
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- ZEDSKTISNTXEQI-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-(4-propylphenyl)phosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound C1=CC(CCC)=CC=C1P(=O)(C(=O)C=1C(=CC=CC=1Cl)Cl)C(=O)C1=C(Cl)C=CC=C1Cl ZEDSKTISNTXEQI-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- 239000006258 conductive agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
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- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
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- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CVDUUPMTIHXQKC-UHFFFAOYSA-N ethene 1,3,5-triazinane-2,4,6-trione Chemical group C=C.O=C1NC(=O)NC(=O)N1 CVDUUPMTIHXQKC-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
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- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 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
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 125000001749 primary amide group Chemical group 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- 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
- C08F122/00—Homopolymers 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
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、ハードコート層上に金属薄膜を形成することができるハードコート層を形成するための活性エネルギー線硬化性ハードコート剤、ハードコート層および積層体に関する。 The present invention relates to an active energy ray-curable hardcoat agent, a hardcoat layer and a laminate for forming a hardcoat layer capable of forming a metal thin film on the hardcoat layer.
透明なプラスチックフィルム基材上に、透明導電性材料を積層させた透明導電性フィルムは、液晶ディスプレイやエレクトロルミネッセンス（以下、ＥＬと略記する）ディスプレイ等のようなフラットパネルディスプレイ、タッチパネル、照明、太陽電池、電気電子等の分野の用途に広く使用されている。 A transparent conductive film in which a transparent conductive material is laminated on a transparent plastic film base material is a flat panel display such as a liquid crystal display or an electroluminescence (hereinafter abbreviated as EL) display, a touch panel, lighting, and the sun. It is widely used in fields such as batteries and electroluminescence.
透明導電性材料としては、可視光透過率が高く、表面抵抗値が比較的低いこと、環境特性に優れていることから、インジウム系酸化物である酸化インジウム-錫（ＩＴＯ／ＩｎｄｉｕｍＴｉｎＯｘｉｄｅ）（以下ＩＴＯと略記する）を主成分としたものが広く用いられている。しかし、ＩＴＯの表面抵抗値の下限は５０Ω／□であり、大型ディスプレイの電極として用いるには、応答性が足りず不適とされている。ＩＴＯ膜は脆く曲げ耐性に劣るうえに、屈曲時の表面抵抗値が高いことから、ディスプレイのフレキシブル化への対応が困難とされている。 As a transparent conductive material, indium-tin oxide (ITO / IndiumTinOxide) (hereinafter referred to as ITO), which is an indium-based oxide, has a high visible light transmittance, a relatively low surface resistance value, and excellent environmental characteristics. (Abbreviated as) is widely used as the main component. However, the lower limit of the surface resistance value of ITO is 50Ω / □, which is unsuitable for use as an electrode of a large display due to insufficient responsiveness. Since the ITO film is brittle and inferior in bending resistance and has a high surface resistance value at the time of bending, it is difficult to make the display flexible.
そのため、銀や銅、アルミニウム合金等の金属材料の薄膜を、真空蒸着法、スパッタリング法等の物理蒸着法（ＰＤＶ／ＰｈｙｓｉｃａｌＶａｐｏｒＤｅｐｏｓｉｔｉｏｎ）、化学蒸着法（ＣＶＤ／Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）等の方法により、基材上に形成させ、微細なパターニングを施すことで、電極パターンを目視で見えなくする金属メッシュや、金属をナノ分散させた導電性インク等、ＩＴＯを代替する材料や技術の開発が行われている。 Therefore, a thin film of a metal material such as silver, copper, or an aluminum alloy is subjected to a substrate by a method such as a vacuum vapor deposition method, a physical vapor deposition method such as a sputtering method (PDV / Physical Vapor Deposition), or a chemical vapor deposition method (CVD / Chemical Vapor Deposition). Materials and technologies that replace ITO, such as metal mesh that makes the electrode pattern visually invisible by forming it on top and finely patterning it, and conductive ink in which metal is nano-dispersed, are being developed. ..
特許文献１には、ポリアミック酸樹脂、感光材、イソシアヌレート化合物、カーボネート化合物、分子量１００～１０，０００のデンドリマー若しくはハイパーブランチポリマーから選ばれる１種、及び溶剤を含む感光性樹脂組成物、多孔質樹脂、回路基板、並びに、回路付サスペンション基板が開示されている。 Patent Document 1 describes a photosensitive resin composition containing a polyamic acid resin, a photosensitive material, an isocyanurate compound, a carbonate compound, a dendrimer having a molecular weight of 100 to 10,000 or a hyperbranched polymer, and a solvent. Resins, circuit boards, and suspension boards with circuits are disclosed.
特許文献２には、ジイソシアネートの３量体と水酸基含有（メタ）アクリレートとを反応させてなるウレタン（メタ）アクリレート系樹脂、並びに、（メタ）アクリル酸のミカエル付加物及び２－（メタ）アクリロイルオキシアルキルカルボン酸モノエステルからなる群から選ばれた少なくとも１種を含む活性エネルギー線硬化性樹脂組成物が開示されている。 Patent Document 2 describes a urethane (meth) acrylate-based resin obtained by reacting a trimer of diisocyanate with a hydroxyl group-containing (meth) acrylate, a Michael adduct of (meth) acrylic acid, and 2- (meth) acryloyl. An active energy ray-curable resin composition containing at least one selected from the group consisting of oxyalkylcarboxylic acid monoesters is disclosed.
特許文献３には、（メタ）アクリロイル基を有する（メタ）アクリレートモノマー及び／又はアクリレートオリゴマー、チオウレア型シランカップリング剤、及び平均粒径１００～５００ｎｍのナノシリカ微粒子を含む紫外線硬化性樹脂組成物及びフィルム並びに導電性フィルムが開示されている。 Patent Document 3 describes an ultraviolet curable resin composition containing a (meth) acrylate monomer and / or an acrylate oligomer having a (meth) acryloyl group, a thiourea type silane coupling agent, and nanosilica fine particles having an average particle size of 100 to 500 nm. Films as well as conductive films are disclosed.
特許文献４には、金属酸化物からなるコート層、並びに、イソシアヌル環を有するトリ（メタ）アクリレート化合物、芳香環を有するジ（メタ）アクリレート、及びテトラヒドロフタルイミド型シランカップリング剤とコロイダルシリカとの反応物を含むプライマー層を有する樹脂材及びその製造方法が開示されている。 Patent Document 4 describes a coat layer made of a metal oxide, a tri (meth) acrylate compound having an isocyanul ring, a di (meth) acrylate having an aromatic ring, and a tetrahydrophthalimide-type silane coupling agent and colloidal silica. A resin material having a primer layer containing a reactant and a method for producing the same are disclosed.
特許文献５には、多価イソシアネート系化合物とε－カプロラクトン由来の構造部位を含む水酸基含有（メタ）アクリレート系化合物を反応させてなるウレタン（メタ）アクリレート系化合物と、ウレタン（メタ）アクリレート以外の窒素含有（メタ）アクリレート化合物を含む活性エネルギー線硬化性樹脂組成物、コーティング剤、並びに、プレコートメタル用コーティング剤が開示されている。 Patent Document 5 describes a urethane (meth) acrylate-based compound obtained by reacting a polyvalent isocyanate-based compound with a hydroxyl group-containing (meth) acrylate-based compound containing a structural moiety derived from ε-caprolactone, and a urethane (meth) acrylate-based compound other than urethane (meth) acrylate. An active energy ray-curable resin composition containing a nitrogen-containing (meth) acrylate compound, a coating agent, and a coating agent for pre-coated metal are disclosed.
金属材料をフィルム基材上に形成するためには、通常プライマー処理が必要となるが、従来のアンカーコート剤による処理は金属材料との良好な密着性を向上させる一方で、表面硬度を低下させるため、導電性フィルムの製造工程や加工工程等における傷付き対策が課題となっている。 In order to form a metal material on a film substrate, primer treatment is usually required, but treatment with a conventional anchor coating agent improves good adhesion to the metal material while lowering the surface hardness. Therefore, measures against scratches in the manufacturing process and processing process of the conductive film have become an issue.
上記課題の解決のため、下記のように、金属材料との親和性に優れた有機材及び又は無機材を含むＵＶ硬化型アンカーコート剤が検討されているが、それらの硬化膜は表面硬度を高めるために架橋密度を高くするとアンカーコートとしての性能が落ち金属材料に対する密着性が低下しやすくなる傾向にある。 In order to solve the above problems, UV curable anchor coating agents containing organic materials and / or inorganic materials having excellent compatibility with metal materials have been studied as described below, but these cured films have a surface hardness. If the crosslink density is increased in order to increase the crosslink density, the performance as an anchor coat is deteriorated and the adhesion to the metal material tends to be deteriorated.
特許文献６には、水酸基、アルキルエステル基及びニトリル基並びに場合により一級アミド基を有するアクリルコポリマー（Ａ）と、イソシアネート基を少なくとも３つ有するポリイソシアネート（Ｂ）と、炭素－炭素二重結合含有基を少なくとも３つ有する活性エネルギー線重合型化合物（Ｃ）と、（イソシアネート基を含む反応性基から選ばれる反応基有する）反応性アルコキシシリル化合物（Ｄ）と、を含有する、銅薄膜付基材用アンダーコート剤が開示されている。 Patent Document 6 contains an acrylic copolymer (A) having a hydroxyl group, an alkyl ester group and a nitrile group, and optionally a primary amide group, a polyisocyanate (B) having at least three isocyanate groups, and a carbon-carbon double bond. A group with a copper thin film containing an active energy ray-polymerized compound (C) having at least three groups and a reactive alkoxysilyl compound (D) (having a reactive group selected from reactive groups including an isocyanate group). Undercoating agents for materials are disclosed.
特許文献７には、ジカルボン酸類及びジオール類を反応成分とするガラス転移温度が８０℃以下のポリエステルポリオール（Ａ）と、イソシアネート基を少なくとも３つ有するポリイソシアネート（Ｂ）と、（イソシアネート基を含む反応性基から選ばれる反応基有する）反応性アルコキシシリル化合物（Ｃ）と炭素－炭素二重結合含有基を少なくとも３つ有する活性エネルギー線重合型化合物（Ｅ）とを含有する、銅薄膜付基材用アンダーコート剤が提案されている。 Patent Document 7 includes a polyester polyol (A) containing dicarboxylic acids and diols as reaction components and having a glass transition temperature of 80 ° C. or lower, a polyisocyanate (B) having at least three isocyanate groups, and (isocyanate groups). A group with a copper thin film containing a reactive alkoxysilyl compound (C) (having a reactive group selected from reactive groups) and an active energy ray-polymerizable compound (E) having at least three carbon-carbon double bond-containing groups. Undercoating agents for materials have been proposed.
上記のように熱架橋性のイナート樹脂と活性エネルギー線重合型化合物の併用では反応性アルコキシル化合物による導電性フィルムの製造工程や加工工程等における耐擦傷性の課題解決までには至っていない。また、高速データ通信の進展に対応して、誘電率や誘電正接の上昇を抑える観点から、アンダーコートへの極性の高い材料の使用も極力抑えなければならない。 As described above, the combined use of the heat-crosslinkable inert resin and the active energy ray-polymerized compound has not yet solved the problem of scratch resistance in the manufacturing process and processing process of the conductive film using the reactive alkoxyl compound. In addition, in response to the progress of high-speed data communication, it is necessary to suppress the use of highly polar materials for the undercoat as much as possible from the viewpoint of suppressing the increase in the dielectric constant and the dielectric loss tangent.
しかしながら、上記文献に開示されている材料では、いずれもハードコート層を形成した際に、高い透明性、硬度、耐擦傷性、耐アルカリ性、金属薄膜との密着性に優れたハードコート層を形成することができなかった。 However, all of the materials disclosed in the above documents form a hardcoat layer having high transparency, hardness, scratch resistance, alkali resistance, and adhesion to a metal thin film when the hardcoat layer is formed. Couldn't.
本発明が解決しようとする課題は、ハードコート層を形成した際に、高い透明性と硬度を有し、耐擦傷性、耐アルカリ性、金属薄膜との密着性に優れたハードコート層を形成するための活性エネルギー線硬化性ハードコート剤を提供することである。 The problem to be solved by the present invention is to form a hardcoat layer having high transparency and hardness when the hardcoat layer is formed, and having excellent scratch resistance, alkali resistance, and adhesion to a metal thin film. Is to provide an active energy ray-curable hardcoat agent for the purpose.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、以下の発明に至った。すなわち、第１の発明は、ハードコート層上に金属薄膜を形成することができるハードコート層を形成するための活性エネルギー線硬化性ハードコート剤であって、（メタ）アクリロイル基を３個以上有する化合物（Ａ）と、イソシアナト基を有するシランカップリング剤（Ｂ）と、光重合開始剤（Ｃ）とを含み、活性エネルギー線硬化性ハードコート剤の不揮発分１００質量部中、前記化合物（Ａ）を７０質量部以上含む活性エネルギー線硬化性ハードコート剤に関する。 As a result of diligent research to solve the above problems, the present inventors have reached the following inventions. That is, the first invention is an active energy ray-curable hardcoat agent for forming a hardcoat layer capable of forming a metal thin film on the hardcoat layer, and has three or more (meth) acryloyl groups. The compound (A), a silane coupling agent (B) having an isocyanato group, and a photopolymerization initiator (C) are contained in 100 parts by mass of the non-volatile content of the active energy ray-curable hardcoat agent. The present invention relates to an active energy ray-curable hardcoat agent containing 70 parts by mass or more of A).
また、第２の発明は、前記化合物（Ａ）が、（メタ）アクリロイル基を３個以上有し、かつ窒素原子を有する化合物（ａ１）を含む前記活性エネルギー線硬化性ハードコート剤に関する。 The second invention relates to the active energy ray-curable hardcoat agent containing the compound (a1) in which the compound (A) has three or more (meth) acryloyl groups and has a nitrogen atom.
また、第３の発明は、前記化合物（ａ１）が、（メタ）アクリロイル基を３個以上有し、かつヌレート環骨格を有する化合物（ａ２）を含む前記活性エネルギー線硬化性ハードコート剤に関する。 The third invention relates to the active energy ray-curable hardcoat agent containing the compound (a2) in which the compound (a1) has three or more (meth) acryloyl groups and has a nurate ring skeleton.
また、第４の発明は、前記シランカップリング剤（Ｂ）を、前記活性エネルギー線硬化性ハードコート剤の不揮発分１００質量部中、５～３０質量部含む、前記活性エネルギー線硬化性ハードコート剤に関する。 Further, in the fourth invention, the active energy ray-curable hard coat containing the silane coupling agent (B) in an amount of 5 to 30 parts by mass in 100 parts by mass of the non-volatile content of the active energy ray-curable hard coat agent. Regarding the agent.
また、第５の発明は、前記活性エネルギー線硬化性ハードコート剤より形成されたハードコート層に関する。 The fifth invention relates to a hard coat layer formed from the active energy ray-curable hard coat agent.
また、第６の発明は、周波数１ＧＨｚ、２３℃における、比誘電率が３．２以下であり、誘電正接が０．０２以下である前記ハードコート層に関する。 The sixth invention relates to the hard coat layer having a relative permittivity of 3.2 or less and a dielectric loss tangent of 0.02 or less at a frequency of 1 GHz and 23 ° C.
また、第7の発明は、基材上に、前記ハードコート層が積層されてなる積層体に関する。 The seventh invention relates to a laminated body in which the hard coat layer is laminated on a base material.
更に、第８の発明は、ハードコート層上に金属薄膜が積層されてなる前記積層体に関する。 Further, the eighth invention relates to the laminated body in which a metal thin film is laminated on a hard coat layer.
本発明によって、ハードコート層を形成した際に、高い透明性と硬度を有し、耐擦傷性、耐アルカリ性、金属薄膜との密着性に優れたハードコート層を形成するための活性エネルギー線硬化性ハードコート剤を提供することができるようになった。 According to the present invention, when a hardcoat layer is formed, active energy ray curing for forming a hardcoat layer having high transparency and hardness, and excellent scratch resistance, alkali resistance, and adhesion to a metal thin film. It has become possible to provide sex hardcourt agents.
以下、本発明の実施形態について説明するが、初めに本明細書で用いられる用語について説明する。尚、本明細書では、「（メタ）アクリル」、「（メタ）アクリロ」、「（メタ）アクリル酸」、「（メタ）アクリレート」、および「（メタ）アクリロイルオキシ」と表記した場合には、特に断りがない限り、それぞれ「アクリルまたはメタクリル」、「アクリロまたはメタクリロ」、「アクリル酸またはメタクリル酸」、「アクリレートまたはメタクリレート」および「アクリロイルオキシまたはメタクリロイルオキシ」を表すものとする。また、特に断りがない限り、「部」とは「質量部」を、「％」とは「質量％」をそれぞれ表すものとする。また、「本発明の活性エネルギー線硬化性ハードコート剤」を「ハードコート剤」、「（メタ）アクリロイル基を３個以上有する化合物（Ａ）」を「化合物（Ａ）」、「イソシアナト基を有するシランカップリング剤（Ｂ）」を「シランカップリング剤（Ｂ）」、「（メタ）アクリロイル基を３個以上有し、かつ窒素原子を有する化合物（ａ１）」を「化合物（ａ１）」、「（メタ）アクリロイル基を３個以上有し、かつヌレート環骨格を有する化合物（ａ２）」を「化合物（ａ２）」、「化合物（ａ２）以外の化合物（Ａ）」を「化合物（ａ）」、「（メタ）アクリロイル基を１または２個有する化合物（ａ０）」を「化合物（ａ０）」と、それぞれ略記することがある。 Hereinafter, embodiments of the present invention will be described, but first, terms used in the present specification will be described. In addition, in this specification, when it is described as "(meth) acrylic", "(meth) acrylo", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acryloyloxy" Unless otherwise specified, "acrylic or methacrylic", "acrylo or methacrylic acid", "acrylic acid or methacrylic acid", "acrylate or methacrylate" and "acryloyloxy or methacryloyloxy" are used. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". Further, the "active energy ray-curable hard coat agent of the present invention" is a "hard coat agent", the "compound (A) having three or more (meth) acryloyl groups" is "compound (A)", and the "isocyanato group". "Silane coupling agent (B)" is "silane coupling agent (B)", and "compound (a1) having three or more (meth) acryloyl groups and having a nitrogen atom" is "compound (a1)". , "Compound (a2) having three or more (meth) acryloyl groups and having a nurate ring skeleton" is "compound (a2)", and "compound (A) other than compound (a2)" is "compound (a)". ) ”,“ Compound (a0) having one or two (meth) acryloyl groups ”may be abbreviated as“ compound (a0) ”, respectively.
本発明のハードコート剤は、化合物（Ａ）と、シランカップリング剤（Ｂ）と、光重合開始剤（Ｃ）とを含み、活性エネルギー線硬化性ハードコート剤の不揮発分１００質量部中、前記化合物（Ａ）を７０質量部以上含むことを特徴とする。 The hard coat agent of the present invention contains the compound (A), the silane coupling agent (B), and the photopolymerization initiator (C), and is contained in 100 parts by mass of the non-volatile content of the active energy ray-curable hard coat agent. It is characterized by containing 70 parts by mass or more of the compound (A).
＜（メタ）アクリロイル基を３個以上有する化合物（Ａ）＞
化合物（Ａ）としては、
例えば、トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（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、ジペンタエリスリトールヘキサ（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、及びペンタエリスリトールテトラ（メタ）アクリレート、等のポリオールポリ（メタ）アクリレート化合物；
トリス（２－アクリロキシエチル）イソシアヌレート、ＥＯ変性トリス（２－アクリロキシエチル）イソシアヌレート、ＰＯ変性トリス（２－アクリロキシエチル）イソシアヌレート、及びε－カプロラクトン変性トリス（２－アクリロキシエチル）イソシアヌレート等のイソシアナト基有する（メタ）アクリレートの三量体（イソシアヌレート）；
その他、（メタ）アクリロイル基が３つ以上のポリアクリルポリ（メタ）アクリレート、ポリウレタンポリ（メタ）アクリレート、及びポリエステル（メタ）アクリレート等のポリマーポリオールのポリアクリレート；
ポリエポキシ（メタ）アクリレート；
等が挙げられるが、これらに限定されない。
<Compound (A) having 3 or more (meth) acryloyl groups>
As compound (A),
For example, trimethylolpropane tri (meth) acrylate, glycerintri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. ) Polypolymer poly (meth) acrylate compounds such as acrylate;
Tris (2-acryloxyethyl) isocyanurate, EO-modified tris (2-acryroxyethyl) isocyanurate, PO-modified tris (2-acryroxyethyl) isocyanurate, and ε-caprolactone-modified tris (2-acryroxyethyl) Trimer of (meth) acrylate having an isocyanate group such as isocyanate (isocyanurate);
In addition, polyacrylates of polymer polyols such as polyacrylic poly (meth) acrylates having three or more (meth) acryloyl groups, polyurethane poly (meth) acrylates, and polyester (meth) acrylates;
Polyepoxy (meth) acrylate;
Etc., but are not limited to these.
さらに、化合物（Ａ）は、金属薄膜に対して密着性の観点から、（メタ）アクリロイル基を３個以上有し、かつ窒素原子を有する化合物（ａ１）を含むことが好ましく、さらに、（メタ）アクリロイル基を３個以上有し、かつヌレート環構造を有する化合物（ａ２）を含むことがより好ましい。化合物（Ａ）が、化合物（ａ１）を含むことにより、硬度、耐擦傷性、金属薄膜に対する密着性に優れたハードコート層が得られる。ヌレート構造は窒素原子を有するイソシアネート化合物の三量体で、六員環であるため、その剛直な六員環の周りで（メタ）クリロイル基の重合が進み反応が起こり、シランカップリング剤（Ｂ）及び金属薄膜双方の親和性との相乗効果により、優れた硬度、耐擦傷性、金属薄膜密着を発現する。 Further, the compound (A) preferably contains the compound (a1) having three or more (meth) acryloyl groups and having a nitrogen atom from the viewpoint of adhesion to the metal thin film, and further, (meth). ) It is more preferable to contain the compound (a2) having three or more acryloyl groups and having a nurate ring structure. When the compound (A) contains the compound (a1), a hard coat layer having excellent hardness, scratch resistance, and adhesion to a metal thin film can be obtained. Since the nurate structure is a trimer of an isocyanate compound having a nitrogen atom and is a six-membered ring, the polymerization of the (meth) cryloyl group proceeds around the rigid six-membered ring and a reaction occurs, and the silane coupling agent (B) ) And the synergistic effect of the affinity of both the metal thin film, excellent hardness, scratch resistance, and adhesion to the metal thin film are exhibited.
化合物（ａ１）としては、（メタ）アクリロイル基を３個以上有するウレタンアクリレートの他、トリス（２－アクリロキシエチル）イソシアヌレート（日立化成社製 ＦＡＮＣＲＹＬ ＦＡ－７３１Ａ、第一工業製薬社製 ＮＥＷ ＦＲＯＮＴＩＥＲ ＴＥＩＣＡ（ＧＸ－８４３０）等）、ＥＯ変性トリス（２－アクリロキシエチル）イソシアヌレート（東亞合成社製アロニクスＭ－３１３、Ｍ－３１５、新中村化学工業社製ＮＫエステル Ａ－９３００、ＡＲＫＥＭＡ社製ＳＡＲＴＯＭＥＲ ＳＲ－３６８等）、ＰＯ変性トリス（２－アクリロキシエチル）イソシアヌレート、ε－カプロラクトン変性トリス（２－アクリロキシエチル）イソシアヌレート（新中村化学工業社製 ＮＫエステル Ａ－９３００－１ＣＬ等）等の市販品が挙げられるが、これらに限定されない。 Examples of the compound (a1) include urethane acrylate having three or more (meth) acryloyl groups, tris (2-acryloxyethyl) isocyanurate (FACRYL FA-731A manufactured by Hitachi Chemical Co., Ltd., and NEW FRONTIER manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). TEICA (GX-8430), etc.), EO-modified tris (2-acryloxyethyl) isocyanurate (Aronix M-313, M-315 manufactured by Toa Synthetic Co., Ltd., NK ester A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., manufactured by ARKEMA) SARTOMER SR-368 etc.), PO-modified tris (2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris (2-acryloxyethyl) isocyanurate (NK ester A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Examples thereof include, but are not limited to, commercial products such as.
本発明の活性エネルギー線硬化性ハードコート剤の不揮発分１００部中、化合物（Ａ）が７０部以上含まれていれば、硬度、及び耐擦傷性に優れた金属薄膜を形成することができるハードコート層が得られる。活性エネルギー線硬化性ハードコート剤の不揮発分１００部中、化合物（Ａ）の含有量の上限は、１００部未満である。 If 70 parts or more of the compound (A) is contained in 100 parts of the non-volatile content of the active energy ray-curable hard coat agent of the present invention, a hard metal thin film having excellent hardness and scratch resistance can be formed. A coat layer is obtained. The upper limit of the content of the compound (A) in 100 parts of the non-volatile content of the active energy ray-curable hard coat agent is less than 100 parts.
＜イソシアナト基を有するシランカップリング剤（Ｂ）＞
シランカップリング剤（Ｂ）は、一般式（１）：Ｘ１－Ｓｉ（Ｒ１）ａ（ＯＲ２）３－ａ（式（１）中、Ｘ１は、イソシアナト基を、Ｒ１は炭素数１～８の炭化水素基を、Ｒ２は炭素数１～８の炭化水素基を、ａは０、１又は２を示す。）で表される反応性アルコキシシリル化合物であることが好ましい。
<Silane coupling agent (B) having an isocyanato group>
The silane coupling agent (B) has a general formula (1): X1-Si (R1) a (OR2) 3-a (in the formula (1), X1 is an isocyanato group and R1 has 1 to 8 carbon atoms. A hydrocarbon group is preferably used, R2 is a hydrocarbon group having 1 to 8 carbon atoms, and a is a reactive alkoxysilyl compound represented by 0, 1 or 2).
シランカップリング剤（Ｂ）としては、３－イソシアナトプロピルトリメトキシシラン、３－イソシアナトプロピルトリエトキシシラン、３－イソシアナトプロピルメチルジメトキシシラン、３－イソシアナトプロピルメチルジエトキシシラン及びこれら化合物の三量体（イソシアヌレート）等が挙げられる。 Examples of the silane coupling agent (B) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and compounds thereof. Examples thereof include a trimer (isocyanurate).
シランカップリング剤（Ｂ）の市販品としては、ＫＢＥ－９００７Ｎ（３－イソシアナトプロピルトリエトキシシラン、信越化学社製）、Ｘ－１２－１１５９（化学構造式不明、信越化学社製）、ＫＢＭ－９６５９（トリス（トリメトキシシリルプロピル）イソシアヌレート、信越化学社製）、ＳＩＬＱＵＥＳＴ Ｓｉｌａｎｅ Ａ－１３１０（３－イソシアナトプロピルトリエトキシシラン、ＭＯＭＥＮＴＩＶＥ社製）、及び、同 Ｙ－５１８７（３－イソシアナトプロピルトリメトキシシラン、ＭＯＭＥＮＴＩＶＥ社製）等が挙げられる。 Commercially available products of the silane coupling agent (B) include KBE-9007N (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), X-12-1159 (chemical structural formula unknown, manufactured by Shin-Etsu Chemical Co., Ltd.), KBM. -9659 (Tris (trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.), SILQUEST Silane A-1310 (3-isosianatopropyltriethoxysilane, manufactured by MOMENTIVE), and Y-5187 (3-isosianato). Propyltrimethoxysilane, manufactured by MOMENTIVE) and the like.
シランカップリング剤（Ｂ）は、硬度及び耐擦傷性、並びに、金属薄膜との密着性の両方の観点から、活性エネルギー線硬化性ハードコート剤の不揮発分１００部中、５～３０部含むことが好ましく、７～２５部含むことがより好ましく、８～１５部含むことがさらに好ましい。 The silane coupling agent (B) contains 5 to 30 parts of the non-volatile content of the active energy ray-curable hardcoat agent from the viewpoints of both hardness and scratch resistance and adhesion to a metal thin film. It is more preferable to contain 7 to 25 parts, and even more preferably 8 to 15 parts.
本発明のハードコート剤は、上記以外に、化合物（ａ０）、イソシアナト基有さないシランカップリング剤やシラン化合物、及びその縮合物、並びに、後述するその他添加剤を含有してもよい。 In addition to the above, the hard coat agent of the present invention may contain a compound (a0), a silane coupling agent or a silane compound having no isocyanato group, a condensate thereof, and other additives described later.
化合物（ａ０）としては、例えば、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（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、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート及びビスフェノールＡのエチレンオキサイド変性ジ（メタ）アクリレート等のジ（メタ）アクリレート類、ポリウレタンポリ（メタ）アクリレート及びポリエステルポリ（メタ）アクリレート等のオリゴマー、並びに２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロペンタニル（メタ）アクリレート、シクロヘキシル（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、及びイソボニル（メタ）アクリレート等のモノ（メタ）アクリレート類が挙げられるが、これらに限定されない。 Examples of the compound (a0) include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and diethylene glycol di (meth). Di (meth) acrylates such as acrylates, neopentyl glycol di (meth) acrylates and ethylene oxide-modified di (meth) acrylates of bisphenol A, oligomers such as polyurethane poly (meth) acrylates and polyester poly (meth) acrylates, and 2 -Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, benzyl (meth) acrylate, cyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobonyl ( Examples include, but are not limited to, mono (meth) acrylates such as meta) acrylates.
＜光重合開始剤（Ｃ）＞
光重合開始剤（Ｃ）としては、例えば、モノカルボニル系光重合開始剤、ジカルボニル系光重合開始剤、アセトフェノン系光重合開始剤、ベンゾインエーテル系光重合開始剤、アシルホスフィンオキシド系光重合開始剤、アミノカルボニル系光重合開始剤が使用できる。
<Photopolymerization initiator (C)>
Examples of the photopolymerization initiator (C) include a monocarbonyl-based photopolymerization initiator, a dicarbonyl-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, a benzoin ether-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator. Agents and aminocarbonyl-based photopolymerization initiators can be used.
例えば、ベンゾフェノン、４－メチルベンゾフェノン、２,４,６－トリメチルベンゾフェノン、メチル－ｏ－ベンゾイルベンゾエート、４－フェニルベンゾフェノン、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、２－／４－イソ－プロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、及び１－クロロ－４－プロポキシチオキサントン等のモノカルボニル系光重合開始剤；
２－エチルアントラキノン、９，１０－フェナントレンキノン、及びメチル－α－オキソベンゼンアセテート等のジカルボニル系光重合開始剤；
２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシ－シクロヘキシルフェニルケトン、ジエトキシアセトフェノン、ジブトキシアセトフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２，２－ジエトキシ－１，２－ジフェニルエタン－１－オン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタン－１－オン、及び１－フェニル－１，２－プロパンジオン－２－（ｏ－エトキシカルボニル）オキシム等のアセトフェノン系光重合開始剤；
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイゾブチルエーテル、及びベンゾインノルマルブチルエーテル等のベンゾインエーテル系光重合開始剤；
２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド、及び４－ｎ－プロピルフェニル－ジ（２，６－ジクロロベンゾイル）ホスフィンオキシド等のアシルホスフィンオキシド系光重合開始剤；
並びに、エチル－４－（ジメチルアミノ）ベンゾエート、２－ｎ－ブトキシエチル－４－（ジメチルアミノ）ベンゾエート、イソアミル－４－（ジメチルアミノ）ベンゾエート、２－（ジメチルアミノ）エチルベンゾエート、４，４´－ビス－４－ジメチルアミノベンゾフェノン、４，４´－ビス－４－ジエチルアミノベンゾフェノン、及び２，５´－ビス（４－ジエチルアミノベンザル）シクロペンタノン等のアミノカルボニル系光重合開始剤；
等が挙げられる。
For example, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Monocarbonyl photopolymerization initiators such as 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone;
Dicarbonyl-based photopolymerization initiators such as 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzeneacetate;
2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexylphenylketone , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[ 4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, and 1-phenyl-1,2-propane Acetphenone-based photopolymerization initiator such as dione-2- (o-ethoxycarbonyl) oxime;
Benzoin ether-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether;
Acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide;
In addition, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, 4,4' -Aminocarbonyl-based photopolymerization initiators such as bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis (4-diethylaminobenzal) cyclopentanone;
And so on.
光重合開始剤（Ｃ）の市販品としては、ＩＧＭ－Ｒｅｓｉｎｓ Ｂ．Ｖ．社製のＯｍｎｉｒａｄ１８４、６５１、５００、９０７、１２７、３６９、７８４、２９５９、エサキュアワン、ＢＡＳＦ（株）社製ルシリンＴＰＯ等が挙げられる。 特に、活性エネルギー線硬化後の耐黄変の観点で、Ｏｍｎｉｒａｄ１８４やエサキュアワンが好ましい。 As a commercially available product of the photopolymerization initiator (C), IGM-Resins B.I. V. Examples thereof include Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, Esacure One, and Lucillin TPO manufactured by BASF Corporation. In particular, Omnirad 184 and Esacure One are preferable from the viewpoint of yellowing resistance after curing with active energy rays.
光重合開始剤（Ｃ）は、２種類以上を混合して用い併用してもよい。また、増感剤と併用してもよい。 Two or more kinds of the photopolymerization initiator (C) may be mixed and used together. It may also be used in combination with a sensitizer.
光重合開始剤（Ｃ）の含有量は、硬化速度、並びに、硬度及び耐擦傷性の両方の観点から、活性エネルギー線硬化性ハードコート剤の不揮発分１００部中、１～１５部含むことが好ましく、３～１０部含むことがより好ましい。 The content of the photopolymerization initiator (C) may be 1 to 15 parts out of 100 parts of the non-volatile content of the active energy ray-curable hard coat agent from the viewpoints of curing speed, hardness and scratch resistance. It is preferable to include 3 to 10 parts, and more preferably.
本発明のハードコート剤は、有機溶剤（Ｄ）を含んでも良い。使用される有機溶剤としては、トルエン、キシレンといった芳香族系有機溶剤、メチルエチルケトン、メチルイソブチルケトンといったケトン系有機溶剤、酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸イソブチル、エステル系有機溶剤、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、などのアルコール系有機溶剤、プロピレングリコールモノメチルエーテル等のグリコエーテル系有機溶剤など公知の有機溶剤を使用できる。特にグリコールエーテル系有機溶剤を含むことが好ましい。 The hard coat agent of the present invention may contain an organic solvent (D). Examples of the organic solvent used include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, ester organic solvents and methanol. Known organic solvents such as alcohol-based organic solvents such as ethanol, n-propanol, isopropanol and n-butanol, and glycoether-based organic solvents such as propylene glycol monomethyl ether can be used. In particular, it is preferable to contain a glycol ether-based organic solvent.
有機溶剤（Ｄ）を含む場合の有機溶剤（Ｄ）の含有量は、塗工性及び成膜性の観点から、本発明のハードコート剤の不揮発分濃度が１～６０％となる範囲であることが好ましい。 The content of the organic solvent (D) when the organic solvent (D) is contained is in the range in which the non-volatile content concentration of the hard coat agent of the present invention is 1 to 60% from the viewpoint of coatability and film forming property. Is preferable.
本発明のハードコート剤には、さらに様々な添加剤を含有してもよい。添加剤としては、熱硬化性樹脂、重合禁止剤、レベリング剤、スリップ剤、消泡剤、界面活性剤、抗菌剤、アンチブロッキング剤、可塑剤、紫外線吸収剤、赤外線吸収剤、酸化防止剤、シランカップリング剤、導電剤、無機充填剤、顔料、染料等が挙げられる。 The hard coat agent of the present invention may further contain various additives. Additives include thermosetting resins, polymerization inhibitors, leveling agents, slip agents, defoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, UV absorbers, infrared absorbers, antioxidants, etc. Examples thereof include silane coupling agents, conductive agents, inorganic fillers, pigments, dyes and the like.
＜積層体＞
本発明の積層体は、基材の表面に、本発明のハードコート剤より形成されたハードコート層が積層されたものである。また、本発明の積層体は、ハードコート層上に、更に金属薄膜が積層されていてもよい。
<Laminated body>
The laminate of the present invention is obtained by laminating a hard coat layer formed from the hard coat agent of the present invention on the surface of a base material. Further, in the laminated body of the present invention, a metal thin film may be further laminated on the hard coat layer.
基材（支持体とも言う）としては、特に限定はなく、ガラス、合成樹脂成型物、フィルムなどが挙げられる。合成樹脂成型物としては、ポリメチルメタクリレート樹脂、メチルメタクリレートを主成分とする共重合体樹脂、ポリスチレン樹脂、スチレン－メチルメタクリレート共重合体樹脂、スチレン－アクリロニトリル共重合体樹脂、ポリカーボネート樹脂、セルロースアセテートブチレート樹脂、ポリアリルジグリコールカーボネート樹脂、ポリ塩化ビニル樹脂、ポリエステル樹脂等の合成樹脂の成型物が挙げられる。 The base material (also referred to as a support) is not particularly limited, and examples thereof include glass, synthetic resin molded products, and films. Examples of the synthetic resin molded product include polymethylmethacrylate resin, copolymer resin containing methylmethacrylate as a main component, polystyrene resin, styrene-methylmethacrylate copolymer resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, and cellulose acetate buty. Examples thereof include moldings of synthetic resins such as rate resins, polyallyl diglycol carbonate resins, polyvinyl chloride resins, and polyester resins.
また、フィルムとしては、例えば、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファンフィルム、ジアセチルセルロースフィルム、トリアセチルセルロース（ＴＡＣ）フィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレンビニルアルコールフィルム、ポリオレフィンフィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテルフィルム、ポリスルフォンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルフォンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ナイロンフィルム、アクリルフィルム等が挙げられる。 Examples of the film include polyester film, polyethylene film, polypropylene film, cellophane film, diacetyl cellulose film, triacetyl cellulose (TAC) film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, and polyvinyl alcohol. Film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethylpentel film, polysulphon film, polyether ether ketone film, polyether sulfone film, polyetherimide film, polyimide film, fluororesin film, nylon film , Acrylic film and the like.
ハードコート層の厚みは、特に限定されないが、通常０．１～５μｍ程度である。 The thickness of the hard coat layer is not particularly limited, but is usually about 0.1 to 5 μm.
金属薄膜としては、例えば、金属蒸着膜、金属スパッタ膜及び金属ＣＶＤ膜が挙げられる。本発明の積層体を電極フィルムに供する場合には、金属薄膜としては、特に金属蒸着膜又は金属スパッタ膜であることが好ましい金属薄膜層の厚みは、特に限定されないが、通常、０．１～２μｍ程度である。金属薄膜を構成する金属としては、銅、アルミニウム、銀等が挙げられるが、これらに限らない。 Examples of the metal thin film include a metal vapor deposition film, a metal sputter film, and a metal CVD film. When the laminate of the present invention is applied to an electrode film, the thickness of the metal thin film layer, which is preferably a metal vapor deposition film or a metal sputter film, is not particularly limited, but is usually 0.1 to 1. It is about 2 μm. Examples of the metal constituting the metal thin film include, but are not limited to, copper, aluminum, silver and the like.
本発明の積層体の製造方法は、特に限定されない。例えば、（１）基材の表面（基材が例えばフィルム状のものであれば片面又は両面）に本発明のハードコート剤を塗布し、（２）該基材に熱を加えた後、（３）更に活性エネルギー線を照射することにより硬化させてハードコート層を形成する工程を経て製造することができる。更に必要に応じて、（４）ハードコート層上に金属薄膜を形成する工程を経て製造する態様が挙げられる。 The method for producing the laminate of the present invention is not particularly limited. For example, (1) the hard coat agent of the present invention is applied to the surface of the base material (for example, one side or both sides if the base material is in the form of a film), and (2) heat is applied to the base material, and then (2) 3) It can be manufactured through a step of further irradiating it with active energy rays to cure it to form a hard coat layer. Further, if necessary, an embodiment of (4) manufacturing through a step of forming a metal thin film on the hard coat layer can be mentioned.
工程（１）に関し、基材の表面（基材が例えばフィルム状のものであれば片面又は両面）にハードコート剤を塗布する条件は、特に限定されず、塗布手段としては、例えば、スプレー、ロールコーター、リバースロールコーター、グラビアコーター、ナイフコーター、バーコーター及びドットコーター等が挙げられる。また、塗工量も特に限定されないが、通常、乾燥不揮発分として０．０１～１０ｇ／ｍ2程度である。 Regarding the step (1), the conditions for applying the hard coat agent to the surface of the base material (for example, one side or both sides if the base material is in the form of a film) are not particularly limited, and the coating means includes, for example, a spray. Examples thereof include a roll coater, a reverse roll coater, a gravure coater, a knife coater, a bar coater and a dot coater. The amount of coating is not particularly limited, but is usually about 0.01 to 10 g / m 2 as the dry non-volatile content.
工程（２）に関し、該基材に熱を加える際の条件も特に限定されないが、通常、温度８０～１５０℃程度で、時間が１０秒～２分程度である。 Regarding the step (2), the conditions for applying heat to the substrate are not particularly limited, but usually, the temperature is about 80 to 150 ° C. and the time is about 10 seconds to 2 minutes.
工程（３）に関し、活性エネルギー線を照射する際の条件も特に限定されない。活性エネルギー線としては、例えば紫外線や電子線が挙げられる。紫外線の供給源としては例えば高圧水銀灯やメタルハライドランプ等が挙げられ、その照射エネルギーは通常１００～２，０００ｍＪ／ｃｍ2程度である。電子線の供給方式としては例えばスキャン式電子線照射、カーテン式電子線照射法等が挙げられ、その照射エネルギーは通常１０～２００ｋＧｙ程度である。 Regarding the step (3), the conditions for irradiating the active energy rays are not particularly limited. Examples of the active energy ray include ultraviolet rays and electron beams. Examples of the source of ultraviolet rays include high-pressure mercury lamps and metal halide lamps, and the irradiation energy thereof is usually about 100 to 2,000 mJ / cm 2 . Examples of the electron beam supply method include a scan type electron beam irradiation method, a curtain type electron beam irradiation method, and the like, and the irradiation energy thereof is usually about 10 to 200 kGy.
工程（４）に関し、ハードコート層に金属薄膜を形成する手段は特に限定されないが、ドライコート法が好ましい。具体的には、例えば、真空蒸着法又はスパッタリング法等の物理的方法や、ＣＶＤ等の化学的方法（化学的気相反応等）が挙げられる。 Regarding the step (4), the means for forming the metal thin film on the hard coat layer is not particularly limited, but the dry coat method is preferable. Specific examples thereof include a physical method such as a vacuum vapor deposition method or a sputtering method, and a chemical method such as CVD (chemical vapor phase reaction or the like).
該導電性フィルムの製法は特に限定されないが、これを電極フィルムとして使用する場合には、前記金属蒸着プラスチックフィルム又は金属スパッタフィルムに各種レジストを塗布し、電極パターンを描写した後でエッチング液（アルカリ溶液）に浸漬し、レジストを除去する方法が挙げられる。電極パターンの形状は細線状、ドット状、メッシュ状及び面状等、如何なる形態であってよい。 The method for producing the conductive film is not particularly limited, but when it is used as an electrode film, various resists are applied to the metal vapor-deposited plastic film or the metal sputter film, an electrode pattern is drawn, and then an etching solution (alkali) is used. A method of immersing in a solution) to remove the resist can be mentioned. The shape of the electrode pattern may be any shape such as a fine line shape, a dot shape, a mesh shape, and a surface shape.
本発明のハードコート層は、電波の屈折や反射による透過損失の抑制および高速伝送による信号ロス低減の観点から、周波数１ＧＨｚ、２３℃における比誘電率は３．２以下であることが好ましく、３以下であることがより好ましい。また、誘電正接は０．０２以下であることが好ましく、０．０１以下であることがより好ましい。 The hard coat layer of the present invention preferably has a relative permittivity of 3.2 or less at a frequency of 1 GHz and 23 ° C. from the viewpoint of suppressing transmission loss due to refraction and reflection of radio waves and reducing signal loss due to high-speed transmission. The following is more preferable. The dielectric loss tangent is preferably 0.02 or less, more preferably 0.01 or less.
以下、実施例及び比較例により、本発明をさらに具体的に説明するが、以下の実施例は、本発明の技術的範囲を何ら制限するものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples do not limit the technical scope of the present invention in any way.
＜アクリルコポリマーの製造（比較例）＞
比較製造例１
撹拌機、温度計、還流冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ヒドロキシエチルアクリレート（ＨＥＡ）４０．８部（１３．６モル％）、（メチルメタアクリレート（ＭＭＡ）７２．０部（２７．７モル％）、ブチルアクリレート（ＢＡ）７９．２部（２３．８モル％）、アクリロニトリル（ＡＮ）４８．０部（約３４．９モル％）、酢酸エチル４４５．７部を仕込み、反応系を７０℃に設定した。次いで、２、２’―アゾビス（２、４―ジメチルバレロニトリル）（ＡＢＮ―Ｖ）１．２部を仕込み、７０℃付近で６時間保温した。次いで、ＡＢＮ―Ｖ ２．４部を仕込み、反応系を同温度付近において更に６時間保温した。その後反応系を室温まで冷却することにより、ガラス転移温度が１３℃及び水酸基価が８０ｍｇＫＯＨ／ｇ、不揮発分３５．０％のアクリルコポリマーの溶液を得た。
<Manufacturing of acrylic copolymer (comparative example)>
Comparative manufacturing example 1
In a reaction vessel equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel and nitrogen introduction tube, 40.8 parts (13.6 mol%) of hydroxyethyl acrylate (HEA), (methyl methacrylate (MMA) 72. 0 parts (27.7 mol%), 79.2 parts (23.8 mol%) of butyl acrylate (BA), 48.0 parts (about 34.9 mol%) of acrylonitrile (AN), 445.7 parts of ethyl acetate. The reaction system was set to 70 ° C. Then, 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (ABN-V) was charged and kept warm at around 70 ° C. for 6 hours. Next, 2.4 parts of ABN-V was charged, and the reaction system was kept warm at the same temperature for another 6 hours. Then, by cooling the reaction system to room temperature, the glass transition temperature was 13 ° C. and the hydroxyl value was 80 mgKOH / g. A solution of acrylic copolymer having a non-volatile content of 35.0% was obtained.
＜ハードコート剤の調製＞
実施例１
アロニックス Ｍ－４０３（東亞合成社製）９０部、ＫＢＥ－９００７Ｎ（３－イソシアナトプロピルトリエトキシシラン、信越化学社製）１０部、及びエサキュアワン（ＤＫＳＨジャパン（株）社製）５部をよく混合し、有機溶剤としてプロピレングリコールモノメチルエーテルを不揮発分濃度４０％となるように調整してハードコート剤を得た。
<Preparation of hard coat agent>
Example 1
Mix 90 parts of Aronix M-403 (manufactured by Toagosei Co., Ltd.), 10 parts of KBE-9007N (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), and 5 parts of Esacure One (manufactured by DKSH Japan Co., Ltd.). Then, propylene glycol monomethyl ether was adjusted as an organic solvent so as to have a non-volatile content concentration of 40% to obtain a hard coat agent.
実施例２～１１、比較例１～５
各成分を表１に示す組成（不揮発分換算）で配合したこと以外は、実施例１と同様にして、不揮発分濃度４０％のハードコート剤をそれぞれ得た。表１中の数値は、特に断りのない限り「部」を表し、空欄は配合していないことを意味する。
Examples 2 to 11 and Comparative Examples 1 to 5
A hard coat agent having a non-volatile content concentration of 40% was obtained in the same manner as in Example 1 except that each component was blended in the composition shown in Table 1 (non-volatile content conversion). The numerical values in Table 1 represent "parts" unless otherwise specified, and blanks mean that they are not mixed.
表１に示す各材料の詳細は、以下のとおりである。
＜化合物（Ａ）＞
・アロニックスＭ－４０３（ジペンタエリスリトールヘキサアクリレート（官能基数：６個）：４０～５０％とジペンタエリスリトールペンタアクリレート（官能基数：５個）：５０～６０％の混合物；東亞合成社製）
＜化合物（ａ１）＞
・Ｍｉｒａｍｅｒ ＰＵ６１０（ウレタンアクリレート、重量平均分子量：１８００、官能基数：６個、ＭＩＷＯＮ社製）
・Ｍｉｒａｍｅｒ ＭＵ９８００（ウレタンアクリレート、重量平均分子量：３５００、官能基：９個、ＭＩＷＯＮ社製）
＜化合物（ａ２）＞
・アロニックス Ｍ－３１５（イソシアヌル酸エチレンオキサイド変性トリアクリレート、官能基数：３個、東亞合成社製）
The details of each material shown in Table 1 are as follows.
<Compound (A)>
-Aronix M-403 (dipentaerythritol hexaacrylate (number of functional groups: 6): 40 to 50% and dipentaerythritol pentaacrylate (number of functional groups: 5): 50 to 60% mixture; manufactured by Toagosei Co., Ltd.)
<Compound (a1)>
-Miramer PU610 (urethane acrylate, weight average molecular weight: 1800, number of functional groups: 6, manufactured by MIWON)
-Miramer MU9800 (urethane acrylate, weight average molecular weight: 3500, functional group: 9, manufactured by MIWON)
<Compound (a2)>
・ Aronix M-315 (Isocyanuric acid ethylene oxide-modified triacrylate, number of functional groups: 3, manufactured by Toagosei Co., Ltd.)
＜イソシアナト基を有するシランカップリング剤（Ｂ）＞
・ＫＢＥ－９００７Ｎ（３－イソシアナトプロピルトリエトキシシラン、信越化学工業社製）
・ＫＢＭ－９６５９（トリス（トリメトキシシリルプロピル）イソシアヌレート、信越化学工業社社製）
・ＳＩＬＱＵＥＳＴ Ｓｉｌａｎｅ Ｙ－５１８７（３－イソシアナトプロピルトリメトキシシラン、ＭＯＭＥＮＴＩＶＥ社製）
＜光重合開始剤（Ｃ）＞
・Ｅｓａｃｕｒｅ Ｏｎｅ（エサキュアワン、アセトフェノン系光重合開始剤 ＤＫＳＨジャパン（株）社製）
<Silane coupling agent (B) having an isocyanato group>
KBE-9007N (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-9569 (Tris (trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.)
-SILQUEST Silane Y-5187 (3-isocyanatopropyltrimethoxysilane, manufactured by MOMENTIVE)
<Photopolymerization initiator (C)>
・ Esacure One (Esacure One, acetophenone-based photopolymerization initiator DKSH Japan Co., Ltd.)
＜その他＞
＜（メタ）アクリロイル基を２個有する化合物（ａ０）＞
・ＮＫエステル Ａ－ＤＣＰ（トリシクロデカンジメタノールジアクリレート、分子量：３０４、アクリロイル基数：２個、新中村化学工業社製）
＜アクリロイル基を有するシランカップリング剤（ｂ０）＞
・ＫＢＭ－５１０３（３－アクリロイルオキシプロピルトリメトキシシラン、信越化学工業社製）
＜アクリルポリオール（比較製造例１）＞
・アクリルポリオール（製造例１で合成したガラス転移温度が１３℃及び水酸基価が８０ｍｇＫＯＨ／ｇ、不揮発分３５．０％のアクリルコポリマーの溶液）
＜アルミナ粒子分散体＞
・ＮＡＮＯＢＹＫ３６１０（アルミナ粒子メトキシプロピレンアセテート分散体、不揮発分濃度：３７％、ビックケミージャパン社製）
<Others>
<Compound (a0) having two (meth) acryloyl groups>
NK ester A-DCP (tricyclodecanedimethanol diacrylate, molecular weight: 304, acryloyl radix: 2, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
<Silane coupling agent having an acryloyl group (b0)>
KBM-5103 (3-acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
<Acrylic Polyol (Comparative Production Example 1)>
Acrylic polyol (a solution of an acrylic copolymer having a glass transition temperature of 13 ° C., a hydroxyl value of 80 mgKOH / g, and a non-volatile content of 35.0% synthesized in Production Example 1).
<Alumina particle dispersion>
NANOBYK3610 (alumina particles methoxypropylene acetate dispersion, non-volatile content concentration: 37%, manufactured by Big Chemie Japan)
≪ハードコート層及び積層体の作製≫
実施例および比較例で得られたハードコート剤を、それぞれ５０μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルム（東レ(株)社製「ルミラーＵ４０３」）上に、バーコーターを用いて、乾燥後の膜厚が１．０μｍになるように塗工した後、高圧水銀ランプで５００ｍＪ／ｃｍ2の紫外線を照射し、ハードコート層を形成し、積層体を作製した。
≪Preparation of hard coat layer and laminate≫
The hard coat agents obtained in Examples and Comparative Examples are placed on a polyethylene terephthalate (PET) film (“Lumilar U403” manufactured by Toray Industries, Inc.) having a thickness of 50 μm, respectively, using a bar coater to obtain a film thickness after drying. After coating to 1.0 μm, a high-pressure mercury lamp was used to irradiate ultraviolet rays of 500 mJ / cm 2 to form a hard coat layer to prepare a laminated body.
≪鉛筆硬度≫
上記作製した積層体について、ＪＩＳ Ｋ５６００－５－４に準じ、各種硬度の鉛筆を４５゜の角度で積層体のハードコート層の表面にあて、荷重をかけて引っ掻き試験を行い、傷がつかない最も硬い鉛筆の硬さを鉛筆硬度とした。
≪Pencil hardness≫
For the above-mentioned laminated body, in accordance with JIS K5600-5-4, a pencil of various hardness is applied to the surface of the hard coat layer of the laminated body at an angle of 45 °, and a scratch test is performed by applying a load to prevent scratches. The hardness of the hardest pencil was defined as the pencil hardness.
≪ヘイズ値の測定≫
上記作製した積層体について、日本電色工業社製「ヘイズメーターＳＨ７０００」によりハードコート層表面のヘイズ値（ＨＺ）を測定した。
・最良：１．０％未満
・良 ：１．０以上２．０％未満
・不良：２．０％以上
≪Measurement of haze value≫
The haze value (HZ) on the surface of the hard coat layer was measured with the "haze meter SH7000" manufactured by Nippon Denshoku Kogyo Co., Ltd. for the above-mentioned laminated body.
・ Best: less than 1.0% ・ Good: 1.0 or more and less than 2.0% ・ Defective: 2.0% or more
≪耐擦傷性≫
上記作成した積層体について、テスター産業社製「学振型摩擦堅牢度試験機」により耐擦傷性を評価した。荷重２００ｇを取り付けた摩擦子（表面積１ｃｍ2）にスチールウール＃００００を取り付け、ハードコート層の表面（１ｃｍ×１５ｃｍ）を１０往復させた。その後、ハードコート層の表面のキズの本数を数え、下記基準で評価した。
・３：傷なし（０本）
・２：傷１本以上１０本以下
・１：傷１１本以上
≪Scratch resistance≫
The scratch resistance of the above-mentioned laminated body was evaluated by a "Gakushin type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. Steel wool # 0000 was attached to a friction element (surface area 1 cm 2 ) to which a load of 200 g was attached, and the surface of the hard coat layer (1 cm × 15 cm) was reciprocated 10 times. Then, the number of scratches on the surface of the hard coat layer was counted and evaluated according to the following criteria.
・ 3: No scratches (0)
・ 2: 1 to 10 scratches ・ 1: 11 or more scratches
≪銅密着性≫
上記作成した積層体のハードコート層上に、真空デバイス社製「マグトロンスパッタＭＳＰ－３０Ｔ」により銅を厚さ３００ｎｍ、５００ｎｍ、及び１μｍになるようにスパッタリングして銅薄膜を形成した。銅薄膜とアンダーハードコート層との密着性は、銅薄膜に１ｍｍの間隔で碁盤目状にカッターで傷を付け、１００マスの格子パターンを形成した後、碁盤目状の傷全体を覆うようにセロハンテープを付着させ、引きはがし、銅薄膜の剥離状態を目視で観察し、以下の基準で評価した。
・５：傷の線の周囲が完全に滑らかで、どの格子にも剥がれがない。
・４：傷の交点周囲に銅薄膜の小さな剥がれが観察されるが、剥がれた面積の合計は碁盤目の５％未満。
・３：傷の縁方向に沿って銅薄膜が剥がれたり、傷の交差点で銅薄膜が剥がれたりしており、剥がれた面積の合計が碁盤目の５％以上１５％未満。
・２：剥がれた面積の合計が碁盤目の１５％以上３５％未満。
・１：剥がれた面積の合計が碁盤目の３５％以上８０％未満。
・０：剥がれた面積の合計が碁盤目の８０％以上であり、碁盤目状の傷の外部にも剥がれが観察される。
≪Copper adhesion≫
A copper thin film was formed on the hardcourt layer of the above-mentioned laminated body by sputtering copper to a thickness of 300 nm, 500 nm, and 1 μm by “Magtron Sputter MSP-30T” manufactured by Vacuum Device Co., Ltd. The adhesion between the copper thin film and the underhard coat layer is such that the copper thin film is scratched in a grid pattern at 1 mm intervals to form a grid pattern of 100 squares, and then the entire grid pattern is covered. The cellophane tape was attached, peeled off, and the peeled state of the copper thin film was visually observed and evaluated according to the following criteria.
・ 5: The circumference of the scratch line is completely smooth, and there is no peeling on any grid.
・ 4: Small peeling of the copper thin film is observed around the intersection of the scratches, but the total peeled area is less than 5% of the grid.
-3: The copper thin film is peeled off along the edge direction of the scratch, or the copper thin film is peeled off at the intersection of the scratches, and the total peeled area is 5% or more and less than 15% of the grid.
・ 2: The total peeled area is 15% or more and less than 35% of the grid.
-1: The total peeled area is 35% or more and less than 80% of the grid.
0: The total peeled area is 80% or more of the grid, and peeling is also observed outside the grid-shaped scratches.
≪耐アルカリ性≫
銅密着性評価をしていない銅薄膜（厚み３００ｎｍ）を有する積層体を、４０℃に加温した５％水酸化ナトリウム水溶液に５分間浸漬した後に十分に水で洗浄し、次いで１００℃に加温したオーブン内で１５分乾燥させて水分を除去した後に、上記と同様に銅密着性を評価した。
≪Alkali resistance≫
A laminate having a copper thin film (thickness 300 nm) that has not been evaluated for copper adhesion is immersed in a 5% sodium hydroxide aqueous solution heated to 40 ° C. for 5 minutes, thoroughly washed with water, and then heated to 100 ° C. After drying in a warm oven for 15 minutes to remove water, the copper adhesion was evaluated in the same manner as above.
≪比誘電率及び誘電正接の測定≫
実施例及び比較例のハードコート剤を市販のポリエステルフィルム（商品名「ルミラーＵ４８」、東レ（株）製、１００μｍ厚）に、乾燥膜厚が８０μｍ程度となるようバーコーターで塗工し、１２０℃で１分間乾燥させた。次いで３００ｍＪ／ｃｍ2でＵＶ硬化させることによって、測定用塗膜（積層体）を得た。得られた測定用塗膜を幅３ｍｍ×長さ１００ｍｍの大きさに切り取り、測定用試験片とした。得られた測定用試験片を、日本電子回路工業会の「フレキシブルプリント配線板およびフレキシブルプリント配線板用材料－その２統合規格－（ＪＰＣＡ－ＤＧ０３）に準拠して、以下の手順で比誘電率及び誘電正接を測定した。エー・イー・ティー社製の比誘電率測定装置「ＡＤＭＳ０１Ｏｃ」に、試験片を３つセットし、空洞共振器法により、測定温度２３℃、測定周波数が１ＧＨｚにおける比誘電率および誘電正接を求めた。結果を表１に示す。
≪Measurement of relative permittivity and dielectric loss tangent≫
The hard coat agents of Examples and Comparative Examples were applied to a commercially available polyester film (trade name "Lumilar U48", manufactured by Toray Industries, Inc., 100 μm thickness) with a bar coater so that the dry film thickness was about 80 μm, and 120 It was dried at ° C for 1 minute. Then, it was UV-cured at 300 mJ / cm 2 to obtain a coating film (laminated body) for measurement. The obtained coating film for measurement was cut into a size of 3 mm in width × 100 mm in length and used as a test piece for measurement. The obtained measurement test piece is subjected to the relative permittivity according to the following procedure in accordance with "Flexible Printed Wiring Board and Material for Flexible Printed Wiring Board-Part 2 Integrated Standard- (JPCA-DG03)" of the Japan Electronic Circuit Industry Association. And the dielectric loss tangent was measured. Three test pieces were set in the relative permittivity measuring device "ADMS01Oc" manufactured by AET Co., Ltd., and the ratio at a measurement temperature of 23 ° C. and a measurement frequency of 1 GHz by the cavity resonator method. The permittivity and the dielectric loss tangent were determined. The results are shown in Table 1.
表１に示す通り、本発明のハードコート剤を用いた場合、高い透明性と硬度を有し、耐擦傷性、耐アルカリ性、金属薄膜との密着性に優れたハードコート層を形成できることが明らかとなった。 As shown in Table 1, it is clear that when the hard coat agent of the present invention is used, a hard coat layer having high transparency and hardness, and excellent scratch resistance, alkali resistance, and adhesion to a metal thin film can be formed. It became.
Claims (8)
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| JP2020211044A JP6979559B1 (en) | 2020-12-21 | 2020-12-21 | Active energy ray-curable hard coat agent, hard coat layer and laminate |
| PCT/JP2021/044546 WO2022138082A1 (en) | 2020-12-21 | 2021-12-03 | Active-energy-curable hard coat agent, hard coat layer, and laminate |
| CN202180074368.0A CN116406391A (en) | 2020-12-21 | 2021-12-03 | Active energy ray-curable hard coating agent, hard coating layer, and laminate |
| KR1020237011420A KR20230060537A (en) | 2020-12-21 | 2021-12-03 | Active energy ray-curable hard coat agent, hard coat layer and laminate |
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| JP6979559B1 (en) | 2021-12-15 |
| CN116406391A (en) | 2023-07-07 |
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