WO2016017799A1 - 光硬化性組成物、及び積層フィルム - Google Patents
光硬化性組成物、及び積層フィルム Download PDFInfo
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- WO2016017799A1 WO2016017799A1 PCT/JP2015/071794 JP2015071794W WO2016017799A1 WO 2016017799 A1 WO2016017799 A1 WO 2016017799A1 JP 2015071794 W JP2015071794 W JP 2015071794W WO 2016017799 A1 WO2016017799 A1 WO 2016017799A1
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- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- SOLZAPJHTKXTOR-UHFFFAOYSA-N cyclohexane;methanol;prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.OC(=O)C=C.C1CCCCC1 SOLZAPJHTKXTOR-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- RJLZSKYNYLYCNY-UHFFFAOYSA-N ethyl carbamate;isocyanic acid Chemical group N=C=O.CCOC(N)=O RJLZSKYNYLYCNY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PWGIEBRSWMQVCO-UHFFFAOYSA-N phosphono prop-2-enoate Chemical compound OP(O)(=O)OC(=O)C=C PWGIEBRSWMQVCO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 238000004439 roughness measurement Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- OWOMRZKBDFBMHP-UHFFFAOYSA-N zinc antimony(3+) oxygen(2-) Chemical compound [O--].[Zn++].[Sb+3] OWOMRZKBDFBMHP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—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
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
Definitions
- the present invention relates to a photocurable composition particularly suitable for a protective coating layer laminated on at least one surface of a base film made of a cyclic olefin resin, and a laminated film.
- a cyclic olefin resin film excellent in high transparency, low hygroscopicity, and refractive index stability has been used as a base film material for an electrode film for a touch panel (see, for example, Patent Document 1).
- a cyclic olefin-based resin film is preferable in terms of characteristics such as transparency and hygroscopicity, but it cannot be said to have sufficient flexibility. Further, since the surface hardness is relatively low, the scratch resistance is low and the surface is easily scratched. For this reason, providing a hard-coat layer in the cyclic olefin resin film is performed.
- the present invention has been proposed in view of such a conventional situation, and provides a photocurable composition and a laminated film capable of obtaining excellent flexibility.
- the present inventor uses an urethane (meth) acrylate oligomer containing a polyether-based urethane (meth) acrylate oligomer, and adds an oligomer elongation when the urethane (meth) acrylate oligomer is photopolymerized. It has been found that a laminated film having excellent flexibility can be obtained by setting the average value to a predetermined value or more.
- the photocurable composition according to the present invention is a urethane (meth) acrylate containing a tri- or higher-functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a polyether-based urethane (meth) acrylate oligomer. It contains an oligomer and a photopolymerization initiator, and the additive average value of the oligomer elongation at a thickness of 80 ⁇ m when the urethane (meth) acrylate oligomer is photopolymerized is 80% or more.
- the laminated film according to the present invention includes a base film made of a cyclic olefin resin, and a protective coat layer formed on at least one surface of the base film, and the protective coat layer has a trifunctional or higher functionality
- multilayer film based on this invention is a urethane (meth) acrylate containing the (meth) acrylate monomer more than trifunctional, a bifunctional (meth) acrylate monomer, and a polyether-type urethane (meth) acrylate oligomer.
- a urethane (meth) acrylate oligomer containing a polyether-based urethane (meth) acrylate oligomer is used, and an additive average value of the oligomer elongation when the urethane (meth) acrylate oligomer is photopolymerized is a predetermined value or more.
- FIG. 1 is a cross-sectional view showing an example of a laminated film.
- FIG. 2 is a cross-sectional view showing an example of a laminated film for a touch panel.
- FIG. 3 is a cross-sectional view showing an example of a laminated film for a touch panel.
- the photocurable composition according to the present embodiment includes a trifunctional or higher functional (meth) acrylate monomer (component (A)), a bifunctional (meth) acrylate monomer (component (B)), and a polyether urethane.
- the additive average value of the oligomer elongation at a thickness of 80 ⁇ m when polymerized is 80% or more.
- (meth) acrylate is meant to include acrylic acid ester (acrylate) and methacrylic acid ester (methacrylate).
- Component (A) Trifunctional or higher functional (meth) acrylate monomer
- a component (A) is for improving the adhesiveness with cyclic olefin resin, and the reactivity of photocurable composition itself.
- Such a component (A) is a polymerizable compound having 3 or more acrylate residues or methacrylate residues (hereinafter referred to as (meth) acrylate residues) in the molecule, and is used in the field of adhesives and the like.
- a tri- or more functional (meth) acrylate monomer can be appropriately selected and used.
- component (A) examples include pentaerythritol triacrylate (PETA), 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-converted triacrylate, ⁇ -caprolactone modified tris-(-2 acryloxy) Ethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), ⁇ -caprolactone modified tris (acryloxyethyl) acrylate, ethoxylated (20) trimethylolpropane triacrylate, propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) Trimethylolpropane triacrylate, ethoxylated (9) Trimethylolpropane triacrylate, propoxylated (3) glyceryl triacrylate, ethoxylated (4) penta Examples include erythritol tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolprop
- pentaerythritol triacrylate can be preferably used in terms of adhesion, reactivity, crosslinkability, surface hardness, and the like.
- Specific examples available on the market include the product name “M305” of Toagosei Co., Ltd. and the product name “TMM-3L” of Shin-Nakamura Chemical Co., Ltd.
- the content of the component (A) in the photocurable composition is too small, properties such as adhesion, reactivity, crosslinkability, and surface hardness tend to deteriorate, and if too large, properties such as flexibility and curl. Therefore, the content is preferably 5 to 50% by mass, more preferably 15 to 40% by mass.
- Component (B): Bifunctional (meth) acrylate monomer A component (B) is for improving the adhesiveness with cyclic olefin resin, and the reactivity of photocurable composition itself similarly to the (meth) acrylate monomer more than trifunctional.
- Such component (B) is a polymerizable compound having two acrylate residues or methacrylate residues (hereinafter referred to as (meth) acrylate residues) in the molecule, and is used in the field of adhesives 2 It can be used by appropriately selecting from functional (meth) acrylate monomers.
- component (B) include dimethylol-tricyclodecane diacrylate, bisphenol AEO-modified diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, propoxylated bisphenol A diacrylate, tri Cyclodecane dimethanol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) diacrylate, cyclohexane di Methanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexanedimethanol diacrylate Ethoxylated (4) bisphenol A diacrylate, ethoxylated (10) bisphenol A diacrylate, polyethylene glycol (600) diacrylate, alkoxylated neopenty
- dimethylol-licyclodecane diacrylate can be preferably used from the viewpoints of adhesion, reactivity, crosslinkability, surface hardness, and the like.
- Specific examples available on the market include Kyoeisha Chemical Co., Ltd. trade name “DCP-A”.
- the content of the component (B) in the photocurable composition is too small, properties such as adhesion, reactivity, crosslinkability, and surface hardness tend to deteriorate, and if too large, properties such as flexibility and curl. Therefore, the content is preferably 5 to 50% by mass, more preferably 5 to 15% by mass.
- Component (C) Urethane (meth) acrylate oligomer
- Component (C) is a urethane (meth) acrylate oligomer containing at least a polyether-based urethane (meth) acrylate oligomer, and more preferably contains two or more polyether-based urethane (meth) acrylate oligomers.
- polyether urethane (meth) acrylate oligomers By including two or more kinds of polyether urethane (meth) acrylate oligomers, excellent scratch resistance can be obtained.
- the polyether-based urethane (meth) acrylate oligomer is a compound having a unit derived from a polyether polyol compound, a polymerizable (meth) acryloyl group, and a urethane bond in the molecule.
- the polyether-based urethane (meth) acrylate oligomer is, for example, a (meth) acrylate having a hydroxyl group in a terminal isocyanate urethane prepolymer obtained by reacting a polyether polyol compound (X) and a polyvalent isocyanate compound (Y). Obtained by reacting (Z).
- the polyether polyol compound (X) can be obtained, for example, by addition polymerization of alkylene oxide using a polyhydric alcohol as an initiator.
- Specific examples of the polyether polyol compound (X) include, for example, polytetramethylene glycol (“PTMG”), polypropylene glycol (“PPG”), polyhydric alcohols such as polyethylene glycol (“PEG”), ethylene oxide, Examples thereof include copolymers with alkylene oxides such as propylene oxide.
- Examples of the polyvalent isocyanate compound (Y) include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate ( Modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone Diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane H6XDI), and the like.
- TDI tolylene diis
- Examples of the (meth) acrylate (Z) having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth).
- Acryloyl phosphate 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) ) Acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, and the like.
- polyether urethane (meth) acrylate oligomers available on the market include Nippon Synthetic Chemical Industry's trade names “UT5490”, “UT5467”, “UT5489”, “UT5522”, “UT5523”, “UT5495”, “UT5496”, “UT5497”, “UT5506” and the like can be mentioned.
- a caprolactone-based urethane (meth) acrylate oligomer using caprolactone diol a polycarbonate-based urethane (meth) acrylate oligomer using polycarbonate diol instead of polyester glycol, and the like can be given.
- the additive average value of the degree of oligomer growth of the component (C) is 80% or more. Thereby, it becomes possible to obtain the excellent flexibility of the laminated film.
- Additivity average value of the degree of oligomer growth of an ingredient (C) can be defined by a following formula.
- Additive average value (%) of oligomer elongation of component (C) ⁇ [(oligomer elongation (%)) ⁇ (ratio (%) in component (C)) / 100]
- the oligomer elongation (breaking elongation) of the polyether-based urethane (meth) acrylate oligomer of component (C) is preferably 5 to 300%. Moreover, when a component (C) contains 2 or more types of polyether type urethane (meth) acrylate oligomers, it is preferable that at least 1 type of oligomer elongation is 200% or more.
- the oligomer elongation is determined by drying a composition obtained by blending 100 parts by mass of component (C) and 3 parts by mass of 2-hydroxy-2-cyclohexylacetophenone as a photopolymerization initiator with a bar coater.
- the content of the component (C) in the photocurable composition is too small, the flexibility tends to deteriorate, and if it is too large, the scratch resistance tends to deteriorate, preferably 40 to 80% by mass, More preferably, it is 55 to 70% by mass.
- Component (D): Photopolymerization initiator As component (D), it can select from a well-known radical photopolymerization initiator suitably, and can use it. Examples of the component (D) include acetophenone photopolymerization initiators, benzyl ketal photopolymerization initiators, phosphorus photopolymerization initiators, and the like, and one or more of these can be used.
- component (D) available on the market include 2-hydroxy-2-cyclohexylacetophenone (IRGACURE 184, manufactured by BASF Japan), ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone (DAROCUR 1173, manufactured by BASF Japan), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651, manufactured by BASF Japan), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (DAROCUR 2959, manufactured by BASF Japan), 2-hydroxy-1- ⁇ 4- [2-hydroxy-2-methyl-propionyl] -benzyl ⁇ phenyl ⁇ -2 -Methyl group Pan-1-one (IRGACURE (IRGACURE) 127, manufactured by BASF Japan Ltd.) and the like.
- DAROCUR 1173 2,2-dimethoxy-2-phenylacetophenone
- DAROCUR 2959 manufactured by BASF Japan
- benzyl ketal photopolymerization initiators examples include benzophenone, fluorenone, dibenzosuberone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 4-hydroxybenzophenone, 4-chlorobenzophenone, 4,4′-dichlorobenzophenone, etc. Is mentioned.
- phosphorous photopolymerization initiators bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819, manufactured by BASF Japan), (2,4,6-trimethylbenzoyl-diphenylphosphine) And oxide (DAROCURE TPO, manufactured by BASF Japan Ltd.), etc.
- acetophenone-based photopolymerization initiator from the viewpoint of realizing smooth photocuring.
- the content of the component (D) in the photocurable composition is too small, there is a tendency that the adhesiveness is decreased due to the decrease in hardness performance or the hardness is insufficient. Since it tends to decrease, the content is preferably 0.5 to 25% by mass, more preferably 1 to 10% by mass.
- the photocurable composition preferably further contains inorganic fine particles (component (E)) as necessary.
- component (E) inorganic fine particles
- Component (E) includes fine metal oxide particles such as silicon oxide (silica), aluminum oxide, and zirconium oxide.
- the surface treatment is performed with a coupling agent or the like, and in particular, the surface treatment is performed with a silane coupling agent having an alkyl group or a (meth) acryloyl group in order to improve the affinity and binding property with the binder component. It is preferable that
- component (E) available on the market include trade names manufactured by CIK Nanotech Co., Ltd .: M23, H83, E83, M06, M44, H94, M18, E65, H58, K26, Nissan Chemical Industries, Ltd.
- Product names methanol silica sol, MEK-ST (silica sol dispersed in methyl ethyl ketone), IPA-ST (silica sol dispersed in isopropyl alcohol), and the like.
- the component (E) is preferably an aggregate having an average particle size of 10 nm to 50 nm.
- the average particle diameter of the component (E) is an image of visual observation or image from a secondary electron emission image photograph obtained by scanning electron microscope (SEM) or the like in the case of an aggregate of primary particles. It can be obtained by processing or measuring with a particle size distribution meter using a dynamic light scattering method, a static light scattering method or the like.
- the average particle diameter here refers to the number average particle diameter.
- a particle when a particle is not spherical, it means the diameter of a circle corresponding to the projected area.
- the content of the component (E) in the photocurable composition is preferably 7 to 15% by mass.
- the content is preferably 9 to 13% by mass.
- the photocurable composition contains additives such as a solvent, a leveling agent, a hue adjusting agent, a colorant, an ultraviolet absorber, an antistatic agent, and various thermoplastic resin materials as long as the effects of the present invention are not impaired.
- additives such as a solvent, a leveling agent, a hue adjusting agent, a colorant, an ultraviolet absorber, an antistatic agent, and various thermoplastic resin materials as long as the effects of the present invention are not impaired. can do.
- the antistatic agent for example, conductive carbon, inorganic fine particles, inorganic fine powder, surfactant, ionic liquid and the like can be used. These antistatic agents may be used alone or in combination of two or more.
- the material of the inorganic fine particles and the inorganic fine powder include a material mainly composed of a conductive metal oxide.
- the conductive metal oxide for example, tin oxide, indium oxide, ATO (antimony-doped tin oxide), ITO (indium-doped t
- the photocurable composition is produced by uniformly mixing the above-described components (A) to (D), and further, if necessary, the component (E) and various additives according to a conventional method.
- the photocurable composition described above has a breaking elongation at a thickness of 80 ⁇ m when photopolymerized, of 15% or more, more preferably 35% or more. Further, the breaking elongation is preferably 60% or less. Thereby, excellent flexibility and scratch resistance can be obtained. Further, the Martens hardness at a thickness of 80 ⁇ m when photopolymerized is preferably 100 N / mm 2 or more. The higher the Martens hardness, the better the scratch resistance.
- Such a photocurable composition is particularly useful as a composition of a protective coat layer formed on at least one surface of a base film made of a cyclic olefin resin, and in the flexibility test, the protective coat layer and the cyclic olefin The occurrence of cracks on the surface of the resin film can be suppressed. Moreover, since it is excellent also in abrasion resistance, it can utilize preferably for a touchscreen use.
- the laminated film according to the present embodiment includes a base film made of a cyclic olefin-based resin and a protective coat layer formed on at least one surface of the base film, and the protective coat layer is a trifunctional or higher functional (meta).
- the photocurable composition is a photopolymerization.
- FIG. 1 is a cross-sectional view showing an example of a laminated film.
- the laminated film 13 has a structure in which protective coating layers 12 are laminated on both surfaces of the base film 11.
- the base film 11 is formed by forming a cyclic olefin resin into a sheet shape.
- a resin (COP) having a cycloolefin as a monomer and having an alicyclic structure obtained by ring-opening metathesis polymerization of a cyclic olefin (for example, norbornenes) and subsequent hydrogenation reaction examples thereof include a resin (COC) obtained by addition polymerization of a cyclic olefin (for example, norbornenes) and an ⁇ -olefin (for example, ethylene).
- COP include polytetracyclododecene identified by the trade name “ZEONOR” of Nippon Zeon Co., Ltd.
- COC include ethylene norbornene copolymer identified by the trade name “TOPAS” of TOPAS Advanced Polymers, and ethylene tetracyclododecene identified by the trade name “APEL” of Mitsui Chemicals, Inc. -Methacrylic acid ester copolymer, etc. can be mentioned.
- a retardation function may be imparted to the film made of these cyclic olefin resins by a known method.
- the thickness of the base film 11 varies depending on the type and performance of the optical device to which it is applied, but is usually 25 to 200 ⁇ m, preferably 40 to 150 ⁇ m. Further, the elongation at break of the base film 11 at a thickness of 80 ⁇ m is usually 20% or less regardless of the MD direction and the TD direction, that is, regardless of the in-plane direction of the film.
- the protective coat layer 12 is obtained by photopolymerizing the photocurable composition described above.
- the thickness of the protective coat layer 12 is usually 0.5 to 8 ⁇ m, preferably 0.8 to 7 ⁇ m.
- the protective coat layer 12 may be laminated only on one side of the base film 11.
- FIG. 2 and 3 are sectional views showing an example of a laminated film for a touch panel.
- a laminated film for touch panel 15 ⁇ / b> A shown in FIG. 2 has a protective coating layer 12 formed on both surfaces of a substrate film 11, and a known transparent electrode 14 such as ITO is formed on the surface of the protective coating layer 12.
- a known transparent electrode 14 such as ITO is formed on the surface of the protective coating layer 12.
- an optical adjustment layer 16 such as a known retardation film is formed between the protective coat layer 12 and the transparent electrode 14.
- a transparent electrode using an ITO film, conductive fine particles, nanowire-shaped material, or the like on at least one surface of the laminated film as described above, it can be preferably used as a laminated film for a touch panel. Furthermore, by laminating such a laminated film for a touch panel on an image display element such as a liquid crystal display element or an organic EL display element, it can be preferably applied as an image display / input device for a smart phone or a personal computer.
- the method for producing a laminated film according to the present embodiment includes a trifunctional or higher functional (meth) acrylate monomer (component (A)), a bifunctional (meth) acrylate monomer (component (B)), and a polyether urethane.
- a photocurable composition containing inorganic fine particles (component (E)) is used according to a conventional method using a stirrer such as a disper. Mix and adjust evenly.
- This photo-curable composition is preferably not only having translucency, but also having a hue that does not significantly change the hue of transmitted light and the amount of transmitted light due to coloring and haze.
- the solvent is not particularly limited as long as it sufficiently dissolves the resin raw material to be used, and a known organic solvent can be used.
- the organic solvent include ketone solvents such as MEK, MIBK, and ANON; alcohol solvents such as IPA, n-BuOH, and t-BuOH; ester solvents such as butyl acetate and ethyl acetate, and glycol ether solvents. Can be mentioned.
- a surface treatment by an oxidation method or an uneven method for the purpose of improving the adhesion between the substrate film and the cured product layer made of the photocurable composition, one or both surfaces of the substrate film are subjected to a surface treatment by an oxidation method or an uneven method.
- the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
- the photocurable composition prepared as described above is applied onto the base film.
- the coating method is not particularly limited, and a known method can be used.
- Known coating methods include, for example, micro gravure coating method, wire bar coating method, direct gravure coating method, die coating method, dip method, spray coating method, reverse roll coating method, curtain coating method, comma coating method, knife coating method. And spin coating method.
- Drying conditions are not particularly limited, and may be natural drying or artificial drying that adjusts drying humidity, drying time, and the like.
- energy rays such as gamma rays, alpha rays, and electron beams can be applied in addition to ultraviolet rays.
- it can manufacture according to the manufacturing method of this laminated film also about the manufacturing method of the laminated film for touch panels.
- First Example> In the first embodiment, a tri- or higher functional (meth) acrylate monomer (component (A)), a bifunctional (meth) acrylate monomer (component (B)), and a urethane (meth) acrylate oligomer (component (C )) And a photopolymerization initiator (component (D)) were prepared. And the breaking elongation and Martens hardness of the cured film which photopolymerized the photocurable composition were measured. Moreover, the cured layer which consists of a photocurable composition was formed in both surfaces of the base film, the laminated film was produced, and the high-speed flexibility of the laminated film and the scratch resistance were evaluated. The present invention is not limited to these examples.
- Measurement of elongation at break, measurement of Martens hardness, production of laminated film, evaluation of high-speed flexibility of laminated film, and evaluation of scratch resistance of laminated film were performed as follows.
- each of the components (A) to (C) was measured in the same manner.
- the photocurable composition After applying the photocurable composition to the peeled PET film with a bar coater, the photocurable composition was photopolymerized under irradiation conditions of 300 mJ / cm 2 to obtain a cured film having a thickness of 80 ⁇ m.
- the opposite side of the measurement surface of the cured film (test piece: 70 mm ⁇ 20 mm) was fixed to the slide glass with Aron Alpha manufactured by Toagosei Co., Ltd.
- the surface hardness was measured with a Vickers indenter so that an arbitrary place on the measurement surface was selected and the maximum indentation depth was 10% or less of the average thickness of the cured film.
- the measurement was performed using a Martens hardness meter (HM500, Fisher Instruments Co., Ltd.). Practically, the Martens hardness of the cured film is desired to be 100 N / mm 2 or more. In order to minimize the influence of the adhesive for fixing, it is preferable to apply the adhesive as thinly as possible.
- HM500 Martens hardness meter
- a 75 ⁇ m-thick cyclic olefin resin film subjected to corona treatment a film obtained by dispersing about 10% of a styrene-based elastomer in a COC resin with respect to the resin component, and the elongation at break is MD The direction and TD direction were less than 6%).
- coating a photocurable composition on both surfaces of this base film it photopolymerized on the irradiation conditions of 300 mJ / cm ⁇ 2 >, respectively, formed the protective coating layer on both surfaces of the base film, and obtained the laminated
- a laminated film (test piece: 100 mm x 50 mm) is attached to a scratch tester (product name: Gakushin type friction fastness tester, Tester Sangyo Co., Ltd.), a load of 250 g is added to # 0000 steel wool, and the hardened layer surface was scratched 20 times (10 reciprocations), and the presence or absence of scratches was visually observed. A case where no scratch was observed was evaluated as “good”, and a case where a scratch was observed was evaluated as “bad”.
- a laminated film (test piece: 100 mm ⁇ 50 mm) is attached to a scratch tester (product name: Gakushin type friction fastness tester, Tester Sangyo Co., Ltd.), a load of 250 g is applied to an alcohol swab, and the surface of the hardened layer is applied.
- the scratch test was performed 20 times (10 reciprocations), and the presence or absence of scratches was visually observed. A case where no scratch was observed was evaluated as “good”, and a case where a scratch was observed was evaluated as “bad”.
- component (A) 24.3 wt%
- component (B) 9.7 wt%
- component (C1) (UT5467) 19.4 wt%
- component (C2) (UT5490) 43.6 wt%
- the photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 2 As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 25.0 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 38.0 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.4%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 3 As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 13.0 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 50.0 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.3%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 4 As shown in Table 1, the same components as in Example 1 were used, and component (A) 20.8 wt%, component (B) 8.3 wt%, component (C1) (UT5467) 20.9 wt%, component (C2 ) (UT5490) 47.0 wt% and component (D) were uniformly mixed at a solute component concentration of 3.0 wt% to prepare a photocurable composition, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 49%, and the Martens hardness of the cured film was 118 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 5 As shown in Table 1, the same components as in Example 1 were used, and component (A) 27.7 wt%, component (B) 11.1 wt%, component (C1) (UT5467) 17.9 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 40.3 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.9%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 39%, and the Martens hardness of the cured film was 119 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 6 As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 8.0 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 55.0 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 219.4%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 61%, and the Martens hardness of the cured film was 94 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of scratch resistance by steel wool of the laminated film was x, and the evaluation of scratch resistance by alcohol swab of the laminated film was x.
- Example 7 As shown in Table 1, the same components as in Example 1 were used, and component (A) 17.3 wt%, component (B) 6.9 wt%, component (C1) (UT5467) 22.4 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 50.4 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 56%, and the Martens hardness of the cured film was 95 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of scratch resistance by steel wool of the laminated film was x, and the evaluation of scratch resistance by alcohol swab of the laminated film was x.
- Example 8 As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 29.1 wt%, component (C2 ) (UT5490) 33.9 wt% and component (D) A photocurable composition was prepared by mixing uniformly at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 138.7%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 31%, and the Martens hardness of the cured film was 140 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 8, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 9 As shown in Table 1, the same components as in Example 1 were used, and component (A) 31.2 wt%, component (B) 12.5 wt%, component (C1) (UT5467) 16.4 wt%, component (C2 ) (UT5490) 36.9 wt% and component (D) 3.0 wt% solute component concentration was uniformly mixed to prepare a photocurable composition, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 34%, and the Martens hardness of the cured film was 134 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 7, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- ⁇ 4-2 Relationship between Additive Average Value of Oligomer Elongation of Component (C) and High-Speed Flexibility 2>
- the type of the component (C) was changed, and the relationship between the additive average value of the oligomer elongation of the component (C) and the high-speed flexibility was verified.
- a component (C1) a polyether urethane oligomer (UT5467, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and an oligomer elongation of 9%.
- Ether-based urethane oligomer (UT5490, manufactured by Nippon Synthetic Chemical Co., Ltd.), component (C3), polyether-based urethane oligomer (UT5489, manufactured by Nippon Synthetic Chemical Co., Ltd.), component having 6 functional groups and 34% oligomer elongation
- C4 a polyether urethane oligomer (UT5506, Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and 39% oligomer elongation was used.
- the same components as in Example 1 were used.
- Example 10 As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C1) (UT5467) 19.0 wt%, component (C2) (UT5490) 44.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 177.3%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 11 As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C1) (UT5467) 33.0 wt%, component (C2) (UT5490) 30.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 123.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 20%, and the Martens hardness of the cured film was 150 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 8, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 12 As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C1) (UT5467) 33.0 wt%, component (C2) (UT5490) 30.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 85.5%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 15%, and the Martens hardness of the cured film was 160 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 7, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 13 As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C3) (UT5489) 19.0 wt%, component (C2) (UT5490) 44.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 184.9%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 51%, and the Martens hardness of the cured film was 100 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 14 As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C2) (UT5490) 44.0 wt%, component (C4) (UT5506) 19.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 186.4%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 55%, and the Martens hardness of the cured film was 95 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was x, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 15 As shown in Table 2, component (A) 29.0 wt%, component (B) 12.0 wt%, component (C1) (UT5467) 20.0 wt%, component (C2) (UT5490) 36.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 163.9%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 30%, and the Martens hardness of the cured film was 140 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 8, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- component (C1) a polyether urethane oligomer (UT5467, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and an oligomer elongation of 9%
- component (C2) a component having 2 functional groups and an oligomer elongation of 250.
- Polyether urethane oligomer (UT5490, manufactured by Nippon Synthetic Chemical Co., Ltd.) As component (C3), polyether urethane oligomer (UT5489, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 6 functional groups and an oligomer elongation of 34% ), Polyether urethane oligomer (UT5522, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 5 functional groups and 72% oligomer elongation as component (C4), 4 functional groups and 110% oligomer elongation as component (C5) Polyether urethane oligomer (UT5523, manufactured by Nippon Synthetic Chemical Co., Ltd.), component (C6), functional group 10.
- component (C3) polyether urethane oligomer having 6 functional groups and an oligomer elongation of 34% ), Polyether urethane oligomer (UT5522, manufactured by Nippon Synthetic Chemical Co., Ltd.) having
- Polyether urethane oligomer (UT5595, manufactured by Nippon Synthetic Chemical Co., Ltd.) having an oligomer elongation of 16%, and a polyether urethane oligomer (UT5596, Japan) having 10 functional groups and 13% oligomer elongation.
- a polyether urethane oligomer (UT5597, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and an oligomer elongation of 50%
- a component (C9) A polyether urethane oligomer (UT5506, manufactured by Nippon Synthetic Chemical Co., Ltd.) having a group number of 10 and an oligomer elongation of 39% was used.
- the same components as in Example 1 were used.
- Comparative Example 1 As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C3) (UT5489) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 26.3%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 11%, and the Martens hardness of the cured film was 214 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- the breaking elongation of the cured film was 14%, and the Martens hardness of the cured film was 199 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 4, the evaluation of the abrasion resistance of the laminated film with steel wool was ⁇ , and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was x.
- the breaking elongation of the cured film was 18%, and the Martens hardness of the cured film was 183 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 5, the evaluation of the abrasion resistance of the laminated film with steel wool was ⁇ , and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was x.
- the breaking elongation of the cured film was 10%, and the Martens hardness of the cured film was 222 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 0, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Comparative Example 5 As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C7) (UT5596) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 11.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 10%, and the Martens hardness of the cured film was 223 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 0, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- component (A) 24.3 wt%
- component (B) 9.7 wt%
- component (C1) (UT5467) 19.4 wt%
- component (C8) (UT5597) 43.6 wt%
- the photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 37.4%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 12%, and the Martens hardness of the cured film was 208 N / mm 2 . Further, the number of good times of the high-speed flexibility of the laminated film was 1, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was x.
- the breaking elongation of the cured film was 11%, and the Martens hardness of the cured film was 212 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Comparative Example 8 As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C4) (UT5522) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 72.0%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 17%, and the Martens hardness of the cured film was 187 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 4, the evaluation of the abrasion resistance of the laminated film with steel wool was ⁇ , and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was x.
- Example 16 As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C5) (UT5523) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 110.0%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 24%, and the Martens hardness of the cured film was 164 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 7, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was x.
- Example 17 As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C2) (UT5590) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 250.0%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 86%, and the Martens hardness of the cured film was 82 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was x.
- Comparative Example 9 As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C8) (UT5523) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 50.0%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 14%, and the Martens hardness of the cured film was 200 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 6, the evaluation of scratch resistance by steel wool of the laminated film was ⁇ , and the evaluation of scratch resistance by alcohol swab of the laminated film was x.
- component (B1) tricyclodecane dimethanol diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.), as component (B2), isocyanuric acid EO-converted diacrylate (M215, manufactured by Toagosei Co., Ltd.), component (CO1) is a caprolactone-based urethane oligomer (UT5236) with 9 functional groups and an oligomer elongation of 35%, and the component (CO2) is a urethane acrylate oligomer (UV7605, Nippon Synthetic Chemical) with 6 functional groups and an oligomer elongation of 0.8%.
- DCP-A tricyclodecane dimethanol diacrylate
- component (B2) isocyanuric acid EO-converted diacrylate
- component (CO1) is a caprolactone-based urethane oligomer (UT5236) with 9 functional groups and an oligomer elongation of 35%
- component (D1) 2-hydroxy-1- ⁇ 4- [2-hydroxy-2-methyl-propionyl] -benzyl ⁇ phenyl ⁇ -2-methyl-propan-1-one (Irgacure ( IRGACURE) 127, manufactured by BASF Japan Ltd.) and 2-Hydro as component (D2) Shi-2-cyclohexyl-acetophenone was used (IRGACURE (IRGACURE) 184, manufactured by BASF Japan Ltd.). Other than these, the same components as in Example 1 were used.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 6, the evaluation of the abrasion resistance of the laminated film with steel wool was x, and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was ⁇ .
- the breaking elongation of the cured film was 35%, and the Martens hardness of the cured film was 118 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 5, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- the component (A) is 9.7 wt%
- the component (B2) is 29.1 wt%
- the component (CO1) is 58.2 wt%
- the component (D1) is 3.0 wt% and the solute component concentration is uniform.
- a photocurable composition was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 35.0%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 20%, and the Martens hardness of the cured film was 160 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 4, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- the component (A) is 9.7 wt%
- the component (B2) is 38.8 wt%
- the component (CO1) is 48.5 wt%
- the component (D1) is 3.0 wt% and the solute component concentration is uniform.
- a photocurable composition was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 35.0%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 15%, and the Martens hardness of the cured film was 180 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- the component (A) is 9.7 wt%
- the component (B2) is 48.5 wt%
- the component (CO1) is 38.8 wt%
- the component (D1) is 3.0 wt% and the solute component concentration is uniform.
- a photocurable composition was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 35.0%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 13%, and the Martens hardness of the cured film was 194 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 1, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- component (A) 9.7 wt%, component (B2) 29.1 wt%, component (CO1) 19.4 wt%, component (CO2) 38.8 wt%, and component (D1) 3
- a photocurable composition was prepared by uniformly mixing at a solute component concentration of 0.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 12.2%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 5%, and the Martens hardness of the cured film was 206 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 0, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- component (A) 9.7 wt%, component (B2) 29.1 wt%, component (CO1) 29.1 wt%, component (CO2) 29.1 wt%, and component (D1) 3
- a photocurable composition was prepared by uniformly mixing at a solute component concentration of 0.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 17.9%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 7%, and the Martens hardness of the cured film was 194 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 1, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- component (A) 9.7 wt%, component (B2) 29.1 wt%, component (CO1) 38.8 wt%, component (CO2) 19.4 wt%, and component (D1) 3
- a photocurable composition was prepared by uniformly mixing at a solute component concentration of 0.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared.
- Additivity average value of the degree of oligomer growth of an ingredient (C) was 23.6%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 10%, and the Martens hardness of the cured film was 182 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- component (D) 2-hydroxy-1- ⁇ 4- [2-hydroxy-2-methyl-propionyl] -benzyl ⁇ phenyl ⁇ -2-methyl-propan-1-one (IRGACURE 127, BASF Japan 2-hydroxy-2-cyclohexylacetophenone (IRGACURE 184, manufactured by BASF Japan) was used as the component (D2).
- component (D1) 2-hydroxy-1- ⁇ 4- [2-hydroxy-2-methyl-propionyl] -benzyl ⁇ phenyl ⁇ -2-methyl-propan-1-one
- IRGACURE 127 BASF Japan 2-hydroxy-2-cyclohexylacetophenone
- Example 1 the same components as in Example 1 were used.
- Example 18 As shown in Table 5, component (A) 24.5 wt%, component (B) 9.8 wt%, component (C1) (UT5467) 19.6 wt%, component (C2) (UT5490) 44.1 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D1) at a solute component concentration of 2.0 wt% to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was x, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 19 As shown in Table 5, component (A) 24.0 wt%, component (B) 9.6 wt%, component (C1) (UT5467) 19.2 wt%, component (C2) (UT5490) 43.2 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D1) at a solute component concentration of 4.0 wt% to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 20 As shown in Table 5, component (A) 23.8 wt%, component (B) 9.5 wt%, component (C1) (UT5467) 19.0 wt%, component (C2) (UT5490) 42.8 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D1) at a solute component concentration of 5.0 wt% to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 21 As shown in Table 5, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C2) (UT5490) 43.6 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D2) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was x, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 22 As shown in Table 6, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 23 As shown in Table 6, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 24 As shown in Table 6, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 4 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- Example 25 As shown in Table 6, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 5 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . In addition, the number of good high-speed flexibility of the laminated film was 8, the evaluation of scratch resistance by steel wool of the laminated film was x, and the evaluation of scratch resistance by alcohol swab of the laminated film was ⁇ .
- Second Embodiment> a photocurable composition containing inorganic fine particles (component (E)) in addition to the components (A) to (D) was prepared.
- component (E) inorganic fine particles
- the elongation at break and Martens hardness of the cured film obtained by photopolymerization of the photocurable composition were measured.
- the cured layer which consists of a photocurable composition was formed in both surfaces of the base film, the laminated film was produced, and the high-speed flexibility of the laminated film and the scratch resistance were evaluated.
- the adhesiveness and anti-blocking function of the laminated film were evaluated, and the surface roughness and haze of the laminated film were measured.
- the present invention is not limited to these examples.
- Adhesion evaluation, anti-blocking function evaluation, surface roughness measurement, and haze measurement were performed as follows.
- the blocking performance value of the laminated film was measured. That is, the laminated film in which the surfaces of the protective coat layers were adhered to each other was cut into a strip shape, a load (g) was applied to an adhesion area of 4 cm 2 (2 cm ⁇ 2 cm), and the appearance state was defined as a blocking performance value.
- the surface roughness of the protective coating layer of the laminated film was measured using AFM (SPA400, manufactured by Hitachi High-Tech Science Co., Ltd.).
- Example 1 As shown in Table 7, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C2) (UT5490) 43.7 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.5 nm, and haze was 0.23%.
- Example 26 As shown in Table 7, component (E) was added to the component of Example 1, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%.
- a photo-curable composition was prepared by uniformly mixing the components (C2) (UT5490) 40.6 wt%, the component (D) 2.8 wt%, and the component (E) 7.0 wt%. Then, a cured film having a thickness of 80 ⁇ m was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 2.0 nm, and haze was 0.23%.
- Example 27 As shown in Table 7, the component (E) was added to the component of Example 1, the component (A) 22.1 wt%, the component (B) 8.8 wt%, the component (C1) (UT5467) 17.7 wt%.
- a photocurable composition was prepared by uniformly mixing the components (C2) (UT5490) 39.6 wt%, the component (D) 2.7 wt%, and the component (E) 9.0 wt% solute component concentrations. Then, a cured film having a thickness of 80 ⁇ m was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.3 nm, and haze was 0.23%.
- Example 28 As shown in Table 7, the component (E) was added to the component of Example 1, the component (A) 21.6 wt%, the component (B) 8.6 wt%, the component (C1) (UT5467) 17.3 wt%.
- a photo-curable composition was prepared by uniformly mixing the components (C2) (UT5490) 38.8 wt%, the component (D) 2.7 wt%, and the component (E) 11.0 wt%. Then, a cured film having a thickness of 80 ⁇ m was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.7%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 4.6 nm, and haze was 0.24%.
- Example 29 As shown in Table 7, component (E) was added to the component of Example 1, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt% A photo-curable composition was prepared by uniformly mixing the components (C2) (UT5490) 38.0 wt%, the component (D) 2.6 wt%, and the component (E) 13.0 wt%. Then, a cured film having a thickness of 80 ⁇ m was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 6.0 nm, and the haze was 0.25%.
- Example 30 As shown in Table 7, the component (E) was added to the component of Example 1, the component (A) 20.6 wt%, the component (B) 8.2 wt%, the component (C1) (UT5467) 16.5 wt%.
- a photocurable composition was prepared by uniformly mixing the components (C2) (UT5490) 37.1 wt%, the component (D) 2.6 wt%, and the component (E) 15.0 wt%. Then, a cured film having a thickness of 80 ⁇ m was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 8.0 nm, and the haze was 0.36%.
- Example 31 As shown in Table 7, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 29 to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 6.5 nm
- the haze was 0.25%.
- Example 32 As shown in Table 7, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 29 to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 2.0 nm
- the haze was 0.25%.
- Example 26 to Example 30 it was found that an excellent antiblocking function can be obtained by adding the component (E) in the range of 9.0 wt% to 15.0 wt%. Moreover, from Examples 29, 31, and 32, it was found that an excellent antiblocking function can be obtained when the thickness of the protective coating layer is 1 ⁇ m or more and 3 ⁇ m or less.
- Example 2 Addition of component (E) to Example 2> [Example 2] As shown in Table 8, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 25.0 wt%, component (C2) (UT5490) 38.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.4%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.5 nm, and haze was 0.23%.
- Example 33 As shown in Table 8, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 23.3 wt%, component (C2) (UT5490) 35.3 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.2%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.8 nm, and haze was 0.23%.
- Example 34 As shown in Table 8, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 22.8 wt%, component (C2) (UT5490) 34.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.1%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.3 nm, and haze was 0.23%.
- Example 35 As shown in Table 8, component (A) 21.6 wt%, component (B) 8.6 wt%, component (C1) (UT5467) 22.3 wt%, component (C2) (UT5490) 33.8 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 11.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.2%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 4.6 nm, and haze was 0.24%.
- Example 36 As shown in Table 8, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 21.8 wt%, component (C2) (UT5490) 33.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.3%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 6.0 nm, and the haze was 0.25%.
- Example 37 As shown in Table 8, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 21.3 wt%, component (C2) (UT5490) 32.3 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.2%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 35%, and the Martens hardness of the cured film was 128 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 8.0 nm, and the haze was 0.36%.
- Example 38 As shown in Table 8, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 26, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.3%. Further, a protective coating layer having a thickness of 1 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the anti-blocking function was ⁇
- the surface roughness was 6.4 nm
- the haze was 0.25%.
- Example 39 As shown in Table 8, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 26, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.3%. Further, a protective coating layer having a thickness of 3 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 2.0 nm
- the haze was 0.25%.
- Example 2 Even when the component (E) is added to Example 2, the component (E) is added in the range of 9.0 wt% to 15.0 wt% in the same manner as when the component (E) is added to Example 1. Thus, it was found that an excellent anti-blocking function can be obtained. It was also found that an excellent antiblocking function can be obtained when the thickness of the protective coating layer is 1 ⁇ m or more and 3 ⁇ m or less.
- Example 3 Addition of component (E) to Example 3> [Example 3] As shown in Table 9, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 13.0 wt%, component (C2) (UT5490) 50.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.3%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ .
- evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.5 nm, and haze was 0.23%.
- Example 40 As shown in Table 9, component (A) 22.6 wt%, component (B) 9.1 wt%, component (C1) (UT5467) 12.1 wt%, component (C2) (UT5490) 46.4 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.2%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 2.3 nm, and haze was 0.23%.
- Example 41 As shown in Table 9, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 11.8 wt%, component (C2) (UT5490) 45.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.3 nm, and haze was 0.23%.
- Example 42 As shown in Table 9, component (A) 21.6 wt%, component (B) 8.6 wt%, component (C1) (UT5467) 11.6 wt%, component (C2) (UT5490) 44.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 11.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.2%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 4.6 nm, and haze was 0.24%.
- Example 43 As shown in Table 9, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 11.3 wt%, component (C2) (UT5490) 43.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 6.0 nm, and the haze was 0.25%.
- Example 44 As shown in Table 9, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 11.1 wt%, component (C2) (UT5490) 42.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.1%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 48%, and the Martens hardness of the cured film was 110 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 8.0 nm, and the haze was 0.36%.
- Example 45 As shown in Table 9, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 33 to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. Further, a protective coating layer having a thickness of 1 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the anti-blocking function was ⁇
- the surface roughness was 6.4 nm
- the haze was 0.25%.
- Example 46 As shown in Table 9, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 33 to prepare a cured film having a thickness of 80 ⁇ m. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. Further, a protective coating layer having a thickness of 3 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 2.0 nm
- the haze was 0.25%.
- Example 3 Even when the component (E) is added to Example 3, the component (E) is added in the range of 9.0 wt% to 15.0 wt% in the same manner as when the component (E) is added to Example 1. Thus, it was found that an excellent anti-blocking function can be obtained. It was also found that an excellent antiblocking function can be obtained when the thickness of the protective coating layer is 1 ⁇ m or more and 3 ⁇ m or less.
- methacrylic aggregate having an average particle size of 20 nm> As the component (E), an aggregate (M23, manufactured by CIK Nanotech Co., Ltd.) having an average particle diameter of 20 nm which was surface-treated with a silane coupling agent having a methacryl group was used. Other than this, the same components as in Example 1 were used.
- Example 47 As shown in Table 10, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%, component (C2) (UT5490) 40.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.8 nm, and haze was 0.23%.
- Example 48 As shown in Table 10, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 17.7 wt%, component (C2) (UT5490) 39.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.6 nm, and haze was 0.23%.
- Example 49 As shown in Table 10, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt%, component (C2) (UT5490) 38.0 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 4.2 nm, and the haze was 0.25%.
- Example 50 As shown in Table 10, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 16.5 wt%, component (C2) (UT5490) 37.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the antiblocking function was ⁇ , the surface roughness was 5.5 nm, and the haze was 0.36%.
- Example 51 As shown in Table 10, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 49, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the anti-blocking function was ⁇
- the surface roughness was 5.1 nm
- the haze was 0.25%.
- Example 52 As shown in Table 10, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 49, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 2.0 nm
- the haze was 0.25%.
- methacrylic aggregate having an average particle size of 30 nm> As the component (E), an aggregate (M06, manufactured by CIK Nanotech Co., Ltd.) having an average particle size of 30 nm, which was surface-treated with a silane coupling agent having a methacryl group, was used. Other than this, the same components as in Example 1 were used.
- Example 53 As shown in Table 11, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%, component (C2) (UT5490) 40.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.6 nm, and haze was 0.23%.
- Example 54 As shown in Table 11, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 17.7 wt%, component (C2) (UT5490) 39.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 2.5 nm, and haze was 0.23%.
- Example 55 As shown in Table 11, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt%, component (C2) (UT5490) 38.0 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the antiblocking function was ⁇ , the surface roughness was 4.3 nm, and the haze was 0.25%.
- Example 56 As shown in Table 11, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 16.5 wt%, component (C2) (UT5490) 37.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the antiblocking function was ⁇ , the surface roughness was 5.5 nm, and the haze was 0.36%.
- Example 57 As shown in Table 11, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 55, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 5.4 nm
- the haze was 0.25%.
- Example 58 As shown in Table 11, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 55, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 2.0 nm
- the haze was 0.25%.
- Example 53 to Example 56 it was found that an excellent antiblocking function can be obtained by adding component (E) in the range of 9.0 wt% to 15.0 wt%. Moreover, from Examples 55, 57, and 58, it was found that an excellent antiblocking function was obtained when the thickness of the protective coating layer was 1 ⁇ m or more and 3 ⁇ m or less. That is, it was found that even when a methacrylic aggregate having an average particle diameter of 30 nm was added as the component (E), an excellent antiblocking function was obtained.
- methacrylic aggregate having an average particle size of 40 nm> As the component (E), an aggregate (M18, manufactured by CIK Nanotech Co., Ltd.) having an average particle diameter of 40 nm that was surface-treated with a silane coupling agent having a methacryl group was used. Other than this, the same components as in Example 1 were used.
- Example 59 As shown in Table 12, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%, component (C2) (UT5490) 40.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.7 nm, and haze was 0.23%.
- Example 60 As shown in Table 12, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 17.7 wt%, component (C2) (UT5490) 39.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 2.6 nm, and haze was 0.23%.
- Example 61 As shown in Table 12, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt%, component (C2) (UT5490) 38.0 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the anti-blocking function was ⁇ , the surface roughness was 4.8 nm, and the haze was 0.25%.
- Example 62 As shown in Table 12, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 16.5 wt%, component (C2) (UT5490) 37.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- the breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was ⁇ , the antiblocking function was ⁇ , the surface roughness was 5.5 nm, and the haze was 0.36%.
- Example 63 As shown in Table 12, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 61, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 5.5 nm
- the haze was 0.25%.
- Example 64 As shown in Table 12, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 61, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 .
- the number of good high-speed flexibility of the laminated film was 10
- the evaluation of the scratch resistance of the laminated film with steel wool was ⁇
- the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇
- the evaluation of adhesion was ⁇
- the antiblocking function was ⁇
- the surface roughness was 2.0 nm
- the haze was 0.25%.
- Example 59 to Example 62 it was found that an excellent antiblocking function can be obtained by adding the component (E) in the range of 9.0 wt% to 15.0 wt%. Moreover, from Examples 61, 63, and 64, it was found that an excellent antiblocking function was obtained when the thickness of the protective coating layer was 1 ⁇ m or more and 3 ⁇ m or less. That is, it was found that even when a methacrylic aggregate having an average particle diameter of 40 nm was added as the component (E), an excellent antiblocking function was obtained.
- component (E) As component (E1), silica sol having an average particle size of 15 nm (MEK-ST (silica sol dispersed in methyl ethyl ketone), manufactured by Nissan Chemical Industries, Ltd.), and as component (E2), a silane cup having a methacryl group having an average particle size of 30 nm Dispersion surface-treated with a ring agent (H83, manufactured by CIK Nanotech Co., Ltd.) As component (E3), a dispersion treated with a silane coupling agent having an alkyl group with an average particle diameter of 30 nm (E83, CIK Nanotech ( Co., Ltd.), as component (E4), an aggregate (H94, manufactured by CIK Nanotech Co., Ltd.) surface-treated with a silane coupling agent having an alkyl group with an average particle size of 30 nm, and as component (E5), the average particle size 50 nm silica sol (MEK-S) As component (E1), silica
- component (A) 21.1 wt%
- component (B) 8.4 wt%
- component (C1) (UT5467) 16.9 wt%
- component (C2) (UT5490) 38.0 wt%
- component (D) 2.
- a photocurable composition was prepared by uniformly mixing at a solute component concentration of 6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 ⁇ m was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%.
- a protective coating layer having a thickness of 2 ⁇ m was formed on both surfaces of the 75 ⁇ m-thick base film to prepare a laminated film.
- Example 65 As shown in Table 13, the elongation at break of the cured film when the component (E1) was added was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.6 nm, and haze was 0.23%.
- Example 66 As shown in Table 13, when the component (E2) was added, the elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), the antiblocking function was x, surface roughness was 1.1 nm, and haze was 0.25%.
- Example 67 As shown in Table 13, when the component (E3) was added, the elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 2.0 nm, and haze was 0.25%.
- Example 68 As shown in Table 13, the breaking elongation of the cured film when the component (E4) and the dispersant were added was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was x, the anti-blocking function was ⁇ , the surface roughness was 2.9 nm, and the haze was 0.25%.
- Example 69 As shown in Table 13, the elongation at break of the cured film when the component (E5) was added was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.23%.
- Example 70 As shown in Table 13, when the component (E6) was added, the elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.23%.
- Example 71 As shown in Table 13, when the component (E7) was added, the elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was x, the antiblocking function was x, the surface roughness was 0.9 nm, and the haze was 0.24%.
- Example 72 As shown in Table 13, when the component (E8) was added, the elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Further, the evaluation of adhesion was x, the antiblocking function was x, the surface roughness was 0.9 nm, and the haze was 0.24%.
- Example 73 As shown in Table 13, the elongation at break of the cured film when the component (E9) was added was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.0 nm, and haze was 0.25%.
- Example 74 As shown in Table 13, when the component (E10) was added, the fracture elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.27%.
- Example 75 As shown in Table 13, the elongation at break of the cured film when the component (E11) was added was 45%, and the Martens hardness of the cured film was 115 N / mm 2 . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ⁇ , and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ⁇ . Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.26%.
- an excellent antiblocking function can be obtained by adding inorganic fine particles that are aggregates having an average particle diameter of 10 nm to 50 nm. Moreover, it was found that the surface treatment with the silane coupling agent having an alkyl group or a (meth) acryloyl group improves the affinity and binding properties with the binder component and provides an excellent antiblocking function. .
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KR20180037106A (ko) * | 2016-10-03 | 2018-04-11 | 키모토 컴파니 리미티드 | 무기 화합물층 접착용 하드코팅 필름, 및 그 하드코팅 필름을 사용한 투명도전성 필름 및 터치 패널 |
US11053393B2 (en) * | 2018-08-02 | 2021-07-06 | Benq Materials Corporation | Hard coating layered optical film, polarizer comprising the same, and image display comprising the hard coating layered optical film and/or the polarizer comprising the same |
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JP2016204587A (ja) * | 2015-04-28 | 2016-12-08 | 日本合成化学工業株式会社 | 光硬化性組成物および樹脂成形体 |
JP6983586B2 (ja) * | 2016-09-07 | 2021-12-17 | 東山フイルム株式会社 | 透明導電性フィルム用のハードコートフィルム |
JP6363769B1 (ja) * | 2017-06-19 | 2018-07-25 | グンゼ株式会社 | カバーフィルム |
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