CN117529405A - Hard coating film, method for producing the same, and display - Google Patents
Hard coating film, method for producing the same, and display Download PDFInfo
- Publication number
- CN117529405A CN117529405A CN202280044028.8A CN202280044028A CN117529405A CN 117529405 A CN117529405 A CN 117529405A CN 202280044028 A CN202280044028 A CN 202280044028A CN 117529405 A CN117529405 A CN 117529405A
- Authority
- CN
- China
- Prior art keywords
- hard coat
- layer
- group
- coat layer
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000010410 layer Substances 0.000 claims abstract description 170
- 239000000203 mixture Substances 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 42
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 33
- 239000008199 coating composition Substances 0.000 claims abstract description 30
- 125000000524 functional group Chemical group 0.000 claims abstract description 28
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 22
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 17
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 7
- -1 silane compound Chemical class 0.000 claims description 86
- 229910000077 silane Inorganic materials 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 229920001721 polyimide Polymers 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 239000012461 cellulose resin Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 25
- 239000003505 polymerization initiator Substances 0.000 abstract description 24
- 238000001723 curing Methods 0.000 description 20
- 239000003085 diluting agent Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000003504 photosensitizing agent Substances 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000010702 perfluoropolyether Substances 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000003678 scratch resistant effect Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000004474 heteroalkylene group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FEWSKCAVEJNPBX-UHFFFAOYSA-N 2-(2-hydroxy-2-phenylacetyl)benzenesulfonic acid Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1S(O)(=O)=O FEWSKCAVEJNPBX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OMVWRPLDWTUXAS-UHFFFAOYSA-N 2-(propoxymethyl)oxetane Chemical compound CCCOCC1CCO1 OMVWRPLDWTUXAS-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DWTLFALXXQAKBJ-UHFFFAOYSA-N O1C2CC(CCC21)CCCCC[Si](OC)(OC)C Chemical compound O1C2CC(CCC21)CCCCC[Si](OC)(OC)C DWTLFALXXQAKBJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Chemical class CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- GQVVQDJHRQBZNG-UHFFFAOYSA-N benzyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1=CC=CC=C1 GQVVQDJHRQBZNG-UHFFFAOYSA-N 0.000 description 1
- PBKYCFJFZMEFRS-UHFFFAOYSA-L beryllium bromide Chemical compound [Be+2].[Br-].[Br-] PBKYCFJFZMEFRS-UHFFFAOYSA-L 0.000 description 1
- 229910001621 beryllium bromide Inorganic materials 0.000 description 1
- 229910001627 beryllium chloride Inorganic materials 0.000 description 1
- JUCWKFHIHJQTFR-UHFFFAOYSA-L beryllium iodide Chemical compound [Be+2].[I-].[I-] JUCWKFHIHJQTFR-UHFFFAOYSA-L 0.000 description 1
- 229910001639 beryllium iodide Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- YRMPTIHEUZLTDO-UHFFFAOYSA-N cyclopentyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCC1 YRMPTIHEUZLTDO-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- RWHQSBVLPQVZPR-UHFFFAOYSA-N dimethoxy-methyl-[3-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]silane Chemical compound C1C(CCC[Si](C)(OC)OC)CCC2OC21 RWHQSBVLPQVZPR-UHFFFAOYSA-N 0.000 description 1
- VEJGXMMRLUIHLA-UHFFFAOYSA-N dimethoxy-methyl-[4-(7-oxabicyclo[4.1.0]heptan-4-yl)butyl]silane Chemical compound C1C(CCCC[Si](C)(OC)OC)CCC2OC21 VEJGXMMRLUIHLA-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 125000005348 fluorocycloalkyl group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- VRINOTYEGADLMW-UHFFFAOYSA-N heptyl(trimethoxy)silane Chemical compound CCCCCCC[Si](OC)(OC)OC VRINOTYEGADLMW-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical class [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- UBMUZYGBAGFCDF-UHFFFAOYSA-N trimethoxy(2-phenylethyl)silane Chemical compound CO[Si](OC)(OC)CCC1=CC=CC=C1 UBMUZYGBAGFCDF-UHFFFAOYSA-N 0.000 description 1
- JEPXSTGVAHHRBD-UHFFFAOYSA-N trimethoxy(nonyl)silane Chemical compound CCCCCCCCC[Si](OC)(OC)OC JEPXSTGVAHHRBD-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DBUFXGVMAMMWSD-UHFFFAOYSA-N trimethoxy-[3-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]silane Chemical compound C1C(CCC[Si](OC)(OC)OC)CCC2OC21 DBUFXGVMAMMWSD-UHFFFAOYSA-N 0.000 description 1
- ZOWVSEMGATXETK-UHFFFAOYSA-N trimethoxy-[4-(7-oxabicyclo[4.1.0]heptan-4-yl)butyl]silane Chemical compound C1C(CCCC[Si](OC)(OC)OC)CCC2OC21 ZOWVSEMGATXETK-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The hard coating film (10) is provided with a hard coating layer (3) and a top coating layer (5) in this order on the transparent film (1), and the top coating layer is positioned on the outermost surface. The thickness of the hard coating is 0.5-100 mu m, and the thickness of the top coating is 2-20 mu m. The hard coat layer is a cured product of a hard coat composition containing a polyorganosiloxane compound containing an alicyclic epoxy group and a photo-cationic polymerization initiator. The topcoat layer is a cured product of a topcoat composition containing a multifunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule and a photo-radical polymerization initiator. The top coating composition preferably further contains a fluorine compound containing a functional group containing a radical polymerizable double bond and a fluorine atom in 1 molecule.
Description
Technical Field
The present invention relates to a hard coating film and a method for producing the same. The invention also relates to a display with the hard coating film.
Background
Flexible displays and foldable displays are being developed, and the window covers (covers) of the displays require the use of flexible plastic film materials. The window cover material for a foldable display is required to have characteristics such as bending durability, transparency, surface hardness, scratch resistance, impact resistance, and the like. In general-purpose plastic films, it is difficult to achieve sufficient surface hardness and scratch resistance, and therefore a hard coating film provided with a hard coating layer on the surface of the plastic film is used as a window covering material.
For example, patent document 1 discloses a hard coat film in which a hard coat layer and a scratch resistant layer are provided on the surface of a plastic film.
Prior art literature
Patent literature
Patent document 1: WO2020/021931
Disclosure of Invention
Problems to be solved by the invention
In patent document 1, the hard coat layer is made to have high hardness, the scratch resistant layer formed thereon is made to have scratch resistance, and adhesion is ensured by providing a primer layer between these layers. However, when the hard coat layer is formed in a multilayer structure in order to improve the surface hardness and scratch resistance, there are problems such as a decrease in bending resistance and an increase in warpage (curling). The purpose of the present invention is to provide a hard-coated film which exhibits excellent surface hardness and scratch resistance and has little warpage.
Solution for solving the problem
The hard coating film of the invention is provided with a hard coating and a top coating on a transparent film in sequence, and the top coating is positioned on the outermost surface. The thickness of the hard coat layer is preferably 0.5 to 100. Mu.m, and the thickness of the top coat layer is preferably 2 to 20. Mu.m. The thickness of the top coat is preferably 0.05 to 1 times the thickness of the hard coat.
The hard coat layer is a cured product of a hard coat composition containing a polyorganosiloxane compound containing an alicyclic epoxy group and a photo-cationic polymerization initiator. The polyorganosiloxane compound containing an alicyclic epoxy group is a condensate of a silane compound, and the condensate of a silane compound contains a silane compound represented by the general formula (1).
In the general formula (1), Y is a 2-valent organic group with the number of elements of the main chain being 2 or more, R 1 Is hydrogen atom or alkyl with 1-10 carbon atoms, R 2 Is a hydrogen atom or a 1-valent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and x is 2 or 3.
The number of alicyclic epoxy groups contained in the polyorganosiloxane compound may be 0.5 to 1 times the total number of Si atoms.
The topcoat layer is a cured product of a topcoat composition containing a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule and a photo radical polymerization initiator. The functional group equivalent of the (meth) acryloyl group of the multifunctional (meth) acrylate is preferably 80 to 150g/eq.
The top coating composition preferably further contains a fluorine compound containing a functional group containing a radical polymerizable double bond and a fluorine atom in 1 molecule. The radical polymerizable functional group of the fluorine compound is preferably a (meth) acryloyl group.
The transparent film may be a transparent film containing 1 or more resin materials selected from the group consisting of polyesters, polycarbonates, polyamides, polyimides, cyclic polyolefins, acrylic resins, and cellulose resins.
The hard coat film having the hard coat layer and the top coat layer in this order on the transparent film can be obtained by applying the hard coat composition on the transparent film, curing the composition by irradiation with an active energy ray to form a hard coat layer, and applying the top coat composition on the hard coat layer, and curing the composition by irradiation with an active energy ray to form a top coat layer.
The hard coat film can be used, for example, as a window cover for an image display device. An image display device according to one embodiment includes an image display panel and the above-described hard coat film, and a top coat layer of the hard coat film is disposed on a top surface of the recognition side.
ADVANTAGEOUS EFFECTS OF INVENTION
The hard coated film of the present invention exhibits excellent surface hardness and scratch resistance, and has little warpage. The hard coating film of the present invention can be suitably used as a window covering material for an image display device. In addition, the hard coating film of the present invention has high bending resistance, and thus can be suitably used as a window covering material for a foldable display.
Drawings
Fig. 1 is a cross-sectional view of a hard coated film according to an embodiment.
Detailed Description
Fig. 1 is a cross-sectional view of a hard coated film according to an embodiment of the present invention. The hard coat film 10 has a hard coat layer 3 on the transparent film 1, and a top coat layer 5 on the hard coat layer 3.
The hard coat layer 3 is a polysiloxane-based resin cured layer containing a cured product of a polyorganosiloxane compound having an epoxy group. The topcoat 5 is an acrylic resin cured layer containing a cured product of a polyfunctional (meth) acrylate having 3 or more functions. The topcoat layer 5 is a layer disposed on the outermost surface of the hard coat film, and when the topcoat layer 5 contains a fluorine compound or a cured product thereof, the topcoat layer tends to impart stain resistance and sliding properties to the topcoat layer, function as a scratch resistant layer, and improve the scratch resistance of the hard coat film.
A primer layer or the like may be provided between the transparent film 1 and the hard coat layer 3. A primer layer or the like may be provided between the hard coat layer 3 and the topcoat layer 5. Since the topcoat 5 is the outermost layer, no other layer is provided on the topcoat 5.
In fig. 1, the embodiment in which the hard coat layer 3 and the top coat layer 5 are provided on one side of the transparent film 1 is shown, but the hard coat layer and the top coat layer may be provided on both sides of the transparent film. The hard coat layer and the top coat layer may be provided on one surface of the transparent film 1, and the single-layer hard coat layer may be provided on the other surface of the transparent film 1.
[ transparent film ]
The transparent resin film 1 is a film base material that serves as a base when the hard coat layer 3 is formed. The total light transmittance of the transparent film is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The haze of the transparent film 1 is preferably 2% or less, more preferably 1% or less.
The thickness of the transparent film 1 is, for example, about 1 to 1000. Mu.m. The thickness of the transparent film 1 is preferably 5 to 500. Mu.m, more preferably 10 to 200. Mu.m, still more preferably 15 to 150. Mu.m. When the thickness is too small, the hardness is insufficient, and when the thickness is too large, the bendability tends to be deteriorated.
The resin material constituting the transparent film is not particularly limited as long as it is a transparent resin. Examples of the transparent resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins such as polymethyl methacrylate (PMMA), cellulose resins such as cellulose Triacetate (TAC), polycarbonates, polyamides, transparent polyimides, cyclic polyolefins, and the like.
Among them, polyester such as PET and transparent polyimide are preferable from the viewpoint of high mechanical strength. When the hard coat film is used for a window cover of a display, a transparent polyimide is particularly preferable as a resin material for the transparent film because excellent heat resistance and mechanical strength are required for the film base material. While a general wholly aromatic polyimide is colored in yellow or brown, a transparent polyimide having high visible light transmittance can be obtained by introducing an alicyclic structure, introducing a curved structure, introducing a fluorine substituent, or the like.
The transparent film 1 may contain 2 or more kinds of resin materials. The transparent film may contain a stabilizer such as an ultraviolet absorber or a radical scavenger for imparting weather resistance, a coloring matter such as a bluing material for adjusting color tone, and a pigment.
The transparent film 1 may be a single layer or a multilayer structure. For example, the transparent film may be a laminate of a plurality of films, or may be a film having a functional layer such as an easy-to-adhere layer, an antistatic layer, or an antireflection layer provided on the surface (the hard coat layer 3 formation surface and/or the hard coat layer non-formation surface) of the film.
[ hard coating ]
The hard coat composition is coated on the transparent film 1 and cured, thereby forming a hard coat layer 3.
Hard coating composition
The hard coating composition contains a polyorganosiloxane compound containing an alicyclic epoxy group as a curable resin component. Such hard coat compositions are disclosed in WO2014/204010, WO2018/096729, WO2020/040209, etc., to which reference is made. The hard coat composition contains a photo cation polymerization initiator in addition to the polyorganosiloxane compound as the curable resin component.
< polyorganosiloxane Compound >
The polyorganosiloxane compound is obtained by condensing a silane compound.
(silane Compound)
The silane compound having an alicyclic epoxy group is represented by the following general formula (1).
In the general formula (1), R 1 Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, cyclohexyl, and ethylhexyl groups.
The silane compound represented by the general formula (1) has 2 OR 3 (-OR) s in one molecule 1 ). Due to Si-OR 1 Since the polyorganosiloxane compound is hydrolyzable, the polyorganosiloxane compound can be obtained by condensation of the silane compound. From the viewpoint of hydrolyzability, the water-soluble polymer,R 1 the number of carbon atoms of (2) is preferably 3 or less, particularly preferably R 1 Is methyl.
In the general formula (1), R 2 Is a hydrogen atom or a 1-valent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms. Specific examples of the hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, cyclohexyl, ethylhexyl, benzyl, phenyl, tolyl, xylyl, naphthyl, and phenethyl.
In the general formula (1), x is 2 OR 3, in the case where x=3 (i.e., 3 alkoxy groups (OR hydroxy groups) -OR are bonded to the Si atom) 1 In the case of (2), the silane compound does not have R 2 . In general formula (1), x=3 is preferable from the viewpoints of formation of a network-like polyorganosiloxane compound and improvement of hardness of a cured film by increasing the number of epoxy groups contained in the polyorganosiloxane compound. A silane compound of x=2 and a silane compound of x=3 may also be used in combination. In addition, in order to adjust the molecular weight and the like of the polyorganosiloxane compound obtained by condensation, a silane compound having x of 1 may be used in addition to a silane compound having x of 2 or 3.
In the general formula (1), Y is a 2-valent organic group having 2 or more main chain elements, and may be linear or branched. The number of elements of the main chain of Y may be 16 or less, 12 or less, or 10 or less. Y may be an alkylene group or may contain an atom other than carbon in the main chain. For example, Y may be a heteroalkylene group, or may contain an ether bond, an ester bond, an amide bond, a carbonyl group, an imino group, or the like. The Y is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably an ethylene group.
Specific examples of the silane compound represented by the general formula (1) include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3, 4-epoxycyclohexyl) propylmethyldimethoxysilane, 4- (3, 4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3, 4-epoxycyclohexyl) butylmethyldimethoxysilane, 5- (3, 4-epoxycyclohexyl) pentylmethyltrimethoxysilane and 5- (3, 4-epoxycyclohexyl) pentylmethyldimethoxysilane.
The polyorganosiloxane compound as a condensate of the silane compound may be a condensate of the silane compound of the general formula (1) with other silane compounds. Examples of the other silane compound, that is, the silane compound containing no alicyclic epoxy group, include a silane compound represented by the general formula (2).
R 3 -(Si(OR 1 ) x R 2 3-x )…(2)
In the general formula (2), R 1 、R 2 And x is the same as formula (1). In the general formula (2), R 3 Is a 1-valent organic group containing no alicyclic epoxy group.
As R 3 Preferred are a substituted or unsubstituted double bond-containing group, a substituted or unsubstituted cycloalkyl-containing group, a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted alkyl group, a glycidyl group-containing group, or an oxetane group-containing group. As R 3 Specific examples of (a) include vinyl, allyl, acryloxypropyl, methacryloxypropyl, cyclopentyl, cyclohexyl, benzyl, phenyl, tolyl, xylyl, naphthyl, phenethyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, 3-glycidoxypropyl, 8-glycidoxypctyl and the like.
Specific examples of the silane compound represented by the general formula (2) include vinyltrimethoxysilane, allyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, benzyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, xylyltrimethoxysilane, naphthyltrimethoxysilane, phenethyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, 3-glycidoxyproptrimethoxysilane, 8-glycidoxycryltrimethoxysilane, 3-ethyl-3- (3' -trimethoxysilyl) propoxymethyl oxetane and the like.
(hydrolysis and condensation of silane Compound)
Si-OR of the silane compound by reacting the above silane compound with water 1 Partially hydrolyzed, and the hydrolysis product is condensed, thereby forming si—o—si bond, thereby producing condensate of silane compound (polyorganosiloxane compound). The amount of water required for the hydrolysis and condensation reactions is relative to the-OR bonded to the Si atom 1 The 1 equivalent of the group is preferably 0.3 to 3 equivalents, more preferably 0.5 to 2 equivalents. When the amount of water is too small, OR remains unhydrolyzed 1 Since the polyorganosiloxane compound has a large number of groups and a small molecular weight, the hard coat layer tends to have insufficient hardness. If the amount of water is too large, the reaction rate of hydrolysis and condensation reaction is high, and a condensate having a high molecular weight is formed, so that the transparency and flexibility of the hard coat layer tend to be lowered.
As described above, as the silane compound, in addition to the silane compound containing an alicyclic epoxy group represented by the general formula (1), a silane compound containing no alicyclic epoxy group represented by the general formula (2) may be used. The ratio of the silane compound of the general formula (1) to the total amount of the silane compounds is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more. By making the polyorganosiloxane compound contain an alicyclic epoxy group, the hard coat layer after curing has an effect of counteracting warping caused by curing shrinkage of the top coat layer. The higher the ratio of the silane compound of the general formula (1), the larger the amount of the alicyclic epoxy group contained in the polyorganosiloxane compound, and the less the warpage of the hard coat film tends to be.
In the hydrolysis and condensation reaction of the silane compound, the-O in the general formula (1) and the general formula (2)R 1 The functional group bonded to the Si atom does not react except for a side reaction such as ring opening of the epoxy group. Thus, in the polyorganosiloxane compound, Y and the alicyclic epoxy group in the general formula (1), and R in the general formula (2) 3 And (3) a retaining structure.
Therefore, the ratio of the number of alicyclic epoxy groups to the total number of Si atoms contained in the polyorganosiloxane compound is substantially equal to the ratio of the silane compound of the general formula (1) to the total amount of the silane compound. In the polyorganosiloxane compound obtained by hydrolyzing and condensing only the silane compound represented by the general formula (1), if the residual ratio of alicyclic epoxy groups after the reaction is 100%, the number of alicyclic epoxy groups is equal to the total number of Si atoms. The number of alicyclic epoxy groups contained in the polyorganosiloxane compound is preferably 0.5 times or more, more preferably 0.7 times or more, and still more preferably 0.8 times or more, relative to the total number of Si atoms.
From the viewpoint of improving the hardness of the cured film (hard coat layer), the weight average molecular weight of the polyorganosiloxane compound is preferably 500 or more. In addition, the weight average molecular weight of the polyorganosiloxane compound is also preferably 500 or more from the viewpoint of suppression of volatilization. On the other hand, when the molecular weight is too large, cloudiness may occur due to a decrease in compatibility with other compositions or the like. Therefore, the weight average molecular weight of the polyorganosiloxane compound is preferably 20000 or less. The weight average molecular weight of the polyorganosiloxane compound is more preferably 1000 to 18000, still more preferably 1500 to 16000, and may be 2000 to 14000 or 2800 to 12000.
In the hydrolysis reaction and condensation reaction of the silane compound, the reaction is preferably carried out under neutral or alkaline conditions from the viewpoint of suppressing ring opening of the epoxy group. In particular, from the viewpoint of reducing the T3/T2 ratio of the polyorganosiloxane compound obtained as a condensate of the silane compound, it is preferable to carry out the hydrolysis and condensation reaction in the presence of a neutral salt catalyst.
The polyorganosiloxane compound produced by hydrolysis and condensation of the silane compound may contain a silane compound having a T unit structure of x=3 in the general formula (1) and the general formula (2)3 alkoxy groups (Si-OR) 1 ) All undergo condensation reaction to form Si-O-Si bond structure (called "SiO 3/2 The "or" T3 "moiety), and 2 of the 3 alkoxy groups undergo a condensation reaction to form Si-O-Si bonds (referred to as" SiO ") 2/2 Body "or" T2 body ").
The polyorganosiloxane compound is sometimes preferably SiO 3/2 Body (T3 body) and SiO 2/2 Molar ratio of body (T2 body): the T3/T2 ratio is less than 5. The T3/T2 ratio may be 4 or less, 3.5 or less, 3 or less, or 2.5 or less. The polyorganosiloxane compound may be a composition containing no SiO 3/2 A compound of the bulk (i.e. a T3/T2 ratio of 0). The T3/T2 ratio may be 0.5 or more, 1 or more, 1.5 or more, or 2 or more.
By carrying out the reaction in the presence of a neutral salt catalyst, [ SiO ] 3/2 Body]/[SiO 2/2 Body]There is a tendency to become smaller. The neutral salt catalyst may be a salt of an acid and a base, preferably a salt of a cation of an alkali metal or alkaline earth metal and an anion of a halogen. Specific examples of the neutral salt include lithium chloride, sodium chloride, potassium chloride, beryllium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, beryllium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, beryllium iodide, magnesium iodide, calcium iodide, and the like.
< ingredients other than polyorganosiloxane Compounds >
The hard coat composition contains the above-mentioned polyorganosiloxane compound as a curable resin component, and further contains a photo-cationic polymerization initiator. The hard coating composition may further contain a leveling agent, a reactive diluent, a photosensitizer, particles, and other additives as solid components (non-volatile components). From the viewpoint of forming a hard coat layer excellent in mechanical strength, the content of the polyorganosiloxane compound in the hard coat composition is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, and still more preferably 60 parts by weight or more, relative to 100 parts by weight of the total of solid components (nonvolatile components).
(photo cationic polymerization initiator)
The photo-cation polymerization initiator is a compound (photoacid generator) that generates an acid by irradiation with active energy rays. The hard coat material is cured by the intermolecular crosslinking formed by the ring-opening and polymerization reaction of the epoxy group of the polyorganosiloxane compound by the acid generated from the photoacid generator.
Examples of the photo cation polymerization initiator include strong acids such as toluene sulfonic acid, antimony hexafluoride, boron tetrafluoride, phosphorus hexafluoride, fluoroalkyl phosphorus fluoride, and fluoroalkyl gallium fluoride; onium salts such as sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, and selenonium salts; iron-allene complexes; silanol-metal chelates; sulfonic acid derivatives such as disulfones, disulfonyl diazomethane, disulfonyl benzoylmethane, imide sulfonate, benzoin sulfonate and the like; organic halogen compounds, and the like. Among them, from the viewpoint of high stability of the hard coat composition, aromatic sulfonium salts or aromatic iodonium salts are preferable.
The content of the photo-cationic polymerization initiator in the hard coat composition is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.2 to 2 parts by weight, relative to 100 parts by weight of the polyorganosiloxane compound.
(leveling agent)
The hard coating composition may comprise a leveling agent. As the leveling agent, an organosilicon leveling agent and a fluorine leveling agent are preferable. By including the leveling agent, it is possible to expect a reduction in the surface tension and an improvement in the surface smoothness of the hard coat composition.
The content of the leveling agent in the hard coat composition is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and still more preferably 0.05 to 1 part by weight or less based on 100 parts by weight of the polyorganosiloxane compound.
(reactive diluent)
The hard coat composition may comprise a reactive diluent. Examples of the reactive diluent include cationic polymerizable compounds other than the polyorganosiloxane compounds described above. As the reactive diluent for photo-cationic polymerization, a compound having a cationically polymerizable functional group is used. Examples of the cationically polymerizable functional group of the reactive diluent include an epoxy group, a vinyl ether group, an oxetanyl group and an alkoxysilyl group. Among them, a reactive diluent having an epoxy group is preferable from the viewpoint of high reactivity with an epoxy group of the polyorganosiloxane compound.
The content of the reactive diluent in the hard coat composition is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the polyorganosiloxane compound.
(photosensitizer)
The hard coat composition may contain a photosensitizer in order to improve photosensitivity of the photo cation polymerization initiator (photoacid generator) and the like. As the photosensitive agent, any one of a type that improves the photosensitivity of the photo-cationic polymerization initiator by absorbing light in a wavelength region that the photo-cationic polymerization initiator cannot absorb and a type that improves the photosensitivity of the photo-cationic polymerization initiator although there is no large difference from the wavelength region of the absorption of the photo-cationic polymerization initiator may be used. As the type of the photosensitizer that absorbs light in a wavelength region that cannot be absorbed by the photo-cationic polymerization initiator, a photosensitizer that has strong absorption in a wavelength region different from the absorption wavelength region of the photo-cationic polymerization initiator is preferable. Examples of the photosensitizer include anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoin derivatives, naphthalene derivatives, and the like.
The content of the photosensitizer in the hard coat composition is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 10 parts by weight or less, relative to 100 parts by weight of the above photo-cationic polymerization initiator.
(particles)
The hard coat composition may contain particles for the purpose of adjusting film properties such as surface hardness and flex resistance. As the particles, organic particles, inorganic particles, organic-inorganic composite particles, and the like may be appropriately selected and used. The particles may be surface-modified, or may be surface-modified to introduce polymerizable functional groups.
The average particle diameter of the particles is, for example, about 5nm to 10. Mu.m. The average particle diameter is preferably 1000nm or less, more preferably 500nm or less, further preferably 300nm or less, particularly preferably 100nm or less, from the viewpoint of improving the transparency of the hard coat layer. The particle size can be measured by a laser diffraction/scattering type particle size distribution measuring apparatus, and the volume-based median particle size is used as the average particle size.
The content of the particles in the hard coat composition is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the polyorganosiloxane compound.
(solvent)
The hard coat composition may be solvent-free or may contain a solvent. When the hard coat composition contains a solvent, it is preferable that the solvent of the transparent film 1 as a base material is not dissolved. On the other hand, the adhesion between the transparent film 1 and the hard coat layer 3 may be improved by using a solvent having solubility to swell the transparent film. The content of the solvent is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and still more preferably 100 parts by weight or less, based on 100 parts by weight of the polyorganosiloxane compound.
(other Components)
The hard coating composition may contain additives such as inorganic pigments, organic pigments, surface modifiers, plasticizers, dispersants, wetting agents, thickeners, defoamers, ultraviolet stabilizers, and the like. The hard coat composition may contain a thermoplastic, thermosetting or photocurable resin material other than the polyorganosiloxane compound. In the case where the polyorganosiloxane compound and/or a resin material other than the polyorganosiloxane compound has radical polymerizability, the hard coat composition may contain a radical polymerization initiator in addition to the photo cation polymerization initiator.
< formation of hard coating >)
The hard coat layer 3 is formed by applying a hard coat composition onto the transparent film 1, drying and removing the solvent as necessary, and then curing. The surface of the transparent film 1 may be subjected to surface treatment such as corona treatment and plasma treatment before the hard coat composition is applied. In addition, an easy-to-adhere layer (primer layer) or the like may be provided on the surface of the transparent resin substrate. The hard coat layer formed by curing the hard coat composition containing the polyorganosiloxane compound may not be provided with an easy-to-adhere layer or the like because it exhibits high adhesion to the resin film. That is, in the hard coat film 10, the transparent film 1 and the hard coat layer 3 may be in contact.
The curing is performed by irradiating the hard coat composition with active energy rays, generating an acid from a photo-cationic polymerization initiator, opening the epoxy group of the polyorganosiloxane compound, and cationic polymerization. In the case where the hard coat composition contains a reactive diluent, polymerization of the epoxy group of the polyorganosiloxane compound and the reactive diluent occurs in addition to polymerization of the polyorganosiloxane compounds with each other. In addition, when the hard coat composition contains particles having reactive functional groups on the surface, the epoxy groups of the polyorganosiloxane compound may react with the functional groups on the particle surface to form chemical crosslinks.
The active energy rays irradiated during the photocuring include visible rays, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays, electron beams, and the like. From the viewpoints of high curing reaction rate and excellent energy efficiency, ultraviolet rays are preferable as active energy rays. The cumulative irradiation amount of the active energy rays is, for example, 50 to 10000mJ/cm 2 The amount of the photo-cation polymerization initiator may be set according to the kind and amount of the photo-cation polymerization initiator, the thickness of the hard coat layer, and the like. The curing temperature is not particularly limited, and is usually 100℃or lower. The heating may be performed after the irradiation of the active energy rays. By heating, the reaction of unreacted epoxy groups remaining in the hard coat layer (composition) is sometimes promoted, and the mechanical strength of the hard coat layer is improved.
The thickness of the hard coat layer 3 is preferably 0.5 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, particularly preferably 5 μm or more, and may be 10 μm or more, 20 μm or more, or 30 μm or more. The greater the thickness of the hard coat layer, the higher the surface hardness tends to be. On the other hand, the thickness of the hard coat layer is preferably 100 μm or less, more preferably 80 μm or less, and may be 70 μm or less from the viewpoint of transparency and bending resistance.
[ Top coat ]
The topcoat composition is applied on the hard coat layer 3 and cured, thereby forming a topcoat layer 5. The topcoat layer 5 located at the outermost surface of the hard coat film may have a function as a scratch-resistant layer.
< Top coating composition >)
The top coating composition contains, as a curable resin component, a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule. The top coating composition contains a photo radical polymerization initiator in addition to the polyfunctional (meth) acrylate as a curable resin component. The topcoat composition preferably further contains a fluorine compound containing a photopolymerizable functional group containing an ethylenically unsaturated bond and a fluorine atom in 1 molecule.
< multifunctional (meth) acrylate >
The multifunctional (meth) acrylate is a (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule. In the present specification, (meth) acrylic acid is acrylic acid and/or methacrylic acid, and (meth) acryl is acryl and/or methacryl. The inclusion of 3 or more (meth) acryl groups in the 1 molecule means that the total of acryl groups and methacryl groups in the 1 molecule is 3 or more.
By curing a compound having 3 or more (meth) acryloyl groups in 1 molecule, the top coat layer 5 having high hardness is formed, and therefore the hard coat film has high hardness and excellent scratch resistance. From the viewpoint of improving the curing density of the top coat layer, the functional group equivalent of the (meth) acryl groups of the multifunctional (meth) acrylate, that is, the molecular weight per 1 (meth) acryl group is preferably 80 to 150g/eq, more preferably 85 to 120g/eq.
Specific examples of the 3-functional or higher (meth) acrylate include glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Among them, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethylacrylate, or a mixture of dipentaerythritol pentamethacrylate and dipentaerythritol hexamethylacrylate is preferable from the viewpoint of high crosslinking density and excellent scratch resistance.
< ingredients other than multifunctional (meth) acrylate >
The top coating composition contains the above-mentioned multifunctional (meth) acrylate as a curable resin component, and further contains a photo radical polymerization initiator. The top coating composition preferably further comprises a fluorine compound as a photocurable resin component. The topcoat composition may further contain leveling agents, reactive diluents, photosensitizers, particulates, and other additives as solid components (non-volatile components). From the viewpoint of forming a top coat layer excellent in mechanical strength, the content of the 3-functional or higher polyfunctional (meth) acrylate in the top coat composition is preferably 50 parts by weight or more, more preferably 60 parts by weight or more, still more preferably 70 parts by weight or more, and particularly preferably 80 parts by weight or more, relative to 100 parts by weight of the total of solid components (nonvolatile components).
(fluorine Compound)
The fluorine compound contained in the topcoat composition contains a functional group containing a radical polymerizable double bond and a fluorine atom in 1 molecule. The topcoat layer contains a fluorine compound or a cured product thereof, and thus the slidability and stain resistance of the topcoat layer tend to be imparted to the topcoat layer, and the scratch resistance of the hard coat film tends to be improved.
The fluorine compound has low compatibility with the polyfunctional (meth) acrylate, and thus the fluorine compound tends to be present in the vicinity of the surface in a biased manner when the top coat is applied. Further, since the fluorine compound includes a photopolymerizable functional group and is bonded to the polyfunctional (meth) acrylate during the photocuring reaction, the fluorine compound is fixed to the resin matrix in the vicinity of the surface of the topcoat layer 5. Therefore, (the cured product of) the fluorine compound is less likely to fall off from the top coat layer, and the scratch resistance of the hard coat film can be maintained well for a long period of time.
The functional group containing a radical polymerizable double bond (ethylenic unsaturated bond) is a functional group capable of causing radical polymerization reaction by irradiation of active energy rays such as ultraviolet rays, electron beams, and the like, and examples thereof include (meth) acryl, (meth) acryloyloxy, vinyl, allyl, cinnamoyl, and the like. From the viewpoint of high reactivity with the (meth) acryloyl group of the polyfunctional (meth) acrylate, the polymerizable functional group in the fluorine compound is particularly preferably a (meth) acryloyl group or a (meth) acryloyloxy group.
The fluorine compound is preferably a compound having a structure represented by the following general formula (3).
R f [-R 4 (-R 5 ) n )] m …(3)
In the general formula (3), R f Is (per) fluoroalkyl or (per) fluoropolyether, R 4 Is a single bond or a linking group, R 5 Is a functional group containing a free radical polymerizable double bond. n is R and 4 r of the bond 5 M is a number equal to R f Bonded [ -R 4 (-R 5 ) n )]N and m are each independently integers from 1 to 3.
(per) fluoroalkyl means fluoroalkyl and/or perfluoroalkyl, and (per) fluoropolyether means fluoropolyether and/or perfluoropolyether.
The number of carbon atoms of the (per) fluoroalkyl group is preferably 1 to 20, more preferably 1 to 10. (per) fluoroalkyl may be-CF 2 CF 3 、-CH 2 (CF 2 ) 4 H、-CH 2 (CF 2 ) 8 CF 3 、-CH 2 CH 2 (CF 2 ) 4 H, etc., may be-CH (CF) 3 ) 2 、-CH 2 CF(CF 3 ) 2 、-CH(CH 3 )CF 2 CF 3 、-CH(CH 3 )(CF 2 ) 5 CF 2 H and other groups having a branched chain may be groups having an alicyclic structure such as perfluorocyclohexyl and perfluorocyclopentyl.
The (per) fluoropolyether group means that the (per) fluoroalkyl group has an ether bond, and may be a group having a valence of 1 or more than 2. As the fluoropolyether group, for example, there may be mentioned-CH 2 OCH 2 CF 2 CF 3 、-CH 2 CH 2 OCH 2 C 4 F 8 H、-CH 2 CH 2 OCH 2 CH 2 C 8 F 17 、-CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H. And a 4-20 carbon-atom fluorocycloalkyl group having 4 or more fluorine atoms. Examples of the perfluoropolyether group include- (CF) 2 O) h -(CF 2 CF 2 O) k -、-[CF(CF 3 )CF 2 O] h -[CF(CF 3 )] k -、-(CF 2 CF 2 CF 2 O) h -、-(CF 2 CF 2 O) h -and the like. Each of h and k is independently an integer of 0 to 20, and h+k is 1 or more. h+k is preferably 1 to 83, more preferably 1 to 43, and still more preferably 5 to 23.
R in the general formula (3) from the viewpoint of improving scratch resistance f Groups having a high fluorine content are preferred. R is R f Particularly preferred comprises- (CF) 2 O) h -(CF 2 CF 2 O) k -the perfluoropolyether group shown. The content of fluorine atoms in the fluorine compound is preferably 20% by mass or more, more preferably 30 to 70% by mass, and still more preferably 40 to 70% by mass.
A linking group R in the general formula (3) 4 Examples of the linking group include alkylene groups, arylene groups, heteroalkylene groups, and combinations thereof. R is R 4 Functional groups such as oxo, carbonyl, carbonyloxy, carbonylimino, and sulfonamide groups may also be included. As R 4 Ethylene, or ethylene bonded to a carbonylimino group, is preferred.
As functional group R containing free radical polymerizable double bond 5 As described above, (meth) acryl, (meth) acryloyloxy, vinyl, allyl, cinnamoyl, and the like can be exemplified, and among them, (meth) acryl or (meth) acryloyloxy is particularly preferable. R is R 5 Any of these functional groups may be substituted with a fluorine atom.
From the viewpoint of improving the scratch resistance of the hard coat film, the fluorine compound preferably contains perfluoroPolyether groups and have a functional group containing 2 or more radical polymerizable double bonds. Namely, the fluorine compound is preferably represented by the general formula (3), R f Comprises a perfluoropolyether, and the product of n and m (n×m) is 2 or more. n×m is more preferably 4 or more.
The fluorine compound may be any of a monomer, an oligomer, and a polymer. Monomers or oligomers are preferred from the viewpoint of ease of segregation to the surface of the topcoat and reactivity with polyfunctional (meth) acrylates. The weight average molecular weight of the fluorine compound is preferably 400 or more and less than 50000, more preferably 400 or more and less than 30000, still more preferably 400 or more and less than 25000.
As the fluorine compound, there may be mentioned Daikin Industries, R-2020, M-2020, R-3833, M-3833 and OPTOOL DAC manufactured by Ltd; MEGAFACE F-171, F-172, F-179A, RS-78, RS-90 and Defenser (Du. Japan: du-on) MCF-300, MCF-323 and the like manufactured by DIC.
When the topcoat layer contains a fluorine compound, the content of the fluorine compound is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 8 parts by weight, particularly preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the total of solid components (nonvolatile components). By setting the content of the fluorine compound to the above range, a hard coat film having high surface hardness and excellent scratch resistance can be obtained.
(photo radical polymerization initiator)
The photoradical polymerization initiator is a compound (photoradical generator) that generates radicals as an active species by irradiation with active energy rays. As the photo-radical polymerization initiator, known photo-radical polymerization initiators such as acetophenones, oxime esters, benzoins, benzophenones, thioxanthones, and acylphosphine oxides can be used without particular limitation.
The photoradical polymerization of the multifunctional (meth) acrylate proceeds by the photoradical generated by the photoradical generator. When the top-coating composition contains the fluorine compound, the photo radical polymerization of the fluorine compound proceeds in addition to the photo radical polymerization of the polyfunctional (meth) acrylate.
The content of the photo radical polymerization initiator in the top coating composition is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, still more preferably 1 to 5 parts by weight, relative to 100 parts by weight of the multifunctional (meth) acrylate.
(reactive additive)
The topcoat composition may include a reactive diluent. Examples of the reactive diluent include the above-mentioned polyfunctional (meth) acrylate and radically polymerizable compounds other than fluorine compounds. As the photo radical polymerizable reactive diluent, monofunctional or 2-functional (meth) acrylate is preferable.
The content of the reactive diluent in the top coating composition is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 10 parts by weight or less, and may be 0, based on 100 parts by weight of the 3-functional or more polyfunctional (meth) acrylate.
(solvent)
The topcoat composition may be solvent-free or may contain a solvent. The content of the solvent is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and still more preferably 100 parts by weight or less, based on 100 parts by weight of the polyfunctional (meth) acrylate.
(other Components)
The topcoat composition may contain particles, various additives, in addition to the above. Specific examples of these components include those described above for the hard coat composition. In the case of a resin material in which the top coating composition has cationic polymerizability, the top coating composition may contain a photo-cationic polymerization initiator in addition to the photo-radical polymerization initiator.
< formation of topcoat >
The topcoat composition is applied to the hard coat layer 3, and if necessary, the solvent is removed by drying, and then the topcoat composition is cured by irradiation with active energy rays, thereby forming the topcoat layer 5. The surface of the hard coat layer 3 may be subjected to surface treatment such as corona treatment and plasma treatment before the top coat composition is applied. In addition, an easy-to-adhere layer (primer layer) or the like may be provided on the surface of the hard coat layer.
Curing is performed by radical polymerization of a multifunctional (meth) acrylate by irradiation of active energy rays to the topcoat composition, generating radicals from a photo radical polymerization initiator. When the top coating composition contains a fluorine compound having a radical polymerizable double bond, polymerization reaction of fluorine compounds with each other and reaction of the multifunctional (meth) acrylate with the fluorine compound occur in addition to photopolymerization of the multifunctional (meth) acrylate with each other.
When the top coating composition contains a fluorine compound, the compatibility of the multifunctional (meth) acrylate with the fluorine compound is low in the liquid composition, and thus the fluorine compound tends to exist on the surface in a biased manner (segregate). The fluorine compound that is present in the vicinity of the surface is biased to form a chemical bond with the multifunctional (meth) acrylate, thereby forming (a polymer of) the fluorine compound that is biased to be present in the top coat 5 in the vicinity of the surface. The surface coating layer 5 has a high fluorine atom ratio in the vicinity of the surface, and thus has high stain resistance and sliding properties, contributing to improvement of the scratch resistance of the hard coating film. In the topcoat 5, it is preferable that 30% or more of the fluorine compound contained in the topcoat composition is present in a region within 100nm from the surface. The proportion of the fluorine compound contained in the topcoat layer 5 in (the polymer of) the region within 100nm from the surface of the topcoat layer 5 is preferably 30% or more, more preferably 50% or more, and may be 60% or more, 70% or more, or 80% or more.
The active energy rays irradiated during the photocuring include visible rays, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays, electron beams, and the like. From the viewpoints of high curing reaction rate and excellent energy efficiency, ultraviolet rays are preferable as active energy rays. The cumulative irradiation amount of the active energy rays is, for example, 50 to 10000mJ/cm 2 The amount of the photo radical polymerization initiator may be set depending on the kind and amount of the photo radical polymerization initiator, the thickness of the topcoat layer, and the like. The curing temperature is not particularly limited, and is usually 100℃or lower.
In curing the top coating composition, it is preferable to cure the top coating composition in a low oxygen concentration atmosphere such as a nitrogen atmosphere, from the viewpoint of promoting a photo-curing reaction and obtaining a top coating layer having high hardness. The oxygen concentration of the atmosphere at the time of photocuring of the topcoat layer is preferably 1000ppm or less, more preferably 500ppm or less, and still more preferably 100ppm or less.
The thickness of the topcoat 5 is preferably 2 μm to 20 μm, more preferably 2 μm to 10 μm, particularly preferably 3 μm to 8 μm. When the thickness of the topcoat 5 is 2 μm or more, the scratch resistance of the hard coat film tends to be improved, and the warp of the hard coat film tends to be reduced. In addition, by setting the thickness of the top coat layer to 20 μm or less, the occurrence of cracking and crazing of the top coat layer 5 can be suppressed, and a hard coat film excellent in flexibility and bending resistance can be obtained.
[ Properties of hard coating film ]
The hard coat film 10 includes a hard coat layer 3 and a top coat layer 5 in this order on a transparent film 1, and the top coat layer 5 is the outermost layer. The thickness of the hard coat layer 3 is 0.5-100 mu m, and the thickness of the top coat layer 5 is 2-20 mu m.
As described above, by setting the thickness of the topcoat 5 to 2 μm or more, there is a tendency that the warping of the hard coat film is reduced in addition to the scratch resistance. One of the putative factors for reducing warpage is the balance between stress caused by curing of the hard coat layer 3 and stress caused by curing of the topcoat layer 5.
The polyorganosiloxane compound having an alicyclic epoxy group as a curable resin component in the hard coat composition tends to expand due to curing. Therefore, the hard coat film having only the hard coat layer 3 provided on the transparent film 1 tends to curl with the hard coat layer 3 as the outer side. On the other hand, polyfunctional (meth) acrylates, which are curable resin components in the topcoat composition, tend to shrink due to curing. If the thickness of the topcoat 5 is 2 μm or more, it is considered that the stress due to the shrinkage strain of the topcoat 5 is sufficient to cancel the stress due to the expansion strain of the hard coat 3, and therefore warping (curling) of the hard coat film can be suppressed.
From the viewpoint of reducing warpage by balancing the stress caused by the expansion strain of the hard coat layer 3 and the stress caused by the contraction strain of the top coat layer 5, the ratio of the thickness of the top coat layer 5 to the thickness of the hard coat layer 3 (top coat layer/hard coat layer) is preferably 0.05 to 1, more preferably 0.1 to 0.8, and still more preferably 0.2 to 0.5.
The warpage amount of the hard coat film cut into 10cm square is preferably 20mm or less, more preferably 15mm or less, further preferably 10mm or less, and may be 5mm. The warpage amount is desirably 0.
The warpage amount was measured using a sample obtained by allowing a hard coating film cut into 10cm square to stand at 23℃for 24 hours at 55% RH and then performing temperature and humidity control. The hard coat film was placed on a horizontal mesa so that the concave surface (the surface on the inner side of the curl) of the film faced upward, and the heights from the mesa to the 4 corners of the film were measured, respectively, and the maximum value was used as the warpage amount.
In the hard coat film having the hard coat layer 3 and the top coat layer 5 on the transparent film 1, the hard coat layer 3 and the top coat layer 5 each have high hardness and adhesion between the layers is high, so that the hard coat film can achieve high surface hardness. The surface hardness (pencil hardness) of the surface of the hard coat film on the side of the topcoat 5 is preferably HB or more, more preferably H or more, still more preferably 2H or more, and may be 3H or more or 4H or more.
The hard coat film has a high surface hardness as described above, and the hard coat layer 3 is a cured resin layer of polysiloxane system, whereby the bending resistance is also excellent. When the hard coat film is subjected to a cylindrical shaft test with the surface on which the top coat layer is formed as the inner side, the shaft diameter of the hard coat layer 3 and/or the top coat layer 5 at which cracks occur is preferably 8mm or less, more preferably 6mm or less, and may be 4mm or less or 2mm or less.
The total light transmittance of the hard coat film is preferably 80% or more, more preferably 85% or more, and still more preferably 88% or more. The haze of the hard coat film is preferably 1.5% or less, more preferably 0.9% or less, further preferably 0.6% or less, particularly preferably 0.5% or less.
[ application of hard coating film ]
The hard coat film may be provided with various functional layers on the hard coat layer or on the hard coat layer non-forming surface of the transparent resin substrate. Examples of the functional layer include an antireflection layer, an antiglare layer, an antistatic layer, and a transparent electrode. In addition, a transparent adhesive layer may be attached to the hard coat film.
The hard coating film is excellent in transparency and hardness and scratch resistance, and therefore is suitable as a window cover material provided on the surface of an image display panel. The hard-coated film is also excellent in bending resistance, and thus can be suitably used as a window cover for curved displays, flexible displays, foldable displays, and the like.
[ gist of the invention ]
The present invention has been described above based on preferred embodiments, but the present invention is not limited to these embodiments. The gist of the present invention is as follows.
[1] A hard coat film comprising a transparent film, a hard coat layer and a top coat layer sequentially provided on the transparent film, wherein the top coat layer is positioned on the outermost surface,
the hard coat layer is a cured product of a hard coat composition containing a polyorganosiloxane compound which is a condensate of a silane compound comprising a silane compound represented by the general formula (1),
the topcoat is a cured product of a topcoat composition containing a multifunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule and a photo-radical polymerization initiator,
the thickness of the hard coating layer is 0.5-100 mu m,
the thickness of the surface coating is 2-20 mu m;
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in the general formula (1), Y is a 2-valent organic group having 2 or more main chain elements,
R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R 2 is a hydrogen atom or a 1-valent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms,
x is 2 or 3.
[2] The hard coat film according to [1], wherein the top coating composition further contains a fluorine compound containing a functional group containing a radical polymerizable double bond and a fluorine atom in 1 molecule.
[3] The hard coat film according to [2], wherein the functional group containing a radical polymerizable double bond of the fluorine compound is a (meth) acryl group.
[4] The hard coat film according to any one of [1] to [3], wherein the functional group equivalent of the (meth) acryl group of the multifunctional (meth) acrylate is 80 to 150g/eq.
[5] The hard coat film according to any one of [1] to [4], wherein the thickness of the top coat layer is 0.05 to 1 time the thickness of the hard coat layer.
[6] The hard coat film according to any one of [1] to [5], wherein the number of alicyclic epoxy groups contained in the polyorganosiloxane compound is 0.5 to 1 times the total number of Si atoms.
[7] The hard coat film according to any one of [1] to [6], wherein the transparent film comprises 1 or more resin materials selected from the group consisting of polyesters, polycarbonates, polyamides, polyimides, cyclic polyolefins, acrylic resins and cellulose resins.
[8] A method for producing a hard coat film according to any one of [1] to [7],
in the method of the present invention,
coating the hard coating composition on a transparent film, irradiating active energy rays to cure the composition to form a hard coating,
and applying the topcoat composition onto the hard coat layer, and irradiating the hard coat layer with active energy rays to cure the topcoat composition to form a topcoat layer.
[9] A display comprising an image display panel, and the hard coat film of any one of [1] to [7],
the topcoat layer of the hard coating film is disposed on the outermost surface of the identification side.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples.
[ Synthesis of polyorganosiloxane Compound ]
66.5g (270 mmol) of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (SILQUEST A-186 made by Momentive Performance Materials) and 16.5g of 1-methoxy-2-Propanol (PGME) were charged into a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, and stirred uniformly. To this mixture was added dropwise a solution of 0.039g (0.405 mmol) of magnesium chloride as a catalyst in a mixture of 9.7g (539 mmol) of water and 5.8g of methanol over 5 minutes, and the mixture was stirred until uniform. Then, the temperature was raised to 80℃and polycondensation was carried out for 6 hours while stirring. After the reaction, the solvent and water were distilled off by a rotary evaporator to obtain a polyorganosiloxane compound.
The weight average molecular weight Mn in terms of polystyrene measured by GPC equipment "HLC-8220GPC" (column: TSKgel GMHXL. Times.2, TSKgel G3000HXL, TSKgel G2000 HXL) manufactured by Tosoh was 3000. From 600MHz-NMR using Agilent 29 Si-NMR measurement of calculated [ SiO ] 3/2 Body]/[SiO 2/2 Body]The ratio was 2.3. 400MHz-NMR from Bruker, determined from deuterated acetone as solvent 1 The residual rate of the epoxy group calculated by H-NMR spectrum was 95% or more.
Example 1
< preparation of hard coating composition >
2 parts by weight of a photo-cationic polymerization initiator (diphenyl (4-phenylsulfanylphenyl) sulfonium SbF in terms of solid content was compounded with respect to 100 parts by weight of the polyorganosiloxane compound 6 Propylene carbonate 50% solution; san-Apro ltd. CPI-101A "), 0.25 parts by weight of a silicone-based leveling agent (a 52% xylene/isobutanol solution of polyether-modified polydimethylsiloxane; BYK "BYK-300"), propylene Glycol Monomethyl Ether (PGME) as a diluent solvent, to give a hard coat composition having a solid content of 50% by weight.
< preparation of Top coating composition >
100 parts by weight of a polyfunctional acrylate (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; manufactured by Toyama Synthesis "ARONIX M-403"), 3.75 parts by weight of a fluorine compound having an acryl group (manufactured by DIC Synthesis "MEGAFACE RS-90"), 2 parts by weight of a photo radical polymerization initiator (1-hydroxycyclohexyl phenyl ketone; manufactured by Fuji film and Wako pure chemical industries, ltd.) in terms of solid content, and PGME as a diluting solvent were compounded to obtain a top-coating composition having a solid content concentration of 50% by weight.
< preparation of hard coating film >
The hard coat composition was applied to a transparent polyimide film substrate having a thickness of 50. Mu.m, so that the dry film thickness became 20. Mu.m, by a bar coater, and heated at 120℃for 10 minutes. Then, the cumulative light amount at a wavelength of 250 to 390nm was 1000mJ/cm using a high-pressure mercury lamp in an atmosphere of 50 DEG C 2 The hard coat composition is cured by irradiation with ultraviolet rays.
At 600Wmin/m 2 After corona discharge treatment of the surface of the hard coat layer, the top coating composition was applied to the hard coat layer so that the dry film thickness became 2 μm using a bar coater, and heated at 120℃for 10 minutes. Then, the cumulative light quantity at a wavelength of 250 to 390nm was 1000mJ/cm by using a high-pressure mercury lamp at room temperature under a nitrogen atmosphere 2 And (3) irradiating ultraviolet rays to cure the top-coating composition. Then, heat treatment was performed at 120℃for 10 minutes to obtain a hard coat film having a hard coat layer having a thickness of 20 μm and a top coat layer having a thickness of 2 μm in this order on the transparent polyimide film substrate.
Examples 2 to 7 and comparative example 1
The thickness of the hard coat layer, the compounding amount of the fluorine compound (RS-90) of the top coat composition, and the thickness of the top coat layer were changed as shown in Table 1. A hard coat film was obtained in the same manner as in example 1, except that the film was a hard coat film.
Comparative example 2
For 100 parts by weight of the above-mentioned polyorganosiloxane compound, 2 parts by weight of a photo-cationic polymerization initiator (San-Apro Ltd. Co., ltd. "CPI-101A") in terms of a solid content, 0.5 part by weight of a fluorine compound having an acryl group (DIC. "MEGAFACE RS-90"), 1 part by weight of a photo-radical polymerization initiator (1-hydroxycyclohexyl phenyl ketone) in terms of a solid content, and PGME as a diluting solvent were compounded to obtain a composition having a solid content concentration of 50% by weight.
[ production of hard-coated film ]
The composition was applied to a transparent polyimide film substrate having a thickness of 50. Mu.m, and heated at 120℃for 10 minutes by a bar coater so that the dry film thickness became 15. Mu.m. Then, the cumulative light quantity at a wavelength of 250 to 390nm was 1000mJ/cm by using a high-pressure mercury lamp at room temperature under a nitrogen atmosphere 2 The composition is cured by irradiation with ultraviolet rays. Then, heat treatment was performed at 120℃for 10 minutes to obtain a hard coat film having a hard coat layer with a thickness of 15. Mu.m on the transparent polyimide film substrate. No topcoat is formed on the hard coat.
Comparative example 3
A hard coat film was obtained in the same manner as in comparative example 2, except that the thickness of the hard coat layer was set to 20 μm.
[ evaluation of hard-coated film ]
< scratch resistance (Steel wool test) >)
The surface of the hard coat film was subjected to a rubbing test under the following conditions using a reciprocating rubbing tester (TYPE 30, new east scientific Co., ltd.).
Friction piece: steel WOOL #0000 (NIHON STEEL WOOL Co., ltd.)
Load: 1kg of
Friction member contact area: phi 1cm, circular
Friction distance (single pass): 5cm
Friction speed: 10 cm/sec (1 round trip/sec)
The hard coat film after the friction test for the predetermined number of rounds was visually observed, and the scratch resistance was evaluated according to the following criteria.
A: no damage was observed after 2000 rounds
B: no damage was observed after 1000 rounds, but after 2000 rounds, damage was observed
C: no damage was observed after 500 rounds, but after 1000 rounds the damage was observed
D: damage was observed after 500 rounds
< warp >
The hard coat film was cut into 10cm square, and left to stand at 23℃at 55% RH for 24 hours, followed by conditioning (temperature and humidity control). The hard coat film was placed on a horizontal mesa so that the concave surface of the film faced upward, and the heights from the mesa to the 4 corners of the film were measured, respectively, and the maximum value was regarded as warpage.
< surface hardness >
According to JIS K5600-5-4:1999, pencil hardness of the hard coat forming face was measured at a load of 750 g.
Flexible
According to JIS K5600-5-1:1999, a cylindrical axis test of a hard coat film was performed with the surface formed with the top coat layer (hard coat layer formed surface in comparative examples 2 and 3) as the inner side using a type 1 tester. In any of the examples/comparative examples, the minimum value of the shaft diameter at which the hard coat layer and/or the top coat layer does not generate cracks was 2mm, showing good flexibility.
< total light transmittance and haze >)
Haze meter HZ-V3 manufactured by Suga Test Instruments co., ltd. Was used, and the haze meter was manufactured by JIS K7361-1:1999 and JIS K7136:2000, the method described in 2000. In the measurement, the D65 light source was used, and the total light transmittance was calculated as the ratio of the total transmitted light beam (parallel light component and diffuse light component) to the parallel incident light beam to the hard coat film.
The constitution of the hard coat films (the compositions of the hard coat composition and the top coat composition, the thicknesses of the hard coat layer and the top coat layer) and the evaluation results of the examples and the comparative examples are shown in table 1.
TABLE 1
The hard coat films of examples 1 to 7, which have a top coat layer obtained by curing a composition containing a photocurable fluorine compound containing an acryl group in addition to a polyfunctional acrylate, have good transparency, flexibility and hardness, and further have excellent scratch resistance. The warpage of the hard coat films of examples 1 to 7 was 10mm or less.
On the other hand, in comparative example 1 in which the thickness of the topcoat layer was 1 μm, the scratch resistance was poor and the warpage was large. In comparative examples 2 and 3, which did not have a top coat layer and contained a fluorine compound as the outermost layer, also had poor scratch resistance and increased warpage.
From these results, it was found that a hard coat film excellent in scratch resistance and less in warpage can be obtained by providing a polysiloxane-based hard coat layer on a transparent film, and providing an acrylic-based top coat layer containing a photocurable fluorine compound thereon, wherein the thickness of the top coat layer is 2 μm or more.
Description of the reference numerals
1 transparent resin film
3 hard coating
5 surface coating (scratch resistant layer)
10 hard coat film
Claims (9)
1. A hard coat film comprising a transparent film, a hard coat layer and a top coat layer sequentially provided on the transparent film, wherein the top coat layer is positioned on the outermost surface,
the hard coat layer is a cured product of a hard coat composition containing a polyorganosiloxane compound which is a condensate of a silane compound comprising a silane compound represented by the general formula (1),
the topcoat is a cured product of a topcoat composition containing a multifunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule and a photo-radical polymerization initiator,
The thickness of the hard coating layer is 0.5-100 mu m,
the thickness of the surface coating is 2-20 mu m;
in the general formula (1), Y is a 2-valent organic group having 2 or more main chain elements,
R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R 2 is a hydrogen atom or a 1-valent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms,
x is 2 or 3.
2. The hard coat film according to claim 1, wherein the top coating composition further contains a fluorine compound containing a functional group containing a radical polymerizable double bond and a fluorine atom in 1 molecule.
3. The hard coat film according to claim 2, wherein the functional group containing a radical polymerizable double bond of the fluorine compound is a (meth) acryl group.
4. The hard coat film according to claim 1 or 2, wherein the functional group equivalent of the (meth) acryl of the multifunctional (meth) acrylate is 80 to 150g/eq.
5. The hard coat film according to claim 1 or 2, wherein the thickness of the top coat layer is 0.05 to 1 times the thickness of the hard coat layer.
6. The hard coat film according to claim 1 or 2, wherein the number of alicyclic epoxy groups contained in the polyorganosiloxane compound is 0.5 to 1 times the total number of Si atoms.
7. The hard coat film according to claim 1 or 2, wherein the transparent film comprises 1 or more resin materials selected from the group consisting of polyesters, polycarbonates, polyamides, polyimides, cyclic polyolefins, acrylic resins, and cellulose resins.
8. A method for producing a hard coat film according to claim 1 or 2,
in the method of the present invention,
coating the hard coating composition on a transparent film, irradiating active energy rays to cure the composition to form a hard coating,
and applying the topcoat composition onto the hard coat layer, and irradiating the hard coat layer with active energy rays to cure the topcoat composition to form a topcoat layer.
9. A display comprising an image display panel, and the hard coat film according to claim 1 or 2,
the topcoat layer of the hard coating film is disposed on the outermost surface of the identification side.
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| JP2021-102343 | 2021-06-21 | ||
| JP2021102343 | 2021-06-21 | ||
| PCT/JP2022/024559 WO2022270471A1 (en) | 2021-06-21 | 2022-06-20 | Hard coating film, method for producing same, and display |
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| JP2007070523A (en) * | 2005-09-08 | 2007-03-22 | Nippon Kayaku Co Ltd | Photo-sensitive resin composition and film comprising its cured membrane |
| JP2017087523A (en) * | 2015-11-09 | 2017-05-25 | 大日本印刷株式会社 | Optical laminate, picture display unit and curable composition |
| JP6702022B2 (en) * | 2016-06-24 | 2020-05-27 | 大日本印刷株式会社 | Touch panel, multilayer film, and method for manufacturing multilayer film |
| EP3525016B1 (en) * | 2016-10-07 | 2022-05-11 | Nippon Paint Automotive Coatings Co., Ltd. | Optical multilayer member |
| JP2018189800A (en) * | 2017-05-02 | 2018-11-29 | 株式会社ダイセル | Hard coat film for curved surface display, transparent substrate with hard coat film, and display device |
| JP2021070800A (en) * | 2019-11-01 | 2021-05-06 | 株式会社カネカ | Hard coat film and image display device |
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