KR20100055160A - Hard coating solution, hard coating film and image display device useing them - Google Patents
Hard coating solution, hard coating film and image display device useing them Download PDFInfo
- Publication number
- KR20100055160A KR20100055160A KR1020080114104A KR20080114104A KR20100055160A KR 20100055160 A KR20100055160 A KR 20100055160A KR 1020080114104 A KR1020080114104 A KR 1020080114104A KR 20080114104 A KR20080114104 A KR 20080114104A KR 20100055160 A KR20100055160 A KR 20100055160A
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- hard coating
- weight
- polyfunctional
- 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.)
- Ceased
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 103
- 238000000576 coating method Methods 0.000 title claims abstract description 103
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 116
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229920003023 plastic Polymers 0.000 claims abstract description 15
- 239000004033 plastic Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 15
- -1 hydroxyalkyl acrylate Chemical compound 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 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 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 239000013557 residual solvent Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 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 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 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 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 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 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 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 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 239000007888 film coating Substances 0.000 description 5
- 238000009501 film coating Methods 0.000 description 5
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000981595 Zoysia japonica Species 0.000 description 2
- 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 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons 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
- 238000009835 boiling Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical group CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241001547860 Gaya Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- LRHPSIAOZILDQN-UHFFFAOYSA-N bis(1-hydroxy-5,6-dimethylcyclohexa-2,4-dien-1-yl)methanone Chemical compound CC1C(C)=CC=CC1(O)C(=O)C1(O)C(C)C(C)=CC=C1 LRHPSIAOZILDQN-UHFFFAOYSA-N 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
본 발명은 하드코팅액, 이를 사용한 하드코팅 필름 및 화상표시장치에 관한 것이다. The present invention relates to a hard coating liquid, a hard coating film and an image display apparatus using the same.
본 발명은 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올과 다관능성 (메타)아크릴레이트 모노머의 반응으로 제조되는 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진 하드코팅액을 제공하고, 이를 플라스틱 기재필름 상에 코팅한 후, 광조사하여 하드코팅층을 형성하여, 경도 및 광투과율이 개선되면서, 특히, 경화수축에 의한 필름의 컬(Curl)이 현저히 개선되는 하드코팅 필름을 제공하고, 상기의 하드코팅 필름이 구비된 화상표시장치를 제공하다. The present invention provides a photocurable (meth) acrylate oligomer, a polyfunctional (meth) acrylate monomer, a photoinitiator prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer. After providing a hard coating liquid consisting of a residual amount of solvent, coating it on a plastic base film, and then irradiated with light to form a hard coating layer, while improving the hardness and light transmittance, in particular, curl of the film by curing shrinkage (Curl) Provided is a hard coat film which is remarkably improved, and an image display device provided with the hard coat film.
Description
본 발명은 하드코팅액, 이를 사용한 하드코팅 필름 및 화상표시장치에 관한 것으로서, 보다 상세하게는, 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아클릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진 하드코팅액을 제공하고, 기재필름 상에 상기 하드코팅액을 코팅하여 하드코팅층을 형성함에 따라, 경도 및 광투과율이 개선되면서, 특히 경화수축에 의한 필름의 컬(Curl) 현상이 현저히 개선되는 하드코팅 필름 및 이를 구비한 화상표시장치에 관한 것이다. The present invention relates to a hard coating liquid, a hard coating film and an image display device using the same, and more particularly, to a photocurable (meth) acrylate oligomer, a polyfunctional (meth) acrylate monomer, a photoinitiator, and a residual solvent. By providing a hard coating liquid, and coating the hard coating liquid on the base film to form a hard coating layer, the hardness and light transmittance is improved, in particular, the hard coating film that significantly improves the curl (Curl) phenomenon due to curing shrinkage And an image display device having the same.
고분자 물질은 플라스틱의 형태로 우리의 실생활에 다양한 용도로 적용되고 있으며, 가공의 용이성, 대량 생산성, 가격의 안정성 측면에서 기존 고분자 재료들이 많은 부분에 새롭게 채택되어 사용되고 있다.Polymer materials are used in various forms in our real life in the form of plastics, and existing polymer materials are newly adopted and used in many parts in terms of ease of processing, mass productivity, and price stability.
최근에는 정보산업 및 멀티미디어의 발달로 각종 디스플레이 분야에 고분자 재료들이 사용되고 있으며, 그 대표적인 일례로 LCD 및 PDP와 같은 평판 디스플레가 있다. 특히, 디스플레이 소자의 윈도우는 일상생활에서의 내스크래치성, 각종 유기용제에 대한 저항성 및 증착, 구부림 등의 가공에 따른 열적 특성이 요구됨에 따라 기재필름 상에 하드코팅이 이루어진다. Recently, polymer materials have been used in various display fields due to the development of the information industry and multimedia, and representative examples thereof are flat panel displays such as LCD and PDP. In particular, the window of the display device is hard-coated on the base film as the scratch resistance in daily life, the resistance to various organic solvents and the thermal characteristics of the process such as deposition, bending, etc. are required.
하드코팅액은 크게 실리콘계, 멜라민계 등의 열경화형 하드코팅액 및 자외선 경화형 하드코팅액으로 크게 구분되나, 경화반응성의 제조성 면에서 자외선 경화형 하드코팅액이 바람직하다.The hard coating liquid is largely classified into thermosetting hard coating liquids such as silicone-based, melamine-based, and ultraviolet curing hard coating liquids, but UV-curable hard coating liquids are preferable from the viewpoint of curing reactivity.
일반적인 자외선 광경화형 하드코팅액 으로서는 불포화 폴리에스테르 수지계, 아크릴계 등의 라디컬 중합성 하드코팅액 및 에폭시계, 비닐에테르계 등의 양이온 중합성 하드코팅액기 사용할 수 있다. As a general ultraviolet light-curable hard coating liquid, radical polymerizable hard coating liquids, such as unsaturated polyester resin type and an acryl type, and cationic polymerizable hard coating liquids, such as an epoxy type and a vinyl ether type, can be used.
종래의 하드코팅제로 사용되는 고분자로는 아크릴성 중합체, 우레탄 중합체, 에폭시 중합체, 규소 중합체, 또는 실리카 화합물 등이 있다.Polymers used as conventional hard coating agents include acrylic polymers, urethane polymers, epoxy polymers, silicon polymers, silica compounds, and the like.
이러한 대부분의 하드코팅액은 가교 밀도를 증가시킬수록 내마모성은 증가하지만 코팅층의 수축성으로 인해 크랙(Crack)이 발생될 수 있으며 코팅 이음매의 변형을 가져올 수 있고, 이로 인하여 재질과의 접착력이 감소되어 약간의 접착에도 쉽게 떨어져 나가는 결과를 초래하는 문제점이 있다.Most of these hard coating liquids have increased abrasion resistance as the crosslinking density increases, but cracks may occur due to shrinkage of the coating layer, which may lead to deformation of the coating joint. There is a problem that results in easy peeling off even in the adhesion.
또한, 최근 화상표시 장치의 박형화가 요구되면서 하드코팅 필름의 종래 80~125㎛정도 두께의 절반 정도의 두께를 가지는 기재필름의 사용이 요구되고있는 바, 기재필름의 두께가 얇아질수록 하드코팅층의 경화수축에 의해 컬(Curl)이 발생되며 열적 가공을 할 경우 휘어짐 및 색 변화의 문제가 있다.In addition, as the image display device is required to be thin in recent years, the use of a base film having a thickness of about half of the thickness of the conventional 80 to 125 μm of the hard coating film is required. Curl is generated by hardening shrinkage, and there is a problem of warpage and color change when thermal processing is performed.
상기 컬(Curl)현상을 방지하기 위하여 분자량이 긴 올리고머 또는 비반응형 아크릴 수지 등을 사용하는 방법이 있으나, 이는 경도가 약해지는 문제점이 있다. 이에, 무기물인 콜로이드 실리카 입자를 포함하는 다양한 유-무기 코팅액이 하드코팅필름 의 경도 및 내마모성을 향상시키기 위해 사용되고 있으나, 이러한 유-무기 코팅액은 실리카 입자에 사용할 수 있는 용매가 물과 알코올류로 한정되어 있으므로 응용분야가 제한적이다. 또한, 상기 실리카 입자가 메틸 에틸 케톤, 메틸 이소부틸 케톤 등과 같은 케톤류 용매에 분산되어 있는 유-무기 코팅액도 있기는 하지만, 가격이 고가이며 겔화 또는 침전 등의 액상 안정성에 관한 문제점이 있다.In order to prevent the curl phenomenon, there is a method using a long molecular weight oligomer or non-reactive acrylic resin, etc., but this has a problem in that the hardness is weakened. Therefore, various organic-inorganic coating liquids including colloidal silica particles as inorganic materials are used to improve the hardness and wear resistance of the hard coating film, but such organic-inorganic coating liquids are limited to solvents that can be used for the silica particles as water and alcohols. Applications are limited. In addition, although the organic-inorganic coating liquid in which the silica particles are dispersed in ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and the like is expensive, there is a problem in terms of liquid stability such as gelation or precipitation.
이에, 본 발명자들은 종래기술의 문제를 해결하기 위하여 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올 및 (메타)아크릴산의 반응으로 제조된 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진 하드코팅액을 제공하고, 이를 플라스틱 기재필름 상에 코팅하여 제조된 하드코팅 필름이 고경도가 유지되면서 경화수축에 의한 컬(Curl)이 개선됨을 확인함으로써, 본 발명을 완성하였다.Accordingly, the present inventors, in order to solve the problems of the prior art, a photocurable (meth) acrylate oligomer prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and (meth) acrylic acid, a multifunctional (meth) By providing a hard coating solution consisting of an acrylate monomer, a photoinitiator and a residual amount of solvent, and coating it on a plastic base film to confirm that the hard coating film is maintained at high hardness while improving curl due to curing shrinkage. The present invention has been completed.
본 발명의 목적은 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올 및 다관능성 (메타)아크릴레이트 모노머의 반응으로 제조된 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진 하드코팅액을 제공하는 것이다.An object of the present invention is a photocurable (meth) acrylate oligomer prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate monomer, It is to provide a hard coating solution consisting of a photoinitiator and a residual solvent.
본 발명의 다른 목적은 플라스틱 기재필름 상에 상기의 하드코팅액이 적용되어 경화수축에 의한 컬(Curl)이 개선된 하드코팅 필름을 제공하는 것이다. Another object of the present invention is to provide a hard coating film having a hard curling by applying the hard coating solution on the plastic base film (Curl) by curing shrinkage.
본 발명의 또 다른 목적은 상기 하드코팅 필름이 구비되는 화상표시장치를 제공하는 것이다. Still another object of the present invention is to provide an image display device having the hard coating film.
상기 목적을 달성하기 위하여, 본 발명은 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올 및 다관능성 (메타)아크릴레이트 모노머의 반응으로 제조된 광경화형 (메타)아크릴레이트 올리고머 10 내지 55중량%; 다관능성 (메타)아크릴레이트 모노머 5 내지 30중량%; 광개시제 0.1 내지 10중량%; 및 잔량의 용매로 이루어지는 하드코팅액을 제공한다.In order to achieve the above object, the present invention is 10 to 55% by weight of a photocurable (meth) acrylate oligomer prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer ; 5 to 30 weight percent of a multifunctional (meth) acrylate monomer; 0.1 to 10% by weight photoinitiator; And it provides a hard coating liquid consisting of a residual amount of solvent.
상기 광경화형 (메타)아크릴레이트 올리고머가 하이드록시기 2~40개를 포함하고 분자량 200~4,000인 폴리에스테르 폴리올 50 내지 80중량% 및 다관능성 (메타)아크릴레이트 모노머 20~50중량%가 반응하여 제조된다.The photocurable (meth) acrylate oligomer comprises 2 to 40 hydroxyl groups, 50 to 80% by weight of a polyester polyol having a molecular weight of 200 to 4,000 and 20 to 50% by weight of a polyfunctional (meth) acrylate monomer Are manufactured.
상기 다관능성 (메타)아크릴레이트 모노머가 2관능성 이상의 다관능성 (메타)아크 릴레이트 모노머 단독; 또는 1관능성 (메타)아크릴레이트 모노머 및 2관능성 이상의 (메타)아크릴레이트 모노머의 혼합; 형태이다. The polyfunctional (meth) acrylate monomer is a bifunctional or higher polyfunctional (meth) aract monomer alone; Or a mixture of a monofunctional (meth) acrylate monomer and a bifunctional or higher (meth) acrylate monomer; Form.
이때, 상기 다관능성 (메타)아크릴레이트 모노머가 에폭시(메타)아크릴레이트, 폴리에스테르아크릴레이트, 우레탄아크릴레이트, 폴리올 펜타에리쓰리톨의 아크릴 모노머, 디펜타에리쓰리톨의 아크릴 모노머 및 히드록시알킬아크릴레트로 이루어진 군에서 선택되는 어느 하나 이상이며, 상기 1관능성 (메타)아크릴레이트 모노머가 (메타)아크릴산, (메타)아크릴산메틸, (메타)아크릴산에틸, (메타)아크릴산부틸, (메타)아크릴산헥실, (메타)아크릴산옥틸, (메타)아크릴산-2-에틸헥실로 이루어진 군에서 선택된 (메타)아크릴산 C1-C20알킬에스테르 또는 (메타)아크릴산시클로헥실, (메타)아크릴산페닐, (메타)아크릴산벤질, (메타)아크릴산-2-히드록시에틸, (메타)아크릴산-2-히드록시프로필로 이루어진 군에서 선택된 (메타)아크릴산히드록시 C2-C4알킬에스테르이다. At this time, the polyfunctional (meth) acrylate monomer is epoxy (meth) acrylate, polyester acrylate, urethane acrylate, acrylic monomer of polyol pentaerythritol, acrylic monomer of dipentaerythritol and hydroxyalkylacrylic At least one selected from the group consisting of retro, wherein the monofunctional (meth) acrylate monomer is (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate (Meth) acrylic acid C 1 -C 20 alkyl ester selected from the group consisting of octyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid benzyl (meth) acrylate, 2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl These (meth) acrylic acid C 2 -C 4 hydroxy-alkyl from the group consisting of A hotel.
나아가, 본 발명은 상기의 하드코팅액이 적용된 하드코팅 필름을 제공한다. 보다 구체적으로, 플라스틱 기재필름 상에, 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올 및 다관능성 (메타)아크릴레이트 모노머의 반응으로 제조된 광경화형 (메타)아크릴레이트 올리고머 10 내지 55중량%; 다관능성 (메타)아크릴레이트 모노머 5 내지 30중량%; 광개시제 0.1 내지 10중량%; 및 잔량의 용매; 로 이루어진 하드코팅액이 코팅된 후, 광조사하여 경화된 하드코팅층으로 이루어진 하드코팅 필름을 제공한다.Furthermore, the present invention provides a hard coating film to which the hard coating solution is applied. More specifically, 10 to 55% by weight of a photocurable (meth) acrylate oligomer prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer on a plastic base film ; 5 to 30 weight percent of a multifunctional (meth) acrylate monomer; 0.1 to 10% by weight photoinitiator; And residual solvent; After the coating is made of a hard coating liquid, it provides a hard coating film consisting of a hard coating layer cured by light irradiation.
이때, 상기 광경화형 (메타)아크릴레이트 올리고머가 하이드록시기 2~40개를 포함하고 분자량 200~4,000인 폴리에스테르 폴리올 50 내지 80중량% 및 다관능성 (메타)아크릴레이트 모노머 20~50중량%가 반응하여 제조된 것이다.At this time, the photocurable (meth) acrylate oligomer contains 2 to 40 hydroxyl groups, 50 to 80% by weight of a polyester polyol having a molecular weight of 200 to 4,000 and 20 to 50% by weight of a polyfunctional (meth) acrylate monomer It is prepared by reaction.
이때, 상기 플라스틱 기재필름의 두께가 80㎛ 이하이며, 상기 하드코팅층의 두께가 3~30㎛이다.At this time, the thickness of the plastic base film is 80㎛ or less, the thickness of the hard coating layer is 3 ~ 30㎛.
또한, 상기 하드코팅 필름의 경화수축에 의한 컬(Curl)이 10mm이하이다. In addition, the curl due to curing shrinkage of the hard coat film is 10mm or less.
더 나아가, 본 발명은 상기의 하드코팅 필름이 구비된 화상표시장치를 제공한다. Furthermore, the present invention provides an image display device provided with the hard coating film.
본 발명은 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올 및 다관능성 (메타)아크릴레이트 모노머의 반응으로 제조된 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진 하드코팅액을 제조하고, 이를 플라스틱 기재필름 상에 코팅 후, 광조사하여 하드코팅층을 형성함으로써, 고경도를 가지며 내스크래치성이 우수하면서, 특히 경화수축에 의한 컬(Curl)이 개선된 하드코팅 필름을 제공할 수 있다.The present invention provides a photocurable (meth) acrylate oligomer prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate monomer, a photoinitiator and By preparing a hard coating solution consisting of a residual amount of solvent, coating it on a plastic base film, and then irradiating with light to form a hard coating layer, it has a high hardness and excellent scratch resistance, in particular curl due to curing shrinkage It is possible to provide an improved hard coat film.
이하, 본 발명을 더욱 상세히 설명하고자 한다. Hereinafter, the present invention will be described in more detail.
본 발명은 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올 및 다관능성 (메타)아크릴레이트 모노머의 반응으로 제조된 광경화형 (메타)아크릴레이트 올리고머 10 내지 55중량%; 다관능성 (메타)아크릴레이트 모노머 5 내지 30중량%; 광개시제 0.1 내지 10중량%; 및 잔량의 용매로 이루어지는 하드코팅액을 제공한다.The present invention is 10 to 55% by weight of a photocurable (meth) acrylate oligomer prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer; 5 to 30 weight percent of a multifunctional (meth) acrylate monomer; 0.1 to 10% by weight photoinitiator; And it provides a hard coating liquid consisting of a residual amount of solvent.
본 발명에서 사용되는 광경화형 (메타)아크릴레이트 올리고머는 하이드록시기 2~40개를 포함하고 분자량 200~4,000인 폴리에스테르 폴리올 50 내지 80중량% 및 다관능성 (메타)아크릴레이트 모노머 20~50중량% 간의 축합반응에 의해 제조될 수 있다. The photocurable (meth) acrylate oligomers used in the present invention include 2 to 40 hydroxyl groups and 50 to 80% by weight of a polyester polyol having a molecular weight of 200 to 4,000 and 20 to 50% by weight of a polyfunctional (meth) acrylate monomer. It can be prepared by the condensation reaction between%.
상기 광경화형 (메타)아크릴레이트 올리고머는 저점도의 올리고머로서 하드코팅층 형성 시에, 통상의 아크릴레이트 올리고머의 적용에 비하여 최종 코팅된 막의 경도(hardness)를 증가시킨다.The photocurable (meth) acrylate oligomers are low viscosity oligomers, which, when forming a hard coat layer, increase the hardness of the final coated film compared to the application of conventional acrylate oligomers.
상기 광경화형 (메타)아크릴레이트 올리고머는 10 내지 55 중량%의 함량이 바람직하며, 10 중량% 미만일 경우에는 막의 크랙이 발생하기 쉽고, 함량이 55 중량%를 초과할 경우에는 최종 하드코팅액의 점도가 높아질 우려가 있어 바람직하지 않다.The photocurable (meth) acrylate oligomer is preferably in a content of 10 to 55% by weight, less than 10% by weight of the film is likely to crack, when the content is more than 55% by weight of the final hard coating liquid It is not preferable because it may increase.
상기 다관능(메타)아크릴레이트 모노머는 막의 강도를 높여주고 하드코팅제의 점도를 낮추어주는 역할을 하며, 5 내지 30중량%의 함량이 바람직하다. 함량이 5 중량% 미만일 경우에는 코팅막의 경도가 약화되며, 함량이 30 중량% 초과일 경우에는 코팅막에 크랙이 발생하는 문제점이 있어 바람직하지 않다.The polyfunctional (meth) acrylate monomer serves to increase the strength of the film and lower the viscosity of the hard coating agent, the content of 5 to 30% by weight is preferred. If the content is less than 5% by weight, the hardness of the coating film is weakened. If the content is more than 30% by weight, there is a problem that cracks occur in the coating film is not preferable.
상기 광경화형 (메타)아크릴레이트 올리고머는 폴리에스테르 폴리올 50 내지 80중량% 및 다관능성 (메타)아크릴레이트 모노머 20~50중량% 간의 축합반응에 의해 제조될 수 있으며, 상기의 반응으로 제조된 우레탄 아크릴레이트 수지가 사용될 수 있다. The photocurable (meth) acrylate oligomer may be prepared by a condensation reaction between 50 to 80% by weight of polyester polyol and 20 to 50% by weight of polyfunctional (meth) acrylate monomer, and the urethane acrylic prepared by the above reaction. Rate resins can be used.
이때, 상기 폴리에스테르 폴리올이 50중량% 미만이면 코팅막의 경도 및 밀착성을 약화시키는 문제점이 있고, 80중량%를 초과하면 최종 조성물의 점도가 높아져 바람 직하지 않다. 또한, 상기 폴리에스테르 폴리올은 하이드록시기 2~40개를 포함하는 것으로 하이드록시기가 2개인 글리콜 즉, 에틸렌글리콜, 프로필렌글리콜, 부틸렌글리콜, 네오펜틸글리콜, 헥사메틸렌글리콜 등의 에스테르화 축합반응으로 얻어질 수 있으며 분자량 200~4,000이 바람직하다. At this time, when the polyester polyol is less than 50% by weight, there is a problem of weakening the hardness and adhesion of the coating film, and when the amount exceeds 80% by weight, the final composition has a high viscosity, which is not preferable. In addition, the polyester polyol contains 2 to 40 hydroxyl groups, and esterification condensation reactions such as glycols having 2 hydroxyl groups, that is, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and hexamethylene glycol. Can be obtained and molecular weights of 200 to 4,000 are preferred.
상기 다관능성 (메타)아크릴레이트 모노머로는 2관능성 이상의 다관능성 (메타)아크릴레이트 모노머 단독 또는 1관능성 (메타)아크릴레이트 모노머 및 2관능성 이상의 (메타)아크릴레이트 모노머의 혼합 형태인 혼합 다관능성 (메타)아크릴레이트가 사용될 수 있다. As said polyfunctional (meth) acrylate monomer, the mixture which is a mixed form of a bifunctional or more than one polyfunctional (meth) acrylate monomer or monofunctional (meth) acrylate monomer, and a bifunctional or more (meth) acrylate monomer is mixed. Multifunctional (meth) acrylates can be used.
상기 다관능성 (메타)아크릴레이트 모노머는 분자내에 2개 이상의 에폭시기를 갖는 화합물에 (메타)아크릴산을 반응시켜 얻어지는 에폭시 (메타)아크릴레이트, 다가알코올과 다가카르복실산 및 그 무수물과 (메타)아크릴산을 에스테르화시켜 얻어지는 폴리에스테르아크릴레이트, 다가알코올과 다가이소시아네이트, 수산기 함유 아크릴레이트를 반응시켜 얻어지는 우레탄아크릴레이트 등의 혼합물이 사용될 수 있다. 또한, 다관능성 (메타)아크릴레이트 모노머로 폴리올 펜타에리쓰리톨, 디펜타에리쓰리톨의 아크릴 모노머 및 히드록시알킬아크릴레이트가 사용될 수 있으며, 디펜타에리쓰리톨의 아크릴 모노머로 디펜타에리스리톨헥사아크릴레이트(DPHA), 히드록시알킬아크릴레이트로 2-하이드록시에틸메타크릴레이트(HEMA)가 사용될 수 있다. The said polyfunctional (meth) acrylate monomer is epoxy (meth) acrylate obtained by making (meth) acrylic acid react with the compound which has two or more epoxy groups in a molecule | numerator, polyhydric alcohol, polyhydric carboxylic acid, its anhydride, and (meth) acrylic acid Polyester acrylate obtained by esterifying, polyhydric alcohol, polyhydric isocyanate, and mixtures, such as urethane acrylate obtained by making hydroxyl-containing acrylate react, can be used. In addition, polyol pentaerythritol, an acrylic monomer of dipentaerythritol, and hydroxyalkyl acrylate may be used as the polyfunctional (meth) acrylate monomer, and dipentaerythritol hexaacryl as the acrylic monomer of dipentaerythritol. 2-hydroxyethyl methacrylate (HEMA) can be used as the rate (DPHA), hydroxyalkyl acrylate.
또한, 사용 가능한 1관능성 (메타)아크릴레이트 모노머 일례로, (메타)아크릴산, (메타)아크릴산메틸, (메타)아크릴산에틸, (메타)아크릴산부틸, (메타)아크릴산헥실, (메타)아크릴산옥틸, (메타)아크릴산-2-에틸헥실로 이루어진 군에서 선택되는 (메타)아크릴산 C1-C20 알킬에스테르 또는 (메타)아크릴산시클로헥실, (메타)아크릴산페닐, (메타)아크릴산벤질, (메타)아크릴산-2-히드록시에틸, (메타)아크릴산-2-히드록시프로필로 이루어진 군에서 선택되는 (메타)아크릴산히드록시 C2-C4 알킬에스테르 등이 있으며, 이들의 공중합 가능한 모노머는 단독으로 또는 이들을 조합하여 사용할 수 있다.Moreover, as an example of the monofunctional (meth) acrylate monomer which can be used, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and octyl (meth) acrylate (Meth) acrylic acid C 1 -C 20 alkyl ester or (meth) acrylic acid cyclohexyl, (meth) phenyl acrylate, (meth) acrylic acid benzyl, (meth) (Meth) acrylic acid hydroxy C 2 -C 4 alkyl ester selected from the group consisting of 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylic acid, and these copolymerizable monomers are used alone or These can be used in combination.
본 발명에 사용되는 광개시제는 벤조페논계 화합물, 벤질 디메탈 케탈계 화합물, 아세토페논계 화합물, 안트라퀴논계 화합물, 벤질케탈계 화합물, 이들의 혼합물 등이 있으며, 구체적으로는 2,2-디메톡시-2-페닐아세토페논, 1-하이드록시사이클로헥실페닐 케톤, 1-하이드록시디메틸페닐케톤등이 바람직하게 사용될 수 있다. 광개시제는 0.1 내지 10 중량%로 사용하는 것이 바람직하며, 함량이 0.1 중량% 미만일 경우에는 충분히 경화하지 않는 경우가 발생하여 코팅막의 경도가 약화될 수 있고, 10 중량%를 초과할 경우에는 개시제 자체가 라디칼과 반응하여 중합을 억제하는 현상이 발생하여 바람직하지 않다.Photoinitiators used in the present invention include benzophenone compounds, benzyl dimetal ketal compounds, acetophenone compounds, anthraquinone compounds, benzyl ketal compounds, mixtures thereof, and the like, specifically 2,2-dimethoxy 2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxydimethylphenyl ketone and the like can be preferably used. Preferably, the photoinitiator is used in an amount of 0.1 to 10% by weight, and if the content is less than 0.1% by weight, it may not be sufficiently cured, and thus the hardness of the coating film may be weakened. The phenomenon of inhibiting polymerization by reacting with radicals occurs, which is undesirable.
본 발명에 사용되는 용매는 하드코팅액의 잔량, 보다 바람직하게는 5 내지 70 중량%가 함유된다. 상기 용매로 벤젠, 톨루엔, 크실렌 등의 방향족 탄화수소, 헥산, 헵탄, 옥탄, 노난, 데칸 등의 지방족 탄화수소, 메틸에틸케톤, 디에틸케톤, 디이소프로필케톤 등의 케톤 및 이들의 혼합물 등이 사용될 수 있으며, 보다 바람직하게는 방향족 화합물인 톨루엔과 케톤계 화합물인 메틸에틸케톤을 1:1의 비율로 사용 하는바, 이는 고비점용제인 톨루엔과 저비점용제인 메틸에틸케톤을 균일하게 사용함으로써 하드코팅층의 경도와 밀착성의 균형을 잡고 필름의 투명성에 영향을 미치지 않기 때문이다. The solvent used in the present invention contains the remaining amount of the hard coating solution, more preferably 5 to 70% by weight. As the solvent, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, nonane and decane, ketones such as methyl ethyl ketone, diethyl ketone and diisopropyl ketone, and mixtures thereof may be used. More preferably, toluene, which is an aromatic compound, and methyl ethyl ketone, which is a ketone compound, are used in a ratio of 1: 1, which uniformly uses toluene, which is a high boiling point solvent, and methyl ethyl ketone, which is a low boiling point solvent. This is because it balances the adhesiveness with and does not affect the transparency of the film.
본 발명의 하드코팅액은 상기 물질 이외에도 각종 첨가성분으로 안티글레어성을 부여하기 위한 충전제, 반응성 실리콘 화합물, 열적고분자화 금지제, 가교제, 산화방지제, 자외선 흡수제, 광안정제, 레벨링제, 소포제등을 적절히 함유할 수 있다. In addition to the above materials, the hard coating solution of the present invention may be suitably used as a filler, a reactive silicone compound, a thermal polymerization inhibitor, a crosslinking agent, an antioxidant, a UV absorber, a light stabilizer, a leveling agent, an antifoaming agent, etc. It may contain.
또한, 본 발명의 하드코팅액은 기재필름상의 도포를 쉽게 하기위해서 희석제 5 내지 70 중량%를 함유할 수 있으며, 희석제의 배합량은 요구되는 점도가 되도록 적절히 선정할 수 있다. 상기 희석제의 일례로 벤젠, 톨루엔, 크실렌 등의 방향족 탄화수소, 헥산, 헵탄, 옥탄, 노난, 데칸 등의 지방족 탄화수소, 메틸에틸케톤, 디에틸케톤, 디이소프로필케톤 등의 케톤이 있다. In addition, the hard coating liquid of the present invention may contain 5 to 70% by weight of the diluent to facilitate the coating on the base film, the compounding amount of the diluent may be appropriately selected so that the required viscosity. Examples of the diluent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, nonane and decane, ketones such as methyl ethyl ketone, diethyl ketone and diisopropyl ketone.
나아가, 본 발명은 상기의 하드코팅액이 적용된 하드코팅 필름을 제공한다. 보다 구체적으로, Furthermore, the present invention provides a hard coating film to which the hard coating solution is applied. More specifically,
플라스틱 기재필름 상에, 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올 및 다관능성 (메타)아크릴레이트 모노머의 반응으로 제조된 광경화형 (메타)아크릴레이트 올리고머 10 내지 55중량%, 다관능성 (메타)아크릴레이트 모노머 5 내지 30중량%, 광개시제 0.1 내지 10중량% 및 잔량의 용매로 이루어진 하드코팅액이 코팅된 후, 광조사하여 경화되어 형성된 하드코팅층으로 이루어진 하드코팅 필름을 제공한다.On the plastic base film, 10 to 55% by weight of a photocurable (meth) acrylate oligomer prepared by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer, and polyfunctional ( Meta) acrylate monomer 5 to 30% by weight, photoinitiator 0.1 to 10% by weight and the remaining amount of the solvent is coated, and then irradiated with light to provide a hard coating film consisting of a hard coating layer formed.
상기 플라스틱 기재필름은 특별히 제한되지 않으며, 종래 광학용 하드코팅 필름의 기재로서 공지된 플라스틱필름 중에서 용도에 따라 투명 또는 반투명 중 적절히 선택해서 이용할 수 있으며, 그 일례로 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등의 폴리에스테르 필름, 폴리에틸렌 필름, 폴리프로필렌필름, 셀로판, 디아세틸셀룰로오스필름, 트리아세틸셀룰로오스필름, 아세틸셀룰로오스부틸레이트필름, 폴리염화비닐필름, 폴리염화비닐리덴필름, 폴리비닐알코올필름, 에틸렌-아세트산비닐공중합체필름, 폴리스티렐필름, 폴리카보네이트필름, 폴리메틸펜텐필름, 폴리설폰필름, 폴리에테르에테르케톤필름, 폴리에테르설폰필름, 폴리에테르이미드필름, 폴리이미드필름, 불소수지필름, 폴리아미드필름, 아크릴수지필름, 노르보르넨계 수지 필름, 시클로올레핀수지필름 등이 있으며, 투명성 및 광학적으로 이방성이 없다는 점에서 무색투명의 트리아세틸셀룰로오스필름 또는 폴리메틸메타아크릴레이트 필름이 보다 적합하다.The plastic base film is not particularly limited, and may be appropriately selected from transparent plastic or translucent according to the use of a plastic film known as a substrate of a conventional optical hard coating film, and examples thereof include polyethylene terephthalate and polybutylene terephthalate. , Polyester film such as polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film , Ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyetherimide film, polyimide film, fluororesin film, Polyamide Film, Arc Resin films, norbornene resin films, cycloolefin resin films and the like, and optically transparent is more suitable in that the anisotropy is a triacetyl cellulose film or a polymethyl methacrylate film having a transparent and colorless.
상기 플라스틱 기재필름의 두께는 특별한 제한은 없으며, 상황에 따라서 적절히 선정되지만, 컬(Curl)현상 억제작용이 효과적으로 발휘되는 관점에서, 80㎛이하가 바람직하고, 보다 바람직하게는 20~80㎛의 범위이다. The thickness of the plastic base film is not particularly limited and may be appropriately selected depending on the situation, but from the viewpoint of effectively suppressing curl phenomenon, 80 μm or less is preferable, and more preferably in the range of 20 to 80 μm. to be.
상기 하드코팅액은 폴리에스테르 폴리올 및 다관능성 (메타)아크릴레이트의 반응으로 제조되는 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진다.The hard coating solution consists of a photocurable (meth) acrylate oligomer, a polyfunctional (meth) acrylate monomer, a photoinitiator and a residual solvent prepared by the reaction of a polyester polyol and a polyfunctional (meth) acrylate.
이때, 상기 광경화형 (메타)아크릴레이트 올리고머는 하이드록시기 2~40개를 포함하고 분자량 200~4,000인 폴리에스테르 폴리올 50 내지 80중량% 및 다관능성 (메 타)아크릴레이트 모노머 20~50중량%의 축합반응으로 제조될 수 있다. At this time, the photocurable (meth) acrylate oligomer includes 2 to 40 hydroxyl groups, 50 to 80% by weight of a polyester polyol having a molecular weight of 200 to 4,000 and 20 to 50% by weight of a polyfunctional (meth) acrylate monomer. It can be prepared by the condensation reaction of.
또한, 상기 하드코팅액의 조성 비율은 이를 기재필름에 코팅시 도막의 경도, 밀착성, 휘어짐(curl), 조성물의 점도 등을 고려하여 최적화한 것이다. In addition, the composition ratio of the hard coating solution is optimized in consideration of the hardness of the coating film, the adhesion, the curvature (curl), the viscosity of the composition and the like when coating the base film.
상기 하드코팅액의 조성물에 대한 상세한 설명은 앞서 설명된 내용과 동일하며, 플라스틱 기재필름 상에 바 코팅법, 나이프 코팅법, 롤 코팅법, 블레이드 코팅법, 다이 코팅법, 그라비아 코팅법, 스핀코팅법 등으로 도포될 수 있다. Detailed description of the composition of the hard coating solution is the same as described above, the bar coating method, knife coating method, roll coating method, blade coating method, die coating method, gravure coating method, spin coating method on a plastic base film Or the like.
상기 광조사는 자외선 및 전자선이 적용될 수 있으며, 자외선은 고압수은 램프, 퓨전 H램프, 크세논 램프 등에 의해서 얻어지고, 조사량은 통상 100~500mJ/㎠이다. 한편 전자선은 전자선가속기등에 의해서 얻어질 수 있으며 조사량은150~350㎸이다. 활성 에너지선으로서 특히 자외선이 보다 바람직하며, 전자선을 사용하는 경우는 광개시제를 첨가하지 않고 경화막을 얻을 수 있다.Ultraviolet rays and electron beams may be applied to the light irradiation, and the ultraviolet rays are obtained by a high pressure mercury lamp, a fusion H lamp, a xenon lamp, and the like, and an irradiation amount is usually 100 to 500 mJ / cm 2. On the other hand, the electron beam can be obtained by an electron beam accelerator and the irradiation amount is 150 ~ 350150. Especially as an active energy ray, an ultraviolet-ray is more preferable, and when using an electron beam, a cured film can be obtained without adding a photoinitiator.
상기 하드코팅층의 두께는 3~30㎛, 보다 바람직하게는 3~10㎛범위이며, 연필강도 3H이상 고경도의 하드코팅 필름을 얻을 수 있는 두께이다.The hard coating layer has a thickness of 3 to 30 µm, more preferably 3 to 10 µm, and a thickness of hard coating film having a hardness of 3H or higher pencil strength.
또한, 상기 하드코팅 필름은 광투과율 90%이상의 고투명성이 유지되면서, 경화수축에 의한 컬(Curl)이 10mm 미만으로 개선된다.In addition, the hard coating film is maintained in a high transparency of 90% or more light transmittance, the curl (curl) by curing shrinkage is improved to less than 10mm.
더 나아가, 본 발명은 상기의 하드코팅 필름이 구비된 화상표시장치를 제공할 수 있다. Furthermore, the present invention can provide an image display device provided with the hard coating film.
즉, 본 발명은 하이드록시기 2~40개를 포함하는 폴리에스테르 폴리올에 다관능성 (메타)아크릴레이트를 축합반응시킴으로써 제조된 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어 진 하드코팅액을 사용함으로써, 하드코팅액이 기재필름에 코팅시 (메타)아크릴로일기를 포함함으로써 하드코팅층 형성시에 향상된 가교성으로 인해 경화 수축을 완화하여 컬의 발생을 방지할 수 있고, 필름의 경도가 개선될 수 있다. That is, the present invention is a photocurable (meth) acrylate oligomer, polyfunctional (meth) acrylate monomer prepared by condensation reaction of a polyfunctional (meth) acrylate to a polyester polyol containing 2 to 40 hydroxyl groups, By using a hard coating solution composed of a photoinitiator and a residual amount of solvent, the hard coating solution contains a (meth) acryloyl group when coated on the base film, thereby relieving cure shrinkage due to improved crosslinkability in forming a hard coating layer, thereby preventing curl generation. Can be prevented and the hardness of the film can be improved.
이하, 본 발명을 실시예에 의하여 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to examples.
하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. The following examples are merely illustrative of the present invention, but the scope of the present invention is not limited to the following examples.
<실시예 1>≪ Example 1 >
다관능 우레탄 아크릴레이트(일본화약 사, 가야야드 디펜타에리트리톨헥사아크릴레이트(DPHA-40)) 20 중량%, 디펜타에리트리톨헥사아크릴레이트(DPHA)(산노푸코 사, NOPCOMER 4612) 와 2-하이드록시에틸메타크릴레이트(HEMA)(데구사 사, HEMA 98) 혼합물 10 중량%, 1-하이드록시사이클로헥실페닐케톤(시바게이지 사, Igacure 184) 1중량%, 실리콘 첨가제(데구사 사, Glide 440) 0.5 중량%, 톨루엔 25 중량%, 메틸에틸케톤 25 중량%, 사이클로헥사논 2 중량%를 혼합하여 상온에서 30분 동안 교반기를 이용하여 800rpm으로 충분히 교반(stirring)시켜 하드코팅액을 제조하였다. 제조된 하드코팅액을 투명기재 필름(TAC, 40㎛)위에 바코터로 도포하고, 60℃에서 3분간 건조한 후, 500mJ/㎠으로 경화시켜 하드코팅 필름을 제조하였다. 이때, 제조된 필름 코팅층의 두께는 5㎛이었다.20% by weight of polyfunctional urethane acrylate (Gaya Chemical Co., Ltd., yardyard dipentaerythritol hexaacrylate (DPHA-40)), 2-pentaerythritol hexaacrylate (DPHA) (Sannofuco, NOPCOMER 4612) and 2- 10% by weight of a mixture of hydroxyethyl methacrylate (HEMA) (Degussa, HEMA 98), 1% by weight of 1-hydroxycyclohexylphenylketone (Shibagauge, Igacure 184), silicone additive (Degussa, Glide) 440) 0.5% by weight, 25% by weight of toluene, 25% by weight of methyl ethyl ketone, and 2% by weight of cyclohexanone were mixed and sufficiently stirred at 800 rpm using a stirrer at room temperature for 30 minutes to prepare a hard coating solution. The prepared hard coating solution was coated on a transparent base film (TAC, 40㎛) with a bar coater, dried at 60 ° C. for 3 minutes, and cured at 500 mJ / cm 2 to prepare a hard coating film. At this time, the thickness of the prepared film coating layer was 5㎛.
<실시예 2><Example 2>
폴리에스테르 아크릴레이트 20 중량%, 디펜타에리트리톨헥사아크릴레이트(DPHA)(산 노푸코 사, NOPCOMER 4612) 와 2-하이드록시에틸메타크릴레이트(HEMA)(데구사 사, HEMA 98) 혼합물 10 중량%, 1-하이드록시사이클로헥실페닐케톤(시바게이지 사, Igacure 184) 1중량%, 실리콘 첨가제(데구사 사, Glide 440) 0.5 중량%, 메틸에틸케톤 25 중량%, 사이클로헥사논 2 중량%를 혼합하여 상온에서 30분 동안 교반기를 이용하여 800rpm으로 충분히 교반시켜 하드코팅액을 제조하였다. 제조된 하드코팅액을 투명기재 필름(TAC, 40㎛)위에 바코터로 도포하고, 60℃에서 3분간 건조한 후, 500mJ/㎠으로 경화시켜 하드코팅 필름을 제조하였다. 이때, 제조된 필름 코팅층의 두께는 5㎛이었다.20 wt% polyester acrylate, 10 wt% mixture of dipentaerythritol hexaacrylate (DPHA) (NOPCOMER 4612, Sannofuco) and 2-hydroxyethyl methacrylate (HEMA) (Degusa, HEMA 98) %, 1% by weight of 1-hydroxycyclohexylphenyl ketone (Shiba gauge, Igacure 184), 0.5% by weight silicone additive (Degussa, Glide 440), 25% by weight methyl ethyl ketone, 2% by weight cyclohexanone The mixture was stirred sufficiently at 800 rpm using a stirrer at room temperature for 30 minutes to prepare a hard coating solution. The prepared hard coating solution was coated on a transparent base film (TAC, 40㎛) with a bar coater, dried at 60 ° C. for 3 minutes, and cured at 500 mJ / cm 2 to prepare a hard coating film. At this time, the thickness of the prepared film coating layer was 5㎛.
<실시예 3><Example 3>
폴리에스테르(메타)아크릴레이트 80중량% 및 디펜타에리트리톨헥사(메타)아크릴레이트 20중량%의 축합반응에 의해 제조된 광경화형 (메타)아크릴레이트 올리고머 20중량%, 디펜타에리트리톨헥사아크릴레이트(DPHA)(산노푸코 사, NOPCOMER 4612) 와 2-하이드록시에틸메타크릴레이트(HEMA)(데구사 사, HEMA 98) 혼합물 10 중량%, 1-하이드록시사이클로헥실페닐케톤(시바게이지 사, Igacure 184) 1중량%, 실리콘 첨가제(데구사 사, Glide 440) 0.5 중량%, 메틸에틸케톤 25 중량%, 사이클로헥사논 2 중량%를 혼합하여 상온에서 30분 동안 교반기를 이용하여 800rpm으로 충분히 교반시켜 하드코팅액을 제조하였다. 제조된 하드코팅액을 투명기재 필름(TAC, 40㎛)위에 바코터로 도포하고, 60℃에서 3분간 건조한 후, 500mJ/㎠으로 경화시켜 하드코팅 필름을 제조하였다. 이때, 제조된 필름 코팅층의 두께는 5㎛이었다.20 wt% of photocurable (meth) acrylate oligomers prepared by condensation of 80 wt% of polyester (meth) acrylate and 20 wt% of dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexaacrylate (DPHA) (NOPCOMER 4612, Sanofucco, Inc.) and 10% by weight of 2-hydroxyethyl methacrylate (HEMA) (Degussa, HEMA 98), 1-hydroxycyclohexylphenyl ketone (Shibagauge, Igacure) 184) 1% by weight, 0.5% by weight of a silicone additive (Degussa, Glide 440), 25% by weight of methyl ethyl ketone, 2% by weight of cyclohexanone and thoroughly stirred at 800 rpm using a stirrer at room temperature for 30 minutes A hard coating solution was prepared. The prepared hard coating solution was coated on a transparent base film (TAC, 40㎛) with a bar coater, dried at 60 ° C. for 3 minutes, and cured at 500 mJ / cm 2 to prepare a hard coating film. At this time, the thickness of the prepared film coating layer was 5㎛.
<비교예 1>Comparative Example 1
우레탄 아크릴레이트(일본화약 사, 가야야드 디펜타에리트리톨헥사아크릴레이트(DPHA-40)) 20 중량%, 펜타에리트리톨트리(메타)아크릴레이트(PETA)(미원상사, M340) 10 중량%, 1-하이드록시사이클로헥실페닐케톤(시바게이지 사, Igacure 184) 1중량%, 실리콘 첨가제(데구사 사, Glide 440) 0.5 중량%, 톨루엔 25 중량%, 메틸에틸케톤 25 중량%, 사이클로헥사논 2 중량%를 혼합하여 상온에서 30분 동안 교반기를 이용하여 800rpm으로 충분히 교반(stirring)시켜 하드코팅액을 제조하였다. 제조된 하드코팅액을 투명기재 필름(TAC, 40㎛)위에 바코터로 도포하고, 60℃에서 3분간 건조한 후, 500mJ/㎠으로 경화시켜 하드코팅 필름을 제조하였다. 이때, 제조된 필름 코팅층의 두께는 5㎛이었다.20% by weight of urethane acrylate (Gayayard Dipentaerythritol hexaacrylate (DPHA-40)), 10% by weight of pentaerythritol tri (meth) acrylate (PETA) (Miwon Corporation, M340), 1 -1% by weight of hydroxycyclohexylphenyl ketone (Shiba gauge, Igacure 184), 0.5% by weight of silicone additive (Degussa, Glide 440), 25% by weight of toluene, 25% by weight of methyl ethyl ketone, 2 parts of cyclohexanone Mixing the% by using a stirrer for 30 minutes at room temperature sufficiently stirred (800rrm) to prepare a hard coating solution. The prepared hard coating solution was coated on a transparent base film (TAC, 40㎛) with a bar coater, dried at 60 ° C. for 3 minutes, and cured at 500 mJ / cm 2 to prepare a hard coating film. At this time, the thickness of the prepared film coating layer was 5㎛.
<비교예 2>Comparative Example 2
폴리에스테르 아크릴레이트 20 중량%, 펜타에리트리톨트리(메타)아크릴레이트(PETA)(미원상사, M340) 10 중량%, 1-하이드록시사이클로헥실페닐케톤(시바게이지 사, Igacure 184) 1중량%, 실리콘 첨가제(데구사 사, Glide 440) 0.5 중량부, 메틸에틸케톤 25 중량%, 사이클로헥사논 2 중량%를 혼합하여 상온에서 30분 동안 교반기를 이용하여 800rpm으로 충분히 교반시켜 하드코팅액을 제조하였다. 제조된 하드코팅액을 투명기재 필름(TAC, 40㎛)위에 바코터로 도포하고, 60℃에서 3분간 건조한 후, 500mJ/㎠으로 경화시켜 하드코팅 필름을 제조하였다. 이때, 제조된 필름 코팅층의 두께는 5㎛이었다.20% by weight of polyester acrylate, 10% by weight of pentaerythritol tri (meth) acrylate (PETA) (Miwon Corporation, M340), 1% by weight of 1-hydroxycyclohexylphenyl ketone (Shibagauge, Igacure 184), 0.5 parts by weight of a silicon additive (Degus Co., Ltd., Glide 440), 25% by weight of methyl ethyl ketone, and 2% by weight of cyclohexanone were sufficiently mixed at 800 rpm using a stirrer at room temperature for 30 minutes to prepare a hard coating solution. The prepared hard coating solution was coated on a transparent base film (TAC, 40㎛) with a bar coater, dried at 60 ° C. for 3 minutes, and cured at 500 mJ / cm 2 to prepare a hard coating film. At this time, the thickness of the prepared film coating layer was 5㎛.
<실험예>Experimental Example
상기 실시예 및 비교예에서 제조된 하드코팅 필름에 대하여 투과율 및 헤이즈, 스 크래치 저항도 및 경화수축에 대한 컬(Curl)을 측정하여 하기 표1에 기재하였다. The hard coat films prepared in Examples and Comparative Examples were measured and curled for haze, scratch resistance, and curing shrinkage, and are shown in Table 1 below.
1. 투과율 및 헤이즈 측정1. Transmittance and haze measurement
분광광도계(HM-150, 일본 무라카미사)를 이용하여 전광선투과율(Total Transmittance)과 헤이즈(Haze)를 측정하였다.Total light transmittance and total haze were measured using a spectrophotometer (HM-150, Murakami, Japan).
2. 스크래치(Scretch)에 대한 저항강도 측정2. Measurement of resistance strength against scratch
연필경도 시험기(PHT, 한국 석보과학사)를 이용하여 500g 하중을 걸고 연필경도를 측정하였다. 연필은 미쯔비시 제품을 사용하고 한 연필경도당 5회 실시로 긁힘(scretch)이 발생되는 연필심의 경도를 측정하였다.Pencil hardness was measured using a pencil hardness tester (PHT, Korea Seokbo Science). As a pencil, Mitsubishi products were used and five times per pencil hardness, the hardness of the pencil lead, which caused scratches, was measured.
3. 경화수축에 의한 컬(Curl) 측정3. Curling by hardening shrinkage
하드코팅필름을 10cm 사방 직각으로 절단한 시료를 평탄한 글라스 판 위에, 필름의 도포된 면을 위로해서 두고, 4각의 유리판으로부터 떨어진 거리를 23℃, 55%RH에서 측정하여 평균값을 기재하였다.The sample which cut | disconnected the hard-coating film at 10 cm square at right angles was put on the flat glass plate with the coated surface of the film facing up, and the distance from the four glass plate was measured at 23 degreeC and 55% RH, and the average value was described.
상기 실험결과에 따라, 본 발명의 특정 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진 하드코팅액을 적용한 실시예 1 내지 3은 연필경도 3H의 고경도를 보이면서, 경화수축에 의한 컬(Curl)이 각각 9.6mm, 8.7mm 및 9.1mm로 현저히 개선되었다. According to the experimental results, Examples 1 to 3 to which a hard coating liquid consisting of a specific photocurable (meth) acrylate oligomer of the present invention, a polyfunctional (meth) acrylate monomer, a photoinitiator and a residual solvent are applied, have a high hardness of pencil hardness 3H. As shown, the curl due to hardening shrinkage was significantly improved to 9.6 mm, 8.7 mm and 9.1 mm, respectively.
본 발명은 하드코팅액으로서 히드록시기 2~40개를 포함하는 폴리에스테르 폴리올에 다관능성 (메타)아크릴레이트 모노머을 축합반응시킴으로써 제조된 광경화형 (메타)아크릴레이트 올리고머, 다관능성 (메타)아크릴레이트 모노머, 광개시제 및 잔량의 용매로 이루어진 하드코팅액을 사용함으로서, 이를 플라스틱 기재필름에 코팅 후, 광조사하여 하드코팅층 형성 시에 경도 및 광투과도가 개선되고, 특히, 경화수축에 의한 컬(Curl) 현상이 현저하게 개선된 하드코팅 필름이 제공되어 LCD 및 PDP 등의 각종 평판 디스플레이의 화상표시장치로의 적용이 용이하다. The present invention provides a photocurable (meth) acrylate oligomer, a polyfunctional (meth) acrylate monomer, and a photoinitiator prepared by condensation of a polyfunctional (meth) acrylate monomer to a polyester polyol containing 2 to 40 hydroxyl groups as a hard coating solution. And by using a hard coating liquid consisting of a residual amount of the solvent, after coating it on a plastic base film, and the light irradiation to improve the hardness and light transmittance when forming a hard coating layer, in particular, the curl phenomenon due to curing shrinkage remarkably The improved hard coating film is provided to facilitate application of various flat panel displays such as LCD and PDP to image display devices.
이상에서 본 발명은 기재된 실시예에 대해서만 상세히 기술되었지만, 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications belong to the appended claims.
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