TWI821528B - Liquid crystal panels and liquid crystal display devices - Google Patents
Liquid crystal panels and liquid crystal display devices Download PDFInfo
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- TWI821528B TWI821528B TW109105868A TW109105868A TWI821528B TW I821528 B TWI821528 B TW I821528B TW 109105868 A TW109105868 A TW 109105868A TW 109105868 A TW109105868 A TW 109105868A TW I821528 B TWI821528 B TW I821528B
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- liquid crystal
- adhesive layer
- polarizing film
- layer
- meth
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 174
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- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 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
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 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 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- CGQIJXYITMTOBI-UHFFFAOYSA-N hex-5-enyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCC=C CGQIJXYITMTOBI-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 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 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 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 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical group CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RKYSDIOEHLMYRS-UHFFFAOYSA-N triethoxy(hex-5-enyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCC=C RKYSDIOEHLMYRS-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical group CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- LAGQNGWYNLUQRI-UHFFFAOYSA-N trioctylmethylammonium bis(trifluoromethylsulfonyl)imide Chemical compound FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC LAGQNGWYNLUQRI-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Liquid Crystal (AREA)
- Polarising Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本發明為一種液晶面板,其具有液晶單元與附黏著劑層之偏光薄膜,且在前述附黏著劑層之偏光薄膜的側面具有導通結構,該液晶單元具有於兩面夾持液晶層的第1透明基板及第2透明基板,且該附黏著劑層之偏光薄膜未隔著導電層而透過第1黏著劑層配置於前述液晶單元之視辨側的第1透明基板之側;前述附黏著劑層之偏光薄膜依序具有第1偏光薄膜及第1黏著劑層,前述第1偏光薄膜含有碘濃度6重量%以下之偏光件,且前述第1黏著劑層係由含有(甲基)丙烯酸系聚合物(A)及陽離子成分之分子量為210以下之離子性化合物(B)的黏著劑組成物所形成。本發明之液晶面板的抗靜電機能良好,且可滿足在高溫區域下之導通可靠性。The present invention is a liquid crystal panel, which has a liquid crystal unit and a polarizing film with an adhesive layer, and has a conductive structure on the side of the polarizing film with an adhesive layer. The liquid crystal unit has a first transparent layer sandwiching a liquid crystal layer on both sides. The substrate and the second transparent substrate, and the polarizing film with the adhesive layer is disposed on the side of the first transparent substrate on the viewing side of the liquid crystal unit through the first adhesive layer without interposing the conductive layer; the aforementioned adhesive layer The polarizing film has a first polarizing film and a first adhesive layer in sequence, the aforementioned first polarizing film contains a polarizer with an iodine concentration of less than 6% by weight, and the aforementioned first adhesive layer is made of a (meth)acrylic acid-based polymer. It is formed from an adhesive composition of substance (A) and an ionic compound (B) whose molecular weight of the cationic component is 210 or less. The liquid crystal panel of the present invention has good antistatic performance and can meet the conduction reliability in high temperature areas.
Description
本發明涉及具有液晶單元及於該液晶單元之視辨側具有預定附黏著劑層之偏光薄膜之液晶面板。並且,本發明涉及一種使用該液晶面板之液晶顯示裝置。使用有本發明液晶面板之液晶顯示裝置亦可與應用於液晶顯示裝置之視辨側之觸控面板等輸入裝置一同使用,且可作為附觸控感測機能之液晶顯示裝置作為各種輸入顯示裝置使用。 The present invention relates to a liquid crystal panel having a liquid crystal unit and a polarizing film having a predetermined adhesive layer on the viewing side of the liquid crystal unit. Furthermore, the present invention relates to a liquid crystal display device using the liquid crystal panel. A liquid crystal display device using the liquid crystal panel of the present invention can also be used with input devices such as a touch panel applied to the viewing side of the liquid crystal display device, and can be used as a liquid crystal display device with a touch sensing function as various input display devices use.
液晶顯示裝置一般依其影像形成方式,係於液晶單元兩側透過黏著劑層貼合有偏光薄膜。且,於液晶顯示裝置之顯示畫面搭載觸控面板之產品業已實用化。就觸控面板而言,有電容式、阻抗膜式、光學式、超音波式或電磁感應式等各種格式,近來多採用電容式。近年有在使用內嵌有電容感測器作為觸控感測器部的附觸控感測機能之液晶顯示裝置。 Liquid crystal display devices generally have polarizing films bonded to both sides of the liquid crystal unit through an adhesive layer according to their image formation method. Moreover, products equipped with touch panels on the display screen of liquid crystal display devices have been put into practical use. As for touch panels, there are various formats such as capacitive type, resistive film type, optical type, ultrasonic type or electromagnetic induction type. Recently, capacitive type is mostly used. In recent years, liquid crystal display devices with touch sensing functions embedded with capacitive sensors as the touch sensor portion have been used.
另一方面,於製造液晶顯示裝置時,將前述附黏著劑層之偏光薄膜貼附於液晶單元時,會從附黏著劑層之偏光薄膜的黏著劑層剝離脫模薄膜,而剝離該脫模薄膜會產生靜電。另,在剝離貼附於液晶單元之偏光薄膜的表面保護薄膜時、或是在剝離覆蓋窗的表面保護薄膜時也會產生靜電。因而產生的靜電會影響液晶顯示裝置內部的液晶層定向,導致不良。所以,例如藉由在偏光薄膜外面形成抗靜電層,可抑制靜電的產生。 On the other hand, when manufacturing a liquid crystal display device, when the polarizing film with the adhesive layer is attached to the liquid crystal unit, the release film will be peeled off from the adhesive layer of the polarizing film with the adhesive layer, and the release film will be peeled off. Films can generate static electricity. In addition, static electricity is also generated when peeling off the surface protective film of the polarizing film attached to the liquid crystal cell or when peeling off the surface protective film covering the window. The static electricity generated thereby affects the orientation of the liquid crystal layer inside the liquid crystal display device, causing defects. Therefore, for example, by forming an antistatic layer on the outside of the polarizing film, the generation of static electricity can be suppressed.
另一方面,附觸控感測機能之液晶顯示裝置的電容感測器係用以檢測使用者手指接近其表面時,透明電極圖案與手指所形成之微弱的電容量。如果於上述透明電極圖案與使用者手指之間具有如抗靜電層般之導電層,驅動電 極與感測器電極之間的電場便會紊亂,造成感測器電極容量不穩定,降低觸控面板敏感度而成為誤動作之原因。就附觸控感測機能之液晶顯示裝置來說,在抑制產生靜電的同時還要求抑制電容感測器之誤動作。例如針對前述課題,有文獻提議在附觸控感測機能之液晶顯示裝置中,於液晶層之視辨側配置具有表面電阻值為1.0×109~1.0×1011Ω/□之抗靜電層的偏光薄膜,以減低顯示不良或誤動作的發生(專利文獻1)。又,提出有將配置於視辨側之偏光薄膜透過含有抗靜電劑之黏著劑層與含有導電聚合物之錨固層等配置(專利文獻2、3)。 On the other hand, the capacitive sensor of a liquid crystal display device with a touch sensing function is used to detect the weak capacitance formed by the transparent electrode pattern and the finger when the user's finger approaches the surface. If there is a conductive layer such as an antistatic layer between the above-mentioned transparent electrode pattern and the user's finger, the electric field between the driving electrode and the sensor electrode will be disordered, resulting in unstable sensor electrode capacity and degradation of the touch panel. Sensitivity may cause malfunction. For a liquid crystal display device with a touch sensing function, it is required to suppress the generation of static electricity while also suppressing the malfunction of the capacitive sensor. For example, to address the aforementioned issues, some literature proposes that in a liquid crystal display device with a touch sensing function, an antistatic layer with a surface resistance of 1.0×10 9 ~1.0×10 11 Ω/□ be disposed on the viewing side of the liquid crystal layer. polarizing film to reduce the occurrence of display defects or malfunctions (Patent Document 1). Furthermore, it is proposed to arrange the polarizing film placed on the viewing side through an adhesive layer containing an antistatic agent and an anchor layer containing a conductive polymer (Patent Documents 2 and 3).
先前技術文獻 Prior technical literature
專利文獻 patent documents
專利文獻1:日本專利特開2013-105154號公報 Patent Document 1: Japanese Patent Application Publication No. 2013-105154
專利文獻2:日本特開2017-068022號公報 Patent Document 2: Japanese Patent Application Publication No. 2017-068022
專利文獻3:日本特開2011-528448號公報 Patent Document 3: Japanese Patent Application Publication No. 2011-528448
根據專利文獻1中記載之具有抗靜電層的偏光薄膜,可某程度抑制靜電產生。但專利文獻1中,抗靜電層的配置處離產生靜電的源頭位置較遠,所以效果比不上對黏著劑層賦予抗靜電機能之情形。且已知,在附觸控感測機能之液晶顯示裝置中,藉由於偏光薄膜側面設置導通結構,可賦予來自側面的導通性,不過當抗靜電層很薄時,因側面與導通結構的接觸面積小,便無法獲得充分的導電性而發生導通不良。另一方面已知當抗靜電層一旦變厚,觸控感測器敏感度會下降。又已知,設在偏光薄膜外面的抗靜電層在加濕或加熱環境下(加濕或加熱可靠性試驗後)可能會因為與設在側面之導通結構的密著性不良而無法獲得充分的導電性,引發導通不良。 According to the polarizing film having an antistatic layer described in Patent Document 1, the generation of static electricity can be suppressed to a certain extent. However, in Patent Document 1, the antistatic layer is disposed far away from the source of static electricity, so the effect is not as good as when the antistatic function is imparted to the adhesive layer. It is also known that in a liquid crystal display device with a touch sensing function, by providing a conductive structure on the side of the polarizing film, conductivity from the side can be provided. However, when the antistatic layer is very thin, due to the contact between the side and the conductive structure If the area is small, sufficient electrical conductivity cannot be obtained and poor conduction may occur. On the other hand, it is known that once the antistatic layer becomes thicker, the sensitivity of the touch sensor will decrease. It is also known that the antistatic layer provided on the outside of the polarizing film may not be able to obtain sufficient protection due to poor adhesion to the conductive structure provided on the side in a humidified or heated environment (after a humidified or heated reliability test). conductivity, causing poor conduction.
另一方面,又根據專利文獻2、3記載之使用有具有導電性黏著劑 層等之偏光薄膜的液晶面板,相較於專利文獻1更可抑制靜電不均。尤其,以於液晶單元之視辨側未隔著導電層而配置附黏著劑層之偏光薄膜之態樣的液晶面板來說,係要求高導電性。惟,在將液晶面板應用於車載用途之液晶顯示裝置時,會暴露在較應用於一般電視或手機等時更高溫之環境下,故會要求在高溫區域下之導電特性,而即便利用專利文獻2、3記載之液晶面板仍無法滿足在高溫區域下之導電特性。並且,以車載用途之液晶表示裝置來說會要求在高溫區域下之耐久性。 On the other hand, according to the use of conductive adhesives described in Patent Documents 2 and 3, A liquid crystal panel with a polarizing film layer can suppress static unevenness better than Patent Document 1. In particular, a liquid crystal panel in which a polarizing film with an adhesive layer is disposed on the viewing side of the liquid crystal cell without a conductive layer interposed therebetween is required to have high conductivity. However, when the liquid crystal panel is used in a vehicle-mounted liquid crystal display device, it will be exposed to a higher temperature environment than when used in general TVs or mobile phones, so conductive properties in high-temperature areas are required, and even if patent documents are used The liquid crystal panels described in 2 and 3 still cannot meet the conductive characteristics in high temperature areas. In addition, liquid crystal display devices for automotive use require durability in high-temperature areas.
本發明目的在於提供一種液晶面板,其具有液晶單元及應用在其視辨側之附黏著劑層之偏光薄膜,該液晶面板之抗靜電機能良好,且可滿足在高溫區域下之導通可靠性及耐久性。 The object of the present invention is to provide a liquid crystal panel, which has a liquid crystal unit and a polarizing film with an adhesive layer applied to the viewing side. The liquid crystal panel has good antistatic performance and can meet the conduction reliability and reliability in high temperature areas. Durability.
且本發明之目的還在於提供一種使用有前述液晶面板之液晶顯示裝置。 Another object of the present invention is to provide a liquid crystal display device using the above-mentioned liquid crystal panel.
本發明人等為解決前述課題而反覆地努力檢討之結果,發現藉由下述液晶面板可解決上述課題,遂而完成本發明。 As a result of repeated efforts to solve the above-mentioned problems, the inventors found that the above-mentioned problems can be solved by the following liquid crystal panel, and thus completed the present invention.
亦即本發明涉及一種液晶面板,其具有液晶單元與附黏著劑層之偏光薄膜,且在前述附黏著劑層之偏光薄膜的側面具有導通結構,該液晶單元具有液晶層、於兩面夾持前述液晶層的第1透明基板及第2透明基板,該液晶層包含在無電場存在之狀態下平行定向之液晶分子,且該附黏著劑層之偏光薄膜未隔著導電層而透過第1黏著劑層配置於前述液晶單元之視辨側的第1透明基板之側;該液晶面板之特徵在於:前述附黏著劑層之偏光薄膜依序具有第1偏光薄膜及第1黏著劑層,前述偏光薄膜含有碘濃度為6重量%以下之偏光件,且 前述第1黏著劑層係由含有(甲基)丙烯酸系聚合物(A)及陽離子成分之分子量為210以下之離子性化合物(B)的黏著劑組成物所形成。 That is, the present invention relates to a liquid crystal panel, which has a liquid crystal unit and a polarizing film with an adhesive layer, and has a conductive structure on the side of the polarizing film with an adhesive layer. The liquid crystal unit has a liquid crystal layer sandwiching the aforementioned polarizing film on both sides. The first transparent substrate and the second transparent substrate of the liquid crystal layer. The liquid crystal layer contains liquid crystal molecules oriented in parallel in the absence of electric field, and the polarizing film attached to the adhesive layer does not pass through the first adhesive through the conductive layer. The layer is disposed on the side of the first transparent substrate on the viewing side of the liquid crystal unit; the liquid crystal panel is characterized in that: the polarizing film with the adhesive layer has a first polarizing film and a first adhesive layer in sequence, and the polarizing film Polarizing elements containing an iodine concentration of less than 6% by weight, and The first adhesive layer is formed from an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B) with a molecular weight of cationic component of 210 or less.
前述液晶面板中,前述陽離子成分宜為鋰離子。 In the aforementioned liquid crystal panel, the aforementioned cationic component is preferably lithium ion.
前述液晶面板中,相對於前述(甲基)丙烯酸系聚合物(A)100重量份,宜含有1~13重量份之前述離子性化合物(B)。 The liquid crystal panel preferably contains 1 to 13 parts by weight of the ionic compound (B) based on 100 parts by weight of the (meth)acrylic polymer (A).
前述液晶面板中,前述第1偏光薄膜宜含有厚度大於10μm之偏光件。 In the aforementioned liquid crystal panel, the aforementioned first polarizing film preferably contains a polarizing element with a thickness greater than 10 μm .
前述液晶面板中,前述導通結構宜至少設置於下述位置:當在85℃、500小時之環境下進行前述附黏著劑層之偏光薄膜的尺寸收縮試驗時,前述附黏著劑層之偏光薄膜在薄膜面方向上之尺寸變化量成為400μm以下之側面的點b。 In the above-mentioned liquid crystal panel, the above-mentioned conductive structure should be provided at least in the following position: when the size shrinkage test of the above-mentioned polarizing film with the adhesive layer is carried out in an environment of 85°C and 500 hours, the polarizing film with the adhesive layer is The amount of dimensional change in the film surface direction becomes point b on the side surface of 400 μm or less.
前述液晶面板中,前述第1偏光薄膜宜為具有偏光件及於前述偏光件之兩面具有保護薄膜之雙面保護偏光薄膜。 In the above-mentioned liquid crystal panel, the first polarizing film is preferably a double-sided protective polarizing film having a polarizing element and protective films on both sides of the polarizing element.
前述內置型液晶面板中,前述液晶單元可使用內置型液晶單元,該內置型液晶單元係於前述第1透明基板與第2透明基板之間具有觸控感測器及觸控驅動機能相關的觸控感測電極部。 In the aforementioned built-in liquid crystal panel, the aforementioned liquid crystal unit may be a built-in liquid crystal unit. The built-in liquid crystal unit has a touch sensor and a touch driving function between the first transparent substrate and the second transparent substrate. control sensing electrode part.
前述液晶面板中,可於前述液晶單元之第2透明基板側具有透過第2黏著劑層配置的第2偏光薄膜。 In the liquid crystal panel, a second polarizing film disposed through the second adhesive layer may be provided on the second transparent substrate side of the liquid crystal unit.
又,本發明涉及一種具有前述液晶面板的液晶顯示裝置。 Furthermore, the present invention relates to a liquid crystal display device having the above-mentioned liquid crystal panel.
本發明液晶面板中視辨側的附黏著劑層之偏光薄膜係於黏著劑層含有離子性化合物,藉由該黏著劑層可提升抗靜電性能,且,前述附黏著劑層之偏光薄膜於側面與導通結構接觸。因此,即便是在將附黏著劑層之偏光薄膜未隔著導電層而設於液晶單元之視辨側時,該附黏著劑層之偏光薄膜之側面的導通仍受到確 保,而可抑制導通不良所造成之靜電不均發生。 The polarizing film attached to the adhesive layer on the viewing side of the liquid crystal panel of the present invention contains an ionic compound in the adhesive layer, and the antistatic performance can be improved through the adhesive layer. Moreover, the polarizing film attached to the adhesive layer is on the side and Conductive structure contacts. Therefore, even when the polarizing film with the adhesive layer is placed on the viewing side of the liquid crystal unit without interposing the conductive layer, the conduction of the side surface of the polarizing film with the adhesive layer is still ensured. It can prevent uneven static electricity caused by poor conduction.
如同前述,藉由於黏著劑層添加離子性化合物可提升導電特性,但已知黏著劑層之硬度(膠位移量)會因所添加之離子性化合物的種類而異,黏著劑層因添加離子性化合物而變柔軟者,黏著劑層之位移量會變大,在高溫(尤其是高於80℃)之環境下易發生斷線所造成之導通不良。另,偏光薄膜之加熱收縮可藉由使用薄型偏光件來控制得較小,因而可使前述斷線之影響較小,但若偏光件變薄則每單位厚度之碘濃度會有變高之傾向,從而在薄型偏光件中碘濃度會變高,因此使用薄型偏光件時,在高溫(尤其是高於80℃)之環境下易發生偏光件之多烯化,而光學特性不足。 As mentioned above, the conductive properties can be improved by adding ionic compounds to the adhesive layer. However, it is known that the hardness (glue displacement) of the adhesive layer will vary depending on the type of ionic compound added. If the adhesive layer becomes soft due to the compound, the displacement of the adhesive layer will become larger, and poor conduction caused by disconnection may easily occur in a high-temperature environment (especially above 80°C). In addition, the heating shrinkage of the polarizing film can be controlled to a small extent by using a thin polarizing element, so the impact of the aforementioned breakage can be smaller. However, if the polarizing element becomes thinner, the iodine concentration per unit thickness will tend to become higher. As a result, the iodine concentration in thin polarizers will become higher. Therefore, when using thin polarizers, polyolefinization of the polarizer will easily occur in a high temperature (especially higher than 80°C) environment, resulting in insufficient optical properties.
在本發明中,已知陽離子成分之分子量小的離子性化合物即便在高溫(尤其是高於80℃)之環境下仍可抑制黏著劑層之位移量,因此作為離子性化合物係使用陽離子成分之分子量為210以下者。尤其已知當在使用鋰鹽作為離子性化合物的陽離子成分時,抑制位移量之效果佳。 In the present invention, it is known that an ionic compound with a small molecular weight of a cationic component can suppress the displacement of the adhesive layer even in a high-temperature (especially higher than 80°C) environment. Therefore, the ionic compound is one with a cationic component. Those with a molecular weight of 210 or less. In particular, it is known that when a lithium salt is used as the cationic component of the ionic compound, the displacement amount is effectively suppressed.
如以上,本發明中,偏光薄膜係使用含有碘濃度6重量%以下之偏光件者,且前述離子性化合物設為陽離子成分之分子量為210以下者,藉此可滿足在高溫區域(尤其高於80℃)下之導通可靠性及耐久性。 As mentioned above, in the present invention, the polarizing film uses a polarizer containing an iodine concentration of 6% by weight or less, and the ionic compound is a cationic component with a molecular weight of 210 or less, thereby satisfying the requirements in high temperature areas (especially higher than 80℃) conduction reliability and durability.
A,A′:附黏著劑層之偏光薄膜 A, A′: Polarizing film with adhesive layer
B:液晶單元(內置型液晶單元) B: Liquid crystal unit (built-in liquid crystal unit)
C:液晶面板(內置型液晶面板) C: LCD panel (built-in LCD panel)
1,11:第1、第2偏光薄膜 1,11: 1st and 2nd polarizing film
2,12:第1、第2黏著劑層 2,12: 1st and 2nd adhesive layer
3:錨固層 3: Anchor layer
4:表面處理層 4: Surface treatment layer
20:液晶層 20: Liquid crystal layer
31:觸控感測器電極 31:Touch sensor electrode
32:觸控驅動電極 32: Touch drive electrode
33:觸控驅動電極兼感測器電極 33: Touch drive electrode and sensor electrode
41,42:第1、第2透明基板 41,42: 1st and 2nd transparent substrate
50,51:導通結構 50,51: conduction structure
a,a′,b1,b1′,b2,b2′:點 a,a′,b1,b1′,b2,b2′: points
a,b:邊 a, b: side
圖1係顯示用在本發明液晶面板之視辨側的附黏著劑層之偏光薄膜一例的截面圖。 FIG. 1 is a cross-sectional view showing an example of a polarizing film used as an adhesive layer on the viewing side of the liquid crystal panel of the present invention.
圖2係用以說明用於本發明液晶面板之視辨側的附黏著劑層之偏光薄膜在薄膜面方向上之收縮前後之尺寸變化狀態的俯視概念圖之一例。 2 is an example of a top view conceptual diagram illustrating the dimensional change state of the polarizing film used in the adhesive layer on the viewing side of the liquid crystal panel of the present invention before and after shrinkage in the film surface direction.
圖3係顯示本發明液晶面板之一例的截面圖。 FIG. 3 is a cross-sectional view showing an example of the liquid crystal panel of the present invention.
圖4係顯示本發明內置型液晶面板一例的截面圖。 FIG. 4 is a cross-sectional view showing an example of the built-in liquid crystal panel of the present invention.
圖5係顯示本發明內置型液晶面板一例的截面圖。 FIG. 5 is a cross-sectional view showing an example of the built-in liquid crystal panel of the present invention.
圖6係顯示本發明內置型液晶面板一例的截面圖。 FIG. 6 is a cross-sectional view showing an example of the built-in liquid crystal panel of the present invention.
圖7係顯示本發明內置型液晶面板一例的截面圖。 FIG. 7 is a cross-sectional view showing an example of the built-in liquid crystal panel of the present invention.
圖8係顯示本發明內置型液晶面板一例的截面圖。 FIG. 8 is a cross-sectional view showing an example of the built-in liquid crystal panel of the present invention.
圖9係於計算偏光件之碘濃度時做出之檢量曲線。 Figure 9 is a calibration curve made when calculating the iodine concentration of polarizers.
以下參照圖式說明本發明。用於本發明液晶面板之視辨側的附黏著劑層之偏光薄膜A具有第1偏光薄膜1、第1黏著劑層2。又,前述附黏著劑層之偏光薄膜A可於第1偏光薄膜1之視辨側具有表面處理層4,且可於第1偏光薄膜1與第1黏著劑層2之間具有錨固層3。圖1係例示依序具有表面處理層4、第1偏光薄膜1、錨固層3、第1黏著劑層2之情況。另,圖1中雖未記載,不過可在本發明之附黏著劑層之偏光薄膜A的第1黏著劑層2設置分離件,且可在表面處理層4設置表面保護薄膜。 The present invention will be described below with reference to the drawings. The polarizing film A used for the adhesive layer on the viewing side of the liquid crystal panel of the present invention has a first polarizing film 1 and a first adhesive layer 2 . In addition, the polarizing film A with the adhesive layer may have a surface treatment layer 4 on the viewing side of the first polarizing film 1, and may have an anchoring layer 3 between the first polarizing film 1 and the first adhesive layer 2. FIG. 1 illustrates a case where the surface treatment layer 4, the first polarizing film 1, the anchor layer 3, and the first adhesive layer 2 are provided in this order. In addition, although not shown in FIG. 1 , a separator can be provided on the first adhesive layer 2 of the polarizing film A with an adhesive layer of the present invention, and a surface protection film can be provided on the surface treatment layer 4 .
又,第1偏光薄膜1可使用於偏光件之單面或兩面具有保護薄膜者,但由光學耐久性之觀點來看,相較於僅於偏光件之單面具有保護薄膜之單面保護偏光薄膜,宜使用於兩面具有保護薄膜之雙面保護偏光薄膜(無圖式)。 In addition, the first polarizing film 1 can be used with a protective film on one or both sides of a polarizer. However, from the perspective of optical durability, compared with a single-sided polarizing protection film having a protective film on only one side of a polarizer, The film should be used as a double-sided protective polarizing film with protective films on both sides (no picture).
又,在本發明之液晶面板中,係選擇在附黏著劑層之偏光薄膜的側面上加熱收縮較小之處(亦即尺寸變化量為400μm以下)來設置導通結構,藉此可滿足在高溫區域(尤其是高於80℃)下之導通可靠性及耐久性。 In addition, in the liquid crystal panel of the present invention, the conductive structure is selected to be provided on the side of the polarizing film with the adhesive layer where the heating shrinkage is smaller (that is, the dimensional change is less than 400 μm), so that it can meet the requirements at high temperatures. conduction reliability and durability in areas (especially above 80°C).
圖2係顯示在將前述附黏著劑層之偏光薄膜A投入85℃之環境下500小時進行尺寸收縮試驗時,投入前與投入後在薄膜面方向上之收縮前後之尺寸變化狀態的俯視概念圖之一例。圖2中係顯示前述投入前之附黏著劑層之偏光薄膜A與投入後已收縮之狀態下的附黏著劑層之偏光薄膜A'。附黏著劑層之偏光薄膜A之尺寸變化量為前述附黏著劑層之偏光薄膜A之側面的預定點與附黏著劑層之偏光薄膜A'之側面的預定點之距離。至少於前述尺寸變化量為400μm以下 之點b設置導通結構。前述尺寸變化量宜為350μm,且300μm以下更佳,又以250μm以下為佳,200μm以下更佳。 Figure 2 is a top view conceptual diagram showing the dimensional change state before and after shrinkage in the direction of the film surface before and after the polarizing film A with the adhesive layer is put into an environment of 85°C for 500 hours for a dimensional shrinkage test. An example. Figure 2 shows the polarizing film A with the adhesive layer before being put in and the polarizing film A ' with the adhesive layer in a shrunk state after being put in. The dimensional change amount of the polarizing film A with the adhesive layer is the distance between the predetermined point on the side of the polarizing film A with the adhesive layer and the predetermined point on the side of the polarizing film A ' with the adhesive layer. A conductive structure is provided at least at point b where the dimensional change amount is 400 μm or less. The aforementioned dimensional change amount is preferably 350 μm, and more preferably not more than 300 μm, and preferably not more than 250 μm, and more preferably not more than 200 μm.
針對圖2之附黏著劑層之偏光薄膜A,就吸收軸方向與正交於吸收軸之方向(慢軸方向)的關係說明點b。圖2之附黏著劑層之偏光薄膜A中,係例示位於與吸收軸方向相同方向之側面的點b1與附黏著劑層之偏光薄膜A'的點b1'的距離(慢軸方向之尺寸變化量)滿足前述尺寸變化量400μm以下時之情形。另,以圖2之附黏著劑層之偏光薄膜A來說,吾等認為只要就點b1滿足尺寸變化量400μm以下,在邊b的各點上便亦會滿足尺寸變化量400μm以下。又,圖2之附黏著劑層之偏光薄膜A中,係針對於矩形之角部施有加工之異形物,例示位於連結吸收軸方向與慢軸方向之各側面之曲線的側面的點b2與附黏著劑層之偏光薄膜A'的點b2'的距離滿足前述尺寸變化量400μm以下時之情形。 Regarding the polarizing film A with an adhesive layer in Figure 2, point b will be described regarding the relationship between the absorption axis direction and the direction orthogonal to the absorption axis (slow axis direction). In the polarizing film A with the adhesive layer in Figure 2, the distance (dimensional change in the slow axis direction) between point b1 located on the side surface in the same direction as the absorption axis and point b1 ' of the polarizing film A ' with the adhesive layer is exemplified. amount) meets the aforementioned dimensional change amount of 400 μm or less. In addition, taking the polarizing film A with the adhesive layer in Figure 2 as an example, we believe that as long as the dimensional change at point b1 is 400 μm or less, the dimensional change at each point on side b will also be 400 μm or less. In addition, in the polarizing film A with the adhesive layer in Figure 2, for a special-shaped object with processing applied to the corners of a rectangle, points b2 and The distance between the point b2 ′ of the polarizing film A ′ with the adhesive layer satisfies the above-mentioned dimensional change amount of 400 μm or less.
另一方面,圖2之附黏著劑層之偏光薄膜A中,係例示位於慢軸方向之側面的點a與附黏著劑層之偏光薄膜A'的點a'的距離(吸收軸方向之尺寸變化量)不滿足前述尺寸變化量400μm以下時之情形。另,以圖3之附黏著劑層之偏光薄膜A來說,吾等認為只要就點a滿足尺寸變化量400μm以下,在邊a的各點上便亦不會滿足尺寸變化量400μm以下。 On the other hand, in the polarizing film A with the adhesive layer in Figure 2, the distance (the size in the absorption axis direction) between the point a on the side in the slow axis direction and the point a ' of the polarizing film A ' with the adhesive layer is exemplified. Change amount) does not meet the above-mentioned dimensional change amount of 400 μm or less. In addition, taking the polarizing film A with an adhesive layer in Figure 3 as an example, we believe that as long as the dimensional change at point a is 400 μm or less, the dimensional change at each point on side a will not be 400 μm or less.
又,本發明之附黏著劑層之偏光薄膜A中,由保持其與設於側面之導通結構的密著性的觀點來看,在前述點b之尺寸變化量b(μm)與吸收軸方向之尺寸變化量a(μm)的比(b/a)滿足小於0.8之範圍較佳。比(b/a)宜為0.7以下,且0.6以下更佳。此外,本發明所用偏光薄膜(附黏著劑層之偏光薄膜A)之大小無特別限制,例如以矩形物來說,宜為長50~1500mm、寬50~1500mm者。 Furthermore, in the polarizing film A with the adhesive layer of the present invention, from the viewpoint of maintaining the adhesion with the conductive structure provided on the side, the dimensional change amount b (μm) at the aforementioned point b and the direction of the absorption axis are It is preferable that the ratio (b/a) of the dimensional change amount a (μm) satisfies the range of less than 0.8. The ratio (b/a) is preferably 0.7 or less, and more preferably 0.6 or less. In addition, the size of the polarizing film (polarizing film A with adhesive layer) used in the present invention is not particularly limited. For example, for a rectangular object, it is preferably 50 to 1500 mm long and 50 to 1500 mm wide.
本發明之液晶面板C中,前述附黏著劑層之偏光薄膜A如圖3所示,未隔著導電層而透過前述黏著劑層2配置於液晶單元B(在圖4至圖8中為內置型液晶單元B)之視辨側的第1透明基板41之側。又,前述液晶面板C中,於前述附 黏著劑層之偏光薄膜A的側面具有導通結構50。 In the liquid crystal panel C of the present invention, as shown in Figure 3, the polarizing film A with the adhesive layer is disposed in the liquid crystal unit B through the adhesive layer 2 without intervening the conductive layer (it is built-in in Figures 4 to 8). The side of the first transparent substrate 41 on the viewing side of the liquid crystal cell B). In addition, in the above-mentioned liquid crystal panel C, in the above-mentioned appendix The side surface of the polarizing film A of the adhesive layer has a conductive structure 50 .
<附黏著劑層之偏光薄膜> <Polarizing film with adhesive layer>
以下說明附黏著劑層之偏光薄膜A。如上述,本發明附黏著劑層之偏光薄膜A具有第1偏光薄膜、第1黏著劑層。 The following describes the polarizing film A with the adhesive layer. As mentioned above, the polarizing film A with an adhesive layer of the present invention has a first polarizing film and a first adhesive layer.
第1偏光薄膜一般可使用具有偏光件及於前述偏光件之單面或兩面具有保護薄膜者。偏光件並無特別限定,可使用各種偏光件。作為偏光件,可舉如使聚乙烯醇系薄膜、部分縮甲醛化聚乙烯醇系薄膜、乙烯-乙酸乙烯酯共聚物系部分皂化薄膜等親水性高分子薄膜吸附碘並加以單軸延伸者等。該等之中又以由聚乙烯醇系薄膜與碘構成之偏光件較適宜。該等偏光件之厚度無特別限制,一般在80μm左右以下。 The first polarizing film generally has a polarizing element and a protective film on one or both sides of the polarizing element. The polarizer is not particularly limited, and various polarizers can be used. Examples of polarizers include hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films, which are uniaxially stretched after adsorbing iodine. . Among them, a polarizer composed of a polyvinyl alcohol-based film and iodine is more suitable. The thickness of these polarizers is not particularly limited, but is generally below about 80 μm.
又,由耐熱性之觀點來看,作為偏光件宜使用碘濃度6重量%以下之偏光件。由耐熱性之觀點來看,前述碘濃度宜為5重量%以下,更宜為4重量%以下。此外,由光學特性之觀點來看,前述偏光件中之碘濃度宜為1重量%以上,且宜為1.5重量%以上,更宜為2重量%以上。又,偏光件若碘濃度變高,尺寸變化量便多,加熱收縮所造成之導通結構的密著性不足而易引起導通不良,因此偏光件之碘濃度宜在前述範圍內作調整。 In addition, from the viewpoint of heat resistance, it is preferable to use a polarizer with an iodine concentration of 6% by weight or less. From the viewpoint of heat resistance, the iodine concentration is preferably 5% by weight or less, more preferably 4% by weight or less. Furthermore, from the viewpoint of optical properties, the iodine concentration in the polarizer is preferably 1 wt% or more, more preferably 1.5 wt% or more, and more preferably 2 wt% or more. In addition, if the iodine concentration of the polarizer becomes higher, the dimensional changes will increase. The adhesion of the conductive structure caused by heating shrinkage will be insufficient, which may easily cause conduction failure. Therefore, the iodine concentration of the polarizer should be adjusted within the aforementioned range.
又,由耐熱性之觀點來看,作為偏光件宜使用厚度大於10μm之偏光件。前述厚度宜大於10μm且至25μm,且以10~22μm為佳,10~20μm更佳。又,偏光件愈厚,尺寸變化量便多,加熱收縮所造成之導通結構的密著性不足而易引起導通不良,因此偏光件之厚度宜在前述範圍內作調整。 In addition, from the viewpoint of heat resistance, it is preferable to use a polarizer with a thickness greater than 10 μm. The aforementioned thickness should be greater than 10 μm and reach 25 μm, with 10 to 22 μm being preferred, and 10 to 20 μm being more preferred. In addition, the thicker the polarizer, the greater the dimensional change. Insufficient adhesion of the conductive structure caused by heating shrinkage may easily lead to poor conduction. Therefore, the thickness of the polarizer should be adjusted within the aforementioned range.
作為構成保護薄膜的材料,可使用例如透明性、機械強度、熱穩定性、水分阻隔性、各向同性等優異之熱塑性樹脂。所述熱塑性樹脂的具體例可舉例如三醋酸纖維素等之纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸樹脂、環狀 聚烯烴樹脂(降莰烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂及該等之混合物。此外,在偏光件的單側,保護薄膜係藉由接著劑層而貼合,而在另一側,保護薄膜可使用(甲基)丙烯酸系、胺甲酸酯系、丙烯酸胺甲酸酯系、環氧系、聚矽氧系等熱硬化性樹脂或紫外線硬化型樹脂。保護薄膜中亦可含有1種以上任意適當的添加劑。 As a material constituting the protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, and the like can be used. Specific examples of the thermoplastic resin include cellulose resins such as cellulose triacetate, polyester resin, polyether resin, polyurethane resin, polycarbonate resin, polyamide resin, polyimide resin, polyamide resin, etc. Olefin resin, (meth)acrylic resin, cyclic Polyolefin resin (norbornene resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin and mixtures thereof. In addition, on one side of the polarizer, the protective film is bonded with an adhesive layer, and on the other side, the protective film can be (meth)acrylic, urethane, or acrylic urethane. , epoxy series, polysilicone series and other thermosetting resins or ultraviolet curing resins. The protective film may contain one or more types of any appropriate additives.
前述保護薄膜(透明保護薄膜)之材料,由可將黏著劑層之表面電阻值的變動控制得較小來看以纖維素樹脂、(甲基)丙烯酸樹脂為佳。此外,(甲基)丙烯酸樹脂宜使用具有內酯環結構之(甲基)丙烯酸系樹脂。具有內酯環結構之(甲基)丙烯酸系樹脂可列舉日本特開2000-230016號公報、日本特開2001-151814號公報、日本特開2002-120326號公報、日本特開2002-254544號公報、日本特開2005-146084號公報等中記載之具有內酯環結構的(甲基)丙烯酸系樹脂。尤其是纖維素樹脂在會在單面保護偏光薄膜造成課題之抑制偏光件裂痕上較(甲基)丙烯酸樹脂更有效,就此觀點來看較佳。 The material of the protective film (transparent protective film) is preferably cellulose resin or (meth)acrylic resin because it can control the change in the surface resistance value of the adhesive layer to a small level. In addition, it is preferable to use a (meth)acrylic resin having a lactone ring structure as the (meth)acrylic resin. Examples of the (meth)acrylic resin having a lactone ring structure include Japanese Patent Application Publication No. 2000-230016, Japanese Patent Application Publication No. 2001-151814, Japanese Patent Application Publication No. 2002-120326, and Japanese Patent Application Publication No. 2002-254544. , a (meth)acrylic resin having a lactone ring structure described in Japanese Patent Application Laid-Open No. 2005-146084, etc. In particular, cellulose resin is more effective than (meth)acrylic resin in suppressing cracks in polarizers that can cause problems in single-sided protective polarizing films, so it is better from this point of view.
前述保護薄膜亦可使用相位差薄膜、擴散薄膜等。相位差薄膜可舉如具有正面相位差40nm以上及/或厚度方向相位差80nm以上之相位差者。正面相位差通常係控制在40~200nm之範圍,厚度方向相位差通常係控制在80~300nm之範圍。使用相位差薄膜作為保護薄膜時,由於該相位差薄膜亦可作為偏光件保護薄膜發揮功能,故可謀求薄型化。 As the protective film, a retardation film, a diffusion film, etc. can also be used. Examples of the retardation film include those having a front surface retardation of 40 nm or more and/or a thickness direction retardation of 80 nm or more. The frontal phase difference is usually controlled in the range of 40~200nm, and the thickness direction phase difference is usually controlled in the range of 80~300nm. When a retardation film is used as a protective film, the retardation film can also function as a polarizer protective film, so that the thickness can be reduced.
前述保護薄膜與偏光件係透過接著劑層、黏著劑層、底塗層(primer layer;底漆層)等中介層來積層。此時期望可藉由中介層將兩者無空氣間隙地積層。前述保護薄膜與偏光件宜透過接著劑層積層。用於前述偏光件與保護薄膜的貼合之接著劑只要在光學上是透明的,則可無特別限制地使用水系、溶劑系、熱熔膠系、自由基硬化型、陽離子硬化型之各種形態的接著劑,惟水系接著劑或自由基硬化型接著劑較適宜。 The aforementioned protective film and polarizer are laminated through an intermediary layer such as an adhesive layer, an adhesive layer, and a primer layer (primer layer). At this time, it is expected that the two can be laminated without air gaps through an interposer layer. It is preferable that the protective film and the polarizer are laminated through an adhesive. As long as the adhesive used for bonding the polarizer and the protective film is optically transparent, various forms including water-based, solvent-based, hot-melt adhesive-based, radical curing type, and cation curing type can be used without any particular restrictions. Of the adhesives, water-based adhesives or free radical hardening adhesives are more suitable.
<第1黏著劑層> <1st adhesive layer>
前述第1黏著劑層係由含有(甲基)丙烯酸系聚合物(A)及離子性化合物(B)之黏著劑組成物形成。 The first adhesive layer is formed from an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B).
前述(甲基)丙烯酸系聚合物(A)含有(甲基)丙烯酸烷基酯為主成分作為單體單元。另,(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯,本發明之(甲基)亦為同義。 The (meth)acrylic polymer (A) contains alkyl (meth)acrylate as a main component as a monomer unit. In addition, (meth)acrylate refers to acrylate and/or methacrylate, and (meth) in the present invention is also synonymous.
構成(甲基)丙烯酸系聚合物(A)之主骨架的(甲基)丙烯酸烷基酯,可以例示直鏈狀或支鏈狀烷基碳數1~18者。例如前述烷基可例示如甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、己基、環己基、庚基、2-乙基己基、異辛基、壬基、癸基、異癸基、十二基、異肉豆蔻基、月桂基、十三基、十五基、十六基、十七基、十八基等。該等可單獨使用或可組合來使用。該等烷基的平均碳數宜為3~9。 Examples of the alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms. For example, the aforementioned alkyl group may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, and nonyl. , decyl, isodecyl, dodecyl, isomyristyl, lauryl, thirteenth, fifteenth, sixteenth, seventeenth, eighteenth, etc. These may be used alone or in combination. The average carbon number of the alkyl groups is preferably 3 to 9.
前述(甲基)丙烯酸烷基酯之重量比率,作為單體單元於構成(甲基)丙烯酸系聚合物(A)之總構成單體(100重量%)之重量比率中宜為70重量%以上。前述(甲基)丙烯酸烷基酯之重量比率可視為其他共聚單體之剩餘部分作考量。前述(甲基)丙烯酸烷基酯之重量比率若設在前述範圍內,於確保接著性上為佳。 The weight ratio of the alkyl (meth)acrylate is preferably 70% by weight or more as a monomer unit in the weight ratio of the total monomers (100% by weight) constituting the (meth)acrylic polymer (A). . The aforementioned weight ratio of alkyl (meth)acrylate can be considered as the remaining portion of other comonomers. If the weight ratio of the alkyl (meth)acrylate is within the above range, it is preferable to ensure adhesion.
為了改善接著性及耐熱性,除前述(甲基)丙烯酸烷基酯之單體單元外,可於前述(甲基)丙烯酸系聚合物(A)中,藉由共聚來導入1種以上具有具(甲基)丙烯醯基或乙烯基等不飽和雙鍵之聚合性官能基的共聚單體。 In order to improve the adhesion and heat resistance, in addition to the monomer unit of the alkyl (meth)acrylate, one or more types of compounds having specific properties may be introduced into the (meth)acrylic polymer (A) through copolymerization. Comonomer of polymerizable functional groups of unsaturated double bonds such as (meth)acryl group or vinyl group.
前述共聚單體可舉例如含羧基單體、含羥基單體、含醯胺基單體等含官能基單體。 Examples of the copolymerizable monomer include functional group-containing monomers such as carboxyl group-containing monomers, hydroxyl group-containing monomers, and amide group-containing monomers.
含羧基單體係一於其結構中含有羧基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羧基單體之具體例可舉例如(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、 巴豆酸等。從共聚性、價格及黏著特性的觀點來看,前述含羧基單體中以丙烯酸為宜。 Carboxyl-containing monosystem is a compound that contains carboxyl groups in its structure and contains polymerizable unsaturated double bonds such as (meth)acrylyl groups and vinyl groups. Specific examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, Crotonic acid, etc. From the viewpoint of copolymerizability, price and adhesive properties, acrylic acid is preferred among the aforementioned carboxyl group-containing monomers.
含羥基單體係一於其結構中含有羥基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羥基單體的具體例可舉例如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯等(甲基)丙烯酸羥基烷基酯或(4-羥甲基環己基)-甲基丙烯酸酯等。由耐久性之觀點,前述含羥基單體中宜為(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸4-羥丁酯,尤以(甲基)丙烯酸4-羥丁酯為佳。 Hydroxyl-containing monosystem is a compound that contains hydroxyl groups in its structure and polymerizable unsaturated double bonds such as (meth)acrylyl groups and vinyl groups. Specific examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-(meth)acrylate. Hydroxyalkyl (meth)acrylate or (4- Hydroxymethylcyclohexyl)-methacrylate, etc. From the viewpoint of durability, among the aforementioned hydroxyl-containing monomers, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred, and 4-hydroxybutyl (meth)acrylate is particularly preferred. .
含羧基單體、含羥基單體在黏著劑組成物含有交聯劑時會成為其與交聯劑的反應點。含羧基單體、含羥基單體在分子間與交聯劑之反應性佳,故適宜用於提升所得第1黏著劑層之凝集性及耐熱性。又,就兼具耐久性與重工性之觀點而言,含羧基單體較為理想,而就重工性之觀點而言,以含羥基單體較為理想。 Carboxyl-containing monomers and hydroxyl-containing monomers will become reaction points with the cross-linking agent when the adhesive composition contains a cross-linking agent. Carboxyl group-containing monomers and hydroxyl group-containing monomers have good intermolecular reactivity with cross-linking agents, so they are suitable for improving the cohesion and heat resistance of the obtained first adhesive layer. Furthermore, from the viewpoint of both durability and heavy workability, a carboxyl group-containing monomer is preferable, and from the viewpoint of heavy workability, a hydroxyl group-containing monomer is preferable.
含羧基單體的前述重量比率宜為10重量%以下,且宜為0.01~8重量%,0.05~6重量%更佳,又以0.1~5重量%更佳。將含羧基單體的重量比率設為0.01重量%以上由耐久性之觀點來看為佳。另一方面,超過10重量%時以重工性之觀點來看不宜。 The aforementioned weight ratio of the carboxyl group-containing monomer is preferably 10% by weight or less, and preferably 0.01~8% by weight, more preferably 0.05~6% by weight, and even more preferably 0.1~5% by weight. The weight ratio of the carboxyl group-containing monomer is preferably 0.01% by weight or more from the viewpoint of durability. On the other hand, when it exceeds 10% by weight, it is unfavorable from the viewpoint of heavy workability.
含羥基單體的前述重量比率宜為3重量%以下,且宜為0.01~3重量%,0.1~2重量%更佳,且更佳為0.2~2重量%。由交聯第1黏著劑層之觀點、耐久性或黏著特性之觀點來看,含羥基單體的重量比率設為0.01重量%以上為佳。另一方面,超過3重量%時,以耐久性觀點來看不宜。 The aforementioned weight ratio of the hydroxyl-containing monomer is preferably 3% by weight or less, and preferably 0.01~3% by weight, more preferably 0.1~2% by weight, and more preferably 0.2~2% by weight. From the viewpoint of crosslinking the first adhesive layer, durability or adhesive properties, the weight ratio of the hydroxyl-containing monomer is preferably 0.01% by weight or more. On the other hand, when it exceeds 3% by weight, it is unfavorable from the viewpoint of durability.
含醯胺基單體係一於其結構中含有醯胺基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含醯胺基單體之具體例可舉(甲基)丙 烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺、胺甲基(甲基)丙烯醯胺、胺乙基(甲基)丙烯醯胺、巰甲基(甲基)丙烯醯胺、巰乙基(甲基)丙烯醯胺等丙烯醯胺系單體;N-(甲基)丙烯醯基嗎福林、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶等N-丙烯醯基雜環單體;N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺等含N-乙烯基內醯胺系單體等。含醯胺基單體在可抑制歷時性的(尤其在加濕環境下的)表面電阻值的上升或滿足耐久性來看為佳。尤其在含醯胺基單體之中,由可抑制歷時性(尤其在加濕環境下)表面電阻值的上升或滿足對透明導電層(觸控感測器層)之耐久性來看,以含N-乙烯基內醯胺系單體尤佳。 The amide group-containing monosystem is a compound that contains a amide group in its structure and contains polymerizable unsaturated double bonds such as (meth)acrylyl group and vinyl group. Specific examples of the amide group-containing monomer include (methyl)propyl Enamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(methyl)acrylamide )Acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl-N-propane (Meth)acrylamide, Aminomethyl(meth)acrylamide, Aminoethyl(meth)acrylamide, Mercaptomethyl(meth)acrylamide, Mercaptoethyl(meth)acrylamide Acrylamide-based monomers such as amines; N-acrylamides such as N-(meth)acrylamide, N-(meth)acrylylpiperidine, and N-(meth)acrylylpyrrolidine Heterocyclic monomers; N-vinyllactam-containing monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, etc. The amide group-containing monomer is preferable in that it can suppress an increase in the surface resistance value over time (especially in a humidified environment) or satisfy durability. Especially among the amide group-containing monomers, it can suppress the increase in surface resistance value over time (especially in a humidified environment) or satisfy the durability of the transparent conductive layer (touch sensor layer). Monomers containing N-vinyl lactam are particularly preferred.
含醯胺基單體的前述重量比率一大,有對光學薄膜之投錨性降低之傾向,故前述重量比率宜為10重量%以下,且以5重量%以下更佳。從可抑制歷時性(特別在加濕環境下)表面電阻值的上升之觀點來看,含醯胺基單體之前述重量比率宜為0.1重量%以上。前述重量比率宜為0.3重量%以上,更宜為0.5重量%以上。含醯胺基單體就與本發明之第1黏著劑層所含有之離子性化合物(B)的關係來看較為適宜。 A large weight ratio of the amide group-containing monomer tends to reduce the anchoring property of the optical film. Therefore, the weight ratio is preferably 10% by weight or less, and more preferably 5% by weight or less. From the viewpoint of suppressing an increase in the surface resistance value over time (especially in a humidified environment), the aforementioned weight ratio of the amide group-containing monomer is preferably 0.1% by weight or more. The aforementioned weight ratio is preferably 0.3% by weight or more, more preferably 0.5% by weight or more. The amide group-containing monomer is suitable in view of its relationship with the ionic compound (B) contained in the first adhesive layer of the present invention.
用於形成前述第1黏著劑層的黏著劑組成物中,在有被導入基底聚合物之(甲基)丙烯酸系聚合物(A)中之側鏈的醯胺基存在時,藉由該醯胺基之存在,即使在加濕環境下仍能抑制藉由摻混離子性化合物(B)而經調整的第1黏著劑層的表面電阻值變動而大增,從而可維持在所期望之值的範圍內,由此看來較佳。吾等認為藉由作為共聚單體之官能基被導入前述(甲基)丙烯酸系聚合物(A)中之側鏈的醯胺基之存在,能提高(甲基)丙烯酸系聚合物(A)與離子性化合物(B)的相溶性。 In the adhesive composition used to form the first adhesive layer, when there is a amide group introduced into the side chain of the (meth)acrylic polymer (A) of the base polymer, through the amide group The presence of the amine group can suppress the change and increase in the surface resistance value of the first adhesive layer adjusted by blending the ionic compound (B) even in a humidified environment, thereby maintaining it at the desired value. Within the range, it seems better. We believe that the presence of the amide group in the side chain introduced into the (meth)acrylic polymer (A) as a functional group of the comonomer can improve the performance of the (meth)acrylic polymer (A). Compatibility with ionic compound (B).
又,前述第1黏著劑層在有被導入基底聚合物之(甲基)丙烯酸系聚 合物(A)中之側鏈的醯胺基存在時,對玻璃及透明導電層(ITO層等)的耐久性皆良好,而可抑制在貼附於液晶面板之狀態下發生剝落或浮凸等。且,在加濕環境下(加濕可靠性試驗後)依舊可滿足耐久性。 Furthermore, the first adhesive layer has a (meth)acrylic-based polymer introduced into the base polymer. When the amide group in the side chain of compound (A) is present, the durability of both glass and transparent conductive layers (ITO layers, etc.) is good, and peeling or embossing can be suppressed while attached to the liquid crystal panel. wait. Moreover, the durability is still satisfactory in a humidified environment (after humidification reliability test).
又,共聚單體例如可使用含芳香環(甲基)丙烯酸酯。含芳香環(甲基)丙烯酸酯係一於其結構中含有芳香環結構且含有(甲基)丙烯醯基之化合物。作為芳香環,可舉如苯環、萘環或聯苯環。 In addition, as the comonomer, for example, aromatic ring-containing (meth)acrylate can be used. Aromatic ring-containing (meth)acrylate is a compound that contains an aromatic ring structure and a (meth)acrylyl group in its structure. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring.
含芳香環(甲基)丙烯酸酯的具體例可舉例如(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸鄰苯基苯酚酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸苯氧丙酯、苯氧基二乙二醇(甲基)丙烯酸酯、環氧乙烷改質壬苯酚(甲基)丙烯酸酯、環氧乙烷改質甲酚(甲基)丙烯酸酯、苯酚環氧乙烷改質(甲基)丙烯酸酯、2-羥-3-苯氧丙基(甲基)丙烯酸酯、甲氧基苄基(甲基)丙烯酸酯、氯苄基(甲基)丙烯酸酯、(甲基)丙烯酸甲苯酚酯、(甲基)丙烯酸聚苯乙烯酯等具有苯環之物;羥乙基化β-萘酚丙烯酸酯、(甲基)丙烯酸2-萘酚乙酯、丙烯酸2-萘氧乙酯、2-(4-甲氧基-1-萘氧基)乙基(甲基)丙烯酸酯等具有萘環之物;(甲基)丙烯酸聯苯酯等具有聯苯環者。 Specific examples of aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, and phenoxy (meth)acrylate. , Phenoxyethyl (meth)acrylate, Phenoxypropyl (meth)acrylate, Phenoxydiethylene glycol (meth)acrylate, Ethylene oxide modified nonylphenol (meth)acrylate, Ethylene oxide modified cresol (meth)acrylate, phenol ethylene oxide modified (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, methoxybenzyl hydroxyethylated β-naphthalene Phenol acrylate, 2-naphthol ethyl (meth)acrylate, 2-naphthoxyethyl acrylate, 2-(4-methoxy-1-naphthyloxy)ethyl (meth)acrylate, etc. have naphthalene Ring substances; those with biphenyl rings such as (meth)acrylic acid biphenyl ester.
由黏著特性及耐久性之觀點,前述含芳香環(甲基)丙烯酸酯宜為(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧乙酯,且尤為(甲基)丙烯酸苯氧乙酯。 From the viewpoint of adhesive properties and durability, the aforementioned aromatic ring-containing (meth)acrylate is preferably benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and especially phenoxyethyl (meth)acrylate .
含芳香環(甲基)丙烯酸酯的前述重量比率宜為25重量%以下,且宜為3~25重量%,以10~22重量%為佳,14~20重量%更佳。含芳香環(甲基)丙烯酸酯的重量比率為3重量%以上時,由抑制顯示不均來看為佳。另一方面,若超過25重量%,顯示不均的抑制反而不夠充分,有耐久性降低之傾向。 The aforementioned weight ratio of the aromatic ring-containing (meth)acrylate is preferably 25% by weight or less, and preferably 3% to 25% by weight, preferably 10% to 22% by weight, and more preferably 14% to 20% by weight. When the weight ratio of the aromatic ring-containing (meth)acrylate is 3% by weight or more, it is preferable from the viewpoint of suppressing display unevenness. On the other hand, if it exceeds 25% by weight, the suppression of display unevenness is insufficient, and the durability tends to decrease.
上述以外之其他共聚單體之具體例可舉馬來酸酐、伊康酸酐等含酸酐基單體;丙烯酸的己內酯加成物;烯丙基磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、磺丙基(甲基)丙烯酸酯等含磺酸基單體;2- 羥乙基丙烯醯基磷酸酯等含磷酸基單體等。 Specific examples of comonomers other than the above include acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; allylsulfonic acid and 2-(meth)acrylamide Sulfonic acid group-containing monomers such as 2-methylpropanesulfonic acid, (meth)acrylamide propanesulfonic acid, sulfopropyl (meth)acrylate; 2- Phosphate group-containing monomers such as hydroxyethylacrylyl phosphate, etc.
又,以改質為目的的單體之例還可列舉(甲基)丙烯酸胺乙酯、N,N-二甲基胺乙基(甲基)丙烯酸酯、三級丁基胺乙基(甲基)丙烯酸酯等(甲基)丙烯酸烷基胺基烷基酯;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體;N-環己基馬來醯亞胺或N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺或N-苯基馬來醯亞胺等馬來醯亞胺系單體;N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體等。 Examples of monomers intended for modification include amine ethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tertiary butylamine ethyl (meth)acrylate. Alkylaminoalkyl (meth)acrylate and other acrylic esters; Alkoxyalkyl (meth)acrylate such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate Esters; N-(meth)acryloxymethylenesuccinimide or N-(meth)acryl-6-oxyhexamethylenesuccinimide, N-(meth)propylene Succinimide-based monomers such as acyl-8-oxyoctamethylenesuccinimide; N-cyclohexylmaleimide or N-isopropylmaleimide, N-laurylmaline Maleimide-based monomers such as leimide or N-phenylmaleimide; N-methylyconimide, N-ethylyconimide, and N-butyliconide Ikonimide, N-octylicotrimide, N-2-ethylhexylicotrimide, N-cyclohexylicotrimide, N-laurylicotrimide, etc. Imine monomers, etc.
並且,改質單體也可使用乙酸乙烯酯、丙酸乙烯酯等乙烯基系單體;丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體;(甲基)丙烯酸環氧丙酯等含環氧基(甲基)丙烯酸酯;(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯等二醇系(甲基)丙烯酸酯;(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯或2-甲氧基乙基丙烯酸酯等(甲基)丙烯酸酯單體等。更可列舉異戊二烯、丁二烯、異丁烯、乙烯基醚等。 In addition, vinyl-based monomers such as vinyl acetate and vinyl propionate; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; glycidyl (meth)acrylate, etc. can also be used as the modifying monomer. Containing epoxy (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methyl (meth)acrylate Diol-based (meth)acrylates such as oxypolypropylene glycol ester; tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, polysiloxy (meth)acrylate or 2-methoxyethyl (meth)acrylate monomers such as acrylic acid esters, etc. Further examples include isoprene, butadiene, isobutylene, vinyl ether, etc.
並且,上述以外之可共聚單體可舉如含有矽原子之矽烷系單體等。作為矽烷系單體,可列舉例如3-丙烯醯氧丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯氧癸基三甲氧基矽烷、10-丙烯醯氧癸基三甲氧基矽烷、10-甲基丙烯醯氧癸基三乙氧基矽烷、10-丙烯醯氧癸基三乙氧基矽烷等。 Examples of copolymerizable monomers other than the above include silane-based monomers containing silicon atoms. Examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4- Vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-propylene Cyloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, etc.
又,作為共聚單體,也可使用三丙二醇二(甲基)丙烯酸酯、四乙二 醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物等的具有2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵之多官能性單體,或在聚酯、環氧、胺甲酸乙酯等的骨架上附加2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵作為與單體成分相同的官能基的聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯等。 In addition, as comonomers, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc. can also be used. Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate Acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopenterythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate Esterates of (meth)acrylic acid and polyols such as esters, dipenterythritol hexa(meth)acrylate, caprolactone-modified dipenterythritol hexa(meth)acrylate, etc. have more than 2 Polyfunctional monomers with unsaturated double bonds such as (meth)acrylyl and vinyl groups, or two or more (meth)acrylyl groups attached to the skeleton of polyester, epoxy, urethane, etc. Polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, etc., which have unsaturated double bonds such as vinyl as the same functional group as the monomer component.
在前述(甲基)丙烯酸系聚合物(A)之總構成單體(100重量%)的重量比率中,(甲基)丙烯酸系聚合物(A)中前述其他共聚單體的比率宜為0~10重量%左右,且宜為0~7重量%左右,更宜為0~5重量%左右。 In the weight ratio of the total monomers (100% by weight) of the (meth)acrylic polymer (A), the ratio of the other comonomers in the (meth)acrylic polymer (A) is preferably 0 ~10% by weight, preferably around 0~7% by weight, more preferably around 0~5% by weight.
本發明之(甲基)丙烯酸系聚合物(A)通常重量平均分子量宜為100萬~250萬。若考慮耐久性、尤其是耐熱性,重量平均分子量宜為120萬~200萬。以耐熱性觀點來看,重量平均分子量如果在100萬以上為宜。又,重量平均分子量若大於250萬,有黏著劑容易變硬的傾向,而易發生剝落。另,顯示分子量分布之重量平均分子量(Mw)/數量平均分子量(Mn)宜為1.8以上且10以下,較宜為1.8~7,更宜為1.8~5。分子量分布(Mw/Mn)若大於10,由耐久性觀點來看不宜。此外,重量平均分子量、分子量分布(Mw/Mn)是依照GPC(凝膠滲透層析法)來測定且從以聚苯乙烯換算所算出之值而求得。 The (meth)acrylic polymer (A) of the present invention usually has a weight average molecular weight of 1 million to 2.5 million. Considering durability, especially heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. From the viewpoint of heat resistance, it is appropriate if the weight average molecular weight is 1 million or more. In addition, if the weight average molecular weight exceeds 2.5 million, the adhesive tends to harden easily and peel off easily. In addition, the weight average molecular weight (Mw)/number average molecular weight (Mn) showing the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, more preferably 1.8 to 5. If the molecular weight distribution (Mw/Mn) exceeds 10, it is unfavorable from the viewpoint of durability. In addition, the weight average molecular weight and molecular weight distribution (Mw/Mn) are measured in accordance with GPC (gel permeation chromatography) and are determined from values calculated in terms of polystyrene.
所述(甲基)丙烯酸系聚合物(A)的製造,可適當選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等公知的製造方法。又,所得(甲基)丙烯酸系聚合物(A)可為無規共聚物、嵌段共聚物、接枝共聚物等任一者。 The (meth)acrylic polymer (A) can be produced by appropriately selecting a known production method such as solution polymerization, block polymerization, emulsion polymerization, and various radical polymerizations. Moreover, the obtained (meth)acrylic polymer (A) may be any of a random copolymer, a block copolymer, a graft copolymer, etc.
此外,溶液聚合中,聚合溶劑可使用例如乙酸乙酯、甲苯等。作為具體之溶液聚合例,反應可於氮等非活性氣體氣流下添加聚合引發劑,且一般 係於50~70℃左右、5~30小時左右之反應條件下進行。 In addition, in solution polymerization, a polymerization solvent such as ethyl acetate, toluene, etc. can be used. As a specific example of solution polymerization, a polymerization initiator can be added to the reaction under a flow of inert gas such as nitrogen, and generally It is carried out under reaction conditions of about 50~70℃ and about 5~30 hours.
自由基聚合所使用之聚合引發劑、鏈轉移劑、乳化劑等無特別限定可適當選擇並使用。此外,(甲基)丙烯酸系聚合物(A)之重量平均分子量可藉由聚合引發劑、鏈轉移劑的使用量及反應條件來控制,並可因應其等之種類來適當調整其使用量。 The polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of the (meth)acrylic polymer (A) can be controlled by the usage amounts and reaction conditions of the polymerization initiator and chain transfer agent, and the usage amounts can be appropriately adjusted according to their types.
<離子性化合物(B)> <Ionic compound (B)>
形成本發明之第1黏著劑層之黏著劑組成物含有之離子性化合物(B)係使用陽離子成分的分子量為210以下者。由抑制在高溫環境下斷線造成之導通不良之觀點,前述陽離子成分的分子量更宜為150以下,且110以下更佳,又以50以下為佳,10以下更佳。前述陽離子成分的分子量愈大,愈會阻礙黏著劑層中的(甲基)丙烯酸聚合物彼此纏結,而有使黏著劑層之物性變柔軟的傾向。因此,前述分子量愈小,第1黏著劑層之物性便愈不易變柔軟,且前述分子量愈小愈可抑制在高溫環境下斷線造成之導通不良。又,前述陽離子成分的分子量愈小,第1黏著劑層之表面電阻值便愈容易降低而能抑制靜電不均,由此觀點來看亦較佳。 The ionic compound (B) contained in the adhesive composition forming the first adhesive layer of the present invention is a cationic component with a molecular weight of 210 or less. From the viewpoint of suppressing conduction failure caused by disconnection in a high-temperature environment, the molecular weight of the cationic component is more preferably 150 or less, more preferably 110 or less, more preferably 50 or less, and more preferably 10 or less. The larger the molecular weight of the cationic component is, the more it will hinder the entanglement of the (meth)acrylic acid polymers in the adhesive layer, thereby tending to soften the physical properties of the adhesive layer. Therefore, the smaller the molecular weight is, the less likely the physical properties of the first adhesive layer will become soft, and the smaller the molecular weight is, the more likely it is to suppress poor conduction caused by disconnection in a high-temperature environment. In addition, it is also preferable from this point of view that the smaller the molecular weight of the cationic component is, the easier it is to reduce the surface resistance value of the first adhesive layer and suppress electrostatic unevenness.
又,前述離子性化合物(B)可適宜使用鹼金屬鹽及/或有機陽離子-陰離子鹽。鹼金屬鹽可使用鹼金屬之有機鹽及無機鹽。另,本發明中所謂的「有機陽離子陰離子鹽」係指:其為有機鹽且其陽離子成分係由有機物所構成之物,陰離子成分可為有機物亦可為無機物。「有機陽離子-陰離子鹽」亦稱為離子性液體、離子性固體。藉由使前述第1黏著劑層含有離子性化合物(B),可使第1黏著劑層之表面電阻值降低而抑制靜電產生,從而可抑制靜電打亂液晶層之定向而發生漏光(帶電不均)。 In addition, an alkali metal salt and/or an organic cation-anion salt can be suitably used as the ionic compound (B). As the alkali metal salt, organic salts and inorganic salts of alkali metal can be used. In addition, the "organic cation anion salt" in the present invention refers to an organic salt whose cation component is composed of an organic substance, and the anion component may be an organic substance or an inorganic substance. "Organic cation-anion salts" are also called ionic liquids and ionic solids. By making the first adhesive layer contain the ionic compound (B), the surface resistance value of the first adhesive layer can be reduced and the generation of static electricity can be suppressed. This can suppress the static electricity from disrupting the orientation of the liquid crystal layer and causing light leakage (charge failure). all).
<鹼金屬鹽> <Alkali metal salt>
構成鹼金屬鹽之陽離子成分的鹼金屬離子可舉鋰、鈉、鉀之各離子。該等鹼金屬離子之中以鋰離子為佳。 Examples of the alkali metal ions constituting the cation component of the alkali metal salt include lithium, sodium, and potassium ions. Among the alkali metal ions, lithium ions are preferred.
鹼金屬鹽之陰離子成分可以有機物構成,亦可以無機物構成。構成有機鹽之陰離子成分例如可使用CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、C4F9SO3 -、C3F7COO-、(CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -、PF6 -、CO3 2-或下述通式(1)至(4)所示者等:(1):(CnF2n+1SO2)2N-(惟,n為0~10之整數)、(2):CF2(CmF2mSO2)2N-(惟,m為1~10之整數)、(3):-O3S(CF2)lSO3 -(惟,l為1~10之整數)、(4):(CpF2p+1SO2)N-(CqF2q+1SO2)(惟,p、q為1~10之整數)。 The anionic component of the alkali metal salt can be composed of organic matter or inorganic matter. Examples of the anionic component constituting the organic salt include CH 3 COO - , CF 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , (CF 3 SO 2 ) 3 C - , C 4 F 9 SO 3 - , C 3 F 7 COO - , (CF 3 SO 2 )(CF 3 CO)N - , - O 3 S(CF 2 ) 3 SO 3 - , PF 6 - , CO 3 2- or the following general formula (1) to Those shown in (4): (1): (C n F 2n+1 SO 2 ) 2 N - (but, n is an integer from 0 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N - (but, m is an integer from 1 to 10), (3): - O 3 S(CF 2 ) l SO 3 - (but, l is an integer from 1 to 10), (4): (C p F 2p+1 SO 2 )N - (C q F 2q+1 SO 2 ) (However, p and q are integers from 1 to 10).
特別是含氟原子之陰離子成分由於可獲得離子解離性佳的離子化合物故適於使用。構成無機鹽之陰離子成分可使用Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-等。陰離子成分宜為(CF3SO2)2N-、(C2F5SO2)2N-等前述通式(1)所示(全氟烷基磺醯基)醯亞胺,尤以(CF3SO2)2N-所示(三氟甲磺醯基)醯亞胺為宜。 In particular, anionic components containing fluorine atoms are suitable for use because an ionic compound with excellent ion dissociation properties can be obtained. As the anionic component constituting the inorganic salt, Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , (CN) 2 N - , etc. The anion component is preferably (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N -, etc. (perfluoroalkylsulfonyl)imide represented by the aforementioned general formula (1), especially ( CF 3 SO 2 ) 2 N - (trifluoromethanesulfonyl) acyl imine is suitable.
鹼金屬之有機鹽具體上可舉如醋酸鈉、海藻酸鈉、木質磺酸鈉、甲苯磺酸鈉、LiCF3SO3、Li(CF3SO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C、KO3S(CF2)3SO3K、LiO3S(CF2)3SO3K等,其等之中以LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C等為佳,Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N等屬雙(氟磺醯基)醯亞胺鋰鹽之含氟鋰醯亞胺鹽較佳,(全氟烷基磺醯基)醯亞胺鋰鹽尤佳。其他還可舉4,4,5,5-四氟-1,3,2-二四氫噻唑-1,1,3,3-四氧化鋰鹽等。 Specific examples of organic salts of alkali metals include sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, KO 3 S(CF 2 ) 3 SO 3 K, LiO 3 S(CF 2 ) 3 SO 3 K, etc., among which LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, etc. are preferred, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 Fluorine-containing lithium imide salts such as N and other bis(fluorosulfonyl)imide lithium salts are preferred, and (perfluoroalkylsulfonyl)imide lithium salts are particularly preferred. Others include 4,4,5,5-tetrafluoro-1,3,2-ditetrahydrothiazole-1,1,3,3-lithium tetraoxide salt and the like.
而鹼金屬的無機鹽可列舉如過氯酸鋰、碘化鋰。 Examples of inorganic salts of alkali metals include lithium perchlorate and lithium iodide.
<有機陽離子-陰離子鹽> <Organic cation-anion salt>
本發明所用之有機陽離子-陰離子鹽係由陽離子成分與陰離子成分構成,且前述陽離子成分為有機物所構成之物。作為陽離子成分,具體而言可舉如吡啶陽 離子、哌啶陽離子、吡咯啶陽離子、具二氫吡咯骨架的陽離子、具吡咯骨架的陽離子、咪唑陽離子、四氫嘧啶陽離子、二氫嘧啶陽離子、吡唑陽離子、吡唑啉陽離子、四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子等。 The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the aforementioned cation component is composed of organic matter. Specific examples of the cationic component include pyridinium cation Ion, piperidine cation, pyrrolidine cation, cation with dihydropyrrole skeleton, cation with pyrrole skeleton, imidazole cation, tetrahydropyrimidine cation, dihydropyrimidine cation, pyrazole cation, pyrazoline cation, tetraalkylammonium cation, trialkyl sulfonium cation, tetraalkyl phosphonium cation, etc.
陰離子成分例如可使用Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-、C4F9SO3 -、C3F7COO-、((CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -或下述通式(1)至(4)所示者等:(1):(CnF2n+1SO2)2N-(惟,n為0~10之整數)、(2):CF2(CmF2mSO2)2N-(惟,m為1~10之整數)、(3):-O3S(CF2)lSO3 -(惟,l為1~10之整數)、(4):(CpF2p+1SO2)N-(CqF2q+1SO2)(惟,p、q為1~10之整數)。 Examples of the anionic component include Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , (CF 3 SO 2 ) 3 C - , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , (CN) 2 N - , C 4 F 9 SO 3 - , C 3 F 7 COO - , ((CF 3 SO 2 )(CF 3 CO)N - , - O 3 S(CF 2 ) 3 SO 3 - or the following general formulas (1) to (4) Indicates: (1): (C n F 2n+1 SO 2 ) 2 N - (but, n is an integer from 0 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N - (However, m is an integer from 1 to 10), (3): - O 3 S(CF 2 ) l SO 3 - (However, l is an integer from 1 to 10), (4): (C p F 2p+ 1 SO 2 )N - (C q F 2q+1 SO 2 ) (However, p and q are integers from 1 to 10).
其中特別是含氟原子之陰離子成分因可獲得離子解離性良好的離子化合物故適於使用。 Among them, anionic components containing fluorine atoms are particularly suitable for use because an ionic compound with good ion dissociation properties can be obtained.
有機陽離子-陰離子鹽可適當選擇由上述陽離子成分與陰離子成分組合構成之化合物來使用。有機陽離子-陰離子鹽之較佳具體例可舉例如甲基三辛基銨雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、乙基甲基咪唑鎓雙(氟磺醯基醯亞胺)。其中更宜為1-甲基-1-丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、乙基甲基咪唑鎓雙(氟磺醯基醯亞胺)。 The organic cation-anion salt can be used by appropriately selecting a compound composed of a combination of the above-mentioned cation component and anion component. Preferred specific examples of organic cation-anion salts include methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonate) acyl) acyl imine, ethylmethylimidazolium bis(fluorosulfonyl acyl imine). Among them, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide and ethylmethylimidazolium bis(fluorosulfonyl)imide are more preferred.
又,離子性化合物(B)除了前述鹼金屬鹽、有機陽離子-陰離子鹽之外,尚可列舉如氯化銨、氯化鋁、氯化銅、氯化亞鐵、氯化鐵、硫酸銨等之無機鹽。 In addition to the aforementioned alkali metal salts and organic cation-anion salts, examples of the ionic compound (B) include ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, etc. of inorganic salts.
前述離子性化合物(B)為鹼金屬鹽時,鋰、鈉、鉀等鹼金屬離子係分子量為210以下之陽離子成分,故可適宜使用以該等鹼金屬離子作為陽離子成分之鹼金屬鹽。尤其,由與黏著劑之相溶性之觀點來看,宜為鹼金屬鹽之陰離子 成分以有機物構成之鹼金屬的有機鹽。且,前述鹼金屬離子宜為分子量最小之鋰離子。前述離子性化合物(B)宜為鋰鹽,且鋰的有機鹽尤佳。另一方面,前述離子性化合物(B)為有機陽離子-陰離子鹽時,宜從前述例示之陽離子成分中選擇分子量為210以下來使用。尤其由上述觀點來看,宜為陰離子成分以有機物構成之有機陽離子-陰離子鹽。 When the ionic compound (B) is an alkali metal salt, alkali metal ions such as lithium, sodium, and potassium are cationic components with a molecular weight of 210 or less. Therefore, alkali metal salts containing these alkali metal ions as cationic components can be suitably used. In particular, from the viewpoint of compatibility with the adhesive, an anion of an alkali metal salt is preferred. Organic salts of alkali metals composed of organic matter. Furthermore, the alkali metal ions are preferably lithium ions with the smallest molecular weight. The aforementioned ionic compound (B) is preferably a lithium salt, and an organic salt of lithium is particularly preferred. On the other hand, when the ionic compound (B) is an organic cation-anion salt, it is preferable to select a molecular weight of 210 or less from the cationic components exemplified above. Especially from the above viewpoint, it is preferable to use an organic cation-anion salt in which the anionic component is composed of an organic substance.
為了獲得所期望的電阻值,前述離子性化合物(B)可單獨使用或可將多種併用。尤其當目的是將第1黏著劑層之表面電阻值控制在1×1010~1×1012Ω/□之範圍內時,就前述離子性化合物(B)來說,在可提高抗靜電性能之觀點上以鹼金屬鹽為佳,藉由使用鹼金屬鹽,即使只有少量的摻混份數也可獲得抗靜電性能高的黏著劑。另一方面,當目的是將第1黏著劑層之表面電阻值控制在1×108~1×1011Ω/□之範圍內時,就前述離子性化合物(B)來說,在可提高抗靜電性能之觀點上以有機陽離子-陰離子鹽為佳,藉由使用有機陽離子-陰離子鹽,即使只有少量的摻混份數也可獲得抗靜電性能高的黏著劑。 In order to obtain a desired resistance value, the aforementioned ionic compound (B) may be used alone or in combination of multiple types. Especially when the purpose is to control the surface resistance value of the first adhesive layer within the range of 1×10 10 ~1×10 12 Ω/□, the aforementioned ionic compound (B) can improve the antistatic performance. From this point of view, alkali metal salts are preferred. By using alkali metal salts, an adhesive with high antistatic properties can be obtained even with a small blending ratio. On the other hand, when the purpose is to control the surface resistance value of the first adhesive layer within the range of 1×10 8 ~1×10 11 Ω/□, the aforementioned ionic compound (B) can improve From the perspective of antistatic properties, organic cation-anion salts are preferred. By using organic cation-anion salts, an adhesive with high antistatic properties can be obtained even with a small blending ratio.
本發明之黏著劑組成物的離子性化合物(B)比率宜適當調整成可滿足第1黏著劑層之抗靜電特性與觸控面板的敏感度。例如,為使第1黏著劑層的表面電阻值成為1.0×108~1.0×1012Ω/□之範圍,宜一邊考慮偏光薄膜之保護薄膜的種類等,一邊因應內嵌觸控感測機能之液晶面板的種類來調整離子性化合物(B)之比率。例如,圖8所示之內置型內嵌觸控感測機能之液晶面板中,第1黏著劑層之初始的表面電阻值宜控制在1×108~1×1011Ω/□之範圍。又,欲控制前述第1黏著劑層2之導電性時,從抗靜電機能與觸控感測器敏感度的觀點來看,前述第1黏著劑層2之表面電阻值宜為1×108~1×1012Ω/□,1×108~1×1011Ω/□較佳,1×108~1×1010Ω更佳。 The ratio of the ionic compound (B) in the adhesive composition of the present invention should be appropriately adjusted to satisfy the antistatic properties of the first adhesive layer and the sensitivity of the touch panel. For example, in order to make the surface resistance value of the first adhesive layer fall into the range of 1.0×10 8 ~1.0×10 12 Ω/□, it is advisable to consider the type of protective film of the polarizing film and the embedded touch sensing function. Adjust the ratio of ionic compound (B) according to the type of liquid crystal panel. For example, in the LCD panel with built-in touch sensing function shown in Figure 8, the initial surface resistance value of the first adhesive layer should be controlled in the range of 1×10 8 ~1×10 11 Ω/□. In addition, when it is desired to control the conductivity of the first adhesive layer 2, from the viewpoint of antistatic performance and touch sensor sensitivity, the surface resistance value of the first adhesive layer 2 is preferably 1×10 8 ~1×10 12 Ω/□, 1×10 8 ~1×10 11 Ω/□ is better, 1×10 8 ~1×10 10 Ω is better.
前述離子性化合物(B)若變多,離子性化合物(B)可能會析出,進而易發生加濕剝落。且前述離子性化合物(B)若變多,會有表面電阻值變得過低而 發生基線變動(因表面電阻值過低造成觸控時之誤動作),使觸控面板的敏感度降低之虞。前述離子性化合物(B)之比率,例如相對於(甲基)丙烯酸系聚合物(A)100重量份,一般宜為40重量份以下,且20重量份以下更佳,並以13重量份以下為佳。若過少則會有抗靜電性差之虞,過多則會有觸控敏感度降低、離子性化合物析出、黏著劑之加濕剝落惡化之虞。另一方面,以使抗靜電性能提升來看,宜使用0.1重量份以上之前述離子性化合物(B)。基於此觀點,前述離子性化合物(B)宜為1重量份以上,更宜為5重量份以上。 If the amount of the ionic compound (B) increases, the ionic compound (B) may precipitate, which may cause humidification peeling. Furthermore, if the amount of the aforementioned ionic compound (B) increases, the surface resistance value may become too low and the There is a risk that the sensitivity of the touch panel will decrease due to baseline changes (malfunction during touch due to low surface resistance value). The ratio of the ionic compound (B), for example, relative to 100 parts by weight of the (meth)acrylic polymer (A), is generally preferably 40 parts by weight or less, more preferably 20 parts by weight or less, and 13 parts by weight or less. Better. If it is too little, there is a risk of poor antistatic properties. If it is too much, there is a risk of reduced touch sensitivity, precipitation of ionic compounds, and deterioration of humidification peeling of the adhesive. On the other hand, in order to improve the antistatic performance, it is preferable to use 0.1 parts by weight or more of the aforementioned ionic compound (B). From this viewpoint, the amount of the ionic compound (B) is preferably 1 part by weight or more, and more preferably 5 parts by weight or more.
本發明之黏著劑組成物可含有交聯劑(C)。作為交聯劑(C),可使用有機系交聯劑或多官能性金屬螯合物。有機系交聯劑可舉出如異氰酸酯系交聯劑、過氧化物系交聯劑、環氧系交聯劑、亞胺系交聯劑等。多官能性金屬螯合物是多價金屬與有機化合物共價鍵結或配位鍵結之物。多價金屬原子可列舉Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。有機化合物中可共價鍵結或配位鍵結之原子可舉如氧原子等,有機化合物可舉如烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。 The adhesive composition of the present invention may contain a cross-linking agent (C). As the cross-linking agent (C), an organic cross-linking agent or a polyfunctional metal chelate compound can be used. Examples of organic cross-linking agents include isocyanate cross-linking agents, peroxide cross-linking agents, epoxy cross-linking agents, imine cross-linking agents, and the like. Multifunctional metal chelates are covalent or coordination bonds between multivalent metals and organic compounds. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. Examples of atoms in organic compounds that can be covalently or coordinately bonded include oxygen atoms, and examples of organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, etc.
交聯劑(C)宜為異氰酸酯系交聯劑及/或過氧化系交聯劑。 The cross-linking agent (C) is preferably an isocyanate-based cross-linking agent and/or a peroxide-based cross-linking agent.
異氰酸酯系交聯劑(C)可使用具有至少2個異氰酸酯基之化合物。例如,一般會使用胺甲酸乙酯化反應所用之公知的脂肪族聚異氰酸酯、脂環族聚異氰酸酯、芳香族聚異氰酸酯等。 As the isocyanate cross-linking agent (C), a compound having at least two isocyanate groups can be used. For example, generally known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, etc. used in the urethanization reaction are used.
過氧化物只要是經加熱或光照射會產生自由基活性種而使黏著劑組成物之基底聚合物進行交聯者即可適當使用,但考慮到作業性及穩定性,宜使用1分鐘半衰期溫度在80℃~160℃之過氧化物,且較宜使用在90℃~140℃之過氧化物。 Peroxides can be used appropriately as long as they generate free radical active species when heated or irradiated with light to cross-link the base polymer of the adhesive composition. However, considering workability and stability, it is advisable to use a half-life temperature of 1 minute. Peroxide at 80℃~160℃, and it is more suitable to use peroxide at 90℃~140℃.
可使用之過氧化物可舉如二(2-乙基己基)過氧二碳酸酯(1分鐘半衰期溫度:90.6℃)、二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度: 92.1℃)、過氧二碳酸二-二級丁酯(1分鐘半衰期溫度:92.4℃)、過氧新癸酸三級丁酯(1分鐘半衰期溫度:103.5℃)、過氧化三甲基乙酸三級己酯(1分鐘半衰期溫度:109.1℃)、過氧化三甲基乙酸三級丁酯(1分鐘半衰期溫度:110.3℃)、二月桂醯基過氧化物(1分鐘半衰期溫度:116.4℃)、二正辛醯基過氧化物(1分鐘半衰期溫度:117.4℃)、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯(1分鐘半衰期溫度:124.3℃)、二(4-甲基苯甲醯基)過氧化物(1分鐘半衰期溫度:128.2℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度:130.0℃)、過異丁酸三級丁酯(1分鐘半衰期溫度:136.1℃)、1,1-二(三級己基過氧基)環己烷(1分鐘半衰期溫度:149.2℃)等。其中,尤從交聯反應效率佳之觀點來看,以二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度:92.1℃)、二月桂醯基過氧化物(1分鐘半衰期溫度:116.4℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度:130.0℃)等適於使用。 Peroxides that can be used include bis(2-ethylhexyl)peroxydicarbonate (1-minute half-life temperature: 90.6°C), bis(4-tertiary butylcyclohexyl)peroxydicarbonate (1 Minute half-life temperature: 92.1℃), di-secondary butyl peroxydicarbonate (1-minute half-life temperature: 92.4℃), tertiary butyl peroxyneodecanoate (1-minute half-life temperature: 103.5℃), trimethylperoxyacetate Grade hexyl ester (1-minute half-life temperature: 109.1°C), tertiary butyl peroxytrimethylacetate (1-minute half-life temperature: 110.3°C), dilauryl peroxide (1-minute half-life temperature: 116.4°C), Di-n-octyl peroxide (half-life temperature in 1 minute: 117.4℃), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (half-life temperature in 1 minute: 124.3℃), Bis(4-methylbenzoyl)peroxide (half-life temperature in 1 minute: 128.2°C), diphenylbenzoyl peroxide (half-life temperature in 1 minute: 130.0°C), tertiary butyl perisobutyrate (half-life temperature in 1 minute: 136.1°C), 1,1-di(tertiary hexylperoxy)cyclohexane (half-life temperature in 1 minute: 149.2°C), etc. Among them, especially from the viewpoint of good cross-linking reaction efficiency, bis(4-tertiary butylcyclohexyl)peroxydicarbonate (half-life temperature of 1 minute: 92.1°C), dilauryl peroxide (1 minute Half-life temperature: 116.4°C), benzyl peroxide (half-life temperature in 1 minute: 130.0°C), etc. are suitable for use.
相對於(甲基)丙烯酸系聚合物(A)100重量份,交聯劑(C)之使用量宜為3重量份以下,且較宜為0.01~3重量份,更宜為0.02~2重量份,又更宜為0.03~1重量份。另,交聯劑(C)低於0.01重量份時,第1黏著劑層恐交聯不足而無法滿足耐久性或黏著特性;另一方面,若多過3重量份,第1黏著劑層會變得太硬而有耐久性降低之傾向。 The usage amount of the cross-linking agent (C) is preferably 3 parts by weight or less relative to 100 parts by weight of the (meth)acrylic polymer (A), and is more preferably 0.01 to 3 parts by weight, and more preferably 0.02 to 2 parts by weight. parts, and more preferably 0.03~1 parts by weight. In addition, when the cross-linking agent (C) is less than 0.01 parts by weight, the first adhesive layer may not be cross-linked enough to meet the durability or adhesive properties; on the other hand, if it exceeds 3 parts by weight, the first adhesive layer may be Becomes too hard and has a tendency to reduce durability.
本發明之黏著劑組成物中可含有矽烷耦合劑(D)。藉由使用矽烷耦合劑(D)可提高耐久性。作為矽烷耦合劑,具體上可舉例如3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3-4-環氧環己基)乙基三甲氧基矽烷等含環氧基之矽烷耦合劑;3-胺丙基三甲氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙胺、N-苯基-γ-胺丙基三甲氧基矽烷等含胺基之矽烷耦合劑;3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等含(甲基)丙烯醯基之矽烷耦合劑;3-異氰酸酯丙基三乙氧基矽烷等含異氰酸酯基之矽 烷耦合劑等。前述例示之矽烷耦合劑宜為含環氧基之矽烷耦合劑。 The adhesive composition of the present invention may contain a silane coupling agent (D). Durability can be improved by using silane coupling agent (D). Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyl Diethoxysilane, 2-(3-4-epoxycyclohexyl)ethyltrimethoxysilane and other silane coupling agents containing epoxy groups; 3-aminopropyltrimethoxysilane, N-2-(amine Ethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-γ-aminepropylamine Silane coupling agents containing amine groups such as trimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. containing (meth)acrylyl groups Silane coupling agent; 3-isocyanatepropyltriethoxysilane and other isocyanate-containing silicones Alkane coupling agent, etc. The silane coupling agent exemplified above is preferably a silane coupling agent containing an epoxy group.
又,矽烷耦合劑(D)亦可使用於分子內具有多個烷氧矽基者。具體上可列舉如信越化學公司製X-41-1053、X-41-1059A、X-41-1056、X-41-1805、X-41-1818、X-41-1810、X-40-2651等。該等於分子內具有多個烷氧矽基之矽烷耦合劑由於不易揮發且具有多個烷氧矽基,因此可有效提升耐久性而較為理想。尤其是在附黏著劑層之光學薄膜的被黏著體為較玻璃更不易與烷氧矽基反應的透明導電層(例如ITO等)時,耐久性仍佳。又,於分子內具有多個烷氧矽基之矽烷耦合劑宜為於分子內具有環氧基者,且環氧基於分子內具有多個更佳。於分子內具有多個烷氧矽基且具有環氧基之矽烷耦合劑在被黏著體為透明導電層(例如ITO等)時耐久性仍有良好之傾向。於分子內具有多個烷氧矽基且具有環氧基之矽烷耦合劑的具體例可舉信越化學公司製X-41-1053、X-41-1059A、X-41-1056,尤以環氧基含量多的信越化學公司製X-41-1056為佳。 In addition, the silane coupling agent (D) can also be used if it has a plurality of alkoxysilyl groups in the molecule. Specifically, X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, and wait. The silane coupling agent having multiple alkoxysilyl groups in the molecule is ideal because it is not volatile and has multiple alkoxysilyl groups, so it can effectively improve the durability. Especially when the adherend of the optical film with the adhesive layer is a transparent conductive layer (such as ITO, etc.) that is less likely to react with silicon alkoxide than glass, the durability is still good. In addition, the silane coupling agent having a plurality of alkoxysilyl groups in the molecule is preferably one having an epoxy group in the molecule, and it is more preferable that the epoxy group has a plurality of epoxy groups in the molecule. Silane coupling agents with multiple alkoxysilyl groups and epoxy groups in the molecule still tend to have good durability when the adherend is a transparent conductive layer (such as ITO, etc.). Specific examples of silane coupling agents having multiple alkoxysilyl groups and epoxy groups in the molecule include X-41-1053, X-41-1059A, and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd., especially epoxy X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd., which has a large base content, is preferred.
前述矽烷耦合劑(D)可單獨使用,亦可將2種以上混合來使用,但整體含量相對於前述(甲基)丙烯酸系聚合物(A)100重量份,宜為5重量份以下,且0.001~5重量份為佳,較宜為0.01~1重量份,更宜為0.02~1重量份,並且以0.05~0.6重量份為佳。是可提升耐久性之量。 The aforementioned silane coupling agent (D) can be used alone or in mixture of two or more kinds, but the total content is preferably 5 parts by weight or less based on 100 parts by weight of the aforementioned (meth)acrylic polymer (A), and It is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, more preferably 0.02 to 1 part by weight, and preferably 0.05 to 0.6 parts by weight. This is the amount that increases durability.
並且本發明黏著劑組成物中亦可含有其他公知的添加劑,例如可視使用用途適當添加具有反應性矽基之聚醚化合物、聚丙二醇等聚伸烷基二醇的聚醚化合物、著色劑、顏料等粉體、染料、界面活性劑、塑化劑、增黏劑、表面潤滑劑、調平劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機或有機的充填劑、金屬粉、粒子狀、箔狀物等。又,亦可在可控制的範圍內採用添加還原劑的氧化還原系。該等添加劑相對於(甲基)丙烯酸系聚合物(A)100重量份宜在5重量份以下、較宜在3重量份以下且更宜在1重量份以下的範圍使用。 Furthermore, the adhesive composition of the present invention may also contain other well-known additives. For example, polyether compounds with reactive silicon groups, polyalkylene glycol polyether compounds such as polypropylene glycol, colorants, and pigments may be appropriately added depending on the intended use. Such as powders, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or Organic fillers, metal powders, particles, foils, etc. Alternatively, a redox system in which a reducing agent is added can be used within a controllable range. These additives are preferably used in a range of 5 parts by weight or less, more preferably 3 parts by weight or less, and more preferably 1 part by weight or less based on 100 parts by weight of the (meth)acrylic polymer (A).
形成第1黏著劑層的方法可藉由例如以下方法來製作:將前述黏著劑組成物塗佈於經剝離處理過的分離件等,並乾燥去除聚合溶劑等形成第1黏著劑層後轉印到光學薄膜(偏光薄膜)之方法;或者將前述黏著劑組成物塗佈於光學薄膜(偏光薄膜)後,乾燥去除聚合溶劑等以在光學薄膜形成第1黏著劑層的方法。另,於塗佈黏著劑時可適當另外添加聚合溶劑以外之一種以上溶劑。 The method of forming the first adhesive layer can be produced by, for example, the following method: applying the aforementioned adhesive composition to a release-treated separation member, etc., drying and removing the polymerization solvent, etc. to form the first adhesive layer and then transferring it. to an optical film (polarizing film); or a method of coating the aforementioned adhesive composition on an optical film (polarizing film) and then drying and removing the polymerization solvent to form a first adhesive layer on the optical film. In addition, when applying the adhesive, one or more solvents other than the polymerization solvent may be appropriately added.
第1黏著劑層之厚度無特別限制,例如為1~100μm左右。宜為2~50μm,較宜為2~40μm,更宜為5~35μm。 The thickness of the first adhesive layer is not particularly limited, but is, for example, about 1 to 100 μm. It is preferably 2~50μm, more preferably 2~40μm, and more preferably 5~35μm.
從確保耐久性及確保與側面導通結構之接觸面積的觀點來看,前述第1黏著劑層2之厚度宜為5~100μm,5~50μm較佳,10~35μm更佳。 From the viewpoint of ensuring durability and ensuring the contact area with the side conductive structure, the thickness of the first adhesive layer 2 is preferably 5 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 35 μm.
<錨固層> <Anchor layer>
錨固層可利用各種材料來形成。錨固層之厚度宜為0.01~0.5μm,且宜為0.01~0.2μm,更宜為0.01~0.1μm。 The anchoring layer can be formed using a variety of materials. The thickness of the anchoring layer is preferably 0.01~0.5μm, more preferably 0.01~0.2μm, more preferably 0.01~0.1μm.
欲對錨固層賦予導電性時,由抗靜電機能之觀點來看,其表面電阻值宜為1×106~1×109Ω/□。導電性之錨固層可由各種抗靜電劑組成物形成。就形成錨固層之抗靜電劑而言,以離子性界面活性劑系、導電性聚合物、導電性微粒子等為宜。 When it is desired to impart conductivity to the anchoring layer, from the viewpoint of antistatic performance, the surface resistance value is preferably 1×10 6 ~1×10 9 Ω/□. The conductive anchoring layer can be formed from various antistatic agent compositions. As the antistatic agent forming the anchor layer, ionic surfactant systems, conductive polymers, conductive fine particles, etc. are suitable.
從光學特性、外觀、抗靜電效果及抗靜電效果於加熱時、加濕時之穩定性的觀點來看,該等抗靜電劑中又宜使用導電性聚合物。尤其宜使用聚苯胺、聚噻吩等導電性聚合物。導電性聚合物可適當使用有機溶劑可溶性、水溶性、水分散性者,惟宜使用水溶性導電性聚合物或水分散性導電性聚合物。因為水溶性導電性聚合物或水分散性導電性聚合物可將形成抗靜電層時的塗佈液調製成水溶液或水分散液,該塗佈液無須使用非水系有機溶劑,即可抑制光學薄膜基材因該有機溶劑變質的情況。又,水溶液或水分散液可含有水以外的水系溶劑。可舉如甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇、三級丁醇、正 戊醇、異戊醇、二級戊醇、三級戊醇、1-乙基-1-丙醇、2-甲基-1-丁醇、正己醇、環己醇等醇類。 From the viewpoints of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, conductive polymers are preferably used as such antistatic agents. In particular, conductive polymers such as polyaniline and polythiophene are suitable. As the conductive polymer, those that are soluble in organic solvents, water-soluble, or water-dispersible can be appropriately used, but water-soluble conductive polymers or water-dispersible conductive polymers are preferably used. Because water-soluble conductive polymers or water-dispersible conductive polymers can be used to prepare the coating liquid when forming the antistatic layer into an aqueous solution or aqueous dispersion, the coating liquid can suppress optical films without using a non-aqueous organic solvent. The base material is deteriorated by the organic solvent. Moreover, the aqueous solution or aqueous dispersion may contain an aqueous solvent other than water. Examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, normal Pentanol, isoamyl alcohol, secondary pentanol, tertiary pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols.
又,前述聚苯胺、聚噻吩等水溶性導電性聚合物或水分散性導電性聚合物宜於分子中具有親水性官能基。親水性官能基可舉如磺酸基、胺基、醯胺基、亞胺基、四級銨鹽基、羥基、巰基、肼基、羧基、硫酸酯基、磷酸酯基或該等之鹽等。因為分子內具有親水性官能基,可輕易溶於水或可以微粒子狀輕易地分散於水中,而可易調製出前述水溶性導電性聚合物或水分散性導電性聚合物。 In addition, the water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline and polythiophene preferably has a hydrophilic functional group in the molecule. Examples of hydrophilic functional groups include sulfonic acid group, amine group, amide group, imine group, quaternary ammonium salt group, hydroxyl group, mercapto group, hydrazine group, carboxyl group, sulfate group, phosphate group or salts thereof, etc. . Because it has hydrophilic functional groups in the molecule, it can be easily dissolved in water or can be easily dispersed in water in the form of fine particles, and the aforementioned water-soluble conductive polymer or water-dispersible conductive polymer can be easily prepared.
就水溶性導電聚合物之市售物例子來說,可列舉聚苯胺磺酸(Mitsubishi Rayon Co.,Ltd.製,聚苯乙烯換算所得重量平均分子量150000)等。就水分散性導電聚合物之市售物例子來說,可列舉聚噻吩系導電性聚合物(Nagase ChemteX Co.製、商品名Denatron系列)等。 Examples of commercially available water-soluble conductive polymers include polyaniline sulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight in terms of polystyrene: 150,000). Examples of commercially available water-dispersed conductive polymers include polythiophene-based conductive polymers (manufactured by Nagase ChemteX Co., trade name: Denatron series).
又,就錨固層之形成材料而言,在提升抗靜電劑之皮膜形成性、對光學薄膜之密著性等目的下,亦可連同前述抗靜電劑一起添加黏結劑成分。抗靜電劑為水溶性導電性聚合物或水分散性導電性聚合物之水系材料時,使用水溶性或水分散性之黏結劑成分。黏結劑之例子可舉如含唑啉基聚合物、聚胺甲酸乙酯系樹脂、聚酯系樹脂、丙烯酸系樹脂、聚醚系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、環氧樹脂、聚乙烯基吡咯啶酮、聚苯乙烯系樹脂、聚乙二醇、新戊四醇等。尤其以聚胺甲酸乙酯系樹脂、聚酯系樹脂、丙烯酸系樹脂為宜。該等黏結劑可依其用途適當使用1種或2種以上。 In addition, as for the material forming the anchor layer, a binder component may be added together with the antistatic agent for the purpose of improving the film-forming properties of the antistatic agent and the adhesion to the optical film. When the antistatic agent is a water-based material of a water-soluble conductive polymer or a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of binders include Oxazoline-based polymer, polyurethane resin, polyester resin, acrylic resin, polyether resin, cellulose resin, polyvinyl alcohol resin, epoxy resin, polyvinylpyrrolidone, Polystyrene resin, polyethylene glycol, neopentyl erythritol, etc. In particular, polyurethane resin, polyester resin, and acrylic resin are suitable. One or more types of these binders may be used appropriately depending on the purpose.
抗靜電劑、黏結劑之使用量依該等之種類而定,不過宜控制成所得錨固層之表面電阻值成為1×106~1×109Ω/□。 The amount of antistatic agent and adhesive used depends on their types, but it should be controlled so that the surface resistance of the anchor layer obtained is 1×10 6 ~1×10 9 Ω/□.
<表面處理層> <Surface treatment layer>
作為前述表面處理層可設置硬塗層、防眩處理層、抗反射層、抗黏結層或防 眩層等之機能層。前述表面處理層可設於前述保護薄膜之不接著偏光件之面。 As the aforementioned surface treatment layer, a hard coating layer, an anti-glare treatment layer, an anti-reflection layer, an anti-adhesion layer or an anti-glare treatment layer can be provided. Functional layer such as dazzling layer. The surface treatment layer may be provided on the surface of the protective film that is not attached to the polarizer.
又,欲對述表面處理層4控制導電性時,從抗靜電機能及觸控感測器敏感度的觀點來看,前述表面處理層4之表面電阻值宜為1×107~1×1011Ω/□,1×107~1×1010Ω/□較佳,1×107~1×109Ω更佳。 In addition, when it is desired to control the conductivity of the surface treatment layer 4, from the viewpoint of antistatic performance and touch sensor sensitivity, the surface resistance value of the surface treatment layer 4 is preferably 1×10 7 ~1×10 11 Ω/□, 1×10 7 ~1×10 10 Ω/□ is better, 1×10 7 ~1×10 9 Ω is better.
欲對前述表面處理層賦予導電性時,表面處理層宜形成為表面電阻值為1×107~1×1011Ω/□。對於前述表面處理層,可藉由使其含有抗靜電劑來賦予導電性。表面處理層可設於第1偏光薄膜所用之保護薄膜上,除此之外亦可另外設成與保護薄膜為相異個體。用以賦予前述表面處理層導電性的抗靜電劑可使用前述示例之物,惟宜含有選自離子性界面活性劑、導電性微粒子及導電性聚合物中之至少任1種。從光學特性、外觀、抗靜電效果及抗靜電效果在加熱時、加濕時之穩定性的觀點來看,用於表面處理層之抗靜電劑宜為導電性微粒子。 When it is desired to impart conductivity to the surface-treated layer, the surface-treated layer is preferably formed to have a surface resistance value of 1×10 7 to 1×10 11 Ω/□. The surface treatment layer can be provided with conductivity by containing an antistatic agent. The surface treatment layer can be provided on the protective film used for the first polarizing film, or it can also be provided separately from the protective film. The antistatic agent used to impart conductivity to the surface treatment layer can be those exemplified above, but it is preferable to contain at least one selected from the group consisting of ionic surfactants, conductive fine particles, and conductive polymers. From the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, the antistatic agent used in the surface treatment layer is preferably conductive fine particles.
前述表面處理層宜為硬塗層。硬塗層的形成材料可適用例如熱可塑性樹脂、可藉由熱或放射線硬化之材料。前述材料可列舉熱硬化型樹脂或紫外線硬化型樹脂、電子束硬化型樹脂等的放射線硬化性樹脂。該等中又以紫外線硬化型樹脂為宜,該紫外線硬化型樹脂可藉由利用紫外線照射的硬化處理,以簡單的加工操作有效率地形成硬化樹脂層。該等硬化型樹脂可舉聚酯系、丙烯酸系、胺甲酸酯系、醯胺系、聚矽氧系、環氧系、三聚氰胺系等各種樹脂,且包含該等之單體、寡聚物、聚合物等。從加工速度的迅速性、對基材之熱損少的觀點來看,尤以放射線硬化型樹脂、特別是紫外線硬化型樹脂為宜。可適宜使用的紫外線硬化型樹脂可舉例如具有紫外線聚合性官能基者,其中包含具有2個以上該官能基、特別是具有3~6個該官能基之丙烯酸系單體或寡聚物成分者。又,紫外線硬化型樹脂中摻混有光聚合起始劑。 The aforementioned surface treatment layer is preferably a hard coat layer. The hard coat layer may be formed of a material such as a thermoplastic resin or a material that can be cured by heat or radiation. Examples of the material include thermosetting resins, radiation curing resins such as ultraviolet curing resins and electron beam curing resins. Among them, an ultraviolet curable resin is preferred because the ultraviolet curable resin can efficiently form a cured resin layer with a simple processing operation through curing treatment using ultraviolet irradiation. Such hardening resins can include various resins such as polyester, acrylic, urethane, amide, polysiloxane, epoxy, melamine, etc., and include monomers and oligomers thereof. , polymers, etc. From the viewpoint of rapid processing speed and low heat loss to the base material, radiation-curable resin, especially ultraviolet curable resin, is suitable. Examples of ultraviolet curable resins that can be suitably used include those having ultraviolet polymerizable functional groups, including those containing an acrylic monomer or oligomer component having 2 or more such functional groups, particularly 3 to 6 such functional groups. . In addition, a photopolymerization initiator is blended with the ultraviolet curable resin.
又,就前述表面處理層來說,可設置以提升視辨性為目的之防眩處理層或抗反射層。且可於前述硬塗層上設置防眩處理層或抗反射層。防眩處理 層之構成材料無特別限定,譬如可使用放射線硬化型樹脂、熱硬化型樹脂、熱塑性樹脂等。抗反射層可使用氧化鈦、氧化鋯、氧化矽、氟化鎂等。抗反射層可設置多層。除此之外,表面處理層還可舉抗黏結層等。 In addition, the aforementioned surface treatment layer may be provided with an anti-glare treatment layer or an anti-reflection layer for the purpose of improving visibility. And an anti-glare treatment layer or an anti-reflective layer can be provided on the aforementioned hard coating layer. Anti-glare treatment The material constituting the layer is not particularly limited, and for example, radiation curing resin, thermosetting resin, thermoplastic resin, etc. can be used. Titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, etc. can be used as the anti-reflection layer. The anti-reflection layer can be provided with multiple layers. In addition, the surface treatment layer can also include an anti-adhesion layer.
前述表面處理層之厚度可按表面處理層種類適當設定,一般宜為0.1~100μm。譬如,硬塗層之厚度宜為0.5~20μm。硬塗層厚度並無特別限制,不過,太薄會無法獲得作為硬塗層的充分硬度,而太厚又容易產生破裂或剝離。硬塗層厚度較宜為1~10μm。 The thickness of the aforementioned surface treatment layer can be appropriately set according to the type of surface treatment layer, and is generally 0.1 to 100 μm. For example, the thickness of the hard coating should be 0.5~20μm. The thickness of the hard coat layer is not particularly limited. However, if it is too thin, sufficient hardness as a hard coat layer cannot be obtained, and if it is too thick, cracking or peeling may easily occur. The thickness of the hard coating is preferably 1~10μm.
前述表面處理層的抗靜電劑、黏結劑(樹脂材料等)之使用量依該等之種類而定,不過宜將所得表面處理層之表面電阻值控制成1×107~1×1011Ω/□。通常,相對於抗靜電劑100重量份,黏結劑宜為1000重量份以下,更宜為10~200重量份。 The amount of antistatic agent and adhesive (resin material, etc.) used in the surface treatment layer depends on the type. However, it is advisable to control the surface resistance value of the surface treatment layer to 1×10 7 ~1×10 11 Ω. /□. Generally, relative to 100 parts by weight of the antistatic agent, the amount of the binder is preferably less than 1,000 parts by weight, and more preferably 10 to 200 parts by weight.
<其他層> <Other layers>
對於本發明之附黏著劑層之偏光薄膜,除了前述各層以外,亦可於第1偏光薄膜之設置錨固層之側的表面設置易接著層或施行電暈處理、電漿處理等各種易接著處理。 For the polarizing film with an adhesive layer of the present invention, in addition to the above-mentioned layers, an easy-adhesion layer can also be provided on the surface of the first polarizing film on the side where the anchor layer is provided, or various easy-adhesion treatments such as corona treatment and plasma treatment can be performed. .
以下說明液晶單元B及液晶面板C。 The liquid crystal cell B and the liquid crystal panel C will be described below.
(液晶單元B) (Liquid crystal unit B)
如圖3所示,液晶單元B具有液晶層20、於兩面夾持前述液晶層20之第1透明基板41及第2透明基板42,該液晶層20含有在電場不存在之狀態下平行定向的液晶分子。圖3中係省略液晶單元B內之電極。 As shown in FIG. 3 , the liquid crystal cell B has a liquid crystal layer 20 , a first transparent substrate 41 and a second transparent substrate 42 sandwiching the liquid crystal layer 20 on both sides. The liquid crystal layer 20 contains parallel-oriented elements in the absence of an electric field. Liquid crystal molecules. In Figure 3, the electrodes in the liquid crystal cell B are omitted.
液晶單元B所用之液晶層20可使用包含在電場不存在之狀態下平行定向之液晶分子的液晶層。就液晶層20來說,適宜使用譬如IPS方式之液晶層。除此之外,液晶層20譬如可使用TN型或STN型、π型、VA型等任意類型之液晶層。前述液晶層20之厚度例如為1.5μm~4μm左右。 The liquid crystal layer 20 used in the liquid crystal cell B may use a liquid crystal layer containing liquid crystal molecules that are aligned in parallel in the absence of an electric field. As the liquid crystal layer 20, it is suitable to use, for example, an IPS liquid crystal layer. In addition, the liquid crystal layer 20 may be any type of liquid crystal layer such as TN type, STN type, π type, VA type, etc. The thickness of the liquid crystal layer 20 is, for example, about 1.5 μm to 4 μm.
形成前述透明基板之材料可列舉如玻璃或聚合物薄膜。前述聚合物薄膜可舉如聚對苯二甲酸乙二酯、聚環烯烴、聚碳酸酯等。前述透明基板係由玻璃形成時,其厚度例如為0.1mm~1mm左右。前述透明基板係由聚合物薄膜形成時,其厚度例如為10μm~200μm左右。上述透明基板可於其表面具有易接著層或硬塗層。 Materials used to form the transparent substrate include glass or polymer films. Examples of the polymer film include polyethylene terephthalate, polycycloolefin, polycarbonate, and the like. When the transparent substrate is made of glass, its thickness is, for example, about 0.1 mm to 1 mm. When the transparent substrate is formed of a polymer film, its thickness is, for example, about 10 μm to 200 μm. The above-mentioned transparent substrate may have an easy-adhesion layer or a hard coat layer on its surface.
(內置型液晶單元B) (Built-in liquid crystal unit B)
前述液晶單元B可使用圖4至圖8所示內置型液晶單元B。又,內置型液晶單元B係於前述第1透明基板41與第2透明基板42之間具有觸控感測器及觸控驅動機能相關的觸控感測電極部。 The aforementioned liquid crystal unit B can be a built-in type liquid crystal unit B shown in FIGS. 4 to 8 . In addition, the built-in liquid crystal unit B has a touch sensing electrode portion related to a touch sensor and a touch driving function between the first transparent substrate 41 and the second transparent substrate 42 .
如圖4、圖5、圖8所示,前述觸控感測電極部可利用觸控感測器電極31及觸控驅動電極32形成。在此所指觸控感測器電極為觸控偵測(接收)電極。前述觸控感測器電極31及觸控驅動電極32可分別獨立以各種圖案形成。譬如,將內置型液晶單元B設為平面時,該等可以分別獨立設於X軸方向、Y軸方向之形式呈直角交錯的圖案作配置。又,圖4、圖5、圖8中,前述觸控感測器電極31係配置在比前述觸控驅動電極32更靠前述第1透明基板41之側(視辨側),但亦可與前述相反地將前述觸控驅動電極32配置在比前述觸控感測器電極31更靠前述第1透明基板41之側(視辨側)。 As shown in FIG. 4 , FIG. 5 , and FIG. 8 , the aforementioned touch sensing electrode portion may be formed by using the touch sensor electrode 31 and the touch driving electrode 32 . The touch sensor electrodes referred to here are touch detection (receiving) electrodes. The aforementioned touch sensor electrodes 31 and touch driving electrodes 32 can be independently formed in various patterns. For example, when the built-in liquid crystal unit B is set as a plane, they can be arranged independently in the X-axis direction and the Y-axis direction in a right-angle staggered pattern. Furthermore, in FIGS. 4 , 5 , and 8 , the touch sensor electrode 31 is disposed closer to the first transparent substrate 41 (the viewing side) than the touch drive electrode 32 , but it may also be disposed on the first transparent substrate 41 side. On the contrary, the touch driving electrodes 32 are arranged on the side (the viewing side) of the first transparent substrate 41 than the touch sensor electrodes 31 .
另一方面,如圖6、圖7所示,前述觸控感測電極部可使用觸控感測器電極及觸控驅動電極一體形成的電極33。 On the other hand, as shown in FIGS. 6 and 7 , the touch sensing electrode portion may use an electrode 33 in which a touch sensor electrode and a touch driving electrode are integrated.
又,前述觸控感測電極部可配置在前述液晶層20與前述第1透明基板41或與第2透明基板42之間。圖4、圖6係前述觸控感測電極部配置在前述液晶層20與前述第1透明基板41之間(比前述液晶層20更靠視辨側)的情況。圖5、圖7係前述觸控感測電極部配置在前述液晶層20與前述第2透明基板42之間(比前述液晶層20更靠背光側)的情況。 In addition, the touch sensing electrode portion may be disposed between the liquid crystal layer 20 and the first transparent substrate 41 or the second transparent substrate 42 . 4 and 6 show the case where the touch sensing electrode portion is arranged between the liquid crystal layer 20 and the first transparent substrate 41 (to the viewing side than the liquid crystal layer 20 ). 5 and 7 show the case where the touch sensing electrode portion is arranged between the liquid crystal layer 20 and the second transparent substrate 42 (toward the backlight side of the liquid crystal layer 20 ).
又,如圖8所示,前述觸控感測電極部於前述液晶層20與第1透明基板41之間具有觸控感測器電極31,且於前述液晶層20與第2透明基板42之間具有觸控驅動電極32。 In addition, as shown in FIG. 8 , the touch sensing electrode portion has a touch sensor electrode 31 between the liquid crystal layer 20 and the first transparent substrate 41 , and between the liquid crystal layer 20 and the second transparent substrate 42 There are touch driving electrodes 32 between them.
另,前述觸控感測電極部之驅動電極(前述觸控驅動電極32、觸控感測器電極及觸控驅動電極一體形成的電極33)可兼作控制液晶層20的共通電極來使用。 In addition, the driving electrodes of the touch sensing electrode portion (the touch driving electrodes 32 , the touch sensor electrodes and the touch driving electrodes 33 formed integrally) can also be used as a common electrode for controlling the liquid crystal layer 20 .
如上述,內置型液晶單元B於液晶單元內具有觸控感測器及觸控驅動機能相關的觸控感測電極部,且於液晶單元外部不具觸控感測器電極。即,在比內置型液晶單元B之第1透明基板41更靠視辨側(比內置型液晶面板C之第1黏著劑層2更靠液晶單元側)之側未設置導電層(表面電阻值為1×1013Ω/□以下)。又,在圖4至圖8中記載之內置型液晶面板C顯示了各構成之順序,不過於內置型液晶面板C可適當具有其他構成。可於液晶單元上(第1透明基板41)設置彩色濾光片基板。 As mentioned above, the built-in liquid crystal unit B has a touch sensor and a touch sensing electrode portion related to the touch driving function inside the liquid crystal unit, and does not have a touch sensor electrode outside the liquid crystal unit. That is, no conductive layer (surface resistance value) is provided on the side closer to the viewing side than the first transparent substrate 41 of the built-in liquid crystal unit B (and closer to the liquid crystal cell side than the first adhesive layer 2 of the built-in liquid crystal panel C). is 1×10 13 Ω/□ or less). In addition, the built-in liquid crystal panel C shown in FIGS. 4 to 8 shows the order of each structure, but the built-in liquid crystal panel C may have other structures as appropriate. A color filter substrate may be provided on the liquid crystal unit (first transparent substrate 41).
形成觸控感測電極部的觸控感測器電極31(電容感測器)、觸控驅動電極32、或觸控感測器電極及觸控驅動電極一體形成的電極33可作為透明導電層而形成。前述透明導電層之構成材料無特別限定,可列舉如金、銀、銅、鉑、鈀、鋁、鎳、鉻、鈦、鐵、鈷、錫、鎂、鎢等金屬及該等金屬之合金等。又,前述透明導電層之構成材料可列舉銦、錫、鋅、鎵、銻、鋯、鎘之金屬氧化物,具體上可列舉氧化銦、氧化錫、氧化鈦、氧化鎘及由該等之混合物等所構成的金屬氧化物。其他可使用由碘化銅等所構成之其他金屬化合物等。前述金屬氧化物中可視需求進一步含有上述群組所示金屬原子之氧化物。宜使用譬如含有氧化錫之氧化銦(ITO)、含銻之氧化錫等,且尤宜使用ITO。ITO宜含有80~99重量%之氧化銦及1~20重量%之氧化錫。 The touch sensor electrode 31 (capacitive sensor) forming the touch sensing electrode part, the touch driving electrode 32, or the electrode 33 in which the touch sensor electrode and the touch driving electrode are integrated can be used as a transparent conductive layer And formed. The constituent materials of the aforementioned transparent conductive layer are not particularly limited, and may include metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, tungsten, and alloys of these metals. . In addition, the constituent materials of the transparent conductive layer include metal oxides of indium, tin, zinc, gallium, antimony, zirconium, and cadmium, and specifically include indium oxide, tin oxide, titanium oxide, cadmium oxide, and mixtures thereof. Metal oxides composed of etc. Other metal compounds composed of copper iodide, etc. can be used. The aforementioned metal oxides may further contain oxides of metal atoms shown in the above group if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, etc. are preferably used, and ITO is particularly suitable. ITO should contain 80~99% by weight of indium oxide and 1~20% by weight of tin oxide.
前述觸控感測電極部之電極(觸控感測器電極31、觸控驅動電極 32、觸控感測器電極及觸控驅動電極一體形成的電極33)通常可利用常法以透明電極圖案形成於第1透明基板41及/或第2透明基板42之內側(內置型液晶單元B內之液晶層20側)。上述透明電極圖案通常係與形成於透明基板端部之繞線(未圖示)電連接,上述繞線則與控制器IC(未圖示)連接。透明電極圖案之形狀除了櫛形以外,可視用途採用任意形狀如條紋狀或菱形形狀等。透明電極圖案之高度例如為10nm~100nm,寬為0.1mm~5mm。 The electrodes of the aforementioned touch sensing electrode portion (touch sensor electrode 31, touch driving electrode 32. The electrode 33 in which the touch sensor electrode and the touch driving electrode are integrated can usually be formed in a transparent electrode pattern using a conventional method on the inside of the first transparent substrate 41 and/or the second transparent substrate 42 (built-in liquid crystal unit The liquid crystal layer 20 side in B). The above-mentioned transparent electrode pattern is usually electrically connected to a winding wire (not shown) formed at an end of the transparent substrate, and the above-mentioned winding wire is connected to a controller IC (not shown). In addition to the zigzag shape, the shape of the transparent electrode pattern can be any shape, such as stripe shape or rhombus shape, depending on the application. The height of the transparent electrode pattern is, for example, 10nm~100nm, and the width is 0.1mm~5mm.
(液晶面板C) (LCD panel C)
如圖3所示,本發明之液晶面板C可於液晶單元B之視辨側具有附黏著劑層之偏光薄膜A,且於其相反側具有第2偏光薄膜11。此外,圖4至圖8中係顯示使用有內置型液晶單元B之內置型液晶面板。 As shown in FIG. 3 , the liquid crystal panel C of the present invention can have a polarizing film A with an adhesive layer on the viewing side of the liquid crystal unit B, and a second polarizing film 11 on the opposite side. In addition, Figures 4 to 8 show a built-in liquid crystal panel using a built-in liquid crystal unit B.
前述附黏著劑層之偏光薄膜A未隔著導電層而透過前述第1黏著劑層2配置於前述液晶單元B之第1透明基板41之側。另一方面,於前述液晶單元B之第2透明基板42之側係透過第2黏著劑層12配置有第2偏光薄膜11。前述附黏著劑層之偏光薄膜A的第1偏光薄膜1、第2偏光薄膜11係以各自之偏光件之透射軸(或吸收軸)呈正交的方式配置在液晶層20兩側。 The polarizing film A with the adhesive layer is disposed on the side of the first transparent substrate 41 of the liquid crystal unit B through the first adhesive layer 2 without interposing the conductive layer. On the other hand, the second polarizing film 11 is disposed on the side of the second transparent substrate 42 of the liquid crystal unit B through the second adhesive layer 12 . The first polarizing film 1 and the second polarizing film 11 of the polarizing film A with the adhesive layer are arranged on both sides of the liquid crystal layer 20 in such a manner that the transmission axes (or absorption axes) of their respective polarizers are orthogonal.
第2偏光薄膜11可使用在第1偏光薄膜1中所述之物。第2偏光薄膜11可使用與第1偏光薄膜1相同之物,亦可使用不同物。 The second polarizing film 11 can use the ones described for the first polarizing film 1 . The second polarizing film 11 may be the same as the first polarizing film 1 or may be different.
於第2黏著劑層12之形成可使用第1黏著劑層2中所說明之黏著劑。用來形成第2黏著劑層12之黏著劑可使用與第1黏著劑層2相同之物,亦可使用不同物。第2黏著劑層12之厚度無特別限制,例如為1~100μm左右。宜為2~50μm,較宜為2~40μm,更宜為5~35μm。 The adhesive described in the first adhesive layer 2 can be used to form the second adhesive layer 12 . The adhesive used to form the second adhesive layer 12 may be the same as the first adhesive layer 2 or may be different. The thickness of the second adhesive layer 12 is not particularly limited, but is, for example, about 1 to 100 μm. It is preferably 2~50μm, more preferably 2~40μm, and more preferably 5~35μm.
又,液晶面板C中,如圖3(圖4乃至圖8)所示,於前述附黏著劑層之偏光薄膜A之側面具有導通結構50。另,只要導通結構50有設於含有離子性化合物的第1黏著劑層2之側面,對錨固層3之側面設置導通結構便是任意選項。又, 圖3(圖4至圖8)中,係例示除了導通結構50,將導通構造51設於表面處理層4及第1偏光薄膜1之側面之情況,但設置導通結構51為任意選項。在各層具有導電性時,宜設置導通結構。 In addition, in the liquid crystal panel C, as shown in FIG. 3 (FIG. 4 to FIG. 8), there is a conductive structure 50 on the side surface of the polarizing film A with the adhesive layer. In addition, as long as the conductive structure 50 is provided on the side of the first adhesive layer 2 containing the ionic compound, it is optional to provide the conductive structure on the side of the anchor layer 3 . again, In FIG. 3 (FIG. 4 to FIG. 8), in addition to the conductive structure 50, the conductive structure 51 is provided on the side surface of the surface treatment layer 4 and the first polarizing film 1. However, the conductive structure 51 is optional. When each layer is conductive, a conductive structure should be provided.
導通結構51、50可設置在前述附黏著劑層之偏光薄膜A之側面全部,亦可局部設置。局部設置前述導通結構時,為了確保在側面之導通,前述導通結構宜以佔前述側面面積之1面積%以上、更佳為3面積%以上之比例來設置。另一方面,由配線之觀點來看,前述導通結構宜為前述側面之99面積%以下,更宜為95面積%以下。前述導通結構51、50宜設置於前述附黏著劑層之偏光薄膜A之側面的至少圖2所示之點b(前述尺寸變化量400μm以下)。 The conductive structures 51 and 50 can be disposed on the entire side surface of the polarizing film A with the adhesive layer, or can be disposed partially. When the conductive structure is partially provided, in order to ensure conduction on the side, the conductive structure should be disposed at a ratio of more than 1 area%, preferably more than 3 area%, of the side area. On the other hand, from the perspective of wiring, the conductive structure is preferably 99% or less of the area of the side surface, more preferably 95% or less of the area. The aforementioned conductive structures 51 and 50 are preferably disposed at at least point b shown in FIG. 2 (the aforementioned dimensional change is less than 400 μm ) on the side of the polarizing film A with the adhesive layer.
藉由前述導通結構51、50,可從前述附黏著劑層之偏光薄膜A之側面於其他的適當位置連接電位,藉以抑制靜電產生。形成導通結構51、50之材料可列舉如銀、金或其他金屬糊等導電性糊,其他亦可使用導電性接著劑及其他任意的適當導電材料。導通結構51、50亦可以從前述附黏著劑層之偏光薄膜A之側面延伸的線狀形成。 Through the conductive structures 51 and 50, the potential can be connected to other appropriate positions from the side of the polarizing film A with the adhesive layer, thereby suppressing the generation of static electricity. Materials for forming the conductive structures 51 and 50 include conductive pastes such as silver, gold or other metal pastes. In addition, conductive adhesives and any other appropriate conductive materials may also be used. The conductive structures 51 and 50 may also be formed in a line shape extending from the side surface of the polarizing film A on which the adhesive layer is attached.
除此之外,配置在液晶層20視辨側的第1偏光薄膜1及配置在液晶層20視辨側之相反側的第2偏光薄膜11,可分別就各配置位置的適性而與其他光學薄膜積層來使用。前述其他光學薄膜可舉例如反射板或反透射板、相位差薄膜(包含1/2或1/4等的波長板)、視角補償薄膜、增亮薄膜等可成為用於形成液晶顯示裝置等之光學層者。該等可使用1層或2層以上。 In addition, the first polarizing film 1 arranged on the viewing side of the liquid crystal layer 20 and the second polarizing film 11 arranged on the opposite side of the viewing side of the liquid crystal layer 20 can be combined with other optical films according to the suitability of each arrangement position. Use thin film lamination. The aforementioned other optical films include, for example, reflective plates or anti-transmission plates, retardation films (including 1/2 or 1/4 wavelength plates), viewing angle compensation films, brightness enhancement films, etc., which can be used to form liquid crystal display devices, etc. Optical layer. These can be used with 1 layer or more than 2 layers.
(液晶顯示裝置) (Liquid crystal display device)
使用本發明之液晶面板C的液晶顯示裝置,可適當使用如在照明系統使用背光或反射板等用以形成液晶顯示裝置的構件。 The liquid crystal display device using the liquid crystal panel C of the present invention can appropriately use components for forming the liquid crystal display device such as a backlight or a reflector in the lighting system.
實施例 Example
以下,以製造例、實施例來具體說明本發明,惟本發明不受該等 實施例限定。至於,各例中之份及%皆為重量基準。以下,未特別規定之室溫放置條件皆為23℃且65%RH。 Hereinafter, the present invention will be specifically described with reference to production examples and working examples. However, the present invention is not limited by these examples. Example limitations. As for parts and % in each example, they are based on weight. Below, the room temperature storage conditions not specified are all 23℃ and 65%RH.
<(甲基)丙烯酸系聚合物之重量平均分子量的測定> <Measurement of weight average molecular weight of (meth)acrylic polymer>
(甲基)丙烯酸系聚合物之重量平均分子量(Mw)是利用GPC(凝膠滲透層析法)來測定。針對Mw/Mn亦同樣進行測定。 The weight average molecular weight (Mw) of the (meth)acrylic polymer is measured by GPC (gel permeation chromatography). Mw/Mn was also measured in the same manner.
‧分析裝置:Tosoh(東曹)公司製,HLC-8120GPC ‧Analysis device: Made by Tosoh Corporation, HLC-8120GPC
‧管柱:Tosoh公司製,G7000HXL+GMHXL+GMHXL ‧Pipe string: Made by Tosoh Co., Ltd., G7000H XL +GMH XL +GMH XL
‧管柱尺寸:各7.8mm φ×30cm計90cm ‧Pipe string size: 7.8mm each, φ×30cm, total 90cm
‧管柱溫度:40℃ ‧Column temperature: 40℃
‧流量:0.8mL/min ‧Flow rate: 0.8mL/min
‧注入量:100μL ‧Injection volume: 100μL
‧溶析液:四氫呋喃 ‧Eluent: Tetrahydrofuran
‧檢測器:示差折射計(RI) ‧Detector: Differential Refractometer (RI)
‧標準試料:聚苯乙烯 ‧Standard sample: polystyrene
<製造例1> <Manufacturing Example 1>
(製作附HC之40μmTAC薄膜、附HC之25μmTAC薄膜) (Production of 40μmTAC film with HC and 25μmTAC film with HC)
於將胺甲酸酯丙烯酸酯作為主成分之紫外線硬化型樹脂單體或寡聚物溶解於乙酸丁酯之樹脂溶液(DIC(股)製,商品名:UNIDIC 17-806,固體成分濃度:80%)中,相對於該溶液中之固體成分每100份,添加光聚合引發劑(BASF(股)製,商品名:IRGACURE 907)5份及調平劑(DIC(股)製,商品名:GRANDIC PC4100)0.1份。並且,於前述溶液中以45:55之比率加入環戊酮與丙二醇單甲基醚以使前述溶液中之固體成分濃度成為36%,而製作出硬塗層形成材料。將所製作出之硬塗層形成材料以使硬化後之硬塗層厚度成為7μm之方式塗佈至TJ40UL(富士軟片(Fujifilm)製,原料:三醋酸纖維素系聚合物,厚度:40μm)上而形成塗膜。之後, 於90℃下將塗膜乾燥1分鐘,並以高壓水銀燈對塗膜照射累積光量300mJ/cm2之紫外線,使前述塗膜硬化形成硬塗層(HC)而製作出附HC之40μmTAC薄膜。 A resin solution in which a UV-curable resin monomer or oligomer containing urethane acrylate as the main component is dissolved in butyl acetate (manufactured by DIC Co., Ltd., trade name: UNIDIC 17-806, solid content concentration: 80 %), add 5 parts of photopolymerization initiator (manufactured by BASF Co., Ltd., trade name: IRGACURE 907) and leveling agent (manufactured by DIC Co., Ltd., trade name:) for every 100 parts of the solid content in the solution. GRANDIC PC4100)0.1 part. Furthermore, cyclopentanone and propylene glycol monomethyl ether were added to the aforementioned solution at a ratio of 45:55 so that the solid content concentration in the aforementioned solution became 36%, thereby producing a hard coat forming material. The prepared hard coat layer forming material was applied to TJ40UL (manufactured by Fujifilm, raw material: cellulose triacetate polymer, thickness: 40 μm) so that the thickness of the hard coat layer after hardening became 7 μm. And form a coating film. After that, the coating film was dried at 90°C for 1 minute, and a high-pressure mercury lamp was used to irradiate the coating film with ultraviolet rays with a cumulative light intensity of 300 mJ/cm 2 to harden the coating film to form a hard coat (HC) to produce a 40 μm TAC film with HC. .
<製造例2> <Manufacturing Example 2>
(製作30μm丙烯酸薄膜) (Production of 30μm acrylic film)
於具備攪拌裝置、溫度感測器、冷卻管、氮導入管的容量30L之釜型反應器中,饋入8,000g之甲基丙烯酸甲酯(MMA)、2,000g之2-(羥甲基)丙烯酸甲酯(MHMA)、10,000g之4-甲基-2-戊酮(甲基異丁基酮,MIBK)、5g之正十二硫醇,並一邊使氮通過其中一邊升溫至105℃並回流後,添加5.0g之三級丁基過氧基異丙基碳酸酯(Kayakarubon BIC-7,KAYAKU AKZO CO.,LTD.製)作為聚合引發劑,同時耗時4小時滴下由10.0g之三級丁基過氧基異丙基碳酸酯與230g之MIBK構成之溶液,並在回流下,於約105~120℃下進行溶液聚合,並再耗時4小時進行熟成。 Into a 30L kettle-type reactor equipped with a stirring device, a temperature sensor, a cooling pipe, and a nitrogen inlet pipe, 8,000g of methyl methacrylate (MMA) and 2,000g of 2-(hydroxymethyl) were fed. Methyl acrylate (MHMA), 10,000g of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK), 5g of n-dodecanethiol, and while passing nitrogen through them, the temperature was raised to 105°C and After refluxing, 5.0 g of tertiary butyl peroxy isopropyl carbonate (Kayakarubon BIC-7, manufactured by KAYAKU AKZO CO., LTD.) was added as a polymerization initiator, and 10.0 g of tertiary butylperoxyisopropyl carbonate was added dropwise over 4 hours. A solution composed of grade butylperoxyisopropyl carbonate and 230g of MIBK was solution polymerized at about 105~120°C under reflux, and then matured for another 4 hours.
於所得聚合物溶液中加入30g之磷酸十八酯/磷酸二(十八基)酯混合物(Phoslex A-18,堺化學工業(股)製),並於回流下在約90~120℃下進行5小時環化縮合反應。接著,將所得聚合物溶液以用樹脂量換算為2.0kg/h之處理速度導入通氣孔式雙螺桿擠製機(φ=29.75mm、L/D=30)中,並於該擠製機內進一步進行環化縮合反應與去揮發並進行擠製,藉此製得含內酯環之聚合物的透明丸粒,該通氣孔式雙螺桿擠製機之套筒溫度260℃、旋轉數100rpm、減壓度13.3~400hPa(10~300mmHg)、後通氣孔數1個、前通氣孔數4個。 30 g of stearyl phosphate/octadecyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the obtained polymer solution, and the process was carried out under reflux at about 90 to 120°C. 5 hours cyclization condensation reaction. Next, the obtained polymer solution was introduced into a vented twin-screw extruder (φ=29.75mm, L/D=30) at a processing speed of 2.0kg/h in terms of resin amount, and placed in the extruder. Further perform cyclization condensation reaction, devolatization and extrusion to obtain transparent pellets of the lactone ring-containing polymer. The vented twin-screw extruder has a sleeve temperature of 260°C and a rotation speed of 100 rpm. The pressure reduction degree is 13.3~400hPa (10~300mmHg), the number of rear vents is 1, and the number of front vents is 4.
針對所得含內酯環之聚合物進行動態TG之測定後,檢測出0.17質量%之質量減損。又,該含內酯環之聚合物的重量平均分子量為133,000,熔流速率為6.5g/10min,且玻璃轉移溫度為131℃。 After measuring the dynamic TG of the obtained polymer containing a lactone ring, a mass loss of 0.17% by mass was detected. In addition, the weight average molecular weight of the lactone ring-containing polymer was 133,000, the melt flow rate was 6.5 g/10 min, and the glass transition temperature was 131°C.
使用單軸擠製機(螺桿30mm φ)將所得丸粒與丙烯腈-苯乙烯(AS)樹脂(TOYO AS AS20,TOYO STYRENE CO.,LTD.製)以質量比90/10進行捏合擠製, 藉此獲得透明丸粒。所得丸粒之玻璃轉移溫度為127℃。 The obtained pellets and acrylonitrile-styrene (AS) resin (TOYO AS AS20, manufactured by TOYO STYRENE CO., LTD.) were kneaded and extruded using a single-screw extruder (screw 30 mm φ) at a mass ratio of 90/10. Transparent pellets are thus obtained. The glass transition temperature of the resulting pellets was 127°C.
使用50mm φ之單軸擠製機將該丸粒從400mm寬的衣架式T型模具進行熔融擠製,而製作出厚度120μm之薄膜。使用雙軸延伸裝置將製作出之薄膜在150℃之溫度條件下縱向延伸成2.0倍且橫向延伸成2.0倍,從而獲得厚度30μm之延伸薄膜(30μm丙烯酸薄膜)。測定該延伸薄膜之光學特性後,得全光線透射率為93%,面內相位差△nd為0.8nm,厚度方向相位差Rth為1.5nm。 Using a 50mm φ single-screw extruder, the pellets were melt-extruded from a 400mm wide coat hanger T-shaped die to produce a film with a thickness of 120 μm. The produced film was stretched longitudinally to 2.0 times and transversely to 2.0 times at a temperature of 150° C. using a biaxial stretching device to obtain a stretched film (30 μm acrylic film) with a thickness of 30 μm. After measuring the optical properties of the stretched film, it was found that the total light transmittance was 93%, the in-plane phase difference Δnd was 0.8nm, and the thickness direction phase difference Rth was 1.5nm.
<製作偏光薄膜(1)> <Making polarizing film(1)>
將厚度45μm的聚乙烯醇薄膜在速度比不同之輥件間,於30℃且0.3%濃度的碘溶液中染色1分鐘並延伸達3倍為止。之後,一邊在60℃且含有4%濃度之硼酸、10%濃度之碘化鉀的水溶液中浸漬0.5分鐘,一邊進行延伸使總延伸倍率達6倍為止。接著,於30℃且含有1.5%濃度之碘化鉀之水溶液中浸漬10秒藉此洗淨後,在50℃下進行4分鐘乾燥,而獲得厚18μm之偏光件。利用聚乙烯醇系接著劑於該偏光件的單面貼合製造例1所得經皂化處理之附HC之40μmTAC薄膜(三醋酸纖維素薄膜側),並於另一單面貼合製造例2所得30μm丙烯酸薄膜,而製出偏光薄膜(1)。 A polyvinyl alcohol film with a thickness of 45 μm was dyed in an iodine solution with a concentration of 0.3% at 30°C for 1 minute between rollers with different speed ratios until it was extended 3 times. Thereafter, the film was stretched while being immersed in an aqueous solution containing 4% boric acid and 10% potassium iodide at 60° C. for 0.5 minutes until the total stretching ratio reached 6 times. Next, it was washed by immersing it in an aqueous solution containing 1.5% potassium iodide at 30° C. for 10 seconds, and then dried at 50° C. for 4 minutes to obtain a polarizing element with a thickness of 18 μm. Use a polyvinyl alcohol-based adhesive to laminate the saponified HC-attached 40 μm TAC film (triacetyl cellulose film side) obtained in Production Example 1 on one side of the polarizer, and laminate the product of Production Example 2 on the other side. 30μm acrylic film to produce a polarizing film (1).
<製作偏光薄膜(2)> <Making polarizing film(2)>
(製作薄型偏光件A) (Production of thin polarizer A)
於吸水率0.75%、Tg75℃之非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯(IPA共聚PET)薄膜(厚度:100μm)基材的單面上施加電暈處理,並在該電暈處理面上於25℃下塗佈以9:1之比含有聚乙烯醇(聚合度4200,皂化度99.2莫耳%)及乙醯乙醯基改質聚乙烯醇(聚合度1200,乙醯乙醯基改質度4.6%,皂化度99.0莫耳%以上,日本合成化學工業公司製,商品名「Gohsefimer Z200」)的水溶液並乾燥,形成厚度11μm的聚乙烯醇系樹脂層,而製作出積層體。 Corona treatment is applied to one side of the base material of an amorphous isophthalic acid copolymer polyethylene terephthalate (IPA copolymer PET) film (thickness: 100 μm) with a water absorption rate of 0.75% and a Tg of 75°C, and the The corona-treated surface is coated at 25°C containing polyvinyl alcohol (degree of polymerization 4200, saponification degree 99.2 mol%) and acetate-acetyl-modified polyvinyl alcohol (degree of polymerization 1200, acetyl alcohol) in a ratio of 9:1. It is produced by drying an aqueous solution of acetoacetyl group modification degree 4.6% and saponification degree 99.0 mol% or more (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gohsefimer Z200") to form a polyvinyl alcohol-based resin layer with a thickness of 11 μm. Out of the layered body.
將所得積層體在120℃之烘箱內於周速相異的輥件間沿縱方向(長邊方向)進 行自由端單軸延伸2.0倍(空中輔助延伸處理)。 The obtained laminated body was advanced in the longitudinal direction (long side direction) between rollers with different circumferential speeds in an oven at 120°C. The free end of the line can be uniaxially extended by 2.0 times (air-assisted extension processing).
接著,使積層體浸漬於液溫30℃的不溶解浴(相對於水100重量份摻混4重量份之硼酸而得的硼酸水溶液)中30秒(不溶解處理)。 Next, the laminated body was immersed in an insolubilization bath (a boric acid aqueous solution in which 4 parts by weight of boric acid was mixed with 100 parts by weight of water) having a liquid temperature of 30°C for 30 seconds (insolubilization treatment).
接著,一邊使其浸漬於液溫30℃的染色浴中一邊調整碘濃度、浸漬時間以使偏光板成為預定之透射率。本實施例係使其浸漬於相對於100重量份的水摻混0.2重量份的碘、1.0重量份的碘化鉀所得之碘水溶液中60秒(染色處理)。 Next, while immersing it in a dyeing bath with a liquid temperature of 30° C., the iodine concentration and the immersion time were adjusted so that the polarizing plate would have a predetermined transmittance. In this example, the material was immersed in an iodine aqueous solution in which 0.2 parts by weight of iodine and 1.0 parts by weight of potassium iodide were mixed with 100 parts by weight of water for 60 seconds (dyeing treatment).
接著,使其浸漬於液溫30℃的交聯浴(相對於水100重量份摻混3重量份的碘化鉀並摻混3重量份的硼酸而得之硼酸水溶液)中30秒(交聯處理)。 Next, it was immersed in a crosslinking bath (a boric acid aqueous solution in which 3 parts by weight of potassium iodide and 3 parts by weight of boric acid were mixed with 100 parts by weight of water) with a liquid temperature of 30° C. for 30 seconds (crosslinking treatment). .
其後,一邊使積層體浸漬於液溫70℃之硼酸水溶液(相對於100重量份的水摻混4重量份硼酸並摻混5重量份碘化鉀所得之水溶液)中,一邊於不同周速之輥件間沿縱方向(長邊方向)進行單軸延伸以使總延伸倍率達5.5倍(水中延伸)。 Thereafter, the laminated body was immersed in a boric acid aqueous solution with a liquid temperature of 70° C. (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide per 100 parts by weight of water), while rolling it on rollers with different peripheral speeds. The parts are uniaxially extended along the longitudinal direction (long side direction) so that the total extension ratio reaches 5.5 times (extension in water).
之後,使積層體浸漬於液溫30℃的洗淨浴(相對於水100重量份摻混4重量份的碘化鉀而得之水溶液)中(洗淨處理)。 Thereafter, the laminated body was immersed in a cleaning bath (an aqueous solution in which 4 parts by weight of potassium iodide was mixed with 100 parts by weight of water) having a liquid temperature of 30° C. (washing treatment).
以上述方式獲得了包含厚度5μm之偏光件的光學薄膜積層體。 In the above manner, an optical film laminated body including a polarizer with a thickness of 5 μm was obtained.
(製作應用於透明保護薄膜之接著劑) (Making adhesives for transparent protective films)
將丙烯醯基嗎福林45重量份、1,9-壬二醇二丙烯酸酯45份、(甲基)丙烯酸單體聚合而成的丙烯酸系寡聚物(ARUFON UP1190,東亞合成公司製)10份、光聚合引發劑(IRGACURE 907,BASF公司製)3份、聚合引發劑(KAYACURE DETX-S,日本化藥公司製)1.5份混合,而調製出紫外線硬化型接著劑。 Acrylic oligomer (ARUFON UP1190, manufactured by Toagosei Co., Ltd.) 10 obtained by polymerizing 45 parts by weight of acrylomorphine, 45 parts by 1,9-nonanediol diacrylate, and (meth)acrylic acid monomer. parts, 3 parts of photopolymerization initiator (IRGACURE 907, manufactured by BASF Corporation), and 1.5 parts of polymerization initiator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) were mixed to prepare an ultraviolet curable adhesive.
在上述光學薄膜積層體之偏光件A的表面上,一邊將上述紫外線硬化型接著劑以使硬化後之接著劑層厚度成為1μm的方式進行塗佈,一邊貼合上述製造例1所得附HC之25μmTAC薄膜(三醋酸纖維素薄膜側)後,照射紫外線作為活性能量線使接著劑硬化。紫外線照射是使用充有鎵之金屬鹵素燈,照射裝置:Fusion UV Systems,Inc公司製的Light HAMMER10,燈泡:V燈泡,峰值照度: 1600mW/cm2,累積照射量1000/mJ/cm2(波長380~440nm),紫外線照度則使用Solatell公司製的Sola-Check系統來測定。接著將非晶性PET基材剝離而製出使用有薄型偏光件之偏光薄膜(2)。所得偏光薄膜之光學特性為單體透射率42.8%、偏光度99.99%。 On the surface of the polarizer A of the above-mentioned optical film laminate, the above-mentioned ultraviolet curable adhesive was applied so that the thickness of the adhesive layer after curing would be 1 μm, and the HC-attached film obtained in the above-mentioned Production Example 1 was bonded. After the 25 μm TAC film (cellulose triacetate film side) is irradiated, ultraviolet rays are irradiated as active energy rays to harden the adhesive. Ultraviolet irradiation uses a metal halide lamp filled with gallium, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illumination: 1600mW/cm 2 , cumulative irradiation dose 1000/mJ/cm 2 (wavelength 380~440nm), and the ultraviolet illuminance was measured using the Sola-Check system manufactured by Solatell. Then, the amorphous PET base material is peeled off to produce a polarizing film (2) using a thin polarizer. The optical properties of the obtained polarizing film were a single transmittance of 42.8% and a polarization degree of 99.99%.
上述所得偏光薄膜(1)之偏光件的碘濃度為3.2重量%。又,上述所得偏光薄膜(2)之偏光件的碘濃度為7.2重量%。另,偏光件之碘濃度(重量%)可在製造偏光件時透過例如將聚乙烯醇系薄膜或聚乙烯醇層在預定濃度之碘水溶液中僅浸漬預定時間來調整。表2所示偏光薄膜(1)之各偏光件的碘濃度係透過變更在調製偏光薄膜(1)時用以將聚乙烯醇薄膜染色之碘溶液的濃度來調整。 The iodine concentration of the polarizer of the polarizing film (1) obtained above was 3.2% by weight. Furthermore, the iodine concentration of the polarizer of the polarizing film (2) obtained above was 7.2% by weight. In addition, the iodine concentration (wt%) of the polarizer can be adjusted by, for example, immersing the polyvinyl alcohol film or polyvinyl alcohol layer in an iodine aqueous solution of a predetermined concentration for a predetermined time when manufacturing the polarizer. The iodine concentration of each polarizer of the polarizing film (1) shown in Table 2 is adjusted by changing the concentration of the iodine solution used to dye the polyvinyl alcohol film when preparing the polarizing film (1).
<偏光件之膜厚> <Film thickness of polarizer>
使用分光膜厚計MCPD-1000(大塚電子(股)製)測定偏光件之膜厚(μm)。試樣(上述調製出之偏光薄膜(1)或(2))所含偏光件係藉由將試樣浸漬於溶劑使偏光件保護薄膜溶解來取出。於溶劑中舉例而言可分別在偏光件保護薄膜為三醋酸纖維素樹脂時使用二氯甲烷,而在偏光件保護薄膜為丙烯酸樹脂時使用甲基乙基酮。此外,當設置於偏光件之一面的偏光件保護薄膜之樹脂與設置於另一面的偏光件保護薄膜之樹脂相異時,則使用上述溶劑依次分別使各樹脂溶解。 The film thickness (μm) of the polarizer was measured using a spectroscopic film thickness meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The polarizer contained in the sample (the polarizing film (1) or (2) prepared above) is taken out by immersing the sample in a solvent to dissolve the polarizer protective film. For example, dichloromethane can be used as a solvent when the polarizer protective film is made of cellulose triacetate resin, and methyl ethyl ketone can be used when the polarizer protective film is made of acrylic resin. In addition, when the resin of the polarizer protective film provided on one side of the polarizer is different from the resin of the polarizer protective film provided on the other side, the above-mentioned solvent is used to dissolve each resin in sequence.
<偏光件之碘濃度> <Iodine concentration of polarizer>
偏光件之碘濃度係以以下方法測定。另外,試樣中所含之偏光件依與測定偏光件之膜厚時同樣方式,藉由將試樣浸漬於溶劑中使偏光件保護薄膜溶解來取出。 The iodine concentration of the polarizer is measured by the following method. In addition, the polarizer contained in the sample is taken out by immersing the sample in a solvent to dissolve the polarizer protective film in the same manner as when measuring the film thickness of the polarizer.
(螢光X射線測定) (fluorescence X-ray measurement)
測定偏光件之碘濃度時,首先係使用螢光X射線分析之檢量曲線法來定量碘濃度。裝置係使用螢光X射線分析裝置ZSX-PRIMUS IV((股)Rigaku製)。利用螢光X射線分析裝置直接取得之值並非各元素之濃度,而是各元素固有之波長的螢 光X射線強度(kcps)。因此,欲求得偏光件所含碘濃度,須使用檢量曲線將螢光X射線強度轉換為濃度。本說明書等中之偏光件的碘濃度係指以偏光件之重量為基準之碘濃度(重量%)。 When measuring the iodine concentration of polarizers, the calibration curve method of fluorescence X-ray analysis is first used to quantify the iodine concentration. As the device, a fluorescence X-ray analysis device ZSX-PRIMUS IV (manufactured by Rigaku Co., Ltd.) was used. The value directly obtained by using the fluorescence X-ray analysis device is not the concentration of each element, but the fluorescence of the wavelength specific to each element. Light X-ray intensity (kcps). Therefore, in order to obtain the iodine concentration contained in the polarizer, a calibration curve must be used to convert the fluorescence X-ray intensity into concentration. The iodine concentration of the polarizing element in this manual etc. refers to the iodine concentration (% by weight) based on the weight of the polarizing element.
(作成檢量曲線) (Create a calibration curve)
依以下程序作成檢量曲線。 Follow the following procedure to prepare a calibration curve.
1.使已知量的碘化鉀溶解至聚乙烯醇水溶液中,製作出7種含有已知濃度之碘的聚乙烯醇水溶液。將該聚乙烯醇水溶液塗佈於聚對苯二甲酸乙二酯並乾燥後剝離,製作出含有已知濃度之碘的聚乙烯醇薄膜之試料1~7。 1. Dissolve a known amount of potassium iodide into a polyvinyl alcohol aqueous solution to prepare seven types of polyvinyl alcohol aqueous solutions containing iodine of known concentrations. This polyvinyl alcohol aqueous solution was applied to polyethylene terephthalate, dried and then peeled off to prepare samples 1 to 7 of polyvinyl alcohol films containing iodine of a known concentration.
此外,聚乙烯醇薄膜的碘濃度(重量%)係利用以下數學式1算出。 In addition, the iodine concentration (weight%) of the polyvinyl alcohol film was calculated using the following mathematical formula 1.
[數學式1] 碘濃度(重量%)={碘化鉀量(g)/(碘化鉀量(g)+聚乙烯醇重量(g))}×(127/166) [Mathematical formula 1] Iodine concentration (% by weight) = {amount of potassium iodide (g)/(amount of potassium iodide (g) + weight of polyvinyl alcohol (g))} × (127/166)
(碘的分子量:127,鉀的分子量:39) (Molecular weight of iodine: 127, molecular weight of potassium: 39)
2.針對所製作出之聚乙烯醇薄膜,使用螢光X射線分析裝置ZSX-PRIMUS IV((股)Rigaku製),測定出對應碘的螢光X射線強度(kcps)。此外,螢光X射線強度(kcps)係取螢光X射線光譜之峰值。且,使用分光膜厚計MCPD-1000(大塚電子(股)製)測定製出之聚乙烯醇薄膜之膜厚。 2. For the produced polyvinyl alcohol film, the fluorescence X-ray intensity (kcps) corresponding to iodine was measured using a fluorescence X-ray analyzer ZSX-PRIMUS IV (manufactured by Rigaku Co., Ltd.). In addition, the fluorescence X-ray intensity (kcps) is taken as the peak value of the fluorescence X-ray spectrum. Furthermore, the film thickness of the produced polyvinyl alcohol film was measured using a spectroscopic film thickness meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.).
3.將螢光X射線強度除以聚乙烯醇薄膜之厚度(μm),算出薄膜每單位厚度之螢光X射線強度(kcps/μm)。於表1顯示各試料之碘濃度與每單位厚度之螢光X射線強度。 3. Divide the fluorescence X-ray intensity by the thickness of the polyvinyl alcohol film (μm) to calculate the fluorescence X-ray intensity per unit thickness of the film (kcps/μm). Table 1 shows the iodine concentration and fluorescence X-ray intensity per unit thickness of each sample.
[表1]
4.以表1所示結果為基礎,以(聚乙烯醇(PVA)薄膜每單位厚度之螢光X射線強度(kcps/μm)為橫軸,並以聚乙烯醇薄膜所含碘濃度(重量%:wt%)為縱軸,作出檢量曲線。於圖9顯示作成之檢量曲線。可從由檢量曲線得聚乙烯醇薄膜每單位厚度之螢光X射線強度求出碘濃度的數學式定如數學式2所示。此外,圖9中之R2係相關係數。 4. Based on the results shown in Table 1, take the fluorescent X-ray intensity per unit thickness (kcps/μm) of the polyvinyl alcohol (PVA) film as the horizontal axis, and take the iodine concentration (weight %: wt%) as the vertical axis, draw a calibration curve. The prepared calibration curve is shown in Figure 9. The mathematics of iodine concentration can be calculated from the fluorescence X-ray intensity per unit thickness of the polyvinyl alcohol film obtained from the calibration curve. The formula is determined as shown in mathematical formula 2. In addition, R2 in Figure 9 is the correlation coefficient.
[數學式2] (碘濃度)(重量%)=14.474×(聚乙烯醇薄膜每單位厚度的螢光X射線強度)(kcps/μm) [Mathematical formula 2] (iodine concentration) (weight %) = 14.474 × (fluorescence X-ray intensity per unit thickness of polyvinyl alcohol film) (kcps/μm)
(偏光件中之碘濃度之計算) (Calculation of iodine concentration in polarizer)
將測定試樣而得之螢光X射線強度除以厚度,求出每單位厚度之螢光X射線強度(kcps/μm)。將各試樣的每單位厚度的螢光X射線強度代入數學式2來求出碘濃度。 Divide the fluorescence X-ray intensity obtained by measuring the sample by the thickness to obtain the fluorescence X-ray intensity per unit thickness (kcps/μm). The fluorescent X-ray intensity per unit thickness of each sample was substituted into Mathematical Expression 2 to determine the iodine concentration.
實施例1 Example 1
(調製丙烯酸系聚合物(A)) (Preparation of acrylic polymer (A))
在備有攪拌葉片、溫度計、氮氣導入管、冷卻器的4口燒瓶中饋入含有丙烯酸丁酯77.9份、丙烯酸苯氧乙酯16份、N-乙烯基-2-吡咯啶酮1份、丙烯酸5份及丙 烯酸4-羥丁酯0.1份之單體混合物。並相對於前述單體混合物(固體成分)100份,將作為聚合引發劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100份一起饋入,一邊緩慢攪拌一邊導入氮氣進行氮取代後,將燒瓶內的液溫保持在55℃附近,進行8小時聚合反應,調製出重量平均分子量(Mw)195萬並且Mw/Mn=3.9之丙烯酸系聚合物之溶液。 Into a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen inlet pipe, and a cooler, add 77.9 parts of butyl acrylate, 16 parts of phenoxyethyl acrylate, 1 part of N-vinyl-2-pyrrolidone, and acrylic acid. 5 parts and C 0.1 part of monomer mixture of 4-hydroxybutyl enoate. And with respect to 100 parts of the aforementioned monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was fed together with 100 parts of ethyl acetate, and nitrogen gas was introduced while slowly stirring. After nitrogen substitution, the liquid temperature in the flask was maintained at around 55° C., and a polymerization reaction was performed for 8 hours to prepare a solution of an acrylic polymer with a weight average molecular weight (Mw) of 1.95 million and Mw/Mn = 3.9.
(調製黏著劑組成物) (Prepare adhesive composition)
相對於上述所得丙烯酸系聚合物溶液之固體成分100份,摻混雙(三氟甲磺醯基)醯亞胺鋰8份、異氰酸酯交聯劑(Tosoh公司製之Coronate L,三羥甲丙烷二異氰酸甲苯酯)0.6份及過氧化苯甲醯(日本油脂公司製之NYPER BMT)0.1份,而調製出丙烯酸系黏著劑溶液。 With respect to 100 parts of the solid content of the acrylic polymer solution obtained above, 8 parts of lithium bis(trifluoromethanesulfonyl)acyl imide, isocyanate cross-linking agent (Coronate L manufactured by Tosoh Corporation, trimethylolpropane di 0.6 parts of toluyl isocyanate) and 0.1 part of benzoyl peroxide (NYPER BMT manufactured by Nippon Oils and Fats Co., Ltd.) to prepare an acrylic adhesive solution.
(製作附黏著劑層之偏光薄膜) (Production of polarizing film with adhesive layer)
接著,以使乾燥後的黏著劑層的厚度成為20μm,將上述丙烯酸系黏著劑組成物之溶液塗佈於經聚矽氧系剝離劑處理過之聚對苯二甲酸乙二酯薄膜(分離薄膜:三菱化學聚酯薄膜(股)製,MRF38)的單面上,並以155℃乾燥1分鐘,而於分離薄膜表面形成黏著劑層。接著,將形成於分離薄膜上的黏著劑層轉印至上述製出之偏光薄膜(1)之丙烯酸薄膜側,而製作出了附黏著劑層之偏光薄膜。 Next, the solution of the above-mentioned acrylic adhesive composition was applied to a polyethylene terephthalate film (release film) treated with a polysiloxy release agent so that the thickness of the dried adhesive layer became 20 μm. : Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) on one side and dried at 155°C for 1 minute to form an adhesive layer on the surface of the separation film. Next, the adhesive layer formed on the release film is transferred to the acrylic film side of the polarizing film (1) produced above, thereby producing a polarizing film with an adhesive layer attached.
實施例2~6、比較例1~3 Examples 2 to 6, Comparative Examples 1 to 3
於實施例1中,如表2所示,將偏光薄膜的種類、調製黏著劑組成物所用離子性化合物(B)之種類變更成如表2所示,除此之外依與實施例1相同方式而製出附黏著劑層之偏光薄膜。 In Example 1, as shown in Table 2, the type of polarizing film and the type of ionic compound (B) used to prepare the adhesive composition were changed to those shown in Table 2. Otherwise, the process was the same as Example 1. In this way, a polarizing film with an adhesive layer is produced.
針對上述實施例及比較例所得附黏著劑層之偏光薄膜進行以下的評估。將評估結果列於表2。 The following evaluation was performed on the polarizing films with adhesive layers obtained in the above examples and comparative examples. The evaluation results are listed in Table 2.
<表面電阻值(Ω/□):導電性> <Surface resistance value (Ω/□): Conductivity>
黏著劑層之表面電阻值係針對形成在分離薄膜上的黏著劑層表面進行測 定。測定是使用三菱化學ANALYTECH公司製的MCP-HT450來進行。 The surface resistance value of the adhesive layer is measured on the surface of the adhesive layer formed on the separation film. Certainly. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical ANALYTECH.
<尺寸變化量> <Dimensional change>
將附黏著劑層之偏光薄膜裁切成10cm(吸收軸方向)×10cm(慢軸方向),再貼附於無鹼玻璃(康寧公司製)並將所得之物作為試樣。將試樣投入85℃之加熱試驗機。500小時後取出試樣,測定從投入加熱試驗機前之附黏著劑層之偏光薄膜的位置到投入加熱試驗後之附黏著劑層之偏光薄膜位置之差,將其作為尺寸變化量。測定係針對點a:與矩形試樣之慢軸方向相同方向之側面(於吸收軸方向收縮)的中央點與點b:與矩形之吸收軸方向相同方向之側面(與慢軸方向收縮)的中央點進行。 The polarizing film with the adhesive layer was cut into 10 cm (absorption axis direction) × 10 cm (slow axis direction), and then attached to alkali-free glass (made by Corning Corporation), and the resultant was used as a sample. Put the sample into the heating testing machine at 85°C. After 500 hours, take out the sample and measure the difference from the position of the polarizing film with the adhesive layer attached before being put into the heating test machine to the position of the polarizing film with the adhesive layer attached after being put into the heating test, and use it as the dimensional change. The measurement is based on point a: the center point of the side in the same direction as the slow axis of the rectangular sample (shrinking in the direction of the absorption axis) and point b: the side in the same direction as the absorption axis of the rectangle (shrinking in the direction of the slow axis). Perform at the center point.
<加熱後ESD試驗> <ESD test after heating>
將分離薄膜從附黏著劑層之偏光薄膜剝離後,如圖7所示(惟不具有錨固層)貼合於內置型液晶單元之視辨側。接著,於已貼合之附黏著劑層之偏光薄膜的側面部點b塗佈寬5mm的銀糊以覆蓋硬塗層、偏光薄膜、黏著劑層之各側面部,乾燥後,於85℃或95℃下將該液晶單元保管120小時後取出,並與來自外部之接地電極連接。然後將內置型液晶單元內部之透明電極圖案周邊部的繞線配線(未圖示)與控制器IC(未圖示)連接,製出內嵌觸控感測機能之液晶顯示裝置。在施加電壓15kV下對該液晶顯示裝置之偏光薄膜面發射靜電放電槍(Electrostatic discharge Gun),測定因電氣而出現泛白之部分消失的時間,並以下述基準進行判斷。 After the separation film is peeled off from the polarizing film with the adhesive layer, it is attached to the viewing side of the built-in liquid crystal unit as shown in Figure 7 (but without the anchoring layer). Then, apply silver paste with a width of 5 mm at point b on the side of the polarizing film with the adhesive layer to cover the hard coating, polarizing film, and adhesive layer. After drying, heat it at 85°C or The liquid crystal cell was stored at 95° C. for 120 hours, then taken out and connected to an external ground electrode. Then, the winding wiring (not shown) at the periphery of the transparent electrode pattern inside the built-in liquid crystal unit is connected to the controller IC (not shown) to create a liquid crystal display device with built-in touch sensing function. An electrostatic discharge gun was fired at the polarizing film surface of the liquid crystal display device under an applied voltage of 15 kV, and the time it took for the whitened part due to electricity to disappear was measured, and the judgment was made based on the following criteria.
(評估基準) (Evaluation Basis)
◎:1秒以內。 ◎: Within 1 second.
○:超過1秒至10秒以內。 ○: More than 1 second and within 10 seconds.
△:超過10秒至30秒以內。 △: More than 10 seconds to within 30 seconds.
×:超過30秒。 ×: More than 30 seconds.
<多烯化> <Polyene>
在高溫高濕環境下,偏光薄膜積層體的單體透射率會降低。吾等推測聚乙烯醇的多烯化即造成該降低之原因。多烯係指-(CH=CH)n-,經加熱會形成於偏光膜中。多烯會顯著使偏光膜之透射率降低。且,在高溫高濕環境下,聚乙烯醇-多碘錯合物會被破壞而易生成I-及I2。吾等推測聚乙烯醇之多烯化係因在高溫高濕環境下生成之碘(I2)與加熱會促進脫水反應,因而發生(化學式1)。 In a high-temperature and high-humidity environment, the single transmittance of the polarizing film laminate decreases. We speculate that polyethylenization of polyvinyl alcohol is responsible for this decrease. Polyene refers to -(CH=CH)n-, which will be formed in the polarizing film after heating. Polyene will significantly reduce the transmittance of polarizing films. Moreover, in a high-temperature and high-humidity environment, the polyvinyl alcohol-polyiodine complex will be destroyed and easily generate I- and I2 . We speculate that the polyenization of polyvinyl alcohol occurs because iodine (I 2 ) generated in a high-temperature and high-humidity environment and heating promote a dehydration reaction (Chemical Formula 1).
推測是存在於偏光件中之聚乙烯醇-多碘錯合物因加熱而被破壞因而產生之I2與聚乙烯醇中之OH基形成電荷轉移錯合物(HO‧‧‧I2),而在這之後經由OI基而多烯化。 It is speculated that the polyvinyl alcohol-polyiodine complex present in the polarizer is destroyed by heating and the I 2 produced forms a charge transfer complex (HO‧‧‧I 2 ) with the OH group in the polyvinyl alcohol. After that, polyene is formed via the OI group.
<評估多烯化> <Evaluation of polyene>
將附黏著劑層之偏光薄膜供於95℃之環境下500小時的加熱試驗,並於其前後測定試料的單體透射率,以下式求出單體透射率的變化量△Ts。 The polarizing film with the adhesive layer was subjected to a heating test at 95°C for 500 hours, and the single transmittance of the sample was measured before and after. The change in the single transmittance ΔTs was calculated by the following formula.
△Ts=Ts(500)-Ts(0) △Ts=Ts(500)-Ts(0)
此處,Ts(0)係試料加熱前之單體透射率,Ts(500)係在105℃之環境下加熱500小時後之單體透射率。 Here, Ts(0) is the monomer transmittance of the sample before heating, and Ts(500) is the monomer transmittance after heating in an environment of 105°C for 500 hours.
按下述基準評估該試樣。 The sample was evaluated according to the following criteria.
(評估基準) (Evaluation Basis)
○:△Ts為0以上 ○: △Ts is 0 or more
×:△Ts小於0 ×: △Ts is less than 0
表2中:BA表示丙烯酸丁酯、PEA表示丙烯酸苯氧乙酯、AA表示丙烯酸、NVP表示N-乙烯基-2-吡咯啶酮、HBA表示丙烯酸4-羥丁酯、異氰酸酯系表示異氰酸酯交聯劑(Tosoh公司製之CORONATE L,三羥甲丙烷二異氰酸甲苯酯)、BPO表示氧化苯甲醯(日本油脂公司製之NYPER BMT)、Li-TFSI表示雙(三氟甲磺醯基)醯亞胺鋰、K-TFSI表示雙(三氟甲磺醯基)醯亞胺鉀 In Table 2: BA represents butyl acrylate, PEA represents phenoxyethyl acrylate, AA represents acrylic acid, NVP represents N-vinyl-2-pyrrolidone, HBA represents 4-hydroxybutyl acrylate, and isocyanate represents isocyanate cross-linking. agent (CORONATE L, produced by Tosoh Co., Ltd., toluene trimethylolpropane diisocyanate), BPO represents benzoyl oxide (NYPER BMT produced by Nippon Oils and Fats Co., Ltd.), Li-TFSI represents bis(trifluoromethanesulfonyl) Lithium acyl imide, K-TFSI stands for potassium bis(trifluoromethanesulfonyl) acyl imide
EMP-TFSI表示乙基甲基吡咯啶鎓-雙(三氟磺醯基醯亞胺)、TMPA-TFSI表示三甲基丙基銨-雙(三氟磺醯基醯亞胺)、TBMA-TFSI表示三丁基甲基銨-雙(三氟磺醯基醯亞胺)、MTOA-TFSI表示甲基三辛基銨-雙(三氟磺醯基醯亞胺)。 EMP-TFSI stands for ethylmethylpyrrolidinium-bis(trifluorosulfonylcarboxylimide), TMPA-TFSI stands for trimethylpropylammonium-bis(trifluorosulfonylcarboxylic acid imide), TBMA-TFSI represents tributylmethylammonium-bis(trifluorosulfonylcarboxylimide), and MTOA-TFSI represents methyltricoctylammonium-bis(trifluorosulfonylcarbamateimide).
A:附黏著劑層之偏光薄膜 A: Polarizing film with adhesive layer
B:液晶單元(內置型液晶單元) B: Liquid crystal unit (built-in liquid crystal unit)
C:液晶面板(內置型液晶面板) C: LCD panel (built-in LCD panel)
1,11:第1、第2偏光薄膜 1,11: 1st and 2nd polarizing film
2,12:第1、第2黏著劑層 2,12: 1st and 2nd adhesive layer
3:錨固層 3: Anchor layer
4:表面處理層 4: Surface treatment layer
20:液晶層 20: Liquid crystal layer
41,42:第1、第2透明基板 41,42: 1st and 2nd transparent substrate
50,51:導通結構 50,51: conduction structure
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