JP2011006620A - Composition for hard coat - Google Patents
Composition for hard coat Download PDFInfo
- Publication number
- JP2011006620A JP2011006620A JP2009153125A JP2009153125A JP2011006620A JP 2011006620 A JP2011006620 A JP 2011006620A JP 2009153125 A JP2009153125 A JP 2009153125A JP 2009153125 A JP2009153125 A JP 2009153125A JP 2011006620 A JP2011006620 A JP 2011006620A
- Authority
- JP
- Japan
- Prior art keywords
- group
- elastic rubber
- meth
- general formula
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- -1 acryl group Chemical group 0.000 claims description 52
- 239000004033 plastic Substances 0.000 claims description 20
- 229920003023 plastic Polymers 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 125000003566 oxetanyl group Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 230000005855 radiation Effects 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 45
- 239000011248 coating agent Substances 0.000 description 28
- 239000010408 film Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002585 base Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 3
- OKRLWHAZMUFONP-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)ON1C(=O)CCC1=O OKRLWHAZMUFONP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012769 display material Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229960001597 nifedipine Drugs 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- PFHLXMMCWCWAMA-UHFFFAOYSA-N [4-(4-diphenylsulfoniophenyl)sulfanylphenyl]-diphenylsulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 PFHLXMMCWCWAMA-UHFFFAOYSA-N 0.000 description 2
- QFKJMDYQKVPGNM-UHFFFAOYSA-N [benzenesulfonyl(diazo)methyl]sulfonylbenzene Chemical compound C=1C=CC=CC=1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=CC=C1 QFKJMDYQKVPGNM-UHFFFAOYSA-N 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- HYIMSNHJOBLJNT-UHFFFAOYSA-N nifedipine Chemical compound COC(=O)C1=C(C)NC(C)=C(C(=O)OC)C1C1=CC=CC=C1[N+]([O-])=O HYIMSNHJOBLJNT-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000006410 propenylene group Chemical group 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 1
- KFJJYOKMAAQFHC-UHFFFAOYSA-N (4-methoxy-5,5-dimethylcyclohexa-1,3-dien-1-yl)-phenylmethanone Chemical compound C1C(C)(C)C(OC)=CC=C1C(=O)C1=CC=CC=C1 KFJJYOKMAAQFHC-UHFFFAOYSA-N 0.000 description 1
- 125000004814 1,1-dimethylethylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical class C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
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- 150000002923 oximes Chemical class 0.000 description 1
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- 150000004714 phosphonium salts Chemical class 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Silicon Polymers (AREA)
Abstract
Description
本発明は、活性エネルギー線照射により硬化し、プラスチック表面に優れた硬度を発現する硬化物を与える活性エネルギー線硬化性組成物に関する。さらに詳しくは、ディスプレイをはじめとする表示材料、電子機器、光学用レンズ等の表面ハードコート剤に関する。 The present invention relates to an active energy ray-curable composition that is cured by irradiation with active energy rays and gives a cured product that exhibits excellent hardness on a plastic surface. More specifically, the present invention relates to a surface hard coating agent for display materials including displays, electronic devices, optical lenses and the like.
従来よりプラスチックは軽量、機械特性に優れ、易加工性を有することから金属やガラスに替わる構造部材として使用されている。しかし金属やガラスに比べ表面硬度が劣る欠点がある。このため摩擦等によって表面がキズつきやすい。これを改良するためにプラスチック表面を処理（これをハードコート処理と呼んでいる）する方法が種々提案されている。 Conventionally, plastic has been used as a structural member to replace metal and glass because it is lightweight, excellent in mechanical properties, and easy to process. However, there is a drawback that the surface hardness is inferior compared to metals and glass. For this reason, the surface is easily scratched by friction or the like. In order to improve this, various methods for treating a plastic surface (this is called a hard coat treatment) have been proposed.
例えば硬化性組成物に、表面を修飾したシリカ粒子を配合したものが提案されている（例えば特許文献１）。 For example, what mix | blended the silica particle which modified the surface with the curable composition is proposed (for example, patent document 1).
また、特に硬度を高める手段としては、たとえばテトラアルコキシシランを使用してゾルーゲル法により、二酸化ケイ素薄膜を設ける方法がある。この方法では脆く、割れやすいという欠点をもつ。これを改良する方法としてポリエチレングリコールを添加し、脆弱性をなくす提案がなされている（例えば特許文献２）。 In particular, as a means for increasing the hardness, there is a method of providing a silicon dioxide thin film by a sol-gel method using, for example, tetraalkoxysilane. This method has the disadvantage of being brittle and easy to break. As a method for improving this, a proposal has been made to add polyethylene glycol to eliminate brittleness (for example, Patent Document 2).
しかし、ディスプレイなどの表示材料の用途においては、ポリエチレンテレフタレート（ＰＥＴ）、ポリカーボネート、三酢酸化セルロース（ＴＡＣ）などを基材とすることが多く、これらの柔軟なフィルム上で満足な硬度を達成するに至っていない ため、ハードコート層のさらなる高硬度化が求められている。
また、特許文献２で提案されている方法では、ある程度の表面硬度と柔軟性を達成するものの、その加工法において加熱を長時間行うことが基材に対して悪影響を及ぼすことがある。
そこで、本発明は軟質フィルム上にコーティングする場合においても十分な表面硬度を達成し、かつ透明性、密着性に優れた活性エネルギー線硬化性ハードコート剤を提供することを目的とする。
However, in display materials such as displays, polyethylene terephthalate (PET), polycarbonate, triacetated cellulose (TAC) and the like are often used as base materials, and satisfactory hardness is achieved on these flexible films. Therefore, further increase in hardness of the hard coat layer is required.
Moreover, although the method proposed in Patent Document 2 achieves a certain degree of surface hardness and flexibility, performing the heating for a long time in the processing method may adversely affect the substrate.
Therefore, an object of the present invention is to provide an active energy ray-curable hard coat agent that achieves sufficient surface hardness even when coated on a soft film, and is excellent in transparency and adhesion.
本発明者らは、上記の目的を達成するべく検討を行った結果、本発明に到達した。
すなわち、本発明は特定の化学構造式で表されるアルコキシシラン化合物（A）と平均粒子径が１μｍ以下の弾性ゴム粒子（B）と光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）を必須成分として含有することを特徴とする活性エネルギー線硬化性組成物；特定の化学構造式で表される少なくとも１個の（メタ）アクリル基を有するアルコキシシラン化合物（A２）、平均粒子径が１μｍ以下の弾性ゴム粒子（B）、光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）および光ラジカル重合開始剤（Ｄ）を含有することを特徴とする活性エネルギー線硬化性組成物；並びにこれらの活性エネルギー線硬化性組成物硬化させて得られるプラスチックハードコート用硬化物である。
The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention relates to an alkoxysilane compound (A) represented by a specific chemical structural formula, elastic rubber particles (B) having an average particle size of 1 μm or less, a photoacid generator (C1) or a photobase generator (C2). An active energy ray-curable composition characterized by comprising: an alkoxysilane compound (A2) having at least one (meth) acryl group represented by a specific chemical structural formula, having an average particle size of An active energy ray-curable composition comprising elastic rubber particles (B) of 1 μm or less, a photoacid generator (C1) or a photobase generator (C2), and a photoradical polymerization initiator (D); Moreover, it is a hardened | cured material for plastic hard coats obtained by hardening these active energy ray curable compositions.
本発明はプラスチック材料上にコーティングするハードコート剤であって、透明性に優れかつ非常に高硬度な層を形成させることができる。特に軟質フィルム上にコーティングする場合においても十分な表面硬度を達成し、かつ透明性、密着性に優れたハードコートフィルムを得ることができる。 The present invention is a hard coating agent for coating on a plastic material, and can form a layer having excellent transparency and extremely high hardness. In particular, even when coating on a soft film, it is possible to obtain a hard coat film that achieves sufficient surface hardness and is excellent in transparency and adhesion.
本願の第１発明の活性エネルギー線硬化性組成物は、下記一般式（１）で表されるアルコキシシラン化合物（Ａ）と、平均粒子径が１μｍ以下の弾性ゴム粒子（Ｂ）と、光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）を必須成分として含有し、活性エネルギー線照射により透明性に優れかつ非常に高硬度な塗膜を得ることができる。 The active energy ray-curable composition of the first invention of the present application comprises an alkoxysilane compound (A) represented by the following general formula (1), elastic rubber particles (B) having an average particle diameter of 1 μm or less, and a photoacid A generator (C1) or photobase generator (C2) is contained as an essential component, and a coating film having excellent transparency and extremely high hardness can be obtained by irradiation with active energy rays.
本発明におけるアルコキシシラン化合物（Ａ）としては、下記一般式（１）で表される。 The alkoxysilane compound (A) in the present invention is represented by the following general formula (1).
ＹnＳｉ（ＯＲ）4−n （１） Y n Si (OR) 4−n (1)
式（１）中、Ｙは下記一般式（２）で表される１価の基であり、Ｒはアルキル基またはフェニル基であり、ｎは０〜２の整数を表す。 In formula (1), Y is a monovalent group represented by the following general formula (2), R is an alkyl group or a phenyl group, and n is an integer of 0-2.
−X−Ｚ−Ｗ （２） -X-Z-W (2)
式（１）中のＲとしては、炭素数１〜８のアルキル基が挙げられ、例えばメチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基などの直鎖アルキル基、イソプロピル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基などの分岐アルキル基、シクロペンチル基、シクロヘキシル基などの環状アルキル基が挙げられる。
好ましいのは炭素数１〜４であり、反応性の観点からより好ましいのはメチル基、エチル基である。
Examples of R in the formula (1) include an alkyl group having 1 to 8 carbon atoms. For example, a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, an isopropyl group, sec- Examples thereof include branched alkyl groups such as butyl group and tert-butyl group, and cyclic alkyl groups such as cyclopentyl group and cyclohexyl group.
Preferred are those having 1 to 4 carbon atoms, and more preferred are methyl group and ethyl group from the viewpoint of reactivity.
Ｙを表す式（２）中、Xは炭素数１〜８のアルキレン基またはアルケニレン基であり、Zは酸素原子、硫黄原子または下記一般式（３）で表されるオルガノポリシロキサンを有する２価の有機基であり、Ｗは水素原子またはビニル基、アリル基、（メタ）アクリロイル基、エポキシ基、オキセタニル基を表す。 In the formula (2) representing Y, X is an alkylene group or alkenylene group having 1 to 8 carbon atoms, and Z is a divalent having an oxygen atom, a sulfur atom or an organopolysiloxane represented by the following general formula (3) W represents a hydrogen atom, a vinyl group, an allyl group, a (meth) acryloyl group, an epoxy group, or an oxetanyl group.
式（３）中、Ｑはそれぞれ独立に炭素数１〜４のアルコキシ基、フェノキシ基、炭素数１〜４のアルキル基またはフェニル基であり、ｍは１〜５０の整数を表す。 In formula (3), Q is each independently an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and m represents an integer of 1 to 50.
式（２）中におけるXについて、アルキレン基としては、炭素数１〜８のものが挙げられ、例えばメチレン基、エチレン基、プロピレン基、ブチレン基などの直鎖アルキル基、エチリデン基、１−メチルエチレン基、１−メチルプロピレン基、１，１−ジメチルエチレン基、１，２−ジメチルエチレン基などの分岐アルキル基、１，３−シクロペンチレン基、１，４−シクロヘキシレン基、シクロヘキシリデン基などの環状アルキル基が挙げられる。
好ましいのは炭素数１〜４であり、より好ましいのはメチレン基、エチレン基である。
As for X in the formula (2), examples of the alkylene group include those having 1 to 8 carbon atoms, such as linear alkyl groups such as methylene group, ethylene group, propylene group, butylene group, ethylidene group, 1-methyl. Branched alkyl groups such as ethylene group, 1-methylpropylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, cyclohexylidene And cyclic alkyl groups such as a group.
Preferred are those having 1 to 4 carbon atoms, and more preferred are a methylene group and an ethylene group.
式（２）中におけるXについて、アルケニレン基としては炭素数２〜８のものが挙げられ、ビニレン基、プロペニレン基、１−ブテニレン基、２−ブテニレン基などが挙げられる。好ましいのは炭素数１〜４、より好ましいのは炭素数２〜３のビニレン基、プロペニレン基である。 Regarding X in the formula (2), examples of the alkenylene group include those having 2 to 8 carbon atoms, such as vinylene group, propenylene group, 1-butenylene group, and 2-butenylene group. A vinylene group or propenylene group having 1 to 4 carbon atoms and more preferably 2 to 3 carbon atoms is more preferable.
式（２）中においてＺとしては、酸素原子、硫黄原子あるいは上記一般式（３）で表されるオルガノポリシロキサンを有する２価の有機基が挙げられる。 In formula (2), examples of Z include an oxygen atom, a sulfur atom, or a divalent organic group having an organopolysiloxane represented by the above general formula (3).
式（２）中においてＷは、水素原子またはビニル基、アリル基、（メタ）アクロイル基、エポキシ基、オキセタニル基を表し、エポキシ基、オキセタニル基はその一部が置換されていてもよい。 In formula (2), W represents a hydrogen atom, a vinyl group, an allyl group, a (meth) acryloyl group, an epoxy group, or an oxetanyl group, and the epoxy group and the oxetanyl group may be partially substituted.
式（３）中における置換基Ｑの炭素数１〜４のアルコキシ基としては、メトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基が挙げられる。
反応性の観点から好ましくはメトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、さらに好ましくはメトキシ基、エトキシ基である。
Examples of the alkoxy group having 1 to 4 carbon atoms of the substituent Q in the formula (3) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. Is mentioned.
From the viewpoint of reactivity, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.
式（３）中における置換基Ｑの炭素数１〜４のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。好ましいのはメチル基、エチル基である。 Examples of the alkyl group having 1 to 4 carbon atoms of the substituent Q in the formula (3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned. A methyl group and an ethyl group are preferable.
式（３）中におけるｍは、置換基Ｑを有するシロキサンを構造単位とする個数のことであり、１〜５０の整数を表す。好ましくは１〜４０であり、特に好ましくは５〜３０である。５０を超えると塗膜の硬度が低下する。 M in Formula (3) is the number of siloxanes having the substituent Q as structural units, and represents an integer of 1 to 50. Preferably it is 1-40, Most preferably, it is 5-30. If it exceeds 50, the hardness of the coating film decreases.
本発明における弾性ゴム粒子（Ｂ）としては、弾性を有していれば特にその化学組成は限定されず、市販のものを適宜使用することができる。
例えばローム＆ハース社製のパラロイドＫＣＡ８０１、ＢＴＡ７３１Ｊ、ＢＴＡ７０５等；カネカ社製のカネエースＢ−１１Ａ、Ｂ−２２、Ｂ−５６１等が挙げられる。
The elastic rubber particles (B) in the present invention are not particularly limited in chemical composition as long as they have elasticity, and commercially available ones can be used as appropriate.
Examples include Paraloid KCA801, BTA731J, and BTA705 manufactured by Rohm &Haas; Kaneace B-11A, B-22, and B-561 manufactured by Kaneka.
本発明における弾性ゴム粒子（Ｂ）のガラス転移点は、十分な可とう性を得るための観点から、通常が５０℃以下、好ましくは３０℃以下である。 The glass transition point of the elastic rubber particles (B) in the present invention is usually 50 ° C. or less, preferably 30 ° C. or less, from the viewpoint of obtaining sufficient flexibility.
本発明における弾性ゴム粒子（Ｂ）の平均粒径は１μ以下であることが必要である。１μｍを超えると透明性が悪化する。特に好ましくは０．５μｍ以下である。 The average particle size of the elastic rubber particles (B) in the present invention needs to be 1 μm or less. If it exceeds 1 μm, the transparency deteriorates. Particularly preferably, it is 0.5 μm or less.
本発明におけるアルコキシシラン化合物（Ａ）と弾性ゴム粒子（Ｂ）ＳＰ値の差が、通常２．０以内であることが好ましい。さらに好ましくは１．９以内、特に好ましくは１．８以内である。ＳＰ値の差が、２．０を超えると、弾性ゴム粒子が塗膜中で相分離してしまい、透明性が悪化する。
ここでＳＰ値とは、溶解度パラメーターを表し、その値はＦｅｄｏｒｓらが提案した下記文献に記載の方法によって計算されるものである。
「ＰＯＬＹＭＥＲ ＥＮＧＩＮＥＥＲＩＮＧ ＡＮＤ ＳＣＩＥＮＣＥ，ＦＥＢＲＵＡＲＹ，１９７４，Ｖｏｌ．１４，Ｎｏ．２，ＲＯＢＥＲＴ Ｆ．ＦＥＤＯＲＳ．（１４７〜１５４頁）」
The difference between the alkoxysilane compound (A) and the elastic rubber particles (B) SP value in the present invention is usually preferably within 2.0. More preferably, it is within 1.9, and particularly preferably within 1.8. If the difference in SP value exceeds 2.0, the elastic rubber particles are phase-separated in the coating film, and transparency is deteriorated.
Here, the SP value represents a solubility parameter, and the value is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"
本発明におけるアルコキシシラン化合物（Ａ）と弾性ゴム粒子（Ｂ）との重量比（Ａ）／（Ｂ）は、通常９９／１〜８０／２０、好ましくは９５／５〜８０／２０である。弾性ゴム粒子（Ｂ）が多くなると塗膜の硬度が低下してしまう。 The weight ratio (A) / (B) between the alkoxysilane compound (A) and the elastic rubber particles (B) in the present invention is usually 99/1 to 80/20, preferably 95/5 to 80/20. When the elastic rubber particles (B) increase, the hardness of the coating film decreases.
本発明における弾性ゴム粒子（Ｂ）は樹脂溶液へ添加してもよいし、予め溶剤で分散させておいたものを樹脂溶液へ添加してもよい。均一分散性の観点から、予め溶剤で分散させておいたものを樹脂溶液へ添加が好ましい。 The elastic rubber particles (B) in the present invention may be added to the resin solution, or those previously dispersed with a solvent may be added to the resin solution. From the viewpoint of uniform dispersibility, it is preferable to add to the resin solution what has been previously dispersed with a solvent.
本発明において、光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）が必須成分である。これらは、活性エネルギー線照射により酸または塩基を発生し、硬化反応を促進する。 In the present invention, the photoacid generator (C1) or the photobase generator (C2) is an essential component. These generate acids or bases by irradiation with active energy rays, and accelerate the curing reaction.
本発明における光酸発生剤（Ｃ１）は、活性エネルギー線照射により酸を発生する化合物であり、硬化反応を促進するために添加されるものである。
（Ｃ１）としては、下記の（ｉ）スルホン化合物、（ｉｉ）スルホン酸エステル化合物、（ｉｉｉ）スルホンイミド化合物、（ｉｖ）ジスルホニルジアゾメタン、（ｖ）オニウム塩等が挙げられる。
（ｉ）スルホン化合物
フェナシルフェニルスルホン、４−トリスフェナシルスルホン−ケトスルホン、β−スルホニルスルホンおよびこれらのα−ジアゾ化合物等
The photoacid generator (C1) in the present invention is a compound that generates an acid upon irradiation with active energy rays, and is added to accelerate the curing reaction.
Examples of (C1) include the following (i) sulfone compounds, (ii) sulfonic acid ester compounds, (iii) sulfonimide compounds, (iv) disulfonyldiazomethane, and (v) onium salts.
(I) Sulfone compounds Phenacylphenylsulfone, 4-trisphenacylsulfone-ketosulfone, β-sulfonylsulfone, α-diazo compounds thereof and the like
（ｉｉ）スルホン酸エステル化合物
ベンゾイントシラート、ピロガロールトリストリフルオロメタンスルホナート、ピロガロールメタンスルホン酸トリエステル、α−メチロールベンゾイントシラートおよびα−メチロールベンゾインドデシルスルホナート等
(Ii) Sulfonic acid ester compounds Benzoin tosylate, pyrogallol tris trifluoromethanesulfonate, pyrogallol methanesulfonic acid triester, α-methylol benzoin tosylate, α-methylol benzoindodecyl sulfonate, etc.
（ｉｉｉ）スルホンイミド化合物
Ｎ−（トリフルオロメチルスルホニルオキシ）スクシンイミド、Ｎ−（ｐ−トルエンスルホニルオキシ）ビシクロ[２．２．１]ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（パーフルオロオクタンスルホニルオキシ）ナフチルイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）スクシンイミド、Ｎ−（ベンゼンスルホニルオキシ）ビシクロ[２．２．１]ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（ベンゼンスルホニルオキシ）ビシクロ[２．２．１]ヘプタン−５，６−オキシ−２，３−ジカルボキシイミドおよびＮ−（ベンゼンスルホニルオキシ）ナフチルイミド等
(Iii) Sulfonimide compound N- (trifluoromethylsulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorooctanesulfonyloxy) naphthylimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (benzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (benzenesulfonyloxy) naphthylimide and the like
（ｉｖ）ジスルホニルジアゾメタン
ビス（トリフルオロメチルスルホニル）ジアゾメタン、ビス（フェニルスルホニル）ジアゾメタン、ビス（ｐ−トルエンスルホニル）ジアゾメタン、ビス（２，４−ジメチルベンゼンスルホニル）ジアゾメタン、ビス（１−メチルエチルスルホニル）ジアゾメタンおよびビス（１，４−ジオキサスピロ[４．５]デカン−７−スルホニル）ジアゾメタン等
(Iv) Disulfonyldiazomethane Bis (trifluoromethylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, bis (1-methylethylsulfonyl) ) Diazomethane and bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane, etc.
（ｖ）オニウム塩
スルホニウム塩：トリフェニルスルホニウムヘキサフルオロホスファート、４−（フェニルチオ）フェニルジフェニルスルホニウムヘキサフルオロホスファート、ビス〔４−（ジフェニルスルホニオ）フェニル〕スルフィドビスヘキサフルオロアンチモナート等
ヨードニウム塩：ジフェニルヨードニウムヘキサフルオロホスファート、４−（イソブチル）フェニルフェニルヨードニウムトリフルオロメタンスルホナート、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムビストリフルオロメタンスルホニルイミド等
ホスホニウム塩：エチルトリフェニルホスソニウムテトラフェニルボレート等
ジアゾニウム塩：フェニルジアゾニウムヘキサフルオロホスファート等
アンモニウム塩：１−ベンジル−２−シアノピリジニウムヘキサフルオロホスファート等
(V) Onium salt Sulfonium salt: Triphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, etc. Iodonium salt: Diphenyliodonium hexafluorophosphate, 4- (isobutyl) phenylphenyliodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium bistrifluoromethanesulfonylimide, etc. Phosphonium salt: Ethyltriphenylphossonium tetraphenylborate, etc. Diazonium Salt: Phenyldiazonium hexafluorophosphate, etc. Ammonium salt: 1-benzyl-2-cyanopyridy Umm hexafluorophosphate, etc.
（Ｃ１）のうち好ましいのはオニウム塩、スルホンイミド化合物、ジスルホニルジアゾメタンであり、さらに好ましくは、４−（フェニルチオ）フェニルジフェニルスルホニウムヘキサフルオロホスファート、ビス〔４−（ジフェニルスルホニオ）フェニル〕スルフィドビスヘキサフルオロアンチモナート、Ｎ−（トリフルオロメチルスルホニルオキシ）スクシンイミド、ビス（フェニルスルホニル）ジアゾメタンである。 Of (C1), preferred are onium salts, sulfonimide compounds, and disulfonyldiazomethane, and more preferred are 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide. Bishexafluoroantimonate, N- (trifluoromethylsulfonyloxy) succinimide, and bis (phenylsulfonyl) diazomethane.
本発明における光塩基発生剤（Ｃ２）は、活性エネルギー線照射により塩基を発生する化合物であり、硬化反応を促進するために添加されるものである。
（Ｃ２）としては、下記の（ｉ）ニフェジピン化合物、（ｉｉ）オキシム化合物、（ｉｉｉ）カルバメート化合物、（ｉｖ）金属錯体、（ｖ）オニウム塩等が挙げられる。
（ｉ）ニフェジピン化合物
３，５−ジカルボン酸ジメチル−２，６−ジメチル−４−（２−ニトロフェニル）−１，４−ジヒドロピリジン、Ｎ−メチル−３，５−ジカルボン酸ジメチル−２，６−ジメチル−４−（２−ニトロフェニル）−１，４−ジヒドロピリジン等
The photobase generator (C2) in the present invention is a compound that generates a base by irradiation with active energy rays, and is added to accelerate the curing reaction.
Examples of (C2) include the following (i) nifedipine compound, (ii) oxime compound, (iii) carbamate compound, (iv) metal complex, (v) onium salt and the like.
(I) Nifedipine compound Dimethyl-2,6-dimethyl-4- (2-nitrophenyl) -1,4-dihydropyridine 3,5-dicarboxylate, dimethyl-2,6-dicarboxylate N-methyl-3,5-dicarboxylate Dimethyl-4- (2-nitrophenyl) -1,4-dihydropyridine, etc.
（ｉｉ）オキシム化合物
２−アセトナフトン＝Ｏ−フェニルアセチルオキシム、アセトフェノン＝Ｏ−フェニルアセチルオキシム、２−アセトナフトン＝Ｏ−シクロヘキシルカルバモイルオキシム、アセトフェノン＝Ｏ−フェニルカルバモイルオキシム等
(Ii) Oxime compounds 2-acetonaphthone = O-phenylacetyloxime, acetophenone = O-phenylacetyloxime, 2-acetonaphthone = O-cyclohexylcarbamoyloxime, acetophenone = O-phenylcarbamoyloxime, etc.
（ｉｉｉ）カルバメート化合物
２−ニトロベンジル−Ｎ−シクロヘキシルカルバメート、４，５−ジメトキシ−２−ニトロベンジル−Ｎ−シクロヘキシルカルバメート等
(Iii) Carbamate compounds 2-nitrobenzyl-N-cyclohexyl carbamate, 4,5-dimethoxy-2-nitrobenzyl-N-cyclohexyl carbamate, etc.
（ｉｖ）金属錯体
ヘキサアンミンコバルト（ＩＩＩ）テトラフェニルボレート塩、カリウムテトラキスチオシアナートビスアンミンクロメート（ＩＩＩ）、ビスアセチルアセトナート白金（ＩＩ）等
(Iv) Metal complex Hexamminecobalt (III) tetraphenylborate salt, potassium tetrakisthiocyanate bisamminechromate (III), bisacetylacetonate platinum (II), etc.
（ｖ）オニウム塩等
２−（トリブチルアンモニオメチルカルボニル）ナフタレントリフェニルブチルボラート、トリフェニルベンズヒドリルアンモニウムヨーダイド、１−フェナシル−１，４−ジアザビシクロ[２．２．２]オクタニウムジメチルジチオカルバマート、１−（４−ベンゾイルフェニルメチル）１，８−ジアザビシクロ［５．４．０］−７−ウンデニウムテトラフェニルボレート、８−（９−オキソ−９Ｈ−チオキサンテン−２−イル）メチル−１，８−ジアザビシクロ〔５．４．０〕−７−ウンデセニウムテトラフェニルボレート等
(V) Onium salt 2- (tributylammoniomethylcarbonyl) naphthalene triphenylbutyl borate, triphenylbenzhydrylammonium iodide, 1-phenacyl-1,4-diazabicyclo [2.2.2] octanium dimethyl Dithiocarbamate, 1- (4-benzoylphenylmethyl) 1,8-diazabicyclo [5.4.0] -7-undenium tetraphenylborate, 8- (9-oxo-9H-thioxanthen-2-yl) Methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate, etc.
（Ｃ２）のうち好ましいのはニフェジピン化合物、オキシム化合物、カルバメート化合物、オニウム塩であり、さらに好ましくは、オキシム化合物、カルバメート化合物、オニウム塩である。 Among (C2), a nifedipine compound, an oxime compound, a carbamate compound, and an onium salt are preferable, and an oxime compound, a carbamate compound, and an onium salt are more preferable.
光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）の含有量は、アルコキシシラン化合物（Ａ）に対して、通常０．１〜２０重量％、好ましくは１．０〜１０重量％である。２０重量％を超えると塗膜の硬度が悪化する。 The content of the photoacid generator (C1) or photobase generator (C2) is usually 0.1 to 20% by weight, preferably 1.0 to 10% by weight, based on the alkoxysilane compound (A). . If it exceeds 20% by weight, the hardness of the coating film deteriorates.
本発明の活性エネルギー線硬化性組成物は、必要により多官能（メタ）アクリレートモノマー（Ｆ）を含有していてもよい。 The active energy ray-curable composition of the present invention may contain a polyfunctional (meth) acrylate monomer (F) as necessary.
多官能（メタ）アクリレートモノマー（Ｆ）としては、公知の多官能（メタ）アクリレートモノマーであれば特に限定されずに用いられ、２官能（メタ）アクリレート（Ｆ１１）、３官能（メタ）アクリレート（Ｆ１２）、４〜６官能（メタ）アクリレート（Ｆ１３）が挙げられる。 The polyfunctional (meth) acrylate monomer (F) is not particularly limited as long as it is a known polyfunctional (meth) acrylate monomer, and is used as a bifunctional (meth) acrylate (F11), trifunctional (meth) acrylate ( F12), a 4-6 functional (meth) acrylate (F13) is mentioned.
２官能（メタ）アクリレート（Ｆ１１）としては、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレンジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、１，１０−デカンジオールジ（メタ）アクリレート、３−メチル−１，５−ペンタンジオールジ（メタ）アクリレート、２−ブチル−２−エチル１，３−プロパンジオールジ（メタ）アクリレート、ジメチロールトリシクロデカンジ（メタ）アクリレート、ビスフェノールＡのエチレンオキサイド付加物のジ（メタ）アクリレート、ビスフェノールＡのプロピレンオキサイド付加物のジ（メタ）アクリレート、ヒドロキシピバレン酸ネオペンチルグリコールジ（メタ）アクリレート等が例示される。 As the bifunctional (meth) acrylate (F11), ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, polypropylene di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl 1,3- The Pandiol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, di (meth) acrylate of bisphenol A ethylene oxide adduct, di (meth) acrylate of propylene oxide adduct of bisphenol A, hydroxypivalate neo Examples include pentyl glycol di (meth) acrylate.
３官能（メタ）アクリレート（Ｆ１２）としては、グリセリントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパンのエチレンオキサイド付加物のトリ（メタ）アクリレート等が例示される。 Trifunctional (meth) acrylate (F12) includes glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tri (meth) acrylate of trimethylolpropane ethylene oxide adduct. Etc. are exemplified.
４〜６官能（メタ）アクリレート（Ｆ１３）としては、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が例示される。 Examples of the 4- to 6-functional (meth) acrylate (F13) include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
多官能（メタ）アクリレートモノマー（Ｆ）のうち好ましいのは（Ｆ１２）及び（Ｆ１３）であり、さらに好ましくはジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートおよびこれらの併用である。市場から容易に入手できる（Ｆ）としては、例えばアロニックスＭ−４０３（東亜合成（株）製）、ライトアクリレートＰＥ−３Ａ（共栄社化学（株）製）、ネオマーＤＡ−６００（三洋化成（株）製）等が挙げられる。 Of the polyfunctional (meth) acrylate monomers (F), (F12) and (F13) are preferable, and dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and combinations thereof are more preferable. is there. Examples of (F) that can be easily obtained from the market include Aronix M-403 (manufactured by Toa Gosei Co., Ltd.), Light Acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), Neomer DA-600 (Sanyo Kasei Co., Ltd.) Manufactured) and the like.
多官能（メタ）アクリレートモノマー（Ｆ）の含有量は、アルコキシシラン化合物（Ａ）と多官能（メタ）アクリレートモノマー（Ｆ）との重量比（Ａ）／（Ｆ）として９５／５〜４０／６０である。多官能（メタ）アクリレートモノマー（Ｆ）が多くなると十分な塗膜硬度を得ることができない。 The content of the polyfunctional (meth) acrylate monomer (F) is 95/5 to 40 / as a weight ratio (A) / (F) between the alkoxysilane compound (A) and the polyfunctional (meth) acrylate monomer (F). 60. When the polyfunctional (meth) acrylate monomer (F) is increased, sufficient film hardness cannot be obtained.
本発明の活性エネルギー線硬化性組成物は、必要によりさらにその他成分（Ｇ）を含有していてもよい。（Ｇ）としては、増感剤（Ｇ１）、重合禁止剤（Ｇ２）、溶剤（Ｇ３）およびその他添加剤（例えばシランカップリング剤、レベリング剤等）が挙げられる。 The active energy ray-curable composition of the present invention may further contain other component (G) as necessary. Examples of (G) include a sensitizer (G1), a polymerization inhibitor (G2), a solvent (G3), and other additives (for example, a silane coupling agent and a leveling agent).
増感剤（Ｇ１）としては、カルボニル化合物（例えば、アントラキノン、１，２−ナフトキノン、１，４−ナフトキノン、ベンズアントロン、４、４‘−テトラメチルジアミノベンゾフェノン、クロラニル等）、ニトロ化合物（例えば、ニトロベンゼン、ｐ−ジニトロベンゼン、２−ニトロフルオレン等）、芳香族炭化水素（例えば、アントラセン、クリセン、ピレン等）、複素環化合物（例えば、キサントン、チオキサントン、キナゾリン等）が挙げられる。 Examples of the sensitizer (G1) include carbonyl compounds (eg, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, 4,4′-tetramethyldiaminobenzophenone, chloranil, etc.), nitro compounds (eg, Nitrobenzene, p-dinitrobenzene, 2-nitrofluorene, etc.), aromatic hydrocarbons (eg, anthracene, chrysene, pyrene), and heterocyclic compounds (eg, xanthone, thioxanthone, quinazoline, etc.).
増感剤（Ｇ１）の含有量は、光酸発生剤（Ｃ１）及び光塩基発生剤（Ｃ２）の重量に対し通常０．１〜１００％、好ましくは０．５〜８０％、特に好ましくは１〜７０％である。 The content of the sensitizer (G1) is usually 0.1 to 100%, preferably 0.5 to 80%, particularly preferably based on the weight of the photoacid generator (C1) and the photobase generator (C2). 1 to 70%.
重合禁止剤（Ｇ２）としては、特に限定はなく公知のものが用いられる。具体的には、ジフェニルヒドラジル、トリ−ｐ−ニトロフェニルメチル、Ｎ−（３−Ｎ−オキシアニリノ１，３−ジメチルブチリデン）アニリンオキシド、ｐ−ベンゾキノンｐ−ｔｅｒｔ−ブチルカテコール、ニトロベンゼン、ピクリン酸、ジチオベンゾイルジスルフィド及び塩化銅（ＩＩ）等が挙げられる。 As a polymerization inhibitor (G2), there is no limitation and a well-known thing is used. Specifically, diphenylhydrazyl, tri-p-nitrophenylmethyl, N- (3-N-oxyanilino 1,3-dimethylbutylidene) aniline oxide, p-benzoquinone p-tert-butylcatechol, nitrobenzene, picric acid , Dithiobenzoyl disulfide, and copper (II) chloride.
重合禁止剤（Ｇ２）の含有量は、組成物中０．００５〜１．０％が好ましく、さらに好ましくは０．０１〜０．５％、特に好ましくは０．０２〜０．１％である。 The content of the polymerization inhibitor (G2) is preferably 0.005 to 1.0% in the composition, more preferably 0.01 to 0.5%, and particularly preferably 0.02 to 0.1%. .
溶剤（Ｇ３）は、塗工の際、塗工に適した粘度に調整するために用いることができる。溶剤の使用量としては組成物の重量に対し通常２０００％以下、好ましくは１０〜５００％である。 The solvent (G3) can be used for adjusting the viscosity suitable for coating during coating. The amount of the solvent used is usually 2000% or less, preferably 10 to 500%, based on the weight of the composition.
溶剤（Ｇ３）としては、本発明の樹脂成分を溶解するものであれば特に限定されない。具体的には、脂肪族および芳香族炭化水素（例えばヘキサン、シクロヘキサン、トルエン、キシレン、エチルベンゼン等）、エステル（酢酸エチル、酢酸ブチル、メトキシブチルアセテート、γ−ブチロラクトン等）、エーテル（ジエチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、プロピレングリコールジメチルエーテル等）、ケトン（アセトン、メチルエチルケトン、ジｎ−ブチルケトン、メチルプロピルケトン、メチルイソブチルケトン、シクロヘキサノン等）、アルコール（メタノー、エタノール、イソプロパノール、ｔｅｒｔ−ブチルアルコール、２−エチルヘキサノール、ベンジルアルコール、エチレングリコール等）、アミド（ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等）、スルホキシド（ジメチルスルホキシド等）、水、これらの２種以上の混合溶剤が挙げられる。 The solvent (G3) is not particularly limited as long as it dissolves the resin component of the present invention. Specifically, aliphatic and aromatic hydrocarbons (eg hexane, cyclohexane, toluene, xylene, ethylbenzene, etc.), esters (ethyl acetate, butyl acetate, methoxybutyl acetate, γ-butyrolactone, etc.), ethers (diethyl ether, tetrahydrofuran) , Ethylene glycol monomethyl ether, propylene glycol dimethyl ether, etc.), ketones (acetone, methyl ethyl ketone, di-n-butyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), alcohols (methanol, ethanol, isopropanol, tert-butyl alcohol, 2- Ethyl hexanol, benzyl alcohol, ethylene glycol, etc.), amide (dimethylformamide, dimethylacetamide, N-methylpyrrole) Emissions, etc.), sulfoxides (dimethyl sulfoxide, etc.), water, these mixed solvent of two or more thereof.
本発明における活性エネルギー線には、紫外線、電子線、Ｘ線、赤外線および可視光線が含まれる。これらの活性エネルギー線のうち硬化性と樹脂劣化の観点から好ましいのは紫外線である。 The active energy rays in the present invention include ultraviolet rays, electron beams, X-rays, infrared rays and visible rays. Among these active energy rays, ultraviolet rays are preferable from the viewpoints of curability and resin deterioration.
本発明の活性エネルギー線硬化性樹脂組成物を紫外線照射で硬化させる場合は、種々の紫外線照射装置（例えば「ＣＶ−１１０Ｑ−Ｇ」；フュージョンＵＶシステムズ製）、光源としてはキセノンランプ、高圧水銀灯、メタルハライドランプ等を使用することができる。紫外線照射量は通常１０〜１０，０００ｍＪ／ｃｍ２、好ましくは１００〜５，０００ｍＪ／ｃｍ２である。 When the active energy ray-curable resin composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses (for example, “CV-110Q-G”; manufactured by Fusion UV Systems), as a light source, a xenon lamp, a high-pressure mercury lamp, A metal halide lamp or the like can be used. UV irradiation dose is usually 10~10,000mJ / cm 2, preferably 100~5,000mJ / cm 2.
次に本願の第２発明について説明する。
本願の第２発明の活性エネルギー線硬化性組成物は、少なくとも１個の（メタ）アクリル基を有するアルコキシシラン化合物（Ａ２）と弾性ゴム粒子（Ｂ）と光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）、およびラジカル重合開始剤（Ｄ）を含有し、活性エネルギー線照射により第１の発明と同様、透明性に優れかつ非常に高硬度なコーティング膜を得ることができる。
Next, the second invention of the present application will be described.
The active energy ray-curable composition of the second invention of the present application comprises an alkoxysilane compound (A2) having at least one (meth) acryl group, elastic rubber particles (B), a photoacid generator (C1) or a photobase. A coating film containing the generator (C2) and the radical polymerization initiator (D) and having excellent transparency and extremely high hardness can be obtained by irradiation with active energy rays as in the first invention.
少なくとも１個の（メタ）アクリル基を有するアルコキシシラン化合物（A２）としては、第１の発明中のアルコキシシラン化合物（Ａ）で説明したとおりである。 The alkoxysilane compound (A2) having at least one (meth) acryl group is as described for the alkoxysilane compound (A) in the first invention.
この少なくとも１個の（メタ）アクリル基を有するアルコキシシラン化合物（A２）は下記一般式（４）で表される。 The alkoxysilane compound (A2) having at least one (meth) acryl group is represented by the following general formula (4).
ＹnＳｉ（ＯＲ）4−n （４）
［式（４）中、Ｙは下記一般式（５）で表され、Ｒはアルキル基またはフェニル基を表し、ｎは１または２の整数を表す。］
−X−Z−Ｗ’ （５）
［上式（５）中、Xは炭素数１〜８のアルキル基またはアルケニル基を表す。Zは酸素原子、硫黄原子または下記一般式（３）で表されるオルガノポリシロキサンを有する２価の有機基を表す。Ｗ’は（メタ）アクリロイル基を表す。］
Y n Si (OR) 4−n (4)
[In formula (4), Y is represented by the following general formula (5), R represents an alkyl group or a phenyl group, and n represents an integer of 1 or 2. ]
-X-Z-W '(5)
[In the above formula (5), X represents an alkyl or alkenyl group having 1 to 8 carbon atoms. Z represents an oxygen atom, a sulfur atom or a divalent organic group having an organopolysiloxane represented by the following general formula (3). W ′ represents a (meth) acryloyl group. ]
［上式（３）中、Ｑはそれぞれ独立に炭素数１〜４のアルコキシ基、フェノキシ基、炭素数１〜４のアルキル基またはフェニル基を表し、ｍは１〜５０の整数を表す。］ [In said Formula (3), Q represents a C1-C4 alkoxy group, a phenoxy group, a C1-C4 alkyl group, or a phenyl group each independently, and m represents the integer of 1-50. ]
なお、この第２の発明のアルコキシシラン化合物（Ａ２）を表す一般式（４）において、式（４）中のＹとＲは、第１発明の一般式（１）で説明したＹとＲと同様のものである。
さらに、一般式（５）中のＸとＺは、第１発明の一般式（１）で説明したＸとＺと同様のものである。
In the general formula (4) representing the alkoxysilane compound (A2) of the second invention, Y and R in the formula (4) are the same as Y and R described in the general formula (1) of the first invention. It is the same thing.
Furthermore, X and Z in the general formula (5) are the same as X and Z described in the general formula (1) of the first invention.
一般式（５）のＷ’は、第１発明の一般式（２）のＷと相違し、（メタ）アクリロイル基である。
従って、少なくとも１個の（メタ）アクリル基を有するアルコキシシラン化合物（A２）は、第１の発明中のアルコキシシラン化合物（Ａ）のうちの特定のものである。
W ′ in the general formula (5) is different from W in the general formula (2) of the first invention and is a (meth) acryloyl group.
Therefore, the alkoxysilane compound (A2) having at least one (meth) acryl group is a specific one of the alkoxysilane compounds (A) in the first invention.
本発明におけるアルコキシシラン化合物（Ａ２）と弾性ゴム粒子（Ｂ）ＳＰ値の差は、通常２．０以内であることが好ましい。さらに好ましくは１．９以内、特に好ましくは１．８以内である。ＳＰ値の差が、２．０を超えると、弾性ゴム粒子が塗膜中で相分離してしまい、透明性が悪化する。 The difference between the alkoxysilane compound (A2) and the elastic rubber particles (B) SP value in the present invention is usually preferably within 2.0. More preferably, it is within 1.9, and particularly preferably within 1.8. If the difference in SP value exceeds 2.0, the elastic rubber particles are phase-separated in the coating film, and transparency is deteriorated.
本発明におけるアルコキシシラン化合物（Ａ２）と弾性ゴム粒子（Ｂ）との重量比（Ａ２）／（Ｂ）は、通常９９／１〜８０／２０、好ましくは９５／５〜８０／２０である。弾性ゴム粒子（Ｂ）が多くなると塗膜の硬度が低下してしまう。 The weight ratio (A2) / (B) between the alkoxysilane compound (A2) and the elastic rubber particles (B) in the present invention is usually 99/1 to 80/20, preferably 95/5 to 80/20. When the elastic rubber particles (B) increase, the hardness of the coating film decreases.
本願の第２発明で必須成分の光ラジカル重合開始剤（Ｄ）としては、例えばベンジルメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンゾフェノン、メチルベンゾイルフォルメート、４，４−ビス（ジメチルアミノ）ベンゾフェノン、３，３−ジメチル−４−メトキシ−ベンゾフェノン、アントラキノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシアセトフェノン、２−ヒドロキシ−２−メチルプロピオフェノン、４−イソプロピル−２−ヒドロキシ−２−メチルプロピオフェノン、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノ−１−プロパノン、２−クロロチオキサントン、ジエチルチオキサントン、イソプロピルチオキサントン、ベンジル−２，４，６−（トリハロメチル）トリアジン、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾリル二量体、９−フェニルアクリジン、１，７−ビス（９−アクリジニル）ヘプタン、１，５−ビス（９−アクリジニル）ペンタン、１，３−ビス（９−アクリジニル）プロパン、トリメチルベンゾイルジフェニルホスフィンオキシド、トリブロモメチルフェニルスルホン及び２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オン等が挙げられる。（Ｄ）は１種で用いても良いし、２種以上用いても良い。 As the radical photopolymerization initiator (D) as an essential component in the second invention of the present application, for example, benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone Methylbenzoylformate, 4,4-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropi Phenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, benzyl -2,4,6- (trihalomethyl) triazine, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1, 5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone and 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butane-1-o Etc. The. (D) may be used alone or in combination of two or more.
光ラジカル重合開始剤（Ｄ）は、市販のものが容易に入手可能であり、例えば２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノ−１−プロパノンとしては「イルガ９０７」、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オンとしては「イルガ３６９」（以上チバ・ジャパン製）等が挙げられる。 As the radical photopolymerization initiator (D), a commercially available product can be easily obtained. For example, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone is “IRGA 907”, 2 Examples of -benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one include “Irga 369” (manufactured by Ciba Japan).
本発明の活性エネルギー線硬化性組成物は、以下の３つの活性エネルギー線硬化性組成に分類される。
（１）第３発明
第１発明のアルコキシシラン化合物（A）と平均粒子径が１μｍ以下の弾性ゴム粒子（B）を、酸（Ｅ１）または塩基（Ｅ２）の存在下で、加水分解と縮合反応により硬化させて得られるプラスチックハードコート用硬化物
（２）第４発明
光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）を含む第１発明の活性エネルギー線硬化性組成物を、活性エネルギー線を照射して硬化させて得られるプラスチックハードコート用硬化物
（３）第５発明
光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）、およびラジカル重合開始剤（Ｄ）を含む第２発明の活性エネルギー線硬化性組成物を、活性エネルギー線を照射して硬化させて得られるプラスチックハードコート用硬化物
以下に、説明する。
The active energy ray-curable composition of the present invention is classified into the following three active energy ray-curable compositions.
(1) Third Invention Hydrolysis and condensation of the alkoxysilane compound (A) of the first invention and the elastic rubber particles (B) having an average particle diameter of 1 μm or less in the presence of an acid (E1) or a base (E2). Hardened product for plastic hard coat obtained by curing by reaction (2) Fourth invention The active energy ray-curable composition of the first invention containing the photoacid generator (C1) or photobase generator (C2) is activated. Hardened product for plastic hard coat obtained by curing by irradiating energy rays (3) Fifth invention A photoacid generator (C1) or photobase generator (C2) containing a radical polymerization initiator (D) The hardened material for plastic hard coat obtained by irradiating and curing the active energy ray-curable composition of the invention 2 is described below.
本願の第３発明の活性エネルギー線硬化性組成物は、アルコキシシラン化合物（A）と平均粒子径が１μｍ以下の弾性ゴム粒子（B）を、酸（Ｅ１）または塩基（Ｅ２）の存在下で、加水分解と縮合反応により硬化させることにより、光照射を用いなくとも同様の塗膜を得ることができる。 The active energy ray-curable composition of the third invention of the present application comprises an alkoxysilane compound (A) and elastic rubber particles (B) having an average particle diameter of 1 μm or less in the presence of an acid (E1) or a base (E2). By curing by hydrolysis and condensation reaction, a similar coating film can be obtained without using light irradiation.
酸（Ｅ１）としては、蟻酸、酢酸、シュウ酸、乳酸、クエン酸、酒石酸、フタル酸、ｐ−トルエンスルホン酸、トリフルオロ酢酸、トリフルオロメタンスルホン酸などの有機酸、塩酸、リン酸、硝酸、硫酸、フッ酸、臭素酸、過塩素酸などの無機酸などが挙げられる。
入手の容易さ、扱いやすさの観点から、有機酸としては酢酸、シュウ酸、ｐ−トルエンスルホン酸、無機酸としては塩酸、硝酸、硫酸が好ましい。さらに無機酸は水溶液で用いることが扱いやすくより好ましい。
Examples of the acid (E1) include formic acid, acetic acid, oxalic acid, lactic acid, citric acid, tartaric acid, phthalic acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and other organic acids, hydrochloric acid, phosphoric acid, nitric acid, Examples include inorganic acids such as sulfuric acid, hydrofluoric acid, bromic acid, and perchloric acid.
From the viewpoint of easy availability and ease of handling, acetic acid, oxalic acid, p-toluenesulfonic acid is preferable as the organic acid, and hydrochloric acid, nitric acid, and sulfuric acid are preferable as the inorganic acid. Furthermore, it is easier to handle an inorganic acid in an aqueous solution, and it is more preferable.
塩基（Ｅ２）としては、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、水酸化マグネシウム、水酸化カルシウムなどのアルカリ土類水酸化物、アンモニア、メチルアミン、エチルアミン、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン等有機アミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等第４級アンモニウム塩などが挙げられる。
入手の容易さ、扱いやすさの観点から、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、アンモニア、メチルアミン、エチルアミン、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン等有機アミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等第４級アンモニウム塩が好ましく、常温下で気体であるアンモニア、メチルアミン等あるいはアルカリ金属水酸化物、第４級アンモニウム塩は水溶液で用いることが扱いやすくより好ましい。
Examples of the base (E2) include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide, ammonia, methylamine, ethylamine, dimethylamine, diethylamine, Examples thereof include organic amines such as trimethylamine and triethylamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.
From the viewpoint of easy availability and ease of handling, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, organic amines such as ammonia, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, and triethylamine, tetramethylammonium Quaternary ammonium salts such as hydroxide and tetraethylammonium hydroxide are preferred. Ammonia, methylamine and the like, or alkali metal hydroxides and quaternary ammonium salts, which are gases at room temperature, are easy to handle and more preferred.
本発明において、酸（Ｅ１）または塩基（Ｅ２）のいずれかを存在させることにより、アルコキシシラン化合物（A）を加水分解と縮合反応により硬化させることができる。
酸触媒では加水分解と脱水縮合が同じくらいの頻度で進み、どちらかというと線状ポリマーになりやすい。一方、塩基触媒では加水分解が優先するので架橋が進みやすく、架橋ポリマーになりやすく、その結果、シリカ粒子ができやすい。
酸（Ｅ１）または塩基（Ｅ２）のいずれを存在させてもよいが、均一塗膜形成の容易さの観点で酸（Ｅ１）を用いることが好ましい。
In the present invention, the alkoxysilane compound (A) can be cured by hydrolysis and condensation reaction by the presence of either the acid (E1) or the base (E2).
In the case of an acid catalyst, hydrolysis and dehydration condensation proceed with the same frequency, and it tends to be a linear polymer. On the other hand, hydrolysis is prioritized with a base catalyst, so that crosslinking is likely to proceed and a crosslinked polymer is likely to be formed, and as a result, silica particles are likely to be formed.
Either acid (E1) or base (E2) may be present, but it is preferable to use acid (E1) from the viewpoint of easy formation of a uniform coating film.
酸（Ｅ１）または塩基（Ｅ２）の添加量はアルコキシシラン化合物（A）の重量に対し
０．０１％〜１０％、好ましくは０．１％〜１．０％である。
The amount of acid (E1) or base (E2) added is 0.01% to 10%, preferably 0.1% to 1.0%, based on the weight of the alkoxysilane compound (A).
硬化させる好ましい温度としては２０℃〜１５０℃である。ただし塗布するプラスチック基材の耐熱性に応じて適宜設定できる。また硬化時間としては１〜２４時間、好ましくは５時間〜１８時間である。 A preferable temperature for curing is 20 ° C to 150 ° C. However, it can be appropriately set according to the heat resistance of the plastic substrate to be applied. The curing time is 1 to 24 hours, preferably 5 to 18 hours.
本願の第４発明のプラスチックハードコート用硬化物は、光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）を含む第１発明の活性エネルギー線硬化性組成物を、活性エネルギー線を照射して硬化させることで得られる。 The cured product for plastic hard coat of the fourth invention of the present application is obtained by irradiating the active energy ray-curable composition of the first invention containing the photoacid generator (C1) or the photobase generator (C2) with active energy rays. Obtained by curing.
本願の第５発明のプラスチックハードコート用硬化物は、光酸発生剤（Ｃ１）または光塩基発生剤（Ｃ２）、およびラジカル重合開始剤（Ｄ）を含む第２発明の活性エネルギー線硬化性組成物を、活性エネルギー線を照射して硬化させることで得られる。 The cured product for plastic hard coat of the fifth invention of the present application is an active energy ray-curable composition of the second invention comprising a photoacid generator (C1) or a photobase generator (C2), and a radical polymerization initiator (D). It can be obtained by irradiating an active energy ray to cure the product.
本願の第４および第５発明のプラスチックハードコート用硬化物は、より強固な塗膜を得るために必要に応じ活性エネルギー線を照射後加熱することが好ましい。硬化させる好ましい温度としては２０℃〜１５０℃である。ただし塗布するプラスチック基材の耐熱性に応じて適宜設定できる。 It is preferable that the cured product for plastic hard coat of the fourth and fifth inventions of the present application is heated after irradiation with active energy rays as necessary in order to obtain a stronger coating film. A preferable temperature for curing is 20 ° C to 150 ° C. However, it can be appropriately set according to the heat resistance of the plastic substrate to be applied.
本発明の活性エネルギー線硬化性組成物およびプラスチックハードコート用硬化物は、各種のハードコート加工用に有用である。
例えば、プラスチックレンズ用ハードコート（光学レンズ、サングラス等）、光ディスク用ハードコート、自動車ヘッドランプレンズ用ハードコート、光学フィルム保護用ハードコート、各種ディスプレイ用ハードコートに適用できる。
The active energy ray-curable composition and the cured product for plastic hard coat of the present invention are useful for various hard coat processes.
For example, it can be applied to a hard coat for plastic lenses (optical lenses, sunglasses, etc.), a hard coat for optical disks, a hard coat for automobile headlamp lenses, a hard coat for protecting optical films, and a hard coat for various displays.
以下、実施例及び比較例により本発明をさらに説明するが、本発明はこれらに限定されるものではない。以下、特に定めない限り、％は重量％、部は重量部を示す。 Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.
製造例１（アクリレート基を有するオルガノポリシロキサン（Ａ−２）の製造方法）
加熱冷却・攪拌装置、還流冷却管、滴下ロートおよび窒素導入管を備えたガラス製コルベンに、３−アクリロキシプロピルトリエトキシシラン（「ＫＢＭ５１０３」、信越化学製）４６部（０．２モル部）、ジフェニルジメトキシシラン（「ＫＢＭ２０２ＳＳ」、信越化学製）１６０部（０．６５モル部）とイオン交換水４５ｇ（２．５モル部）と、シュウ酸０．１部（０．００１モル部）を仕込み、６０℃、６時間の条件で加熱攪拌し、さらにエバポレーターを用いて、加水分解により副生したメタノールを減圧下で、４０℃にて２時間かけて留去し透明液状物を得た。
１Ｈ−ＮＭＲ、ＩＲ、ＧＰＣにより、この液状物は数平均分子量Ｍｎ２，１００、アクリル基含有オルガノポリシロキサン（Ａ−２）であった。
Production Example 1 (Method for producing organopolysiloxane (A-2) having an acrylate group)
46 parts (0.2 mole part) of 3-acryloxypropyltriethoxysilane ("KBM5103", manufactured by Shin-Etsu Chemical Co., Ltd.) on a glass Kolben equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introducing pipe , 160 parts (0.65 mol) of diphenyldimethoxysilane ("KBM202SS", manufactured by Shin-Etsu Chemical), 45 g (2.5 mol) of ion-exchanged water, and 0.1 part (0.001 mol) of oxalic acid The mixture was heated and stirred under conditions of 60 ° C. for 6 hours, and further, by using an evaporator, methanol by-produced by hydrolysis was distilled off under reduced pressure at 40 ° C. over 2 hours to obtain a transparent liquid.
By 1 H-NMR, IR, and GPC, this liquid was a number average molecular weight Mn2,100 and an acrylic group-containing organopolysiloxane (A-2).
製造例２
（光塩基発生剤Ｃ２−１の製造法）
４−ブロモメチルベンゾフェノン（アルドリッチ製）７．７６ｇと１，８−ジアザビシクロ〔５．４．０〕ウンデセン−７（「ＤＢＵ」サンアプロ製）４．３３ｍＬをアセトニトリル３０ｍＬに溶解させた。液温を２５℃で温調したまま２４時間攪拌した。その後アセトニトリルを減圧下で留去し、黄色固体を得た。それにメタノール５０ｍＬを加え溶解させ、テトラフェニルホウ酸ナトリウム１０ｇをメタノール２０ｍＬに溶解させたものと混合した。液温を２５℃に温調したまま３時間攪拌した。生じた沈殿物を濾過で除去し、メタノールを減圧下で留去した。ノルマルヘキサンにより洗浄することで白色固体を得た。
１Ｈ−ＮＭＲ、ＩＲによりこの白色固体が塩基発生剤（Ｃ２−１）であることを確認した。
Production Example 2
(Method for producing photobase generator C2-1)
7.76 g of 4-bromomethylbenzophenone (manufactured by Aldrich) and 4.33 mL of 1,8-diazabicyclo [5.4.0] undecene-7 (manufactured by “DBU” San Apro) were dissolved in 30 mL of acetonitrile. It stirred for 24 hours, adjusting liquid temperature at 25 degreeC. Thereafter, acetonitrile was distilled off under reduced pressure to obtain a yellow solid. 50 mL of methanol was added and dissolved therein, and mixed with 10 g of sodium tetraphenylborate dissolved in 20 mL of methanol. It stirred for 3 hours, adjusting liquid temperature to 25 degreeC. The resulting precipitate was removed by filtration, and methanol was distilled off under reduced pressure. A white solid was obtained by washing with normal hexane.
It was confirmed by 1 H-NMR and IR that the white solid was a base generator (C2-1).
実施例１
ガラス製容器にテトラメトキシシランの部分縮合物（「ＭＫＣシリケート ＭＳ−５６」、三菱化学製、テトラメトキシシランの一部を加水分解し、脱水縮合させて得られたもの）（A−１）９０部、弾性ゴム粒子（Ｂ−１；「ＢＴＡ７０５」、ローム＆ハース製を１０重量％メチルエチルケトン分散液としたもの）１００部、光酸発生剤（「ＣＰＩ−１１０Ｐ」、サンアプロ製）（Ｃ１−１）５部、メチルエチルケトン１０部を仕込み、均一になるまで攪拌することにより本発明の組成物（Ｓ−１）を得た。
Example 1
Partial condensate of tetramethoxysilane in a glass container ("MKC silicate MS-56", manufactured by Mitsubishi Chemical, obtained by hydrolyzing a part of tetramethoxysilane and dehydrating it) (A-1) 90 Parts, 100 parts of elastic rubber particles (B-1; “BTA705”, manufactured by Rohm & Haas as a 10 wt% methyl ethyl ketone dispersion), photoacid generator (“CPI-110P”, San Apro) (C1-1) ) 5 parts and 10 parts of methyl ethyl ketone were charged and stirred until uniform to obtain the composition (S-1) of the present invention.
実施例２
実施例１において、アルコキシシラン（Ａ−１）を製造例１で製造した（Ａ−２）８０部、多官能モノマーとしてネオマーＤＡ−６００（三洋化成製、平均官能基数５である多官能アクリレートモノマー）（Ｆ−１）１０部、光酸発生剤（Ｃ１−１）の代わりにラジカル重合開始剤（「イルガキュア１８４」チバ・ジャパン製）（Ｄ−１）５部とした以外は、実施例１と同様な操作を行い、本発明の組成物（Ｓ−２）を得た。
Example 2
In Example 1, 80 parts of alkoxysilane (A-1) produced in Production Example 1 (A-2), Neomer DA-600 (manufactured by Sanyo Chemical Industries, polyfunctional acrylate monomer having an average functional group number of 5) as the polyfunctional monomer Example 1 except that 10 parts of (F-1) and 5 parts of radical polymerization initiator ("Irgacure 184" manufactured by Ciba Japan) (D-1) instead of the photoacid generator (C1-1) were used. The same operation as above was performed to obtain the composition (S-2) of the present invention.
実施例３
実施例１において、光酸発生剤（Ｃ１−１）の代わりに光塩基発生剤（Ｃ２−１）５部とした以外は、実施例１と同様な操作を行い、本発明の組成物（Ｓ−３）を得た。
Example 3
In Example 1, the same operation as in Example 1 was performed except that 5 parts of the photobase generator (C2-1) was used instead of the photoacid generator (C1-1), and the composition (S -3) was obtained.
実施例４
実施例２において、さらに光酸発生剤（Ｃ１−１）５部を加えた以外は、実施例２と同様な操作を行い、本発明の組成物（Ｓ−４）を得た。
Example 4
In Example 2, except having further added 5 parts of photo-acid generators (C1-1), operation similar to Example 2 was performed and the composition (S-4) of this invention was obtained.
比較例１
ガラス製容器にアルコキシシラン（A−１）１００部、光酸発生剤（Ｃ１−１）５部、メチルエチルケトン１００部を仕込み、均一になるまで攪拌することにより比較のための組成物（Ｓ’−１）を得た。
Comparative Example 1
In a glass container, 100 parts of alkoxysilane (A-1), 5 parts of photoacid generator (C1-1) and 100 parts of methyl ethyl ketone were charged and stirred until they were uniform (S′- 1) was obtained.
比較例２
比較例１において、アルコキシシラン（Ａ−１）を（Ａ−２）９０部、さらにネオマーＤＡ−６００（三洋化成製）１０部、光酸発生剤（Ｃ１−１）をラジカル重合開始剤（Ｄ−１；「イルガキュア１８４」チバ・ジャパン製）５部とした以外は、比較例１と同様な操作を行い、比較のための組成物（Ｓ’−２）を得た。
Comparative Example 2
In Comparative Example 1, 90 parts of (A-2) alkoxysilane (A-1), 10 parts of neomer DA-600 (manufactured by Sanyo Chemical), and radical polymerization initiator (D1-1) of photoacid generator (C1-1) -1; “Irgacure 184” (manufactured by Ciba Japan), except for 5 parts, the same operation as in Comparative Example 1 was performed to obtain a composition (S′-2) for comparison.
比較例３
比較例２において、さらに光酸発生剤（Ｃ１−１）５部を加えた以外は、比較例２と同様な操作を行い、比較のための組成物（Ｓ’−３）を得た。
Comparative Example 3
In Comparative Example 2, the same operation as in Comparative Example 2 was carried out except that 5 parts of a photoacid generator (C1-1) was further added to obtain a composition (S′-3) for comparison.
比較例４
ガラス製容器にネオマーＤＡ−６００（三洋化成製）８０部、シリカ粒子（「デソライトＺ−７５０３」ＪＳＲ製２０部、ラジカル重合開始剤（Ｄ−１；「イルガキュア１８４」チバ・ジャパン製）５部、メチルエチルケトン１００部を仕込み、均一になるまで攪拌することにより比較のための組成物（Ｓ’−４）を得た。
Comparative Example 4
In a glass container, 80 parts of Neomer DA-600 (manufactured by Sanyo Kasei), 20 parts of silica particles ("Desolite Z-7503" manufactured by JSR, 5 parts of radical polymerization initiator (D-1; "Irgacure 184" manufactured by Ciba Japan)) Then, 100 parts of methyl ethyl ketone was charged and stirred until uniform to obtain a composition (S′-4) for comparison.
比較例５
ガラス製容器にアルコキシシラン（A−１；「ＭＫＣシリケート ＭＳ−５６」三菱化学製）５０部、可とう性付与剤としてＰＥＧ−１０００（三洋化成工業社品、数平均分子量１，０００のポリエチレングリコール）を５部、溶剤としてメタノール／水の混合溶媒（重量比＝１／５）１２０部を仕込み、均一になるまで攪拌することにより比較のための組成物（Ｓ’−５）を得た。
Comparative Example 5
In a glass container, 50 parts of alkoxysilane (A-1; “MKC silicate MS-56” manufactured by Mitsubishi Chemical), PEG-1000 (manufactured by Sanyo Chemical Industries, polyethylene glycol having a number average molecular weight of 1,000 as a flexibility imparting agent) ) And 120 parts of a methanol / water mixed solvent (weight ratio = 1/5) as a solvent, and stirred until uniform to obtain a composition (S′-5) for comparison.
＜塗膜の形成＞
ＴＡＣ（セルロース三酢酸）フィルムに実施例１〜４、および比較例１〜５で作成した組成物（Ｓ−１）〜（Ｓ’−５）をバーコーター（Ｎｏ．８、安田精機製作所）にて塗布し、７０℃で１分間乾燥後、ベルトコンベア式ＵＶ照射機（「ＣＶ−１１０Ｑ−Ｇ」；フュージョンＵＶシステムズ製）を用いて１５０ｍＪ／ｃｍ２の露光量にて露光した。さらに７０℃にて６時間加熱処理を行い、塗膜を作成した。
なお、比較例５においてはＵＶ照射を行わず、７０℃で加熱乾燥後、さらに７０℃で６時間加熱処理を行った。
<Formation of coating film>
A bar coater (No. 8, Yasuda Seiki Seisakusho) was prepared by applying the compositions (S-1) to (S′-5) prepared in Examples 1 to 4 and Comparative Examples 1 to 5 to a TAC (cellulose triacetate) film. After being coated at 70 ° C. for 1 minute, it was exposed at an exposure amount of 150 mJ / cm 2 using a belt conveyor type UV irradiator (“CV-110Q-G”; manufactured by Fusion UV Systems). Further, a heat treatment was performed at 70 ° C. for 6 hours to prepare a coating film.
In Comparative Example 5, UV irradiation was not performed, and after heat drying at 70 ° C., heat treatment was further performed at 70 ° C. for 6 hours.
＜塗膜均一形成性＞
上記の方法で作成した塗膜の均一形成性について、外観（ひび割れ、白濁等）を目視で確認した。
透明で均一な塗膜が形成されるものについて○、ひび割れなどが起こり、均一透明な塗膜が形成されないものについて×とした。
<Uniform film formability>
The appearance (cracking, cloudiness, etc.) of the coating film prepared by the above method was visually confirmed.
The case where a transparent and uniform coating film was formed was evaluated as “Good”, and the case where cracks and the like occurred and a uniform transparent coating film was not formed was evaluated as “X”.
＜鉛筆硬度＞
ＪＩＳ Ｋ−５４００に基づき塗膜表面硬度を測定した。
<Pencil hardness>
The coating film surface hardness was measured based on JIS K-5400.
＜耐折度＞
作成した塗膜を９０°に繰り返し折り曲げ、割れ等 が起こるまでの回数を測定した。
以下の判定基準で判定した。
○：５０回以上折り曲げても割れと折り曲げ痕として白化現象が認められない
△：１１〜４９回で割れまたは白化現象が発生
×：１０回以下で割れまたは白化現象が発生
<Folding resistance>
The number of times until the prepared coating film was repeatedly bent at 90 ° and cracked was measured.
The determination was made according to the following criteria.
◯: No whitening phenomenon is observed as cracks and bending marks even when bent 50 times or more. Δ: Cracking or whitening phenomenon occurs after 11 to 49 times. ×: Cracking or whitening phenomenon occurs after 10 times or less.
実施例１〜４で作成した本発明の組成物（Ｓ−１）〜（Ｓ−４）、および比較例１〜５で作成した比較のための組成物（Ｓ’−１）〜（Ｓ’−５）について、均一塗膜形成性、）鉛筆硬度、および耐折度を前述した方法で測定した。
その結果を表１に示す。
Compositions (S-1) to (S-4) of the present invention prepared in Examples 1 to 4 and compositions (S′-1) to (S ′) for comparison prepared in Comparative Examples 1 to 5 With respect to -5), the uniform film-forming property, the pencil hardness, and the folding resistance were measured by the methods described above.
The results are shown in Table 1.
表１の結果から、本発明の組成物が従来から提案されている組成物と比較し、高硬度でありかつ均一塗膜形成性および耐折度に優れた、プラスチック表面のハードコート剤であることが分かる。
比較用の組成物のうち、弾性ゴム微粒子を含まない（Ｓ’−１）〜（Ｓ’−３）では、均一な塗膜を得られなかった。
従来から提案されているシリカ粒子を添加した（Ｓ’−４）では塗膜硬度と耐折度が不十分であった。また可とう付与剤としてポリエチレングリコールを加えた（Ｓ’−５）では耐折度が不足した。
From the results shown in Table 1, the composition of the present invention is a hard coating agent on the plastic surface that is higher in hardness and more excellent in uniform film forming properties and folding resistance than the conventionally proposed compositions. I understand that.
Among the comparative compositions, a uniform coating film could not be obtained with (S′-1) to (S′-3) not containing elastic rubber fine particles.
With the conventionally proposed silica particles added (S′-4), the coating film hardness and folding resistance were insufficient. Moreover, when polyethylene glycol was added as a flexible imparting agent (S′-5), the folding resistance was insufficient.
本発明のハードコート用組成物は、表面硬度ならびに均一塗膜形成性が優れているため、プラスチック材料上にコーティングするハードコート剤として有用である。また、本発明の組成物用いたハードコート剤は特にディスプレイをはじめとする表示材料等の表面ハードコート剤として有用である。 The composition for hard coat of the present invention is useful as a hard coat agent for coating on a plastic material because of excellent surface hardness and uniform film-forming property. The hard coat agent using the composition of the present invention is particularly useful as a surface hard coat agent for display materials such as displays.
Claims (9)
ＹnＳｉ（ＯＲ）4−n （１）
［式（１）中、Ｙは 下記一般式（２）で表される１価の基；Ｒはアルキル基またはフェニル基；ｎは０〜２の整数を表す。］
−X−Z−Ｗ （２）
［式（２）中、Xは炭素数１〜８のアルキル基またはアルケニル基；Zは酸素原子、硫黄原子または下記一般式（３）で表されるオルガノポリシロキサンを有する２価の有機基；Ｗは水素原子またはビニル基、アリル基、（メタ）アクリロイル基、エポキシ基、オキセタニル基を表す。］
Y n Si (OR) 4−n (1)
[In formula (1), Y represents a monovalent group represented by the following general formula (2); R represents an alkyl group or a phenyl group; n represents an integer of 0-2. ]
-X-Z-W (2)
[In formula (2), X is an alkyl group or alkenyl group having 1 to 8 carbon atoms; Z is an oxygen atom, a sulfur atom or a divalent organic group having an organopolysiloxane represented by the following general formula (3); W represents a hydrogen atom, a vinyl group, an allyl group, a (meth) acryloyl group, an epoxy group, or an oxetanyl group. ]
ＹnＳｉ（ＯＲ）4−n （４）
［式（４）中、Ｙは下記一般式（５）で表され、Ｒはアルキル基またはフェニル基を表し、ｎは１または２の整数を表す。］
−X−Z−Ｗ’ （５）
［上式（５）中、Xは炭素数１〜８のアルキル基またはアルケニル基を表す。Zは酸素原子、硫黄原子または下記一般式（３）で表される オルガノポリシロキサンを有する２価の有機基を表す。Ｗ’は（メタ）アクリロイル基を表す。］
Y n Si (OR) 4−n (4)
[In formula (4), Y is represented by the following general formula (5), R represents an alkyl group or a phenyl group, and n represents an integer of 1 or 2. ]
-X-Z-W '(5)
[In the above formula (5), X represents an alkyl or alkenyl group having 1 to 8 carbon atoms. Z represents an oxygen atom, a sulfur atom or a divalent organic group having an organopolysiloxane represented by the following general formula (3). W ′ represents a (meth) acryloyl group. ]
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| JP2013091698A (en) * | 2011-10-25 | 2013-05-16 | Nippon Kasei Chem Co Ltd | Antistatic hard coat resin composition, and film having antistatic hard coat layer |
| JP2014189604A (en) * | 2013-03-26 | 2014-10-06 | Sumitomo Osaka Cement Co Ltd | Coating material for forming hard coat film, method for producing coating material for forming hard coat film, hard coat film, plastic base material including the same, and touch panel |
| WO2015163201A1 (en) * | 2014-04-24 | 2015-10-29 | セントラル硝子株式会社 | Curable composition, temporary adhesive material, and method for temporarily bonding member using same and substrate |
| KR20170104417A (en) * | 2017-09-01 | 2017-09-15 | 엘지이노텍 주식회사 | Voice coil motor |
| WO2018038226A1 (en) * | 2016-08-24 | 2018-03-01 | 日立化成株式会社 | Curable resin composition, image display device and manufacturing method of image display device |
| JPWO2021177425A1 (en) * | 2020-03-04 | 2021-09-10 |
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| JP2001261765A (en) * | 2000-03-17 | 2001-09-26 | Three Bond Co Ltd | Silicone gel composition |
| JP2002060463A (en) * | 2000-08-17 | 2002-02-26 | Jsr Corp | Photocurable resin composition and three-dimensional object |
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| JP2013091698A (en) * | 2011-10-25 | 2013-05-16 | Nippon Kasei Chem Co Ltd | Antistatic hard coat resin composition, and film having antistatic hard coat layer |
| JP2014189604A (en) * | 2013-03-26 | 2014-10-06 | Sumitomo Osaka Cement Co Ltd | Coating material for forming hard coat film, method for producing coating material for forming hard coat film, hard coat film, plastic base material including the same, and touch panel |
| WO2015163201A1 (en) * | 2014-04-24 | 2015-10-29 | セントラル硝子株式会社 | Curable composition, temporary adhesive material, and method for temporarily bonding member using same and substrate |
| WO2018038226A1 (en) * | 2016-08-24 | 2018-03-01 | 日立化成株式会社 | Curable resin composition, image display device and manufacturing method of image display device |
| WO2018037516A1 (en) * | 2016-08-24 | 2018-03-01 | 日立化成株式会社 | Curable resin composition, image display device and manufacturing method of image display device |
| KR20170104417A (en) * | 2017-09-01 | 2017-09-15 | 엘지이노텍 주식회사 | Voice coil motor |
| JPWO2021177425A1 (en) * | 2020-03-04 | 2021-09-10 | ||
| WO2021177425A1 (en) * | 2020-03-04 | 2021-09-10 | 旭化成株式会社 | Laminate, hard-coat coating film, and coating material composition |
| JP7576379B2 (en) | 2020-03-04 | 2024-10-31 | 旭化成株式会社 | Laminate, hard coat film, and coating composition |
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