JP2020111715A - Cured product - Google Patents
Cured product Download PDFInfo
- Publication number
- JP2020111715A JP2020111715A JP2019005781A JP2019005781A JP2020111715A JP 2020111715 A JP2020111715 A JP 2020111715A JP 2019005781 A JP2019005781 A JP 2019005781A JP 2019005781 A JP2019005781 A JP 2019005781A JP 2020111715 A JP2020111715 A JP 2020111715A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- cured product
- parts
- mass
- 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.)
- Granted
Links
- 239000000126 substance Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- 230000004313 glare Effects 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 123
- 229920000642 polymer Polymers 0.000 description 78
- 239000000203 mixture Substances 0.000 description 47
- -1 2-ethylhexyl Chemical group 0.000 description 32
- 238000000576 coating method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 30
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 9
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229940059574 pentaerithrityl Drugs 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 239000012780 transparent material Substances 0.000 description 4
- RYWGNBFHIFRNEP-UHFFFAOYSA-N (4-benzoylphenyl) 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 RYWGNBFHIFRNEP-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical group CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- HZRPIZSSEMKEEW-UHFFFAOYSA-N C1CO1.O=C1NC(=O)NC(=O)N1 Chemical compound C1CO1.O=C1NC(=O)NC(=O)N1 HZRPIZSSEMKEEW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- SCEFCWXRXJZWHE-UHFFFAOYSA-N 1,2,3-tribromo-4-(2,3,4-tribromophenyl)sulfonylbenzene Chemical compound BrC1=C(Br)C(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C(Br)=C1Br SCEFCWXRXJZWHE-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VMCRQYHCDSXNLW-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2-dichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)Cl)C=C1 VMCRQYHCDSXNLW-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- JHGGYGMFCRSWIZ-UHFFFAOYSA-N 2,2-dichloro-1-(4-phenoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C(Cl)Cl)=CC=C1OC1=CC=CC=C1 JHGGYGMFCRSWIZ-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
本発明は、艶消し性、光拡散性に優れ、ぎらつきを抑制できるしわ状の表面構造を有する硬化物に関する。 The present invention relates to a cured product having a matt and light diffusing property and having a wrinkle-like surface structure capable of suppressing glare.
壁紙等の建築建材、ディスプレイ関連、加飾フィルム等の用途に、艶消し性、光拡散性、凹凸感等を付与し、視認性、意匠性等を向上するために、基材の表面に微細な凹凸を付与することが行われている。
たとえば、特許文献１には、建材用化粧シートや冷蔵庫、洗濯機などの家電製品、パソコンなどのＯＡ製品の各種部品や包装容器などを成型により製造する際の転写箔用フィルムとして、ヘアーライン加工やサンドブラスト加工、梨地加工等により凹凸形状を設ける方法が開示されている。
また特許文献２には、液晶ディスプレイのバックライトユニットに用いられる光拡散フィルムの表面凹凸の形成方法として、樹脂バインダーにアクリル系粒子を分散させる方法が開示されている。
For the purposes of building construction materials such as wallpaper, displays, and decorative films, to impart matteness, light diffusivity, unevenness, etc. It is performed to give such unevenness.
For example, in Patent Document 1, as a film for a transfer foil when a decorative sheet for building materials, a household electric appliance such as a refrigerator and a washing machine, various parts of an OA product such as a personal computer and a packaging container are manufactured by molding, a hairline processing or A method of providing an uneven shape by sandblasting, satin finishing, etc. is disclosed.
In addition, Patent Document 2 discloses a method of dispersing acrylic particles in a resin binder as a method of forming surface irregularities of a light diffusion film used in a backlight unit of a liquid crystal display.
しかし特許文献１記載の、ヘアーライン加工や梨地加工では十分な艶消し効果得られず、また、サンドブラスト加工では、フィルム中に残った砂が品質上の問題となることがある。
また特許文献２に記載の方法では、アクリル系粒子が使用中に脱落することで、ディスプレイの視認性に支障をきたすことがある。
本発明はこれらの問題を解決することを目的とする。
However, hair line processing and satin processing described in Patent Document 1 do not provide a sufficient matting effect, and in sand blasting, the sand remaining in the film may be a quality problem.
In the method described in Patent Document 2, the acrylic particles may fall off during use, which may impair the visibility of the display.
The present invention aims to solve these problems.
本発明の要旨は、表面に、しわ状構造を有する硬化物であって、前記硬化物の表面の算術平均粗さＲａが０．０１μｍ以上である硬化物にある。 The gist of the present invention is a cured product having a wrinkled structure on the surface thereof, wherein the surface of the cured product has an arithmetic average roughness Ra of 0.01 μm or more.
本発明の硬化物は、ぎらつきが抑制され、艶消し性に優れた表面が得られ、建築建材、ディスプレイ関連、加飾フィルム等の表面の視認性、意匠性等を向上することができる。 The hardened|cured material of this invention can suppress glare, can obtain the surface excellent in mattness, and can improve the visibility, the designability, etc. of the surface of a building building material, a display connection, a decorative film, etc.
本発明の硬化物は表面にしわ状構造を有する。本発明において、しわ状構造とは、一般にリンクル構造として知られている、表面層が座屈して得られる波上の凹凸構造であり、たとえば図１に示すような迷路状の構造をいう。
本発明における、前記硬化物の表面の算術平均粗さＲａは、０．０１μｍ以上である。
前記算術平均粗さＲａが０．０１μｍ以下では、艶消し性が不十分となる。
前記算術平均粗さＲａは、硬化物の耐擦傷性と艶消し性を両立させる観点から、０．０５μｍ以上、２μｍ以下が好ましい。
また本発明における前記しわ状構造の凹凸の傾斜角θaは硬化物の耐擦傷性と艶消し性を両立させる観点から０．５°以上２０°以下が好ましく、より好ましくは５°以上１７°以下、さらに好ましくは７°以上１５°以下である。
前記傾斜角θaは、本発明の硬化物の耐擦傷性の点から低い方が好ましく、艶消し性の点から高いほうが好ましい。
さらに本発明の硬化物の凹凸周期（粗さ曲線要素の平均長さ）Ｒｓｍは０．５μｍ以上３０μｍ以下が好ましく、より好ましくは２μｍ以上２０μｍ以下、さらに好ましくは３μｍ以上１５μｍ以下である。前記Ｒｓｍが３０μｍを超えると、本発明の硬化物を防眩性フィルムとして用いた場合に表面のぎらつきが問題となり、０．５μｍより低いと十分な艶消し性が得られない。
また本発明における前記しわ状構造の最大高さＲｚは硬化物の耐擦傷性と艶消し性を両立させる観点から、０．０２μｍ以上５μｍ以下が好ましく、より好ましくは０．２μｍ以上４μｍ以下、さらに好ましくは０．５μｍ以上３μｍ以下である。
前記Ｒｚは、本発明の硬化物の耐擦傷性の点から低い方が好ましく、艶消し性の点から高いほうが好ましい。
本発明における前記しわ状構造の算術平均粗さＲａ、平均長さＲｓｍ、最大高さＲｚ、傾斜角θaは、ＪＩＳ Ｂ ０６０１−２００１に準拠し、光干渉法にて測定した値である。
なお、測定は、表面形状計測システム（株式会社日立ハイテクノロジーズ「ＶｅｒｔＳｃａｎ」（登録商標）Ｒ５５００）を用いて、硬化物表面において、縦２３７．６５μｍ、横１７８．２５μｍの四角形の領域の測定を行い、補完およびベースライン補正を行い、データを読み取った。なお、測定時における対物レンズの倍率は２０倍に設定した。
また本発明のしわ状構造を有する硬化物の６０°光沢度は艶消し性と透明性を両立させる観点から１以上９０以下であり、より好ましくは３以上７０以下、さらに好ましくは５以上５０以下である。
さらに、本発明のしわ状構造を有する硬化物を防眩性フィルム等の透明性を必要とする用途に用いる場合、ヘイズ１５％以上、全光線透過率８５%以上であることが好ましい。
The cured product of the present invention has a wrinkled structure on the surface. In the present invention, the wrinkle-like structure is a corrugated structure obtained by buckling of the surface layer, which is generally known as a wrinkle structure, and means a labyrinth-like structure as shown in FIG. 1, for example.
In the present invention, the arithmetic mean roughness Ra of the surface of the cured product is 0.01 μm or more.
When the arithmetic average roughness Ra is 0.01 μm or less, the matteness becomes insufficient.
The arithmetic average roughness Ra is preferably 0.05 μm or more and 2 μm or less from the viewpoint of achieving both scratch resistance and matting property of the cured product.
The inclination angle θa of the unevenness of the wrinkled structure in the present invention is preferably 0.5° or more and 20° or less, and more preferably 5° or more and 17° or less from the viewpoint of achieving both scratch resistance and matting property of the cured product. , And more preferably 7° or more and 15° or less.
The inclination angle θa is preferably low from the viewpoint of scratch resistance of the cured product of the present invention, and is preferably high from the viewpoint of matting property.
Further, the irregularity cycle (average length of roughness curve element) Rsm of the cured product of the present invention is preferably 0.5 μm or more and 30 μm or less, more preferably 2 μm or more and 20 μm or less, and further preferably 3 μm or more and 15 μm or less. When the Rsm is more than 30 μm, when the cured product of the present invention is used as an antiglare film, surface glare becomes a problem, and when it is less than 0.5 μm, sufficient matting properties cannot be obtained.
Further, the maximum height Rz of the wrinkled structure in the present invention is preferably 0.02 μm or more and 5 μm or less, more preferably 0.2 μm or more and 4 μm or less, from the viewpoint of achieving both scratch resistance and matting property of the cured product. It is preferably 0.5 μm or more and 3 μm or less.
The Rz is preferably low from the viewpoint of scratch resistance of the cured product of the present invention, and is preferably high from the viewpoint of matting property.
The arithmetic average roughness Ra, the average length Rsm, the maximum height Rz, and the inclination angle θa of the wrinkled structure in the present invention are values measured by an optical interference method in accordance with JIS B 0601-2001.
The measurement was performed using a surface shape measuring system (Hitachi High-Technologies Corporation “VertScan” (registered trademark) R5500) to measure a rectangular area of 237.65 μm in length and 178.25 μm in width on the surface of the cured product. The data were read after supplementation and baseline correction. The magnification of the objective lens at the time of measurement was set to 20 times.
The cured product having a wrinkle-like structure of the present invention has a 60° gloss value of 1 or more and 90 or less, more preferably 3 or more and 70 or less, and further preferably 5 or more and 50 or less from the viewpoint of achieving both matteness and transparency. Is.
Furthermore, when the cured product having a wrinkle-like structure of the present invention is used for applications requiring transparency such as an antiglare film, it is preferable that the haze is 15% or more and the total light transmittance is 85% or more.
前記ヘイズは硬化物の透明性と艶消し性を両立させる観点から１５％以上９５％以下が好ましく、より好ましくは２０％以上９３％以下、さらに好ましくは５０％以上９０％以下である。前記ヘイズは艶消し性の点から高いほうが好ましく、透明性の点から低い方が好ましい。
また、前記全光線透過率は硬化物の透明性と艶消し性を両立させる観点から、８５％以上９９％以下が好ましく、好ましくは８７％以上９７％以下、さらに好ましくは８９％以上９５％以下である。前記全光線透過率は、透明性の点から高いほうが好ましく、艶消し性の点から低い方が好ましい。
なお前記ヘイズ及び全光線透過率は、ＪＩＳ Ｚ８７２２（透過物体の照射及び受光の幾何条件）及びＪＩＳ Ｋ７３６１−１（プラスチック−透明材料の全光線透過率の試験方法）ＪＩＳ Ｋ７１３６（プラスチック−透明材料のヘ−ズの求め方）に準拠し、日本電色工業株式会社製ＳＨ７０００を用いたときの波長５５０ｎｍにおける測定値である。
The haze is preferably 15% or more and 95% or less, more preferably 20% or more and 93% or less, and further preferably 50% or more and 90% or less, from the viewpoint of achieving both transparency and matte properties of the cured product. The haze is preferably high from the viewpoint of matting property and is preferably low from the viewpoint of transparency.
The total light transmittance is preferably 85% or more and 99% or less, more preferably 87% or more and 97% or less, and further preferably 89% or more and 95% or less, from the viewpoint of achieving both transparency and matteness of the cured product. Is. The total light transmittance is preferably high from the viewpoint of transparency and is preferably low from the viewpoint of matting property.
The haze and the total light transmittance are JIS Z8722 (geometric condition for irradiation and light reception of a transparent object) and JIS K7361-1 (Plastic-test method for total light transmittance of transparent material) JIS K7136 (Plastic-transparent material) This is a measured value at a wavelength of 550 nm when SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. is used according to the method for obtaining haze).
さらに、本発明の硬化物の断面構造は、厚み方向に架橋密度の異なる２層以上の構造を有している。
表面側の層の厚さを３００ｎｍ以下とし、且つ、他の層の合計が、３００ｎｍより大きいものとすることで良好な透明性を確保しつつ、表面にしわ状の凹凸構造を発現することができる。
前記断面構造は、例えば、透過型電子顕微鏡（ＴＥＭ）、走査型プローブ顕微鏡（ＳＰＭ）の位相モード、ナノ赤外分光光度計、顕微ラマン分光等で確認できる。ＴＥＭでの観察は、硬化物の表層を接着剤（ヘンケルジャパン株式会社製ロックタイト）で固定後、ウルトラミクロトームを用いて厚さ１００ｎｍの垂直断面の切片を作製し、透過型電子顕微鏡（株式会社日立ハイテクノロジーズ社製ＴＥＭ Ｈ７６００型）を用いて行った。
前記断面構造における、厚み方向に架橋密度の異なる２層は、硬化膜の最表面の層に紫外線活性基を有する重合体Ａが配置され、最表面から２番目の層に多官能(メタ)アクリレートＢが配置されることで形成される。このため、厚み方向に架橋密度の異なる２層はいずれも有機物である。
Furthermore, the cross-sectional structure of the cured product of the present invention has a structure of two or more layers having different crosslink densities in the thickness direction.
When the thickness of the layer on the surface side is 300 nm or less and the total thickness of the other layers is greater than 300 nm, good transparency can be ensured and a wrinkle-like uneven structure can be developed on the surface. it can.
The cross-sectional structure can be confirmed by, for example, a transmission electron microscope (TEM), a scanning probe microscope (SPM) phase mode, a nano-infrared spectrophotometer, and microscopic Raman spectroscopy. For observation with TEM, after fixing the surface layer of the cured product with an adhesive (Loctite manufactured by Henkel Japan Co., Ltd.), a vertical cross section with a thickness of 100 nm was prepared using an ultramicrotome, and a transmission electron microscope (Hitachi Co., Ltd.) was used. It was performed using a TEM H7600 type manufactured by High Technologies.
In the two layers having different cross-linking densities in the thickness direction in the cross-sectional structure, the polymer A having an ultraviolet active group is arranged on the outermost surface layer of the cured film, and the polyfunctional (meth)acrylate is formed on the second layer from the outermost surface. It is formed by arranging B. Therefore, the two layers having different crosslink densities in the thickness direction are both organic substances.
次に、本発明の硬化物の製造方法の一例を示す。
本発明の硬化物のしわ状構造は、硬化性重合体組成物が硬化する際に塗膜の表面が先に硬化し硬化被膜を形成し、その後、塗膜の内部が硬化する際の収縮応力により、表面の硬化被膜が収縮し発現すると考えられる。
本発明の硬化物のしわ状構造は、活性エネルギー線の照射強度を強化し硬化性組成物の硬化時間を短くすることで、より小さいしわ状構造を得ることができ、活性エネルギー線の照射強度を低下し硬化性組成物の硬化時間を長くすることでより大きいしわ状構造を得ることができる。
さらに、本発明の硬化物のしわ状構造は、硬化性組成物の溶剤を除いた粘度を高くし流動性を低下させることで、より小さいしわ状構造を得ることができ、硬化性組成物の溶剤を除いた粘度を低く流動性を向上させることでより大きいしわ状構造を得ることができる。
Next, an example of the method for producing the cured product of the present invention will be described.
The wrinkled structure of the cured product of the present invention has a shrinkage stress when the surface of the coating film is first cured to form a cured coating film when the curable polymer composition is cured, and then the inside of the coating film is cured. It is considered that, due to this, the cured film on the surface contracts and develops.
The wrinkled structure of the cured product of the present invention can obtain a smaller wrinkled structure by strengthening the irradiation intensity of the active energy ray and shortening the curing time of the curable composition. By increasing the curing time of the curable composition, a larger wrinkle-like structure can be obtained.
Further, the wrinkled structure of the cured product of the present invention has a smaller wrinkled structure by increasing the viscosity of the curable composition excluding the solvent and lowering the fluidity. A larger wrinkle structure can be obtained by lowering the viscosity excluding the solvent and improving the fluidity.
本発明の硬化物は、たとえば、紫外線活性基を有する重合体Ａ、多官能(メタ)アクリレートＢ及び有機溶媒Ｃを含む硬化性重合体組成物を、基材に塗布した後、熱風乾燥により溶剤を留去し、活性エネルギー線を照射することで得られる。
前記活性エネルギー線としては、例えば、α線、β線、γ線、紫外線等が挙げられる。汎用性の観点から、活性エネルギー線としては紫外線が好ましい。
紫外線の発生源としては、例えば、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、メタルハライドランプ、マグネトロンを利用した無電極ＵＶランプ、ＬＥＤ等が挙げられる。
前記硬化性重合体組成物を硬化させる際の雰囲気としては、空気、窒素、アルゴン等の不活性ガスが挙げられる。実用性及び経済性の観点から、空気もしくは窒素が好ましい。活性エネルギー線として紫外線を使用する場合の好ましい硬化条件としては、例えば、高圧水銀灯を用いて波長３４０〜３８０ｎｍの積算光量が１０以上３０００ｍＪ／ｃｍ２以下となるように照射することが好ましい。
The cured product of the present invention is obtained, for example, by applying a curable polymer composition containing a polymer A having a UV-active group, a polyfunctional (meth)acrylate B and an organic solvent C to a substrate and then drying with a hot air to form a solvent. It is obtained by distilling away and irradiating with active energy rays.
Examples of the active energy rays include α rays, β rays, γ rays, and ultraviolet rays. From the viewpoint of versatility, ultraviolet rays are preferable as the active energy rays.
Examples of the source of ultraviolet rays include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless UV lamp using a magnetron, and an LED.
Examples of the atmosphere for curing the curable polymer composition include air, nitrogen, and an inert gas such as argon. From the viewpoint of practicality and economy, air or nitrogen is preferable. As a preferable curing condition when ultraviolet rays are used as the active energy rays, for example, it is preferable to irradiate using a high pressure mercury lamp so that the integrated light amount at a wavelength of 340 to 380 nm is 10 or more and 3000 mJ/cm 2 or less.
前記重合体Ａは紫外線活性基を有する。本発明における紫外線活性基とは、活性エネルギー線の照射により、多官能アクリレートと重合体Ａ自身を架橋させることができる官能基である。中でも紫外線等の活性エネルギー線の照射により分子内開裂反応、水素引き抜き反応、電子移動反応等によってラジカルを発生するものが好ましい。
本発明では、発生したラジカルが多官能(メタ)アクリレートＢと反応し架橋構造を形成できる。
前記紫外線活性基としては、通常、光開始剤に含まれるベンゾフェノン基、アセトフェノン基、ベンゾイン基、α−ヒドロキシケトン基、α−アミノケトン基、α−ジケトン基、α−ジケトンジアルキルアセタール基、アントラキノン基、チオキサントン基、ホスフィンオキシド基、１−[４−(２−ヒドロキシエトキシ)−フェニル]−２−ヒドロキシ−２−メチル−1−プロパン−1−オン）基等が挙げられ、本発明の硬化性重合体組成物の硬化時に酸素阻害を受けにくく、表面硬化性が良好となる点でベンゾフェノン基、アセトフェノン基が好ましい。
The polymer A has an ultraviolet active group. The ultraviolet active group in the present invention is a functional group capable of crosslinking the polyfunctional acrylate and the polymer A itself by irradiation with active energy rays. Among them, those that generate radicals by intramolecular cleavage reaction, hydrogen abstraction reaction, electron transfer reaction and the like by irradiation with active energy rays such as ultraviolet rays are preferable.
In the present invention, the generated radicals can react with the polyfunctional (meth)acrylate B to form a crosslinked structure.
The ultraviolet active group is usually a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group contained in a photoinitiator, Thioxanthone group, phosphine oxide group, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one) group and the like. A benzophenone group and an acetophenone group are preferable because they are less susceptible to oxygen inhibition during curing of the combined composition and have good surface curability.
前記重合体Ａは、前記紫外線活性基を有する単量体を含む単量体混合物を共重合することで得られる。
前記紫外線活性基を有する単量体としては、ベンゾフェノン類、アセトフェノン類、ベンゾイン類、α−ヒドロキシケトン類、α−アミノケトン類、α−ジケトン類、α−ジケトンジアルキルアセタール類、アントラキノン類、チオキサントン類、ホスフィンオキシド類に不飽和二重結合が付与された化合物が挙げられる。
また、前記重合体Ａが、紫外線活性基を有する(メタ)アクリル酸エステル由来の繰り返し単位を含むことが好ましい。(メタ)アクリル酸エステル由来の繰り返し単位を含むことで、本発明の硬化性重合体組成物を基材に塗布し硬化する際に、塗膜表面側の前記重合体Ａの濃度が高くなり、硬化物の表面にしわ状の凹凸構造を発現しやすくなる。
前記重合体Ａは、単量体として前記紫外線活性基を有する(メタ)アクリル酸エステルを含む単量体混合物を共重合することで得られる。
前記紫外線活性基としてベンゾフェノン基を有する単量体としては、ＭＣＣユニテック株式会社の４−メタクリロイルオキシベンゾフェノンや、ＡＬＬＮＥＸ社のＥＢＥＣＲＹＬ Ｐ３６やＥＢＥＣＲＹＬ Ｐ３７などが挙げられる。
また、前記紫外線活性基を有する単量体は、２−(メタ)アクリロイルオキシエチルイソシアナートに１−[４−(２−ヒドロキシエトキシ)−フェニル]−２−ヒドロキシ−２−メチル−1−プロパン−1−オンを付加させる方法や、(メタ)アクリル酸無水物や（メタ）アクリル酸クロリドに１−[４−(２−ヒドロキシエトキシ)−フェニル]−２−ヒドロキシ−２−メチル−1−プロパン−1−オンを付加させる方法などによって調製することができる。
The polymer A can be obtained by copolymerizing a monomer mixture containing the monomer having an ultraviolet active group.
As the monomer having an ultraviolet active group, benzophenones, acetophenones, benzoins, α-hydroxyketones, α-aminoketones, α-diketones, α-diketone dialkyl acetals, anthraquinones, thioxanthones, Examples thereof include compounds having an unsaturated double bond added to phosphine oxides.
Further, it is preferable that the polymer A contains a repeating unit derived from a (meth)acrylic acid ester having an ultraviolet active group. By containing a repeating unit derived from a (meth)acrylic acid ester, when the curable polymer composition of the present invention is applied to a substrate and cured, the concentration of the polymer A on the coating film surface side becomes high, It becomes easy to develop a wrinkle-like uneven structure on the surface of the cured product.
The polymer A can be obtained by copolymerizing a monomer mixture containing the (meth)acrylic acid ester having an ultraviolet active group as a monomer.
Examples of the monomer having a benzophenone group as the ultraviolet active group include 4-methacryloyloxybenzophenone manufactured by MCC Unitech Co., Ltd., EBECRYL P36 and EBECRYL P37 manufactured by ALLNEX.
The monomer having an ultraviolet active group is 2-(meth)acryloyloxyethyl isocyanate in 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane. 1-one addition method, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-(4-methyacrylic acid anhydride) or (meth)acrylic acid chloride It can be prepared by a method such as addition of propan-1-one.
前記重合体Ａは、紫外線活性基を有する単量体と紫外線活性基を有さない単量体を、溶液重合法、懸濁重合法などの一般的な重合法によって（共）重合することで製造することができる。操作が簡便で生産性が高い点で溶液重合法が好ましい。
また、前記重合体Ａは、紫外線活性基を有さない炭素数４以上のアルキル基を有する(メタ)アクリル酸エステル由来の繰り返し単位を含むことが好ましい。
前記紫外線活性基を有さない炭素数４以上のアルキル基を有さない(メタ)アクリル酸エステル由来の繰り返し単位を含むことで、本発明の硬化性重合体組成物を基材に塗布し硬化する際に、硬化物の表面の前記重合体Ａの濃度が高くなり、しわ状の凹凸構造を発現しやすくなる。
前記繰り返し単位の前記重合体Ａ１００質量部中の含有量は、１質量部以上９０質量部以下であることが好ましく、５質量部以上８０質量部以下がより好ましく、１０質量部以上６０質量部以下がさらに好ましい。
前記紫外線活性基を有さない炭素数４以上のアルキル基を有する単量体としては、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、パルミチル（メタ）アクリレートおよびステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、トリシクロデカン（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレートなど挙げられる。これらの中でも、硬化物表面の前記重合体Ａの濃度が高くなり、しわ状の凹凸構造を発現させる点で、ステアリル（メタ）アクリレート、ドデシル（メタ）アクリレート、イソボルニル（メタ）アクリレートが好ましい。
The polymer A is obtained by (co)polymerizing a monomer having an ultraviolet active group and a monomer having no ultraviolet active group by a general polymerization method such as a solution polymerization method or a suspension polymerization method. It can be manufactured. The solution polymerization method is preferable because the operation is simple and the productivity is high.
Further, the polymer A preferably contains a repeating unit derived from a (meth)acrylic acid ester having an alkyl group having 4 or more carbon atoms and having no ultraviolet active group.
The curable polymer composition of the present invention is applied to a substrate and cured by including a repeating unit derived from a (meth)acrylic acid ester having no UV-active group-containing alkyl group having 4 or more carbon atoms. In doing so, the concentration of the polymer A on the surface of the cured product becomes high, and a wrinkle-shaped uneven structure is likely to appear.
The content of the repeating unit in 100 parts by mass of the polymer A is preferably 1 part by mass or more and 90 parts by mass or less, more preferably 5 parts by mass or more and 80 parts by mass or less, and 10 parts by mass or more and 60 parts by mass or less. Is more preferable.
Examples of the monomer having an alkyl group having 4 or more carbon atoms which does not have an ultraviolet active group include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl. (Meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate and stearyl (meth)acrylate, behenyl (meth)acrylate, dicyclopentenyl Examples thereof include oxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate and adamantyl (meth)acrylate. Among these, stearyl (meth)acrylate, dodecyl (meth)acrylate, and isobornyl (meth)acrylate are preferable in that the concentration of the polymer A on the surface of the cured product becomes high and a wrinkle-like uneven structure is developed.
さらに、前記重合体Ａは、硬化物表面からの硬化を行う点で水酸基、メルカプト基、アミノ基、アミド基等の水素供与性官能基を有する単量体由来の繰り返し単位を含むことが好ましい。
前記繰り返し単位の前記重合体Ａ１００質量部中の含有量は、１質量部以上４０質量部以下が好ましく、２質量部以上３５質量部以下がより好ましく、５質量部以上２５質量部以下がさらに好ましい。
前記水素供与性官能基を有する単量体としては、２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、８−ヒドロキシオクチル（メタ）アクリレート、１０−ヒドロキシデシル（メタ）アクリレート、１２−ヒドロキシラウリル（メタ）アクリレートなどの水酸基を有する単量体、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−ビニルカプロラクタム、Ｎ−ビニルピロリドン、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、２−［（ブチルアミノ）カルボニル］オキシ］エチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、ビニルアセトアミドなどのアミノ基もしくはアミド基を有する単量体などが挙げられる。これらの中でも、紫外線活性基との併用において硬化促進効果に優れる点で、２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートや、（Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレートが好ましい。
なお、前記重合体Ａは、前記以外のその他の繰り返し単位を含んでいてもよく、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、フェニルジオキシエチル（メタ）アクリレート、ノニルフェニルオキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、モルフォリン（メタ）アクリレート、エチルカルビトール（メタ）アクリレート等の単量体由来の構成単位を含んでいても良い。
Further, the polymer A preferably contains a repeating unit derived from a monomer having a hydrogen-donating functional group such as a hydroxyl group, a mercapto group, an amino group or an amide group from the viewpoint of curing from the surface of the cured product.
The content of the repeating unit in 100 parts by mass of the polymer A is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 2 parts by mass or more and 35 parts by mass or less, and further preferably 5 parts by mass or more and 25 parts by mass or less. ..
Examples of the monomer having a hydrogen-donating functional group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, Monomers having hydroxyl groups such as 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N,N-diethyl. (Meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylate, 2-[(butylamino)carbonyl]oxy]ethyl(meth) Acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N, N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine, vinylacetamide, etc. Examples include a polymer. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and (N, N-dimethylacrylamide, N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate are preferred.
In addition, the polymer A may contain other repeating units other than the above, and is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, phenyldioxyethyl (meth)acrylate, nonyl. Even if it contains monomer-derived constituent units such as phenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, morpholine (meth)acrylate, and ethylcarbitol (meth)acrylate. good.
前記硬化性重合体組成物中の紫外線活性基を有する重合体Ａの濃度は、硬化性重合体組成物の硬化性、生産性を確保することと、しわ状の凹凸構造を良好に形成する観点から０．３ｍｍｏｌ／ｇ以上３．０ｍｍｏｌ／ｇ以下が好ましい。
さらに前記重合体Ａの重量平均分子量は１０００以上５０００００以下が好ましい。硬化性重合体組成物を基材に塗布し硬化する際に、塗膜表面側の前記重合体Ａの濃度が高くなり、硬化物の表面にしわ状の凹凸構造を発現しやすくなる点で、２０００以上１０００００以下がより好ましく、３０００以上５００００以下がさらに好ましい。
The concentration of the polymer A having an ultraviolet active group in the curable polymer composition is such that the curability and productivity of the curable polymer composition are ensured and that a wrinkle-like uneven structure is favorably formed. Therefore, it is preferably 0.3 mmol/g or more and 3.0 mmol/g or less.
Further, the weight average molecular weight of the polymer A is preferably 1,000 or more and 500,000 or less. When the curable polymer composition is applied to a base material and cured, the concentration of the polymer A on the coating film surface side becomes high, and a wrinkled uneven structure is easily developed on the surface of the cured product. It is more preferably 2,000 or more and 100,000 or less, still more preferably 3,000 or more and 50,000 or less.
本発明において重量平均分子量はゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）により測定した標準ポリスチレン換算による値である。
前記重量平均分子量は以下測定条件によって測定することができる。
（ＧＰＣ測定条件）
カラム：「ＴＳＫ−ｇｅｌ ｓｕｐｅｒＨＺＭ−Ｍ」、「ＴＳＫ−ｇｅｌ ＨＺＭ−Ｍ」、「ＴＳＫ−ｇｅｌ ＨＺ２０００」
溶離液：ＴＨＦ
流量：０．３５ｍＬ／ｍｉｎ
注入量：１０μＬ
カラム温度：４０℃
検出器：ＵＶ−８０２０
熱風乾燥時に紫外線活性基を有する重合体Ａを気層界面に濃縮させ、活性エネルギー線照射時に表面にしわ状の凹凸構造を発現させやすくなる点で前記重合体Ａのガラス転移温度は−３０℃以上１３０℃以下が好ましく、０℃以上１１０℃以下がより好ましく、２５℃以上１００℃以下がより好ましい。
本発明においてガラス転移温度は以下のＦｏｘの式による共重合体のガラス転移温度Ｔｇ（℃）の関係式で計算した値である。
１／（２７３＋Ｔｇ）＝Σ｛Ｗｉ／（２７３＋Ｔｇｉ）｝
Ｗｉ：単量体ｉの質量分率
Ｔｇｉ：単量体ｉの単独重合体のＴｇ（℃）
尚、単独重合体のガラス転移温度は、「ポリマーハンドブック 第４版 Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ著」に記載の数値を用いた値である。
In the present invention, the weight average molecular weight is a value in terms of standard polystyrene measured by a gel permeation chromatography method (GPC method).
The weight average molecular weight can be measured under the following measurement conditions.
(GPC measurement conditions)
Column: "TSK-gel super HZM-M", "TSK-gel HZM-M", "TSK-gel HZ2000"
Eluent: THF
Flow rate: 0.35 mL/min
Injection volume: 10 μL
Column temperature: 40°C
Detector: UV-8020
The glass transition temperature of the polymer A is −30° C. in that the polymer A having an ultraviolet active group is concentrated on the interface of the gas layer at the time of hot air drying to easily develop a wrinkle-like uneven structure on the surface at the time of irradiation with active energy rays. It is preferably 130° C. or lower, more preferably 0° C. or higher and 110° C. or lower, and even more preferably 25° C. or higher and 100° C. or lower.
In the present invention, the glass transition temperature is a value calculated by the relational expression of the glass transition temperature Tg (° C.) of the copolymer according to the following Fox equation.
1/(273+Tg)=Σ{Wi/(273+Tgi)}
Wi: Mass Fraction of Monomer i Tgi: Tg (°C) of Homopolymer of Monomer i
The glass transition temperature of the homopolymer is a value using the numerical value described in "Polymer Handbook, 4th Edition, John Wiley &Sons".
前記硬化性重合体組成物中の重合体Ａの含有量は、硬化物の表面への凹凸形状の付与及び紫外線硬化性を良好とする点で硬化性重合体組成物１００質量部中に０．５質量部以上２０．０質量部以下が好ましく、０．７質量部以上１０．０質量部以下がより好ましく、１．０質量部以上７．０質量部以下がさらに好ましい。 The content of the polymer A in the curable polymer composition is 0. 0 in 100 parts by mass of the curable polymer composition from the viewpoint of imparting unevenness to the surface of the cured product and improving the ultraviolet curability. The amount is preferably 5 parts by mass or more and 20.0 parts by mass or less, more preferably 0.7 parts by mass or more and 10.0 parts by mass or less, and further preferably 1.0 parts by mass or more and 7.0 parts by mass or less.
前記多官能(メタ)アクリレートＢは、一分子中に２つ以上の不飽和二重結合を有する化合物である。多官能(メタ)アクリレートＢは、得られる硬化物の硬度や硬化性重合体組成物の硬化性を高める作用がある。
前記多官能(メタ)アクリレートＢとしては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、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、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレートモノステアレート、グリシジルエーテルのジ（メタ）アクリレート、カプロラクトン変性ジ（メタ）アクリレート、エチレンオキサイド変性ジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジ（メタ）アクリレート、プロピレンオキサイド変性ジ（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、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テトラ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールエトキシテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（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、ジメチロールプロパントリ（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、トリメチロールプロパンエトキシトリ（メタ）アクリレート、ジメチロールプロパンテトラ（メタ）アクリレート、トリペンタエリスリトール（メタ）アクリレート等の多官能（メタ）アクリレートが挙げられる。また、上記化合物のアルキル変性（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、エチレンオキサイド変性（メタ）アクリレート、プロピレンオキサイド変性（メタ）アクリレートや、上記以外の脂肪族ポリオールの（メタ）アクリレート、さらに、デンドリマーまたはハイパーブランチポリマーと称される、アクリレート基を末端に有する樹枝状脂肪族化合物が挙げられる。アクリレート基を末端に有する樹枝状脂肪族化合物は市販品としてビスコートＶ＃１０００、Ｖ＃５０２０、ＳＴＡＲ−５０１（何れも大阪有機化学工業社製）などが挙げられる。前記の多官能アクリレート化合物は、単独で使用してもよく、２種以上を併用してもよい。
前記多官能（メタ）アクリレートＢのなかでも得られる硬化物の硬度や硬化性重合体組成物の硬化性が高くなる点でジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスリトールテトラ（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トリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート、ジメチロールプロパントリ（メタ）アクリレート、トリペンタエリスリトール（メタ）アクリレート、ビスコートＶ＃１０００、Ｖ＃５０２０、ＳＴＡＲ−５０１などが好ましい。
また、硬化性重合体組成物の硬化性が良好となる点から、前記多官能（メタ）アクリレートＢの含有量は、硬化性重合体組成物１００質量部に対し８０．０質量部以上９９．５質量部以下が好ましく、９０．０質量部以上９９．３質量部以下がより好ましく、９３．０質量部以上９９．０質量部以下がさらに好ましい。
The polyfunctional (meth)acrylate B is a compound having two or more unsaturated double bonds in one molecule. The polyfunctional (meth)acrylate B has an effect of increasing the hardness of the obtained cured product and the curability of the curable polymer composition.
Examples of the polyfunctional (meth)acrylate B include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, glycidyl ether di(meth)acrylate, caprolactone modified di(meth) ) Acrylate, ethylene oxide modified di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, propylene oxide modified di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol ethoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dimethylolpropane tri(meth) ) Polyfunctional (meth)acrylates such as acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, dimethylolpropane tetra(meth)acrylate and tripentaerythritol (meth)acrylate. Further, alkyl-modified (meth)acrylates of the above compounds, caprolactone-modified (meth)acrylates, ethylene oxide-modified (meth)acrylates, propylene oxide-modified (meth)acrylates, and (meth)acrylates of aliphatic polyols other than the above, Examples thereof include dendritic aliphatic compounds having acrylate groups at the ends, which are called dendrimers or hyperbranched polymers. Examples of the dendritic aliphatic compound having an acrylate group at the end include commercially available products such as Viscoat V#1000, V#5020 and STAR-501 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.). The polyfunctional acrylate compounds may be used alone or in combination of two or more.
Among the polyfunctional (meth)acrylates B, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, penta Erythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, dimethylolpropane tri(meth)acrylate, tripentaerythritol (meth)acrylate, biscoat V#1000, V #5020, STAR-501 and the like are preferable.
Further, from the viewpoint that the curability of the curable polymer composition is good, the content of the polyfunctional (meth)acrylate B is 80.0 parts by mass or more and 99.99 parts by mass or more with respect to 100 parts by mass of the curable polymer composition. It is preferably 5 parts by mass or less, more preferably 90.0 parts by mass or more and 99.3 parts by mass or less, and further preferably 93.0 parts by mass or more and 99.0 parts by mass or less.
また、本発明の硬化性組成物は紫外線活性基を有する重合体Ａと有機溶媒Ｃを除いた成分の粘度が、２５℃の条件下にてＥ型粘度計で測定したときに、３．０ｍＰａ・ｓ以上３００００ｍＰａ・ｓ以下となるよう調整するのが好ましい。より好ましくは５．０ｍＰａ・ｓ以上２００００ｍＰａ・ｓ以下であり、さらに好ましくは、１０ｍＰａ・ｓ以上６５００ｍＰａ・ｓ以下である。
粘度の好適な範囲は、活性エネルギー線を照射する際の雰囲気の温度にも依るが、前記粘度を、３００００ｍＰａ・ｓ以下とすることにより、前記硬化物の表面の算術平均粗さＲａを０．０１μｍ以上とすることができる。
Further, the curable composition of the present invention has a viscosity of 3.0 mPa when the viscosity of the components excluding the polymer A having an ultraviolet active group and the organic solvent C is measured with an E-type viscometer at 25° C. It is preferable to adjust the pressure to be s or more and 30,000 mPa·s or less. It is more preferably 5.0 mPa·s or more and 20000 mPa·s or less, and further preferably 10 mPa·s or more and 6500 mPa·s or less.
The preferred range of the viscosity depends on the temperature of the atmosphere when the active energy ray is irradiated, but by setting the viscosity to 30,000 mPa·s or less, the arithmetic mean roughness Ra of the surface of the cured product is set to 0. It can be set to 01 μm or more.
さらに本発明では前記有機溶媒Ｃを含むことにより、本発明の硬化性重合体組成物を基材に塗布する際の作業性が向上する。
前記有機溶媒Ｃとしてはトルエン、キシレン等の芳香族系溶媒；メチルエチルケトン、アセトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、アニソール、フェネトール等のエーテル系溶媒；酢酸エチル、酢酸ブチル、酢酸イソプロピル、エチレングリコールジアセテート等のエステル系溶媒；ジメチルホルムアミド、ジエチルホルムアミド、Ｎ−メチルピロリドン等のアミド系溶媒；メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ等のセロソルブ系溶媒；メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール系溶媒；ジクロロメタン、クロロホルム等のハロゲン系溶媒；等が挙げられる。これらの溶媒は１種を単独で使用してもよく、また２種以上を併用してもよい。
これらの溶媒のうち、塗布における作業性が向上する点でエステル系溶媒、エーテル系溶媒、アルコール系溶媒及びケトン系溶媒が好ましい。
また前記有機溶媒Ｃの含有量は、硬化性重合体組成物１００質量部に対し塗布操作における操作性が向上する点で、１０質量部以上１９００質量部以下が好ましく、４０質量部以上４００質量部以下がより好ましい。
さらに、前記硬化性重合体組成物は有機溶媒、重合開始剤、レべリング剤、無機粒子、その他の成分を含んでいてもよい。
Further, in the present invention, the inclusion of the organic solvent C improves workability in applying the curable polymer composition of the present invention to a substrate.
As the organic solvent C, an aromatic solvent such as toluene and xylene; a ketone solvent such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone And the like; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, butanol; halogen-based solvents such as dichloromethane, chloroform, and the like. These solvents may be used alone or in combination of two or more.
Among these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferable from the viewpoint of improving workability in coating.
Further, the content of the organic solvent C is preferably 10 parts by mass or more and 1900 parts by mass or less, and 40 parts by mass or more and 400 parts by mass in terms of improving operability in coating operation with respect to 100 parts by mass of the curable polymer composition. The following is more preferable.
Further, the curable polymer composition may contain an organic solvent, a polymerization initiator, a leveling agent, inorganic particles, and other components.
前記硬化性重合体組成物は、紫外線の照射によりラジカルを発生する紫外線活性基を有する重合体Ａにより十分な光硬化性を有するが、硬化性を促進する目的で重量平均分子量１０００以下の光重合開始剤を添加することができる。
前記光重合開始剤としては、例えば、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、ベンゾイン−ｎ−ブチルエーテル、ベンゾインフェニルエーテル、ベンジルジフェニルジスルフィド、ジベンジル、ジアセチル、アントラキノン、ナフトキノン、３，３’−ジメチル−４−メトキシベンゾフェノン、ベンゾフェノン、ｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノン、４，４’−ビス（ジエチルアミノ）ベンゾフェノン、ピバロインエチルエーテル、ベンジルジメチルケタール、１，１−ジクロロアセトフェノン、ｐ−ｔ−ブチルジクロロアセトフェノン、２−クロロチオキサントン、２−メチルチオキサントン、２，４−ジエチルチオキサントン、２，２−ジエトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジクロロ−４−フェノキシアセトフェノン、フェニルグリオキシレート、α−ヒドロキシイソブチルフェノン、ジベンゾスパロン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチル−１−プロパノン、２−メチル−［４−（メチルチオ）フェニル］−２−モルフォリノ−１−プロパノン、トリブロモフェニルスルホン、トリブロモメチルフェニルスルホン等が挙げられる。
前記光重合開始剤は、重合体Ａより優先して硬化をしない程度に添加するのが良い。重合体組成物１００質量部に対する前記光重合開始剤の添加量は、３質量部以下が好ましく、２質量部以下がより好ましく、１質量部以下がさらに好ましく、０．５質量部以下が特に好ましい。
The curable polymer composition has sufficient photocurability due to the polymer A having an ultraviolet active group that generates radicals upon irradiation with ultraviolet rays, but is photopolymerized with a weight average molecular weight of 1,000 or less for the purpose of promoting curability. Initiators can be added.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyldiphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, and 3'. -Dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, p-t-butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro- 4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio) Phenyl]-2-morpholino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone and the like.
The photopolymerization initiator is preferably added in such an extent that it does not cure in preference to the polymer A. The amount of the photopolymerization initiator added to 100 parts by mass of the polymer composition is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 1 part by mass or less, particularly preferably 0.5 parts by mass or less. ..
前記硬化性重合体組成物は、粘度の調整や活性エネルギー線による硬化速度の調整のため、一分子中に１つの不飽和二重結合を有する単官能（メタ）アクリレートを添加することができる。
前記単官能（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチルアクリレート、ヘキシルアクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、クレゾール（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、７−アミノ−３，７−ジメチルオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、エチルジエチレングリコール（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ポリウレタンモノ（メタ）アクリレート、ポリエポキシモノ（メタ）アクリレート、ポリエステルモノ（メタ）アクリレート等が挙げられる。
To the curable polymer composition, a monofunctional (meth)acrylate having one unsaturated double bond in one molecule can be added in order to adjust the viscosity and the curing rate by active energy rays.
Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acrylate, octyl (meth). Acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cresol (meth)acrylate, di Cyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-ethylhexyl (meth ) Acrylate, ethyldiethylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, polyurethane mono (meth)acrylate, polyepoxy mono (meth)acrylate, polyester mono (meth) ) Acrylate and the like can be mentioned.
前記硬化性重合体組成物は、硬化物外観を向上させるため、レベリング剤を添加することができる。レベリング剤としては、アクリル系レベリング剤、シリコーン系レベリング剤、フッ素系レベリング剤等が挙げられる。また、レベリング剤は１種のみで用いても２種以上を組み合わせて用いてもよい。 The curable polymer composition may include a leveling agent in order to improve the appearance of the cured product. Examples of the leveling agent include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. The leveling agents may be used alone or in combination of two or more.
前記硬化性重合体組成物は、艶消し性をさらに向上させる場合には、平均一次粒子径が０．０１μｍ以上１０μｍ以下の有機もしくは無機粒子を硬化性重合体組成物に添加させることでより高い艶消し性を有する硬化物を得ることができる。前記有機粒子および前記無機粒子は２種以上を用いても良い。
また、前記無機粒子は(メタ)アクリロイル基などの反応性基を有するシランカップリング剤で表面修飾した粒子でも良い。表面修飾した粒子は、例えば、重合体と無機粒子とを酸や塩基、アセチルアセトンアルミニウム等のシランカップリング反応触媒の存在下に２５℃〜１２０℃で１時間〜２４時間程度反応させる方法が挙げられる。
In the case of further improving the matting property, the curable polymer composition is higher by adding organic or inorganic particles having an average primary particle diameter of 0.01 μm or more and 10 μm or less to the curable polymer composition. A cured product having matte properties can be obtained. Two or more kinds of the organic particles and the inorganic particles may be used.
The inorganic particles may be particles whose surface is modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. Examples of the surface-modified particles include a method in which the polymer and the inorganic particles are reacted at 25° C. to 120° C. for about 1 to 24 hours in the presence of an acid, a base, or a silane coupling reaction catalyst such as acetylacetone aluminum. ..
前記硬化性重合体組成物は、本発明の効果を損なわない範囲で、チオール基を含有する化合物などの重合促進剤、帯電防止剤、可塑剤、界面活性剤、酸化防止剤、紫外線吸収剤等を添加しても良い。 The curable polymer composition, as long as the effect of the present invention is not impaired, a polymerization accelerator such as a compound containing a thiol group, an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, etc. May be added.
本発明の硬化物は、前記硬化性重合体組成物を基材に塗布した後、得られた硬化物を乾燥し、紫外線を照射し得られる。
前記基材としては各種重合体フィルム及び重合体板、重合体成形体等を使用することができる。重合体フィルムとして、例えば、トリアセチルセルロース（ＴＡＣ）フィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ジアセチレンセルロースフィルム、アセテートブチレートセルロースフィルム、ポリエーテルスルホンフィルム、ポリアクリル系重合体フィルム、ポリウレタン系重合体フィルム、ポリカーボネートフィルム、ポリスルホンフィルム、ポリエーテルフィルム、ポリメチルペンテンフィルム、ポリエーテルケトンフィルム、（メタ）アクリルニトリルフィルム、シクロオレフィンポリマー（ＣＯＰ）フィルム、延伸ポリプロピレンフィルム、無延伸ポリプロピレンフィルム等が挙げられる。また、重合体板及び重合体成形体として、例えばアクリル板、トリアセチルセルロース板、ポリエチレンテレフタレート板、ジアセチレンセルロース板、アセテートブチレートセルロース板、ポリエーテルスルホン板、ポリウレタン板、ポリカーボネート板、ポリスルホン板、ポリエーテル板、ポリメチルペンテン板、ポリエーテルケトン板、（メタ）アクリルニトリル板等が挙げられる。また、必要に応じてガラス等を使用することもできる。なお、基材の厚さは、用途に応じて適時選択することができるが、一般に２５μｍ〜1,００００μｍ程度のものが用いられる。
塗布の方法は特段限定されないが、ディップコート法、エアーナイフコート法、カーテンコート法、スピンコート法、ローラーコート法、バーコート法、ワイヤーバーコート法、グラビアコート法、スプレーコート等の方法により塗布することができる。
The cured product of the present invention can be obtained by applying the curable polymer composition to a substrate, drying the obtained cured product, and irradiating with ultraviolet rays.
As the base material, various polymer films, polymer plates, polymer molded products and the like can be used. Examples of the polymer film include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic polymer film, polyurethane polymer film. , A polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyetherketone film, a (meth)acrylonitrile film, a cycloolefin polymer (COP) film, a stretched polypropylene film, a non-stretched polypropylene film and the like. Further, as the polymer plate and the polymer molded product, for example, an acrylic plate, a triacetyl cellulose plate, a polyethylene terephthalate plate, a diacetylene cellulose plate, an acetate butyrate cellulose plate, a polyether sulfone plate, a polyurethane plate, a polycarbonate plate, a polysulfone plate, Examples thereof include a polyether plate, a polymethylpentene plate, a polyetherketone plate, and a (meth)acrylonitrile plate. Further, glass or the like can be used if necessary. The thickness of the base material can be appropriately selected according to the application, but a thickness of about 25 μm to 10000 μm is generally used.
The coating method is not particularly limited, but it may be applied by a method such as a dip coating method, an air knife coating method, a curtain coating method, a spin coating method, a roller coating method, a bar coating method, a wire bar coating method, a gravure coating method or a spray coating method. can do.
硬化性重合体組成物の乾燥は、硬化性重合体組成物を硬化させる前に予め加熱乾燥させることが好ましい。塗布された塗膜を硬化させる前に加熱乾燥する場合は、３０℃以上２００℃以下が好ましく、４０℃以上１５０℃以下がより好ましい。また、乾燥時間は、０．０１分以上３０分以下が好ましく、０．１分以上１０分以下がより好ましい。予め加熱乾燥させることにより、塗膜中の溶媒を効果的に除去することが可能であり、本発明の硬化性重合体組成物を基材に塗布し硬化する際に、塗膜表面側の前記重合体Ａの濃度が高くなり、硬化物の表面にしわ状の凹凸構造を発現しやすくなる。
紫外線の照射は、生産性の点から積算光量が１００ｍＪ／ｃｍ２以上３０００ｍＪ／ｃｍ２以下となるよう照射することが好ましい。光源としては、中圧水銀灯、高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、あるいは走査型、カーテン型電子線加速路による電子線等高圧水銀灯、超高圧水銀灯等、低圧水銀灯などを用いることができる。
The curable polymer composition is preferably dried by heating in advance before curing the curable polymer composition. When heating and drying the applied coating film before curing, the temperature is preferably 30°C or higher and 200°C or lower, and more preferably 40°C or higher and 150°C or lower. The drying time is preferably 0.01 minutes or more and 30 minutes or less, more preferably 0.1 minutes or more and 10 minutes or less. By heating and drying in advance, it is possible to effectively remove the solvent in the coating film, and when the curable polymer composition of the present invention is applied to a substrate and cured, the coating film surface side is The concentration of the polymer A is increased, and the surface of the cured product is likely to exhibit a wrinkle-like uneven structure.
UV irradiation, it is preferable to perform irradiation to the integrated light quantity from the viewpoint of productivity is 100 mJ / cm 2 or more 3000 mJ / cm 2 or less. As the light source, use a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a scanning type, a high-pressure mercury lamp such as an electron beam by a curtain type electron beam accelerating path, an ultra-high pressure mercury lamp, etc. You can
以下、本発明を実施例及び比較例によりさらに詳しく説明するが、本発明はこれらに限定されるものではない。なお、評価は以下の方法によって行った。
＜評価方法＞
＜評価サンプル＞
硬化性重合体組成物の塗布液を、厚さ１００μｍのＰＥＴフィルム（三菱ケミカル（株）製、Ｏ３２１Ｅ１００）に＃７のバーコーターで塗布し、得られた塗膜を１００℃に加熱した熱風乾燥機で６０秒間乾燥を行うことで溶剤を揮発させた。次いで、アイグラフィックス株式会社製のＵＶコンベアを用いて、高圧水銀灯により空気下で塗膜の硬化を行ったものを評価サンプルとした。
紫外線による硬化は、波長３００〜３９０ｎｍの積算光量が、岩崎電気株式会社製の照度計（アイ紫外線積算照度計 ＵＶＰＦ―Ａ１、ＰＤ−３６５）で測定した際に、２５０ｍＪ／ｃｍ２（２５０ｍＷ/Ｊ／ｃｍ２）となるように調整し、約１秒の照射を２回（５００ｍＪ／ｃｍ２）行った。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation was performed by the following method.
<Evaluation method>
<Evaluation sample>
The coating liquid of the curable polymer composition was applied to a PET film having a thickness of 100 μm (O321E100 manufactured by Mitsubishi Chemical Co., Ltd.) with a #7 bar coater, and the obtained coating film was dried with hot air heated to 100° C. The solvent was volatilized by drying for 60 seconds with a machine. Then, a UV conveyor manufactured by iGraphics Co., Ltd. was used to cure the coating film in the air with a high pressure mercury lamp to obtain an evaluation sample.
The curing by ultraviolet rays is 250 mJ/cm 2 (250 mW/J when the integrated light amount of wavelength 300 to 390 nm is measured by an illuminometer manufactured by Iwasaki Electric Co., Ltd. (eye ultraviolet integrated illuminometer UVPF-A1, PD-365). /Cm 2 ), and the irradiation for about 1 second was performed twice (500 mJ/cm 2 ).
＜ヘイズ、全光線透過率＞
ヘイズおよび全光線透過率は、ＪＩＳ Ｚ８７２２Z（透過物体の照射及び受光の幾何条件）及びＪＩＳ Ｋ７３６１−１（プラスチック−透明材料の全光線透過率の試験方法）ＪＩＳ Ｋ７１３６（プラスチック−透明材料のヘ−ズの求め方）に準拠し、日本電色工業製ＳＨ７０００を用いて波長５５０ｎｍにおける値を測定した。
<Haze, total light transmittance>
The haze and the total light transmittance are JIS Z8722Z (geometric condition of irradiation and light reception of a transparent object) and JIS K7361-1 (Testing method of total light transmittance of plastic-transparent material) JIS K7136 (Plastic-transparent material The value at a wavelength of 550 nm was measured using SH7000 manufactured by Nippon Denshoku Industries Co., Ltd.
＜光沢度＞
ＪＩＳ Ｚ ８７４１に準拠し、日本電色工業社製グロスメーターＶＧ２０００を用いて、６０°鏡面光沢度（６０°グロス）の測定を行った。
<Glossiness>
The 60° specular gloss (60° gloss) was measured using a gloss meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z8741.
＜表面形状＞
前記粗さ曲線要素の平均長さＲｓｍ、最大高さＲｚ、算術平均粗さＲａ、傾斜角θaは表面形状計測システム（株式会社日立ハイテクノロジーズ「ＶｅｒｔＳｃａｎ」（登録商標）Ｒ５５００）を用いて、硬化物表面において、２３７．縦２３７．６５μｍ、横１７８．２５μｍの四角形の領域における表面の凹凸形状を光干渉法にて測定し、補完およびベースライン補正を行い、データを読み取った。なお、測定時における対物レンズの倍率は２０倍に設定した。
<Surface shape>
The average length Rsm, the maximum height Rz, the arithmetic average roughness Ra, and the inclination angle θa of the roughness curve element are cured using a surface profile measuring system (Hitachi High-Technologies Corporation "VertScan" (registered trademark) R5500). 237. The unevenness of the surface in a quadrangle region of 237.65 μm in length and 178.25 μm in width was measured by an optical interferometry method, supplementation and baseline correction were performed, and the data was read. The magnification of the objective lens at the time of measurement was set to 20 times.
＜硬化膜の垂直断面構造＞
硬化物の表層を接着剤（ヘンケルジャパン株式会社製ロックタイト）で固定後、ウルトラミクロトームを用いて厚さ１００ｎｍの垂直断面の切片を作製した。作製した切片を透過型電子顕微鏡（株式会社日立ハイテクノロジーズ社製ＴＥＭ Ｈ７６００型）を用いて観察した。
<Vertical cross-section structure of cured film>
After fixing the surface layer of the cured product with an adhesive (Loctite manufactured by Henkel Japan Co., Ltd.), a vertical section having a thickness of 100 nm was prepared using an ultramicrotome. The produced section was observed using a transmission electron microscope (TEM H7600 manufactured by Hitachi High-Technologies Corporation).
＜艶消し性＞
蛍光灯を灯した室内で、蛍光灯と評価サンプルの距離を２．５ｍに設定して評価サンプルの表面への蛍光灯の映り込みを目視で評価した。
○：蛍光灯の反射像は、強くぼやけており、蛍光灯の輪郭が確認できない。
△：蛍光灯の反射像は、ぼやけているが、うっすらと輪郭を確認することができる。
×：蛍光灯の反射像は、鮮明ではっきりと輪郭を確認することができる。
<Matte>
In a room illuminated with a fluorescent lamp, the distance between the fluorescent lamp and the evaluation sample was set to 2.5 m, and the reflection of the fluorescent lamp on the surface of the evaluation sample was visually evaluated.
◯: The reflection image of the fluorescent lamp is strongly blurred and the outline of the fluorescent lamp cannot be confirmed.
Δ: The reflected image of the fluorescent lamp is blurred, but the outline can be confirmed slightly.
X: The reflected image of the fluorescent lamp is clear and its contour can be confirmed clearly.
＜硬化性＞
硬化性重合体組成物を、厚さ１００μｍのＰＥＴフィルム（三菱ケミカル（株）製、Ｏ３２１Ｅ１００）に＃７のバーコーターで塗布し、得られた塗膜を１００℃に加熱した熱風乾燥機で６０秒間乾燥を行った。乾燥後に、高圧水銀灯を用いて空気下、波長３００〜３９０ｎｍの積算光量が、岩崎電気株式会社製の照度計（アイ紫外線積算照度計 ＵＶＰＦ―Ａ１、ＰＤ−３６５）で測定した際に、２５０ｍＪ／ｃｍ２（２５０ｍＷ/Ｊ／ｃｍ２）となるように調整し紫外線照射を行った。硬化物表面のタック（粘着性）が無くなるまでの照射回数を測定することで、硬化性重合体組成物の硬化性を評価した。
○：照射回数１回（２５０ｍＪ／ｃｍ２）で硬化膜表面のタック性が無くなる
△：照射回数２回（５００ｍＪ／ｃｍ２）で硬化膜表面のタック性が無くなる
×：照射回数３回（７５０ｍＪ／ｃｍ２）でも硬化膜表面のタック性は無くならない。
<Curability>
The curable polymer composition was applied to a PET film having a thickness of 100 μm (O321E100 manufactured by Mitsubishi Chemical Co., Ltd.) with a #7 bar coater, and the obtained coating film was heated to 100° C. with a hot air drier 60. It was dried for 2 seconds. After drying, the integrated light amount of wavelength 300 to 390 nm was measured with an illuminometer manufactured by Iwasaki Electric Co., Ltd. (eye UV integrated illuminometer UVPF-A1, PD-365) under air using a high pressure mercury lamp to give 250 mJ/ It was adjusted to be cm 2 (250 mW/J/cm 2 ) and ultraviolet irradiation was performed. The curability of the curable polymer composition was evaluated by measuring the number of irradiations until the tack (adhesiveness) on the surface of the cured product disappeared.
○: tackiness of the cured film surface irradiation times one (250 mJ / cm 2) is lost △: irradiated 2 times (500 mJ / cm 2) tackiness of the cured film surface is eliminated by ×: number of irradiations 3 times (750 mJ /Cm 2 ) the tackiness of the cured film surface does not disappear.
＜紫外線活性基を有する重合体Ａ−１＞
撹拌機、冷却管及び温度計を備えたフラスコ中に、メチルイソブチルケトン（ＭＩＢＫ）７８．０部を入れて撹拌した。次いで、フラスコ内を窒素置換し６５℃に昇温してメチルメタクリレート（三菱ケミカル（株）製、商品名：アクリエステルＭ）３０．０部、ステアリルメタクリレート（三菱ケミカル（株）製、商品名：アクリルエステルＳ）２０．０部、４―メタクリロイルオキシベンゾフェノン（ＭＣＣユニテック（株）製）５０．０部、３−メルカプトプロピルトリメトキシシラン（信越化学工業（株）製、商品名：ＫＢＭ−８０３）３．０部、アゾビス（２,４−ジメチルバレロニトリル)（和光純薬工業（株）製、商品名：Ｖ−６５）１．０部、ＭＩＢＫ７８．０部の混合溶液を２時間かけて滴下した。さらに２時間後、アゾビス（２,４−ジメチルバレロニトリル)（和光純薬工業（株）製、商品名：Ｖ−６５）０．５部、ＭＩＢＫ０．６部の混合液を投入し、５時間保持した。その後、反応液を４０℃に冷却することで紫外線活性基を有する重合体Ａ−１を重合した。前記Ａ−１の固形分は４０％であり、重量平均分子量（Ｍｗ）は１０,７００であった。また、ガラス転移温度は９５℃であった。
<Polymer A-1 having ultraviolet active group>
In a flask equipped with a stirrer, a condenser and a thermometer, 78.0 parts of methyl isobutyl ketone (MIBK) was put and stirred. Next, the inside of the flask was replaced with nitrogen and the temperature was raised to 65° C., and 30.0 parts of methyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd., trade name: Acryester M), stearyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd., trade name: Acrylic ester S) 20.0 parts, 4-methacryloyloxybenzophenone (manufactured by MCC Unitech Co., Ltd.) 50.0 parts, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) A mixed solution of 3.0 parts, 1.0 part of azobis(2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd., trade name: V-65), and 78.0 parts of MIBK was added dropwise over 2 hours. did. After a further 2 hours, a mixed solution of 0.5 parts of azobis(2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd., trade name: V-65) and 0.6 parts of MIBK was put therein, and the reaction was continued for 5 hours. Held Then, the reaction liquid was cooled to 40° C. to polymerize the polymer A-1 having an ultraviolet active group. The solid content of A-1 was 40%, and the weight average molecular weight (Mw) was 10,700. The glass transition temperature was 95°C.
＜紫外線活性基を有する重合体Ａ−２＞
撹拌機、冷却管及び温度計を備えたフラスコ中に、メチルイソブチルケトン（ＭＩＢＫ）７８．０部を入れて撹拌した。次いで、フラスコ内を窒素置換し６５℃に昇温して２−エチルヘキシルメタクリレート（三菱ケミカル株式会社製、商品名：アクリエステルＥＨ）３０．０部、ステアリルメタクリレート（三菱ケミカル株式会社製、商品名：アクリルエステルＳ）１０．０部、ジメチルアミノエチルメタクリレート（三菱ケミカル株式会社製、商品名：アクリエステルＤＭ）１０．０部、２−ヒドロキシエチルメタクリレート（三菱ケミカル株式会社製、商品名：アクリルエステルＨＯ）１０．０部、４―メタクリロイルオキシベンゾフェノン（ＭＣＣユニテック株式会社製）４０．０部、３−メルカプトプロピルトリメトキシシラン（信越化学工業株式会社製、商品名：ＫＢＭ−８０３）３．０部、アゾビス（２,４−ジメチルバレロニトリル)（和光純薬工業株式会社製、商品名：Ｖ−６５）１．０部、ＭＩＢＫ７８．０部の混合溶液を２時間かけて滴下した。さらに２時間後、アゾビス（２,４−ジメチルバレロニトリル)（和光純薬工業株式会社製、商品名：Ｖ−６５）０．５部、ＭＩＢＫ０．６部の混合液を投入し、５時間保持した。その後、反応液を４０℃に冷却することで紫外線活性基を有する重合体Ａ−２を重合した。前記Ａ−２の固形分は４０％であり、重量平均分子量（Ｍｗ）は５,７００であった。また、ガラス転移温度は４６℃であった。
<Polymer A-2 having ultraviolet active group>
In a flask equipped with a stirrer, a condenser and a thermometer, 78.0 parts of methyl isobutyl ketone (MIBK) was put and stirred. Then, the inside of the flask was replaced with nitrogen and the temperature was raised to 65° C., and 30.0 parts of 2-ethylhexyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester EH) and stearyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acrylic ester S) 10.0 parts, dimethylaminoethyl methacrylate (Mitsubishi Chemical Co., Ltd., trade name: Acryester DM) 10.0 parts, 2-hydroxyethyl methacrylate (Mitsubishi Chemical Co., Ltd., trade name: Acrylic ester HO) ) 10.0 parts, 4-methacryloyloxybenzophenone (manufactured by MCC Unitech Co., Ltd.) 40.0 parts, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) 3.0 parts, A mixed solution of 1.0 part of azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) and 78.0 parts of MIBK was added dropwise over 2 hours. After 2 hours, a mixed solution of 0.5 parts of azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) and 0.6 parts of MIBK was added and kept for 5 hours. did. Then, the reaction liquid was cooled to 40° C. to polymerize the polymer A-2 having an ultraviolet active group. The solid content of A-2 was 40%, and the weight average molecular weight (Mw) was 5,700. The glass transition temperature was 46°C.
＜実施例１＞
撹拌子を備えたフラスコ中に、紫外線活性基を有する重合体ＡとしてＡ−１を固形分として２．５質量部、多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）（Ｅ型粘度計で測定した粘度６８５０ｍＰａ・ｓ）を固形分として９０．０質量部とペンタエリスリトールトリアクリレート（大阪有機化学工業(株)製 商品名：Ｖ＃３００）（Ｅ型粘度計で測定した粘度５００ｍＰａ・ｓ）を固形分として１０．０質量部、有機溶剤Ｃとして、プロピレングリコールモノメチルエーテル（ＰＧＭ）１０５．６質量部、メチルエチルケトン（ＭＥＫ）４５．３質量部を添加した後に均一になるまで撹拌を行い、硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す。
<Example 1>
In a flask equipped with a stirrer, 2.5 parts by mass of A-1 as a polymer A having an ultraviolet active group as a solid content and dipentaerythritol hexaacrylate as a polyfunctional acrylate B (manufactured by Nippon Kayaku Co., Ltd.) 90.0 parts by mass of pentaerythritol triacrylate (Osaka Organic Chemical Industry Co., Ltd. product name: V#300) (trade name: KAYARAD DPHA) (viscosity 6850 mPa·s measured by E-type viscometer) as solid content A viscosity of 500 mPa·s measured by an E-type viscometer is 10.0 parts by mass as a solid content, and as the organic solvent C, 105.6 parts by mass of propylene glycol monomethyl ether (PGM) and 45.3 parts by mass of methyl ethyl ketone (MEK). After the addition, the mixture was stirred until it became uniform to prepare a coating solution of the curable polymer composition. Table 1 shows the evaluation results of cured products of the obtained coating liquid.
＜実施例２＞
多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）を固形分として８０．０質量部とペンタエリスリトールトリアクリレート（大阪有機化学工業(株)製 商品名：Ｖ＃３００）を固形分として２０．０質量部とした以外は実施例１と同様に硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す。
<Example 2>
As the polyfunctional acrylate B, 80.0 parts by mass of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (trade name of Osaka Organic Chemical Industry Co., Ltd.) A coating solution of the curable polymer composition was prepared in the same manner as in Example 1 except that the solid content of V#300) was 20.0 parts by mass. Table 1 shows the evaluation results of cured products of the obtained coating liquid.
＜実施例３＞
多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）を固形分として７０．０質量部とペンタエリスリトールトリアクリレート（大阪有機化学工業(株)製 商品名：Ｖ＃３００）を固形分として３０．０質量部とした以外は実施例１と同様に硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す。
<Example 3>
As the polyfunctional acrylate B, 70.0 parts by mass of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (trade name of Osaka Organic Chemical Industry Co., Ltd.) A coating solution of the curable polymer composition was prepared in the same manner as in Example 1 except that the solid content of V#300) was 30.0 parts by mass. Table 1 shows the evaluation results of cured products of the obtained coating liquid.
＜実施例４＞
多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）を固形分として６０．０質量部とペンタエリスリトールトリアクリレート（大阪有機化学工業(株)製 商品名：Ｖ＃３００）を固形分として４０．０質量部とした以外は実施例１と同様に硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す。
<Example 4>
As the polyfunctional acrylate B, 60.0 parts by mass of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (trade name of Osaka Organic Chemical Industry Co., Ltd.) A coating liquid of the curable polymer composition was prepared in the same manner as in Example 1 except that the solid content of V#300) was 40.0 parts by mass. Table 1 shows the evaluation results of cured products of the obtained coating liquid.
＜実施例５＞
多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）を固形分として８０．０質量部とペンタエリスリトールトリアクリレート（大阪有機化学工業(株)製 商品名：Ｖ＃３００）を固形分として２０．０質量部とした以外は実施例５と同様に硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す。
<Example 5>
As the polyfunctional acrylate B, 80.0 parts by mass of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (trade name of Osaka Organic Chemical Industry Co., Ltd.) A coating liquid of the curable polymer composition was prepared in the same manner as in Example 5 except that the solid content of V:300 was 20.0 parts by mass. Table 1 shows the evaluation results of cured products of the obtained coating liquid.
＜実施例６＞
多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）を固形分として６０．０質量部とペンタエリスリトールトリアクリレート（大阪有機化学工業(株)製 商品名：Ｖ＃３００）を固形分として４０．０質量部とした以外は実施例５と同様に硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す
<Example 6>
As the polyfunctional acrylate B, 60.0 parts by mass of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (trade name of Osaka Organic Chemical Industry Co., Ltd.) A coating solution of the curable polymer composition was prepared in the same manner as in Example 5 except that the solid content of V:300 was 40.0 parts by mass. The evaluation results of the cured product of the obtained coating liquid are shown in Table 1.
＜比較例１＞
撹拌子を備えたフラスコ中に、紫外線活性基を有する重合体ＡとしてＡ−１を固形分として２．５質量部、多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）（Ｅ型粘度計で測定した粘度６８５０ｍＰａ・ｓ）を固形分として１００．０質量部、有機溶剤Ｃとして、プロピレングリコールモノメチルエーテル（以下、ＰＧＭ）１０５．６質量部、メチルエチルケトン（以下、ＭＥＫ）４５．３質量部添加した後に均一になるまで撹拌を行い、硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す。
<Comparative Example 1>
In a flask equipped with a stirrer, 2.5 parts by mass of A-1 as a polymer A having an ultraviolet active group as a solid content and dipentaerythritol hexaacrylate as a polyfunctional acrylate B (manufactured by Nippon Kayaku Co., Ltd.) Brand name: KAYARAD DPHA) (viscosity measured with an E-type viscometer: 6850 mPa·s) is 100.0 parts by mass as a solid content, and propylene glycol monomethyl ether (hereinafter, PGM) is 105.6 parts by mass as an organic solvent C and methyl ethyl ketone. (Hereinafter, MEK) After adding 45.3 parts by mass, the mixture was stirred until it became uniform to prepare a coating solution of the curable polymer composition. Table 1 shows the evaluation results of cured products of the obtained coating liquid.
＜比較例２＞
撹拌子を備えたフラスコ中に、紫外線活性基を有さない重合体として三菱ケミカル株式会社製 ダイヤナールＢＲ８０を固形分として１０．０質量部、アクリル系微粒子として綜研化学株式会社製ＭＸ−３００を固形分として１０．０質量部、多官能のアクリレートＢとしてジペンタエリスリトールヘキサアクリレート（日本化薬(株)製 商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ）を固形分として８０．０質量部、光開始剤としてＩＧＭ Ｒｅｓｉｎｓ社製 Ｏｍｎｉｒａｄ１２７を固形分として３．０質量部、有機溶剤Ｃとして、プロピレングリコールモノメチルエーテル（以下、ＰＧＭ）１７３．３質量部、メチルエチルケトン（以下、ＭＥＫ）６０．０質量部添加した後に均一になるまで撹拌を行い、硬化性重合体組成物の塗布液を調製した。得られた塗布液の硬化物の評価結果を表１に示す。
<Comparative example 2>
In a flask equipped with a stir bar, 10.0 parts by mass of DIANYL BR80 manufactured by Mitsubishi Chemical Co., Ltd. as a polymer having no UV active group as a solid content, and MX-300 manufactured by Soken Chemical Co., Ltd. as acrylic fine particles are used. 10.0 parts by mass as a solid content, 80.0 parts by mass as a solid content of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) as a polyfunctional acrylate B, and IGM Resins as a photoinitiator. 3.0 parts by mass of Omnirad 127 manufactured by the same company as a solid content, 173.3 parts by mass of propylene glycol monomethyl ether (hereinafter, PGM) as an organic solvent C, and 60.0 parts by mass of methyl ethyl ketone (hereinafter, MEK) become uniform after addition. Stirring was performed until a curable polymer composition coating solution was prepared. Table 1 shows the evaluation results of cured products of the obtained coating liquid.
比較例１では、多官能（メタ）アクリレートＢの粘度が高いため、硬化物の表面の算術平均粗さＲａが小さくなり、艶消し性が得られなかった。
比較例２では、しわ状の構造が得られず、艶消し性が得られず、ぎらつきの抑制が不十分であった。
In Comparative Example 1, since the viscosity of the polyfunctional (meth)acrylate B was high, the arithmetic average roughness Ra of the surface of the cured product was small, and the matte property was not obtained.
In Comparative Example 2, a wrinkle-like structure was not obtained, matteness was not obtained, and the suppression of glare was insufficient.
Claims (7)
前記硬化物の表面の算術平均粗さＲａが０．０１μｍ以上である硬化物。 A cured product having a wrinkled structure on the surface,
A cured product having an arithmetic average roughness Ra of 0.01 μm or more on the surface of the cured product.
表面側の層の厚さが３００ｎｍ以下であり、
他の層の合計が、３００ｎｍより大きい請求項１から請求項４のいずれか１項に記載の硬化物。 The cured product has a structure of two or more layers having different crosslink densities in the thickness direction,
The thickness of the surface layer is 300 nm or less,
The cured product according to any one of claims 1 to 4, wherein the total of the other layers is larger than 300 nm.
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| JP7363034B2 (en) | 2023-10-18 |
| JP2023143995A (en) | 2023-10-06 |
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