JP7363034B2 - cured product - Google Patents
cured product Download PDFInfo
- Publication number
- JP7363034B2 JP7363034B2 JP2019005781A JP2019005781A JP7363034B2 JP 7363034 B2 JP7363034 B2 JP 7363034B2 JP 2019005781 A JP2019005781 A JP 2019005781A JP 2019005781 A JP2019005781 A JP 2019005781A JP 7363034 B2 JP7363034 B2 JP 7363034B2
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- JP
- Japan
- Prior art keywords
- meth
- acrylate
- cured product
- parts
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- 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.)
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 131
- 229920000642 polymer Polymers 0.000 claims description 82
- 239000000126 substance Substances 0.000 claims description 23
- 238000002834 transmittance Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 3
- 206010027339 Menstruation irregular Diseases 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 48
- 238000000576 coating method Methods 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 31
- -1 etc. Substances 0.000 description 30
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 239000000178 monomer Substances 0.000 description 17
- 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
- 238000011156 evaluation Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 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
- 238000005259 measurement 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
- 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
- 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
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate 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
- 230000004313 glare Effects 0.000 description 4
- 239000003999 initiator 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
- 238000003756 stirring Methods 0.000 description 4
- 238000010998 test method Methods 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
- 238000006243 chemical reaction Methods 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
- 239000011259 mixed solution Substances 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
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002344 surface layer Substances 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
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 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
- 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
- 238000012937 correction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 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
- 239000010419 fine particle 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
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 238000000465 moulding Methods 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
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 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
- 238000012545 processing Methods 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
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 229940042596 viscoat Drugs 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
- 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
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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。 TECHNICAL FIELD The present invention relates to a cured product having a wrinkle-like surface structure that is excellent in matte properties and light diffusing properties and can suppress 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 applications such as architectural construction materials such as wallpaper, displays, decorative films, etc., fine particles are applied to the surface of the base material in order to impart matte properties, light diffusion properties, unevenness, etc., and improve visibility and design. It is practiced to provide roughness.
For example, Patent Document 1 describes the use of hairline processing and transfer foil films for manufacturing decorative sheets for building materials, home appliances such as refrigerators and washing machines, various parts and packaging containers for OA products such as computers, and packaging containers. A method of providing an uneven shape by sandblasting, satin finishing, etc. is disclosed.
Further, 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, hairline processing and satin finishing described in Patent Document 1 do not provide a sufficient matte effect, and sandblasting may cause quality problems due to sand remaining in the film.
Furthermore, in the method described in Patent Document 2, the acrylic particles may fall off during use, which may impede 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 resides in a cured product having a wrinkle-like structure on its surface, the arithmetic mean roughness Ra of the surface of the cured product being 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 cured product of the present invention suppresses glare, provides a surface with excellent matte properties, and can improve the visibility, design, etc. of surfaces of architectural materials, display-related materials, decorative films, 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 wrinkle-like structure on the surface. In the present invention, the wrinkled structure is generally known as a wrinkle structure, which is an uneven structure on waves obtained by buckling the surface layer, and refers to, for example, a labyrinth-like structure as shown in FIG.
In the present invention, the arithmetic mean roughness Ra of the surface of the cured product is 0.01 μm or more.
If the arithmetic mean roughness Ra is 0.01 μm or less, the matting properties will be insufficient.
The arithmetic mean roughness Ra is preferably 0.05 μm or more and 2 μm or less from the viewpoint of achieving both scratch resistance and matte property of the cured product.
Further, 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, more preferably 5° or more and 17° or less, from the viewpoint of achieving both scratch resistance and matte property of the cured product. , more preferably 7° or more and 15° or less.
The inclination angle θa is preferably lower from the viewpoint of scratch resistance of the cured product of the present invention, and preferably higher from the viewpoint of matte property.
Furthermore, the irregularity period (average length of roughness curve elements) 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 still more preferably 3 μm or more and 15 μm or less. When the Rsm exceeds 30 μm, surface glare becomes a problem when the cured product of the present invention is used as an antiglare film, and when it is lower 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, and more preferably 0.2 μm or more and 4 μm or less, from the viewpoint of achieving both scratch resistance and matte property of the cured product. Preferably it is 0.5 μm or more and 3 μm or less.
The Rz is preferably lower from the viewpoint of scratch resistance of the cured product of the present invention, and higher from the viewpoint of matte property.
The arithmetic mean roughness Ra, average length Rsm, maximum height Rz, and inclination angle θa of the wrinkled structure in the present invention are values measured by optical interferometry in accordance with JIS B 0601-2001.
The measurement was carried out using a surface shape measurement 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. , performed imputation and baseline correction, and read the data. Note that the magnification of the objective lens during the measurement was set to 20 times.
In addition, the 60° glossiness of the cured product having a wrinkled structure of the present invention is 1 or more and 90 or less, more preferably 3 or more and 70 or less, and even more preferably 5 or more and 50 or less, from the viewpoint of achieving both matteness and transparency. It is.
Further, when the cured product having a wrinkled structure of the present invention is used for applications requiring transparency such as an anti-glare 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, still more preferably 50% or more and 90% or less, from the viewpoint of achieving both transparency and matteness of the cured product. The haze is preferably higher from the viewpoint of matte properties, and lower from the viewpoint of transparency.
Further, from the viewpoint of achieving both transparency and matte properties of the cured product, the total light transmittance is preferably 85% or more and 99% or less, preferably 87% or more and 97% or less, and more preferably 89% or more and 95% or less. It is. The total light transmittance is preferably higher from the viewpoint of transparency, and lower from the viewpoint of matteness.
The above haze and total light transmittance are determined according to JIS Z8722 (Geometric conditions for irradiation and light reception of transparent objects) and JIS K7361-1 (Test method for total light transmittance of plastics-transparent materials) and JIS K7136 (Test method for total light transmittance of plastics-transparent materials). This is a measured value at a wavelength of 550 nm using SH7000 manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with the method for determining 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.
By setting the thickness of the layer on the surface side to 300 nm or less and making the total thickness of the other layers larger than 300 nm, it is possible to ensure good transparency and develop a wrinkle-like uneven structure on the surface. can.
The cross-sectional structure can be confirmed using, for example, a transmission electron microscope (TEM), a phase mode of a scanning probe microscope (SPM), a nano-infrared spectrophotometer, a Raman microscope, or the like. For observation with a TEM, after fixing the surface layer of the cured product with an adhesive (Loctite, manufactured by Henkel Japan Ltd.), a vertical section with a thickness of 100 nm was prepared using an ultramicrotome, and a transmission electron microscope (Hitachi Ltd.) was used. The test was carried out using a TEM H7600 model manufactured by Hi-Technologies Corporation.
In the cross-sectional structure, the two layers having different crosslinking densities in the thickness direction are the polymer A having ultraviolet active groups in the outermost layer of the cured film, and the polyfunctional (meth)acrylate in the second layer from the outermost surface. It is formed by arranging B. Therefore, both of the two layers having different crosslink densities in the thickness direction are 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 a method for producing a cured product of the present invention will be shown.
The wrinkle-like structure of the cured product of the present invention is caused by the shrinkage stress caused by the surface of the coating film being cured first to form a cured film when the curable polymer composition is cured, and then the inside of the coating film being cured. It is thought that this causes the hardened film on the surface to shrink and develop.
The wrinkle-like structure of the cured product of the present invention can be obtained by increasing the irradiation intensity of active energy rays and shortening the curing time of the curable composition. A larger wrinkled structure can be obtained by decreasing the curing time of the curable composition and increasing the curing time of the curable composition.
Furthermore, the wrinkle-like structure of the cured product of the present invention can be obtained by increasing the viscosity of the curable composition excluding the solvent and reducing the fluidity. A larger wrinkled structure can be obtained by lowering the viscosity excluding the solvent and improving 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 can be obtained, for example, by applying a curable polymer composition containing a polymer A having an ultraviolet active group, a polyfunctional (meth)acrylate B, and an organic solvent C to a base material, and then drying it with hot air to remove the solvent. It can be obtained by distilling off and irradiating it 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 preferred as the active energy rays.
Examples of sources of ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electrodeless UV lamps using magnetrons, LEDs, and the like.
The atmosphere for curing the curable polymer composition includes air, nitrogen, inert gas such as argon, and the like. From the viewpoint of practicality and economy, air or nitrogen is preferred. When using ultraviolet rays as active energy rays, preferred curing conditions include, for example, irradiation using a high-pressure mercury lamp such that the cumulative amount of light with 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 that can crosslink the polyfunctional acrylate and the polymer A itself by irradiation with active energy rays. Among these, those that generate radicals through intramolecular cleavage reactions, hydrogen abstraction reactions, electron transfer reactions, etc. upon irradiation with active energy rays such as ultraviolet rays are preferred.
In the present invention, the generated radicals can react with polyfunctional (meth)acrylate B to form a crosslinked structure.
The ultraviolet active group usually includes a benzophenone group, acetophenone group, benzoin group, α-hydroxyketone group, α-aminoketone group, α-diketone group, α-diketone dialkyl acetal group, anthraquinone group, Examples include thioxanthone group, phosphine oxide group, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one) group, and the curable polymer of the present invention Benzophenone groups and acetophenone groups are preferred because they are less likely to be inhibited by oxygen 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 the ultraviolet active group.
The monomers having the ultraviolet active group include benzophenones, acetophenones, benzoins, α-hydroxyketones, α-aminoketones, α-diketones, α-diketone dialkyl acetals, anthraquinones, thioxanthones, Examples include compounds in which an unsaturated double bond is 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 including repeating units derived from (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 surface side becomes high, A wrinkle-like uneven structure is likely to appear on the surface of the cured product.
The polymer A is obtained by copolymerizing a monomer mixture containing the (meth)acrylic acid ester having the 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 Unitec Co., Ltd., and EBECRYL P36 and EBECRYL P37 manufactured by ALLNEX.
Further, the monomer having the ultraviolet active group is 2-(meth)acryloyloxyethyl isocyanate and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane. A method of adding -1-one, or a method of adding 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1- to (meth)acrylic anhydride or (meth)acrylic acid chloride. It can be prepared by adding 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 can be obtained by (co)polymerizing a monomer having a UV-active group and a monomer not having a UV-active group by a general polymerization method such as a solution polymerization method or a suspension polymerization method. can be manufactured. Solution polymerization is preferred because it is easy to operate and has high productivity.
Moreover, it is preferable that the polymer A 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 containing repeating units derived from (meth)acrylic acid esters that do not have an alkyl group having 4 or more carbon atoms and do not have an ultraviolet active group. When this is done, the concentration of the polymer A on the surface of the cured product increases, making it easier to develop a wrinkled uneven structure.
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 even more preferable.
Examples of the monomer having an alkyl group having 4 or more carbon atoms and not having 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 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 preferred because they increase the concentration of the polymer A on the surface of the cured product and develop a wrinkled uneven structure.
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, an amide group, etc., in order to perform 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 even more 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 with 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, A monomer having an amino group or an amide group such as N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine, vinyl acetamide, etc. Examples include quantitative substances. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (N, N-dimethylacrylamide, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate are preferred.
The polymer A may contain other repeating units other than those mentioned above, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, phenyldioxyethyl (meth)acrylate, nonyl Even if it contains structural units derived from monomers such as phenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, morpholine (meth)acrylate, and ethyl carbitol (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 determined from the viewpoints of ensuring the curability and productivity of the curable polymer composition and forming a wrinkled uneven structure well. 0.3 mmol/g or more and 3.0 mmol/g or less is preferable.
Further, the weight average molecular weight of the polymer A is preferably 1,000 or more and 500,000 or less. When applying the curable polymer composition to a substrate and curing it, the concentration of the polymer A on the surface side of the coating film increases, and the surface of the cured product tends to develop a wrinkle-like uneven structure. It is more preferably 2,000 or more and 100,000 or less, and even 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 measured by gel permeation chromatography (GPC method) in terms of standard polystyrene.
The weight average molecular weight can be measured under the following measurement conditions.
(GPC measurement conditions)
Column: "TSK-gel superHZM-M", "TSK-gel HZM-M", "TSK-gel HZ2000"
Eluent: THF
Flow rate: 0.35mL/min
Injection volume: 10μL
Column temperature: 40℃
Detector: UV-8020
The glass transition temperature of Polymer A is -30°C in that the Polymer A having ultraviolet active groups is concentrated at the air layer interface during hot air drying, and a wrinkle-like uneven structure is likely to appear on the surface when irradiated with active energy rays. The temperature is preferably 130°C or higher, more preferably 0°C or higher and 110°C or lower, and more preferably 25°C or higher and 100°C or lower.
In the present invention, the glass transition temperature is a value calculated using a relational expression of the glass transition temperature Tg (° C.) of a copolymer according to the following Fox equation.
1/(273+Tg)=Σ{Wi/(273+Tgi)}
Wi: Mass fraction of monomer i Tgi: Tg of homopolymer of monomer i (°C)
Note that the glass transition temperature of the homopolymer is a value using the numerical value described in "Polymer Handbook, 4th Edition, by 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 0.00 parts by mass per 100 parts by mass of the curable polymer composition in order to impart an uneven shape to the surface of the cured product and to improve UV curability. It 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 even more 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. Polyfunctional (meth)acrylate B has the effect of increasing the hardness of the resulting cured product and the curability of the curable polymer composition.
The polyfunctional (meth)acrylate B includes 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 ) 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)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, dimethylolpropane tetra(meth)acrylate, tripentaerythritol (meth)acrylate, and other polyfunctional (meth)acrylates. In addition, alkyl-modified (meth)acrylates, caprolactone-modified (meth)acrylates, ethylene oxide-modified (meth)acrylates, propylene oxide-modified (meth)acrylates of the above compounds, and (meth)acrylates of aliphatic polyols other than the above, Examples include dendritic aliphatic compounds having acrylate groups at the ends, which are called dendrimers or hyperbranched polymers. Examples of commercially available dendritic aliphatic compounds having an acrylate group at the end include Viscoat V#1000, V#5020, and STAR-501 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.). The above 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, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. Erythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, dimethylolpropane tri(meth)acrylate, tripentaerythritol(meth)acrylate, Viscoat V#1000, V #5020, STAR-501, etc. are preferred.
Further, in order to improve the curability of the curable polymer composition, the content of the polyfunctional (meth)acrylate B is 80.0 parts by mass or more and 99.0 parts by mass or more based on 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 even more 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。
Furthermore, the curable composition of the present invention has a viscosity of 3.0 mPa when the components excluding the ultraviolet active group-containing polymer A and the organic solvent C are measured with an E-type viscometer at 25°C. - It is preferable to adjust the pressure so that it is not less than s and not more than 30,000 mPa·s. More preferably, it is 5.0 mPa·s or more and 20,000 mPa·s or less, and even more preferably 10 mPa·s or more and 6,500 mPa·s or less.
The preferred range of the viscosity depends on the temperature of the atmosphere during irradiation with active energy rays, but by setting the viscosity to 30,000 mPa·s or less, the arithmetic mean roughness Ra of the surface of the cured product can be reduced to 0. It can be set to 0.01 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。
Furthermore, in the present invention, by including the organic solvent C, the workability when applying the curable polymer composition of the present invention to a substrate is improved.
The organic solvent C includes aromatic solvents such as toluene and xylene; ketone solvents 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, and phenetol; Ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone Amide solvents such as; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; halogen solvents such as dichloromethane and 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 preferred from the viewpoint of improving workability during 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, from the viewpoint of improving the operability in the coating operation based on 100 parts by mass of the curable polymer composition. The following are more preferred.
Furthermore, 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 for the purpose of promoting curability, photopolymerization with a weight average molecular weight of 1000 or less is used. An initiator 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, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3' -dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-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, tribromomethyl phenyl sulfone, and the like.
The photopolymerization initiator is preferably added to the extent that it does not cause curing prior to 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, even more preferably 1 part by mass or less, and 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。
A monofunctional (meth)acrylate having one unsaturated double bond in one molecule can be added to the curable polymer composition in order to adjust the viscosity and the curing speed by active energy rays.
The monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acrylate, and octyl (meth)acrylate. 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 ) 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 ) acrylate, etc.
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。 A leveling agent may be added to the curable polymer composition 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. Moreover, the leveling agent may be used alone or in combination of two or more types.
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。
When the matting properties of the curable polymer composition are further improved, organic or inorganic particles having an average primary particle diameter of 0.01 μm or more and 10 μm or less can be added to the curable polymer composition to further improve the matting properties. A cured product with matte properties can be obtained. Two or more kinds of the organic particles and the inorganic particles may be used.
Furthermore, the inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The surface-modified particles can be obtained by, for example, reacting a polymer and an inorganic particle at 25° C. to 120° C. for about 1 hour to 24 hours in the presence of an acid, a base, or a silane coupling reaction catalyst such as aluminum acetylacetonate. .
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 may contain a polymerization accelerator such as a compound containing a thiol group, an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, etc., within a range that does not impair the effects of the present invention. 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 base material, drying the resulting cured product, and irradiating it with ultraviolet rays.
As the base material, various polymer films, polymer plates, polymer moldings, etc. 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, and polyurethane polymer film. , polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth)acrylonitrile film, cycloolefin polymer (COP) film, stretched polypropylene film, unstretched polypropylene film, and the like. In addition, examples of polymer plates and polymer moldings include acrylic plates, triacetyl cellulose plates, polyethylene terephthalate plates, diacetylene cellulose plates, acetate butyrate cellulose plates, polyether sulfone plates, polyurethane plates, polycarbonate plates, polysulfone plates, Examples include polyether plates, polymethylpentene plates, polyetherketone plates, (meth)acrylonitrile plates, and the like. Further, glass or the like may be used as necessary. The thickness of the base material can be appropriately selected depending on the application, but generally a thickness of about 25 μm to 1,0000 μm is used.
The coating method is not particularly limited, but coating may be performed by dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, spray coating, or the like. 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。
It is preferable to dry the curable polymer composition by heating it in advance before curing the curable polymer composition. When drying by heating before curing the applied coating film, the temperature is preferably 30°C or more and 200°C or less, more preferably 40°C or more and 150°C or less. Further, the drying time is preferably 0.01 minutes or more and 30 minutes or less, and 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 applying the curable polymer composition of the present invention to a substrate and curing it, it is possible to The concentration of polymer A becomes high, and the surface of the cured product becomes more likely to develop a wrinkle-like uneven structure.
From the viewpoint of productivity, the ultraviolet rays are preferably irradiated so that the cumulative amount of light is 100 mJ/cm 2 or more and 3000 mJ/cm 2 or less. As a 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, or an electron beam using a scanning or curtain-type electron beam acceleration path, or a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a low-pressure mercury lamp. I can do it.
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。
EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Note that the evaluation was performed by the following method.
<Evaluation method>
<Evaluation sample>
The coating solution of the curable polymer composition was applied to a 100 μm thick PET film (Mitsubishi Chemical Corporation, O321E100) using a #7 bar coater, and the resulting coating film was dried with hot air heated to 100°C. The solvent was evaporated by drying in a machine for 60 seconds. Next, the coating film was cured in air using a high-pressure mercury lamp using a UV conveyor manufactured by Eye Graphics Co., Ltd., and an evaluation sample was obtained.
For curing by ultraviolet rays, the cumulative amount of light with a wavelength of 300 to 390 nm is 250 mJ/cm 2 (250 mW/J) when measured with an illuminance meter (I UVF-A1, PD-365) manufactured by Iwasaki Electric Co., Ltd. /cm 2 ), and 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>
Haze and total light transmittance are determined according to JIS Z8722Z (geometric conditions for irradiation and light reception of transparent objects), JIS K7361-1 (test method for total light transmittance of plastic transparent materials), and JIS K7136 (test method for plastic transparent materials). The value at a wavelength of 550 nm was measured using SH7000 manufactured by Nippon Denshoku Kogyo (Nippon Denshoku Kogyo).
＜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>
In accordance with JIS Z 8741, 60° specular gloss (60° gloss) was measured using a gloss meter VG2000 manufactured by Nippon Denshoku Industries.
＜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, maximum height Rz, arithmetic mean roughness Ra, and inclination angle θa of the roughness curve elements were determined by hardening using a surface shape measurement system (Hitachi High-Technologies Corporation "VertScan" (registered trademark) R5500). On the surface of things, 237. The surface unevenness in a rectangular area measuring 237.65 μm in length and 178.25 μm in width was measured by optical interference method, interpolation and baseline correction were performed, and the data was read. Note that the magnification of the objective lens during the 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-sectional 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 with a thickness of 100 nm was prepared using an ultramicrotome. The prepared sections were 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 lit with fluorescent light, the distance between the fluorescent light and the evaluation sample was set at 2.5 m, and the reflection of the fluorescent light on the surface of the evaluation sample was visually evaluated.
○: The reflected image of the fluorescent light is strongly blurred, and the outline of the fluorescent light cannot be confirmed.
Δ: The reflected image of the fluorescent light is blurred, but the outline can be seen faintly.
×: The reflected image of the fluorescent light is clear and the outline can be clearly confirmed.
＜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 100 μm thick PET film (manufactured by Mitsubishi Chemical Corporation, O321E100) using a #7 bar coater, and the resulting coating film was dried for 60 minutes in a hot air dryer heated to 100°C. Drying was performed for seconds. After drying, the cumulative amount of light at a wavelength of 300 to 390 nm was measured in air using a high-pressure mercury lamp with an illuminance meter manufactured by Iwasaki Electric Co., Ltd. (I UVF-A1, PD-365), and the cumulative amount of light was 250 mJ/ 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 surface of the cured product became tack free.
○: The tackiness of the cured film surface disappears after 1 irradiation (250 mJ/cm 2 ) △: The tackiness of the cured film surface disappears after 2 irradiations (500 mJ/cm 2 ) ×: 3 irradiations (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>
78.0 parts of methyl isobutyl ketone (MIBK) was placed in a flask equipped with a stirrer, a condenser, and a thermometer 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 Corporation, trade name: Acryester M) and stearyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acrylic ester S) 20.0 parts, 4-methacryloyloxybenzophenone (manufactured by MCC Unitec 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 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. did. After another 2 hours, a mixed solution of 0.5 part of azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) and 0.6 part of MIBK was added, and for 5 hours held. Thereafter, the reaction solution was cooled to 40° C. to polymerize a 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. Further, 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>
78.0 parts of methyl isobutyl ketone (MIBK) was placed in a flask equipped with a stirrer, a condenser, and a thermometer and stirred. Next, the inside of the flask was replaced with nitrogen, 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 Corporation, trade name: Acryester DM) 10.0 parts, 2-hydroxyethyl methacrylate (Mitsubishi Chemical Corporation, trade name: Acrylic ester HO) ) 10.0 parts, 4-methacryloyloxybenzophenone (manufactured by MCC Unitec 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 another 2 hours, a mixture of 0.5 part of azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) and 0.6 part of MIBK was added and kept for 5 hours. did. Thereafter, the reaction solution was cooled to 40° C. to polymerize a 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. Moreover, 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 stirring bar, 2.5 parts by mass of A-1 as a solid content as a polymer A having an ultraviolet active group, and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional acrylate B. Product name: KAYARAD DPHA) (viscosity 6850 mPa・s measured with an E-type viscometer) as a solid content of 90.0 parts by mass and pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name: V#300) ( The solid content (viscosity 500 mPa s measured with an E-type viscometer) was 10.0 parts by mass, the organic solvent C was 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, stirring was performed until the mixture became uniform, thereby preparing a coating solution of the curable polymer composition. Table 1 shows the evaluation results of the cured product 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 polyfunctional acrylate B, 80.0 parts by mass of dipentaerythritol hexaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) A coating liquid of a curable polymer composition was prepared in the same manner as in Example 1, except that the solid content was 20.0 parts by mass. Table 1 shows the evaluation results of the cured product 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 polyfunctional acrylate B, 70.0 parts by mass of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a solid content and pentaerythritol triacrylate (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) were used. A coating liquid of a curable polymer composition was prepared in the same manner as in Example 1, except that the solid content was 30.0 parts by mass. Table 1 shows the evaluation results of the cured product 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 polyfunctional acrylate B, 60.0 parts by mass of dipentaerythritol hexaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) A coating liquid of a curable polymer composition was prepared in the same manner as in Example 1, except that the solid content was 40.0 parts by mass. Table 1 shows the evaluation results of the cured product 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 polyfunctional acrylate B, 80.0 parts by mass of dipentaerythritol hexaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) A coating liquid of a curable polymer composition was prepared in the same manner as in Example 5, except that the solid content was 20.0 parts by mass. Table 1 shows the evaluation results of the cured product 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 polyfunctional acrylate B, 60.0 parts by mass of dipentaerythritol hexaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as solid content and pentaerythritol triacrylate (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) A coating liquid of a curable polymer composition was prepared in the same manner as in Example 5, except that the solid content 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 stirring bar, 2.5 parts by mass of A-1 as a solid content as a polymer A having an ultraviolet active group, and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional acrylate B. Product name: KAYARAD DPHA) (viscosity 6850 mPa・s measured with an E-type viscometer) as solid content: 100.0 parts by mass, organic solvent C: propylene glycol monomethyl ether (hereinafter referred to as PGM) 105.6 parts by mass, methyl ethyl ketone (hereinafter referred to as MEK) was added in an amount of 45.3 parts by mass and stirred until uniform, thereby preparing a coating liquid of a curable polymer composition. Table 1 shows the evaluation results of the cured product 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 stirring bar, 10.0 parts by mass of Dianal BR80 (manufactured by Mitsubishi Chemical Corporation) as a solid content as a polymer having no ultraviolet active group, and MX-300 (manufactured by Soken Chemical Co., Ltd.) as acrylic fine particles were added. 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., product name: KAYARAD DPHA) as polyfunctional acrylate B, IGM Resins as a photoinitiator. After adding 3.0 parts by mass of Omnirad 127 manufactured by Omnirad 127 as solid content, 173.3 parts by mass of propylene glycol monomethyl ether (hereinafter referred to as PGM) and 60.0 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) as organic solvent C, it becomes uniform. A coating solution of a curable polymer composition was prepared. Table 1 shows the evaluation results of the cured product 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 polyfunctional (meth)acrylate B was high, the arithmetic mean roughness Ra of the surface of the cured product was small, and matte properties could not be obtained.
In Comparative Example 2, a wrinkled structure was not obtained, matte properties were not obtained, and glare was insufficiently suppressed.
Claims (7)
表面の算術平均粗さＲａが０．０１μｍ以上であり、紫外線活性基を有する重合体Ａ及び多官能（メタ）アクリレートＢを含有し、前記重合体Ａが（メタ）アクリル酸エステル由来の繰り返し単位を含み、前記重合体Ａの重量平均分子量が２０００以上１０００００以下である硬化物。 A cured product having a wrinkle-like structure on the surface and a total light transmittance of 85% or more,
The surface has an arithmetic mean roughness Ra of 0.01 μm or more, contains a polymer A having an ultraviolet active group and a polyfunctional (meth)acrylate B , and the polymer A is a repeating unit derived from a (meth)acrylic acid ester. A cured product comprising: the polymer A having a weight average molecular weight of 2,000 or more and 100,000 or less.
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３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 with different crosslinking densities in the thickness direction,
The thickness of the layer on the surface side is 300 nm or less,
The cured product according to any one of claims 1 to 3, wherein the total thickness of the other layers is larger than 300 nm.
前記硬化物の最表面をなす１番目の層は、前記硬化物の最表面から２番目の層より、前記重合体Ａの濃度が高い、請求項１から請求項３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 with different crosslinking densities in the thickness direction,
According to any one of claims 1 to 3, the first layer forming the outermost surface of the cured product has a higher concentration of the polymer A than the second layer from the outermost surface of the cured product. cured product.
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