JP2008247940A - Water-soluble photoinitiator, and photopolymerizable/crosslinkable composition comprising the same - Google Patents
Water-soluble photoinitiator, and photopolymerizable/crosslinkable composition comprising the same Download PDFInfo
- Publication number
- JP2008247940A JP2008247940A JP2007087237A JP2007087237A JP2008247940A JP 2008247940 A JP2008247940 A JP 2008247940A JP 2007087237 A JP2007087237 A JP 2007087237A JP 2007087237 A JP2007087237 A JP 2007087237A JP 2008247940 A JP2008247940 A JP 2008247940A
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- compound
- soluble
- meth
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- -1 sulfonic acid salt Chemical class 0.000 abstract description 27
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 150000001734 carboxylic acid salts Chemical class 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000000049 pigment Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000006185 dispersion 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
- 238000001723 curing Methods 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 239000012965 benzophenone Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000005641 methacryl group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical class N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 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
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005907 ketalization reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- 0 *C(C(c1ccccc1)=O)(c1ccccc1)O* Chemical compound *C(C(c1ccccc1)=O)(c1ccccc1)O* 0.000 description 1
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical class C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- DSQSKFCQCCTXCD-UHFFFAOYSA-N 1,4-diethylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(CC)=CC=C2CC DSQSKFCQCCTXCD-UHFFFAOYSA-N 0.000 description 1
- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 1
- UWSLXWIOAMSNGU-UHFFFAOYSA-N 1-chloro-2-propan-2-yloxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(Cl)C(OC(C)C)=CC=C3SC2=C1 UWSLXWIOAMSNGU-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- CTWRMVAKUSJNBK-UHFFFAOYSA-N 2-(2,4-dimethoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 CTWRMVAKUSJNBK-UHFFFAOYSA-N 0.000 description 1
- RXAYEPUDXSKVHS-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(3-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC(C2=C(NC(=N2)C=2C(=CC=CC=2)Cl)C=2C=C(OC)C=CC=2)=C1 RXAYEPUDXSKVHS-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SNFCQJAJPFWBDJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 SNFCQJAJPFWBDJ-UHFFFAOYSA-N 0.000 description 1
- BUWHNKZFUTUGJW-UHFFFAOYSA-N 2-(4-methoxyphenyl)-5-phenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC=C(C=2C=CC=CC=2)N1 BUWHNKZFUTUGJW-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- VZMLJEYQUZKERO-UHFFFAOYSA-N 2-hydroxy-1-(2-methylphenyl)-2-phenylethanone Chemical compound CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 VZMLJEYQUZKERO-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XUDUTRMKKYUAKI-UHFFFAOYSA-N 3-[1-(1-phenylethyl)piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound C1CC(N2C(NC3=CC=CC=C32)=O)CCN1C(C)C1=CC=CC=C1 XUDUTRMKKYUAKI-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000010953 Ames test Methods 0.000 description 1
- 231100000039 Ames test Toxicity 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000562 Poly(ethylene adipate) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ARNIZPSLPHFDED-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 ARNIZPSLPHFDED-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- NJVHCUNZAMFQNA-UHFFFAOYSA-N azane;n-hydroxy-n-phenylnitrous amide Chemical compound N.O=NN(O)C1=CC=CC=C1 NJVHCUNZAMFQNA-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- ZTHZCEHSJHFZBS-UHFFFAOYSA-N butane-1,1-diol;phthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=CC=C1C(O)=O ZTHZCEHSJHFZBS-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical group C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- QYZOHCUQJUKDLD-UHFFFAOYSA-N hexane-1,1-diol;phthalic acid Chemical compound CCCCCC(O)O.OC(=O)C1=CC=CC=C1C(O)=O QYZOHCUQJUKDLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BZCKRPHEZOHHBK-UHFFFAOYSA-N methyl 2-phenoxyacetate Chemical compound COC(=O)COC1=CC=CC=C1 BZCKRPHEZOHHBK-UHFFFAOYSA-N 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QUANRIQJNFHVEU-UHFFFAOYSA-N oxirane;propane-1,2,3-triol Chemical compound C1CO1.OCC(O)CO QUANRIQJNFHVEU-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- FJWSMXKFXFFEPV-UHFFFAOYSA-N prop-2-enamide;hydrochloride Chemical class Cl.NC(=O)C=C FJWSMXKFXFFEPV-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は新規な水溶性光開始剤、及びそれを用いた光重合／架橋性組成物に関するものである。 The present invention relates to a novel water-soluble photoinitiator and a photopolymerizable / crosslinkable composition using the same.
光硬化反応を利用するＵＶ硬化システムは、溶媒を使用しないクリーンな硬化方法として、また極めて短時間に硬化反応が終了するために高速な硬化方法として注目を浴びている。そのために、高精細を要求されるレジストの製造、高速化を要求される印刷などにＵＶインクとしていろんな分野に使われている。また、最近ではインクジェットの分野でも、高速で乾燥不要な印刷方法として普及してきた。 A UV curing system utilizing a photocuring reaction is attracting attention as a clean curing method that does not use a solvent and as a fast curing method because the curing reaction is completed in a very short time. For this reason, it is used in various fields as a UV ink for producing resists requiring high definition and printing requiring high speed. In recent years, it has become widespread as a printing method that does not require drying at a high speed in the field of inkjet.
また、ＵＶ光源も従来の高圧水銀灯、低圧水銀灯の他に光の波長３６５ｎｍの発光ダイオード（ＬＥＤ）が実用されつつあり、大きな発展を遂げようとしている。 In addition to the conventional high pressure mercury lamp and low pressure mercury lamp, a light emitting diode (LED) having a light wavelength of 365 nm is being put into practical use as a UV light source, and is going to achieve great development.
ＵＶ印刷インク、インクジェットインクでは、高速化、乾燥なしを特徴と生かすために溶媒を使用せず、光重合／架橋性のモノマー／オリゴマー／ポリマーと光開始剤を基本材料とする硬化システムが実用化されている。しかしながら、近年の環境意識の高まりとともに、水を溶媒に用いて感作性などが懸念される光重合／架橋性のモノマー／オリゴマーの使用量を減らした水性の光硬化システムの必要性が高まっており、さまざまな提案がされている。しかしながら、ほとんどの光開始剤は油溶性のもので、水溶性が不足し、十分な感度が得られていない。 For UV printing ink and inkjet ink, a curing system based on photopolymerization / crosslinkable monomer / oligomer / polymer and photoinitiator is put into practical use without using a solvent to take advantage of high speed and no drying. Has been. However, with the recent increase in environmental awareness, there is a growing need for an aqueous photocuring system that uses water as a solvent and reduces the amount of photopolymerization / crosslinking monomers / oligomers that are concerned about sensitization. Various proposals have been made. However, most photoinitiators are oil-soluble, lacking water solubility, and sufficient sensitivity is not obtained.
それを克服するために、水溶性の光開始剤もいろいろ提案されている。特開平６−２２８２１８号公報にはヒドロキシエトキシ基を２−ヒドロキシ−２−メチル−１−フェニル−１−オンまたはベンゾフェノンに導入した開始剤、特開２００３−１９２７１２号公報にはポリアルキレンオキシド基をα位に置換したアルキルフェノン誘導体、特開２００１−５２５８８７号公報にはハロメチル−１，３，５−トリアジン陰イオンの光重合開始剤、特開２０００−２７３１１０号公報にはシクロアルカノール構造を有する水溶性光開始剤、特開２０００−１８６２４２号公報には２−ヒドロキシ−２−メチル−１−フェニル−１−オンのエチレンオキシド付加物が開示されている。 In order to overcome this, various water-soluble photoinitiators have been proposed. JP-A-6-228218 discloses an initiator in which a hydroxyethoxy group is introduced into 2-hydroxy-2-methyl-1-phenyl-1-one or benzophenone, and JP-A-2003-192712 discloses a polyalkylene oxide group. Alkylphenone derivatives substituted at the α-position, Japanese Patent Application Laid-Open No. 2001-525887 discloses a photopolymerization initiator of a halomethyl-1,3,5-triazine anion, and Japanese Patent Application Laid-Open No. 2000-273110 discloses a water solution having a cycloalkanol structure. Japanese Patent Application Laid-Open No. 2000-186242 discloses an ethylene oxide adduct of 2-hydroxy-2-methyl-1-phenyl-1-one.
しかしながら、高圧水銀灯のメイン発光であり、ＬＥＤの発光波長でもあるλ３６５ｎｍの光吸収が少ないために、いずれの光源を用いても硬化が不十分になってしまう。λ３６５ｎｍの光吸収が高く水溶性の高い開始剤として、特開２００５−３０７１９９号公報にアシル水溶性ホスフィン化合物が記載されているが、アシル水溶性ホスフィン化合物はλ４２０ｎｍまで光吸収があるために蛍光灯下でも硬化してしまい、光重合／架橋性組成物として取り扱いが難しく、更にエームズ試験で陽性など安全性で懸念があるため、広く用いることが出来なかった。 However, the main light emission of the high-pressure mercury lamp and the light absorption at λ365 nm, which is the emission wavelength of the LED, is small, so that curing is insufficient even if any light source is used. JP-A-2005-307199 discloses an acyl water-soluble phosphine compound as an initiator having high light absorption at λ 365 nm and high water solubility. However, since an acyl water-soluble phosphine compound has light absorption up to λ 420 nm, Since it hardened even underneath, it was difficult to handle as a photopolymerizable / crosslinkable composition, and there were concerns about safety such as positive in the Ames test, so it could not be used widely.
本発明者はλ３６５ｎｍ光感度の高く、可視光まで光吸収が伸びていない水溶性光開始剤として探索した結果、特公昭５６−０９５９０４号公報に記載されたベンジルケタール化合物に着目した。この化合物はλ３６５ｎｍの光吸収も高く、更にλ４００ｎｍ以上に吸収を持たず、蛍光灯下での作業性も良く、安全性も問題が少ない。 As a result of searching for a water-soluble photoinitiator having high photosensitivity at λ365 nm and no light absorption up to visible light, the present inventor has focused on the benzyl ketal compound described in Japanese Patent Publication No. 56-095904. This compound has high light absorption at λ365 nm, does not absorb at λ400 nm or more, has good workability under a fluorescent lamp, and has few problems with safety.
しかしながら、既存化合物を調査すると水酸基を置換した例として、特開２００４−５１５６１２号公報の実施例に記載されているものの、水にはわずかしか溶解せず、感度を得ることが出来なかった（例えば、特許文献１参照）。また、他の既存化合物を調べたが、特開平５−３１０６３５号公報にアクリル基を導入した化合物が記載されているなど全て油溶性のもののみで、水溶性の光開始剤として用いることが出来ないものばかりであった。
本発明は上記課題に鑑みなされたものであり、本発明の目的は、水性の光重合／架橋性物を与える新規な水溶性光開始剤を提供することにあり、また該水溶性光開始剤を用いて光波長３６５ｎｍでの硬化感度の高く、室内蛍光灯下での保存性がよく、安全な光重合／架橋性組成物を提供することである。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel water-soluble photoinitiator that provides an aqueous photopolymerization / crosslinkable product, and the water-soluble photoinitiator. Is used to provide a photopolymerization / crosslinking composition that has high curing sensitivity at a light wavelength of 365 nm, has good storage stability under an indoor fluorescent lamp, and is safe.
本発明の上記目的は、下記の構成により達成される。 The above object of the present invention can be achieved by the following constitution.
１．下記一般式（１）に下記−Ｘ−Ｙ基を有することを特徴とする水溶性光開始剤。 1. The water-soluble photoinitiator characterized by having the following -X-Y group in the following general formula (1).
（式中、両ベンゼン環の少なくとも１つに−Ｘ−Ｙ基を少なくとも１つ有し、両ベンゼン環には更にハロゲン原子、アルキル基、アルコキシ基またはアルキルチオ基を有してもよい。−Ｘ−Ｙ基において、ＸはＯまたはＳを表し、Ｙはアルキレン−Ｚ（Ｚはカルボン酸塩またはスルホン酸塩）、（アルキレン−Ｏ）n−スルホン酸塩を表す。Ｒ1、Ｒ2は置換または未置換のアルキル基を表す。）
２．前記一般式（１）に前記−Ｘ−Ｙ基を有する水溶性光開始剤が下記一般式（Ａ）、（Ｂ）、（Ｃ）から選ばれることを特徴とする前記１に記載の水溶性光開始剤。
(In the formula, at least one of the benzene rings has at least one —X—Y group, and both benzene rings may further have a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group. In the -Y group, X represents O or S, Y represents alkylene-Z (Z is a carboxylate or sulfonate), (alkylene-O) n -sulfonate, R 1 and R 2 are substituted Or represents an unsubstituted alkyl group.)
2. The water-soluble photoinitiator having the —XY group in the general formula (1) is selected from the following general formulas (A), (B), and (C): Photoinitiator.
（式中、−Ｘ−Ｙ基、Ｒ1、Ｒ2は一般式（１）のそれらと同義であり、両ベンゼン環には更にハロゲン原子、アルキル基、アルコキシ基またはアルキルチオ基を有してもよい。）
３．前記Ｘが酸素原子であることを特徴とする前記１または２に記載の水溶性光開始剤。
(Wherein, -XY group, R 1 and R 2 have the same meanings as those in formula (1), and both benzene rings may further have a halogen atom, an alkyl group, an alkoxy group or an alkylthio group. Good.)
3. 3. The water-soluble photoinitiator as described in 1 or 2 above, wherein X is an oxygen atom.
４．少なくとも、水、エチレン性不飽和基を有する化合物と前記１〜３のいずれか１項に記載の水溶性開始剤を含有することを特徴とする光重合／架橋性組成物。 4). A photopolymerizable / crosslinkable composition comprising at least water, a compound having an ethylenically unsaturated group, and the water-soluble initiator according to any one of 1 to 3 above.
本発明の新規な水溶性光開始剤を用いた水性の光重合／架橋性組成物は、水溶性が高く、水比率の高い水系ＵＶ組成物でも高感度で硬化することができるとともに、蛍光灯下での重合／架橋性組成液の安定性にも優れる。 The aqueous photopolymerizable / crosslinkable composition using the novel water-soluble photoinitiator of the present invention is highly water-soluble and can be cured with high sensitivity even with an aqueous UV composition having a high water ratio. The stability of the polymerizing / crosslinking composition liquid below is also excellent.
本発明者は、前記課題を達成するために、特定構造を持った光解裂と酸基の塩を有する置換基をもったベンジルケタール化合物を使用することが有効であることを見出し、本発明を完成した。 In order to achieve the above object, the present inventors have found that it is effective to use a benzyl ketal compound having a photocleavage having a specific structure and a substituent having a salt of an acid group. Was completed.
より具体的には前記一般式（１）に前記−Ｘ−Ｙ基を有する水溶性光開始剤であり、更には前記一般式（Ａ）、（Ｂ）、（Ｃ）から選ばれる水溶性光開始剤が好ましい。 More specifically, it is a water-soluble photoinitiator having the -XY group in the general formula (1), and further water-soluble light selected from the general formulas (A), (B), and (C). Initiators are preferred.
−Ｘ−Ｙ基において、ＸはＯまたはＳを表し、Ｙはアルキレン−Ｚ（Ｚはカルボン酸塩またはスルホン酸塩）、（アルキレン−Ｏ）n−スルホン酸塩を表す。カルボン酸塩、スルホン酸塩においては、ナトリウム塩、カリウム塩、リチウム塩、４級アンモニウム塩が挙げられる。 In the —X—Y group, X represents O or S, and Y represents alkylene-Z (Z is a carboxylate or sulfonate) or (alkylene-O) n -sulfonate. Examples of carboxylate and sulfonate include sodium salt, potassium salt, lithium salt, and quaternary ammonium salt.
上記におけるアルキレンとしては、エチレン、プロピレン、ブチレンが挙げられ、これらは置換基、例えば、水酸基を有してもよい。 Examples of alkylene in the above include ethylene, propylene, and butylene, and these may have a substituent, for example, a hydroxyl group.
両ベンゼン環には更にハロゲン原子、アルコキシ基、アルキルチオ基を有してもよく、具体的にはフッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基が挙げられる。 Both benzene rings may further have a halogen atom, an alkoxy group or an alkylthio group. Specifically, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a methoxy group Group, ethoxy group, propoxy group, butoxy group, methylthio group, ethylthio group, propylthio group and butylthio group.
Ｒ1、Ｒ2は置換または未置換のアルキル基を表し、未置換のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられ、置換アルキル基としては、ヒドロキシアルキル基（例えば、ヒドロキシエチル基、ヒドロキシプロピル基）、グリシジル基、−（ＣＨ2ＣＨ2Ｏ）nＨ（ｎ＝１〜３）等が挙げられる。 R 1 and R 2 each represents a substituted or unsubstituted alkyl group. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. The substituted alkyl group includes a hydroxyalkyl group ( For example, hydroxyethyl group, hydroxypropyl group), a glycidyl group, - (CH 2 CH 2 O ) n H (n = 1~3) and the like.
前記一般式（Ａ）、（Ｂ）、（Ｃ）において、−Ｘ−Ｙ基、Ｒ1、Ｒ2は一般式（１）のそれらと同義であり、両ベンゼン環には更にハロゲン原子、アルキル基、アルコキシ基またはアルキルチオ基を有してもよい。 In the general formulas (A), (B), and (C), the —X—Y group, R 1 , and R 2 have the same meanings as those in the general formula (1). It may have a group, an alkoxy group or an alkylthio group.
−Ｘ−Ｙ基においてＸは酸素原子が好ましく、一般式（１）、一般式（Ａ）、（Ｂ）、（Ｃ）においてＲ1、Ｒ2はメチル基が好ましい。 In the —X—Y group, X is preferably an oxygen atom, and R 1 and R 2 in the general formulas (1), (A), (B), and (C) are preferably methyl groups.
以下に一般式（１）で表される光開始剤の具体的化合物を示す。 The specific compound of the photoinitiator represented by General formula (1) below is shown.
本発明に係る光開始剤とともに用いるエチレン性不飽和基を有する化合物は、水溶性が好ましいが、水溶性でなくても少量ならば水性の重合性組成物に溶解するため化合物としては特に制限されない。エチレン性不飽和基を有する化合物のイオン性は本発明に係る光開始剤がアニオン性なので、光重合／架橋性組成物中での凝集を引き起こさないためにノニオン性、アニオン性が好ましいが、カチオン性の化合物でも凝集を起こさない量ならば用いることができる。本発明において、光重合／架橋性組成物とは光によって重合、あるいは架橋、またはその両方によって高分子化合物を形成する組成物のことである。 The compound having an ethylenically unsaturated group used together with the photoinitiator according to the present invention is preferably water-soluble, but it is not particularly limited as a compound because it dissolves in an aqueous polymerizable composition as long as it is not water-soluble. . As for the ionicity of the compound having an ethylenically unsaturated group, since the photoinitiator according to the present invention is anionic, nonionicity and anionicity are preferable in order not to cause aggregation in the photopolymerizable / crosslinkable composition. Even if it is an amount which does not cause aggregation, it can be used. In the present invention, the photopolymerizable / crosslinkable composition refers to a composition that forms a polymer compound by being polymerized by light and / or by crosslinking.
《エチレン性不飽和基を有する化合物》
エチレン性不飽和基を有する化合物とは、化合物中に１個以上のエチレン性不飽和基を持つ化合物。具体的にはスチレン基、アクリル基、メタクリル基、アリル基、クロトン酸基、マレイン酸基、イタコン酸基を少なくとも１つ以上分子中に有する化合物をいう。好ましくはアクリル基、メタクリル基を１つ以上分子中に有する化合物である。
<< Compound having an ethylenically unsaturated group >>
The compound having an ethylenically unsaturated group is a compound having one or more ethylenically unsaturated groups in the compound. Specifically, it refers to a compound having at least one styrene group, acrylic group, methacryl group, allyl group, crotonic acid group, maleic acid group, or itaconic acid group in the molecule. A compound having at least one acrylic group or methacryl group in the molecule is preferable.
スチレン基と有する化合物の例をしては、スチレン、スチレンスルホン酸が挙げられる。 Examples of the compound having a styrene group include styrene and styrene sulfonic acid.
アクリル基、メタクリル基（以後、２つあわせて（メタ）アクリル基を記する）の例としては、以下が挙げられる。（メタ）アクリルアミド、２−ヒドロキシ（メタ）アクリレート、（メタ）アクリルアミド。２−ヒドロキシエチル（メタ）アクリレート及び２−ヒドロキシプロピル（メタ）アクリレート、１，４−ブタンジオールモノ（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート。トリメチロールプロパンモノまたはジ（メタ）アクリレート、及びペンタエリスリトールのモノ、ジまたはトリ（メタ）アクリレート等の水酸基を有するポリオールポリ（メタ）アクリレート。エチレングリコールのモノまたはジ（メタ）アクリレート、及びプロピレングリコールのモノまたはジ（メタ）アクリレート等のアルキレングリコールのモノまたはジ（メタ）アクリレート。ヘキサンジオール、ノナンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、トリシクロデカンジメチロール及びジペンタエリスリトール等のポリオールのエチレンオキサイド付加物のポリ（メタ）アクリレート。 The following are mentioned as an example of an acryl group and a methacryl group (henceforth, a (meth) acryl group is described collectively). (Meth) acrylamide, 2-hydroxy (meth) acrylate, (meth) acrylamide. Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 1,4-butanediol mono (meth) acrylate. Polyol poly (meth) acrylate having a hydroxyl group such as trimethylolpropane mono- or di (meth) acrylate and pentaerythritol mono-, di- or tri (meth) acrylate. Mono- or di (meth) acrylates of alkylene glycols such as mono- or di (meth) acrylates of ethylene glycol and mono- or di (meth) acrylates of propylene glycol. Poly (meth) acrylates of ethylene oxide adducts of polyols such as hexanediol, nonanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, tricyclodecane dimethylol and dipentaerythritol.
（メタ）アクリロニトリル並びにビニルアセテート、カチオン性不飽和化合物としては、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）アクリレート及びジエチルアミノ−２−ヒドロキシプロピル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレートの塩酸塩及び硫酸塩等の３級塩。 (Meth) acrylonitrile, vinyl acetate, and cationic unsaturated compounds include dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and diethylamino-2-hydroxypropyl (meth) acrylate Tertiary salts such as hydrochloride and sulfate.
ジメチルアミノプロピル（メタ）アクリルアミド等のジアルキルアミノアルキル（メタ）アクリルアミドの塩酸塩及び硫酸塩等の３級塩、ジアルキルアミノアルキル（メタ）アクリレートの塩化メチル付加物等のロゲン化アルキル付加物及び塩化ベンジル付加物等のハロゲン化アリール付加物等の４級塩。ジアルキルアミノアルキル（メタ）アクリルアミドの塩化メチル付加物等のハロゲン化アルキル付加物及び塩化ベンジル付加物等のハロゲン化アリール付加物等の４級塩。 Dialkylaminoalkyl (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide hydrochlorides and tertiary salts such as sulfates, alkylated alkylated adducts such as methyl chloride adducts of dialkylaminoalkyl (meth) acrylates and benzyl chloride Quaternary salts such as adducts such as aryl halides. Quaternary salts such as halogenated alkyl adducts such as methyl chloride adduct of dialkylaminoalkyl (meth) acrylamide and aryl halide adducts such as benzyl chloride adduct.
エチレン性不飽和基を有する化合物はオリゴマーまたは重合体でもよい。イオン性基としては、カルボキシル基及びスルホン酸等の酸性基の塩、並びにアルキレンオキサイド基、水酸基等が挙げられる。 The compound having an ethylenically unsaturated group may be an oligomer or a polymer. Examples of the ionic group include a salt of an acidic group such as a carboxyl group and sulfonic acid, an alkylene oxide group, and a hydroxyl group.
より具体的には、（メタ）アクリレートと（メタ）アクリル酸との共重合体であるカルボキシル基含有共重合体にグリシジル（メタ）アクリレートを付加させて得られる重合体及びその塩、脂肪酸及びアルキレングリコールモノグリシジルエーテルのエステルに（メタ）アクリル酸を付加させたもの、末端にエチレン性二重結合を持ちアルコール部分にポリアルキレンオキシドを用いたポリウレタン（メタ）アクリレートまたはポリエステル（メタ）アクリレート、（メタ）アクリレートを連結基で介して結合されたポリビニルアルコールポリマーなどが挙げられる。 More specifically, a polymer obtained by adding glycidyl (meth) acrylate to a carboxyl group-containing copolymer, which is a copolymer of (meth) acrylate and (meth) acrylic acid, its salt, fatty acid, and alkylene (Meth) acrylic acid added to an ester of glycol monoglycidyl ether, polyurethane (meth) acrylate or polyester (meth) acrylate with an ethylenic double bond at the end and polyalkylene oxide in the alcohol part, (meta ) A polyvinyl alcohol polymer in which an acrylate is bonded via a linking group.
ポリウレタン（メタ）アクリレートの例としては、多価アルコールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリエーテルポリオールや、エチレングリコールアジペート、ブタンジオールアジペート、ブタンジオールフタレート及びヘキサンジオールフタレート等のポリエステルジオールが挙げられる。 Examples of polyurethane (meth) acrylates include polyhydric alcohols such as polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, ethylene glycol adipate, butanediol adipate, butanediol phthalate and hexanediol phthalate. Examples include polyester diol.
多価イソシアネート化合物としては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート及び水添ジフェニルメタンジイソシアネート等が挙げられる。 Examples of the polyvalent isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.
水酸基含有（メタ）アクリレートとしては、ヒドロキシエチル（メタ）アクリレート及びヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートが挙げられる。 Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
ポリエステル（メタ）アクリレートとしては、ポリエステル型の多価アルコールと（メタ）アクリル酸との反応物を挙げることができる。 Examples of the polyester (meth) acrylate include a reaction product of a polyester-type polyhydric alcohol and (meth) acrylic acid.
ポリエステル型の多価アルコールとしては、例えば、コハク酸、マレイン酸、アジピン酸、セバシン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸及びトリメリット酸等の多塩基酸、並びにその無水物等が挙げられる。アルコール成分としては、エチレングリコール、ブタンジオール、ヘキサンジオール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリメチロールプロパン、ペンタエリスリトール、トリメチロールプロパンのエチレンオキサイド、またはプロピレンオキサイド付加物のトリオール、グリセリンのエチレンオキサイド、またはプロピレンオキサイド付加物のトリオール、及びペンタエリスリトールのエチレンオキサイド、またはプロピレンオキサイド付加物のテトラオール等を反応させたポリエステルアルコール等が挙げられる。 Examples of polyester type polyhydric alcohols include polybasic acids such as succinic acid, maleic acid, adipic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and trimellitic acid, and anhydrides thereof. Can be mentioned. Examples of the alcohol component include ethylene glycol, butanediol, hexanediol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, pentaerythritol, trimethylolpropane ethylene oxide, or propylene oxide adduct triol, glycerin ethylene oxide, Or the triol of a propylene oxide adduct, the polyester alcohol etc. which reacted the ethylene oxide of a pentaerythritol, the tetraol of a propylene oxide adduct, etc. are mentioned.
エチレン性不飽和基を有する化合物は１種でもよいが、２種以上を併用して使用することもできる。 Although the compound which has an ethylenically unsaturated group may be 1 type, it can also be used in combination of 2 or more type.
（メタ）アクリレートを連結基を介して結合されたポリビニルアルコールポリマーの例としては、特開２０００−１８１０６２号公報、特開２００４−１８９８４１号公報記載のように、メタ（アクリル基）を末端に他の末端にアルデヒド基を持つ化合物をポリビニルアルコールの水酸基にアセタール化して結合したポリマーが挙げられる。 Examples of the polyvinyl alcohol polymer in which (meth) acrylate is bonded via a linking group include other compounds having a meth (acrylic group) at the end as described in JP-A Nos. 2000-181062 and 2004-189841. And a polymer obtained by acetalizing and bonding a compound having an aldehyde group to the hydroxyl group of polyvinyl alcohol.
本発明の水溶性光開始剤の配合割合としては、目的に応じて適宜設定すればよいが、重合性組成物量１００質量部に対して０．０５〜１２質量％が好ましく、より好ましくは０．１〜５質量％である。本発明の水溶性光開始剤は水溶性であるため、水系の活性エネルギー線硬化型組成物に好ましく適用できる。重合性組成物量１００質量部に対するエチレン性不飽和基を有する化合物は、乾燥後光照射して硬化させる場合と乾燥前に光照射して硬化させる場合など目的に応じて異なるが、１．０質量部から６０質量部まで広く用いることができる。 The mixing ratio of the water-soluble photoinitiator of the present invention may be appropriately set depending on the purpose, but is preferably 0.05 to 12% by mass, more preferably 0. 0% to 100 parts by mass of the polymerizable composition. 1 to 5% by mass. Since the water-soluble photoinitiator of the present invention is water-soluble, it can be preferably applied to an aqueous active energy ray-curable composition. The compound having an ethylenically unsaturated group with respect to 100 parts by mass of the polymerizable composition varies depending on the purpose, such as when it is cured by light irradiation after drying and when it is cured by light irradiation before drying. Part to 60 parts by mass.
《光開始剤、光増感剤》
本発明においては、本発明に係る光開始剤の他に必要に応じて他の光開始剤や光増感剤を添加してもよい。
<< Photoinitiator, Photosensitizer >>
In the present invention, other photoinitiators and photosensitizers may be added as necessary in addition to the photoinitiator according to the present invention.
添加してもよい他の光開始剤としては下記が挙げられる。 The following are mentioned as another photoinitiator which may be added.
１）ベンゾフェノン、ヒドロキシベンゾフェノン、ビス−Ｎ，Ｎ−ジメチルアミノベンゾフェノン、ビス−Ｎ，Ｎ−ジエチルアミノベンゾフェノン、４−メトキシ−４′−ジメチルアミノベンゾフェノン等のベンゾフェノン類、及びそれらの塩
２）チオキサントン、２，４−ジエチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントン、イソプロポキシクロロチオキサントン等のチオキサントン類、及びそれらの塩
３）エチルアントラキノン、ベンズアントラキノン、アミノアントラキノン、クロロアントラキノン等のアントラキノン類
４）アセトフェノン類
５）ベンゾインメチルエーテル等のベンゾインエーテル類
６）２，４，６−トリハロメチルトリアジン類。
1) Benzophenones such as benzophenone, hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, bis-N, N-diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and salts thereof 2) Thioxanthone, 2 Thioxanthones such as 1,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, and salts thereof 3) anthraquinones such as ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone 4) acetophenones 5) benzoin methyl Benzoin ethers such as ether 6) 2,4,6-trihalomethyltriazines.
７）１−ヒドロキシシクロヘキシルフェニルケトン、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール２量体、２−（ｏ−クロロフェニル）−４，５−ジ（ｍ−メトキシフェニル）イミダゾール２量体、２−（ｏ−フルオロフェニル）−４，５−フェニルイミダゾール２量体、２−（ｏ−メトキシフェニル）−４，５−フェニルイミダゾール２量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール２量体、２−ジ（ｐ−メトキシフェニル）−５−フェニルイミダゾール２量体、２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾール２量体、２，４，５−トリアリールイミダゾール２量体等のイミダゾール類
８）ベンジルジメチルケタール、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−１−プロパノン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、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、フェナントレンキノン、９，１０−フェナンスレンキノン、メチルベンゾイン、エチルベンゾイン等のベンゾイン類。
7) 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-phenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2,4 Imidazoles such as 2,5-triarylimidazole dimer 8) benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, phenanthrenequinone, 9,10-phenanthrenequinone, methylbenzoin, ethylbenzoin, etc. Benzoins.
９）９−フェニルアクリジン、１，７−ビス（９，９′−アクリジニル）ヘプタン等のアクリジン誘導体
１０）ビスアシルフォスフィンオキサイド、ビスフェニルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド
１１）４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、及びこれらのエチレンオキシド付加物。
9) Acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane 10) Bisacylphosphine oxide, bisphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide 11) 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and their ethylene oxide adducts.
また、インクに加える形態は必要に応じて溶解物、または分散物として加えることができる。 Moreover, the form added to ink can be added as a dissolved substance or a dispersion as needed.
光増感剤の例としては、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジメチルアミノ安息香酸イソアミル、エタノールアミン、ジエタノールアミン、トリエタノールアミン等が挙げられる。 Examples of the photosensitizer include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethanolamine, diethanolamine, and triethanolamine.
本発明の光重合／架橋性組成物では、水の他に必要があれば有機溶媒を用いてもよい。有機溶媒は水溶性の溶媒が好ましいが、光重合／架橋性組成物中で溶解していれば特に水溶性でない溶媒も少量用いることができる。 In the photopolymerization / crosslinkable composition of the present invention, an organic solvent may be used if necessary in addition to water. The organic solvent is preferably a water-soluble solvent, but a small amount of a solvent that is not particularly water-soluble can be used as long as it is dissolved in the photopolymerizable / crosslinkable composition.
光重合／架橋性組成物中の水、及び有機溶媒の使用量は、組成物１００質量部あたり２０〜９９質量部であり、好ましくは５０〜９８質量部である。 The amount of water and organic solvent used in the photopolymerization / crosslinking composition is 20 to 99 parts by mass, preferably 50 to 98 parts by mass, per 100 parts by mass of the composition.
本発明の光重合／架橋性組成物のｐＨが５未満の場合は、本発明の水溶性光開始剤の加水分解が起こすために好ましくなく、ｐＨは５．５以上、好ましくは６．５以上が好ましい。 When the pH of the photopolymerizable / crosslinkable composition of the present invention is less than 5, it is not preferable because hydrolysis of the water-soluble photoinitiator of the present invention occurs, and the pH is 5.5 or more, preferably 6.5 or more. Is preferred.
本発明の光重合／架橋性組成物は、塗料等のコーティング剤、接着剤及びレジスト等、ＵＶ硬化性のインク、ＵＶ硬化性のＵＶ印刷インクといった種々の用途に使用することができ、それに応じて顔料、染料、消泡剤、レベリング剤、無機フィラー、有機フィラー及び光安定剤等を配合することもできる。 The photopolymerization / crosslinking composition of the present invention can be used for various applications such as coating agents such as paints, adhesives and resists, UV curable inks, UV curable UV printing inks, and the like. Pigments, dyes, antifoaming agents, leveling agents, inorganic fillers, organic fillers, light stabilizers, and the like can also be incorporated.
本発明の光重合／架橋性組成物の使用方法としては、従来の光硬化型組成物の使用方法に従えばよい。具体的には、光重合／架橋性組成物をバーコーター、ワイヤーバー、インクジェットヘッドなどにより基材上に塗布印刷した後、紫外線を照射し乾燥するか、基材に光重合／架橋性組成物を塗布、加熱により水分を蒸発させた後に、紫外線を照射する方法が挙げられる。 As a method for using the photopolymerizable / crosslinkable composition of the present invention, a conventional method for using a photocurable composition may be used. Specifically, the photopolymerizable / crosslinkable composition is applied and printed on a substrate with a bar coater, a wire bar, an ink jet head or the like, and then dried by irradiating with ultraviolet rays. A method of irradiating ultraviolet rays after evaporating moisture by applying and heating is mentioned.
本発明の光重合／架橋性組成物を硬化させる光源としては、高圧水銀灯、低圧水銀灯、発光ダイオード（ＬＥＤ）、電子線、太陽光などを用いることができるが、本発明の水溶性光開始剤は光の波長λ３６５ｎｍの光吸収感度が高い特性があることから、λ３６５ｎｍ光の出力が強い高圧水銀灯、λ３６５ｎｍに発光スペクトルを有するＬＥＤが特に好ましく用いることができる。 As a light source for curing the photopolymerizable / crosslinkable composition of the present invention, a high pressure mercury lamp, a low pressure mercury lamp, a light emitting diode (LED), an electron beam, sunlight or the like can be used. Has a high light absorption sensitivity at a light wavelength of λ365 nm, a high-pressure mercury lamp having a strong output of λ365 nm light and an LED having an emission spectrum at λ365 nm can be used particularly preferably.
（本発明に用いる材の合成法）
本発明の水溶性光開始剤を得るためには、水溶性光開始剤の前駆体であるベンジル誘導体からケタール化を行い、必要に応じて加水分解等を行うことで目的物を得ることができる。
(Method for synthesizing materials used in the present invention)
In order to obtain the water-soluble photoinitiator of the present invention, the target product can be obtained by performing ketalization from a benzyl derivative that is a precursor of the water-soluble photoinitiator and performing hydrolysis or the like as necessary. .
ベンジル誘導体を得る方法は、対照化合物の場合はフェニル化合物とオキザリルクロリドのフリーデルクラフト反応、またはベンゾインを酸化して得る方法など一般に広く知られている。非対称化合物を得る方法もフェニルアセチルクロリドとフェニル化合物フリーデルクラフト反応でベンジルフェニルケトン誘導体を得た後、臭素化、アルコキシドによる脱臭化水素反応で、ベンジル誘導体を得ることができる。 A method for obtaining a benzyl derivative is generally known in the case of a reference compound such as a Friedel-Craft reaction between a phenyl compound and oxalyl chloride, or a method obtained by oxidizing benzoin. A method for obtaining an asymmetric compound can also be obtained by obtaining a benzyl phenyl ketone derivative by phenyl acetyl chloride and phenyl compound Friedel-Craft reaction, followed by bromination and dehydrobromination by alkoxide.
続くケタール化反応は、塩化チオニルとメタノール、ＤＭＦとナトリウムメトキシドなど酸性条件、塩基性条件での反応が広く知られているが、これらの反応条件では本発明の水溶性光開始剤の前駆体であるケタール化合物はごく少量しか得られず、ｐ−トルエンスルホン酸、トリフルオロメタンスルホン酸を用いて、オルトギ酸エステルとアルコールを用いることが必要であった。また、収率の点からトリフルオロメタンスルホン酸を用いるが好ましい。 Subsequent ketalization reactions are widely known under acidic and basic conditions such as thionyl chloride and methanol, DMF and sodium methoxide, etc. Under these reaction conditions, the precursor of the water-soluble photoinitiator of the present invention. Only a small amount of the ketal compound was obtained, and it was necessary to use orthoformate ester and alcohol using p-toluenesulfonic acid and trifluoromethanesulfonic acid. Further, trifluoromethanesulfonic acid is preferably used from the viewpoint of yield.
例示化合物１の合成 Synthesis of Exemplified Compound 1
（化合物Ｂの合成）
塩化アルミニウム１１．７ｇ（８４ｍｍｏｌ）をジクロロメタン３３ｍｌに加え、氷冷する。フェノキシ酢酸メチル（化合物Ａ）６．６ｇ（４０ｍｍｏｌ）を内温１５℃以下で滴下し、次いでオキザリルクロリド２．８ｇ（２２ｍｍｏｌ）をゆっくり滴下する。盛んに塩化水素ガスが発生する。塩化水素ガスの発生の終了後、反応液を氷水１００ｇ中に投入し、酢酸エチル３０ｍｌを加え攪拌すると結晶が析出してくる。この結晶を濾過洗浄して、化合物Ｂ、２．５ｇを白色結晶として得る。
(Synthesis of Compound B)
Add 11.7 g (84 mmol) of aluminum chloride to 33 ml of dichloromethane and cool on ice. 6.6 g (40 mmol) of methyl phenoxyacetate (Compound A) is added dropwise at an internal temperature of 15 ° C. or lower, and then 2.8 g (22 mmol) of oxalyl chloride is slowly added dropwise. Hydrogen chloride gas is generated actively. After the completion of the generation of hydrogen chloride gas, the reaction solution is poured into 100 g of ice water, and 30 ml of ethyl acetate is added and stirred to precipitate crystals. The crystals are filtered and washed to obtain 2.5 g of compound B as white crystals.
（化合物Ｃの合成）
化合物Ｂ、２３．９ｇ（６２ｍｍｏｌ）、オルトギ酸トリメチル６５．６ｇ（６２０ｍｍｏｌ）、メタノール１９．８ｇ（６１８ｍｍｏｌ）、トルエン３６０ｍｌの混合物を還流する。この液にトリフルオロメタンスルホン酸を２．８ｇ（１８．６ｍｍｏｌ）を滴下して加え、還流を５時間続ける。酢酸エチルと炭酸水素ナトリウム水溶液をかき混ぜた液中に、反応液を投入し、酢酸エチル相を分離エバポレートする。カラムで分離精製して、化合物Ｃを白色結晶として１８．８ｇ得る。
(Synthesis of Compound C)
A mixture of Compound B, 23.9 g (62 mmol), trimethyl orthoformate 65.6 g (620 mmol), methanol 19.8 g (618 mmol), and toluene 360 ml is refluxed. To this solution, 2.8 g (18.6 mmol) of trifluoromethanesulfonic acid is added dropwise and reflux is continued for 5 hours. The reaction mixture is poured into a mixture of ethyl acetate and aqueous sodium hydrogen carbonate solution, and the ethyl acetate phase is separated and evaporated. Separation and purification using a column yields 18.8 g of Compound C as white crystals.
（例示化合物１）の合成）
化合物Ｃ、１６．７ｇ、メタノール１３０ｍｌ、水酸化ナトリウムの３０質量％水溶液１０ｍｌを加え、還流を２時間行う。黄色物質が析出してくるので、濾過して取り除いた後、溶媒等を留去する。得られた透明オイルにエタノールを加え、結晶化させる。濾過、乾燥して、例示化合物１を１５．１ｇ得る。
(Synthesis of Exemplified Compound 1)
Compound C, 16.7 g, 130 ml of methanol and 10 ml of a 30% by weight aqueous solution of sodium hydroxide are added and refluxed for 2 hours. Since a yellow substance is deposited, the solvent and the like are distilled off after removing by filtration. Ethanol is added to the obtained transparent oil and crystallized. Filtration and drying give 15.1 g of Exemplified Compound 1.
化合物の確認は1Ｈ−ＮＭＲにて行った。 The compound was confirmed by 1 H-NMR.
（（メタ）アクリレートに連結基を介して結合されたポリビニルアルコールポリマー（アクリル基含有ポリビニルアルコール）の合成）
グリシジルメタクリレート５６ｇ、ｐ−ヒドロキシベンズアルデヒド４８ｇ、ピリジン２ｇ、及びＮ−ニトロソ−フェニルヒドロキシアミンアンモニウム塩１ｇを反応容器に入れ、８０度の湯浴中で８時間攪拌した。
(Synthesis of polyvinyl alcohol polymer (acrylic group-containing polyvinyl alcohol) bonded to (meth) acrylate via a linking group)
56 g of glycidyl methacrylate, 48 g of p-hydroxybenzaldehyde, 2 g of pyridine, and 1 g of N-nitroso-phenylhydroxyamine ammonium salt were put in a reaction vessel, and stirred for 8 hours in a water bath at 80 degrees.
次に、重合度５００、ケン化率８８％のポリ酢酸ビニルケン化物４５ｇをイオン交換水２２５ｇに分散した後、この溶液にリン酸４．５ｇと上記反応で得られたｐ−（３−メタクリロキシ−２−ヒドロキシプロピルオキシ）ベンズアルデヒドをポリビニルアルコールに対して変性率が３モル％になるように加え、９０℃で６時間攪拌した。得られた溶液を室温まで冷却した後、塩基性イオン交換樹脂３０ｇを加え１時間攪拌した。その後イオン交換樹脂を濾過し、イオン交換水にて希釈して濃度１０％のアクリル基含有ポリビニルアルコールを得た。 Next, 45 g of saponified polyvinyl acetate having a polymerization degree of 500 and a saponification rate of 88% was dispersed in 225 g of ion-exchanged water, and then 4.5 g of phosphoric acid and p- (3-methacryloxy-) obtained by the above reaction were added to this solution. 2-hydroxypropyloxy) benzaldehyde was added to polyvinyl alcohol so that the modification rate was 3 mol%, and the mixture was stirred at 90 ° C. for 6 hours. After cooling the obtained solution to room temperature, 30 g of basic ion exchange resin was added and stirred for 1 hour. Thereafter, the ion exchange resin was filtered and diluted with ion exchange water to obtain an acrylic group-containing polyvinyl alcohol having a concentration of 10%.
以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれらに限定されない。なお、実施例中で「％」は、特に断りのない限り質量％を表す。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. In the examples, “%” represents mass% unless otherwise specified.
実施例１（ＵＶ印刷インクの例）
（ブラック顔料分散液の調製）
以下の各添加剤を混合し、０．５ｍｍのジルコニアビーズを体積率で５０％充填したサンドグラインダーを用いて分散し、イオン交換水で希釈してブラック顔料の含有量が１０％のブラック顔料分散液を調製した。このブラック顔料分散液に含まれるブラック顔料粒子の平均粒径は１５４ｎｍであった。なお、粒径測定はマルバーン製ゼータサイザ１０００ＨＳにより行った。
Example 1 (Example of UV printing ink)
(Preparation of black pigment dispersion)
Disperse using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads by mixing the following additives and dilute with ion exchange water to disperse the black pigment with a black pigment content of 10% A liquid was prepared. The average particle diameter of the black pigment particles contained in this black pigment dispersion was 154 nm. The particle size was measured with a Malvern Zetasizer 1000HS.
カーボンブラック １５部
高分子分散剤（スチレン／アクリル酸／ブチルアクリレート共重合体、Ｔｇ６５℃、数平均分子量７０００） ４部
グリセリン １８部
イオン交換水 残り
〔ブラック印刷インク１の調製〕
ブラック顔料分散液 ３０部
Ａ４００（新中村化学製） ２０部
ＴＯ−１３４３（東亞合成製、アクリロイル基を２個以上有する水溶性ポリエステル系アクリルオリゴマー） ５部
ジョンクリル５３７Ｊ（ジョンソンポリマー製、固形分４６％） ８部
水溶性光開始剤（１） ２部
ジエチレングリコール ２０部
水 残り
以下、水溶性光開始剤を表１に記した化合物に変えて、ブラック印刷インク２〜１６を調製した。
Carbon black 15 parts Polymer dispersing agent (styrene / acrylic acid / butyl acrylate copolymer, Tg 65 ° C., number average molecular weight 7000) 4 parts Glycerin 18 parts Ion-exchanged water remaining [Preparation of black printing ink 1]
Black pigment dispersion 30 parts A400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts TO-1343 (manufactured by Toagosei, water-soluble polyester acrylic oligomer having two or more acryloyl groups) 5 parts Jonkrill 537J (manufactured by Johnson polymer, solid content 46 %) 8 parts Water-soluble photoinitiator (1) 2 parts Diethylene glycol 20 parts Water Remaining Black printing inks 2 to 16 were prepared by changing the water-soluble photoinitiator to the compounds shown in Table 1 below.
〔評価〕
（３６５ｎｍＬＥＤでの硬化性）
アート紙上に得られたインクをワイヤーバーでＷｅｔ膜厚１０μｍで塗布し、λ３６５ｎｍのＬＥＤランプ（日亜化学工業製）で１１５ｍＪ／ｃｍ2の照度で照射し、照射後の状態を目視で観察した。
[Evaluation]
(Curability with 365 nm LED)
The ink obtained on the art paper was applied with a wire bar at a wet film thickness of 10 μm, irradiated with an illuminance of 115 mJ / cm 2 with a λ365 nm LED lamp (manufactured by Nichia Corporation), and the state after irradiation was visually observed. .
○：流動性がない
△：一部に流動性がある
×：流動性がある。
○: No fluidity Δ: Some fluidity ×: Fluidity
（高圧水銀灯での硬化性）
アート紙上に得られたインクをワイヤーバーでＷｅｔ膜厚５０μｍで塗布し、高圧水銀灯で（ウシオ電機製）で９６ｍＪ／ｃｍ2の照度で照射し、照射後の状態を目視で観察した。
(Curing property with high-pressure mercury lamp)
The ink obtained on the art paper was applied with a wire bar at a wet film thickness of 50 μm, irradiated with a high-pressure mercury lamp (manufactured by USHIO) at an illuminance of 96 mJ / cm 2 , and the state after irradiation was visually observed.
○：流動性がない
△：一部に流動性がある
×：流動性がある。
○: No fluidity Δ: Some fluidity ×: Fluidity
（蛍光灯下でのインク保存性）
インク２０ｍｌを５０ｍｌビーカーに入れ、上部５０ｃｍより１００Ｗに蛍光灯を２４時間照射し、保存性の評価を行った。
(Ink storage stability under fluorescent light)
20 ml of ink was placed in a 50 ml beaker, and 100 W was irradiated from the upper 50 cm to a fluorescent lamp for 24 hours to evaluate the storage stability.
○：インクに変化がない
△：表面の一部がゲル化している
×：不溶物がある。
○: No change in ink Δ: Part of the surface is gelled ×: Insoluble material exists.
表１より、本発明の水溶性光開始剤を用いたＵＶインクは、３６５ｎｍのＬＥＤ、高圧水銀灯での硬化に優れるとともに、室内蛍光灯下での組成液安定性に優れていることが分かる。 From Table 1, it can be seen that the UV ink using the water-soluble photoinitiator of the present invention is excellent in curing with a 365 nm LED and a high-pressure mercury lamp, and is excellent in composition liquid stability under an indoor fluorescent lamp.
実施例２（インクジェットＵＶインク）
表２中の各顔料分散液は下記のように調製した。
Example 2 (Inkjet UV ink)
Each pigment dispersion in Table 2 was prepared as follows.
Ｃａｂｏｊｅｔ−３００（濃度１５％）：キャボット社製の自己分散型カーボンブラック分散液
ブラック顔料分散液（濃度１５％）：実施例１参照
マゼンタ顔料分散液（濃度１５％）：実施例１のブラック顔料分散液の調製において、カーボンブラックに代えて、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ１２２を使用した以外は同様にして、マゼンタ顔料分散液を調製した。
Cabojet-300 (concentration 15%): self-dispersing carbon black dispersion manufactured by Cabot Corporation Black pigment dispersion (concentration 15%): see Example 1 Magenta pigment dispersion (concentration 15%): black pigment of Example 1 In the preparation of the dispersion, instead of carbon black, C.I. I. A magenta pigment dispersion was prepared in the same manner except that Pigment Red 122 was used.
上記顔料分散液を用いて、表２の組成のインクジェットインクＮｏ．１〜５を調製した。表２に使用する材料は以下の通りである。 Using the pigment dispersion, inkjet ink No. 1 having the composition shown in Table 2 was used. 1-5 were prepared. The materials used in Table 2 are as follows.
Ａ−４００：新中村化学製、ポリエチレンオキシドジアクリレート、分子量５００
ＵＡ−Ｗ２Ａ：新中村化学製、水溶性ウレタンアクリレートオリゴマー
アクリル基含有ポリビニルアルコール（重合度５００、変性率３％、濃度１０％）
ＤＥＧ：ジエチレングリコール
ＥＧ：エチレングリコール
オルフィンＥ１０１０：日信化学製。
A-400: Shin-Nakamura Chemical, polyethylene oxide diacrylate, molecular weight 500
UA-W2A: Shin-Nakamura Chemical Co., Ltd., water-soluble urethane acrylate oligomer Acrylic group-containing polyvinyl alcohol (polymerization degree 500, modification rate 3%, concentration 10%)
DEG: Diethylene glycol EG: Ethylene glycol Orphine E1010: manufactured by Nissin Chemical.
〔評価〕
高圧水銀灯を搭載したＵＶインクジェットプリンターで、アート紙上に１５ｇ／ｍ2の付量になるようにベタ画像を作成した。
[Evaluation]
A solid image was created on a piece of art paper with a UV inkjet printer equipped with a high-pressure mercury lamp so that the amount applied was 15 g / m 2 .
実施例１と同様の評価を行った。 Evaluation similar to Example 1 was performed.
表３、４より、本発明の水溶性光開始剤を用いたＵＶ硬化型インクは、インクジェットインクとして用いても３６５ｎｍのＬＥＤ、高圧水銀灯での硬化に優れるとともに、室内蛍光灯下でのインク保存性に優れていることが分かる。 As can be seen from Tables 3 and 4, the UV curable ink using the water-soluble photoinitiator of the present invention is excellent in curing with a 365 nm LED and a high-pressure mercury lamp even when used as an ink-jet ink, and preserves ink under an indoor fluorescent lamp. It turns out that it is excellent in property.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007087237A JP5070903B2 (en) | 2007-03-29 | 2007-03-29 | Water-soluble photoinitiator and photopolymerization / crosslinking composition using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007087237A JP5070903B2 (en) | 2007-03-29 | 2007-03-29 | Water-soluble photoinitiator and photopolymerization / crosslinking composition using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008247940A true JP2008247940A (en) | 2008-10-16 |
| JP5070903B2 JP5070903B2 (en) | 2012-11-14 |
Family
ID=39973288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007087237A Expired - Fee Related JP5070903B2 (en) | 2007-03-29 | 2007-03-29 | Water-soluble photoinitiator and photopolymerization / crosslinking composition using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5070903B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2075293A1 (en) | 2007-12-28 | 2009-07-01 | Konica Minolta Holdings, Inc. | Ink-jet ink and ink-jet recording method |
| EP2292705A1 (en) | 2009-09-08 | 2011-03-09 | FUJIFILM Corporation | Aqueous ink composition and image forming method |
| EP2325268A1 (en) | 2009-11-09 | 2011-05-25 | FUJIFILM Corporation | Aqueous ink composition and image forming method |
| JP2011116946A (en) * | 2009-10-30 | 2011-06-16 | Canon Inc | Liquid composition, inkjet recording method, inkjet recording device, and recorded image |
| JP2014177023A (en) * | 2013-03-14 | 2014-09-25 | Hitachi Maxell Ltd | Method for manufacturing metal foil-transferred object |
| JP2015091872A (en) * | 2011-02-02 | 2015-05-14 | 東洋合成工業株式会社 | Novel radical polymerization initiator, and photocurable composition and method of producing the same |
| CN108473409A (en) * | 2015-10-23 | 2018-08-31 | 默克专利股份有限公司 | Benzil single ketal and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310602A (en) * | 1986-04-15 | 1988-01-18 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Liquid optical initiator mixture |
| JPH05310635A (en) * | 1992-05-12 | 1993-11-22 | Fuji Photo Film Co Ltd | Benzyl ketal derivative |
| JP2008247939A (en) * | 2007-03-29 | 2008-10-16 | Konica Minolta Holdings Inc | Inkjet ink and inkjet recording method |
-
2007
- 2007-03-29 JP JP2007087237A patent/JP5070903B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310602A (en) * | 1986-04-15 | 1988-01-18 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Liquid optical initiator mixture |
| JPH05310635A (en) * | 1992-05-12 | 1993-11-22 | Fuji Photo Film Co Ltd | Benzyl ketal derivative |
| JP2008247939A (en) * | 2007-03-29 | 2008-10-16 | Konica Minolta Holdings Inc | Inkjet ink and inkjet recording method |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2075293A1 (en) | 2007-12-28 | 2009-07-01 | Konica Minolta Holdings, Inc. | Ink-jet ink and ink-jet recording method |
| EP2292705A1 (en) | 2009-09-08 | 2011-03-09 | FUJIFILM Corporation | Aqueous ink composition and image forming method |
| US8287114B2 (en) | 2009-09-08 | 2012-10-16 | Fujifilm Corporation | Aqueous ink composition and image forming method |
| JP2011116946A (en) * | 2009-10-30 | 2011-06-16 | Canon Inc | Liquid composition, inkjet recording method, inkjet recording device, and recorded image |
| EP2325268A1 (en) | 2009-11-09 | 2011-05-25 | FUJIFILM Corporation | Aqueous ink composition and image forming method |
| US8511812B2 (en) | 2009-11-09 | 2013-08-20 | Fujifilm Corporation | Aqueous ink composition and image forming method |
| JP2015091872A (en) * | 2011-02-02 | 2015-05-14 | 東洋合成工業株式会社 | Novel radical polymerization initiator, and photocurable composition and method of producing the same |
| JP5845196B2 (en) * | 2011-02-02 | 2016-01-20 | 東洋合成工業株式会社 | 2,2-dimethoxy-1,2-di- [4- (meth) acryloyloxy] phenylethane-1-one, production method thereof, radical polymerization initiator and photocurable composition |
| JP2014177023A (en) * | 2013-03-14 | 2014-09-25 | Hitachi Maxell Ltd | Method for manufacturing metal foil-transferred object |
| CN108473409A (en) * | 2015-10-23 | 2018-08-31 | 默克专利股份有限公司 | Benzil single ketal and application thereof |
| CN108473409B (en) * | 2015-10-23 | 2022-01-07 | 默克专利股份有限公司 | Benzil monoketal and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5070903B2 (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5070903B2 (en) | Water-soluble photoinitiator and photopolymerization / crosslinking composition using the same | |
| JP6972813B2 (en) | Curable composition, curable ink, containment vessel, 2D or 3D image forming device, 2D or 3D image forming method, cured product, and curable compound. | |
| EP3033399B1 (en) | Ink-jet printing ink comprising n-vinyloxazolidinone | |
| JP6212856B2 (en) | Active energy ray curable composition, ink for inkjet recording, (meth) acrylic acid ester | |
| CN101755238B (en) | Dual photoinitiator, photocurable composition, use thereof and process for producing a three dimensional article | |
| JP5098397B2 (en) | Ink jet ink and ink jet recording method | |
| JP6615849B2 (en) | Composition for model materials | |
| TW200406425A (en) | Improvement in the storage stability of photoinitiators | |
| JP2015174919A (en) | Photocurable composition for 3d modeling and method for producing 3d model | |
| CN103012317A (en) | Alkyl phenyl derivative and application of alkyl phenyl derivative as photoinitiator | |
| JP5109632B2 (en) | Photoinitiator, photopolymerizable composition, and photocuring method | |
| JP2008280427A (en) | Ultraviolet-curable ink, and image recording method | |
| JP5136035B2 (en) | Ink jet ink and ink jet recording method | |
| JP2013203830A (en) | Curable inkjet solventless ink composition | |
| WO2016111338A1 (en) | Photo-curable colored composition, cured product, and article | |
| JP5545533B2 (en) | Radical photocurable ink composition | |
| JP6547351B2 (en) | Polymerizable composition and active energy ray curable ink jet ink using the same | |
| JP7186508B2 (en) | Composition for model material | |
| JP7382010B2 (en) | Polymerization initiator mixture, polymerizable composition, cured product, and method for producing cured product | |
| JP2014152252A (en) | Polymerizable composition and active energy ray-curable inkjet ink using the same | |
| JP5979280B2 (en) | Radical photocurable ink composition | |
| JP5761413B2 (en) | Radical photocurable ink composition | |
| JP2013203828A (en) | Curable inkjet solventless ink composition | |
| JP2015183146A (en) | Polymerizable composition and active energy ray-curable inkjet ink using the same | |
| US11890806B2 (en) | Additives for build materials and associated printed 3D articles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100311 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20110816 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120717 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120724 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120806 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5070903 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150831 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |