WO2017038244A1 - 水分散物及びその製造方法、並びに画像形成方法 - Google Patents
水分散物及びその製造方法、並びに画像形成方法 Download PDFInfo
- Publication number
- WO2017038244A1 WO2017038244A1 PCT/JP2016/069939 JP2016069939W WO2017038244A1 WO 2017038244 A1 WO2017038244 A1 WO 2017038244A1 JP 2016069939 W JP2016069939 W JP 2016069939W WO 2017038244 A1 WO2017038244 A1 WO 2017038244A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aqueous dispersion
- group
- gel particles
- mass
- polymerizable
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 311
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 230000015572 biosynthetic process Effects 0.000 title abstract description 11
- 239000007863 gel particle Substances 0.000 claims abstract description 336
- 239000003999 initiator Substances 0.000 claims abstract description 160
- 239000011347 resin Substances 0.000 claims abstract description 145
- 229920005989 resin Polymers 0.000 claims abstract description 145
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000007787 solid Substances 0.000 claims abstract description 52
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- -1 isocyanate compound Chemical class 0.000 claims description 190
- 150000001875 compounds Chemical class 0.000 claims description 141
- 239000012948 isocyanate Substances 0.000 claims description 119
- 239000000178 monomer Substances 0.000 claims description 100
- 239000003960 organic solvent Substances 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000839 emulsion Substances 0.000 claims description 20
- 229920002635 polyurethane Polymers 0.000 claims description 19
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000004814 polyurethane Substances 0.000 claims description 18
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 15
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 14
- 238000004945 emulsification Methods 0.000 claims description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 9
- 238000001879 gelation Methods 0.000 claims description 8
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 90
- 239000000976 ink Substances 0.000 description 84
- 239000012071 phase Substances 0.000 description 61
- 239000003921 oil Substances 0.000 description 54
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 43
- 238000011156 evaluation Methods 0.000 description 35
- 239000002245 particle Substances 0.000 description 35
- 239000000758 substrate Substances 0.000 description 30
- 239000007788 liquid Substances 0.000 description 28
- 150000002430 hydrocarbons Chemical group 0.000 description 27
- 239000004094 surface-active agent Substances 0.000 description 27
- 239000000049 pigment Substances 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 230000001588 bifunctional effect Effects 0.000 description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 23
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- 239000002609 medium Substances 0.000 description 21
- 230000035945 sensitivity Effects 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005538 encapsulation Methods 0.000 description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000006228 supernatant Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 229920000570 polyether Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 125000000962 organic group Chemical group 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000001723 curing Methods 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000012790 confirmation Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 125000005529 alkyleneoxy group Chemical group 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 150000008051 alkyl sulfates Chemical class 0.000 description 5
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229940105570 ornex Drugs 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 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 4
- 229940126062 Compound A Drugs 0.000 description 4
- 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 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229940080236 sodium cetyl sulfate Drugs 0.000 description 4
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 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 3
- 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 3
- 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 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XSYZCZPCBXYQTE-UHFFFAOYSA-N cyclodecylcyclodecane Chemical group C1CCCCCCCCC1C1CCCCCCCCC1 XSYZCZPCBXYQTE-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 238000000954 titration curve Methods 0.000 description 3
- 150000003613 toluenes Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- WDFYPITVMAKZRL-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;2-methyloxirane Chemical compound CC1CO1.OCC(C)(C)CO WDFYPITVMAKZRL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- RKOOOVKGLHCLTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.OCC(O)CO RKOOOVKGLHCLTP-UHFFFAOYSA-N 0.000 description 2
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 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 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 238000001227 electron beam curing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920003009 polyurethane dispersion Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 description 1
- UUGXDEDGRPYWHG-UHFFFAOYSA-N (dimethylamino)methyl 2-methylprop-2-enoate Chemical compound CN(C)COC(=O)C(C)=C UUGXDEDGRPYWHG-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- URQQDYIVGXOEDA-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethyl prop-2-enoate Chemical compound C=COCCOCCOC(=O)C=C URQQDYIVGXOEDA-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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZJKWJHONFFKJHG-UHFFFAOYSA-N 2-Methoxy-1,4-benzoquinone Chemical compound COC1=CC(=O)C=CC1=O ZJKWJHONFFKJHG-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-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
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-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
- 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 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- VPSMYZDILAFZIK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane Chemical compound CCC.CC(=C)C(O)=O VPSMYZDILAFZIK-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical class OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical class CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- IMYJBPVLTJBMPO-UHFFFAOYSA-N N=C=O.N=C=O.COC1=CC=CC(C=2C=C(OC)C=CC=2)=C1 Chemical compound N=C=O.N=C=O.COC1=CC=CC(C=2C=C(OC)C=CC=2)=C1 IMYJBPVLTJBMPO-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 244000172533 Viola sororia Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- URLYGBGJPQYXBN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound OCC1CCC(COC(=O)C=C)CC1 URLYGBGJPQYXBN-UHFFFAOYSA-N 0.000 description 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical compound [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OADNRFNXACMWMJ-UHFFFAOYSA-N benzene;isocyanic acid Chemical compound N=C=O.C1=CC=CC=C1 OADNRFNXACMWMJ-UHFFFAOYSA-N 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001058 brown pigment Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 229940011411 erythrosine Drugs 0.000 description 1
- 239000004174 erythrosine Substances 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 235000004554 glutamine Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical group C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- UYERIVYDSGUOJG-UHFFFAOYSA-N morpholine;prop-2-enamide Chemical compound NC(=O)C=C.C1COCCN1 UYERIVYDSGUOJG-UHFFFAOYSA-N 0.000 description 1
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- YNXCGLKMOXLBOD-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCCO1 YNXCGLKMOXLBOD-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 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
- 238000007639 printing Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/728—Polymerisation products of compounds having carbon-to-carbon unsaturated bonds and having isocyanate or isothiocyanate groups or groups forming isocyanate or isothiocyanate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/023—Emulsion inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to an aqueous dispersion, a method for producing the same, and an image forming method.
- Examples of image forming methods for forming an image on a recording medium include an electrophotographic method, a sublimation type thermal transfer method, a melt type thermal transfer method, and an ink jet method.
- the ink jet image forming method has advantages that it can be carried out with an inexpensive apparatus and that the running cost is low because ink can be used efficiently.
- an image forming method using an ink jet ink that can be cured by irradiation with active energy rays such as ultraviolet rays.
- an inkjet ink that can be cured by irradiation with active energy rays may be referred to as a “photo-curable ink”.
- photocurable compositions not only inkjet inks, but also compositions that can be cured by irradiation with active energy rays are sometimes referred to as “photocurable compositions”.
- a solvent-based composition containing an organic solvent as a solvent or dispersion medium for example, solvent-based ink
- water as a solvent or dispersion medium
- a water-based composition containing water may be used.
- water-based photocurable compositions for example, the following compositions are known.
- a resin comprising water, a colorant, and a compound having a radical polymerizable group as an inkjet ink composition having excellent ejection stability while maintaining curability by ultraviolet irradiation in the presence of water or a solvent
- An ink-jet ink composition containing an emulsion, an inorganic particle dispersion, and a photoradical initiator is known (for example, see JP2013-199602A).
- An aqueous emulsion containing a vinyl polymer having a specific acrylic functional group at at least one terminal is known as an aqueous emulsion that can be heat-cured or photocured and can be suitably used for a coating agent or the like (for example, JP, 2000-136211, A).
- compositions are known as a photocurable composition which is not limited to an aqueous composition, for example.
- a photocurable composition which is not limited to an aqueous composition, for example.
- a color-forming photosensitive composition that has good color stability after exposure by infrared laser exposure and that can provide high color development even after exposure over time
- a coloring photosensitive composition containing a microgel encapsulating a dye and a binder polymer is known (see, for example, JP 2011-213114 A).
- Ink jet printing ink that cures upon irradiation includes at least one radiation curable monomer, at least one inert thermoplastic resin, at least one radical photoinitiator, and at least one colorant at 25 ° C.
- Inkjet inks are known having a viscosity of less than 100 mPas, at least one inert resin being present at 2 to 15% by weight relative to the total weight and having a molecular weight of 1,500 to 70,000 (See, for example, JP-T-2009-542833).
- an energy curable aqueous composition with improved characteristics an energy curable aqueous composition containing water, an ethylenically unsaturated oligomer, and a resin not containing an energy curable functional group is known. (See, for example, JP-T 2008-536004).
- a cured film for example, an image
- a photocurable composition for example, a photocurable ink
- an ink-jet ink composition described in JP2013-199602A an aqueous emulsion described in JP2000-136211, a color developing photosensitive composition described in JP2011-213114A
- the energy curable aqueous composition described in JP-A-2008-536004 tends to have insufficient sensitivity to light, and thus the hardness of the formed cured film (image) tends to be insufficient.
- the compositions described in these documents tend to be inferior in storage stability.
- each component of the inkjet ink described in JP-T-2009-542833 is considered to be a component that is difficult to dissolve or disperse in water. Therefore, it is considered difficult to prepare the ink-jet ink described in JP-T-2009-542833 as an aqueous dispersion.
- a cured film for example, an image
- a photocurable composition for example, a photocurable ink
- an object of one embodiment of the present invention is to provide an aqueous dispersion that can form a film excellent in hardness and surface shape and that is excellent in storage stability, and a method for producing the same.
- Another object of one embodiment of the present invention is to provide an image forming method capable of forming an image excellent in hardness and surface shape.
- a resin having a polymerizable group, a polymerizable group, a three-dimensional crosslinked structure containing at least one bond selected from a urethane bond and a urea bond, and encapsulating a photopolymerization initiator An aqueous dispersion comprising gel particles and water, wherein the total solid content of the gel particles is 0.1% by mass to 100% by mass with respect to the total amount of the resin having a polymerizable group.
- ⁇ 2> The water dispersion according to ⁇ 1>, wherein the photopolymerization initiator includes at least one of a carbonyl compound and an acylphosphine oxide compound.
- ⁇ 3> The water dispersion according to ⁇ 1> or ⁇ 2>, in which the gel particles have a hydrophilic group on the surface.
- ⁇ 4> The water dispersion according to any one of ⁇ 1> to ⁇ 3>, wherein the gel particles include a polymerizable monomer.
- ⁇ 5> The water dispersion according to any one of ⁇ 1> to ⁇ 4>, wherein the gel particles include a sensitizer.
- ⁇ 6> The aqueous dispersion according to any one of ⁇ 1> to ⁇ 5>, wherein the resin having a polymerizable group has a polyurethane structure.
- ⁇ 7> The water according to any one of ⁇ 1> to ⁇ 6>, wherein the total solid content of the gel particles is 5% by mass to 75% by mass with respect to the total amount of the resin having a polymerizable group.
- Dispersion. ⁇ 8> The aqueous dispersion according to any one of ⁇ 1> to ⁇ 7>, wherein the content of the resin having a polymerizable group is 2% by mass to 40% by mass with respect to the total amount of the aqueous dispersion.
- the preparation process Oil phase component including photopolymerization initiator, trifunctional or higher functional isocyanate compound, polymerizable monomer, and organic solvent, photopolymerization initiator, trifunctional or higher functional isocyanate compound having a polymerizable group, and organic solvent And an oil phase component selected from an oil phase component containing a photopolymerization initiator, a trifunctional or higher functional isocyanate compound having a polymerizable group, a polymerizable monomer, and an organic solvent, and an aqueous phase component containing water Are mixed and emulsified to obtain an emulsion
- Trifunctional or higher functional isocyanate compounds contained in the oil phase component are isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, m-xylylene diisocyanate, and dicyclohexylmethane 4
- the method for producing an aqueous dispersion according to ⁇ 10> which is an isocyanate compound derived from at least one selected from 4,4′-diisocyanate.
- An image forming method comprising:
- a water dispersion excellent in storage stability and a method for producing the same can be provided, which can form a film having excellent hardness and surface shape.
- an image forming method capable of forming an image excellent in hardness and surface shape is provided.
- a numerical range indicated using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
- process is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.
- light is a concept including active energy rays such as ⁇ rays, ⁇ rays, electron rays, ultraviolet rays, visible rays, and infrared rays.
- active energy rays such as ⁇ rays, ⁇ rays, electron rays, ultraviolet rays, visible rays, and infrared rays.
- ultraviolet rays may be referred to as “UV (Ultra Violet) light”.
- LED Light Emitting Diode
- (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid
- (meth) acrylate is a concept including both acrylate and methacrylate
- (meth) acryloyl group is a concept including both an acryloyl group and a methacryloyl group.
- the aqueous dispersion of the present disclosure includes a tertiary resin including a resin having a polymerizable group (hereinafter also referred to as “polymerizable resin”), a polymerizable group, and at least one bond selected from a urethane bond and a urea bond.
- Polymerizable resin a resin having a polymerizable group
- the aqueous dispersion of the present disclosure contains a polymerizable resin separately from the gel particles (that is, outside the gel particles), and the total solid content of the gel particles is the total amount of the polymerizable resin. In contrast, the content is 0.1% by mass to 100% by mass. That is, the aqueous dispersion of the present disclosure contains a relatively large amount of polymerizable resin (specifically, a content that is greater than or equal to the total solid content of the gel particles) apart from the gel particles.
- that the aqueous dispersion contains a polymerizable resin outside the gel particles means that the aqueous dispersion contains a polymerizable resin that is not encapsulated in the gel particles.
- the total solid content of the gel particles refers to the photopolymerization initiator contained in the gel particles when a solvent (organic solvent, water, etc., the same shall apply hereinafter) is contained in the gel particles.
- the total amount excluding the solvent from the included gel particles means the total amount of the gel particles including the photopolymerization initiator and the like included when the gel particles do not contain the solvent.
- a film excellent in hardness (for example, pencil hardness) and surface shape can be formed. Moreover, the aqueous dispersion of this indication is excellent in storage stability.
- the gel particles have a polymerizable group and include a photopolymerization initiator. That is, in the aqueous dispersion of the present disclosure, a conventional aqueous dispersion (for example, an aqueous emulsion containing a resin particle having a polymerizable group and not containing a photopolymerization initiator, and a photopolymerization initiator); In comparison, the distance between the polymerizable group and the photopolymerization initiator is closer.
- the aqueous dispersion of the present disclosure contains a relatively large amount of the polymerizable resin outside the gel particles (specifically, at a content equal to or higher than the total solid content of the gel particles).
- the gel particles function as a photopolymerization initiator with respect to the polymerizable resin having such a content. More specifically, it is considered that the photopolymerization initiator encapsulated in the gel particles acts not only on the polymerizable groups of the gel particles but also on the polymerizable groups of the above-described polymerizable resin. .
- the film can be cured with high sensitivity, so that it is considered that a film having excellent hardness is formed.
- the fact that the three-dimensional cross-linked structure of the gel particles contains at least one kind of bond selected from urethane bonds and urea bonds is considered to contribute to the improvement of the hardness of the film.
- a film having excellent hardness can be formed according to the aqueous dispersion of the present disclosure.
- the present inventors presume as follows.
- One reason why the aqueous dispersion of the present disclosure can form a film having an excellent surface shape is that the aqueous dispersion of the present disclosure contains a relatively large amount of a resin component (specifically, a polymerizable resin).
- a resin component specifically, a polymerizable resin.
- Another reason that the aqueous dispersion of the present disclosure can form a film having an excellent surface shape is that the polymerizable group of the polymerizable resin can improve the uniformity of film curing.
- the present inventors presume as follows. That is, in the aqueous dispersion of the present disclosure, the gel particles encapsulate the photopolymerization initiator, so that the photopolymerization initiator over time is compared with the case where the gel particles do not encapsulate the photopolymerization initiator. Since settling is suppressed, it is considered that the storage stability of the aqueous dispersion is improved.
- the resin emulsion in the inkjet ink composition described in JP2013-199602A and the particles contained in the aqueous emulsion described in JP2000-136211 None of them have a three-dimensional crosslinked structure and are not gel particles.
- the microgel in the color developing photosensitive composition described in JP2011-213114A does not have a polymerizable group.
- the energy curable aqueous composition described in JP-T-2008-536004 does not contain gel particles having a polymerizable group and encapsulating a photopolymerization initiator. Therefore, it is considered that the composition described in any document is inferior in hardness of the formed film and in storage stability as compared with the aqueous dispersion of the present disclosure.
- each component of the inkjet ink described in JP-T-2009-542833 is considered to be a component that is difficult to dissolve or disperse in water. Therefore, it is considered difficult to prepare the ink-jet ink described in JP-T-2009-542833 as an aqueous dispersion.
- the aqueous dispersion of the present disclosure can further form a film having excellent adhesion to the substrate.
- the aqueous dispersion of the present disclosure contains gel particles having a polymerizable group and containing a photopolymerization initiator. It is conceivable that the film can be cured with high sensitivity.
- the aqueous dispersion of the present disclosure contains a resin component (polymerizable resin), thereby suppressing curing shrinkage of the film.
- redispersibility may be required for an aqueous dispersion of particles.
- “redispersibility” means that an aqueous liquid (for example, water, an aqueous solution, an aqueous dispersion, etc.) is supplied to a solidified product formed by evaporation of water in the aqueous dispersion. It means the property that the particles in the solidified material are dispersed again in the aqueous liquid.
- the solidified product include a solidified product of an aqueous dispersion formed on a coating head or an inkjet head.
- the aqueous dispersion of the present disclosure is excellent in redispersibility by containing gel particles.
- the aqueous dispersion of the present disclosure is excellent in dischargeability when used as, for example, an ink composition for ink jet recording (hereinafter, also simply referred to as “ink composition”).
- ink composition for ink jet recording
- the reason for this is considered that the aqueous dispersion of the present disclosure is excellent in redispersibility as described above. That is, even if the water in the water dispersion as the ink composition evaporates and the gel particles are fixed in the vicinity of the nozzle of the ink jet recording apparatus, a new ink composition (that is, the water dispersion) is supplied. The gel particles are easily dispersed again, and the occurrence of nozzle clogging is suppressed.
- the total solid content of the gel particles with respect to the total amount of the polymerizable resin is 0.1% by mass to 100% by mass as described above.
- the “content of the total solid content of the gel particles with respect to the total amount of the polymerizable resin” refers to an amount represented by the following formula.
- the content of the total solid content of the gel particles with respect to the total amount of the polymerizable resin is 0.1% by mass or more, effects such as an improvement in film hardness due to the gel particles are effectively exhibited.
- the content of the total solid content of the gel particles with respect to the total amount of the polymerizable resin is 100% by mass or less, effects such as improvement of the surface state of the film due to the polymerizable resin are effectively exhibited.
- the content of the total solid content of the gel particles with respect to the total amount of the polymerizable resin is 0.1% by mass to 100% by mass as described above, but preferably 0.1% by mass from the viewpoint of film hardness and planarity.
- the content is more than 100% by mass, more preferably 1% by mass to 100% by mass, still more preferably 5% by mass to 75% by mass, and particularly preferably 10% by mass to 50% by mass.
- the content of the polymerizable resin in the aqueous dispersion is preferably 2% by mass to 40% by mass, and more preferably 3% by mass to 30% by mass with respect to the total amount of the aqueous dispersion. It is particularly preferably 7% by mass to 20% by mass.
- the inclusion of the photopolymerization initiator in the gel particles means that the photopolymerization initiator is a photopolymerization initiator having low solubility in water (for example, water solubility at 25 ° C. 1.0% by mass or less) or a photopolymerization initiator having low dispersibility is also easy to use.
- the gel particles encapsulate the photopolymerization initiator, thereby widening the range of selection of the photopolymerization initiator to be used, and consequently, the range of selection of the light source to be used. Therefore, the curing sensitivity can be improved as compared with the conventional case.
- carbonyl compounds and acylphosphine oxide compounds are photopolymerization initiators that are particularly excellent in curing sensitivity to irradiation with active energy rays.
- carbonyl compounds and acylphosphine oxide compounds have low solubility in water, it has heretofore been difficult to contain them in aqueous compositions.
- the gel particles encapsulate the photopolymerization initiator, so that the photopolymerization initiator has excellent sensitivity to light but low solubility in water, such as a carbonyl compound and an acylphosphine oxide compound.
- a photopolymerization initiator can be selected.
- the photopolymerization initiator included in the gel particles preferably contains at least one of a carbonyl compound and an acylphosphine oxide compound, and more preferably contains an acylphosphine oxide compound.
- the photopolymerization initiator is an acylphosphine oxide compound
- sensitivity to light particularly sensitivity to LED light
- the wavelength of the LED light is preferably 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm.
- the gel particles can also contain components (polymerizable monomer, sensitizer, resin, etc.) other than the photopolymerization initiator.
- the aqueous dispersion of the present disclosure can be contained in an aqueous dispersion which is an aqueous composition by encapsulating a substance having low solubility in water in gel particles. This is also one of the advantages of the aqueous dispersion of the present disclosure.
- the photopolymerization initiator is included in the gel particles means that the photopolymerization initiator is contained in the gel particles.
- the “inside of the gel particle” here means a void having a three-dimensional crosslinked structure.
- the encapsulation rate (% by mass) of the photopolymerization initiator is preferably 10% by mass or more, more preferably 50% by mass or more, from the viewpoint of the curing sensitivity of the film.
- the encapsulation rate (% by mass) of the photopolymerization initiator refers to the photopolymerization initiator encapsulated in the gel particles with respect to the total amount of the photopolymerization initiator in the aqueous dispersion when the aqueous dispersion is prepared. It means quantity and refers to the value obtained as follows.
- encapsulation rate (% by mass) of photopolymerization initiator-
- the following operation is performed under the condition of a liquid temperature of 25 ° C.
- the following operations are performed using the aqueous dispersion as it is when the aqueous dispersion does not contain a pigment.
- the aqueous dispersion is first centrifuged by centrifugation. The pigment is removed from the aqueous dispersion, and the dispersion is removed from the aqueous dispersion.
- sample 1 two samples of the same mass
- sample 2 two samples of the same mass
- 500 mass times tetrahydrofuran (THF) with respect to the total solid content in sample 1 is added and mixed to prepare a diluted solution.
- the obtained diluted solution is centrifuged at 80,000 rpm (round per minute; the same applies hereinafter) for 40 minutes.
- a supernatant liquid (hereinafter referred to as “supernatant liquid 1”) generated by centrifugation is collected. By this operation, it is considered that all the photopolymerization initiator contained in the sample 1 is extracted into the supernatant liquid 1.
- the mass of the photopolymerization initiator contained in the collected supernatant liquid 1 is measured by liquid chromatography (for example, a liquid chromatography apparatus manufactured by Waters).
- the mass of the obtained photopolymerization initiator is defined as “total amount of photopolymerization initiator”.
- the sample 2 is subjected to centrifugal separation under the same conditions as the centrifugal separation performed on the diluent.
- a supernatant liquid (hereinafter referred to as “supernatant liquid 2”) generated by centrifugation is collected. By this operation, it is considered that in the sample 2, the photopolymerization initiator that was not included in the gel particles (that is, free) was extracted into the supernatant liquid 2.
- the total amount of the two or more kinds of photopolymerization initiators is defined as “total amount of photopolymerization initiators” and two or more kinds of photopolymerization initiators are liberated.
- the total amount of the photopolymerization initiator may be determined by using the total amount as “free amount of photopolymerization initiator”, and the amount of any one photopolymerization initiator
- the inclusion amount of any one of the photopolymerization initiators may be determined by setting “the total amount” and the free amount of any one of the above photopolymerization initiators as “the free amount of the photopolymerization initiator”.
- Whether or not components other than the photopolymerization initiator are encapsulated in the gel particles can also be confirmed by a method similar to the method for examining whether or not the photopolymerization initiator is encapsulated. However, for compounds having a molecular weight of 1,000 or more, the masses of the compounds contained in the above supernatant liquid 1 and supernatant liquid 2 were measured by gel permeation chromatography (GPC). The amount of inclusion (mass%) of the compound is determined.
- the measurement by gel permeation chromatography uses HLC (registered trademark) -8020GPC (Tosoh Corp.) as a measuring device and TSKgel (registered trademark) Super Multipore HZ- as a column.
- HLC registered trademark
- TSKgel registered trademark
- THF tetrahydrofuran
- the sample concentration is 0.45 mass%
- the flow rate is 0.35 ml / min
- the sample injection amount is 10 ⁇ l
- the measurement temperature is 40 ° C.
- the measurement is performed using an RI detector.
- the calibration curve is “Standard sample TSK standard, polystyrene” of Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500 ",” A-1000 ", and” n-propylbenzene ".
- the “three-dimensional crosslinked structure” refers to a three-dimensional network structure formed by crosslinking.
- gel particles are formed by forming a three-dimensional crosslinked structure in the particles. That is, in the present specification, it is synonymous that the particles have a three-dimensional cross-linking structure and that the particles are gel particles.
- the aqueous dispersion contains gel particles having a three-dimensional crosslinked structure.
- the following operation is performed under the condition of a liquid temperature of 25 ° C.
- the following operations are performed using the aqueous dispersion as it is when the aqueous dispersion does not contain a pigment, and when the aqueous dispersion contains a pigment, the water dispersion is first subjected to centrifugal separation. Removal of the pigment from the dispersion is carried out on the aqueous dispersion from which the pigment has been removed.
- a sample is taken from the aqueous dispersion.
- 500 mass times tetrahydrofuran (THF) with respect to the total solid content in this sample is added and mixed to prepare a diluted solution.
- the obtained diluted solution is centrifuged at 80,000 rpm for 40 minutes. After centrifugation, visually check for residue.
- the residue is re-dispersed with water to prepare a re-dispersion, and the obtained re-dispersion is subjected to light scattering using a wet particle size distribution analyzer (LA-910, manufactured by Horiba, Ltd.).
- LA-910 wet particle size distribution analyzer
- the polymerizable group of the polymerizable resin and the polymerizable group of the gel particle are each preferably a group containing an ethylenic double bond, and at least one of a vinyl group and a 1-methylvinyl group is present. More preferred are groups containing.
- a (meth) acryloyl group is particularly preferable from the viewpoints of polymerization reactivity and the hardness of the formed film.
- Each of the polymerizable resin and the gel particles may contain only one type of polymerizable group, or may contain two or more types. Further, the polymerizable group of the polymerizable resin and the polymerizable group of the gel particles may be the same group or different groups.
- the gel particle has a polymerizable group means that the gel particle includes at least a polymerizable group contained in the three-dimensional crosslinked structure and a polymerizable group not contained in the three-dimensional crosslinked structure. It means having one. That is, in the gel particles, the polymerizable group may exist as a part of the three-dimensional crosslinked structure or may exist as a part other than the three-dimensional crosslinked structure. “The polymerizable group exists as a part other than the three-dimensional crosslinked structure” means that the gel particle contains a polymerizable monomer (that is, a monomer having a polymerizable group). In any case, the polymerizable group is preferably present on the surface part of the gel particle (contact part with water). “The gel particles have a polymerizable group” can be confirmed, for example, by Fourier transform infrared spectroscopy (FT-IR) analysis.
- FT-IR Fourier transform infrared spectroscopy
- the gel particles preferably include a monomer having a polymerizable group (polymerizable monomer) from the viewpoint of sensitivity and film hardness.
- a monomer having a polymerizable group (polymerizable monomer) will be described later.
- a gel particle has a hydrophilic group on the surface.
- the gel particles have a hydrophilic group on the surface thereof, whereby dispersibility in the aqueous dispersion is further improved. Further, the gel particles have a hydrophilic group on the surface, whereby the hydrophilicity of the gel particles is improved and the storage stability and redispersibility are excellent.
- the hydrophilic group may exist as a part of the three-dimensional crosslinked structure, or may exist as a part other than the three-dimensional crosslinked structure.
- the hydrophilic group exists as a part other than the three-dimensional crosslinked structure” means that the gel particle contains a compound having a hydrophilic group, separately from the three-dimensional crosslinked structure.
- hydrophilic groups present on the surface of the gel particles include carboxy group, carboxy group salt, phosphonic acid group, phosphonic acid group salt, phosphoric acid group, phosphoric acid group salt, sulfo group, sulfo group salt, sulfuric acid Groups, sulfate salts, groups having a polyether structure, groups having a betaine structure, and the like.
- the carboxy group salt, the sulfo group salt, the sulfate group salt, the phosphonic acid group salt, and the phosphoric acid group salt described above may be salts formed by neutralization in the production process of the gel particles. Good.
- the gel particle When the gel particle has a hydrophilic group on its surface, the gel particle may have only one kind of hydrophilic group or two or more kinds.
- the “hydrophilic group” is distinguished from an active hydrogen group (hydroxy group, primary amino group, secondary amino group, and mercapto group) described later.
- the hydrophilic group present on the surface of the gel particle is preferably at least one selected from a group having a polyether structure, a carboxy group, and a salt of the carboxy group.
- the group having a polyether structure is preferably a monovalent group containing a polyalkyleneoxy group, and more preferably a group (WS) represented by the following formula (WS).
- R W1 represents an optionally branched alkylene group having 1 to 6 carbon atoms
- R W2 represents an optionally branched alkyl group having 1 to 6 carbon atoms
- nw is Represents an integer of 2 to 200
- * represents a bonding position.
- the optionally substituted alkylene group having 1 to 6 carbon atoms represented by R W1 preferably has 2 to 4 carbon atoms, more preferably 2 or 3, 2 (that is, R W1 is an ethylene group) is particularly preferable.
- the optionally substituted alkyl group having 1 to 6 carbon atoms represented by R W2 preferably has 1 to 4 carbon atoms (that is, R W2 is 1).
- a methyl group) is particularly preferred.
- nw represents an integer of 2 to 200, and nw is preferably an integer of 10 to 200, more preferably an integer of 10 to 150, still more preferably an integer of 20 to 150, 20 to An integer of 100 is particularly preferred.
- the gel particle includes the sensitizer.
- the water dispersion of this indication contains a sensitizer, decomposition
- the gel particles include the sensitizer, the reactivity with the photopolymerization initiator is further improved. As a result, sensitivity and film hardness are further improved. A preferable range of the sensitizer will be described later.
- the polymerizable resin has a polyurethane structure from the viewpoint of further improving the hardness of the film and further improving the adhesion of the film to the substrate (particularly, the adhesion to the polyethylene terephthalate (PET) substrate). It is preferable to have.
- the aqueous dispersion of the present disclosure can be suitably used as a liquid for forming a film (for example, an image) on a substrate (for example, a recording medium).
- the liquid include an ink composition (for example, an ink composition for inkjet recording) for forming an image on a base material as a recording medium, and a coating liquid (for example, for forming a coating film on the base material).
- photosensitive resin compositions such as coating agents, adhesives and paints).
- the aqueous dispersion of the present disclosure is particularly preferably used for inkjet recording (that is, the aqueous dispersion of the present disclosure is used as an ink composition for inkjet recording).
- An ink composition (preferably an ink composition for inkjet recording) that is one of the uses of the aqueous dispersion of the present disclosure includes a transparent ink that does not contain a color material, even if the ink composition contains a color material. It may be a composition (sometimes referred to as “clear ink” or the like). The same applies to a coating liquid that is another application of the aqueous dispersion of the present disclosure.
- the substrate for forming a film using the aqueous dispersion of the present disclosure is not particularly limited, and for example, a known substrate can be used as a support or a recording material.
- a known substrate can be used as a support or a recording material.
- the substrate include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, metal plate such as aluminum, zinc, copper, etc.), plastic film (eg, polychlorinated).
- Polyvinyl Chloride (PVC) resin cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate (PET), polyethylene (PE: Polyethylene), polystyrene (PS) : Polystyrene), polypropylene (PP: Polypropylene), polycarbonate (PC: Polycarbonate), polyvinyl acetal, acrylic resin film, etc.), paper on which the above-mentioned metal is laminated or vapor-deposited, and the above-mentioned metal is laminating. A plastic film which is to or deposited, and the like.
- Non-absorbable substrates include polyvinyl chloride (PVC) substrates, polystyrene (PS) substrates, polycarbonate (PC) substrates, polyethylene terephthalate (PET) substrates, polypropylene (PP) substrates, acrylic resin groups
- PVC polyvinyl chloride
- PS polystyrene
- PC polycarbonate
- PET polyethylene terephthalate
- PP polypropylene
- the aqueous dispersion of the present disclosure contains a polymerizable resin (that is, a resin having a polymerizable group) separately from the gel particles (that is, outside the gel particles).
- a polymerizable resin that is, a resin having a polymerizable group
- the polymerizable resin contributes to improving the hardness of the film, improving the adhesion between the film and the substrate, and improving the surface state of the film.
- the polymerizable resin is a resin, it contributes to the improvement of the surface condition of the film and the suppression of curing shrinkage (improvement of adhesion between the film and the substrate).
- the aqueous dispersion of the present disclosure may contain only one type of polymerizable resin, or may contain two or more types.
- the aqueous dispersion of this indication may contain resin which does not have a polymeric group, unless the effect of this indication is impaired.
- a resin having a polyurethane structure for example, polyurethane
- ethylene oxide-modified acrylate hereinafter also referred to as “EO-modified acrylate”
- water-soluble epoxy acrylate water-soluble
- carboxylic acid-modified acrylates water-soluble phosphoric acid-modified acrylates
- water-soluble polyester acrylates water-soluble
- the polymerizable group in the polymerizable resin is preferably a group containing an ethylenic double bond, more preferably a group containing at least one of a vinyl group and a 1-methylvinyl group, A (meth) acryloyl group is particularly preferred.
- the polymerizable resin is preferably a water-soluble resin or a water-dispersible resin, and more preferably a water-dispersible resin.
- water-soluble in the water-soluble resin refers to a property in which the amount dissolved in 100 g of distilled water at 25 ° C. exceeds 1 g when dried at 105 ° C. for 2 hours.
- water dispersibility in the water dispersible resin refers to the property of being insoluble in water and being dispersed in water.
- water-insoluble refers to the property that the amount dissolved in 100 g of distilled water at 25 ° C. is 1 g or less when dried at 105 ° C. for 2 hours.
- the polymerizable resin includes carboxy group, carboxy group salt, sulfo group, sulfo group salt, sulfuric acid group, sulfuric acid group salt, phosphonic acid group, phosphonic acid group salt, phosphoric acid group, phosphoric acid group salt.
- an alkali metal cation such as sodium or potassium, an alkaline earth metal cation such as calcium or magnesium, an ammonium cation, or a phosphonium cation is preferable, and an alkali metal cation is particularly preferable.
- the alkyl group contained in the ammonium group of the ammonium base is preferably a methyl group or an ethyl group.
- the counter anion of the ammonium base is preferably a halogen anion such as chlorine or bromine, a sulfate anion, a nitrate anion, a phosphate anion, a sulfonate anion, a carboxylate anion, or a carbonate anion, and a halogen anion, a sulfonate anion, or Carboxylic acid anions are particularly preferred.
- a substituent on the nitrogen atom of the carboxylic acid amide group an alkyl group having 8 or less carbon atoms is preferable, and an alkyl group having 6 or less carbon atoms is particularly preferable.
- the resin having an alkyleneoxy group preferably has an alkyleneoxy chain composed of repeating alkyleneoxy groups. The number of alkyleneoxy groups contained in the alkyleneoxy chain is preferably 2 or more, and particularly preferably 4 or more.
- the weight-average molecular weight of the polymerizable resin is preferably 700 or more and 200,000 or less, from the viewpoint of further improving the planarity of the film, the adhesion between the film and the substrate, and the dispersion stability of the aqueous dispersion. Preferably they are 800 or more and 100,000 or less, More preferably, they are 900 or more and 50,000 or less.
- the weight average molecular weight of the polymerizable resin is a value measured by gel permeation chromatography (GPC).
- the volume average particle diameter of the polymerizable resin in the aqueous dispersion is not particularly limited, but is preferable from the viewpoint of dispersibility. Is from 10 nm to 10,000 nm, more preferably from 20 nm to 1000 nm, still more preferably from 30 nm to 500 nm.
- the gel particles are a dispersoid in the aqueous dispersion of the present disclosure, but when the polymerizable resin is a resin particle (for example, a particle made of a water dispersible resin), the polymerizable resin is also an aqueous dispersion of the present disclosure. It can be a dispersoid in the product.
- the polymerizable resin is a resin particle (for example, a particle made of a water dispersible resin)
- the polymerizable resin is also an aqueous dispersion of the present disclosure. It can be a dispersoid in the product.
- the preferred range of the content of the polymerizable resin in the aqueous dispersion is as described above.
- the aqueous dispersion of the present disclosure includes gel particles having a polymerizable group, a three-dimensional cross-linking structure including at least one bond selected from a urethane bond and a urea bond, and including a photopolymerization initiator. contains.
- Gel particles are a dispersoid in the aqueous dispersion of the present disclosure.
- the photopolymerization initiator included in the gel particles includes those present in the voids of the three-dimensional crosslinked structure of the gel particles without being bonded to the three-dimensional crosslinked structure.
- the term “gel particle” includes a photopolymerization initiator and the like present in the voids of the three-dimensional crosslinked structure.
- the aqueous dispersion of the present disclosure includes the gel particles, so that it has excellent dispersibility and redispersibility when solidification occurs, and cures with high sensitivity. A film excellent in solvent resistance can be obtained.
- the adjacent gel particles can be crosslinked with each other, and the gel particles and the polymerizable resin can be crosslinked to form a film. it can.
- the gel particles have a three-dimensional crosslinked structure including at least one type of bond selected from urethane bonds and urea bonds, a film (for example, an image) having excellent strength can be obtained.
- a film for example, an image excellent in mechanical strength can be obtained.
- the gel particles contain a photopolymerization initiator so that they are cured with high sensitivity and have high crosslinkability.
- the three-dimensional cross-linking structure of the gel particles includes at least one type of bond selected from urethane bonds and urea bonds. More preferably, the three-dimensional crosslinked structure includes both a urethane bond and a urea bond.
- the total amount (mmol / g) of urethane bonds and urea bonds contained in 1 g of the three-dimensional crosslinked structure is preferably 1 mmol / g to 10 mmol / g, more preferably 1.5 mmol / g to 9 mmol / g, and 2 mmol / g. ⁇ 8 mmol / g is particularly preferred.
- the three-dimensional crosslinked structure of the gel particles preferably includes the following structure (1).
- the three-dimensional crosslinked structure may include a plurality of the following structures (1), and the plurality of structures (1) may be the same structure or different structures.
- X is a hydrocarbon group which may have a ring structure, —NH—,> N—, —C ( ⁇ O) —, —O—, and —S—. It represents a (p + m + n) -valent organic group formed by linking at least two selected.
- R 1 , R 2 , and R 3 each independently represent a hydrocarbon group having 5 to 15 carbon atoms that may have a ring structure.
- * represents a bonding position, p, m, and n are each 0 or more, and p + m + n is 3 or more.
- the total molecular weight of X, R 1 , R 2 , and R 3 is preferably less than 2000, preferably less than 1500, and more preferably less than 1000.
- the encapsulation rate of the compound encapsulated in the gel particles can be increased.
- the hydrocarbon group in the organic group represented by X is preferably a linear or branched hydrocarbon group having 1 to 15 carbon atoms, and a linear or branched hydrocarbon group having 1 to 10 carbon atoms. Groups are more preferred.
- Examples of the ring structure that the hydrocarbon group in the organic group represented by X and the hydrocarbon group represented by R 1 , R 2 , and R 3 may have include, for example, an alicyclic structure and an aromatic ring Structure is mentioned.
- Examples of the alicyclic structure include a cyclohexane ring structure, a bicyclohexane ring structure, a bicyclodecane ring structure, an isobornene ring structure, a dicyclopentane ring structure, an adamantane ring structure, and a tricyclodecane ring structure.
- Examples of the aromatic ring structure include a benzene ring structure, a naphthalene ring structure, and a biphenyl ring structure.
- p is 0 or more, preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 3.
- m is 0 or more, preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 3.
- n is 0 or more, preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 3.
- p + m + n is preferably an integer of 3 to 10, more preferably an integer of 3 to 8, and still more preferably an integer of 3 to 6.
- the (p + m + n) -valent organic group represented by X is preferably a group represented by any one of the following (X-1) to (X-12).
- n represents an integer of 1 to 200, preferably an integer of 1 to 50, more preferably an integer of 1 to 15, and particularly preferably It is an integer from 1 to 8.
- * represents a bonding position.
- Y represents the following (Y-1).
- * 1 represents a bonding position with S or O in (X-1) to (X-10), and * 2 represents R 1 , R 2 , or R in structure (1).
- 3 represents the binding position.
- R 1 , R 2 , and R 3 each independently represent a hydrocarbon group having 5 to 15 carbon atoms that may have a ring structure.
- the hydrocarbon group in R 1 , R 2 , and R 3 may have a substituent, and examples of the substituent include the hydrophilic groups described above.
- R 1 , R 2 , and R 3 are preferably each independently a group represented by any one of the following (R-1) to (R-20).
- * represents a bonding position.
- the content of the structure (1) in the three-dimensional crosslinked structure is preferably 8% by mass to 100% by mass, more preferably 25% by mass to 100% by mass with respect to the total mass of the three-dimensional crosslinked structure. A mass% to 100 mass% is more preferred.
- the three-dimensional crosslinked structure preferably includes at least one of the following structure (2), structure (3), and structure (4) as structure (1).
- R 1 , R 2 , and R 3 each independently represent a hydrocarbon group having 5 to 15 carbon atoms that may have a ring structure.
- the hydrocarbon group represented by R 1, R 2 and R 3 each, the structure of (1), R 1, R 2, and synonymous with hydrocarbon groups represented by R 3 And the preferred range is also the same.
- * represents a bonding position.
- R 1 , R 2 , and R 3 each independently represent a hydrocarbon group having 5 to 15 carbon atoms that may have a ring structure.
- the hydrocarbon group represented by R 1, R 2 and R 3 each, the structure of (1), R 1, R 2, and synonymous with hydrocarbon groups represented by R 3 And the preferred range is also the same.
- * represents a bonding position.
- R 1 , R 2 , and R 3 each independently represent a hydrocarbon group having 5 to 15 carbon atoms that may have a ring structure.
- the hydrocarbon group represented by R 1, R 2 and R 3 each, the structure of (1), R 1, R 2, and synonymous with hydrocarbon groups represented by R 3 And the preferred range is also the same.
- * represents a bonding position.
- the three-dimensional crosslinked structure in the gel particles can be formed, for example, by a reaction between a trifunctional or higher functional isocyanate compound or a bifunctional isocyanate compound and water or a compound having two or more active hydrogen groups.
- the raw material for producing the gel particles contains at least one compound having three or more reactive groups (isocyanate group or active hydrogen group)
- the crosslinking reaction proceeds more effectively in three dimensions.
- a three-dimensional network structure is formed more effectively.
- the three-dimensional crosslinked structure in the gel particles is preferably a product formed by a reaction between a trifunctional or higher functional isocyanate compound and water.
- the trifunctional or higher functional isocyanate compound is a compound having three or more isocyanate groups in the molecule, and a compound synthesized by a method described later and a known compound can be used.
- Examples of the trifunctional or higher functional isocyanate compound include a trifunctional or higher functional aromatic isocyanate compound and a trifunctional or higher functional aliphatic isocyanate compound.
- Known compounds include, for example, compounds described in “Polyurethane Resin Handbook” (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)).
- the trifunctional or higher functional isocyanate compound a compound having three or more isocyanate groups in the molecule, specifically, a compound represented by the following formula (X) is preferable.
- X 1 represents an n-valent organic group.
- n is 3 or more. n is preferably from 3 to 10, more preferably from 3 to 8, and even more preferably from 3 to 6.
- the trifunctional or higher functional isocyanate compound is preferably a compound derived from a bifunctional isocyanate compound (a compound having two isocyanate groups in the molecule).
- the trifunctional or higher functional isocyanate compound is selected from isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, m-xylylene diisocyanate, and dicyclohexylmethane 4,4′-diisocyanate. More preferably, it is an isocyanate compound derived from at least one kind. “Induced” means that the above compound is used as a raw material and includes a structure derived from the raw material.
- trifunctional or higher functional isocyanate compound for example, a bifunctional isocyanate compound (a compound having two isocyanate groups in the molecule) and a trifunctional or higher functional polyol such as a polyol, polyamine, and polythiol have three or more functional molecules.
- Trifunctional or higher isocyanate compound (adduct type), bifunctional isocyanate compound trimer (biuret type or isocyanurate type), and benzene isocyanate formalin as an adduct (adduct) with a compound having an active hydrogen group
- a compound having three or more isocyanate groups in the molecule such as a condensate is also preferable.
- These trifunctional or higher functional isocyanate compounds may be a mixture containing a plurality of compounds, and a compound represented by the following formula (11A) or (11B) is a main component of these mixtures. Preferably, other components may be included.
- adduct type tri- or higher functional isocyanate compound a compound represented by the following formula (11A) or formula (11B) is preferable.
- X 2 is a (p + m + n) -valent organic group, p, m, and n are each 0 or more, and p + m + n is 3 or more.
- X 3 to X 11 each independently represents O, S, or NH.
- R 1 to R 6 each independently represents a divalent organic group.
- Z represents a divalent organic group.
- X 2 is a hydrocarbon group optionally having a ring structure, —NH—,> N—, —C ( ⁇ O) —, —O—, and A (p + m + n) -valent organic group formed by linking at least two selected from the group consisting of —S— is preferable.
- p + m + n is preferably 3 to 10, more preferably 3 to 8, and still more preferably 3 to 6.
- X 3 to X 11 are each independently preferably O or S, and more preferably O.
- R 1 to R 6 are preferably each independently a hydrocarbon group having 5 to 15 carbon atoms which may have a ring structure.
- preferred embodiments of R 1 to R 6 are each independently the same as the preferred embodiment of R 1 in the structure (1).
- examples of the ring structure when X 2 is a hydrocarbon group which may have a ring structure include an alicyclic structure and an aromatic ring structure.
- examples of the alicyclic structure include a cyclohexane ring structure, a bicyclohexane ring structure, a bicyclodecane ring structure, an isobornene ring structure, a dicyclopentane ring structure, an adamantane ring structure, and a tricyclodecane ring structure.
- examples of the aromatic ring structure include a benzene ring structure, a naphthalene ring structure, and a biphenyl ring structure.
- examples of the ring structure include alicyclic Examples include structures and aromatic ring structures.
- examples of the alicyclic structure include a cyclohexane ring structure, a bicyclohexane ring structure, a bicyclodecane ring structure, an isobornene ring structure, a dicyclopentane ring structure, an adamantane ring structure, and a tricyclodecane ring structure.
- examples of the aromatic ring structure include a benzene ring structure, a naphthalene ring structure, and a biphenyl ring structure.
- the (p + m + n) -valent organic group represented by X 2 is a group represented by any one of the following (X2-1) to (X2-10) It is preferable.
- n represents an integer of 1 to 200, preferably an integer of 1 to 50, more preferably an integer of 1 to 15, particularly preferably 1 to 8. Represents an integer.
- * represents a bonding position.
- the divalent organic group represented by Z has a hydrocarbon group, a group having a polyoxyalkylene structure, a group having a polycaprolactone structure, a group having a polycarbonate structure, or a polyester structure. Groups are preferred.
- the hydrocarbon group in Z may be a linear hydrocarbon group, a branched chain hydrocarbon group, or a cyclic hydrocarbon group.
- the hydrocarbon group in Z preferably has 2 to 30 carbon atoms.
- R 1 to R 6 are each independently preferably a group (R-1) to a group (R-20).
- R 1 to R 6 are each independently a group derived from isophorone diisocyanate (IPDI) (R-3) or a group derived from hexamethylene diisocyanate (HDI).
- R-7 a group derived from trimethylhexamethylene diisocyanate (TMHDI) (R-5), a group derived from m-xylylene diisocyanate (XDI) (R-9), 1,3-bis (isocyanate) More preferably, it is either a group (R-1) derived from (methyl) cyclohexane or a group (R-2) derived from dicyclohexylmethane 4,4′-diisocyanate.
- TMHDI trimethylhexamethylene diisocyanate
- XDI m-xylylene diisocyanate
- R-9 1,3-bis (isocyanate) More preferably, it is either a group (R-1) derived from (methyl) cyclohexane or a group (R-2) derived from dicyclohexylmethane 4,4′-diisocyanate.
- the compound represented by the general formula (11A) is preferably a compound represented by the following formula (11A-1).
- R 1, R 2, and R 3 has the same meaning as R 1, R 2, and R 3 in the formula (11A), and their preferred embodiments are also the same.
- the synthesis of an adduct-type trifunctional or higher functional isocyanate compound can be performed by reacting a compound having three or more active hydrogen groups in a molecule described later with a bifunctional isocyanate compound described later.
- the active hydrogen group means a hydroxy group, a primary amino group, a secondary amino group, and a mercapto group.
- Adduct type trifunctional or higher functional isocyanate compound is, for example, a compound having three or more active hydrogen groups in the molecule and a bifunctional isocyanate compound heated in an organic solvent with stirring (50 ° C. to 100 ° C.) Or by stirring at a low temperature (0 ° C. to 70 ° C.) while adding a catalyst such as stannous octylate (Synthesis Scheme 1 below).
- a catalyst such as stannous octylate
- a bifunctional isocyanate compound having a mole number (number of molecules) of 0.6 times or more with respect to the number of moles (the number of equivalents of active hydrogen groups) is used.
- the number of moles of the bifunctional isocyanate compound is preferably 0.6 to 5 times, more preferably 0.6 to 3 times, more preferably 0.8 to 2 times the number of moles of the active hydrogen group. preferable.
- an adduct-type trifunctional or higher functional isocyanate compound includes the following prepolymer that is an adduct of a compound having two active hydrogen groups in the molecule and a bifunctional isocyanate compound. After synthesis of PP), this prepolymer (PP) can also be obtained by reacting a compound having three or more active hydrogen groups in the molecule.
- bifunctional isocyanate compound examples include a bifunctional aromatic isocyanate compound and a bifunctional aliphatic isocyanate compound.
- bifunctional isocyanate compound examples include isophorone diisocyanate (IPDI), m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate (TDI), naphthalene-1, 4-diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), 3,3′-dimethoxy-biphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, m-xylylene diisocyanate (XDI), p-xylylene diisocyanate, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-diphenyl Safluoroprop
- IPDI isophorone diisocyanate
- HDI hexamethylene diisocyanate
- TMHDI trimethylhexamethylene diisocyanate
- HXDI 1,3-bis (isocyanatomethyl) cyclohexane
- XDI m-xylylene diisocyanate
- dicyclohexylmethane-4,4′-diisocyanate are preferred.
- bifunctional isocyanate compound a bifunctional isocyanate compound derived from the above compound can also be used.
- Duranate registered trademark
- D101, D201, A101 (manufactured by Asahi Kasei Corporation) and the like can be mentioned.
- the compound having three or more active hydrogen groups in the molecule is a compound having three or more groups in the molecule selected from a hydroxy group, a primary amino group, a secondary amino group, and a mercapto group.
- Examples thereof include compounds having structures represented by the following (H-1) to (H-13). In the structure below, n represents an integer selected from 1 to 100.
- adduct type trifunctional or higher functional isocyanate compound it is preferable to use a compound obtained by reacting a compound having two or more active hydrogen groups in the molecule with a bifunctional isocyanate compound in the combinations shown in Table 2 below.
- the adduct type trifunctional or higher functional isocyanate compound is more preferably NCO102 to NCO105, NCO107, NCO108, NCO111, and NCO113 among the compounds shown in Table 2 above.
- adduct type trifunctional or higher functional isocyanate compound commercially available products may be used.
- D-110, D-120N, D-140N, and D-160N are more preferable.
- the isocyanurate type trifunctional or higher functional isocyanate compound a compound represented by the formula (11C) is preferable.
- the biuret type trifunctional or higher functional isocyanate compound is preferably a compound represented by the formula (11D).
- R 1 , R 2 , and R 3 each independently represent a divalent organic group.
- R 1 , R 2 , and R 3 are each independently an alkylene group optionally having a substituent having 1 to 20 carbon atoms, or having 1 to 20 carbon atoms A cycloalkylene group which may have a substituent or an arylene group which may have a substituent having 1 to 20 carbon atoms is preferable.
- R 1 , R 2 , and R 3 are each independently a group selected from the groups represented by the above (R-1) to (R-20) It is particularly preferred that
- R 1 to R 3 are each independently a group derived from isophorone diisocyanate (IPDI) (R-3) or a group derived from hexamethylene diisocyanate (HDI).
- R-7 a group derived from trimethylhexamethylene diisocyanate (TMHDI) (R-5), a group derived from m-xylylene diisocyanate (XDI) (R-9), 1,3-bis (isocyanate) More preferably, it is either a group (R-1) derived from (methyl) cyclohexane or a group (R-2) derived from dicyclohexylmethane 4,4′-diisocyanate.
- isocyanurate-type trifunctional or higher functional isocyanate compound commercially available products may be used.
- D-127, D-170N, D-170HN, D-172N, D-177N Sumijoule N3300, Death module (registered trademark) N3600, N3900, Z4470BA (Sumika Bayer Urethane), Coronate (registered trademark) HX, HK (manufactured by Nippon Polyurethane Co., Ltd.), Duranate (registered trademark) TPA-100 , TKA-100, TSA-100, TSS-100, TLA-100, TSE-100 (manufactured by Asahi Kasei Corporation) and the like.
- biuret type trifunctional or higher functional isocyanate compound commercially available products may be used.
- D-165N, NP1100 manufactured by Mitsui Chemicals
- Desmodur registered trademark
- N3200 household
- Kayl Bayer Urethane Kayl Bayer Urethane
- Duranate registered trademark
- 24A-100 manufactured by Asahi Kasei Corporation
- Duranate registered trademark
- 24A-100 manufactured by Asahi Kasei Co., Ltd.
- D-127 manufactured by Mitsui Chemicals, Inc.
- TKA-100 manufactured by Asahi Kasei Corporation
- TSE -100 manufactured by Asahi Kasei Corporation
- the isocyanate group content (unit: mmol / g) per gram of the tri- or higher functional isocyanate compound is preferably 1 mmol / g to 10 mmol / g, more preferably 1.5 mmol / g to 8 mmol / g, and 2 mmol / g to 6 mmol. / G is more preferable.
- the isocyanate group content is determined by dissolving the target isocyanate compound in dehydrated toluene, adding an excess of di-normal butylamine solution, reacting it, back titrating the remaining di-normal butyl amine with hydrochloric acid, and at the inflection point on the titration curve. It can be calculated from the titer.
- the isocyanate group content was determined by neutralization titration using a potentiometric titrator (AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) at 25 ° C. with a 1 mol / L hydrochloric acid aqueous solution by the method shown in the following blank measurement and sample measurement. And calculated from the following formula (N) from the obtained titers Z1 and Z2.
- Z1 represents a blank titration
- Z2 represents a sample titration
- W represents a solid content of the sample
- Y represents a mass of the sample.
- Blank measurement In a 100 mL beaker, 10 mL of dehydrated toluene, 10.0 mL of 2 mol / L dinormal butylamine solution, and 50 mL of isopropyl alcohol are mixed to prepare a mixed solution. Neutralization titration is performed on this mixed solution using a 1 mol / L hydrochloric acid solution, and an inflection point on the titration curve is taken as an end point, and a titration amount Z1 (mL) up to the end point is obtained.
- Sample measurement A sample (isocyanate compound) Yg having a solid content of W mass% is collected in a 100 mL beaker, dehydrated toluene 20 (mL) is added to the beaker to dissolve the sample, and a solution is prepared. To this solution, 10.0 mL of a 2 mol / L dinormal butylamine solution is added and mixed, and then left to stand for 20 minutes or more. Add 50 mL of isopropyl alcohol to the solution after standing.
- the gel particles are preferably produced by reacting the above-described trifunctional or higher functional isocyanate compound with water or a compound having two or more active hydrogen groups.
- a compound to be reacted with a trifunctional or higher functional isocyanate compound water is generally used.
- By reacting the trifunctional or higher functional isocyanate compound with water a three-dimensional crosslinked structure having a urea bond is formed.
- compounds that react with trifunctional or higher functional isocyanate compounds include compounds having two or more active hydrogen groups. Examples of compounds having two or more active hydrogen groups include polyfunctional alcohols and polyfunctional phenols.
- Polyfunctional amines having a hydrogen atom on the nitrogen atom and polyfunctional thiols can also be used.
- a trifunctional or higher functional isocyanate compound By reacting a trifunctional or higher functional isocyanate compound with a polyfunctional alcohol or polyfunctional phenol, a three-dimensional crosslinked structure having a urethane bond is formed.
- a trifunctional or higher functional isocyanate compound By reacting a trifunctional or higher functional isocyanate compound with a polyfunctional amine having a hydrogen atom on a nitrogen atom, a three-dimensional crosslinked structure having a urea bond is formed.
- polyfunctional alcohol examples include propylene glycol, glycerin, trimethylolpropane, 4,4 ′, 4 ′′ -trihydroxytriphenylmethane, and the like.
- polyfunctional amine examples include diethylenetriamine and tetraethylenepentamine.
- polyfunctional thiol examples include 1,3-propanedithiol and 1,2-ethanedithiol.
- polyfunctional phenol examples include bisphenol A. These compounds may be used individually by 1 type, and may use 2 or more types together.
- the compound having two or more active hydrogen groups includes compounds having three or more active hydrogen groups in the aforementioned molecule.
- the gel particles have a polymerizable group.
- the gel particles may have a polymerizable group by introducing a polymerizable group into the three-dimensional crosslinked structure, and the polymerizable monomer is included in the interior of the gel particle (the void of the three-dimensional crosslinked structure). May have a polymerizable group. Moreover, both may coexist.
- the gel particle has a polymerizable group in the three-dimensional crosslinked structure.
- the gel particles preferably have a polymerizable group on the surface or on the surface of the gel particles and in the vicinity of the surface from the viewpoints of sensitivity and crosslinkability.
- the gel particles have a polymerizable group, gel particles adjacent to each other can be bonded to each other by irradiation with active energy rays to form a crosslinked structure, thereby forming an image having high crosslinkability and excellent film strength. be able to.
- a method for introducing a polymerizable group into the gel particles for example, when forming a three-dimensional cross-linked structure having at least one kind selected from a urethane bond and a urea bond, .
- the polymerizable compound as the polymerizable group-introducing monomer is added to the oil together with the components constituting the gel particles. It was dissolved in component, adding water phase components in the oil phase component, mixing, and a method of emulsification
- Examples of the polymerizable compound used for introducing the polymerizable group into the gel particle include a compound having at least one active hydrogen group and having at least one terminal ethylenically unsaturated bond.
- a compound having at least one active hydrogen group and at least one terminal having an ethylenically unsaturated bond can be represented by the following structural formula (a). L 1 Lc m Z n (a)
- L 1 represents an m + n-valent linking group
- m and n are each independently an integer selected from 1 to 100
- Lc represents a monovalent ethylenically unsaturated group.
- Z represents an active hydrogen group.
- L 1 represents a divalent or higher aliphatic group, a divalent or higher aromatic group, a divalent or higher heterocyclic group, —O—, —S—, —NH—, —N ⁇ , —CO—, —SO. It is preferably —, —SO 2 — or a combination thereof.
- m and n are each independently preferably 1 to 50, more preferably 2 to 20, still more preferably 3 to 10, and particularly preferably 3 to 5.
- Examples of the monovalent ethylenically unsaturated group represented by Lc include an allyl group, a vinyl group, an acryloyl group, and a methacryloyl group.
- Z is preferably OH, SH, NH or NH 2 , more preferably OH or NH 2 , and even more preferably OH.
- n represents an integer selected from 1 to 90, for example.
- a commercially available product may be used.
- Examples thereof include methacrylate, acrylamide (manufactured by KJ Chemicals), A-TMM-3L (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR-399E (manufactured by Sartomer).
- hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.
- A-TMM-3L manufactured by Shin-Nakamura Chemical Co., Ltd.
- SR-399E manufactured by Sartomer
- the introduction of the polymerizable group into the gel particles has an isocyanate group of a trifunctional or higher functional isocyanate compound and at least one active hydrogen group, and at least one terminal is ethylenic.
- An isocyanate compound having a polymerizable group introduced by reacting with an active hydrogen group of a compound having an unsaturated bond is prepared, and the prepared isocyanate compound having an introduced polymerizable group and two or more active hydrogens described above This can be carried out by reacting a group-containing compound.
- an isocyanate compound having a polymerizable group introduced in the production of gel particles a compound having at least one active hydrogen group and at least one terminal having an ethylenically unsaturated bond (in Table 3, a polymerizable group-introducing monomer and It is preferable to use a compound obtained by reacting a display) and a trifunctional or higher functional isocyanate compound (shown as polyisocyanate in Table 3) in combinations shown in Table 3 below.
- the polymerizable group-introducing monomer may be a single type or a combination of two or more types.
- a polyisocyanate that is, a trifunctional or higher functional isocyanate compound
- a polymerizable group-introducing monomer are mixed with the number of moles of active hydrogen groups in the polymerizable group-introducing monomer.
- the reaction may be carried out at a ratio of 0.01 to 0.3 times the number of moles of isocyanate groups (more preferably 0.02 to 0.25 times, still more preferably 0.03 to 0.2 times).
- the isocyanate compound having a polymerizable group introduced may have an average number of functional groups of 3 or less in the isocyanate group. However, even in this case, it is possible to form a three-dimensional crosslinked structure if at least one trifunctional or higher functional isocyanate compound is contained in the raw material for forming the three-dimensional crosslinked structure.
- the gel particles contain at least one photopolymerization initiator. As described above, the gel particles encapsulate the photopolymerization initiator, thereby increasing the sensitivity to light and improving the hardness of the formed film.
- the gel particles include the photopolymerization initiator, it is conventionally possible to use a photopolymerization initiator that is highly sensitive but difficult to use due to low dispersibility in water or low solubility. it can. Thereby, the range of selection of the photopolymerization initiator to be used is expanded, and consequently the range of selection of the light source to be used is also expanded. For this reason, the curing sensitivity can be improved as compared with the conventional case.
- a photopolymerization initiator contained in the gel particles (hereinafter also referred to as an encapsulated photopolymerization initiator), a known photopolymerization initiator can be appropriately selected and used.
- the encapsulated photopolymerization initiator is a compound that absorbs light (that is, active energy rays) to generate a radical that is a polymerization initiating species.
- a known compound can be used as the encapsulated photopolymerization initiator.
- Preferred examples of the encapsulated photopolymerization initiator include (a) carbonyl compounds such as aromatic ketones, (b) acylphosphine oxide compounds, and (c) aromatic onium salts.
- These encapsulated photopolymerization initiators may be used alone or in combination of two or more of the compounds (a) to (m).
- Preferred examples of (a) carbonyl compounds, (b) acylphosphine oxide compounds, and (e) thio compounds include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY”, J. MoI. P. FOUASSIER, J.A. F. RABEK (1993), pp. And compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77-117.
- More preferred examples include ⁇ -thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, ⁇ -substituted benzoin compounds described in JP-B-47-22326, Benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, Benzoin ethers described in JP-A-62-81345, JP-B-1-34242, US Pat. No.
- a carbonyl compound or (b) an acylphosphine oxide compound is more preferable.
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide for example, IRGACURE (registered trademark) 819 manufactured by BASF
- 2- (dimethylamine) -1- (4-morpholinophenyl) -2-benzyl-1-butanone for example, IRGACURE (registered trademark) 369 manufactured by BASF
- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one eg IRGACURE® 907 from BASF
- 1-hydroxy-cyclohexyl-phenyl-ketone eg BASF IRGACURE (registered trademark) 184
- 2,4,6-trime Rubenzoiru - diphenyl - phosphine oxide e.g., DAROCUR (R) TPO, LUC
- the encapsulated photopolymerization initiator is preferably an (b) acylphosphine oxide compound, and a monoacylphosphine oxide compound (particularly preferably 2, 4,6-trimethylbenzoyl-diphenyl-phosphine oxide) or a bisacylphosphine oxide compound (particularly preferred is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide).
- the encapsulated photopolymerization initiator dissolves the encapsulated photopolymerization initiator as an oil phase component together with the components constituting the gel particles, and adds, mixes, and emulsifies the water phase component to the oil phase component. Thus, it can be included inside the gel particles.
- the content of the encapsulated photopolymerization initiator is preferably 0.1% by mass to 25% by mass, more preferably 0.5% by mass to 20% by mass, and still more preferably 1% by mass with respect to the total solid content of the gel particles. % To 15% by mass.
- the gel particles preferably further contain a polymerizable monomer.
- the gel particle does not have a polymerizable group in the three-dimensional crosslinked structure, the gel particle includes a polymerizable monomer, and the polymerizable group of the polymerizable monomer functions as a polymerizable group that the gel particle has.
- the polymerizable monomer encapsulated in the gel particles (hereinafter also referred to as an encapsulated polymerizable monomer) can be selected from polymerizable monomers having radically polymerizable ethylenically unsaturated bonds.
- Examples of the polymerizable monomer having an ethylenically unsaturated bond capable of radical polymerization used as an inclusion polymerizable monomer include compounds having an ethylenically unsaturated group, acrylonitrile, styrene, various unsaturated polyesters, and unsaturated polyethers. And radical polymerizable monomers such as unsaturated polyamide and unsaturated urethane.
- the inclusion polymerizable monomer is preferably a compound having an ethylenically unsaturated group.
- the inclusion polymerizable monomer may be used alone or in combination of two or more.
- inclusion polymerizable monomer examples include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate, bis (4-acrylic).
- Roxypolyethoxyphenyl) propane polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate (for example, A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.), pentaerythritol triacrylate (for example, , Shin-Nakamura Chemical Co., Ltd.
- A-TMM-3L ditrimethylolpropane tetraacrelane
- AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.
- dipentaerythritol pentaacrylate for example, SR-399E manufactured by Sartomer
- dipentaerythritol hexaacrylate for example, A manufactured by Shin-Nakamura Chemical Co., Ltd.
- oligoester acrylate N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, neopentyl glycol propylene oxide adduct Diacrylate (NPGPODA), cyclic trimethylolpropane formal acrylate, tetrahydrofurfuryl acrylate, 2- (2-ethoxyethoxy) ethoxy
- Acrylate monomer methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane Methacrylate monomers such as allyl glycidyl ether, diallyl lid Rate, triallyl trimellitate, N-vinylcaprolactam and the like.
- polyfunctional polymerizable monomers include trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, neopentyl glycol.
- Propylene oxide adduct diacrylate is preferred, and dipentaerythritol pentaacrylate is more preferred.
- Monofunctional polymerizable monomers include cyclic trimethylolpropane formal acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl acrylate, N-vinylcaprolactam Is preferred.
- the inclusion polymerizable monomer is preferably a polyfunctional polymerizable monomer, more preferably a trifunctional or higher functional polymerizable monomer, and further preferably a tetrafunctional or higher functional polymerizable monomer from the viewpoint of crosslinkability and film strength.
- a polyfunctional inclusion polymerizable monomer a methacrylate monomer and an acrylate monomer are preferable, and an acrylate monomer is more preferable.
- the inclusion polymerizable monomer is more preferably a trifunctional or higher functional acrylate monomer, and particularly preferably a tetrafunctional or higher functional acrylate monomer.
- membrane improves by using the above-mentioned monofunctional inclusion polymerizable monomer as an inclusion polymerizable monomer. Furthermore, the adhesiveness of the film is further improved by using a combination of two or more of the aforementioned monofunctional inclusion polymerizable monomers.
- the inclusion polymerizable monomer can be used in combination with two or more monofunctional inclusion polymerizable monomers and a polyfunctional inclusion polymerizable monomer, thereby improving the film adhesion and improving the film hardness. Effect is also obtained.
- Examples of the encapsulating polymerizable monomer include, for example, JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, and JP-A-9-134011.
- photocurable polymerizable monomers used in photopolymerizable compositions described in JP-A-2004-514014 and other publications are known, and these can also be applied to gel particles.
- encapsulated polymerizable monomer commercially available products may be used, for example, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G.
- DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd.
- SR444, SR454, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR494 manufactured by Sartomer
- isocyanuric monomers such as -9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- polymerizable monomers include NPGPODA (neopentyl glycol propylene oxide adduct diacrylate, Sartomer), SR399E (dipentaerythritol pentaacrylate, Sartomer), ATMM-3L (pentaerythritol triacrylate, Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.), A-DHP (dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) M-156 (manufactured by Toagosei Co., Ltd.), V-CAP (manufactured by BASF), biscort Commercially available products such as # 192 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), SR-531, SR-285, SR256 (manufactured by Sartomer) and the like can be suitably used.
- NPGPODA neopentyl glyco
- the encapsulated polymerizable monomer is obtained by dissolving the encapsulated polymerizable monomer as an oil phase component together with the components constituting the gel particle when the gel particles are produced, and adding, mixing and emulsifying the water phase component to the oil phase component. , And can be contained inside the gel particles.
- the molecular weight of the encapsulated polymerizable monomer is preferably from 100 to 100,000, more preferably from 100 to 30,000, even more preferably from 100 to 10,000, even more preferably from 100 to 1,000, as a weight average molecular weight. It is preferably 100 to 900, more preferably 100 to 800, and particularly preferably 150 to 750.
- the weight average molecular weight can be measured by gel permeation chromatography (GPC).
- the content of the encapsulating polymerizable monomer in the total solid content of the gel particles is preferably 0.1% by mass to 75% by mass, more preferably 0.5% by mass to 60% by mass, and still more preferably. 1% by mass to 50% by mass. By setting it as the said range, crosslinkability and the hardness of the film
- the gel particles preferably have a hydrophilic group on the surface.
- the introduction of the hydrophilic group to the surface of the gel particle is performed by reacting the above-described trifunctional or higher isocyanate compound and the above-described compound having two or more active hydrogen groups with the compound having a hydrophilic group. Can be done. Further, when the above-described trifunctional or higher functional isocyanate compound is produced, the bifunctional or higher functional isocyanate compound is reacted with a compound having a hydrophilic group to introduce a hydrophilic group in advance and the two previously described. It can also be performed by reacting the above compound having an active hydrogen group.
- Examples of the compound having a hydrophilic group used for introduction of the hydrophilic group onto the surface of the gel particle include the compounds having the above-described hydrophilic group.
- the preferred range of the hydrophilic group is as described above.
- a compound having a hydrophilic group a compound having a polyether structure, a compound having a carboxy group, or a compound having a salt of a carboxy group is particularly preferable.
- Examples of the compound having a polyether structure include compounds having a polyoxyalkylene chain. Specific examples include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polystyrene oxide, polycyclohexylene oxide, polyethylene oxide-polypropylene oxide-block copolymer, polyethylene oxide-polypropylene oxide random copolymer, and the like. Among these compounds having a polyoxyalkylene chain, polyethylene oxide, polypropylene oxide, and polyethylene oxide-polypropylene oxide block copolymers are preferable, and polyethylene oxide is more preferable.
- Examples of the compound having a polyether structure include polyethylene oxide monoethers (monoethers include, for example, monomethyl ether and monoethyl ether), polyethylene oxide monoesters (monoesters include, for example, , Monoacetic acid ester, mono (meth) acrylic acid ester and the like) are also preferable.
- Specific examples of the compound having an ionic hydrophilic group such as a carboxy group include the following.
- Compounds having an ionic hydrophilic group such as a carboxy group include ⁇ -amino acids (specifically, lysine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, Also included are amino acids such as methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine).
- ⁇ -amino acids specifically, lysine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine.
- amino acids such as methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine).
- a compound having an ionic hydrophilic group such as a carboxy group may be partially neutralized using an inorganic salt machine such as sodium hydroxide and an organic base such as triethylamine.
- an isocyanate compound into which a hydrophilic group has been introduced can also be used for introducing the hydrophilic group into the surface of the gel particle.
- an isocyanate compound into which a hydrophilic group has been introduced a compound having a hydrophilic group and a bifunctional isocyanate compound (preferably isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), 1 , 3-bis (isocyanatomethyl) cyclohexane (HXDI), m-xylylene diisocyanate (XDI), or dicyclohexylmethane-4,4′-diisocyanate (HMDI)).
- IPDI isophorone diisocyanate
- HDI hexamethylene diisocyanate
- TMHDI trimethylhexamethylene diisocyanate
- HXDI m-xylylene diiso
- an isocyanate compound having a hydrophilic group (specifically, a group having a polyether structure) as an isocyanate compound and a bifunctional compound having two or more active hydrogen groups. It is preferable to use an adduct of the above isocyanate compound and a compound having a polyether structure. Preferred embodiments of the compound having two or more active hydrogen groups and the bifunctional isocyanate compound are as described above.
- a compound represented by the following formula (WM) is preferable.
- R W1, R W2, and nw are respectively in the above formula (WS), it has the same meaning as R W1, R W2, and nw, the same preferred embodiments as well, respectively.
- Examples of the adduct of a compound having two or more active hydrogen groups, a bifunctional isocyanate compound and a compound having a polyether structure include trimethylolpropane (TMP), m-xylylene diisocyanate (XDI), and polyethylene glycol monomethyl ether.
- Adducts with (EO) for example, Takenate (registered trademark) D-116N manufactured by Mitsui Chemicals, Inc. are preferred.
- an isocyanate compound into which a hydrophilic group (specifically, a carboxy group or a carboxy group salt) is introduced is used as an 2,2-bis ( Hydroxymethyl) propionic acid (DMPA) or 2,2-bis (hydroxymethyl) propionic acid (DMPA) salt and isophorone diisocyanate (IPDI) reaction product (isocyanate compound containing carboxy group or carboxy group salt)
- DMPA 2,2-bis ( Hydroxymethyl) propionic acid
- DMPA 2,2-bis (hydroxymethyl) propionic acid
- IPDI isophorone diisocyanate
- the salt of the carboxy group is preferably a sodium salt, potassium salt, triethylamine salt or dimethylethanolamine salt, more preferably a sodium salt or triethylamine salt.
- the addition amount of the compound having a hydrophilic group used for introducing the hydrophilic group to the surface of the gel particle is preferably 0.1% by mass to 50% by mass with respect to the mass of the gel particle, and 1% by mass to 45% by mass. Is more preferable, and 3% by mass to 40% by mass is more preferable.
- the gel particles may contain other components other than those described above. Examples of other components that can be included in the gel particles include sensitizers and resins described later.
- the resin that can be encapsulated in the gel particles (hereinafter also referred to as “encapsulated resin”) may have a polymerizable group or may not have a polymerizable group.
- encapsulated resin a resin that can be encapsulated in the gel particles
- a water-insoluble resin can also be used as the inclusion resin.
- the “water-insoluble resin” means a resin having a dissolution amount of 1 g or less with respect to 100 g of distilled water at 25 ° C. when dried at 105 ° C. for 2 hours.
- the water dispersion of the present disclosure can contain a water-insoluble resin in an aqueous dispersion, which is an aqueous composition, by encapsulating a water-insoluble resin having low solubility in water in gel particles. .
- the volume average particle diameter of the gel particles is preferably 0.01 ⁇ m to 10.0 ⁇ m, more preferably 0.01 ⁇ m to 5 ⁇ m, and further preferably 0.05 ⁇ m to 1 ⁇ m from the viewpoint of dispersibility. .
- the volume average particle diameter of the gel particles can be measured by a light scattering method. As the volume average particle diameter in this specification, a value measured by LA-910 (manufactured by Horiba, Ltd.) is used.
- the total solid content of the gel particles with respect to the total amount of the aqueous dispersion is preferably 0.3% by mass to 20.0% by mass, more preferably 0.5% by mass to 15.0% by mass, and 0.6% by mass. % To 13.0% by mass is more preferable, 1.0% to 12.0% by mass is further preferable, and 1.5% to 7.5% by mass is particularly preferable.
- the aqueous dispersion of the present disclosure contains water as a dispersion medium.
- the water content in the aqueous dispersion of the present disclosure is not particularly limited, but the water content is preferably 10% by mass to 99% by mass, and more preferably 20% by mass with respect to the total amount of the aqueous dispersion.
- the mass is from 95% by mass, more preferably from 30% by mass to 90% by mass, and particularly preferably from 50% by mass to 90% by mass.
- the aqueous dispersion of the present disclosure may contain a sensitizer.
- disassembly of the photoinitiator by active energy ray irradiation may be accelerated
- a sensitizer is a substance that absorbs specific active energy rays and enters an electronically excited state. The sensitizer brought into the electronically excited state comes into contact with the photopolymerization initiator, and produces effects such as electron transfer, energy transfer, and heat generation. This promotes chemical changes of the photopolymerization initiator, that is, decomposition, generation of radicals, acids or bases, and the like.
- Examples of the sensitizer include benzophenone, thioxanthone, isopropylthioxanthone, anthraquinone, 3-acyl coumarin derivatives, terphenyl, styryl ketone, 3- (aroylmethylene) thiazoline, camphorquinone, eosin, rhodamine, erythrosine and the like.
- Examples of the sensitizer include compounds represented by general formula (i) described in JP 2010-24276 A, and compounds represented by general formula (I) described in JP 6-107718 A. Can also be suitably used.
- the sensitizer is preferably at least one selected from thioxanthone, isopropyl thioxanthone, and benzophenone, from the viewpoint of compatibility with LED light and reactivity with a photopolymerization initiator, from thioxanthone and isopropyl thioxanthone. At least one selected is more preferable, and isopropylthioxanthone is more preferable.
- the aqueous dispersion of this indication contains a sensitizer, you may contain a sensitizer individually by 1 type or in combination of 2 or more types.
- the sensitizer is included in the gel particle from a viewpoint that the reactivity with a photoinitiator improves more.
- the content of the sensitizer is preferably 0.1% by mass to 25% by mass with respect to the total solid content of the gel particles. It is more preferably 5% by mass to 20% by mass, and further preferably 1% by mass to 15% by mass.
- the aqueous dispersion of the present disclosure may contain at least one colorant.
- the aqueous dispersion contains a colorant
- the aqueous dispersion is preferably contained outside the gel particles.
- a coloring agent It can select from well-known color materials, such as a pigment, a water-soluble dye, a disperse dye, and can use it. Among these, it is more preferable to include a pigment from the viewpoint of excellent weather resistance and rich color reproducibility.
- the pigment is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include known organic pigments and inorganic pigments. Resin particles dyed with dyes, commercially available pigment dispersions and surfaces Treated pigments (for example, pigments dispersed in water, liquid compounds, insoluble resins, etc., and pigment surfaces treated with resins, pigment derivatives, etc.) are also included. Examples of organic pigments and inorganic pigments include yellow pigments, red pigments, magenta pigments, blue pigments, cyan pigments, green pigments, orange pigments, purple pigments, brown pigments, black pigments, and white pigments. When a pigment is used as the colorant, a pigment dispersant may be used as necessary when preparing the pigment particles.
- a pigment dispersant may be used as necessary when preparing the pigment particles.
- paragraphs 0180 to 0200 in JP-A No. 2014-040529 can be appropriately referred to.
- the aqueous dispersion of the present disclosure may contain other components other than those described above as necessary. Other components may be contained in the gel particles or may not be contained in the gel particles.
- the aqueous dispersion of the present disclosure may contain a surfactant.
- a surfactant include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, alkyl benzene sulfonates, sulfosuccinates, naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ethers.
- Examples thereof include phosphate, polyoxyalkylene alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, polyoxyethylene fatty acid amide, and amine oxide.
- the surfactant at least one surfactant selected from alkyl sulfates, alkyl sulfonates, and alkyl benzene sulfonates is preferable, and alkyl sulfates are particularly preferable.
- the surfactant is preferably an alkyl sulfate having an alkyl chain length of 8 to 18 from the viewpoint of dispersibility of the gel particles.
- SDS sodium dodecyl sulfate
- SCS sodium cetyl sulfate
- Alkyl chain length at least one selected from 16
- SCS sodium cetyl sulfate
- the aqueous dispersion of this indication may contain other surfactant other than the above-mentioned surfactant.
- surfactants include those described in JP-A Nos. 62-173463 and 62-183457.
- examples of other surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, and siloxanes.
- An organic fluoro compound may be used as the surfactant.
- the organic fluoro compound is preferably hydrophobic.
- organic fluoro compounds examples include fluorine-based surfactants, oily fluorine-based compounds (for example, fluorine oil), and solid fluorine compound resins (for example, tetrafluoroethylene resin). Columns 8 to 17), and those described in JP-A Nos. 62-135826.
- a surfactant having a weight average molecular weight of less than 1000 (particularly preferably less than 700) is preferable.
- the aqueous dispersion of the present disclosure may contain a polymerization inhibitor.
- the aqueous dispersion of the present disclosure contains a polymerization inhibitor, the storage stability of the aqueous dispersion can be further improved.
- Polymerization inhibitors include p-methoxyphenol, quinones (eg, hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenothiazine, catechol, alkylphenols (eg, dibutylhydroxytoluene (BHT), etc.), alkylbisphenols, dimethyldithiocarbamine Zinc oxide, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole, phosphites, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL), cuperon Al, tris (N-nitroso-N-phenylhydroxylamine) aluminum salt And the like.
- quinones eg, hydroquinone, benzoquinone, methoxy
- At least one selected from p-methoxyphenol, catechols, quinones, alkylphenols, TEMPO, TEMPOL, cuperon Al, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt is preferable. More preferred is at least one selected from methoxyphenol, hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL, cuperon Al, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
- the aqueous dispersion of the present disclosure may contain an ultraviolet absorber.
- an ultraviolet absorber When the aqueous dispersion of the present disclosure contains an ultraviolet absorber, the weather resistance and the like of the film can be further improved.
- the ultraviolet absorber include known ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, triazine compounds, and benzoxazole compounds.
- the aqueous dispersion of the present disclosure may contain an organic solvent.
- the aqueous dispersion of the present disclosure contains an organic solvent, the adhesion between the film and the substrate can be further improved.
- the aqueous dispersion of the present disclosure contains an organic solvent, the content of the organic solvent is preferably 0.1% by mass to 5% by mass with respect to the total amount of the aqueous dispersion. Specific examples of the organic solvent are as follows.
- Alcohols eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.
- Polyhydric alcohols for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 2- Methylpropanediol, etc.
- Polyhydric alcohol ethers for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono
- the aqueous dispersion of the present disclosure is a resin that does not have a photopolymerization initiator, a polymerizable monomer, or a polymerizable group outside the gel particles as necessary from the viewpoint of controlling film physical properties, adhesion, and dischargeability. , Etc. may be contained.
- photopolymerization initiator that can be contained outside the gel particles examples include those similar to the photopolymerization initiator described above (the photopolymerization initiator contained in the gel particles), but are contained outside the gel particles.
- the photopolymerization initiator to be obtained is preferably a water-soluble or water-dispersible photopolymerization initiator.
- DAROCUR registered trademark 1173
- IRGACURE registered trademark 2959
- the “water solubility” in the photopolymerization initiator is synonymous with the “water solubility” in the above-mentioned “water-soluble resin”, and the “water dispersibility” in the photopolymerization initiator is the above-mentioned “water dispersibility”. It is synonymous with “water dispersibility” in “resin”.
- polymerizable monomer that can be contained outside the gel particles examples include radically polymerizable compounds such as compounds having an ethylenically unsaturated group, acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane. Can be mentioned.
- radically polymerizable compounds such as compounds having an ethylenically unsaturated group, acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane.
- a compound having an ethylenically unsaturated group is preferable, and a compound having a (meth) acryloyl group is particularly preferable.
- the polymerizable monomer that can be contained outside the gel particles is preferably a water-soluble or water-dispersible polymerizable monomer.
- Water-soluble in the polymerizable monomer is synonymous with “water-soluble” in the above-mentioned “water-soluble resin”, and “water-dispersible” in the polymerizable monomer is “in the water-dispersible resin”. It is synonymous with “water dispersibility”.
- the polymerizable monomer includes a compound having at least one selected from the group consisting of an amide structure, a polyethylene glycol structure, a polypropylene glycol structure, a carboxy group, and a salt of a carboxy group. preferable.
- polymerizable monomers that can be contained outside the gel particles include (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, N, N-dimethyl.
- the same resin as the above-described polymerizable resin can be used except that it does not have a polymerizable group.
- the resin having no polymerizable group in addition to the resin having a polyurethane structure which is a preferred embodiment of the polymerizable resin, at least one structure selected from the group consisting of a polyester structure, a polyvinyl structure, and a polyolefin structure May be used, or a resin having at least one structure and a polyurethane structure may be used.
- the aqueous dispersion of the present disclosure preferably has a viscosity of 3 mPa ⁇ s to 15 mPa ⁇ s, more preferably 3 mPa ⁇ s to 13 mPa ⁇ s, when the aqueous dispersion is 25 ° C. to 50 ° C. preferable.
- the aqueous dispersion of the present disclosure preferably has a viscosity of 50 mPa ⁇ s or less when the aqueous dispersion is 25 ° C.
- the viscosity of the water dispersion is a value measured using a viscometer (VISCOMETER TV-22, Toki Sangyo Co., Ltd.).
- the method for producing an aqueous dispersion of the present disclosure is not particularly limited as long as the aqueous dispersion of the present disclosure having the above configuration can be produced.
- the method for producing an aqueous dispersion of the present embodiment described below is preferable from the viewpoint of easily obtaining the aqueous dispersion of the present disclosure.
- the method for producing an aqueous dispersion of the present embodiment includes a preparation step of preparing a gel particle dispersion containing the gel particles and water described above, and gel particles.
- the manufacturing method of this embodiment may have another process as needed. According to the manufacturing method of the present embodiment, the above-described aqueous dispersion of the present disclosure can be easily manufactured.
- the preparation step is a step of preparing a gel particle dispersion containing gel particles and water. It is preferable that the gel particle dispersion does not substantially contain a polymerizable resin.
- the content of the polymerizable resin in the gel particle dispersion is preferably less than 1% by mass, and particularly preferably 0% by mass (that is, the gel particle dispersion does not contain a polymerizable resin).
- the preparation process is a process for convenience. That is, in the production method of the present embodiment, a gel particle dispersion prepared in advance may be used for producing the aqueous dispersion of the present disclosure. A gel particle dispersion may be produced and the produced gel particle dispersion may be used.
- the encapsulation rate of the photopolymerization initiator encapsulated in the gel particles is 100 mass times the amount of tetrahydrofuran (THF) for preparing the diluted solution with respect to the total solid content of the gel particle dispersion.
- THF tetrahydrofuran
- the measurement can be performed by the same method as that described in the section “Aqueous dispersion”, except that The preferred range of the encapsulation rate of the photopolymerization initiator in the gel particle dispersion is also the same as the preferred range described in the section “Aqueous dispersion”.
- the method for confirming that the gel particle dispersion contains gel particles having a three-dimensional cross-linked structure is the same as the method for confirming that the amount of tetrahydrofuran (THF) for preparing the diluted solution is based on the total solid content of the gel particle dispersion. Except changing to 100 mass times, it is the same as that of the confirmation method that the water dispersion contains the gel particle which has a three-dimensional crosslinked structure demonstrated in the term of the "water dispersion.”
- the preparation step includes a photopolymerization initiator, an oil phase component (hereinafter also referred to as “oil phase component A”) containing a trifunctional or higher functional isocyanate compound, a polymerizable monomer, and an organic solvent, a photopolymerization initiator, and a polymerizable group.
- oil phase component A an oil phase component containing a trifunctional or higher functional isocyanate compound, a polymerizable monomer, and an organic solvent, a photopolymerization initiator, and a polymerizable group.
- a trifunctional or higher functional isocyanate compound an oil phase component containing an organic solvent (hereinafter also referred to as “oil phase component B”), a photopolymerization initiator, a trifunctional or higher functional isocyanate compound having a polymerizable group, Any oil phase component selected from an oil phase component containing a polymerizable monomer and an organic solvent (hereinafter also referred to as “oil phase component C”) and an aqueous phase component containing water are mixed and emulsified. It is preferable to have an emulsification step for obtaining an emulsion, and a gelation step for obtaining the gel particle dispersion by heating the emulsion.
- the emulsification step is a step of mixing any oil phase component selected from oil phase component A, oil phase component B, and oil phase component C and an aqueous phase component containing water to obtain an emulsion by emulsification. It is.
- a photopolymerization initiator, a trifunctional or higher functional isocyanate compound, a polymerizable monomer, and an oil phase component A containing an organic solvent a photopolymerization initiator, a trifunctional or higher functional isocyanate having a polymerizable group Any one selected from an oil phase component B containing a compound and an organic solvent, and a photopolymerization initiator, a trifunctional or higher functional isocyanate compound having a polymerizable group, a polymerizable monomer, and an organic solvent.
- oil phase component By using the oil phase component, it is possible to finally obtain gel particles having at least a photopolymerization initiator and having a polymerizable group on the surface or on the surface and in the vicinity of the surface.
- Examples of the organic solvent contained in the oil phase component include ethyl acetate and methyl ethyl ketone.
- the oil phase component may contain other components as necessary in addition to the above components.
- the other components include compounds having the above-described hydrophilic group.
- gel particles having a hydrophilic group on the surface can be obtained.
- the trifunctional or higher functional isocyanate compound is selected from isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, m-xylylene diisocyanate, and dicyclohexylmethane 4,4′-diisocyanate.
- An isocyanate compound derived from at least one of the above is preferable.
- the water phase component may contain other components as needed in addition to water.
- an aqueous phase component May contain a neutralizing agent.
- the hydrophilic group such as a carboxy group is neutralized by mixing the oil phase component and the water phase component, A salt such as a carboxy group is formed. This formed salt also functions as a hydrophilic group of the gel particles.
- the neutralizing agent include sodium hydroxide.
- a raw material for forming gel particles having a three-dimensional crosslinked structure containing at least one bond selected from a urethane bond and a urea bond by reaction with an isocyanate group in addition to water, as described above
- a polyfunctional alcohol, a polyfunctional phenol, a polyfunctional amine having a hydrogen atom on a nitrogen atom, a polyfunctional thiol, or the like may be used.
- polyfunctional alcohols for example, propylene glycol, glycerin, trimethylolpropane, etc.
- polyfunctional amines for example, bis (hexamethylene) triamine, ethylenediamine, diethylenetriamine, etc.
- polyfunctional thiols for example, pentaerythritol tetra
- 3-mercaptopropionate and the like
- polyfunctional alcohols are particularly preferred.
- These compounds may be used alone or in combination of two or more. These compounds are added to the oil phase component and / or the aqueous phase component depending on the solubility and the like.
- surfactant in addition to the above-described raw materials.
- the above-mentioned surfactant is mentioned, for example.
- surfactants used for emulsification dispersion are considered to be excellent surfactants having a relatively long-chain hydrophobic group.
- surfactants surfactants described in “Surfactant Handbook” (Nishiichiro et al., Published by Sangyo Tosho (1980)), specifically alkyl sulfates, alkyl sulfonic acids, alkyl benzene sulfonic acids, etc. Alkali metal salts are preferred, and alkyl sulfate salts are more preferred.
- the alkyl chain length of the alkyl sulfate ester salt is preferably 12 or more, and more preferably 16 or more.
- the surfactant may be added to either the oil phase component or the aqueous phase component, but is usually added to the aqueous phase component because of its low solubility in organic solvents.
- the amount of the surfactant is preferably 0.1% by mass to 5% by mass and more preferably 0.5% by mass to 3% by mass with respect to the total solid content of the oil phase component.
- total solid content corresponds to the total solid content of the gel particles to be produced.
- the amount of the photopolymerization initiator in the oil phase component is not particularly limited, and for example, it is preferably 0.1% by mass to 25% by mass with respect to the total solid content.
- the amount of the trifunctional or higher functional isocyanate compound (or the trifunctional or higher functional isocyanate compound having a polymerizable group) in the oil phase component is not particularly limited, and is, for example, 10% by mass to 70% by mass with respect to the total solid content. Preferably there is.
- the amount of the polymerizable monomer in the oil phase component is not particularly limited, and is preferably 0.1% by mass to 75% by mass with respect to the total solid content, for example.
- the amount of the organic solvent is not particularly limited, and is appropriately selected depending on the type and amount of components contained in the oil phase component.
- the amount of water is not particularly limited, and is appropriately selected depending on the type and amount of components contained in the oil phase component.
- the amount of the compound having a hydrophilic group in the oil phase component is not particularly limited, and is, for example, 0.1% by mass to 40% with respect to the total solid content. It is preferable that it is mass%.
- Each component contained in the oil phase component may be simply mixed, all the components may be mixed at once, or each component may be divided into several parts and mixed.
- the method for mixing the oil phase component and the aqueous phase component is not particularly limited, and examples thereof include mixing by stirring.
- the method for emulsifying the mixture obtained by mixing is not particularly limited, and examples thereof include emulsification using an emulsifying device (for example, a disperser) such as a homogenizer.
- the number of rotations of the disperser in the emulsification is, for example, 5000 rpm to 20000 rpm, and preferably 10,000 rpm to 15000 rpm.
- the rotation time in emulsification is, for example, 1 minute to 120 minutes, preferably 3 minutes to 60 minutes, more preferably 3 minutes to 30 minutes, and further preferably 5 minutes to 15 minutes.
- the gelation step is a step of obtaining a gel particle dispersion containing gel particles and water by heating the emulsion.
- a three-dimensional cross-linked structure containing at least one selected from a urethane bond and a urea bond is obtained by the reaction of the trifunctional or higher isocyanate compound with water by crosslinking of the isocyanate groups by heating the emulsion.
- a polymerizable group, and a gel particle dispersion containing gel particles containing at least a photopolymerization initiator can be obtained.
- the heating temperature (reaction temperature) of the emulsion in the gelation step is preferably 35 ° C to 70 ° C, more preferably 40 ° C to 60 ° C.
- the heating time (reaction time) in the gelation step is preferably 6 hours to 50 hours, more preferably 12 hours to 40 hours, and even more preferably 15 hours to 35 hours.
- the gelling step preferably includes a step of distilling off the organic solvent from the emulsion.
- the resin mixing step is a step of obtaining an aqueous dispersion by mixing the gel particle dispersion and the polymerizable resin.
- the gel particle dispersion may be mixed with an aqueous dispersion of a polymerizable resin.
- an aqueous dispersion containing the gel particles described above, a polymerizable resin contained outside the gel particles, and water is obtained.
- the preferred range of the polymerizable resin in the resin mixing step is the same as the preferred range of the polymerizable resin described above.
- the gel particle dispersion and the polymerizable resin are mixed, and in addition to these, other components (for example, a colorant, a surfactant, an organic solvent, and water are selected. At least one component) may be mixed. About another component, it is as having already demonstrated as another component which may be contained in an aqueous dispersion.
- the manufacturing method of this embodiment may have other processes other than an emulsification process, a gelatinization process, and a resin mixing process as needed.
- examples of other steps include a step of adding other components.
- the other components to be added are as already described as other components that can be contained in the aqueous dispersion.
- Image forming method In the image forming method of the present embodiment, the above-described aqueous dispersion of the present disclosure is applied on a recording medium, and light (that is, active energy rays) is applied to the aqueous dispersion applied on the recording medium. And an irradiation step of irradiating.
- the image forming method of this embodiment may have other steps as necessary. According to the image forming method of the present embodiment, an image having excellent hardness and surface shape is formed on a recording medium. This image is also excellent in adhesion to the recording medium.
- the applying step is a step of applying the aqueous dispersion of the present disclosure onto the recording medium.
- the aqueous dispersion is used as an ink composition for ink jet recording, and the aqueous dispersion (that is, an ink composition for ink jet recording) is applied on a recording medium by an ink jet method.
- the aspect to provide is especially preferable.
- a substrate exemplified as “a substrate for forming a film using an aqueous dispersion” can be used as the recording medium.
- the application of the aqueous dispersion by the ink jet method can be performed using a known ink jet recording apparatus.
- a known ink jet recording apparatus There is no restriction
- the well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, any known inkjet recording apparatus including a commercially available product can discharge the aqueous dispersion onto the recording medium in the image forming method.
- Examples of the ink jet recording apparatus include an apparatus including an ink supply system, a temperature sensor, and a heating unit.
- the ink supply system includes, for example, an original tank containing an ink composition that is an aqueous dispersion of the present disclosure, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo inkjet head.
- the piezo-type inkjet head preferably has a multi-size dot of 1 pl to 100 pl, more preferably 8 pl to 30 pl, preferably 320 dpi (dot per inch) ⁇ 320 dpi to 4000 dpi ⁇ 4000 dpi (dot per inch), more preferably 400 dpi ⁇ .
- Driving can be performed so that ejection can be performed at a resolution of 400 dpi to 1600 dpi ⁇ 1600 dpi, more preferably 720 dpi ⁇ 720 dpi.
- dpi represents the number of dots per 2.54 cm (1 inch).
- the irradiation step is a step of irradiating the aqueous dispersion applied on the recording medium with active energy rays.
- the crosslinking reaction of the gel particles in the aqueous dispersion proceeds to fix the image and improve the film strength of the image. It becomes.
- UV light ultraviolet rays
- visible rays visible rays
- electron beams electron beams.
- UV light is preferable.
- the peak wavelength of the active energy ray (light) is preferably 200 nm to 405 nm, more preferably 220 nm to 390 nm, and still more preferably 220 nm to 385 nm. Also, it is preferably 200 nm to 310 nm, and preferably 200 nm to 280 nm.
- Exposure surface illuminance when the active energy ray (light) is irradiated for example, 10mW / cm 2 ⁇ 2000mW / cm 2, preferably 20mW / cm 2 ⁇ 1000mW / cm 2.
- a mercury lamp As a source for generating active energy rays (light), a mercury lamp, a metal halide lamp, a UV fluorescent lamp, a gas laser, a solid laser, and the like are widely known. Further, the replacement of the light source exemplified above with a semiconductor ultraviolet light emitting device is very useful both industrially and environmentally.
- semiconductor ultraviolet light emitting devices LEDs (Light Emitting Diodes) and LDs (Laser Diodes) are small, have a long life, have high efficiency, and are low in cost, and are expected as light sources.
- a metal halide lamp As the light source, a metal halide lamp, an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an LED, or a blue-violet laser is preferable.
- a sensitizer and a photopolymerization initiator when used in combination, an ultra-high pressure mercury lamp capable of irradiating light with a wavelength of 365 nm, 405 nm, or 436 nm, light irradiation with a wavelength of 365 nm, 405 nm, or 436 nm is possible.
- a high-pressure mercury lamp or an LED capable of irradiating light with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is more preferable, and an LED capable of irradiating light with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is most preferable.
- the irradiation time of the active energy ray with respect to the aqueous dispersion applied on the recording medium is, for example, 0.01 seconds to 120 seconds, preferably 0.1 seconds to 90 seconds.
- the irradiation conditions and basic irradiation methods the irradiation conditions and irradiation methods disclosed in JP-A-60-132767 can be similarly applied.
- an active energy ray irradiation method specifically, a light source is provided on both sides of a head unit including an ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method, or another light source that is not driven is used.
- a method of performing irradiation with active energy rays is preferable.
- the irradiation with active energy rays is preferably performed after landing on the aqueous dispersion and heating and drying, followed by a certain time (for example, 0.01 seconds to 120 seconds, preferably 0.01 seconds to 60 seconds). .
- the image forming method may further include a heat drying step after the application step and before the irradiation step, if necessary.
- a heat drying step it is preferable that the aqueous dispersion discharged onto the recording medium fixes the image by evaporating water and an organic solvent used together as necessary by the heating means.
- a heating means it is sufficient if water and an organic solvent used in combination as needed can be dried.
- the heating means is not particularly limited, and examples thereof include a heat drum, hot air, an infrared lamp, a heat oven, and a heat plate heating.
- the heating temperature is preferably 40 ° C. or higher, more preferably about 40 ° C. to 150 ° C., and further preferably about 40 ° C. to 80 ° C.
- the heating time can be appropriately set in consideration of the composition of the aqueous dispersion and the printing speed.
- the aqueous dispersion fixed by heating is irradiated with active energy rays in the irradiation step as necessary, and further light-fixed.
- fixing with UV light is preferable.
- NCO104 ⁇ Synthesis of Isocyanate Compound (NCO104)>
- TMP trimethylolpropane
- HXDI 1,3-bis (isocyanatomethyl) cyclohexane
- AcOEt ethyl acetate
- NCO104 is a trifunctional or higher functional isocyanate compound having no polymerizable group.
- NCO202 is a trimethylolpropane (TMP), 57.91 g of 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), and 169.62 g of ethyl acetate (AcOEt), and the mixture was heated to 50 ° C. 0.261 g of U-600 was added and reacted for 3 hours. After the reaction, 23.43 g of Bremer AP-400 (manufactured by NOF Corporation) and 0.04 g of dihydroxytoluene (BHT) were added thereto and further reacted at 50 ° C. for 3 hours to obtain NCO202.
- NCO202 is a trifunctional or higher functional isocyanate compound having a polymerizable group.
- hydrophilic group-containing isocyanate compound A ⁇ Synthesis of hydrophilic group-containing isocyanate compound A> To a three-necked flask, 45 g of 2,2-bis (hydroxymethyl) propionic acid (DMPA), 223.72 g of isophorone diisocyanate (IPDI), and 499.05 g of ethyl acetate (AcOEt) were added and heated to 50 ° C. 0.7677 g of U-600 was added and reacted for 3 hours to obtain a hydrophilic group-containing isocyanate compound A.
- the hydrophilic group-containing isocyanate compound A is an isocyanate compound having a carboxy group as a hydrophilic group.
- the isocyanate compound introduced with a hydrophilic group in D-116N has, as the hydrophilic group, R W1 is an ethylene group, R W2 is a methyl group, and nw is 90 in the above formula (WS). Has a group.
- the oil phase component and the aqueous phase component were mixed, and the obtained mixture was emulsified at 12000 rpm for 10 minutes using a homogenizer to obtain an emulsion.
- the presence or absence of a residue is visually confirmed. If the residue is confirmed, water is added to this residue and stirred for 1 hour using a stirrer to re-disperse the residue with water. A liquid was obtained. With respect to the obtained re-dispersed liquid, the particle size distribution was measured by a light scattering method using a wet particle size distribution measuring device (LA-910, Horiba, Ltd.). When the particle size distribution was confirmed by the above operation, it was determined that the aqueous dispersion contained gel particles. As a result, it was confirmed that the aqueous dispersion of the gel particles 1 contains gel particles (that is, the gel particles 1 are actually gel particles).
- the aqueous dispersion of the gel particles 1 actually contains gel particles having a polymerizable group (that is, the gel particles 1 are actually It was confirmed that the gel particles have a polymerizable group.
- volume average particle diameter of gel particle 1 The volume average particle diameter of the gel particles 1 in the aqueous dispersion of the gel particles 1 was measured by the light scattering method using the LA-910. As a result, the volume average particle diameter of the gel particles 1 was 0.15 ⁇ m.
- sample 1A tetrahydrofuran
- sample 2A tetrahydrofuran
- the obtained diluted solution was centrifuged at 80,000 rpm for 40 minutes.
- the supernatant liquid produced by centrifugation (hereinafter referred to as “supernatant liquid 1A”) was collected.
- the mass of the photopolymerization initiator contained in the collected supernatant liquid 1A was measured by a liquid chromatography apparatus “Waters 2695” manufactured by Waters.
- the mass of the obtained photopolymerization initiator was defined as “total amount of photopolymerization initiator”.
- the sample 2A was subjected to centrifugation under the same conditions as the centrifugation performed for the diluent.
- the supernatant liquid generated by centrifugation (hereinafter referred to as “supernatant liquid 2A”) was collected.
- the mass of the photopolymerization initiator contained in the collected supernatant 2A was measured by the liquid chromatography apparatus.
- the mass of the obtained photopolymerization initiator was defined as “free amount of photopolymerization initiator”. Based on the “total amount of photopolymerization initiator” and the “free amount of photopolymerization initiator”, the encapsulation rate (% by mass) of the photopolymerization initiator was determined according to the following formula.
- Encapsulation rate of photopolymerization initiator ((total amount of photopolymerization initiator ⁇ free amount of photopolymerization initiator) / total amount of photopolymerization initiator) ⁇ 100
- the encapsulation rate of the photopolymerization initiator was 99% or more, and it was confirmed that the photopolymerization initiator was encapsulated in gel particle 1.
- ⁇ Preparation of aqueous dispersion of gel particles 2 (gel particle dispersion)>
- 19 g of NCO 104 was changed to 38 g of NCO 202 (a trifunctional or higher functional isocyanate compound having a polymerizable group, solid content of 35% by mass)
- the gel particle 2 aqueous dispersion was prepared in the same manner as the preparation of the gel particle 1 aqueous dispersion except that SR-399E (polymerizable monomer) was not contained.
- the prepared aqueous dispersion of gel particles 2 was measured and confirmed in the same manner as the aqueous dispersion of gel particles 1.
- the aqueous dispersion of gel particles 2 includes gel particles actually having a polymerizable group (that is, gel particles 2 are actually gel particles having a polymerizable group. Confirmed).
- the volume average particle diameter of the gel particles 2 was 0.15 ⁇ m.
- the encapsulation rate of the photopolymerization initiator was 99% or more, and it was confirmed that the photopolymerization initiator was encapsulated in the gel particle 2.
- the gel phase except that the oil phase component further contains 2-isopropylthioxanthone (ITX; sensitizer) 0.5 g.
- the same operation as the preparation of the aqueous dispersion 1 was performed to prepare an aqueous dispersion of the gel particles 3.
- the prepared aqueous dispersion of gel particles 3 was measured and confirmed in the same manner as the aqueous dispersion of gel particles 1.
- the aqueous dispersion of gel particles 3 includes gel particles actually having a polymerizable group (that is, the gel particles 3 are gel particles actually having a polymerizable group). Confirmed).
- the volume average particle diameter of the gel particles 3 was 0.15 ⁇ m.
- the encapsulation rate of the photopolymerization initiator was 99% or more, and it was confirmed that the photopolymerization initiator was encapsulated in the gel particles 3.
- the encapsulation rate of the polymerizable monomer was 99% or more, and it was confirmed that the polymerizable monomer was encapsulated in gel particle 3.
- ⁇ Preparation of aqueous dispersion of gel particles 4-6 (gel particle dispersion)> Except that the type of photopolymerization initiator was changed as shown in Table 4, the same operation as in the above-mentioned “Preparation of aqueous dispersion of gel particles 1” was performed.
- Each of the aqueous dispersions of the gel particles 4 to 6 includes gel particles that actually have a polymerizable group as in the aqueous dispersion of the gel particles 1 (that is, each of the gel particles 4 to 6 actually It was confirmed that the gel particles have a polymerizable group.
- the volume average particle diameter of each of the gel particles 4 to 6 was 0.15 ⁇ m.
- the encapsulation rate of the photopolymerization initiator was 99% or more, and it was confirmed that the photopolymerization initiator was encapsulated in the gel particles.
- Table 4 shows an outline of gel particles 1 to 6 (gel particle numbers 1 to 6).
- IRG819 IRGACURE® 819 (acylphosphine oxide compound; specifically, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; manufactured by BASF)
- IRG907 IRGACURE (registered trademark) 907 (carbonyl compound; specifically 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one; manufactured by BASF)
- IRG369 IRGACURE (registered trademark) 369 (carbonyl compound; specifically 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; manufactured by BASF)
- IRG184 ...
- IRGACURE (registered trademark) 184 carbonyl compound; specifically, 1-hydroxy-cyclohexyl-phenyl-ketone; manufactured by BASF)
- Example 1 ⁇ Preparation of ink composition>
- the ink composition of Example 1 which is an aqueous dispersion containing gel particles, a polymerizable resin and water was produced as follows (resin mixing step). Specifically, the gel particle 1, the polymerizable resin, and water are used by using an aqueous dispersion of the gel particle 1, an aqueous dispersion or aqueous solution of the polymerizable resin shown in Table 5 below, and other components in the following composition.
- an aqueous dispersion containing an ink composition having the following composition was prepared.
- the total solid content (% by mass) of the gel particles 1 is the total amount of the ink composition (the total solid content of the gel particles 1) in the aqueous dispersion of the gel particles 1 (that is, the total solid content of the gel particles 1).
- the content is expressed as “total amount of ink”).
- the content (% by mass) of the polymerizable resin is the content of the aqueous dispersion of the polymerizable resin shown in Table 5 or the solid content of the aqueous solution (that is, the polymerizable resin) with respect to the total amount of the ink composition. Amount (the same applies to Tables 6 and 7 described later).
- the evaluation of adhesion was performed using each of the following evaluation sample (PVC), evaluation sample (A-PET), and evaluation sample (Acryl).
- the sample for evaluation (PVC) was obtained by applying the ink composition obtained above to a polyvinyl chloride (PVC) sheet as a base material, with a K hand coater No. of RK PRINT COAT INSTRUMENTS. It was prepared by coating with a thickness of 12 ⁇ m using 2 bars, and drying the resulting coating film by heating at 60 ° C. for 3 minutes.
- the evaluation sample (A-PET) was prepared in the same manner as the evaluation sample (PVC) except that the base material was changed to an amorphous polyethylene terephthalate (A-PET) sheet.
- the evaluation sample (Acryl) was prepared in the same manner as the evaluation sample (PVC) except that the base material was changed to an acrylic resin sheet.
- -PVC sheet "AVERY (registered trademark) 400 GLOSS WHITE PERMANENT” manufactured by Avery Dennison
- A-PET sheet “A-PET” (amorphous polyethylene terephthalate sheet) manufactured by Takiron Co., Ltd.
- -Acrylic resin sheet "Acryase (registered trademark) UV” manufactured by JSP Corporation
- the coating film of each evaluation sample was irradiated with UV light (ultraviolet rays) using the above exposure apparatus, thereby curing the coating film to obtain a cured film.
- the cured film was subjected to a cross hatch test in accordance with ISO 2409 (cross cut method) and evaluated according to the following evaluation criteria. In this cross-hatch test, the cut interval was 1 mm, and 25 square grids of 1 mm square were formed. In the following evaluation criteria, 0 and 1 are practically acceptable levels.
- the pencil hardness of the cured film was evaluated using the evaluation sample (PVC).
- the coating film of the sample for evaluation (PVC) was irradiated with UV light and cured to obtain a cured film.
- a pencil hardness test was performed on the cured film based on JIS K5600-5-4 (1999) using UNI (registered trademark) manufactured by Mitsubishi Pencil Co., Ltd. as a pencil. In this test result, the allowable range of pencil hardness is HB or more, and preferably H or more.
- a printed material having a pencil hardness of B or less is not preferred because scratches may occur when the printed material is handled.
- the ink composition obtained above was ejected from the head of an inkjet printer (SP-300V, manufactured by Roland DG) for 30 minutes, and then the ejection was stopped. After a lapse of 5 minutes from the stop of the discharge, the ink composition was again discharged from the head on the polyvinyl chloride (PVC) sheet to form a solid image of 5 cm ⁇ 5 cm. These images were visually observed to confirm the presence or absence of missing dots due to the occurrence of non-ejection nozzles, and the ejection properties of the ink composition were evaluated according to the following evaluation criteria.
- ⁇ Redispersibility of ink composition> The following operations were performed under yellow light, and the redispersibility of the ink composition obtained above was evaluated.
- FT-IR Fourier transform infrared spectroscopic measurement
- Residual ratio of gel particles (Intensity of peak derived from gel particle in coating film after rubbing with sponge / Intensity of peak derived from gel particle in coating film before rubbing with sponge) ⁇ 100
- the peak derived from the gel particles is a peak at 1700 cm ⁇ 1 .
- the redispersibility of the ink composition was evaluated according to the following evaluation criteria.
- ⁇ Storage stability of ink composition> The ink composition obtained above is sealed in a container and allowed to elapse for 2 weeks at 60 ° C., and then the same evaluation as the above-described evaluation of ejection properties is performed. According to the same evaluation criteria, the storage stability of the ink composition is determined. Sex was evaluated.
- Examples 2 to 50 In preparation of the ink composition of Example 1, at least one of the aqueous dispersion of the polymerizable resin or the type of aqueous solution (type of resin), the type of gel particles (gel particle number), and the total solid content of the gel particles. The same operation as in Example 1 was performed except that one was changed as shown in Tables 5 and 6. The results are shown in Tables 5 and 6.
- Example 5 In the preparation of the ink composition of Example 5, the ink composition did not contain the aqueous dispersion of the gel particles 1, and the external additive initiator shown in Table 6 was added to the ink composition at the content shown in Table 6. The same operation as in Example 5 was carried out except that it was contained.
- the content of the external addition initiator shown in Table 6 is the content of the external addition initiator (solid content when an aqueous dispersion of the initiator is used) with respect to the total amount of the ink composition. The results are shown in Table 6.
- ⁇ Preparation of aqueous dispersion of comparative particle X> In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel, and an air introduction tube, 27.5 parts by mass of the amphiphilic urethane acrylate (a) obtained above, biscoat # 802 (tripentaerythritol acrylate, And dipentaerythritol acrylate and polypentaerythritol acrylate, polymerizable monomer, 9.2 parts by mass of Osaka Organic Chemical Co., Ltd., and LUCIRIN® TPO (2,4,6-trimethylbenzoyl- Then, 3.3 parts by mass of diphenyl-phosphine oxide, photopolymerization initiator (manufactured by BASF) was charged, and while stirring, the temperature in the container was raised to 80 ° C.
- the comparative particles X was obtained by diluting with deionized water so that the concentration of the polymerizable monomer and the photopolymerization initiator) was 20% by mass.
- the comparative particle X is not a gel particle (that is, it is not gelled).
- Example 5 the same operation as in Example 5 was performed except that the aqueous dispersion of gel particles 1 was changed to the aqueous dispersion of comparative particles X.
- Table 6 The results are shown in Table 6.
- Daicel Ornex "UCECOAT 7655" manufactured by Co., Ltd. which has a polymerizable group
- Aqueous dispersion of polyurethane LR8983: “Laromar LR8983” manufactured by BASF an aqueous dispersion of polyurethane having a polymerizable group (volume average particle diameter: 50 nm) 400 AU: “DA-400AU” manufactured by NOF Corporation, having a polymerizable group
- IRGACURE registered trademark
- 2959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; manufactured by BASF
- IRG819DW IRGACURE (registered trademark) 819DW (water dispersion of IRGACURE819; manufactured by BASF)
- Ink compositions (aqueous dispersions) of certain examples were excellent in storage stability, redispersibility, and ejection properties. Furthermore, the film
- Comparative Examples 1 and 2 which did not contain gel particles and contained an external addition initiator, the pencil hardness of the film, the adhesion between the film and the substrate, and the like decreased.
- Comparative Example 1 using IRG2959 as the external addition initiator the pencil hardness of the film and the adhesion between the film and the substrate were reduced as compared with each Example. This is because the sensitivity of IRG2959 is inferior to that of the encapsulated photopolymerization initiator of each Example, and because the solubility of IRG2959 in water is low, the content of IRG2959 is low (1.0% relative to the total amount of the ink composition). (Mass%) is considered to be the cause.
- Comparative Example 2 using IRG819DW as an external additive, the pencil hardness of the film and the adhesion between the film and the substrate were lowered and the storage stability was further lowered as compared with each Example.
- the reason why the pencil hardness and the adhesiveness are lowered is considered to be that the sensitivity is lowered due to the influence of the dispersant used to disperse IRG819 in water in IRG819DW.
- the reason why the storage stability was lowered in Comparative Example 2 was that although a dispersant was used to disperse IRG819 in water, it was still photopolymerized in comparison with the dispersibility of the gel particles in each Example. This is probably because the dispersibility of the initiator is inferior.
- Comparative Example 3 which used the comparative particle X which has not gelatinized instead of the gel particle, storage stability, redispersibility, and discharge property fell. Further, the film formed in Comparative Example 3 was inferior in pencil hardness and adhesion to the substrate as compared with the film formed in Example 5.
- the ink composition of each example was superior to the ink composition of each comparative example in the evaluation of pencil hardness, surface shape, and adhesion using LED light. Results were obtained.
- Comparative Examples 1 to 3 particularly in Comparative Example 1, the curability is remarkably lowered due to the fact that IRG 2959 does not absorb LED light, and the pencil hardness, the surface shape, and the adhesiveness are greatly reduced (Table 1). 6 and Table 7).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polymerisation Methods In General (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Ink Jet (AREA)
Abstract
Description
インクジェット方式の画像形成方法は、安価な装置で実施可能である、インクを効率良く使用できるのでランニングコストが安い、といった利点を有する。
以下、活性エネルギー線の照射によって硬化可能なインクジェット用インクを、「光硬化性インク」ということがある。また、インクジェット用インクに限らず、活性エネルギー線の照射によって硬化可能な組成物を、「光硬化性組成物」ということがある。
例えば、水や溶剤の存在下での紫外線照射による硬化性を維持しつつ、吐出安定性に優れたインクジェット用インク組成物として、水と、色材と、ラジカル重合性基を有する化合物からなる樹脂エマルションと、無機粒子ディスパージョンと、光ラジカル開始剤と、を含むインクジェット用インク組成物が知られている(例えば、特開2013-199602号公報参照)。
熱硬化又は光硬化が可能で、コーティング剤等に好適に使用できる水性エマルションとして、少なくとも一つの末端に特定のアクリル官能性基を有するビニル系重合体を含有する水性エマルションが知られている(例えば、特開2000-136211号公報参照)。
例えば、赤外線レーザー露光によって露光後発色安定性がよく、経時後露光しても高発色が得られる発色感光性組成物として、ガラス転移温度が50℃以上であるポリマー、光開始剤、及び赤外線吸収染料を内包したミクロゲルと、バインダーポリマーと、を含有する発色感光性組成物が知られている(例えば、特開2011-213114号公報参照)。
照射によって硬化するインクジェットプリント用インクとして、少なくとも1つの照射硬化型モノマーと、少なくとも1つの不活性熱可塑性樹脂と、少なくとも1つのラジカル光開始剤と、少なくとも1つの着色剤とを含み、25℃で100mPas未満の粘度を有し、少なくとも1つの不活性樹脂が、全重量に対して2から15重量%で存在し、1,500から70,000の分子量を有する、インクジェット用インクが知られている(例えば、特表2009-542833号公報参照)。
即ち、本発明の一実施形態の目的は、硬度及び面状に優れた膜を形成でき、保存安定性に優れた水分散物及びその製造方法を提供することである。
また、本発明の一実施形態の目的は、硬度及び面状に優れた画像を形成できる画像形成方法を提供することである。
<1> 重合性基を有する樹脂と、重合性基を有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有し、光重合開始剤を内包しているゲル粒子と、水と、を含有し、ゲル粒子の全固形分の含有量が、重合性基を有する樹脂の全量に対し、0.1質量%~100質量%である水分散物。
<3> ゲル粒子が、表面に親水性基を有する<1>又は<2>に記載の水分散物。
<4> ゲル粒子が、重合性モノマーを内包している<1>~<3>のいずれか1つに記載の水分散物。
<5> ゲル粒子が、増感剤を内包している<1>~<4>のいずれか1つに記載の水分散物。
<6> 重合性基を有する樹脂が、ポリウレタン構造を有する<1>~<5>のいずれか1つに記載の水分散物。
<7> ゲル粒子の全固形分の含有量が、重合性基を有する樹脂の全量に対し、5質量%~75質量%である<1>~<6>のいずれか1つに記載の水分散物。
<8> 重合性基を有する樹脂の含有量が、水分散物の全量に対し、2質量%~40質量%である<1>~<7>のいずれか1つに記載の水分散物。
ゲル粒子と水とを含有するゲル粒子分散物を準備する準備工程と、
ゲル粒子分散物と重合性基を有する樹脂とを混合して水分散物を得る樹脂混合工程と、
を有する水分散物の製造方法。
<10> 準備工程は、
光重合開始剤、3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分、光重合開始剤、重合性基を有する3官能以上のイソシアネート化合物、及び有機溶媒を含む油相成分、並びに、光重合開始剤、重合性基を有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分から選ばれるいずれかの油相成分と、水を含む水相成分と、を混合し、乳化させて乳化物を得る乳化工程と、
乳化物を加熱することによりゲル粒子分散物を得るゲル化工程と、
を有する<9>に記載の水分散物の製造方法。
<11> 油相成分に含まれる3官能以上のイソシアネート化合物が、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、トリメチルヘキサメチレンジイソシアネート、1,3-ビス(イソシアネートメチル)シクロヘキサン、m-キシリレンジイソシアネート、及びジシクロヘキシルメタン4,4’-ジイソシアネートから選択される少なくとも1種から誘導されたイソシアネート化合物である<10>に記載の水分散物の製造方法。
記録媒体上に付与された水分散物に、活性エネルギー線を照射する照射工程と、
を有する画像形成方法。
また、本発明の一実施形態によれば、硬度及び面状に優れた画像を形成できる画像形成方法が提供される。
本明細書において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
本明細書では、紫外線を、「UV(Ultra Violet)光」ということがある。
本明細書では、LED(Light Emitting Diode)光源から生じた光を、「LED光」ということがある。
本明細書において、「(メタ)アクリル酸」は、アクリル酸及びメタクリル酸の両方を包含する概念であり、「(メタ)アクリレート」は、アクリレート及びメタクリレートの両方を包含する概念であり、「(メタ)アクリロイル基」は、アクリロイル基及びメタクリロイル基の両方を包含する概念である。
本開示の水分散物は、重合性基を有する樹脂(以下、「重合性樹脂」ともいう)と、重合性基を有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有し、光重合開始剤を内包しているゲル粒子と、水と、を含有し、上記ゲル粒子の全固形分の含有量が、上記重合性樹脂の全量に対し、0.1質量%~100質量%である水分散物である。
本明細書中において、水分散物がゲル粒子の外部に重合性樹脂を含有するとは、水分散物が、ゲル粒子に内包されていない重合性樹脂を含有することを意味する。水分散物がゲル粒子の外部にその他の成分(光重合開始剤、重合性モノマー、等)を含有する場合についても同様である。
また、本明細書中において、ゲル粒子の全固形分とは、ゲル粒子に溶媒(有機溶媒、水等。以下同じ。)が含まれている場合には、内包される光重合開始剤等を含めたゲル粒子から溶媒を除いた全量を意味し、ゲル粒子に溶媒が含まれていない場合には、内包される光重合開始剤等を含めたゲル粒子の全量を意味する。
本開示の水分散物が上記効果を奏し得る理由については明らかではないが、本発明者らは、以下のように推測している。
本開示の水分散物では、ゲル粒子が、重合性基を有し、かつ、光重合開始剤を内包している。即ち、本開示の水分散物では、従来の水分散物(例えば、重合性基を有し光重合開始剤を内包していない樹脂粒子と、光重合開始剤と、を含有する水性エマルション)と比較して、重合性基と光重合開始剤との距離が近くなっている。このため、本開示の水分散物を用いて膜を形成し、形成された膜に光を照射して膜を硬化させた場合には、従来の水分散物を用いた場合と比較して、膜の硬化感度(以下、単に「感度」ともいう。)が向上するので、硬度に優れた膜が形成されると考えられる。
更に、本開示の水分散物は、ゲル粒子の外部に重合性樹脂を、比較的多く(具体的には、ゲル粒子の全固形分の含有量以上の含有量にて)含有している。本開示の水分散物では、かかる含有量の重合性樹脂に対し、ゲル粒子が光重合開始剤として機能すると考えられる。より詳細には、ゲル粒子に内包される光重合開始剤が、ゲル粒子の重合性基に対してだけではなく、上述した含有量の重合性樹脂の重合性基に対しても作用すると考えられる。その結果、本開示の水分散物を用いた場合には、感度良く膜を硬化させることができるので、硬度に優れた膜が形成されると考えられる。
更に、ゲル粒子の三次元架橋構造がウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含むことも、膜の硬度の向上に寄与すると考えられる。
以上の理由により、本開示の水分散物によれば、硬度に優れた膜を形成できると考えられる。
本開示の水分散物が面状に優れた膜を形成できる理由の一つとして、本開示の水分散物が樹脂成分(具体的には重合性樹脂)を比較的多く含有することが考えられる。また、本開示の水分散物が面状に優れた膜を形成できるもう一つの理由として、重合性樹脂の重合性基により、膜の硬化の均一性が向上することも考えられる。
即ち、本開示の水分散物では、ゲル粒子が光重合開始剤を内包していることにより、ゲル粒子が光重合開始剤を内包していない場合と比較して、経時による光重合開始剤の沈降が抑制されるので、水分散物の保存安定性が向上すると考えられる。
したがって、いずれの文献に記載の組成物も、本開示の水分散物と比較して、形成された膜の硬度に劣り、また、保存安定性にも劣ると考えられる。
基材との密着性に優れた膜を形成できる理由として、上述のとおり、本開示の水分散物が、重合性基を有し光重合開始剤を内包しているゲル粒子を含有することにより、感度良く膜を硬化させることができることが考えられる。
また、基材との密着性に優れた膜を形成できる理由として、本開示の水分散物が樹脂成分(重合性樹脂)を含有することにより、膜の硬化収縮が抑制され、これにより、膜の硬化収縮に起因する、膜と基材との密着性の低下が抑制されることも考えられる。
また、基材との密着性に優れた膜を形成できる理由として、重合性樹脂が重合性基を有することにより、重合によって膜と基材との密着性が向上することも考えられる。
ここで、「再分散性」とは、水分散物中の水が蒸発して形成された固化物に対して、水系液体(例えば、水、水溶液、水分散物等)を供給することにより、固化物中の粒子が水系液体中に再び分散する性質を意味する。上記の固化物の例としては、塗布ヘッド又はインクジェットヘッドに形成された水分散物の固化物が挙げられる。
本開示の水分散物は、ゲル粒子を含有することにより、再分散性にも優れる。
この理由は、本開示の水分散物が上述のとおり再分散性に優れるためと考えられる。即ち、インク組成物としての水分散物中の水が蒸発し、インクジェット記録装置のノズル付近にゲル粒子が固着したとしても、新たなインク組成物(即ち、水分散物)が供給されることにより、ゲル粒子が再び容易に分散し、ノズル詰まりの発生が抑制されるため、吐出性にも優れると考えられる。
ここで、「重合性樹脂の全量に対するゲル粒子の全固形分の含有量」とは、下記式で表される量を指す。
重合性樹脂の全量に対するゲル粒子の全固形分の含有量が100質量%以下であると、重合性樹脂による、膜の面状向上等の効果が効果的に発揮される。
重合性樹脂の全量に対するゲル粒子の全固形分の含有量は、上述のとおり0.1質量%~100質量%であるが、膜の硬度及び面状の観点から、好ましくは0.1質量%以上100質量%未満であり、より好ましくは1質量%~100質量%であり、更に好ましくは5質量%~75質量%であり、特に好ましくは10質量%~50質量%である。
本開示の水分散物では、ゲル粒子が光重合開始剤を内包することで、使用する光重合開始剤の選択の幅が広がり、ひいては、用いられる光源の選択の幅も広がる。そのため、従来よりも硬化感度を向上し得る。
しかしながら、カルボニル化合物及びアシルホスフィンオキシド化合物は、水に対する溶解性が低いため、従来は、水系の組成物には含有させることが難しかった。
本開示の水分散物では、ゲル粒子が光重合開始剤を内包することにより、光重合開始剤として、光に対する感度に優れるが水への溶解性が低い、カルボニル化合物及びアシルホスフィンオキシド化合物等の光重合開始剤を選択することができる。
以上の観点から、ゲル粒子に内包される光重合開始剤は、カルボニル化合物及びアシルホスフィンオキシド化合物の少なくとも一方を含むことが好ましく、アシルホスフィンオキシド化合物を含むことがより好ましい。
LED光の波長としては、355nm、365nm、385nm、395nm、又は405nmが好ましい。
本開示の水分散物は、水に対する溶解性が低い物質をゲル粒子に内包させることにより、水系の組成物である水分散物中に含有させることができる。このことも本開示の水分散物の利点の一つである。
本明細書中において、例えば、「光重合開始剤がゲル粒子に内包されている」とは、光重合開始剤がゲル粒子の内部に含まれていることを意味する。ここでいう「ゲル粒子の内部」とは、三次元架橋構造の空隙を意味する。
本開示の水分散物では、膜の硬化感度の観点から、光重合開始剤の内包率(質量%)が、10質量%以上であることが好ましく、50質量%以上であることがより好ましく、70質量%以上が更に好ましく、80質量%以上が更に好ましく、90質量%以上が更に好ましく、95質量%以上が更に好ましく、97質量%以上が更に好ましく、99質量%以上が特に好ましい。
水分散物に光重合開始剤が2種以上含有される場合、少なくとも1種の光重合開始剤の内包率が、上述した好ましい範囲であることが好ましい。
ここで、光重合開始剤の内包率(質量%)とは、水分散物を調製した場合の水分散物中の光重合開始剤の全量に対する、ゲル粒子に内包されている光重合開始剤の量を意味し、以下のようにして求められた値を指す。
以下の操作を、液温25℃の条件で行う。
以下の操作は、水分散物が顔料を含有していない場合にはこの水分散物をそのまま用いて行い、水分散物が顔料を含有している場合には、まず、遠心分離によって水分散物から顔料を除去し、顔料が除去された水分散物に対して行う。
試料1に対し、この試料1中の全固形分に対して500質量倍のテトラヒドロフラン(THF)を加えて混合し、希釈液を調製する。得られた希釈液に対し、80,000rpm(round per minute;以下同じ。)、40分の条件の遠心分離を施す。遠心分離によって生じた上澄み液(以下、「上澄み液1」とする。)を採取する。この操作により、試料1に含まれていた全ての光重合開始剤が、上澄み液1中に抽出されると考えられる。採取された上澄み液1中に含まれる光重合開始剤の質量を、液体クロマトグラフィー(例えば、Waters社の液体クロマトグラフィー装置)によって測定する。得られた光重合開始剤の質量を、「光重合開始剤の全量」とする。
また、試料2に対し、上記希釈液に施した遠心分離と同じ条件の遠心分離を施す。遠心分離によって生じた上澄み液(以下、「上澄み液2」とする。)を採取する。この操作により、試料2において、ゲル粒子に内包されていなかった(即ち、遊離していた)光重合開始剤が、上澄み液2中に抽出されると考えられる。採取された上澄み液2中に含まれる光重合開始剤の質量を、液体クロマトグラフィー(例えば、Waters社の液体クロマトグラフィー装置)によって測定する。得られた光重合開始剤の質量を、「光重合開始剤の遊離量」とする。
上記「光重合開始剤の全量」及び上記「光重合開始剤の遊離量」に基づき、下記の式に従って、光重合開始剤の内包率(質量%)を求める。
光重合開始剤の内包率(質量%) = ((光重合開始剤の全量-光重合開始剤の遊離量)/光重合開始剤の全量)×100
但し、分子量1,000以上の化合物については、上記の上澄み液1及び上澄み液2に含まれる化合物の質量を、ゲルパーミエーションクロマトグラフィー(GPC)によって測定し、それぞれ「化合物の全量」及び「化合物の遊離量」とし、化合物の内包率(質量%)を求める。
検量線は、東ソー(株)の「標準試料TSK standard,polystyrene」:「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、及び「n-プロピルベンゼン」の8サンプルから作製する。
本明細書中において、「三次元架橋構造」とは、架橋によって形成された立体的な網目構造を指す。本開示の水分散物では、粒子内で三次元架橋構造が形成されることにより、ゲル粒子が形成されている。
即ち、本明細書中において、粒子が三次元架橋構造を有することと、粒子がゲル粒子であることとは同義である。
また、以下の操作は、水分散物が顔料を含有していない場合にはこの水分散物をそのまま用いて行い、水分散物が顔料を含有している場合には、まず、遠心分離によって水分散物から顔料を除去し、顔料が除去された水分散物に対して行う。
以上の操作によって粒度分布が確認できた場合を、水分散物が三次元架橋構造を有するゲル粒子を含むと判断する。
本開示の水分散物において、重合性樹脂の重合性基及びゲル粒子の重合性基としては、それぞれ、エチレン性二重結合を含む基が好ましく、ビニル基及び1-メチルビニル基の少なくとも一方を含む基が更に好ましい。
重合性基としては、重合反応性及び形成される膜の硬度の観点から、(メタ)アクリロイル基が特に好ましい。
重合性樹脂及びゲル粒子は、それぞれ、重合性基を1種のみ含有していてもよいし、2種以上含有していてもよい。
また、重合性樹脂の重合性基とゲル粒子の重合性基とは、同種の基であっても異種の基であってもよい。
即ち、ゲル粒子において、重合性基は、三次元架橋構造の一部として存在していてもよいし、三次元架橋構造以外の部分として存在していてもよい。
「重合性基が三次元架橋構造以外の部分として存在する」とは、ゲル粒子に、重合性モノマー(即ち、重合性基を有するモノマー)が含まれていることを指す。
いずれの場合においても、重合性基は、ゲル粒子の表面部分(水との接触部分)に存在していることが好ましい。
「ゲル粒子が重合性基を有する」ことは、例えば、フーリエ変換赤外線分光測定(FT-IR)分析によって確認することができる。
重合性基を有するモノマー(重合性モノマー)の好ましい態様については、後述する。
ゲル粒子は、その表面に親水性基を有することで、水分散物中における分散性がより向上する。
また、ゲル粒子は、表面に親水性基を有することで、ゲル粒子の親水性が向上し、保存安定性及び再分散性に優れる。
ゲル粒子において、親水性基は、三次元架橋構造の一部として存在していてもよいし、三次元架橋構造以外の部分として存在していてもよい。
ここで、「親水性基が三次元架橋構造の一部として存在する」とは、親水性基が三次元架橋構造の親水性基以外の部分と共有結合していることを指す。
また、「親水性基が三次元架橋構造以外の部分として存在する」とは、ゲル粒子に、三次元架橋構造とは別に、親水性基を有する化合物が含まれていることを指す。
上述の、カルボキシ基の塩、スルホ基の塩、硫酸基の塩、ホスホン酸基の塩、及びリン酸基の塩は、ゲル粒子の製造過程で、中和によって形成された塩であってもよい。ゲル粒子がその表面に親水性基を有する場合、ゲル粒子は、親水性基を1種のみ有していてもよいし、2種以上有していてもよい。
なお、本明細書において「親水性基」とは、後述する活性水素基(ヒドロキシ基、1級アミノ基、2級アミノ基、及びメルカプト基)とは区別される。
式(WS)中、RW2で表される炭素数1~6の分岐していてもよいアルキル基の炭素数は、1~4であることが好ましく、1であること(即ち、RW2がメチル基であること)が特に好ましい。
式(WS)中、nwは、2~200の整数を表すが、nwとしては、10~200の整数が好ましく、10~150の整数がより好ましく、20~150の整数が更に好ましく、20~100の整数が特に好ましい。
本開示の水分散物が増感剤を含有する場合には、活性エネルギー線照射による光重合開始剤の分解がより促進され得る。この場合において、ゲル粒子が増感剤を内包する場合には、光重合開始剤との反応性がより向上する。その結果、感度及び膜の硬度がより向上する。
増感剤の好ましい範囲については後述する。
かかる液体としては、記録媒体としての基材に対して画像を形成するためインク組成物(例えば、インクジェット記録用インク組成物)、基材に対して塗膜を形成するための塗布液(例えば、コーティング剤、接着剤、塗料等の感光性樹脂組成物)などが挙げられる。
本開示の水分散物は、特に、インクジェット記録に用いられること(即ち、本開示の水分散物をインクジェット記録用インク組成物として用いること)が好ましい。
本開示の水分散物の用途の一つであるインク組成物(好ましくはインクジェット記録用インク組成物)としては、色材を含有するインク組成物であっても、色材を含有しない透明のインク組成物(「クリアインク」等と呼ばれることもある)であってもよい。
本開示の水分散物の別の用途である塗布液についても同様である。
基材としては、例えば、紙、プラスチック(例えば、ポリエチレン、ポリプロピレン、ポリスチレン等)がラミネートされた紙、金属板(例えば、アルミニウム、亜鉛、銅等の金属の板)、プラスチックフィルム(例えば、ポリ塩化ビニル(PVC:Polyvinyl Chloride)樹脂、二酢酸セルロース、三酢酸セルロース、プロピオン酸セルロース、酪酸セルロース、酢酸酪酸セルロース、硝酸セルロース、ポリエチレンテレフタレート(PET:Polyethylene Terephthalate)、ポリエチレン(PE:Polyethylene)、ポリスチレン(PS:Polystyrene)、ポリプロピレン(PP:Polypropylene)、ポリカーボネート(PC:Polycarbonate)、ポリビニルアセタール、アクリル樹脂等のフィルム)、上述した金属がラミネートされ又は蒸着された紙、上述した金属がラミネートされ又は蒸着されたプラスチックフィルムなどが挙げられる。
非吸収性の基材としては、ポリ塩化ビニル(PVC)基材、ポリスチレン(PS)基材、ポリカーボネート(PC)基材、ポリエチレンテレフタレート(PET)基材、ポリプロピレン(PP)基材、アクリル樹脂基材等のプラスチック基材が好ましい。
本開示の水分散物は、ゲル粒子とは別に(即ち、ゲル粒子の外部に)、重合性樹脂(即ち、重合性基を有する樹脂)を含有する。
重合性樹脂は、重合性基を有することにより、膜の硬度向上、膜と基材との密着性向上、及び膜の面状向上に寄与する。
また、重合性樹脂は、樹脂であることにより、膜の面状向上、及び、硬化収縮の抑制(膜と基材との密着性向上)に寄与する。
本開示の水分散物は、重合性樹脂を1種のみ含有していてもよいし、2種以上含有していてもよい。
また、本開示の水分散物は、本開示の効果を損なわない限りにおいて、重合性基を有しない樹脂を含有していてもよい。
(メタ)アクリロイル基が特に好ましい。
ここで、水溶性樹脂における「水溶性」とは、105℃で2時間乾燥させた場合に、25℃の蒸留水100g対する溶解量が1gを超える性質を指す。
また、水分散性樹脂における「水分散性」とは、水不溶性であって、かつ、水中に分散される性質を指す。ここで、「水不溶性」とは、105℃で2時間乾燥させた場合に、25℃の蒸留水100gに対する溶解量が1g以下である性質を指す。
上述した塩の対カチオンとしては、ナトリウム、カリウム等のアルカリ金属カチオン、カルシウム、マグネシウム等のアルカリ土類金属カチオン、アンモニウムカチオン、又はホスホニウムカチオンが好ましく、アルカリ金属カチオンが特に好ましい。
アンモニウム塩基のアンモニウム基に含まれるアルキル基としては、メチル基又はエチル基が好ましい。
また、アンモニウム塩基の対アニオンとしては、塩素、臭素等のハロゲンアニオン、硫酸アニオン、硝酸アニオン、リン酸アニオン、スルホン酸アニオン、カルボン酸アニオン、又は炭酸アニオンが好ましく、ハロゲンアニオン、スルホン酸アニオン、又はカルボン酸アニオンが特に好ましい。
カルボン酸アミド基の窒素原子上の置換基としては、炭素数8以下のアルキル基が好ましく、炭素数6以下のアルキル基が特に好ましい。
アルキレンオキシ基を有する樹脂は、アルキレンオキシ基の繰り返しからなるアルキレンオキシ鎖を有することが好ましい。アルキレンオキシ鎖に含まれるアルキレンオキシ基の数は、2以上が好ましく、4以上が特に好ましい。
重合性樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)によって測定した値である。
本開示の水分散物は、重合性基を有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有し、光重合開始剤を内包しているゲル粒子を含有する。
ゲル粒子は、本開示の水分散物における分散質である。
ゲル粒子に内包されている光重合開始剤は、ゲル粒子の三次元架橋構造の空隙に、三次元架橋構造とは結合せずに存在しているものを含む。
なお、本明細書においては、三次元架橋構造の空隙に存在する光重合開始剤等も含めて「ゲル粒子」とする。
本開示の水分散物は、上述したとおり、上記ゲル粒子を含むことで、分散性、及び固化が発生した場合の再分散性に優れ、かつ、高感度に硬化し、膜強度(耐水性、耐溶剤性)に優れた膜が得られる。
更に、ゲル粒子が、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有することで、強度に優れた膜(例えば画像)が得られる。また、機械的強度に優れた膜(例えば画像)が得られる。
更に、ゲル粒子が、光重合開始剤を内包することで、高感度で硬化し、架橋性も高い。
三次元架橋構造1gあたりに含まれるウレタン結合及びウレア結合の合計量(mmol/g)は、1mmol/g~10mmol/gが好ましく、1.5mmol/g~9mmol/gがより好ましく、2mmol/g~8mmol/gが特に好ましい。
ゲル粒子の三次元架橋構造は、下記構造(1)を含むことが好ましい。
三次元架橋構造は、下記構造(1)を複数含んでいてもよく、複数の構造(1)は、同じ構造であってもよく、異なる構造であってもよい。
構造(1)中、R1、R2、及びR3は、それぞれ独立に、環構造を有していてもよい炭素数5~15の炭化水素基を表す。
構造(1)中、*は、結合位置を表し、p、m、及びnは、それぞれ0以上であり、p+m+nは3以上である。
脂環構造としては、シクロヘキサン環構造、ビシクロヘキサン環構造、ビシクロデカン環構造、イソボルネン環構造、ジシクロペンタン環構造、アダマンタン環構造、トリシクロデカン環構造、等が挙げられる。
芳香環構造としては、ベンゼン環構造、ナフタレン環構造、ビフェニル環構造、等が挙げられる。
構造(1)中、mは、0以上であり、1~10が好ましく、1~8がより好ましく、1~6が更に好ましく、1~3が特に好ましい。
構造(1)中、nは、0以上であり、1~10が好ましく、1~8がより好ましく、1~6が更に好ましく、1~3が特に好ましい。
構造(1)中、p+m+nは、3~10の整数が好ましく、3~8の整数がより好ましく、3~6の整数が更に好ましい。
式(X-11)~式(X-12)中、*は、結合位置を表す。
式(X-1)~式(X-10)中、Yは、下記の(Y-1)を示す。
R1、R2、及びR3における炭化水素基は、置換基を有していてもよく、置換基としては、前述の親水性基が挙げられる。
構造(2)の、R1、R2及びR3で表される炭化水素基は、それぞれ、構造(1)の、R1、R2、及びR3で表される炭化水素基と同義であり、好ましい範囲も同じである。
構造(2)中、*は、結合位置を表す。
構造(3)の、R1、R2及びR3で表される炭化水素基は、それぞれ、構造(1)の、R1、R2、及びR3で表される炭化水素基と同義であり、好ましい範囲も同じである。
構造(3)中、*は、結合位置を表す。
構造(4)の、R1、R2及びR3で表される炭化水素基は、それぞれ、構造(1)の、R1、R2、及びR3で表される炭化水素基と同義であり、好ましい範囲も同じである。
構造(4)中、*は、結合位置を表す。
特に、ゲル粒子を製造する際の原料が、3つ以上の反応性基(イソシアネート基又は活性水素基)を有する化合物を少なくとも1種含む場合には、架橋反応が三次元でより効果的に進行し、立体的な網目構造がより効果的に形成される。
ゲル粒子における三次元架橋構造は、3官能以上のイソシアネート化合物と水との反応により形成された生成物であることが好ましい。
3官能以上のイソシアネート化合物は、分子内に3つ以上のイソシアネート基を有する化合物であり、後述の方法により合成した化合物、及び公知の化合物を使用することができる。3官能以上のイソシアネート化合物としては、例えば、3官能以上の芳香族イソシアネート化合物、3官能以上の脂肪族イソシアネート化合物などが挙げられる。
公知の化合物としては例えば「ポリウレタン樹脂ハンドブック」(岩田敬治編、日刊工業新聞社発行(1987))に記載されている化合物が挙げられる。
式(X)中、nは3以上である。nは3~10が好ましく、3~8がより好ましく、3~6がさらに好ましい。
なお、「誘導された」とは、原料に上記の化合物を用い、原料に由来する構造を含むことを意味する。
これらの3官能以上のイソシアネート化合物は、複数の化合物が含まれる混合物であってもよく、以下に示す式(11A)又は式(11B)で表される化合物がこれら混合物の主成分であることが好ましく、他の成分を含んでいてもよい。
アダクト型の3官能以上のイソシアネート化合物としては、下記式(11A)又は式(11B)で表される化合物が好ましい。
式(11A)及び式(11B)中、X3~X11は、それぞれ独立に、O、S、又はNHを表す。
式(11A)及び式(11B)中、R1~R6は、それぞれ独立に、2価の有機基を表す。
式(11A)及び式(11B)中、Zは2価の有機基を表す。
式(11A)及び式(11B)中、p+m+nとしては、3~10が好ましく、3~8がより好ましく、3~6がさらに好ましい。
式(11A)及び式(11B)中、X3~X11としては、それぞれ独立に、O又はSが好ましく、Oがより好ましい。
式(11A)及び式(11B)中、R1~R6としては、それぞれ独立に、環構造を有していてもよい炭素数5~15の炭化水素基が好ましい。
式(11A)及び式(11B)中、R1~R6の好ましい態様は、それぞれ独立に、構造(1)におけるR1の好ましい態様と同様である。
脂環構造としては、シクロヘキサン環構造、ビシクロヘキサン環構造、ビシクロデカン環構造、イソボルネン環構造、ジシクロペンタン環構造、アダマンタン環構造、トリシクロデカン環構造、等が挙げられる。
芳香環構造としては、ベンゼン環構造、ナフタレン環構造、ビフェニル環構造、等が挙げられる。
脂環構造としては、シクロヘキサン環構造、ビシクロヘキサン環構造、ビシクロデカン環構造、イソボルネン環構造、ジシクロペンタン環構造、アダマンタン環構造、トリシクロデカン環構造、等が挙げられる。
芳香環構造としては、ベンゼン環構造、ナフタレン環構造、ビフェニル環構造、等が挙げられる。
式(X2-1)~式(X2-10)中、*は、結合位置を表す。
Zにおける炭化水素基は、直鎖状の炭化水素基であってもよいし、分岐鎖状の炭化水素基であってもよいし、環状の炭化水素基であってもよい。
Zにおける炭化水素基の炭素数は、2~30が好ましい。
式(11A)及び式(11B)中、R1~R6としては、それぞれ独立に、イソホロンジイソシアネート(IPDI)から誘導される基(R-3)、ヘキサメチレンジイソシアネート(HDI)から誘導される基(R-7)、トリメチルヘキサメチレンジイソシアネート(TMHDI)から誘導される基(R-5)、m-キシリレンジイソシアネート(XDI)から誘導される基(R-9)、1,3-ビス(イソシアネートメチル)シクロヘキサンから誘導される基(R-1)、及びジシクロヘキシルメタン4,4’-ジイソシアネートから誘導される基(R-2)のいずれかであることがより好ましい。
一般に、分子中に3つ以上の活性水素基を有する化合物と反応させる2官能のイソシアネート化合物のモル数(分子数)は、分子中に3つ以上の活性水素基を有する化合物における活性水素基のモル数(活性水素基の当量数)に対し、0.6倍以上のモル数(分子数)の2官能のイソシアネート化合物が使用される。2官能のイソシアネート化合物のモル数は、上記の活性水素基のモル数の0.6倍~5倍が好ましく、0.6倍~3倍がよりに好ましく、0.8倍~2倍がさらに好ましい。
これらの2官能のイソシアネート化合物の中でも、下記(I-1)~(I-24)に示す構造の化合物が好ましい。
イソシアヌレート型の3官能以上のイソシアネート化合物としては、式(11C)で表される化合物が好ましい。
ビウレット型の3官能以上のイソシアネート化合物としては、式(11D)で表される化合物が好ましい。
式(11C)及び式(11D)中、R1、R2、及びR3は、それぞれ独立に、炭素数1~20の置換基を有していてもよいアルキレン基、炭素数1~20の置換基を有していてもよいシクロアルキレン基、又は炭素数1~20の置換基を有していてもよいアリーレン基であることが好ましい。
式(11C)及び式(11D)中、R1、R2、及びR3は、それぞれ独立に、既述の(R-1)~(R-20)で表される基から選択される基であることが特に好ましい。
また、ビウレット型の3官能以上のイソシアネート化合物としては、上市されている市販品を用いてもよく、例えば、D-165N、NP1100(三井化学株式会社製)、デスモジュール(登録商標)N3200(住化バイエルウレタン)、デュラネート(登録商標)24A-100(旭化成株式会社製)などが挙げられる。
イソシアネート基含有量は、対象のイソシアネート化合物を脱水トルエンに溶解後、過剰のジノルマルブチルアミン溶液を加えて反応させ、残りのジノルマルブチルアミンを塩酸で逆滴定し、滴定曲線上の変曲点での滴定量から算出することができる。
イソシアネート基含有量は、電位差滴定装置(AT-510、京都電子工業(株)製)を用いて、25℃において、1mol/L塩酸水溶液により下記のブランク測定及び試料測定に示す方法で中和滴定を行い、得られる滴定量Z1及びZ2から下記式(N)により算出できる。
100mLビーカーに、脱水トルエン10mL、2mol/Lジノルマルブチルアミン溶液10.0mL、及びイソプロピルアルコール50mLを入れて混合し混合液を調製する。この混合液に対して1mol/L塩酸溶液を用いて中和滴定を行い、滴定曲線上の変曲点を終点として、終点までの滴定量Z1(mL)を求める。
固形分W質量%の試料(イソシアネート化合物)Ygを100mLビーカーに採取し、このビーカーに脱水トルエン20(mL)を加えて、試料を溶解させ、溶液を調製する。この溶液に、2mol/Lジノルマルブチルアミン溶液10.0mLを加えて混合し、その後20分以上静置する。静置後の溶液にイソプロピルアルコール50mLを加える。その後、1mol/L塩酸溶液を用いて中和滴定を行い、滴定曲線上の変曲点を終点として、終点までの滴定量Z2(mL)を求める。
ゲル粒子は、既述の3官能以上のイソシアネート化合物と、水又は2つ以上の活性水素基を有する化合物と、を反応させて製造されることが好ましい。
3官能以上のイソシアネート化合物と反応させる化合物としては、一般に水が使用される。3官能以上のイソシアネート化合物と水とが反応することで、ウレア結合を有する三次元架橋構造が形成される。
また、水以外に3官能以上のイソシアネート化合物と反応させる化合物として、2つ以上の活性水素基を有する化合物が挙げられ、2つ以上の活性水素基を有する化合物として、多官能アルコール、多官能フェノール、窒素原子上に水素原子を有する多官能アミン、多官能チオールも用いることができる。
3官能以上のイソシアネート化合物と、多官能アルコール又は多官能フェノールと、が反応することにより、ウレタン結合を有する三次元架橋構造が形成される。
3官能以上のイソシアネート化合物と、窒素原子上に水素原子を有する多官能アミンと、が反応することにより、ウレア結合を有する三次元架橋構造が形成される。
多官能アミンの具体例としては、ジエチレントリアミン、テトラエチレンペンタミンなどが挙げられる。
多官能チオールの具体例としては、1,3-プロパンジチオール、1,2-エタンジチオールなどが挙げられる。
多官能フェノールの具体例としては、ビスフェノールAなどが挙げられる。
これらの化合物は1種を単独で使用してもよく、2種以上を併用してもよい。
ゲル粒子は、重合性基を有する。
ゲル粒子は、三次元架橋構造中に重合性基が導入されることにより重合性基を有していてもよく、重合性モノマーがゲル粒子の内部(三次元架橋構造の空隙)に含まれることにより重合性基を有していてもよい。また、その両方が併存してもよい。
ゲル粒子の内部に重合性モノマーが含まれない場合、ゲル粒子は、三次元架橋構造中に重合性基を有する。
ゲル粒子は、感度及び架橋性の観点から表面、又はゲル粒子の表面と表面付近に重合性基を有することが好ましい。
少なくとも1つ活性水素基を有し、少なくとも1つ末端にエチレン性不飽和結合を有する化合物は下記構造式(a)で表すことができる。
L1LcmZn (a)
L1は、2価以上の脂肪族基、2価以上の芳香族基、2価以上の複素環基、-O-、-S-、-NH-、-N<、-CO-、-SO-、-SO2-又はそれらの組合せであることが好ましい。
m及びnは、それぞれ独立に、1~50であることが好ましく、2~20であることがより好ましく、3~10であることがさらに好ましく、3~5であることがとくに好ましい。
Lcで表される1価のエチレン性不飽和基としては、アリル基、ビニル基、アクリロイル基、メタクリロイル基等を挙げることができる。
Zは、OH、SH、NH又はNH2であることが好ましく、OH又はNH2であることがより好ましく、OHであることがさらに好ましい。
重合性基を導入したイソシアネート化合物は、イソシアネート基の平均官能基数が3以下である場合もある。しかし、この場合においても、三次元架橋構造を形成するための原料中に3官能以上のイソシアネート化合物が少なくとも1つ含まれていれば、三次元架橋構造を形成することが可能である。
ゲル粒子は、光重合開始剤の少なくとも1種を内包している。
前述のとおり、ゲル粒子が光重合開始剤を内包していることで、光に対する感度が高くなり、形成される膜の硬度が向上する。
また、ゲル粒子が光重合開始剤を内包していることで、従来、高感度であるが水への分散性が低い又は溶解性が低いため用いることが難しかった光重合開始剤を用いることができる。これにより、使用する光重合開始剤の選択の幅が広がり、ひいては、用いられる光源の選択の幅も広がる。このため、従来よりも硬化感度を向上し得る。
内包光重合開始剤は、光(即ち、活性エネルギー線)を吸収して重合開始種であるラジカルを生成する化合物である。
より好ましい例としては、特公昭47-6416号公報記載のα-チオベンゾフェノン化合物、特公昭47-3981号公報記載のベンゾインエーテル化合物、特公昭47-22326号公報記載のα-置換ベンゾイン化合物、特公昭47-23664号公報記載のベンゾイン誘導体、特開昭57-30704号公報記載のアロイルホスホン酸エステル、特公昭60-26483号公報記載のジアルコキシベンゾフェノン、特公昭60-26403号公報、特開昭62-81345号公報記載のベンゾインエーテル類、特公平1-34242号公報、米国特許第4,318,791号パンフレット、ヨーロッパ特許0284561A1号公報に記載のα-アミノベンゾフェノン類、特開平2-211452号公報記載のp-ジ(ジメチルアミノベンゾイル)ベンゼン、特開昭61-194062号公報記載のチオ置換芳香族ケトン、特公平2-9597号公報記載のアシルホスフィンスルフィド、特公平2-9596号公報記載のアシルホスフィン、特公昭63-61950号公報記載のチオキサントン類、特公昭59-42864号公報記載のクマリン類等を挙げることができる。
また、特開2008-105379号公報、特開2009-114290号公報に記載の重合開始剤も好ましい。
これらの中でも、感度向上の観点及びLED光への適合性の観点等から、内包光重合開始剤としては、(b)アシルホスフィンオキシド化合物が好ましく、モノアシルホスフィンオキシド化合物(特に好ましくは、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキシド)、又は、ビスアシルホスフィンオキシド化合物(特に好ましくは、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキシド)がより好ましい。
ゲル粒子は、さらに重合性モノマーを内包していることが好ましい。
なお、ゲル粒子が三次元架橋構造中に重合性基を有さない場合、ゲル粒子は、重合性モノマーを内包しており、重合性モノマーの重合性基はゲル粒子が有する重合性基として機能する。
ゲル粒子が内包している重合性モノマー(以下、内包重合性モノマーともいう)としては、ラジカル重合可能なエチレン性不飽和結合を有する重合性モノマーから選択できる。
内包重合性モノマーは、エチレン性不飽和基を有する化合物が好ましい。
内包重合性モノマーは、1種単独で用いてもよく、2種以上を併用してもよい。
多官能の内包重合性モノマーとしては、メタクリレートモノマー、及びアクリレートモノマーが好ましく、アクリレートモノマーがより好ましい。
内包重合性モノマーは、3官能以上のアクリレートモノマーであることがさらに好ましく、4官能以上のアクリレートモノマーであることが特に好ましい。
また、内包重合性モノマーは、2種以上の単官能の内包重合性モノマーと多官能の内包重合性モノマーとを併用することで、膜の密着性向上の効果に加え、膜の硬度がより向上する効果も得られる。
その他、重合性モノマーとしては、NPGPODA(ネオペンチルグリコールプロピレンオキシド付加物ジアクリレート、サートマー社)、SR399E(ジペンタエリスリトールペンタアクリレート、サートマー社)、ATMM-3L(ペンタエリスリトールトリアクリレート、新中村化学工業(株))、A-DHP(ジペンタエリスリトールヘキサアクリレート、新中村化学工業(株))、アロニックス(登録商標)M-156(東亞合成(株)製)、V-CAP(BASF社製)、ビスコート#192(大阪有機化学工業(株)製)、SR-531、SR-285、SR256(サートマー社製)、等の市販品を好適に用いることができる。
なお、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(GPC)により測定できる。
前述のとおり、ゲル粒子は、表面に親水性基を有することが好ましい。
ゲル粒子の表面への親水性基の導入は、既述の3官能以上のイソシアネート化合物及び既述の2つ以上の活性水素基を有する化合物と、親水性基を有する化合物と、を反応させることで行うことができる。また、既述の3官能以上のイソシアネート化合物を製造する際に、2官能以上のイソシアネート化合物と親水性基を有する化合物とを反応させ、あらかじめ親水性基を導入したイソシアネート化合物と既述の2つ以上の活性水素基を有する化合物とを反応させることで行うこともできる。
親水性基の好ましい範囲については前述のとおりである。
親水性基を有する化合物としては、ポリエーテル構造を有する化合物、カルボキシ基を有する化合物、又はカルボキシ基の塩を有する化合物が特に好ましい。
これらのポリオキシアルキレン鎖を有する化合物の中でも、ポリエチレンオキシド、ポリプロピレンオキシド、ポリエチレンオキシド-ポリプロピレンオキシドブロック共重合体が好ましく、ポリエチレンオキシドがより好ましい。
また、ポリエーテル構造を有する化合物としては、ポリエチレンオキシドのモノエーテル体(モノエーテルとしては、例えば、モノメチルエーテル、モノエチルエーテル等が挙げられる)、ポリエチレンオキシドのモノエステル体(モノエステルとしては、例えば、モノ酢酸エステル、モノ(メタ)アクリル酸エステル等が挙げられる)も好ましい。
前述のとおり、ゲル粒子の表面への親水性基の導入には、親水性基を導入したイソシアネート化合物を用いることもできる。
親水性基を導入したイソシアネート化合物としては、親水性基を有する化合物と、2官能のイソシアネート化合物(好ましくは、イソホロンジイソシアネート(IPDI)、ヘキサメチレンジイソシアネート(HDI)、トリメチルヘキサメチレンジイソシアネート(TMHDI)、1,3-ビス(イソシアネートメチル)シクロヘキサン(HXDI)、m-キシリレンジイソシアネート(XDI)、又はジシクロヘキシルメタン-4,4’-ジイソシアネート(HMDI))と、の反応物が挙げられる。
2つ以上の活性水素基を有する化合物及び2官能のイソシアネート化合物の好ましい態様は前述のとおりである。
ポリエーテル構造を有する化合物としては、下記式(WM)で表される化合物が好ましい。
カルボキシ基の塩としては、ナトリウム塩、カリウム塩、トリエチルアミン塩、ジメチルエタノールアミン塩が好ましく、ナトリウム塩又はトリエチルアミン塩がより好ましい。
ゲル粒子に内包され得るその他の成分としては、後述する増感剤、樹脂等が挙げられる。
ゲル粒子に内包され得る樹脂(以下、「内包樹脂」ともいう)は、重合性基を有していてもよいし、重合性基を有していなくてもよい。
本開示の水分散物が内包樹脂を含有する場合、上記内包樹脂としては、水不溶性樹脂を用いることもできる。
ここで、「水不溶性樹脂」とは、105℃で2時間乾燥させた場合に、25℃の蒸留水100gに対する溶解量が1g以下である樹脂を意味する。
前述のとおり、本開示の水分散物は、水に対する溶解性が低い水不溶性樹脂をゲル粒子に内包させることにより、水系の組成物である水分散物中に水不溶性樹脂を含有させることができる。
ゲル粒子の体積平均粒子径は、分散性の観点から0.01μm~10.0μmであることが好ましく、0.01μm~5μmであることがより好ましく、0.05μm~1μmであることがさらに好ましい。
ゲル粒子の体積平均粒子径は、光散乱法により測定することができる。なお、本明細書における体積平均粒子径は、LA-910(株式会社堀場製作所製)により測定された値が用いられる。
本開示の水分散物は、分散媒として、水を含有する。
本開示の水分散物中の水の含有量には特に制限はないが、水の含有量は、水分散物の全量に対し、好ましくは10質量%~99質量%であり、より好ましくは20質量%~95質量%であり、さらに好ましくは30質量%~90質量%であり、特に好ましくは50質量%~90質量%である。
本開示の水分散物は、増感剤を含有していてもよい。
本開示の水分散物が増感剤を含有すると、活性エネルギー線照射による光重合開始剤の分解がより促進され得る。
増感剤は、特定の活性エネルギー線を吸収して電子励起状態となる物質である。電子励起状態となった増感剤は、光重合開始剤と接触して、電子移動、エネルギー移動、発熱等の作用を生じる。これにより、光重合開始剤の化学変化、即ち、分解、ラジカル、酸又は塩基の生成等が促進される。
また、増感剤としては、特開2010-24276号公報に記載の一般式(i)で表される化合物や、特開平6-107718号公報に記載の一般式(I)で表される化合物も、好適に使用できる。
上記の中でも、増感剤としては、LED光への適合性及び光重合開始剤との反応性の観点から、チオキサントン、イソプロピルチオキサントン、及びベンゾフェノンから選ばれる少なくとも1種が好ましく、チオキサントン及びイソプロピルチオキサントンから選ばれる少なくとも1種がより好ましく、イソプロピルチオキサントンが更に好ましい。
本開示の水分散物が増感剤を含有する場合、増感剤を1種単独で、又は、2種以上組み合わせて含有してもよい。
本開示の水分散物が増感剤を含有する場合、増感剤の含有量は、ゲル粒子の全固形分に対して、0.1質量%~25質量%であることが好ましく、0.5質量%~20質量%であることがより好ましく、1質量%~15質量%であることが更に好ましい。
本開示の水分散物は、着色剤を少なくとも1種含有してもよい。
水分散物が着色剤を含有する場合、水分散物は、ゲル粒子の外部に含有されることが好ましい。
着色剤としては、特に制限はなく、顔料、水溶性染料、分散染料等の公知の色材から任意に選択して使用することができる。この中でも、耐候性に優れ、色再現性に富む点から、顔料を含むことがより好ましい。
有機顔料及び無機顔料としては、例えば、黄色顔料、赤色顔料、マゼンタ顔料、青色顔料、シアン顔料、緑色顔料、橙色顔料、紫色顔料、褐色顔料、黒色顔料、白色顔料等が挙げられる。
着色剤として顔料を用いる場合には、顔料粒子を調製する際に、必要に応じて顔料分散剤を用いてもよい
本開示の水分散物は、必要に応じて、上記で説明した以外のその他の成分を含有していてもよい。
その他の成分は、ゲル粒子に含まれていてもよいし、ゲル粒子に含まれていなくてもよい。
本開示の水分散物は、界面活性剤を含有していてもよい。
本開示の水分散物が界面活性剤を含有すると、ゲル粒子の分散性がより向上し得る。
界面活性剤としては、例えば、高級脂肪酸塩、アルキル硫酸塩、アルキルエステル硫酸塩、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、スルホコハク酸塩、ナフタレンスルホン酸塩、アルキルリン酸塩、ポリオキシアルキレンアルキルエーテルリン酸塩、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシエチレンポリオキシプロピレングリコール、グリセリンエステル、ソルビタンエステル、ポリオキシエチレン脂肪酸アミド、アミンオキシド等が挙げられる。
これらの中でも、界面活性剤としては、アルキル硫酸塩、アルキルスルホン酸塩、及びアルキルベンゼンスルホン酸塩から選ばれる少なくとも1種の界面活性剤が好ましく、アルキル硫酸塩が特に好ましい。
界面活性剤としては、ゲル粒子の分散性の観点から、アルキル鎖長が8~18のアルキル硫酸塩であることが好ましく、ドデシル硫酸ナトリウム(SDS、アルキル鎖長:12)及びセチル硫酸ナトリウム(SCS、アルキル鎖長:16)から選ばれる少なくとも1種であることがより好ましく、セチル硫酸ナトリウム(SCS)であることが更に好ましい。
また、界面活性剤として、有機フルオロ化合物を用いてもよい。
有機フルオロ化合物は、疎水性であることが好ましい。有機フルオロ化合物としては、フッ素系界面活性剤、オイル状フッ素系化合物(例えば、フッ素油)、及び固体状フッ素化合物樹脂(例えば、四フッ化エチレン樹脂)が含まれ、特公昭57-9053号(第8欄~第17欄)、及び特開昭62-135826号の各公報に記載されたものが挙げられる。
本開示の水分散物は、重合禁止剤を含有していてもよい。
本開示の水分散物が重合禁止剤を含有すると、水分散物の保存安定性がより向上し得る。
重合禁止剤としては、p-メトキシフェノール、キノン類(例えば、ハイドロキノン、ベンゾキノン、メトキシベンゾキノン等)、フェノチアジン、カテコール類、アルキルフェノール類(例えば、ジブチルヒドロキシトルエン(BHT)等)、アルキルビスフェノール類、ジメチルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸銅、ジブチルジチオカルバミン酸銅、サリチル酸銅、チオジプロピオン酸エステル類、メルカプトベンズイミダゾール、ホスファイト類、2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)、2,2,6,6-テトラメチル-4-ヒドロキシピペリジン-1-オキシル(TEMPOL)、クペロンAl、トリス(N-ニトロソ-N-フェニルヒドロキシルアミン)アルミニウム塩などが挙げられる。
これらの中でも、p-メトキシフェノール、カテコール類、キノン類、アルキルフェノール類、TEMPO、TEMPOL、クペロンAl、及びトリス(N-ニトロソ-N-フェニルヒドロキシルアミン)アルミニウム塩から選ばれる少なくとも1種が好ましく、p-メトキシフェノール、ハイドロキノン、ベンゾキノン、BHT、TEMPO、TEMPOL、クペロンAl、及びトリス(N-ニトロソ-N-フェニルヒドロキシルアミン)アルミニウム塩から選ばれる少なくとも1種がより好ましい。
本開示の水分散物は、紫外線吸収剤を含有していてもよい。
本開示の水分散物が紫外線吸収剤を含有すると、膜の耐候性等がより向上し得る。
紫外線吸収剤としては、公知の紫外線吸収剤、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物、ベンズオキサゾール系化合物等が挙げられる。
本開示の水分散物は、有機溶剤を含有していてもよい。
本開示の水分散物が有機溶剤を含有すると、膜と基材との密着性がより向上し得る。
本開示の水分散物が有機溶剤を含有する場合、有機溶剤の含有量は、水分散物の全量に対して、0.1質量%~5質量%であることが好ましい。
有機溶剤の具体例は、以下のとおりである。
・アルコール類(例えば、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、イソブタノール、セカンダリーブタノール、ターシャリーブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、ベンジルアルコール等)、
・多価アルコール類(例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリ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、ポリプロピレングリコール、ブチレングリコール、ヘキサンジオール、ペンタンジオール、グリセリン、ヘキサントリオール、チオジグリコール、2-メチルプロパンジオール等)、
・多価アルコールエーテル類(例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル、エチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル等)、
・アミン類(例えば、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、N-メチルジエタノールアミン、N-エチルジエタノールアミン、モルホリン、N-エチルモルホリン、エチレンジアミン、ジエチレンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ポリエチレンイミン、ペンタメチルジエチレントリアミン、テトラメチルプロピレンジアミン等)、
・アミド類(例えば、ホルムアミド、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等)、
・複素環類(例えば、2-ピロリドン、N-メチル-2-ピロリドン、シクロヘキシルピロリドン、2-オキサゾリドン、1,3-ジメチル-2-イミダゾリジノン、γ-ブチロラクトン等)、
・スルホキシド類(例えば、ジメチルスルホキシド等)、
・スルホン類(例えば、スルホラン等)、
・その他(尿素、アセトニトリル、アセトン等)
ゲル粒子の外部に含有され得る光重合開始剤としては、上述の光重合開始剤(ゲル粒子に内包されている光重合開始剤)と同様のものが挙げられるが、ゲル粒子の外部に含有され得る光重合開始剤としては、水溶性又は水分散性の光重合開始剤であることが好ましく、その観点から、例えば、DAROCUR(登録商標)1173、IRGACURE(登録商標)2959、IRGACURE(登録商標)754、DAROCUR(登録商標)MBF、IRGACURE(登録商標)819DW、IRGACURE(登録商標)500(以上、BASF社製)等が好ましいものとして挙げられる。
なお、上記光重合開始剤における「水溶性」は、前述した「水溶性樹脂」における「水溶性」と同義であり、上記光重合開始剤における「水分散性」は、前述した「水分散性樹脂」における「水分散性」と同義である。
ゲル粒子の外部に含有され得る重合性モノマーとしては、エチレン性不飽和基を有する化合物、アクリロニトリル、スチレン、不飽和ポリエステル、不飽和ポリエーテル、不飽和ポリアミド、不飽和ウレタン等のラジカル重合性化合物が挙げられる。
これらの中でも、上記重合性モノマーとしては、エチレン性不飽和基を有する化合物が好ましく、(メタ)アクリロイル基を有する化合物が特に好ましい。
上記重合性モノマーにおける「水溶性」は、前述した「水溶性樹脂」における「水溶性」と同義であり、上記重合性モノマーにおける「水分散性」は、前述した「水分散性樹脂」における「水分散性」と同義である。
水溶性又は水分散性の観点から、上記重合性モノマーとしては、アミド構造、ポリエチレングリコール構造、ポリプロピレングリコール構造、カルボキシ基、及びカルボキシ基の塩からなる群から選択される少なくとも1種を有する化合物が好ましい。
ゲル粒子の外部に含有され得る重合性モノマーの重量平均分子量は、好ましくは700未満である。
ゲル粒子の外部に含有され得る重合性基を有しない樹脂としては、重合性基を有しないこと以外は上述の重合性樹脂と同様のものを用いることができる。
但し、重合性基を有しない樹脂としては、重合性樹脂の好ましい態様であるポリウレタン構造を有する樹脂以外にも、ポリエステル構造、ポリビニル構造、及びポリオレフィン構造からなる群から選択される少なくとも1種の構造を有する樹脂を用いてもよいし、上記少なくとも1種の構造とポリウレタン構造とを有する樹脂を用いてもよい。
本開示の水分散物は、水分散物を25℃~50℃とした場合に、粘度が、3mPa・s~15mPa・sであることが好ましく、3mPa・s~13mPa・sであることがより好ましい。特に、本開示の水分散物は、水分散物を25℃とした場合における粘度が、50mPa・s以下であることが好ましい。水分散物の粘度が上記の範囲であると、水分散物をインクジェット記録用インク組成物として用いた場合に、高い吐出安定性を実現することができる。
なお、水分散物の粘度は、粘度計(VISCOMETER TV-22、東機産業(株))を用いて測定される値である。
本開示の水分散物の製造方法は、上記の構成を有している本開示の水分散物を製造できればよく、特に限定されるものではない。
本開示の水分散物を製造する方法としては、本開示の水分散物を得やすいという観点から、以下で説明する、本実施形態の水分散物の製造方法が好ましい。
本実施形態の製造方法は、必要に応じ、その他の工程を有していてもよい。
本実施形態の製造方法によれば、上述した本開示の水分散物を容易に製造することができる。
なお、各工程で用いる成分の具体例、及び好ましい態様については、上述の水分散物の項に記載したとおりであるため、ここでは説明を省略する。
準備工程は、ゲル粒子と水とを含有するゲル粒子分散物を準備する工程である。
ゲル粒子分散物は、重合性樹脂を実質的に含有しないことが好ましい。ゲル粒子分散物における重合性樹脂の含有量は、1質量%未満であることが好ましく、0質量%であること(即ち、ゲル粒子分散物が重合性樹脂を含有しないこと)が特に好ましい。
準備工程は、便宜上の工程である。即ち、本実施形態の製造方法では、本開示の水分散物を製造するにあたり、予め準備しておいたゲル粒子分散物を用いてもよいし、本開示の水分散物を製造するにあたり、まずゲル粒子分散物を製造し、製造されたゲル粒子分散物を用いてもよい。
また、ゲル粒子分散物が三次元架橋構造を有するゲル粒子を含有することの確認方法も、希釈液を調製するためのテトラヒドロフラン(THF)の量を、ゲル粒子分散物の全固形分に対して100質量倍に変更すること以外は、「水分散物」の項で説明した、水分散物が三次元架橋構造を有するゲル粒子を含有することの確認方法と同様である。
乳化工程は、油相成分A、油相成分B、及び油相成分Cから選ばれるいずれかの油相成分と、水を含む水相成分と、を混合し、乳化させて乳化物を得る工程である。
乳化工程において、油相成分として、光重合開始剤、3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分A、光重合開始剤、重合性基を有する3官能以上のイソシアネート化合物、及び有機溶媒を含む油相成分B、並びに、光重合開始剤、重合性基を有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分Cから選ばれるいずれかの油相成分を使用することで、最終的に、少なくとも光重合開始剤を内包し、表面、又は、表面及び表面付近に重合性基を有するゲル粒子を得ることができる。
油相成分Aが含む重合性モノマー、油相成分Bが含む重合性基を有する3官能以上のイソシアネート化合物、並びに油相成分Cが含む重合性モノマー及び重合性基を有する3官能以上のイソシアネート化合物が有する重合性基が、ゲル粒子の表面、又は、表面及び表面付近に存在する重合性基となると考えられる。
他の成分としては、例えば、上述の親水性基を有する化合物が挙げられる。
油相成分が上述の親水性基を有する化合物を含むことで、表面に親水性基を有するゲル粒子を得ることができる。
油相成分が、親水性基を有する化合物として、カルボキシ基、スルホ基、硫酸基、ホスホン酸基、及びリン酸基から選ばれる少なくとも1種の親水性基を有する化合物を含む場合、水相成分は、中和剤を含んでいてもよい。
油相成分が親水性基を有する化合物を含み、かつ、水相成分が中和剤を含むと、油相成分と水相成分との混合によって、カルボキシ基等の親水性基が中和され、カルボキシ基等の塩が形成される。この形成される塩も、ゲル粒子の親水性基として機能する。これらの塩は、ゲル粒子を水中に分散させる効果に特に優れる。
中和剤としては、例えば、水酸化ナトリウム等が挙げられる。
具体的には、多官能アルコール(例えば、プロピレングリコール、グリセリン、トリメチロールプロパン等)、多官能アミン(例えば、ビス(ヘキサメチレン)トリアミン、エチレンジアミン、ジエチレントリアミン等)、多官能チオール(例えば、ペンタエリスリトールテトラ(3-メルカプトプロピオナート)等)などの化合物が挙げられ、多官能アルコールが特に好ましい。
これらの化合物は、1種単独で用いてもよいし、2種以上併用してもよい。これらの化合物は、その溶解性等に応じて、油相成分及び/又は水相成分に添加される。
一般に、乳化分散に用いる界面活性剤は、比較的長鎖の疎水基を有する界面活性剤が優れているとされている。例えば、界面活性剤としては、「界面活性剤便覧」(西一郎他、産業図書発行(1980))に記載の界面活性剤、具体的には、アルキル硫酸塩、アルキルスルホン酸、アルキルベンゼンスルホン酸等のアルカリ金属塩が好ましく、アルキル硫酸エステル塩がより好ましい。
アルキル硫酸エステル塩のアルキル鎖長は、分散安定性の観点から、12以上が好ましく、16以上がより好ましい。
界面活性剤は、油相成分又は水相成分の何れに添加してもよいが、通常、有機溶媒に対する溶解度が低いため、水相成分に添加する。
界面活性剤の量は、油相成分の全固形分量に対して0.1質量%~5質量%が好ましく、0.5質量%~3質量%がより好ましい。
油相成分中における光重合開始剤の量は、特に限定されず、例えば、全固形分量に対して0.1質量%~25質量%であることが好ましい。
油相成分中における3官能以上のイソシアネート化合物(又は重合性基を有する3官能以上のイソシアネート化合物)の量は、特に限定されず、例えば、全固形分量に対して10質量%~70質量%であることが好ましい。
油相成分が重合性モノマーを含む場合、油相成分中における重合性モノマーの量は、特に限定されず、例えば、全固形分量に対して0.1質量%~75質量%であることが好ましい。
有機溶媒の量は、特に限定されず、油相成分中に含まれる成分の種類、量等により、適宜、選択される。
水の量は、特に限定されず、油相成分中に含まれる成分の種類、量等により、適宜、選択される。
油相成分と水相成分との混合の方法としては、特に限定されず、例えば、攪拌による混合が挙げられる。
乳化における分散機の回転数は、例えば、5000rpm~20000rpmであり、好ましくは10000rpm~15000rpmである。
乳化における回転時間は、例えば、1分間~120分間であり、好ましくは3分間~60分間であり、より好ましくは3分間~30分間であり、更に好ましくは5分間~15分間である。
ゲル化工程は、上記乳化物を加熱することにより、ゲル粒子と水とを含有するゲル粒子分散物を得る工程である。
ゲル化工程では、上記乳化物の加熱によって、3官能以上のイソシアネート化合物と水とが反応し、イソシアネート基同士が架橋することで、ウレタン結合及びウレア結合から選ばれる少なくとも一方を含む三次元架橋構造と、重合性基と、を有し、少なくとも光重合開始剤を内包しているゲル粒子を含有するゲル粒子分散物を得ることができる。
ゲル化工程における加熱時間(反応時間)は、6時間~50時間が好ましく、12時間~40時間がより好ましく、15時間~35時間が更に好ましい。
ゲル化工程は、乳化物から有機溶媒を留去する工程を含むことが好ましい。
樹脂混合工程は、上記ゲル粒子分散物と重合性樹脂とを混合して水分散物を得る工程である。
樹脂混合工程では、上記ゲル粒子分散物と、重合性樹脂の水分散物と、を混合してもよい。
樹脂混合工程により、上述のゲル粒子と、このゲル粒子の外部に含有される重合性樹脂と、水と、を含有する水分散物が得られる。
樹脂混合工程における重合性樹脂の好ましい範囲は、前述した重合性樹脂の好ましい範囲と同様である。
その他の成分については、水分散物に含有され得るその他の成分として既に説明したとおりである。
その他の工程としては、その他の成分を添加する工程が挙げられる。
添加されるその他の成分については、水分散物に含有され得るその他の成分として既に説明したとおりである。
本実施形態の画像形成方法は、上述した本開示の水分散物を記録媒体上に付与する付与工程と、記録媒体上に付与された上記水分散物に、光(即ち、活性エネルギー線)を照射する照射工程と、を有する。
本実施形態の画像形成方法は、必要に応じその他の工程を有していてもよい。
本実施形態の画像形成方法によれば、記録媒体上に、硬度及び面状に優れた画像が形成される。この画像は、記録媒体との密着性にも優れる。
付与工程は、本開示の水分散物を記録媒体上に付与する工程である。
記録媒体上に水分散物を付与する態様としては、上記水分散物をインクジェット記録用インク組成物として用い、記録媒体上に上記水分散物(即ち、インクジェット記録用インク組成物)をインクジェット法によって付与する態様が特に好ましい。
記録媒体としては、「水分散物を用いて膜を形成するための基材」として例示した基材を用いることができる。
インクジェット記録装置としては特に制限はなく、目的とする解像度を達成し得る公知のインクジェット記録装置を任意に選択して使用することができる。すなわち、市販品を含む公知のインクジェット記録装置であれば、いずれも、画像形成方法における記録媒体への水分散物の吐出を行うことができる。
インク供給系は、例えば、本開示の水分散物であるインク組成物を含む元タンク、供給配管、インクジェットヘッド直前のインク供給タンク、フィルター、ピエゾ型のインクジェットヘッドからなる。ピエゾ型のインクジェットヘッドは、好ましくは1pl~100pl、より好ましくは8pl~30plのマルチサイズドットを、好ましくは320dpi(dot per inch)×320dpi~4000dpi×4000dpi(dot per inch)、より好ましくは400dpi×400dpi~1600dpi×1600dpi、さらに好ましくは720dpi×720dpiの解像度で吐出できるよう駆動することができる。なお、dpiとは、2.54cm(1inch)当たりのドット数を表す。
照射工程は、記録媒体上に付与された水分散物に、活性エネルギー線を照射する工程である。
記録媒体上に付与された水分散物に活性エネルギー線を照射することで、水分散物中のゲル粒子の架橋反応が進行し、画像を定着させ、画像の膜強度等を向上させることが可能となる。
また、200nm~310nmであることも好ましく、200nm~280nmであることも好ましい。
また、上記で例示された光源の、半導体紫外発光デバイスへの置き換えは、産業的にも環境的にも非常に有用である。
半導体紫外発光デバイスの中でも、LED(Light Emitting Diode)及びLD(Laser Diode)は、小型、高寿命、高効率、及び低コストであり、光源として期待されている。
光源としては、メタルハライドランプ、超高圧水銀ランプ、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、LED、又は青紫レーザーが好ましい。
これらの中でも、増感剤と光重合開始剤とを併用する場合は、波長365nm、405nm、若しくは436nmの光照射が可能な超高圧水銀ランプ、波長365nm、405nm、若しくは436nmの光照射が可能な高圧水銀ランプ、又は、波長355nm、365nm、385nm、395nm、若しくは405nmの光照射が可能なLEDがより好ましく、波長355nm、365nm、385nm、395nm、若しくは405nmの光照射が可能なLEDが最も好ましい。
照射条件並びに基本的な照射方法は、特開昭60-132767号公報に開示されている照射条件及び照射方法を同様に適用することができる。
活性エネルギー線の照射方式として、具体的には、インクの吐出装置を含むヘッドユニットの両側に光源を設け、いわゆるシャトル方式でヘッドユニット及び光源を走査する方式、又は、駆動を伴わない別光源によって活性エネルギー線の照射を行う方式が好ましい。
活性エネルギー線の照射は、水分散物を着弾して加熱乾燥を行った後、一定時間(例えば0.01秒間~120秒間、好ましくは0.01秒間~60秒間)をおいて行うことが好ましい。
画像形成方法は、必要により付与工程後であって照射工程前に、更に加熱乾燥工程を有していてもよい。
加熱乾燥工程において、記録媒体上に吐出された水分散物は、加熱手段により、水及び必要に応じて併用される有機溶剤が蒸発されることにより画像が定着されることが好ましい。
加熱手段としては、水及び必要に応じて併用される有機溶剤を乾燥させることができればよい。加熱手段は特に限定されないが、ヒートドラム、温風、赤外線ランプ、熱オーブン、ヒート版加熱などが挙げられる。
加熱温度は、40℃以上が好ましく、40℃~150℃程度がより好ましく、40℃~80℃程度が更に好ましい。
なお、加熱時間は、水分散物の組成及び印刷速度を加味して適宜設定することができる。
三口フラスコに、トリメチロールプロパン(TMP)10g、1,3-ビス(イソシアネートメチル)シクロヘキサン(HXDI)57.91g、及び酢酸エチル(AcOEt)126.11gを加え、50℃に加熱した。そこにネオスタンU-600(日東化成株式会社製、無機ビスマス触媒)を0.194g添加し、3時間反応させ、NCO104を得た。
NCO104は、重合性基を有しない3官能以上のイソシアネート化合物である。
三口フラスコに、トリメチロールプロパン(TMP)10g、1,3-ビス(イソシアネートメチル)シクロヘキサン(HXDI)57.91g、及び酢酸エチル(AcOEt)169.62gを加え、50℃に加熱し、そこにネオスタンU-600を0.261g添加し、3時間反応させた。反応後、そこにブレンマーAP-400(日油株式会社製)23.43g、ジヒドロキシトルエン(BHT)0.04g加えてさらに50℃、3時間反応させ、NCO202を得た。
NCO202は、重合性基を有する3官能以上のイソシアネート化合物である。
三口フラスコに、2,2-ビス(ヒドロキシメチル)プロピオン酸(DMPA)45g、イソホロンジイソシアネート(IPDI)223.72g、及び酢酸エチル(AcOEt)499.05gを加え、50℃に加熱し、そこにネオスタンU-600を0.7677g添加し、3時間反応させ、親水性基含有イソシアネート化合物Aを得た。
親水性基含有イソシアネート化合物Aは、親水性基としてカルボキシ基を有するイソシアネート化合物である。
(乳化工程)
-油相成分の作製-
NCO104(3官能以上のイソシアネート化合物、固形分35質量%)(19g)、
親水性基含有イソシアネート化合物A(2.51g)、
トリメチロールプロパンとキシレンジイソシアネートとポリエチレングリコールモノメチルエーテル(EO90)との付加物(親水性基を導入したイソシアネート化合物)の酢酸エチル50質量%溶液(三井化学株式会社製、タケネート(登録商標)D-116N)(3.5g)、
ジペンタエリスリトールペンタアクリレート(サートマー社製SR-399E;重合性モノマー)(6.5g)、及び
IRGACURE(登録商標)819(BASF社製;光重合開始剤(内包光重合開始剤))(2g)を、酢酸エチル(18g)中に溶解させ、油相成分を得た。
ここで、D-116N中の親水性基を導入したイソシアネート化合物は、親水性基として、前述の式(WS)において、RW1がエチレン基でありRW2がメチル基でありnwが90である基を有している。
ドデシル硫酸ナトリウム(SDS;界面活性剤)0.4gを蒸留水50gに溶解させて水相成分を得た。
得られた乳化物を蒸留水15gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃、24時間攪拌し、次いで、固形分濃度(即ち、ゲル粒子1の全固形分量)が30質量%となるように蒸留水を用いて希釈し、ゲル粒子1の水分散物(ゲル粒子分散物)を得た。
以下の方法により、ゲル粒子1の水分散物が実際にゲル粒子を含むかどうか(即ち、ゲル粒子1が、実際にゲル粒子であるかどうか)を確認した。なお、以下の操作は、液温25℃の条件で行った。
上記で得られたゲル粒子1の水分散物から試料を採取した。採取した試料に対し、この試料中の全固形分(ゲル粒子1)の100質量倍のテトラヒドロフラン(THF)を加えて混合し、ゲル粒子1の水分散物の希釈液を調製した。得られた希釈液に対して、遠心分離(80000rpm、40分間)を施した。遠心分離後、目視によって残渣の有無を確認し、残渣が確認された場合には、この残渣に水を加え、スターラーを用いて1時間攪拌することにより、残渣を水で再分散させて再分散液を得た。得られた再分散液について、湿式粒度分布測定装置(LA-910、(株)堀場製作所)を用い、光散乱法によって粒度分布を測定した。以上の操作により、粒度分布が確認された場合を、水分散物がゲル粒子を含むと判断した。
その結果、ゲル粒子1の水分散物がゲル粒子を含むこと(即ち、ゲル粒子1が、実際にゲル粒子であること)が確認された。
また、以上の結果とフーリエ変換赤外線分光測定(FT-IR)の結果とから、ゲル粒子1の水分散物が実際に重合性基を有するゲル粒子を含むこと(即ち、ゲル粒子1が、実際に重合性基を有するゲル粒子であること)が確認された。
ゲル粒子1の水分散物中のゲル粒子1の体積平均粒子径を、上記LA-910を用い、光散乱法によって測定した。その結果、ゲル粒子1の体積平均粒子径は、0.15μmであった。
ゲル粒子1の水分散物について光重合開始剤の内包率(%)を測定することにより、ゲル粒子1に光重合開始剤が実際に内包されているか否かを確認した。詳細を以下に示す。なお、以下の操作は、液温25℃の条件で行った。
上記ゲル粒子1の水分散物から、同質量の試料を2つ(以下、「試料1A」及び「試料2A」とする。)採取した。
試料1Aに対し、この試料1A中の全固形分に対して100質量倍のテトラヒドロフラン(THF)を加えて混合し、希釈液を調製した。得られた希釈液に対し、80,000rpm、40分の条件の遠心分離を施した。遠心分離によって生じた上澄み液(以下、「上澄み液1A」とする。)を採取した。採取された上澄み液1A中に含まれる光重合開始剤の質量を、Waters社の液体クロマトグラフィー装置「Waters2695」によって測定した。得られた光重合開始剤の質量を、「光重合開始剤の全量」とした。
また、試料2Aに対し、上記希釈液に施した遠心分離と同じ条件の遠心分離を施した。遠心分離によって生じた上澄み液(以下、「上澄み液2A」とする。)を採取した。採取された上澄み液2A中に含まれる光重合開始剤の質量を、上記液体クロマトグラフィー装置によって測定した。得られた光重合開始剤の質量を、「光重合開始剤の遊離量」とした。
上記「光重合開始剤の全量」及び上記「光重合開始剤の遊離量」に基づき、下記の式に従って、光重合開始剤の内包率(質量%)を求めた。
ゲル粒子1の水分散物について、重合性モノマーの内包率(%)を測定することにより、ゲル粒子に重合性モノマーが内包されているか否かを確認した。
重合性モノマーの内包の有無の確認は、上記の光重合開始剤の内包の確認と同様の方法により行った。
その結果、ゲル粒子1において、内包率が99%以上であり、重合性モノマーが内包されていることが確認された。
ゲル粒子1の水分散物の作製中の油相成分の作製において、19gのNCO104を38gのNCO202(重合性基を有する3官能以上のイソシアネート化合物、固形分35質量%)に変更したこと、及び、SR-399E(重合性モノマー)を含有させなかったこと以外はゲル粒子1の水分散物の作製と同様の操作を行い、ゲル粒子2の水分散物を作製した。作製されたゲル粒子2の水分散物について、ゲル粒子1の水分散物と同様にして、測定及び確認を行った。
ゲル粒子2の体積平均粒子径は、0.15μmであった。
また、ゲル粒子2において、光重合開始剤の内包率は99%以上であり、光重合開始剤がゲル粒子2に内包されていることが確認された。
ゲル粒子1の水分散物の作製中の油相成分の作製において、油相成分に、更に、2-イソプロピルチオキサントン(ITX;増感剤)(0.5g)を含有させたこと以外はゲル粒子1の水分散物の作製と同様の操作を行い、ゲル粒子3の水分散物を作製した。作製されたゲル粒子3の水分散物について、ゲル粒子1の水分散物と同様にして、測定及び確認を行った。
ゲル粒子3の体積平均粒子径は、0.15μmであった。
ゲル粒子3において、光重合開始剤の内包率は99%以上であり、光重合開始剤がゲル粒子3に内包されていることが確認された。
ゲル粒子3において、重合性モノマーの内包率は99%以上であり、重合性モノマーがゲル粒子3に内包されていることが確認された。
ゲル粒子3の分散液について、増感剤の内包率(%)を測定することにより、ゲル粒子3に増感剤が内包されているか否かを確認した。
増感剤の内包の有無の確認は、上記の光重合開始剤の内包の確認と同様の方法により行った。
その結果、ゲル粒子3において、増感剤の内包率が99%以上であり、増感剤がゲル粒子3に内包されていることが確認された。
光重合開始剤の種類を、表4に示すように変更したこと以外は上述の「ゲル粒子1の水分散物の作製」と同様の操作を行った。
ゲル粒子4~6の水分散物の各々も、ゲル粒子1の水分散物と同様に、実際に重合性基を有するゲル粒子を含むこと(即ち、ゲル粒子4~6の各々が、実際に重合性基を有するゲル粒子であること)が確認された。
ゲル粒子4~6の各々の体積平均粒子径は、0.15μmであった。
また、ゲル粒子4~6の各々において、光重合開始剤の内包率は99%以上であり、光重合開始剤がゲル粒子に内包されていることが確認された。
IRG819 … IRGACURE(登録商標)819(アシルフォスフィンオキシド化合物;詳細には、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シド;BASF社製)
IRG907 … IRGACURE(登録商標)907(カルボニル化合物;詳細には、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン;BASF社製)
IRG369 … IRGACURE(登録商標)369(カルボニル化合物;詳細には、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1;BASF社製)
IRG184 … IRGACURE(登録商標)184(カルボニル化合物;詳細には、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン;BASF社製)
<インク組成物の作製>
以下のようにして、ゲル粒子と重合性樹脂と水とを含有する水分散物である、実施例1のインク組成物を作製した(樹脂混合工程)。
詳細には、上記ゲル粒子1の水分散物、下記表5に示す重合性樹脂の水分散物又は水溶液、及び下記組成中のその他の成分を用い、ゲル粒子1と重合性樹脂と水とを含有する水分散物として、下記組成のインク組成物を調製した。
以下の組成において、ゲル粒子1の全固形分含有量(質量%)は、ゲル粒子1の水分散物中の全固形分(即ち、ゲル粒子1の全固形分)の、インク組成物全量(表5~表7中では、「インク全量」と表記する)に対する含有量である。
また、以下の組成において、重合性樹脂の含有量(質量%)は、表5に示す重合性樹脂の水分散物又は水溶液の固形分(即ち、重合性樹脂)の、インク組成物全量に対する含有量である(後述の表6及び表7についても同様である)。
・ゲル粒子1の全固形分 … 3.0質量%
・重合性樹脂 … 12質量%
・顔料分散液(Pro-jet(登録商標) Cyan APD1000(FUJIFILM Imaging Colorants社製、顔料濃度:14質量%) … 10質量%
・フッ素系界面活性剤(DuPont社製、Capstone FS-31、固形分25質量%) … 0.3質量%
・2-メチルプロパンジオール … 4.3質量%
・水 … 全体で100質量%となる残量
上記インク組成物を用い、以下の評価を行った。
結果を表5に示す。
密着性の評価は、下記の評価用試料(PVC)、評価用試料(A-PET)、及び評価用試料(Acryl)のそれぞれを用いて行った。
評価用試料(PVC)は、基材としてのポリ塩化ビニル(PVC)シートに対し、上記で得られたインク組成物を、RK PRINT COAT INSTRUMENTS社製 KハンドコーターのNo.2バーを用いて12μmの厚みで塗布し、得られた塗膜を60℃で3分間加熱して乾燥させることによって作製した。
評価用試料(A-PET)は、基材を非晶質ポリエチレンテレフタレート(A-PET)シートに変更したこと以外は評価用試料(PVC)の作製と同様にして作製した。
評価用試料(Acryl)は、基材をアクリル樹脂シートに変更したこと以外は評価用試料(PVC)の作製と同様にして作製した。
・PVCシート:エイブリィ・デニソン社製の「AVERY(登録商標) 400 GLOSS WHITE PERMANENT」
・A-PETシート:タキロン(株)製の「A-PET」(非晶質ポリエチレンテレフタレートシート)
・アクリル樹脂シート:(株)JSP製の「アクリエース(登録商標)UV」
硬化膜に対し、ISO2409(クロスカット法)に準拠してクロスハッチテストを実施し、以下の評価基準に従って評価した。
このクロスハッチテストでは、カット間隔を1mmとし、1mm角の正方形の格子を25個形成した。
下記の評価基準において、0及び1が、実用上許容されるレベルである。
下記の評価基準において、格子が剥がれた割合(%)は、下記の式によって求められた値である。下記の式における全格子数は25である。
格子が剥がれた割合(%)=〔(剥がれが生じた格子数)/(全格子数)〕×100
0: 格子が剥がれた割合(%)が0%であった。
1: 格子が剥がれた割合(%)が0%超5%以下であった。
2: 格子が剥がれた割合(%)が5%超15%以下であった。
3: 格子が剥がれた割合(%)が15%超35%以下であった。
4: 格子が剥がれた割合(%)が35%超65%以下であった。
5: 格子が剥がれた割合(%)が65%超であった。
硬化膜の鉛筆硬度の評価は、上記の評価用試料(PVC)を用いて行った。
硬化膜の密着性の評価と同様にして、評価用試料(PVC)の塗膜にUV光を照射して硬化させ、硬化膜とした。
硬化膜に対し、鉛筆として三菱鉛筆(株)製のUNI(登録商標)を用い、JIS K5600-5-4(1999年)に基づき、鉛筆硬度試験を行った。
この試験結果において、鉛筆硬度の許容範囲はHB以上であり、H以上であることが好ましい。鉛筆硬度がB以下である印刷物は、印刷物の取り扱い時に傷が生じる可能性があり好ましくない。
硬化膜の面状の評価は、上記の評価用試料(PVC)を用いて行った。
硬化膜の密着性の評価と同様にして、評価用試料(PVC)の塗膜にUV光を照射して硬化させ、硬化膜とした。
硬化膜の表面を目視で観察し、下記基準に従い、硬化膜の面状を評価した。
A:硬化膜の表面に曇り及び凝集物が観測されず、硬化膜の面状に非常に優れていた。
B:硬化膜の表面に、若干の曇りが観測されるが凝集物は観測されず、硬化膜の面状に優れていた。
C:硬化膜の表面に、曇りが観測され、若干の凝集物も観測され、上記Bと比較して硬化膜の面状に劣っていた。
D:硬化膜の表面に、曇り及び凝集物が観測され、上記Cと比較して硬化膜の面状に更に劣っていた。
上記で得られたインク組成物を、インクジェットプリンタ(SP-300V、ローランド ディー.ジー.社製)のヘッドから30分間吐出した後、吐出を停止した。
吐出の停止から5分間経過した後、上述のポリ塩化ビニル(PVC)シート上に、再び上記のヘッドから上記のインク組成物を吐出させ、5cm×5cmのベタ画像を形成した。
これらの画像を目視で観察し、不吐出ノズルの発生等によるドット欠けの有無を確認し、下記の評価基準に従ってインク組成物の吐出性を評価した。
A:不吐出ノズルの発生等によるドット欠けの発生が認められず、良好な画像が得られた。
B:不吐出ノズルの発生等によるドット欠けの発生がわずかに認められたが、実用上支障を来さない程度であった。
C:不吐出ノズルの発生等によるドット欠けの発生があり、実用に耐えない画像であった。
D:ヘッドから吐出ができなかった。
黄灯下で以下の操作を行い、上記で得られたインク組成物の再分散性を評価した。
RK PRINT COAT INSTRUMENTS社製のKハンドコーターのNo.2バーを用いて、上記で得られたインク組成物をアルミプレートに12μmの厚みで塗布して塗膜を形成した。得られた塗膜を、60℃で3分間加熱して乾燥させた。乾燥後の塗膜の表面を、水を含浸したスポンジでこすった。
スポンジでこする前の塗膜及びこすった後の塗膜のそれぞれについて、フーリエ変換赤外線分光測定(FT-IR)を実施し、得られた結果から、下記式に基づき、ゲル粒子の残存率を算出した。
ゲル粒子の残存率 = (スポンジでこすった後の塗膜におけるゲル粒子由来のピークの強度/スポンジでこする前の塗膜におけるゲル粒子由来のピークの強度)×100
ここで、ゲル粒子由来のピークとは、1700cm-1のピークである。
得られたゲル粒子の残存率に基づき、下記の評価基準に従い、インク組成物の再分散性を評価した。
A:ゲル粒子の残存率が1%以下であり、再分散性に優れていた。
B:ゲル粒子の残存率が1%超5%以下であり、再分散性が実用上許容される範囲内であった。
C:ゲル粒子の残存率が5%超10%以下であり、再分散性が実用上許容される範囲を外れていた。
D:ゲル粒子の残存率が10%超であり、再分散性が極めて悪かった。
上記で得られたインク組成物を容器に密封し、60℃で2週間経時させた後、上記の吐出性の評価と同様の評価を実施し、同様の評価基準に従い、インク組成物の保存安定性を評価した。
実施例1のインク組成物の作製において、重合性樹脂の水分散物又は水溶液の種類(樹脂の種類)、ゲル粒子の種類(ゲル粒子番号)、及びゲル粒子の全固形分含有量の少なくとも1つを、表5及び表6に示すように変更したこと以外は実施例1と同様の操作を行った。
結果を表5及び表6に示す。
実施例5のインク組成物の作製において、インク組成物にゲル粒子1の水分散物を含有させず、かつ、インク組成物に表6に示す外添開始剤を表6に示す含有量にて含有させたこと以外は実施例5と同様の操作を行った。表6に示す外添開始剤の含有量は、インク組成物全量に対する外添開始剤(開始剤の水分散物を用いた場合には固形分)の含有量である。
結果を表6に示す。
<両親媒性ウレタンアクリレート(a)の合成>
攪拌装置、冷却管、滴下ロート、及び空気導入管を備えた反応容器に、444.6質量部のイソホロンジイソシアネート(IPDI)と、202.3質量部の1,12-ドデカンジオールと、を仕込み、攪拌を行いながら、0.26質量部のオクチル酸第1錫を加え、反応容器内の温度を90℃まで昇温し、1.5時間反応させた。反応後、700.0質量部のメトキシPEG1000(メトキシポリエチレングリコール、東邦化学工業(株))と、0.54質量部のオクチル酸第1錫と、を加え、更に1.5時間反応させた。
次いで、この反応容器に、1300.0質量部のジペンタエリスリトールペンタアクリレート(SR399E)と、1.32質量部のメトキノンと、1.06質量部のオクチル酸第1錫と、を仕込み、混合し、空気のバブリング下で反応容器内の温度を85℃まで昇温し、3時間反応させた後、冷却して、両親媒性ウレタンアクリレート(a)を得た。
攪拌装置、冷却管、滴下ロート、及び空気導入管を備えた反応容器に、上記で得られた両親媒性ウレタンアクリレート(a)27.5質量部、ビスコート#802(トリペンタエリスリトールアクリレートと、モノ及びジペンタエリスリトールアクリレートと、ポリペンタエリスリトールアクリレートとの混合物、重合性モノマー、大阪有機化学工業(株))9.2質量部、及びLUCIRIN(登録商標)TPO(2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキシド、光重合開始剤、BASF社製)3.3質量部を仕込み、攪拌しながら、容器内の温度を80℃に昇温し、2時間保温した。
次に、容器内の温度を50℃まで冷却した後、攪拌しながら、60質量部の脱イオン水を加え、40℃で1時間保温した後、不揮発分(両親媒性ウレタンアクリレート(a)、重合性モノマー、及び光重合開始剤)の濃度が20質量%になるように脱イオン水で希釈することにより、比較粒子Xの水分散物を得た。
ここで、比較粒子Xはゲル粒子ではない(即ち、ゲル化していない)。
結果を表6に示す。
R-444 … DSM社製「NeoRad R-444」、重合性基を有するポリウレタンの水分散物
YS-103 … 宇部興産(株)製、重合性基を有するポリウレタンの水分散物
YS-105 … 宇部興産(株)製、重合性基を有するポリウレタンの水分散物
8105 … 宇部興産(株)製、重合性基を有するポリウレタンの水分散物
U7571 … ダイセル・オルネクス(株)製「UCECOAT 7571」、重合性基を有するポリウレタン(重量平均分子量10000)の水分散物
U7849 … ダイセル・オルネクス(株)製「UCECOAT 7849」、重合性基を有するポリウレタン(重量平均分子量10000)の水分散物
U7655 … ダイセル・オルネクス(株)製「UCECOAT 7655」、重合性基を有するポリウレタン(重量平均分子量10000)の水分散物
UV100A … DIC(株)製「ハイドランUV100A」、重合性基を有するポリウレタンの水分散物
UV100B … DIC(株)製「ハイドランUV100B」、重合性基を有するポリウレタンの水分散物
LR8983 … BASF社製「Laromer LR8983」、重合性基を有するポリウレタン(体積平均粒子径50nm)の水分散物
400AU … 日油(株)製「DA-400AU」、重合性基を有するポリウレタン(重量平均分子量800)の水分散物
800AU … 日油(株)製「DA-800AU」、重合性基を有するポリウレタン(重量平均分子量1100)の水溶液
CD9035 … サートマー社製、エチレンオキシド(EO)変性アクリレート(重量平均分子量960)の水溶液
E11 … ダイセル・オルネクス(株)製「EBECRYL 11」、エチレンオキシド(EO)変性アクリレートの水溶液
E2000 … ダイセル・オルネクス(株)製「EBECRYL 2000」、重合性基を有するポリウレタンの水溶液
・表5及び表6(並びに後述の表7)中の外添開始剤の種類は以下のとおりである。
IRG2959 … IRGACURE(登録商標)2959(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;BASF社製)
IRG819DW … IRGACURE(登録商標)819DW(IRGACURE819の水分散体;BASF社製)
一方、ゲル粒子を含有せず、外添開始剤を含有する比較例1及び2では、膜の鉛筆硬度及び膜と基材との密着性等が低下した。
詳細には、外添開始剤としてIRG2959を用いた比較例1では、各実施例と比較して、膜の鉛筆硬度及び膜と基材との密着性が低下した。この理由は、IRG2959の感度が各実施例の内包光重合開始剤よりも劣ること、及び、IRG2959の水に対する溶解度が低いためにIRG2959の含有量を低く(インク組成物全量に対して1.0質量%)せざるを得なかったことが原因と考えられる。
また、外添剤としてIRG819DWを用いた比較例2では、各実施例と比較して、膜の鉛筆硬度及び膜と基材との密着性が低下し、更には保存安定性が低下した。鉛筆硬度及び密着性が低下した理由は、IRG819DWにおいて、IRG819を水分散させるために用いている分散剤の影響により、感度が低下したためと考えられる。また、比較例2で保存安定性が低下した理由は、IRG819を水分散させるために分散剤を用いているとは言え、依然として、各実施例におけるゲル粒子の分散性と比較すれば、光重合開始剤の分散性に劣るためと考えられる。
また、ゲル粒子の代わりに、ゲル化していない比較粒子Xを用いた比較例3では、保存安定性、再分散性、及び吐出性が低下した。また、比較例3で形成された膜は、実施例5で形成された膜と比較して、鉛筆硬度及び基材との密着性にも劣っていた。
下記表7に示す各実施例及び各比較例のインク組成物について、LEDを用いた評価を行った。
詳細には、各実施例における、上述の鉛筆硬度、面状、及び密着性の評価において、露光光源を、実験用385nmUV-LED照射器(CCS株式会社製)に変更し、露光エネルギーを300mJ/cm2に変更したこと以外は同様の操作を行った。
結果を表7に示す。
比較例1~3のうち、特に比較例1では、IRG2959がLED光を吸収しないことに起因して、硬化性が著しく低下し、鉛筆硬度、面状、及び密着性が大幅に低下した(表6及び表7参照)。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
Claims (12)
- 重合性基を有する樹脂と、
重合性基を有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有し、光重合開始剤を内包しているゲル粒子と、
水と、
を含有し、
前記ゲル粒子の全固形分の含有量が、前記重合性基を有する樹脂の全量に対し、0.1質量%~100質量%である水分散物。 - 前記光重合開始剤が、カルボニル化合物及びアシルホスフィンオキシド化合物の少なくとも一方を含む請求項1に記載の水分散物。
- 前記ゲル粒子が、表面に親水性基を有する請求項1又は請求項2に記載の水分散物。
- 前記ゲル粒子が、重合性モノマーを内包している請求項1~請求項3のいずれか1項に記載の水分散物。
- 前記ゲル粒子が、増感剤を内包している請求項1~請求項4のいずれか1項に記載の水分散物。
- 前記重合性基を有する樹脂が、ポリウレタン構造を有する請求項1~請求項5のいずれか1項に記載の水分散物。
- 前記ゲル粒子の全固形分の含有量が、前記重合性基を有する樹脂の全量に対し、5質量%~75質量%である請求項1~請求項6のいずれか1項に記載の水分散物。
- 前記重合性基を有する樹脂の含有量が、水分散物の全量に対し、2質量%~40質量%である請求項1~請求項7のいずれか1項に記載の水分散物。
- 請求項1~請求項8のいずれか1項に記載の水分散物の製造方法であって、
前記ゲル粒子と水とを含有するゲル粒子分散物を準備する準備工程と、
前記ゲル粒子分散物と前記重合性基を有する樹脂とを混合して前記水分散物を得る樹脂混合工程と、
を有する水分散物の製造方法。 - 前記準備工程は、
前記光重合開始剤、3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分、前記光重合開始剤、重合性基を有する3官能以上のイソシアネート化合物、及び有機溶媒を含む油相成分、並びに、前記光重合開始剤、重合性基を有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分から選ばれるいずれかの油相成分と、水を含む水相成分と、を混合し、乳化させて乳化物を得る乳化工程と、
前記乳化物を加熱することにより前記ゲル粒子分散物を得るゲル化工程と、
を有する請求項9に記載の水分散物の製造方法。 - 前記油相成分に含まれる3官能以上のイソシアネート化合物が、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、トリメチルヘキサメチレンジイソシアネート、1,3-ビス(イソシアネートメチル)シクロヘキサン、m-キシリレンジイソシアネート、及びジシクロヘキシルメタン4,4’-ジイソシアネートから選択される少なくとも1種から誘導されたイソシアネート化合物である請求項10に記載の水分散物の製造方法。
- 請求項1~請求項8のいずれか1項に記載の水分散物を、記録媒体上に付与する付与工程と、
前記記録媒体上に付与された前記水分散物に、活性エネルギー線を照射する照射工程と、
を有する画像形成方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017537621A JP6602384B2 (ja) | 2015-08-31 | 2016-07-05 | インクジェット記録用インク組成物及びその製造方法、並びにインクジェット記録方法 |
AU2016315218A AU2016315218B2 (en) | 2015-08-31 | 2016-07-05 | Aqueous dispersion, production method therefor, and image formation method |
EP16841276.5A EP3345967B1 (en) | 2015-08-31 | 2016-07-05 | Ink composition for inkjet recording, method for manufacturing the same, and inkjet recording method |
CN201680046386.7A CN107922729B (zh) | 2015-08-31 | 2016-07-05 | 水分散物及其制造方法、以及图像形成方法 |
US15/866,468 US10662344B2 (en) | 2015-08-31 | 2018-01-10 | Aqueous dispersion, method for manufacturing the same, and image forming method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015-171418 | 2015-08-31 | ||
JP2015171418 | 2015-08-31 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/866,468 Continuation US10662344B2 (en) | 2015-08-31 | 2018-01-10 | Aqueous dispersion, method for manufacturing the same, and image forming method |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017038244A1 true WO2017038244A1 (ja) | 2017-03-09 |
Family
ID=58186991
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/069939 WO2017038244A1 (ja) | 2015-08-31 | 2016-07-05 | 水分散物及びその製造方法、並びに画像形成方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10662344B2 (ja) |
EP (1) | EP3345967B1 (ja) |
JP (1) | JP6602384B2 (ja) |
CN (1) | CN107922729B (ja) |
AU (1) | AU2016315218B2 (ja) |
WO (1) | WO2017038244A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018190204A1 (ja) * | 2017-04-14 | 2018-10-18 | 富士フイルム株式会社 | インクジェットインク及びその製造方法、並びに画像形成方法 |
EP3438210A4 (en) * | 2016-03-31 | 2019-12-25 | C/o Canon Kabushiki Kaisha | PHOTOSETTING INK, INK-CONTAINING BODY, AND IMAGE FORMING METHOD |
JPWO2019058990A1 (ja) * | 2017-09-25 | 2020-07-09 | 富士フイルム株式会社 | インク組成物及びその製造方法、並びに画像形成方法 |
WO2021065151A1 (ja) * | 2019-09-30 | 2021-04-08 | 富士フイルム株式会社 | インクジェット記録用インク組成物、及び、画像記録方法 |
WO2023157430A1 (ja) * | 2022-02-15 | 2023-08-24 | 大生工業株式会社 | 光硬化性ウレタンゲル状体およびその製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017135087A1 (ja) * | 2016-02-05 | 2017-08-10 | 富士フイルム株式会社 | マイクロカプセル、水分散物、水分散物の製造方法、及び画像形成方法 |
JP6510681B2 (ja) | 2016-02-05 | 2019-05-08 | 富士フイルム株式会社 | 水分散物及びその製造方法、並びに画像形成方法 |
JP7362039B2 (ja) * | 2019-11-26 | 2023-10-17 | 株式会社リコー | 活性エネルギー線硬化型水性組成物、活性エネルギー線硬化型水性インク、収容容器、像形成装置、像形成方法、硬化物、及び加飾体 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04166943A (ja) * | 1990-10-31 | 1992-06-12 | Fuji Photo Film Co Ltd | 感光性エレメントおよびその製造法 |
JPH08259888A (ja) * | 1995-03-24 | 1996-10-08 | Dainippon Ink & Chem Inc | 活性エネルギー線硬化性水分散体 |
JPH09157495A (ja) * | 1995-12-02 | 1997-06-17 | Arakawa Chem Ind Co Ltd | 活性エネルギー線硬化性エマルジョンおよびその製造方法 |
JPH10182763A (ja) * | 1996-12-24 | 1998-07-07 | Taisei Kako Kk | 活性エネルギー線硬化型水性樹脂組成物 |
JP2011201973A (ja) * | 2010-03-24 | 2011-10-13 | Seiko Epson Corp | 光重合性ポリマーミセル及びその製造方法、並びに光重合性ポリマーミセルを含むインク組成物 |
WO2016052053A1 (ja) * | 2014-09-29 | 2016-04-07 | 富士フイルム株式会社 | ゲル粒子、インク組成物及びその製造方法、感光性組成物、並びに画像形成方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000136211A (ja) | 1998-08-27 | 2000-05-16 | Kanegafuchi Chem Ind Co Ltd | 水性エマルジョン |
TW200302954A (en) * | 2001-10-31 | 2003-08-16 | Dsm Nv | UV curable powder suitable for use as photoresist |
JP4239637B2 (ja) * | 2003-03-24 | 2009-03-18 | 富士ゼロックス株式会社 | 高分子ゲル組成物及びそれを用いた光学素子 |
EP1611165B1 (en) * | 2003-03-26 | 2009-11-11 | Basf Se | Color-stable superabsorbent polymer composition |
US7479511B2 (en) | 2005-04-12 | 2009-01-20 | Sun Chemical Corporation | Water based energy curable hybrid systems with improved properties |
JP2007146000A (ja) * | 2005-11-28 | 2007-06-14 | Fuji Xerox Co Ltd | 高分子ゲル組成物及びその製造方法、光学素子 |
GB0613583D0 (en) | 2006-07-05 | 2006-08-16 | Sericol Ltd | A printing ink |
EP2549331B1 (en) * | 2010-03-19 | 2015-11-11 | FUJIFILM Corporation | Color developing photosensitive composition, lithographic printing original plate, and method for producing same |
JP5949031B2 (ja) | 2012-03-26 | 2016-07-06 | セイコーエプソン株式会社 | インクジェット用インク組成物及びインクジェット記録方法 |
JP6047904B2 (ja) * | 2012-03-28 | 2016-12-21 | セイコーエプソン株式会社 | インクジェット記録方法、光硬化型インクジェットインク組成物、インクジェット記録装置 |
CN102827382A (zh) * | 2012-09-12 | 2012-12-19 | 江南大学 | 一种基于紫外辐照技术的光活性微凝胶的制备方法 |
CN103642052B (zh) * | 2013-11-22 | 2015-09-23 | 北京迪百斯特科技发展有限公司 | 水性环氧多彩地坪漆及彩色水性环氧树脂凝胶粒子 |
-
2016
- 2016-07-05 AU AU2016315218A patent/AU2016315218B2/en active Active
- 2016-07-05 JP JP2017537621A patent/JP6602384B2/ja active Active
- 2016-07-05 EP EP16841276.5A patent/EP3345967B1/en active Active
- 2016-07-05 WO PCT/JP2016/069939 patent/WO2017038244A1/ja unknown
- 2016-07-05 CN CN201680046386.7A patent/CN107922729B/zh active Active
-
2018
- 2018-01-10 US US15/866,468 patent/US10662344B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04166943A (ja) * | 1990-10-31 | 1992-06-12 | Fuji Photo Film Co Ltd | 感光性エレメントおよびその製造法 |
JPH08259888A (ja) * | 1995-03-24 | 1996-10-08 | Dainippon Ink & Chem Inc | 活性エネルギー線硬化性水分散体 |
JPH09157495A (ja) * | 1995-12-02 | 1997-06-17 | Arakawa Chem Ind Co Ltd | 活性エネルギー線硬化性エマルジョンおよびその製造方法 |
JPH10182763A (ja) * | 1996-12-24 | 1998-07-07 | Taisei Kako Kk | 活性エネルギー線硬化型水性樹脂組成物 |
JP2011201973A (ja) * | 2010-03-24 | 2011-10-13 | Seiko Epson Corp | 光重合性ポリマーミセル及びその製造方法、並びに光重合性ポリマーミセルを含むインク組成物 |
WO2016052053A1 (ja) * | 2014-09-29 | 2016-04-07 | 富士フイルム株式会社 | ゲル粒子、インク組成物及びその製造方法、感光性組成物、並びに画像形成方法 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3438210A4 (en) * | 2016-03-31 | 2019-12-25 | C/o Canon Kabushiki Kaisha | PHOTOSETTING INK, INK-CONTAINING BODY, AND IMAGE FORMING METHOD |
US10850531B2 (en) | 2016-03-31 | 2020-12-01 | Canon Kabushiki Kaisha | Photocurable ink, ink container, and image forming method |
WO2018190204A1 (ja) * | 2017-04-14 | 2018-10-18 | 富士フイルム株式会社 | インクジェットインク及びその製造方法、並びに画像形成方法 |
JPWO2018190204A1 (ja) * | 2017-04-14 | 2020-02-06 | 富士フイルム株式会社 | インクジェットインク及びその製造方法、並びに画像形成方法 |
JPWO2019058990A1 (ja) * | 2017-09-25 | 2020-07-09 | 富士フイルム株式会社 | インク組成物及びその製造方法、並びに画像形成方法 |
WO2021065151A1 (ja) * | 2019-09-30 | 2021-04-08 | 富士フイルム株式会社 | インクジェット記録用インク組成物、及び、画像記録方法 |
JPWO2021065151A1 (ja) * | 2019-09-30 | 2021-04-08 | ||
JP7430731B2 (ja) | 2019-09-30 | 2024-02-13 | 富士フイルム株式会社 | インクジェット記録用インク組成物、及び、画像記録方法 |
WO2023157430A1 (ja) * | 2022-02-15 | 2023-08-24 | 大生工業株式会社 | 光硬化性ウレタンゲル状体およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
AU2016315218B2 (en) | 2018-11-15 |
JPWO2017038244A1 (ja) | 2018-06-21 |
US10662344B2 (en) | 2020-05-26 |
AU2016315218A1 (en) | 2018-02-08 |
EP3345967A1 (en) | 2018-07-11 |
JP6602384B2 (ja) | 2019-11-06 |
EP3345967A4 (en) | 2018-08-29 |
EP3345967B1 (en) | 2020-11-25 |
CN107922729A (zh) | 2018-04-17 |
US20180127612A1 (en) | 2018-05-10 |
CN107922729B (zh) | 2021-01-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6559295B2 (ja) | ゲル粒子 | |
JP6602384B2 (ja) | インクジェット記録用インク組成物及びその製造方法、並びにインクジェット記録方法 | |
JP6305631B2 (ja) | ゲル粒子の水分散物及びその製造方法、並びに画像形成方法 | |
JP6559297B2 (ja) | ゲル粒子 | |
WO2017038243A1 (ja) | 水分散物及びその製造方法、並びに画像形成方法 | |
WO2016151904A1 (ja) | ゲル粒子の水分散物及びその製造方法、並びに画像形成方法 | |
JP6636054B2 (ja) | マイクロカプセル、水分散物、水分散物の製造方法、及び画像形成方法 | |
EP3412694A1 (en) | Aqueous dispersion, production method for same, and image formation method | |
JP6510681B2 (ja) | 水分散物及びその製造方法、並びに画像形成方法 | |
WO2016052055A1 (ja) | ゲル粒子、感光性組成物、インク組成物、ゲル粒子の水分散物の製造方法、及び画像形成方法 | |
WO2018047438A1 (ja) | 水分散物及びその製造方法、並びに画像形成方法 | |
JPWO2017135085A1 (ja) | 水分散物及びその製造方法、並びに画像形成方法 | |
US10557049B2 (en) | Aqueous dispersion, method for manufacturing the same, and image forming method | |
WO2018186224A1 (ja) | インク組成物及びその製造方法、並びに画像形成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16841276 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017537621 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2016315218 Country of ref document: AU Date of ref document: 20160705 Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |