JP2009138150A - Photoinitiator, photopolymerizable composition and photocuring method - Google Patents
Photoinitiator, photopolymerizable composition and photocuring method Download PDFInfo
- Publication number
- JP2009138150A JP2009138150A JP2007318209A JP2007318209A JP2009138150A JP 2009138150 A JP2009138150 A JP 2009138150A JP 2007318209 A JP2007318209 A JP 2007318209A JP 2007318209 A JP2007318209 A JP 2007318209A JP 2009138150 A JP2009138150 A JP 2009138150A
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- Prior art keywords
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- photoinitiator
- salt
- meth
- general formula
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 10
- 229910052717 sulfur Chemical group 0.000 claims abstract description 10
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 125000005647 linker group Chemical group 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000011109 contamination Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- -1 hydroxyethoxy group Chemical group 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 238000004383 yellowing Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- 239000006185 dispersion Substances 0.000 description 5
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
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- 239000013078 crystal Substances 0.000 description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 238000003860 storage Methods 0.000 description 4
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 125000005641 methacryl group Chemical group 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 2
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical class N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 150000005524 benzylchlorides Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- IHJFEQWFCYBCCJ-UHFFFAOYSA-N ethyl 4-(2,6-dimethylphenoxy)-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)COC1=C(C)C=CC=C1C IHJFEQWFCYBCCJ-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
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- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 1
- UWSLXWIOAMSNGU-UHFFFAOYSA-N 1-chloro-2-propan-2-yloxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(Cl)C(OC(C)C)=CC=C3SC2=C1 UWSLXWIOAMSNGU-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- CTWRMVAKUSJNBK-UHFFFAOYSA-N 2-(2,4-dimethoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 CTWRMVAKUSJNBK-UHFFFAOYSA-N 0.000 description 1
- RXAYEPUDXSKVHS-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(3-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC(C2=C(NC(=N2)C=2C(=CC=CC=2)Cl)C=2C=C(OC)C=CC=2)=C1 RXAYEPUDXSKVHS-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SNFCQJAJPFWBDJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 SNFCQJAJPFWBDJ-UHFFFAOYSA-N 0.000 description 1
- BUWHNKZFUTUGJW-UHFFFAOYSA-N 2-(4-methoxyphenyl)-5-phenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC=C(C=2C=CC=CC=2)N1 BUWHNKZFUTUGJW-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
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- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- VZMLJEYQUZKERO-UHFFFAOYSA-N 2-hydroxy-1-(2-methylphenyl)-2-phenylethanone Chemical compound CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 VZMLJEYQUZKERO-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- BNGOFPJWZUXKNR-UHFFFAOYSA-N 2-oxo-2-phenylacetyl chloride Chemical compound ClC(=O)C(=O)C1=CC=CC=C1 BNGOFPJWZUXKNR-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XUDUTRMKKYUAKI-UHFFFAOYSA-N 3-[1-(1-phenylethyl)piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound C1CC(N2C(NC3=CC=CC=C32)=O)CCN1C(C)C1=CC=CC=C1 XUDUTRMKKYUAKI-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、新規な光開始剤、それを用いた光重合性組成物及び光硬化方法に関する。 The present invention relates to a novel photoinitiator, a photopolymerizable composition using the photoinitiator, and a photocuring method.
光硬化反応を利用するＵＶ硬化システムは、溶媒を使用しないクリーンな硬化方法として、また、極めて短時間に硬化反応が終了するために高速な硬化方法として注目を浴びている。そのために、高精細を要求されるレジストの製造、高速化を要求される印刷等、いろいろな分野に使われている。特に、ＵＶ印刷、インクジェット印刷では、高速化、乾燥なしの特徴を生かすために溶媒を使用せず、光重合／架橋性のモノマー／オリゴマー／ポリマーと光開始剤を基本材料とする硬化システムが実用化されている。 A UV curing system that utilizes a photocuring reaction is attracting attention as a clean curing method that does not use a solvent, and as a fast curing method because the curing reaction is completed in a very short time. For this reason, it is used in various fields such as resist production requiring high definition and printing requiring high speed. Especially in UV printing and inkjet printing, a curing system that uses photopolymerization / crosslinkable monomer / oligomer / polymer and photoinitiator as the basic materials without using a solvent to take advantage of the features of high speed and no drying is practical. It has become.
また、ＵＶ光源も従来の高圧水銀灯、低圧水銀灯の他に、波長３６５ｎｍの発光ダイオード（ＬＥＤ）が実用されつつあり、大きな発展を遂げようとしている。 In addition to the conventional high-pressure mercury lamp and low-pressure mercury lamp, a light-emitting diode (LED) having a wavelength of 365 nm is being put into practical use as a UV light source, and is going to achieve great development.
しかしながら、近年の環境意識の高まりとともに、このＵＶ印刷インク、インクジェット印刷でも、水を溶媒に用いて感作性等が懸念される光重合／架橋性のモノマー／オリゴマーの使用量を減らした水性の光硬化システムの必要性が高まっており、さまざまな提案がされている。しかしながら、ほとんどの光開始剤は油溶性であり、市販されている水溶性の光開始剤としては、２−ヒドロキシ−２−メチル−１−（４−ヒドロキシエトキシ）フェニルプロパン−１−オンが挙げられるが、水中にわずか０．５質量％しか溶解性せず、さらに高圧水銀灯のメイン発光波長であり、ＬＥＤの発光波長でもある３６５ｎｍの光吸収も少ないために、充分な光感度が得られていない。 However, with the recent increase in environmental awareness, even in this UV printing ink and ink jet printing, water is used as a solvent to reduce the amount of photopolymerization / crosslinking monomer / oligomer that is concerned about sensitization. The need for photocuring systems is increasing and various proposals have been made. However, most photoinitiators are oil soluble, and commercially available water soluble photoinitiators include 2-hydroxy-2-methyl-1- (4-hydroxyethoxy) phenylpropan-1-one. However, only 0.5% by mass is soluble in water, and the light emission at 365 nm, which is the main light emission wavelength of high-pressure mercury lamps and the light emission wavelength of LEDs, is small, so that sufficient photosensitivity is obtained. Absent.
その対策として、水溶性の光開始剤が提案されている。特開平６−２２８２１８号公報には、ヒドロキシエトキシ基を２−ヒドロキシ−２−メチル−１−フェニル−１−オンまたはベンゾフェノンに導入した光開始剤、特開２００３−１９２７１２号公報にはポリアルキレンオキシド基をα位に置換したアルキルフェノン誘導体の光開始剤、特開２００１−５２５８８７号公報にはハロメチル−１，３，５−トリアジン陰イオンの光開始剤、特開２０００−２７３１１０号公報にはシクロアルカノール構造を有する水溶性の光開始剤、特開２０００−１８６２４２号公報には２−ヒドロキシ−２−メチル−１−フェニル−１−オンのエチレンオキシド付加物の光開始剤が開示されている。 As a countermeasure, a water-soluble photoinitiator has been proposed. JP-A-6-228218 discloses a photoinitiator in which a hydroxyethoxy group is introduced into 2-hydroxy-2-methyl-1-phenyl-1-one or benzophenone, and JP-A-2003-192712 discloses a polyalkylene oxide. Photoinitiators of alkylphenone derivatives substituted at the α position, JP-A 2001-525887 discloses photoinitiators of halomethyl-1,3,5-triazine anions, JP-A 2000-273110 discloses cycloinitiators A water-soluble photoinitiator having an alkanol structure, Japanese Patent Application Laid-Open No. 2000-186242 discloses a photoinitiator of an ethylene oxide adduct of 2-hydroxy-2-methyl-1-phenyl-1-one.
しかしながら、これらの光開始剤も、３６５ｎｍの光吸収が少ないために、いずれの光源を用いても硬化が不十分である。 However, these photoinitiators also have insufficient light absorption at 365 nm, so that curing is insufficient with any light source.
波長３６５ｎｍの光吸収が高い水溶性の高い光開始剤として、特許文献１にアシル水溶性ホスフィン化合物が記載されているが、ホスフィン系化合物の多くは、変異原性試験で陽性等の安全性の問題があること、波長４２０ｎｍまで光吸収があるために蛍光灯下でも硬化し、光重合性組成物として取り扱いが難しいために、広く用いることができなかった。 As a water-insoluble photoinitiator having a high light absorption at a wavelength of 365 nm, an acyl water-soluble phosphine compound is described in Patent Document 1, but many of the phosphine compounds have safety such as positive in a mutagenicity test. Since it has a problem and absorbs light up to a wavelength of 420 nm, it hardens even under a fluorescent lamp and is difficult to handle as a photopolymerizable composition, so it cannot be widely used.
一方、ＵＶ印刷インク、インクジェットインクで光開始剤を用いることによる不都合としては、ＵＶ露光により分解した光開始剤の一部が黄色に変色し、クリアーインクにおいては黄色く色づき、シアンインクにおいては緑色に変色してしまい、色再現性に問題を及ぼすことが挙げられ、光開始剤の使用量を制限する大きな要因になっていた。この黄変に関しては、特許文献２に、フェニル基にさまざまな置換基を置換すれば、黄変が減少することが提案されている。しかし、これらの光開始剤は、油溶性であり、水溶性の光開始剤としては用いることができなかった。
本発明は、上記課題に鑑みなされたものであり、その目的は、高感度で黄変が少ない新規な水溶性の光開始剤を提供することにあり、さらに、色汚染が少なく、色再現性に優れた光重合性組成物及び光硬化方法を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel water-soluble photoinitiator with high sensitivity and little yellowing. Furthermore, there is little color contamination and color reproducibility. An object of the present invention is to provide a photopolymerizable composition and a photocuring method excellent in the above.
本発明の上記課題は、以下の構成により達成される。 The above object of the present invention is achieved by the following configurations.
１．下記一般式（１）で表される化合物であることを特徴とする光開始剤。 1. A photoinitiator characterized by being a compound represented by the following general formula (1).
（式中、Ｘは酸素原子または硫黄原子を表し、Ｙは２価の連結基を表し、Ｚはカルボン酸またはその塩、スルホン酸またはその塩を表し、Ｒ、Ｒ5、Ｒ6はそれぞれアルキル基またはアルコキシル基を表し、Ｒ7はアリール基、ヒドロキシル基、アルキル基またはアルコシル基を表す。ｎは２〜４の自然数を表す。）
２．前記一般式（１）が、下記一般式（２）または（３）で表されることを特徴とする前記１に記載の光開始剤。
(In the formula, X represents an oxygen atom or a sulfur atom, Y represents a divalent linking group, Z represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, and R, R 5 , and R 6 each represents an alkyl group. A group or an alkoxyl group, R 7 represents an aryl group, a hydroxyl group, an alkyl group or an alkoxyl group, and n represents a natural number of 2 to 4.)
2. 2. The photoinitiator according to 1 above, wherein the general formula (1) is represented by the following general formula (2) or (3).
（式中、Ｘは酸素原子または硫黄原子を表し、Ｙは２価の連結基を表し、Ｚはカルボン酸またはその塩、スルホン酸またはその塩を表し、Ｒ、Ｒ5、Ｒ6はそれぞれアルキル基またはアルコキシル基を表し、Ｒ11は水素原子、アルキル基またはアルキレンオキシド基を表す。ｎは２〜４の自然数を表す。） (In the formula, X represents an oxygen atom or a sulfur atom, Y represents a divalent linking group, Z represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, and R, R 5 , and R 6 each represents an alkyl group. A group or an alkoxyl group, R 11 represents a hydrogen atom, an alkyl group or an alkylene oxide group, and n represents a natural number of 2 to 4.)
（式中、Ｘは酸素原子または硫黄原子を表し、Ｙは２価の連結基を表し、Ｚはカルボン酸またはその塩、スルホン酸またはその塩を表し、Ｒはアルキル基またはアルコキシル基を表し、Ｒ12、Ｒ13はアルキル基を表し、Ａｒはアリール基を表す。ｎは２〜４の自然数を表す。）
３．前記１に記載の一般式（１）で表される化合物と、水及び活性エネルギー線を照射することにより重合または架橋するエチレン性不飽和基を有する化合物を含有することを特徴とする光重合性組成物。
(Wherein X represents an oxygen atom or a sulfur atom, Y represents a divalent linking group, Z represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, R represents an alkyl group or an alkoxyl group, R 12 and R 13 represent an alkyl group, Ar represents an aryl group, and n represents a natural number of 2 to 4.)
3. A photopolymerizable product comprising a compound represented by the general formula (1) described in 1 and a compound having an ethylenically unsaturated group that is polymerized or crosslinked by irradiation with water and active energy rays. Composition.
４．前記３に記載の光重合性組成物を、３２０〜３８０ｎｍに主波長を有する発光ダイオードを用いて硬化することを特徴とする光硬化方法。 4). 4. A photocuring method comprising curing the photopolymerizable composition according to 3 above using a light emitting diode having a dominant wavelength of 320 to 380 nm.
本発明によれば、高感度で黄変が少ない新規な水溶性の光開始剤、さらに、色汚染が少なく、色再現性に優れた光重合性組成物及び光硬化方法を提供することができる。 According to the present invention, it is possible to provide a novel water-soluble photoinitiator with high sensitivity and little yellowing, and further, a photopolymerizable composition and a photocuring method with less color contamination and excellent color reproducibility. .
本発明者は、上記課題に鑑み鋭意検討を行った結果、フェニル基に複数のアルキル基を導入し、カルボン酸、スルホン酸またはそれらの塩をペンダントした新規なアルキルフェノン系光開始剤、または新規なベンジルケタール系光開始剤により、高感度で黄変が少ない新規な水溶性の光開始剤が得られることを見出し、本発明に至った。 As a result of intensive studies in view of the above problems, the present inventors have introduced a novel alkylphenone photoinitiator in which a plurality of alkyl groups are introduced into a phenyl group and pendant with a carboxylic acid, a sulfonic acid, or a salt thereof, or a novel The present inventors have found that a novel water-soluble photoinitiator having high sensitivity and little yellowing can be obtained by using such a benzyl ketal photoinitiator.
また、この光開始剤と、水、活性エネルギー線の照射により重合または架橋する重合性／架橋性組成物を含有する光重合性組成物、及びこの光重合性組成物を用いた光硬化方法により、色汚染が少なく、色再現性に優れた光重合性組成物及び光硬化方法が得られることを見出した。 Further, by this photoinitiator, a photopolymerizable composition containing a polymerizable / crosslinkable composition that is polymerized or crosslinked by irradiation with water and active energy rays, and a photocuring method using the photopolymerizable composition The present inventors have found that a photopolymerizable composition and a photocuring method with little color contamination and excellent color reproducibility can be obtained.
このような感度がアップする理由としては、本発明の光開始剤はフェニル基に置換された複数のアルキル基同士の立体障害のために、分子の自由回転が妨げられ、水中でのＵＶ吸収の長波側の裾が延びているためだと考えている。また、黄変が少なくなる理由としては、フェニル基に置換された複数のアルキル基のため、フェニル基に無置換のものと異なり、色素が形成しにくい分解経路をとっていると考えている。 The reason for this increase in sensitivity is that the photoinitiator of the present invention hinders free rotation of the molecule due to steric hindrance between a plurality of alkyl groups substituted with phenyl groups, and prevents UV absorption in water. I think this is because the hem on the long wave side extends. Further, the reason why yellowing is reduced is considered to be due to a plurality of alkyl groups substituted with a phenyl group, and unlike a non-substituted phenyl group, a decomposition route in which a dye is not easily formed is taken.
また、本発明の新規な光開始剤を用いた水性の光重合性組成物は、安全であり、ＵＶ光照射により、十分な光硬化感度が獲られる。さらに、無置換の従来の光開始剤に比べて、光照射後の黄変が少ない特徴があるため、水系ＵＶ印刷インクとしてまた、３６５ｎｍに発光強度を有する発光ダイオード（ＬＥＤ）を用いることにより、最も高い効果を得ることができる。 Further, the aqueous photopolymerizable composition using the novel photoinitiator of the present invention is safe, and sufficient photocuring sensitivity can be obtained by UV light irradiation. Furthermore, since there is a characteristic that yellowing after light irradiation is less compared with an unsubstituted conventional photoinitiator, by using a light emitting diode (LED) having an emission intensity at 365 nm as an aqueous UV printing ink, The highest effect can be obtained.
〔一般式（１）で表される化合物〕
一般式（１）において、Ｘは酸素原子または硫黄原子を表し、Ｙは２価の連結基を表す。２価の連結基としては、具体的には、アルキレン基（例えばメチレン基、エチレン基、プロピレン基、ブチレン基、オクチレン基）、アリレン基（例えばフェニレン基、トリエン基）、アルキレンオキシ基（例えばメチレンオキシ基、アルキレンオキシド基、プロピレンオキシ基、ブチレンオキシ基、ポリ（エチレンオキシ）基）、アルキレンチオ基（例えばメチレンチオ、エチレンチオ、プロピレンチオ、ブチレンチオ）が挙げられる。好ましくは、Ｃ１〜Ｃ４までのアルキレン基、アルキレンオキシド基である。
[Compound represented by the general formula (1)]
In the general formula (1), X represents an oxygen atom or a sulfur atom, and Y represents a divalent linking group. Specific examples of the divalent linking group include an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, and an octylene group), an arylene group (for example, a phenylene group and a triene group), and an alkyleneoxy group (for example, a methylene group). An oxy group, an alkylene oxide group, a propyleneoxy group, a butyleneoxy group, a poly (ethyleneoxy) group) and an alkylenethio group (for example, methylenethio, ethylenethio, propylenethio, butylenethio). Preferably, it is a C1-C4 alkylene group or alkylene oxide group.
Ｚはカルボン酸またはその塩、スルホン酸またはその塩を表す。塩とは、カルボン酸、スルホン酸の塩として作用するカチオン種をいい、例えば、１価のカチオン（例えば、ナトリウムカチオン、リチウムカチオン、カルシウムカチオン、アンモニウムカチオン、トリメチルアンモニウムカチオン、トリエタノールアンモニウムカチオン、ピリジニウムカチオン）が挙げられる。 Z represents carboxylic acid or a salt thereof, sulfonic acid or a salt thereof. The salt refers to a cationic species that acts as a salt of carboxylic acid or sulfonic acid. For example, a monovalent cation (for example, sodium cation, lithium cation, calcium cation, ammonium cation, trimethyl ammonium cation, triethanolammonium cation, pyridinium) Cation).
Ｒ、Ｒ5、Ｒ6はアルキル基またはアルコキシル基を表す。アルキル基としては、例えば、メチル基、エチル、プロピル基、ブチル基が挙げられる。アルコキシル基としては、例えば、例えば、メトキシ基、エトキシ基、プロポキシ基が挙げられる。またＲ5、Ｒ6は結合して環を形成してもよい。形成してもよい環の例としては、−（ＣＨ2）4−、−ＯＣＨ2ＣＨ2Ｏ−等を含む環が挙げられる。 R, R 5 and R 6 each represents an alkyl group or an alkoxyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, and a propoxy group. R 5 and R 6 may combine to form a ring. Examples of the ring that may be formed include a ring containing — (CH 2 ) 4 —, —OCH 2 CH 2 O—, and the like.
Ｒ7はアリール基、ヒドロキシル基、アルキル基またはアルコシル基を表す。アリール基としては、無置換または置換したフェニル基が挙げられる。置換基としては、アルキル基、アルコキシル基、アルキルチオ基が挙げられる。アルキル基、アルコシル基としては、Ｒで表される前記アルキル基、アルコシル基と同義である。 R 7 represents an aryl group, a hydroxyl group, an alkyl group or an alkosyl group. Examples of the aryl group include unsubstituted or substituted phenyl groups. Examples of the substituent include an alkyl group, an alkoxyl group, and an alkylthio group. As an alkyl group and an alkosyl group, it is synonymous with the said alkyl group and alkosyl group which are represented by R.
ｎは２〜４の自然数を表す。 n represents a natural number of 2 to 4.
〔一般式（２）で表される化合物〕
一般式（２）において、Ｘは酸素原子または硫黄原子を表し、Ｙは２価の連結基を表し、Ｚはカルボン酸またはその塩、スルホン酸またはその塩を表し、Ｒ、Ｒ5、Ｒ6はそれぞれアルキル基またはアルコキシル基を表す。
[Compound represented by formula (2)]
In the general formula (2), X represents an oxygen atom or a sulfur atom, Y represents a divalent linking group, Z represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, R, R 5 , R 6 Each represents an alkyl group or an alkoxyl group.
Ｙ、Ｚ、Ｒ、Ｒ5、Ｒ6は、一般式（１）におけるＹ、Ｚ、Ｒ、Ｒ5、Ｒ6と同義である。 Y, Z, R, R 5, R 6 is Y in the general formula (1), Z, R, and R 5, R 6 synonymous.
Ｒ11は水素原子、アルキル基またはアルキレンオキシド基を表す。アルキル基は、一般式（１）におけるアルキル基と同義である。アルキレンオキシド基のアルキレン基としては、メチレン基、エチレン基、プロピレン基が挙げられる。 R 11 represents a hydrogen atom, an alkyl group or an alkylene oxide group. An alkyl group is synonymous with the alkyl group in General formula (1). Examples of the alkylene group of the alkylene oxide group include a methylene group, an ethylene group, and a propylene group.
ｎは２〜４の自然数を表す。 n represents a natural number of 2 to 4.
〔一般式（３）で表される化合物〕
一般式（３）において、Ｘは酸素原子または硫黄原子を表し、Ｙは２価の連結基を表し、Ｚはカルボン酸またはその塩、スルホン酸またはその塩を表し、Ｒはアルキル基またはアルコキシル基を表す。
[Compound represented by formula (3)]
In the general formula (3), X represents an oxygen atom or a sulfur atom, Y represents a divalent linking group, Z represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, and R represents an alkyl group or an alkoxyl group. Represents.
Ｙ、Ｚ、Ｒは、一般式（１）におけるＹ、Ｚ、Ｒと同義である。 Y, Z, and R are synonymous with Y, Z, and R in General formula (1).
Ｒ12、Ｒ13はアルキル基を表し、アルキル基は、一般式（１）におけるアルキル基と同義である。 R 12 and R 13 represent an alkyl group, and the alkyl group has the same meaning as the alkyl group in formula (1).
Ａｒはアリール基を表す。アリール基としては、一般式（２）におけるアリール基と同義である。また、下記一般式（４）で表される基であってもよい。 Ar represents an aryl group. As an aryl group, it is synonymous with the aryl group in General formula (2). Moreover, group represented by following General formula (4) may be sufficient.
式中、Ｘ、Ｙ、Ｚ、Ｒ、ｎは、一般式（１）におけるＸ、Ｙ、Ｚ、Ｒ、ｎと同義である。 In the formula, X, Y, Z, R and n have the same meanings as X, Y, Z, R and n in the general formula (1).
以下に、一般式（１）〜（３）で表される具体的な化合物例を挙げるが、本発明はそれに限定されない。 Specific examples of the compounds represented by the general formulas (1) to (3) are shown below, but the present invention is not limited thereto.
これらの化合物の合成法は実施例に示す。 The synthesis method of these compounds is shown in the Examples.
《エチレン性不飽和基を有する化合物》
本発明の光重合性組成物は、本発明の前記一般式（１）で表される化合物と、水及び活性エネルギー線を照射することにより重合または架橋するエチレン性不飽和基を有する化合物を含有することを特徴とする。
<< Compound having an ethylenically unsaturated group >>
The photopolymerizable composition of the present invention contains the compound represented by the general formula (1) of the present invention and a compound having an ethylenically unsaturated group that is polymerized or cross-linked by irradiation with water and active energy rays. It is characterized by doing.
本発明に係る光開始剤とともに用いるエチレン性不飽和基を有する化合物は、水溶性が好ましいが、水溶性でなくても少量ならば水性の重合性組成物に溶解するため、化合物としては特に制限されない。 The compound having an ethylenically unsaturated group used together with the photoinitiator according to the present invention is preferably water-soluble, but is not particularly limited as a compound because it dissolves in an aqueous polymerizable composition if it is not water-soluble. Not.
エチレン性不飽和基を有する化合物とは、化合物中に１個以上のエチレン性不飽和基を有する化合物をいう。具体的には、スチレン基、アクリル基、メタクリル基、アリル基、クロトン酸基、マレイン酸基、イタコン酸基を少なくとも１つ以上分子中に有する化合物をいう。好ましくはアクリル基、メタクリル基を１つ以上分子中に有する化合物である。 The compound having an ethylenically unsaturated group refers to a compound having one or more ethylenically unsaturated groups in the compound. Specifically, it refers to a compound having at least one styrene group, acrylic group, methacryl group, allyl group, crotonic acid group, maleic acid group, or itaconic acid group in the molecule. A compound having at least one acrylic group or methacryl group in the molecule is preferable.
スチレン基を有する化合物例をしては、スチレン、スチレンスルホン酸が挙げられる。 Examples of the compound having a styrene group include styrene and styrene sulfonic acid.
アクリル基、メタクリル基（以後、２つあわせて（メタ）アクリル基を記する）を有する化合物例としては、（メタ）アクリルアミド、２−ヒドロキシ（メタ）アクリレート、（メタ）アクリルアミド、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、１，４−ブタンジオールモノ（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；トリメチロールプロパンモノまたはジ（メタ）アクリレート、ペンタエリスリトールのモノ、ジまたはトリ（メタ）アクリレート等の水酸基を有するポリオールポリ（メタ）アクリレート；エチレングリコールのモノまたはジ（メタ）アクリレート、及びプロピレングリコールのモノまたはジ（メタ）アクリレート等のアルキレングリコールのモノまたはジ（メタ）アクリレート；ヘキサンジオール、ノナンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、トリシクロデカンジメチロール及びジペンタエリスリトール等のポリオールのエチレンオキサイド付加物のポリ（メタ）アクリレート等が挙げられる。 Examples of compounds having an acryl group and a methacryl group (hereinafter referred to as (meth) acryl group together) include (meth) acrylamide, 2-hydroxy (meth) acrylate, (meth) acrylamide, and 2-hydroxyethyl. Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate; trimethylolpropane mono or di (meth) acrylate, pentaerythritol mono, Polyol poly (meth) acrylate having a hydroxyl group such as di- or tri (meth) acrylate; mono- or di (meth) acrylate of ethylene glycol, and alkylene glycol such as mono- or di (meth) acrylate of propylene glycol Or di (meth) acrylate; poly (meth) acrylate of ethylene oxide adduct of polyols such as hexanediol, nonanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, tricyclodecane dimethylol and dipentaerythritol Can be mentioned.
（メタ）アクリロニトリル並びにビニルアセテート、カチオン性不飽和化合物としては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート及びジエチルアミノ−２−ヒドロキシプロピル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレートの塩酸塩及び硫酸塩等の３級塩が挙げられる。 (Meth) acrylonitrile, vinyl acetate, and cationic unsaturated compounds include dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and diethylamino-2-hydroxypropyl (meth) acrylate And tertiary salts such as sulfate and sulfate.
その他、ジメチルアミノプロピル（メタ）アクリルアミド等のジアルキルアミノアルキル（メタ）アクリルアミドの塩酸塩及び硫酸塩等の３級塩、ジアルキルアミノアルキル（メタ）アクリレートの塩化メチル付加物等のロゲン化アルキル付加物及び塩化ベンジル付加物等のハロゲン化アリール付加物等の４級塩；ジアルキルアミノアルキル（メタ）アクリルアミドの塩化メチル付加物等のハロゲン化アルキル付加物及び塩化ベンジル付加物等のハロゲン化アリール付加物等の４級塩等が挙げられる。 In addition, dialkylaminoalkyl (meth) acrylamide hydrochlorides such as dimethylaminopropyl (meth) acrylamide and tertiary salts such as sulfates, alkylated alkyl adducts such as methyl chloride adducts of dialkylaminoalkyl (meth) acrylates, and Quaternary salts of halogenated aryl adducts such as benzyl chloride adducts; alkyl halide adducts such as methyl chloride adducts of dialkylaminoalkyl (meth) acrylamides and aryl halide adducts such as benzyl chloride adducts, etc. A quaternary salt etc. are mentioned.
エチレン性不飽和基を有する化合物は、オリゴマーまたは重合体でもよい。イオン性基としては、カルボキシル基及びスルホン酸等の酸性基の塩、並びにアルキレンオキサイド基、水酸基等が挙げられる。 The compound having an ethylenically unsaturated group may be an oligomer or a polymer. Examples of the ionic group include a salt of an acidic group such as a carboxyl group and sulfonic acid, an alkylene oxide group, and a hydroxyl group.
より具体的には、（メタ）アクリレートと（メタ）アクリル酸との共重合体であるカルボキシル基含有共重合体に、グリシジル（メタ）アクリレートを付加させて得られる重合体及びその塩、脂肪酸及びアルキレングリコールモノグリシジルエーテルのエステルに（メタ）アクリル酸を付加させたもの、末端にエチレン性二重結合を持ちアルコール部分にポリアルキレンオキシドを用いたポリウレタン（メタ）アクリレートまたはポリエステル（メタ）アクリレート、（メタ）アクリレートを連結基で介して結合されたポリビニルアルコールポリマー等が挙げられる。 More specifically, a polymer obtained by adding glycidyl (meth) acrylate to a carboxyl group-containing copolymer, which is a copolymer of (meth) acrylate and (meth) acrylic acid, its salt, fatty acid, and (Meth) acrylic acid added to an ester of alkylene glycol monoglycidyl ether, polyurethane (meth) acrylate or polyester (meth) acrylate having an ethylenic double bond at the terminal and polyalkylene oxide in the alcohol part, ( Examples thereof include polyvinyl alcohol polymers in which a (meth) acrylate is bonded via a linking group.
ポリウレタン（メタ）アクリレートの例としては、多価アルコールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリエーテルポリオールや、エチレングリコールアジペート、ブタンジオールアジペート、ブタンジオールフタレート及びヘキサンジオールフタレート等のポリエステルジオールが挙げられる。 Examples of polyurethane (meth) acrylates include polyhydric alcohols such as polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, ethylene glycol adipate, butanediol adipate, butanediol phthalate and hexanediol phthalate. Examples include polyester diol.
多価イソシアネート化合物としては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート及び水添ジフェニルメタンジイソシアネート等が挙げられる。 Examples of the polyvalent isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.
水酸基含有（メタ）アクリレートとしては、ヒドロキシエチル（メタ）アクリレート及びヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートが挙げられる。 Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
ポリエステル（メタ）アクリレートとしては、ポリエステル型の多価アルコールと（メタ）アクリル酸との反応物を挙げることができる。 Examples of the polyester (meth) acrylate include a reaction product of a polyester-type polyhydric alcohol and (meth) acrylic acid.
ポリエステル型の多価アルコールとしては、例えば、コハク酸、マレイン酸、アジピン酸、セバシン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸及びトリメリット酸等の多塩基酸、並びにその無水物等が挙げられる。アルコール成分としては、エチレングリコール、ブタンジオール、ヘキサンジオール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリメチロールプロパン、ペンタエリスリトール、トリメチロールプロパンのエチレンオキサイド、またはプロピレンオキサイド付加物のトリオール、グリセリンのエチレンオキサイド、またはプロピレンオキサイド付加物のトリオール、及びペンタエリスリトールのエチレンオキサイド、またはプロピレンオキサイド付加物のテトラオール等を反応させたポリエステルアルコール等が挙げられる。 Examples of polyester type polyhydric alcohols include polybasic acids such as succinic acid, maleic acid, adipic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and trimellitic acid, and anhydrides thereof. Can be mentioned. Examples of the alcohol component include ethylene glycol, butanediol, hexanediol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, pentaerythritol, trimethylolpropane ethylene oxide, or propylene oxide adduct triol, glycerin ethylene oxide, Or the triol of a propylene oxide adduct, the polyester alcohol etc. which reacted the ethylene oxide of a pentaerythritol, the tetraol of a propylene oxide adduct, etc. are mentioned.
エチレン性不飽和基を有する化合物は１種でもよいが、２種以上を併用して使用することもできる。 Although the compound which has an ethylenically unsaturated group may be 1 type, it can also be used in combination of 2 or more type.
（メタ）アクリレートを連結基を介して結合されたポリビニルアルコールポリマーの例としては、特開２０００−１８１０６２号公報、特開２００４−１８９８４１号公報記載のように、メタ（アクリル基）を末端に他の末端にアルデヒド基を持つ化合物をポリビニルアルコールの水酸基にアセタール化して結合したポリマーが挙げられる。 Examples of the polyvinyl alcohol polymer in which (meth) acrylate is bonded via a linking group include other compounds having a meth (acrylic group) at the end as described in JP-A Nos. 2000-181062 and 2004-189841. And a polymer obtained by acetalizing and bonding a compound having an aldehyde group to the hydroxyl group of polyvinyl alcohol.
本発明の水溶性の光開始剤の配合割合としては、目的に応じて適宜設定すればよいが、光重合性組成物に対して０．０５〜１２質量％が好ましく、より好ましくは０．１〜５質量％である。本発明の水溶性の光開始剤は水溶性であるため、水系の活性エネルギー線硬化型組成物に好ましく適用できる。 The blending ratio of the water-soluble photoinitiator of the present invention may be appropriately set depending on the purpose, but is preferably 0.05 to 12% by mass, more preferably 0.1% with respect to the photopolymerizable composition. ˜5 mass%. Since the water-soluble photoinitiator of the present invention is water-soluble, it can be preferably applied to an aqueous active energy ray-curable composition.
エチレン性不飽和基を有する化合物は、重合性組成物量１００質量部に対し、乾燥後光照射して硬化させる場合と乾燥前に光照射して硬化させる場合等目的に応じて異なるが、１．０〜６０質量部まで広く用いることができる。 The compound having an ethylenically unsaturated group differs depending on the purpose, such as the case of curing by irradiation with light after drying and the case of curing by irradiation with light before drying, with respect to 100 parts by mass of the polymerizable composition. It can be widely used from 0 to 60 parts by mass.
《併用できる光開始剤》
本発明においては、本発明に係る光開始剤の他に、必要に応じて他の光開始剤や光増感剤を併用してもよい。
《Photoinitiator that can be used together》
In the present invention, in addition to the photoinitiator according to the present invention, other photoinitiators and photosensitizers may be used in combination as necessary.
併用してもよい他の光開始剤としては下記が挙げられる。 The following is mentioned as another photoinitiator which may be used together.
１）ベンゾフェノン、ヒドロキシベンゾフェノン、ビス−Ｎ，Ｎ−ジメチルアミノベンゾフェノン、ビス−Ｎ，Ｎ−ジエチルアミノベンゾフェノン、４−メトキシ−４′−ジメチルアミノベンゾフェノン等のベンゾフェノン類、及びそれらの塩、
２）チオキサントン、２，４−ジエチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントン、イソプロポキシクロロチオキサントン等のチオキサントン類、及びそれらの塩、
３）エチルアントラキノン、ベンズアントラキノン、アミノアントラキノン、クロロアントラキノン等のアントラキノン類
４）アセトフェノン類、
５）ベンゾインメチルエーテル等のベンゾインエーテル類、
６）２，４，６−トリハロメチルトリアジン類、
７）１−ヒドロキシシクロヘキシルフェニルケトン、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール２量体、２−（ｏ−クロロフェニル）−４，５−ジ（ｍ−メトキシフェニル）イミダゾール２量体、２−（ｏ−フルオロフェニル）−４，５−フェニルイミダゾール２量体、２−（ｏ−メトキシフェニル）−４，５−フェニルイミダゾール２量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール２量体、２−ジ（ｐ−メトキシフェニル）−５−フェニルイミダゾール２量体、２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾール２量体、２，４，５−トリアリールイミダゾール２量体等のイミダゾール類、
８）ベンジルジメチルケタール、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−１−プロパノン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、フェナントレンキノン、９，１０−フェナンスレンキノン、メチルベンゾイン、エチルベンゾイン等のベンゾイン類、
９）９−フェニルアクリジン、１，７−ビス（９，９′−アクリジニル）ヘプタン等のアクリジン誘導体、
１０）ビスアシルフォスフィンオキサイド、ビスフェニルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、
１１）４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、及びこれらのエチレンオキシド付加物。
1) benzophenones such as benzophenone, hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, bis-N, N-diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and salts thereof
2) Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, and salts thereof,
3) Anthraquinones such as ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone 4) acetophenones
5) Benzoin ethers such as benzoin methyl ether,
6) 2,4,6-trihalomethyltriazines,
7) 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-phenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2,4 Imidazoles such as, 5-triarylimidazole dimer,
8) Benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1- Propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one Benzoins such as phenanthrenequinone, 9,10-phenanthrenequinone, methylbenzoin, ethylbenzoin,
9) Acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane,
10) Bisacylphosphine oxide, bisphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
11) 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and their ethylene oxide adducts.
また、インクに加える形態は必要に応じて溶解物、または分散物として加えることができる。 Moreover, the form added to ink can be added as a dissolved substance or a dispersion as needed.
《光増感剤》
本発明の光重合性組成物には光増感剤を用いることが好ましい。光増感剤の例としては、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジメチルアミノ安息香酸イソアミル、エタノールアミン、ジエタノールアミン、トリエタノールアミン等が挙げられる。
<Photosensitizer>
It is preferable to use a photosensitizer in the photopolymerizable composition of the present invention. Examples of the photosensitizer include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethanolamine, diethanolamine, and triethanolamine.
《光重合性組成物》
本発明の光重合性組成物は、前記一般式（１）で表される化合物と、水及び活性エネルギー線を照射することにより重合または架橋する前記エチレン性不飽和基を有する化合物を含有することを特徴とする。
<< Photopolymerizable composition >>
The photopolymerizable composition of the present invention contains the compound represented by the general formula (1) and a compound having the ethylenically unsaturated group that is polymerized or crosslinked by irradiation with water and active energy rays. It is characterized by.
本発明の光重合性組成物では、水の他に必要があれば有機溶媒を用いてもよい。有機溶媒は水溶性の溶媒が好ましいが、光重合性組成物中で溶解していれば、特に水溶性でない溶媒も少量用いることができる。 In the photopolymerizable composition of the present invention, an organic solvent may be used if necessary in addition to water. The organic solvent is preferably a water-soluble solvent, but if it is dissolved in the photopolymerizable composition, a small amount of a solvent that is not particularly water-soluble can also be used.
光重合性組成物中の水及び有機溶媒の使用量は、光重合性組成物１００質量部当たり２０〜９９質量部であり、好ましくは５０〜９８質量部である。 The usage-amount of the water and organic solvent in a photopolymerizable composition is 20-99 mass parts per 100 mass parts of photopolymerizable compositions, Preferably it is 50-98 mass parts.
本発明の光重合性組成物のｐＨは、光開始剤の、エチレン性不飽和基を有する化合物に対するｐＨ安定性により適宜決めることができるが、ｐＨ５．０〜１０．０までの間ならば、特に不都合なく用いることができる。 The pH of the photopolymerizable composition of the present invention can be appropriately determined depending on the pH stability of the photoinitiator with respect to the compound having an ethylenically unsaturated group, and if it is between pH 5.0 and 10.0, It can be used without any particular inconvenience.
《用途》
本発明の光重合性組成物は、塗料等のコーティング剤、接着剤及びレジスト等、ＵＶ硬化性のインク、ＵＶ硬化性のＵＶ印刷インクといった種々の用途に使用することができ、それに応じて顔料、染料、消泡剤、レベリング剤、無機フィラー、有機フィラー及び光安定剤等を配合することもできる。
<Application>
The photopolymerizable composition of the present invention can be used for various applications such as coating agents such as paints, adhesives and resists, UV curable inks, UV curable UV printing inks, and pigments accordingly. , Dyes, antifoaming agents, leveling agents, inorganic fillers, organic fillers, light stabilizers and the like can also be blended.
《光硬化方法》
本発明の光重合性組成物の使用方法としては、従来の光硬化型組成物の使用方法に従えばよい。具体的には、光重合性組成物をバーコーター、ワイヤーバー、インクジェットヘッド等により基材上に塗布印刷した後、紫外線を照射し乾燥するか、基材に光重合性組成物を塗布、加熱により水分を蒸発させた後に、紫外線を照射する方法が挙げられる。
《Photocuring method》
What is necessary is just to follow the usage method of the conventional photocurable composition as a usage method of the photopolymerizable composition of this invention. Specifically, after the photopolymerizable composition is applied and printed on a substrate by a bar coater, a wire bar, an inkjet head or the like, it is irradiated with ultraviolet rays and dried, or the photopolymerizable composition is applied to the substrate and heated. The method of irradiating with ultraviolet rays after evaporating the moisture by the method described above.
本発明の光開始剤は紫外線２５０〜４００ｎｍ付近まで吸収があるため、その領域の紫外線を照射できる光源はすべて用いることができるが、本発明の光開始剤の紫外線吸収は他の光開始剤と比べると特に３２０〜４００ｎｍまで吸収の裾野が延びているという特徴があり、その領域の紫外線を照射する光源を用いることが好ましい。具体的に光重合性組成物を硬化させる光源としては、高圧水銀灯、低圧水銀灯、発光ダイオード（ＬＥＤ）、電子線、太陽光等を用いることができるが、実用的には３６５ｎｍ光の出力が強い高圧水銀灯、３６５ｎｍに発光スペクトルを有する発光ダイオードが好ましく、特に３６５ｎｍに発光強度を有する発光ダイオードを好ましく用いることができる。 Since the photoinitiator of the present invention has absorption up to near ultraviolet rays of 250 to 400 nm, any light source capable of irradiating ultraviolet rays in that region can be used. In comparison, the absorption base extends to 320 to 400 nm, and it is preferable to use a light source that irradiates ultraviolet rays in that region. As a light source for specifically curing the photopolymerizable composition, a high-pressure mercury lamp, a low-pressure mercury lamp, a light emitting diode (LED), an electron beam, sunlight, or the like can be used, but in practice, the output of 365 nm light is strong. A high pressure mercury lamp, a light emitting diode having an emission spectrum at 365 nm is preferable, and a light emitting diode having an emission intensity at 365 nm can be preferably used.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において「部」あるいは「％」の表示を用いるが、特に断りがない限り「質量部」あるいは「質量％」を表す。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.
《合成例》
下記スキームにより合成した。
<Synthesis example>
It was synthesized according to the following scheme.
〔例示化合物Ｓ−１の合成〕
（Ｓ−１Ａ）から（Ｓ−１Ｂ）の合成
ジクロロメタン２０ｍｌに塩化アルミニウム４．４０ｇ（３３ｍｍｏｌ）を加え、１０℃以下になるように冷却した。そこに、２，６−ジメチルフェノキシアセト酢酸エチルエステル（Ｓ−１Ａ）３．１２ｇ（２０ｍｍｏｌ）を滴下後、イソブチロリルクロリド１．７５ｇ（２２ｍｍｏｌ）を滴下した。滴下終了後、液温を室温に戻し、２時間攪拌した。反応終了後、反応液を氷水３００ｇ中に加え、酢酸エチルで抽出、濃縮により、黄色オイル５．４ｇを得た。カラムクロマトグラフィーで目的物を単離精製し、無色透明オイルの（Ｓ−１Ｂ）を２．５ｇ（収率６１％）得た。
[Synthesis of Exemplified Compound S-1]
Synthesis of (S-1A) from (S-1A) 4.40 g (33 mmol) of aluminum chloride was added to 20 ml of dichloromethane, and the mixture was cooled to 10 ° C or lower. Thereto, 3.12 g (20 mmol) of 2,6-dimethylphenoxyacetoacetic acid ethyl ester (S-1A) was added dropwise, and then 1.75 g (22 mmol) of isobutyryl chloride was added dropwise. After completion of the dropwise addition, the liquid temperature was returned to room temperature and stirred for 2 hours. After completion of the reaction, the reaction solution was added to 300 g of ice water, extracted with ethyl acetate, and concentrated to obtain 5.4 g of a yellow oil. The target product was isolated and purified by column chromatography to obtain 2.5 g (61% yield) of colorless transparent oil (S-1B).
（Ｓ−１Ｂ）から（Ｓ−１Ｃ）の合成
１００ｍｌ用三口フラスコに、（Ｓ−１Ｂ）２．２ｇ（８ｍｍｏｌ）、ジクロロメタン２０ｍｌを加え、水冷により液温を２０〜２５℃にした。臭素１．３ｇ（８ｍｍｏｌ）をゆっくり滴下すると、臭化水素の発泡とともに、反応が始まった。反応終了後、水で洗浄後、ジクロロメタンを濃縮し、無色透明オイルの（Ｓ−１Ｃ）を２．６ｇ（収率９２％）得た。
Synthesis of (S-1B) to (S-1C) To a 100 ml three-neck flask, 2.2 g (8 mmol) of (S-1B) and 20 ml of dichloromethane were added, and the liquid temperature was adjusted to 20 to 25 ° C. by water cooling. When 1.3 g (8 mmol) of bromine was slowly added dropwise, the reaction started with the evolution of hydrogen bromide. After completion of the reaction, after washing with water, dichloromethane was concentrated to obtain 2.6 g (yield 92%) of colorless transparent oil (S-1C).
（Ｓ−１Ｃ）から例示化合物Ｓ−１の合成
（Ｓ−１Ｃ）２．５ｇ（７ｍｍｏｌ）をエタノール２０ｍｌに溶解し、水酸化カリウム１．０ｇ（１７ｍｍｏｌ）、水２ｍｌに溶解した溶液を加え、１時間還流した。反応終了後、水５０ｍｌを加え、濃塩酸で酸性にした後、酢酸エチルで抽出した。酢酸エチル相を濃縮して、例示化合物Ｓ−１を１．７ｇ（収率９３％）得た。
Synthesis of Exemplified Compound S-1 from (S-1C) 2.5 g (7 mmol) of (S-1C) was dissolved in 20 ml of ethanol, a solution of 1.0 g (17 mmol) of potassium hydroxide and 2 ml of water was added, Refluxed for 1 hour. After completion of the reaction, 50 ml of water was added, acidified with concentrated hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate phase was concentrated to obtain 1.7 g (yield 93%) of Exemplary Compound S-1.
得られた例示化合物Ｓ−１は、核磁気共鳴スペクトルで構造を確認した。 The obtained exemplary compound S-1 was confirmed in structure by nuclear magnetic resonance spectrum.
ＮＭＲ（ＣＤＣｌ3） δ７．６（ｓ，２Ｈ）、δ４．５（ｓ，２Ｈ）、δ２．５（ｓ，６Ｈ）、δ１．６（ｓ，６Ｈ）
〔例示化合物Ｓ−３の合成〕
例示化合物Ｓ−１の合成において、（Ｓ−１Ａ）から（Ｓ−１Ｂ）の合成で用いた、２，６−ジメチルフェノキシアセト酢酸エチルエステル（Ｓ−１Ａ）の代わりに、３，５−ジメチルフェノキシアセト酢酸エチルエステル（Ｓ−１Ａ）を用いる他は、同様に反応させ、例示化合物Ｓ−３を得た。得られた例示化合物Ｓ−３は、核磁気共鳴スペクトルで構造を確認した。
NMR (CDCl 3 ) δ 7.6 (s, 2H), δ 4.5 (s, 2H), δ 2.5 (s, 6H), δ 1.6 (s, 6H)
[Synthesis of Exemplified Compound S-3]
In the synthesis of exemplary compound S-1, 3,5-dimethyl instead of 2,6-dimethylphenoxyacetoacetic acid ethyl ester (S-1A) used in the synthesis of (S-1B) from (S-1A) Except for using phenoxyacetoacetic acid ethyl ester (S-1A), the reaction was carried out in the same manner to obtain Exemplified Compound S-3. The structure of the obtained exemplary compound S-3 was confirmed by a nuclear magnetic resonance spectrum.
〔例示化合物Ｓ−１０の合成〕
下記スキームにより合成した。
[Synthesis of Exemplified Compound S-10]
It was synthesized according to the following scheme.
例示化合物Ｓ−１の合成において、（Ｓ−１Ａ）から（Ｓ−１Ｂ）の合成で用いたイソブチロリルクロリドの代わりに、シクロヘキシルアセチルクロリドを用いる他は、同様に反応させ、例示化合物Ｓ−１０を得た。得られた例示化合物Ｓ−１０は、核磁気共鳴スペクトルで構造を確認した。 In the synthesis of Exemplified Compound S-1, the Exemplified Compound S was reacted in the same manner except that cyclohexylacetyl chloride was used instead of isobutyryl chloride used in the synthesis of (S-1B) from (S-1A). -10 was obtained. The obtained exemplary compound S-10 was confirmed in structure by a nuclear magnetic resonance spectrum.
〔例示化合物Ｓ−１３の合成〕
下記スキームにより合成した。
[Synthesis of Exemplified Compound S-13]
It was synthesized according to the following scheme.
（Ｓ−１３Ａ）から（Ｓ−１３Ｂ）の合成
ジクロロメタン２０ｍｌに塩化アルミニウム７．３ｇ（５５ｍｍｏｌ）を加え、１０℃以下になるように冷却した。そこに、２，６−キシレノール３．０ｇ（２５ｍｍｏｌ）をジクロロメタン１０ｍｌに溶解した溶液を滴下後、オキザリルクロリド１．６ｇ（１３ｍｍｏｌ）を滴下した。直ちに赤色になり、液温を室温に戻し、塩化水素ガスの発生が止むまで攪拌する反応終了後、反応液を氷水３００ｇ中に加え、酢酸エチルで抽出、濃縮により、黄色オイル５．４ｇを得た。カラムクロマトグラフィーで目的物を単離精製し、淡黄色結晶として（Ｓ−１３Ｂ）を２．５ｇ（収率６７％）得た。
Synthesis of (S-13B) from (S-13A) 7.3 g (55 mmol) of aluminum chloride was added to 20 ml of dichloromethane and cooled to 10 ° C or lower. A solution prepared by dissolving 3.0 g (25 mmol) of 2,6-xylenol in 10 ml of dichloromethane was added dropwise thereto, and 1.6 g (13 mmol) of oxalyl chloride was added dropwise thereto. The reaction immediately turned red, the temperature of the solution was returned to room temperature, and stirring was continued until hydrogen chloride gas ceased to be generated. It was. The target product was isolated and purified by column chromatography to obtain 2.5 g (yield 67%) of (S-13B) as pale yellow crystals.
（Ｓ−１３Ｂ）から（Ｓ−１３Ｃ）の合成
（Ｓ−１３Ｂ）１．４ｇ（４．６ｍｍｏｌ）、クロロ酢酸メチル１．１０ｇ（１０ｍｍｏｌ）、炭酸カリウム１．６ｇ（１２ｍｍｏｌ）、アセトン３０ｍｌを混合し、１０時間還流した。冷却後、水に空け、析出した黄色結晶をろ過により採取し、（Ｓ−１３Ｃ）を１．９ｇ（収率９４％）得た。
Synthesis of (S-13B) from (S-13B) (S-13B) 1.4 g (4.6 mmol), methyl chloroacetate 1.10 g (10 mmol), potassium carbonate 1.6 g (12 mmol), acetone 30 ml mixed And refluxed for 10 hours. After cooling, the mixture was poured into water, and the precipitated yellow crystals were collected by filtration to obtain 1.9 g (yield 94%) of (S-13C).
（Ｓ−１３Ｃ）から（Ｓ−１３Ｄ）の合成
（Ｓ−１３Ｃ）４．４２ｇ（１０ｍｍｏｌ）、オルトギ酸トリメチル１０．６ｇ（１００ｍｏｌ）、メタノール３．２ｇ（１００ｍｍｏｌ）、トルエン５０ｍｌを加え、還流中に、トリフルオロスルホン酸０．３ｇ（２ｍｍｏｌ）を加え、２時間還流を続けた。冷却後、酢酸エチルを加えた後、炭酸水素ナトリウムの水溶液で洗浄後濃縮し、クロマトグラフィーで単離精製し、（Ｓ−１３Ｄ）を白い粉末として、１．９ｇ（収率３９％）得た。
Synthesis of (S-13C) from (S-13C) 4.42 g (10 mmol) of (S-13C), 10.6 g (100 mol) of trimethyl orthoformate, 3.2 g (100 mmol) of methanol and 50 ml of toluene To this was added 0.3 g (2 mmol) of trifluorosulfonic acid, and reflux was continued for 2 hours. After cooling, ethyl acetate was added, washed with an aqueous solution of sodium bicarbonate, concentrated, and isolated and purified by chromatography to obtain 1.9 g (yield 39%) of (S-13D) as a white powder. .
（Ｓ−１３Ｄ）から例示化合物Ｓ−１３の合成
（Ｓ−１３Ｄ）４．９ｇ（１０ｍｍｏｌ）をメタノール３０ｍｌに溶解し、水酸化ナトリウム０．８４ｇ（２１ｍｍｏｌ）の水溶液を加えた。直ちに溶液が黄色に変化するので、還流１０分行った後に、冷却、濃縮した。エタノールを加えて、結晶化させた後に、ろ過により取り出し、黄色粉末の例示化合物Ｓ−１３を３．４ｇ（収率６７％）得た。
Synthesis of Exemplary Compound S-13 from (S-13D) 4.9 g (10 mmol) of (S-13D) was dissolved in 30 ml of methanol, and an aqueous solution of 0.84 g (21 mmol) of sodium hydroxide was added. Since the solution turned yellow immediately, the solution was refluxed for 10 minutes, cooled and concentrated. Ethanol was added to allow crystallization, followed by filtration to obtain 3.4 g (yield 67%) of Exemplary Compound S-13 as a yellow powder.
得られた例示化合物Ｓ−１３は、核磁気共鳴スペクトルで構造を確認した。 The obtained exemplary compound S-13 was confirmed in structure by nuclear magnetic resonance spectrum.
ＮＭＲ（Ｄ2Ｏ） δ７．６（ｓ，２Ｈ）、δ７．１（ｓ，２Ｈ）、δ４．１（ｓ，４Ｈ）、δ３．０（ｓ，６Ｈ），δ２，２（ｓ，６Ｈ）、δ２，１（ｓ，６Ｈ）
〔例示化合物Ｓ−１５の合成〕
下記スキームにより合成した。
NMR (D 2 O) δ 7.6 (s, 2H), δ 7.1 (s, 2H), δ 4.1 (s, 4H), δ 3.0 (s, 6H), δ 2, 2 (s, 6H) , Δ2, 1 (s, 6H)
[Synthesis of Exemplified Compound S-15]
It was synthesized according to the following scheme.
（Ｓ−１５Ａ）から（Ｓ−１５Ｂ）の合成
ジクロロメタン２０ｍｌに塩化アルミニウム６．７ｇ（５０ｍｍｏｌ）を加え、１０℃以下になるように冷却した。そこに、２，６−キシレノール２．４ｇ（２０ｍｍｏｌ）をジクロロメタン１０ｍｌに溶解した溶液を滴下後、ベンゾイルフォルミルクロリド３．４ｇ（２０ｍｍｏｌ）を滴下した。液温を室温に戻し２時間攪拌した。透明液を得るので、反応終了後、反応液を氷水３００ｇ中に加え、酢酸エチルで抽出、濃縮後、カラムクロマトグラフィーで目的物を単離精製し、無色結晶の（Ｓ−１５Ａ）を２．９ｇ（収率５８％）得た。
Synthesis of (S-15A) from (S-15A) 6.7 g (50 mmol) of aluminum chloride was added to 20 ml of dichloromethane and cooled to 10 ° C or lower. A solution prepared by dissolving 2.4 g (20 mmol) of 2,6-xylenol in 10 ml of dichloromethane was added dropwise thereto, and 3.4 g (20 mmol) of benzoylformyl chloride was added dropwise thereto. The liquid temperature was returned to room temperature and stirred for 2 hours. Since a transparent liquid was obtained, after completion of the reaction, the reaction liquid was added to 300 g of ice water, extracted and concentrated with ethyl acetate, and the target product was isolated and purified by column chromatography to obtain (S-15A) as colorless crystals. 9 g (yield 58%) was obtained.
（Ｓ−１５Ｂ）から例示化合物Ｓ−１５までの合成
（Ｓ−１５Ｂ）以下は、（Ｓ−１３Ｂ）以降の合成と同様に行い、例示化合物Ｓ−１５を淡黄色結晶として得た。得られた例示化合物Ｓ−１５は、核磁気共鳴スペクトルで構造を確認した。
Synthesis from (S-15B) to Exemplified Compound S-15 (S-15B) The following was performed in the same manner as the synthesis after (S-13B) to give Exemplified Compound S-15 as pale yellow crystals. The obtained exemplary compound S-15 was confirmed in structure by a nuclear magnetic resonance spectrum.
その他の化合物も同様にして合成できる。 Other compounds can be synthesized in the same manner.
実施例１（ＵＶクリアーインクの例）
《インクの調製》
〔インク１−１の調製〕
Ａ４００（新中村化学製） １８部
ＴＯ−１３４３（東亞合成製、アクリロイル基を２個以上有する水溶性ポリエステル系アクリルオリゴマー） ７部
ジョンクリル５３７Ｊ（ジョンソンポリマー製、固形分４６％） １０部
光開始剤：例示化合物Ｓ−１ ２部
ジエチレングリコール ２０部
以上に、水酸化ナトリウム溶液または塩酸でｐＨを８．２に調整した後、イオン交換水を加えて１００部とし、超音波分散を行った後、０．８μｍのメンブランフィルターでろ過し、インク１−１を得た。
Example 1 (Example of UV clear ink)
<Preparation of ink>
[Preparation of Ink 1-1]
A400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 18 parts TO-1343 (manufactured by Toagosei Co., Ltd., water-soluble polyester acrylic oligomer having two or more acryloyl groups) 7 parts Jonkrill 537J (manufactured by Johnson polymer, solid content 46%) 10 parts Agent: Exemplified compound S-1 2 parts Diethylene glycol 20 parts Above, after adjusting pH to 8.2 with sodium hydroxide solution or hydrochloric acid, add ion-exchanged water to make 100 parts, and after ultrasonic dispersion, Filtration through a 0.8 μm membrane filter gave ink 1-1.
〔インク１−２〜１−１５の調製〕
インク１−１の調製において、光開始剤を表１記載の化合物に代えて、インク１−２〜１−１５を調製した。
[Preparation of Inks 1-2 to 1-15]
Ink 1-1 was prepared by replacing photoinitiators with the compounds shown in Table 1 in the preparation of ink 1-1.
《インクの評価》
作製したインクについて、下記の方法で評価した。
<Evaluation of ink>
The produced ink was evaluated by the following method.
（硬化性）
インクをアート紙上にワイヤーバーでウエット膜厚５０μｍで塗布し、３６５ｎｍに発光強度を有するＬＥＤランプ（日亜化学工業製）で１０ｍＪ／ｃｍ2の照度で照射し、照射後の状態を目視で観察し、下記基準で評価した。
(Curable)
Ink is applied onto art paper with a wire bar with a wet film thickness of 50 μm, irradiated with an LED lamp (manufactured by Nichia Corporation) having an emission intensity of 365 nm at an illuminance of 10 mJ / cm 2 , and the state after irradiation is visually observed. And evaluated according to the following criteria.
○：流動性がない
△：一部に流動性がある
×：流動性がある
（黄変）
インクをアート紙上にワイヤーバーでウエット膜厚５０μｍで塗布し、３６５ｎｍに発光強度を有するＬＥＤランプ（日亜化学工業製）で１０００ｍＪ／ｃｍ2の照度で照射し、照射前後の状態を目視で観察し、下記基準で評価した。
○: No fluidity △: Some fluidity ×: Fluidity (yellowing)
Ink is applied to art paper with a wire bar with a wet film thickness of 50 μm, irradiated with an LED lamp (manufactured by Nichia Corporation) having an emission intensity of 365 nm at an illuminance of 1000 mJ / cm 2 , and the state before and after irradiation is visually observed. And evaluated according to the following criteria.
○：黄変が認められない
△：わずかに黄色を呈するが、許容範囲である
×：明らかに黄変している
（保存性）
インク２０ｍｌを５０ｍｌビーカーに入れ、５０ｃｍ上部より１００Ｗの蛍光灯を２４時間照射し、照射後の状態を目視で観察し、下記基準で評価した。
○: No yellowing is observed △: Slightly yellow, but acceptable level ×: Clearly yellowing (preservation)
20 ml of ink was put into a 50 ml beaker, and a 100 W fluorescent lamp was irradiated for 24 hours from the top of 50 cm, and the state after irradiation was visually observed and evaluated according to the following criteria.
○：インクに変化がない
△：表面の一部がゲル化している
×：不溶物がある
評価の結果を表１に示す。
○: No change in ink Δ: Part of the surface is gelled ×: Insoluble material exists Table 1 shows the evaluation results.
表１より、本発明の光開始剤を用いたインクでは、３６５ｎｍに発光強度を有するＬＥＤでの硬化性が高いとともに、黄変も少なく、さらに室内蛍光灯下での保存性に優れていることが分かる。 From Table 1, the ink using the photoinitiator of the present invention has high curability with an LED having emission intensity at 365 nm, little yellowing, and excellent storage stability under indoor fluorescent lamps. I understand.
実施例２（ＵＶ印刷インクの例）
《インクの調製》
（シアン顔料分散液の調製）
以下の各添加剤を混合し、０．５ｍｍのジルコニアビーズを体積率で５０％充填したサンドグラインダーを用いて分散し、イオン交換水で希釈してシアン顔料の含有量が１０％のシアン顔料分散液を調製した。このシアン顔料分散液に含まれるシアン顔料粒子の平均粒径は１２３ｎｍであった。なお、粒径測定はマルバーン製ゼータサイザ１０００ＨＳにより行った。
Example 2 (Example of UV printing ink)
<Preparation of ink>
(Preparation of cyan pigment dispersion)
Disperse using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads by mixing the following additives, dilute with ion-exchanged water, and disperse cyan pigment with a cyan pigment content of 10% A liquid was prepared. The average particle diameter of the cyan pigment particles contained in this cyan pigment dispersion was 123 nm. The particle size was measured with a Malvern Zetasizer 1000HS.
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３ １５部
高分子分散剤（スチレン／アクリル酸／ブチルアクリレート共重合体、Ｔｇ６５℃、数平均分子量７０００） ４部
グリセリン １８部
これにイオン交換水を加えて１００部とする。
C. I. Pigment Blue 15: 3 15 parts Polymer dispersing agent (styrene / acrylic acid / butyl acrylate copolymer, Tg 65 ° C., number average molecular weight 7000) 4 parts Glycerin 18 parts Add ion-exchanged water to make 100 parts.
〔インク２−１〜２−１５の調製〕
シアン顔料分散液 ３０部
Ａ４００（新中村化学製） ２０部
ＴＯ−１３４３（東亞合成製、アクリロイル基を２個以上有する水溶性ポリエステル系アクリルオリゴマー） ５部
ジョンクリル５３７Ｊ（ジョンソンポリマー製、固形分４６％） ８部
光開始剤：表２記載 ２部
ジエチレングリコール ２０部
これに、水酸化ナトリウム溶液または塩酸でｐＨを８．２に調整した後、イオン交換水を加えて１００部とし、超音波分散を行った後、０．８μｍのメンブランフィルターでろ過し、インク２−１〜２−１５を得た。
[Preparation of Inks 2-1 to 2-15]
Cyan pigment dispersion 30 parts A400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts TO-1343 (manufactured by Toagosei Co., Ltd., water-soluble polyester acrylic oligomer having two or more acryloyl groups) 5 parts Jonkrill 537J (manufactured by Johnson polymer, solid content 46 %) 8 parts Photoinitiator: Table 2 2 parts Diethylene glycol 20 parts After adjusting pH to 8.2 with sodium hydroxide solution or hydrochloric acid, ion-exchanged water was added to make 100 parts, and ultrasonic dispersion was performed. Thereafter, the mixture was filtered through a 0.8 μm membrane filter to obtain inks 2-1 to 2-15.
《インクの評価》
作製したインクについて、下記の方法で評価した。
<Evaluation of ink>
The produced ink was evaluated by the following method.
（硬化性）
インクをアート紙上にワイヤーバーでウエット膜厚１０μｍで塗布し、３６５ｎｍに発光強度を有するＬＥＤランプ（日亜化学工業製）で１１５ｍＪ／ｃｍ2の照度で照射し、照射後の状態を目視で観察し、下記基準で評価した。
(Curable)
Ink was applied to art paper with a wire bar with a wet film thickness of 10 μm, and irradiated with an illuminance of 115 mJ / cm 2 with an LED lamp having a luminous intensity of 365 nm (manufactured by Nichia Corporation), and the state after irradiation was visually observed. And evaluated according to the following criteria.
○：流動性がない
△：一部に流動性がある
×：流動性がある
（黄変）
インクをアート紙上にワイヤーバーでウエット膜厚１０μｍで塗布し、３６５ｎｍに発光強度を有するＬＥＤランプ（日亜化学工業製）で１２００ｍＪ／ｃｍ2の照度で照射し、照射前後の状態を目視で観察し、下記基準で評価した。
○: No fluidity △: Some fluidity ×: Fluidity (yellowing)
Ink was applied on art paper with a wire bar with a wet film thickness of 10 μm, irradiated with an LED lamp having a luminous intensity of 365 nm (manufactured by Nichia Corporation) at an illuminance of 1200 mJ / cm 2 , and the state before and after irradiation was observed visually. And evaluated according to the following criteria.
○：黄変が認められない
△：わずかに黄色を呈するが、許容範囲である
×：明らかに黄変している
（保存性）
インク２０ｍｌを５０ｍｌビーカーに入れ、５０ｃｍ上部より１００Ｗの蛍光灯を２４時間照射し、照射後の状態を目視で観察し、下記基準で評価した。
○: No yellowing is observed △: Slightly yellow, but acceptable level ×: Clearly yellowing (preservation)
20 ml of ink was put into a 50 ml beaker, and a 100 W fluorescent lamp was irradiated for 24 hours from the top of 50 cm, and the state after irradiation was visually observed and evaluated according to the following criteria.
○：インクに変化がない
△：表面の一部がゲル化している
×：不溶物がある
評価の結果を表２に示す。
○: No change in ink Δ: Part of the surface is gelled ×: Insoluble material is present Table 2 shows the evaluation results.
表２より、本発明の光開始剤を用いたインクは、３６５ｎｍに発光強度を有するＬＥＤ、高圧水銀灯での硬化に優れるとともに、黄変が少なく、室内蛍光灯下での保存性に優れていることが分かる。 From Table 2, the ink using the photoinitiator of the present invention is excellent in curing with an LED having a light emission intensity at 365 nm and a high-pressure mercury lamp, has little yellowing, and is excellent in storage stability under an indoor fluorescent lamp. I understand that.
実施例３（インクジェットＵＶインクの例）
《インク３−１の調製》
実施例で用いたシアン顔料分散液 ３０部
アクリル基含有ポリビニルアルコール（重合度５００、変性率３％、濃度１０％）
３０部
光開始剤（表３参照） １部
エチレングリコール １５部
２−ピロリドン ５部
オルフィンＥ１０１０（日信化学製） ０．４部
水酸化ナトリウム溶液または塩酸でｐＨを８．２に調整した後、純水を加えて１００部とし、超音波分散を行った後、０．８μｍのメンブランフィルターでろ過しインクを得た。
Example 3 (Example of inkjet UV ink)
<< Preparation of ink 3-1 >>
Cyan pigment dispersion used in Examples 30 parts Acrylic group-containing polyvinyl alcohol (polymerization degree 500, modification rate 3%, concentration 10%)
30 parts Photoinitiator (see Table 3) 1 part Ethylene glycol 15 parts 2-pyrrolidone 5 parts Orphine E1010 (manufactured by Nissin Chemical) 0.4 part After adjusting the pH to 8.2 with sodium hydroxide solution or hydrochloric acid, Pure water was added to make 100 parts, and ultrasonic dispersion was performed, followed by filtration with a 0.8 μm membrane filter to obtain an ink.
〔インク３−２〜３−１５の調製〕
上記インク３−１と同様にして、表３記載の光開始剤を用いてインク３−２〜３−１５を調製した。
[Preparation of Inks 3-2 to 3-15]
Inks 3-2 to 3-15 were prepared using the photoinitiators described in Table 3 in the same manner as Ink 3-1.
《インクの評価》
ＬＥＤを搭載したＵＶインクジェットプリンターで、アート紙上にベタ画像を形成し、３６５ｎｍに発光強度を有するＬＥＤランプ（日亜化学工業製）で１１５ｍＪ／ｃｍ2の照度になるようにＵＶ光を露光し、下記のようにして黄変の評価、実施例２と同様にして３６５ｎｍに発光強度を有するＬＥＤでの硬化性及び蛍光灯下でのインク保存性の評価を行った。
<Evaluation of ink>
With a UV inkjet printer equipped with LEDs, a solid image is formed on art paper, and UV light is exposed to an illuminance of 115 mJ / cm 2 with an LED lamp (manufactured by Nichia Corporation) having an emission intensity at 365 nm, The yellowing was evaluated as described below, and in the same manner as in Example 2, the curability with an LED having an emission intensity at 365 nm and the ink storage stability under a fluorescent lamp were evaluated.
（黄変）
作製したインクをアート紙上にワイヤーバーでウエット膜厚１０μｍで塗布し、３６５ｎｍに発光強度を有するＬＥＤランプ（日亜化学工業製）で１２００ｍＪ／ｃｍ2の照度で照射し、照射前後の状態を目視で観察し、下記基準で評価した。
(Yellowing)
The prepared ink was applied onto art paper with a wire bar with a wet film thickness of 10 μm, and irradiated with an illuminance of 1200 mJ / cm 2 with an LED lamp having a luminous intensity of 365 nm (manufactured by Nichia Corporation). And evaluated according to the following criteria.
○：黄変が認められない
△：わずかに黄色を呈するが、許容範囲である
×：明らかに黄変している
評価の結果を表３に示す。
○: No yellowing is observed Δ: Slightly yellow, but acceptable level ×: Obviously yellowing Table 3 shows the evaluation results.
表３より、本発明の光開始剤を用いたＵＶ硬化型インクは、インクジェットインクとして用いても、３６５ｎｍに発光強度を有するＬＥＤでの硬化性に優れるとともに、黄変の少ない画像を与え、さらに室内蛍光灯下でのインク保存性に優れていることが分かる。 From Table 3, the UV curable ink using the photoinitiator of the present invention is excellent in curability with an LED having an emission intensity at 365 nm and gives an image with less yellowing even when used as an inkjet ink. It can be seen that the ink storage stability under the indoor fluorescent lamp is excellent.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| WO2012105479A1 (en) * | 2011-02-02 | 2012-08-09 | 東洋合成工業株式会社 | 2,2-dimethoxy-1,2-di-[4-(meth)acryloyloxy]phenylethane-1-one, method for producing same, radical polymerization initiator and photocurable composition |
| US8752952B2 (en) | 2010-11-24 | 2014-06-17 | Seiko Epson Corporation | Recording method, light curable type ink set, and recording apparatus |
| JP2017043079A (en) * | 2015-08-29 | 2017-03-02 | 京セラ株式会社 | Printing method |
| JP2018052873A (en) * | 2016-09-29 | 2018-04-05 | Dic株式会社 | Novel compound, photopolymerization initiator and polymerizable liquid crystal composition |
| CN115073275A (en) * | 2022-08-22 | 2022-09-20 | 天津深蓝化工技术有限公司 | Preparation method of photoinitiator 1-hydroxycyclohexyl phenyl ketone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8752952B2 (en) | 2010-11-24 | 2014-06-17 | Seiko Epson Corporation | Recording method, light curable type ink set, and recording apparatus |
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| JP2018052873A (en) * | 2016-09-29 | 2018-04-05 | Dic株式会社 | Novel compound, photopolymerization initiator and polymerizable liquid crystal composition |
| CN115073275A (en) * | 2022-08-22 | 2022-09-20 | 天津深蓝化工技术有限公司 | Preparation method of photoinitiator 1-hydroxycyclohexyl phenyl ketone |
| CN115073275B (en) * | 2022-08-22 | 2022-11-15 | 天津深蓝化工技术有限公司 | A kind of preparation method of photoinitiator 1-hydroxycyclohexyl phenyl ketone |
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