JP5744273B1 - Cyclic acetal (meth) acrylate composition - Google Patents
Cyclic acetal (meth) acrylate composition Download PDFInfo
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- JP5744273B1 JP5744273B1 JP2014069671A JP2014069671A JP5744273B1 JP 5744273 B1 JP5744273 B1 JP 5744273B1 JP 2014069671 A JP2014069671 A JP 2014069671A JP 2014069671 A JP2014069671 A JP 2014069671A JP 5744273 B1 JP5744273 B1 JP 5744273B1
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- JP
- Japan
- Prior art keywords
- acrylate
- meth
- cyclic acetal
- mol
- trimethylolpropane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 113
- -1 Cyclic acetal Chemical class 0.000 title claims abstract description 76
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000005194 fractionation Methods 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 27
- 239000003112 inhibitor Substances 0.000 description 24
- 238000004817 gas chromatography Methods 0.000 description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 13
- 208000012839 conversion disease Diseases 0.000 description 12
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 241001550224 Apha Species 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003999 initiator Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 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
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-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
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical compound CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- WDNPRAKRASINBZ-UHFFFAOYSA-N 3-(4-benzhydrylpiperazin-1-yl)-1-(4-chlorophenyl)pyrrolidine-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C(N2CCN(CC2)C(C=2C=CC=CC=2)C=2C=CC=CC=2)CC1=O WDNPRAKRASINBZ-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- JIJIZOVOLBQTMU-UHFFFAOYSA-N C(C)(C)(C)C1=C(C(=CC(=C1O)C(C)(C)C)C)N(C)C.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)O Chemical compound C(C)(C)(C)C1=C(C(=CC(=C1O)C(C)(C)C)C)N(C)C.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)O JIJIZOVOLBQTMU-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OLLWNABMMCGNOL-UHFFFAOYSA-M P(=O)([O-])(O)O.P(=O)(O)(O)O.[Rb+] Chemical class P(=O)([O-])(O)O.P(=O)(O)(O)O.[Rb+] OLLWNABMMCGNOL-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Substances CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 description 1
- BQDSDRAVKYTTTH-UHFFFAOYSA-N barium(2+);methanolate Chemical compound [Ba+2].[O-]C.[O-]C BQDSDRAVKYTTTH-UHFFFAOYSA-N 0.000 description 1
- JQWWEWGDIYUXCO-UHFFFAOYSA-N benzyl(trimethyl)azanium;ethanolate Chemical compound CC[O-].C[N+](C)(C)CC1=CC=CC=C1 JQWWEWGDIYUXCO-UHFFFAOYSA-N 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- LGSNSXWSNMARLH-UHFFFAOYSA-N butan-1-ol titanium Chemical compound C(CCC)O.[Ti].C(CCC)O LGSNSXWSNMARLH-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- FVQARXYJIGSYRE-UHFFFAOYSA-N butyl-methyl-oxotin Chemical compound CCCC[Sn](C)=O FVQARXYJIGSYRE-UHFFFAOYSA-N 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical class [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
- AMJQWGIYCROUQF-UHFFFAOYSA-N calcium;methanolate Chemical compound [Ca+2].[O-]C.[O-]C AMJQWGIYCROUQF-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 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
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910021515 thallium hydroxide Inorganic materials 0.000 description 1
- QGYXCSSUHCHXHB-UHFFFAOYSA-M thallium(i) hydroxide Chemical compound [OH-].[Tl+] QGYXCSSUHCHXHB-UHFFFAOYSA-M 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
【課題】紫外線による硬化感度が高い組成物、及び当該組成物を含む紫外線硬化型インクジェット用インクの提供。【解決手段】モノヒドロキシ環式アセタールと（メタ）アクリレートとのエステル交換反応による式（２）で表される環式アセタール（メタ）アクリレートを主成分とし、モノヒドロキシ環式アセタールを０．８モル％以下含む紫外線硬化型組成物。（Ｒ１はメチル基又はエチル基；Ｒ２はＨ、Ｃ１〜３のアルキル基又はＣ１〜３のハロゲン化アルキル基；Ｒ３はＨ又はメチル基）【選択図】なしA composition having high curing sensitivity by ultraviolet rays and an ultraviolet curable ink-jet ink containing the composition are provided. SOLUTION: The main component is a cyclic acetal (meth) acrylate represented by the formula (2) by transesterification of a monohydroxy cyclic acetal and (meth) acrylate, and 0.8 mol of the monohydroxy cyclic acetal. % UV curable composition containing at most%. (R1 is methyl group or ethyl group; R2 is H, C1-3 alkyl group or C1-3 halogenated alkyl group; R3 is H or methyl group) [Selection] None
Description
本発明は、環式アセタール（メタ）アクリレート組成物、及び当該環式アセタール（メタ）アクリレート組成物を含む紫外線硬化型インクジェット用インク、に関する。 The present invention relates to a cyclic acetal (meth) acrylate composition, and an ultraviolet curable inkjet ink containing the cyclic acetal (meth) acrylate composition.
紫外線硬化型インクジェット用インクに添加される紫外線重合性モノマーとしては、トリメチロールプロパン環式ホルマールアクリレートが使用されている。しかし、市販されているトリメチロールプロパン環式ホルマールアクリレートを含む組成物は、紫外線による硬化感度が低く、硬化するまでに時間がかかるという問題があった。 Trimethylolpropane cyclic formal acrylate is used as the ultraviolet polymerizable monomer added to the ultraviolet curable ink jet ink. However, a commercially available composition containing trimethylolpropane cyclic formal acrylate has a problem of low curing sensitivity by ultraviolet rays, and it takes time to cure.
前記トリメチロールプロパン環式ホルマールアクリレートを含む組成物の製造方法として、特許文献１には、モノヒドロキシ単環式アセタールを、触媒としてオルトチタン酸テトライソプロピルを使用して、アクリル酸、メタクリル酸およびアルキル基部分の炭素数１〜４のアルカン酸よりなる群から選ばれたエステル化用の酸のアルキルエステルとエステル交換反応させて、前記モノヒドロキシ単環式アセタールの相当するエステルを製造する方法が開示されている。 As a method for producing a composition containing the trimethylolpropane cyclic formal acrylate, Patent Document 1 discloses monohydroxy monocyclic acetal, tetraisopropyl orthotitanate as a catalyst, acrylic acid, methacrylic acid and alkyl. Disclosed is a method for producing a corresponding ester of the monohydroxy monocyclic acetal by transesterification with an alkyl ester of an esterifying acid selected from the group consisting of alkanoic acids having 1 to 4 carbon atoms in the base moiety. Has been.
本発明は、紫外線による硬化感度が高い環式アセタール（メタ）アクリレート組成物、及び当該環式アセタール（メタ）アクリレート組成物を含む紫外線硬化型インクジェット用インクを提供するものである。 The present invention provides a cyclic acetal (meth) acrylate composition having high curing sensitivity by ultraviolet rays, and an ultraviolet curable inkjet ink containing the cyclic acetal (meth) acrylate composition.
本発明は、下記一般式（１）で表されるモノヒドロキシ環式アセタールと（メタ）アクリレートとのエステル交換反応によって得られる下記一般式（２）で表される環式アセタール（メタ）アクリレートを主成分とする環式アセタール（メタ）アクリレート組成物であって、前記モノヒドロキシ環式アセタールの含有量が０．８モル％以下であることを特徴とする環式アセタール（メタ）アクリレート組成物、に関する。
（式中、Ｒ１はメチル基又はエチル基であり、Ｒ２は水素、炭素数１〜３のアルキル基、又は炭素数１〜３のハロゲン化アルキル基である。）
（式中、Ｒ１はメチル基又はエチル基であり、Ｒ２は水素、炭素数１〜３のアルキル基又は炭素数１〜３のハロゲン化アルキル基であり、Ｒ３は水素又はメチル基である。）
The present invention provides a cyclic acetal (meth) acrylate represented by the following general formula (2) obtained by a transesterification reaction between a monohydroxy cyclic acetal represented by the following general formula (1) and (meth) acrylate. A cyclic acetal (meth) acrylate composition comprising a main component as a cyclic acetal (meth) acrylate composition, wherein the monohydroxy cyclic acetal content is 0.8 mol% or less, About.
(In the formula, R 1 is a methyl group or an ethyl group, and R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms.)
(In the formula, R 1 is a methyl group or an ethyl group, R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms, and R 3 is hydrogen or a methyl group. is there.)
本発明者は、従来のトリメチロールプロパン環式ホルマールアクリレート組成物の硬化感度が低いのは、組成物中に含まれるトリメチロールプロパン環式ホルマールが原因ではないかと考えた。そして、鋭意検討を重ねた結果、上記一般式（１）で表されるモノヒドロキシ環式アセタール（以下、単にモノヒドロキシ環式アセタールともいう）と（メタ）アクリレートとのエステル交換反応によって得られる上記一般式（２）で表される環式アセタール（メタ）アクリレート（以下、単に環式アセタール（メタ）アクリレートともいう）を主成分とする環式アセタール（メタ）アクリレート組成物においては、モノヒドロキシ環式アセタールが、環式アセタール（メタ）アクリレート組成物の硬化感度を阻害することを見出した。 The present inventor thought that the low curing sensitivity of the conventional trimethylolpropane cyclic formal acrylate composition may be caused by the trimethylolpropane cyclic formal contained in the composition. And as a result of earnest examination, the said obtained by transesterification with the monohydroxy cyclic acetal (henceforth only a monohydroxy cyclic acetal) represented by the said General formula (1) and (meth) acrylate is obtained. In the cyclic acetal (meth) acrylate composition mainly composed of the cyclic acetal (meth) acrylate represented by the general formula (2) (hereinafter also simply referred to as cyclic acetal (meth) acrylate), a monohydroxy ring It has been found that the formula acetal inhibits the curing sensitivity of the cyclic acetal (meth) acrylate composition.
また、本発明者は、モノヒドロキシ環式アセタールの含有量が閾値である０．８モル％を超えると、環式アセタール（メタ）アクリレート組成物の硬化感度が低下し始めることを見出した。環式アセタール（メタ）アクリレート組成物中のモノヒドロキシ環式アセタールの含有量は少ないほど好ましいが、組成物中からモノヒドロキシ環式アセタールをできる限り除去しようとすると、多大な労力と長い作業時間が必要になるだけでなく、環式アセタール（メタ）アクリレート組成物の収率も大きく低下するというデメリットがある。本発明のように、環式アセタール（メタ）アクリレート組成物中のモノヒドロキシ環式アセタールの含有量が０．８モル％を超えないように調整すれば、硬化感度が高い環式アセタール（メタ）アクリレート組成物が得られるため、組成物中からモノヒドロキシ環式アセタールをできる限り除去する必要はない。そのため、本発明によれば、組成物中からモノヒドロキシ環式アセタールを除去する際の労力や作業時間を軽減できるだけでなく、収率よく環式アセタール（メタ）アクリレート組成物を得ることができる。 Further, the present inventor has found that the curing sensitivity of the cyclic acetal (meth) acrylate composition starts to decrease when the content of the monohydroxy cyclic acetal exceeds a threshold value of 0.8 mol%. The content of the monohydroxy cyclic acetal in the cyclic acetal (meth) acrylate composition is preferably as low as possible. However, if the monohydroxy cyclic acetal is to be removed from the composition as much as possible, a great amount of labor and a long working time are required. In addition to being required, there is a demerit that the yield of the cyclic acetal (meth) acrylate composition is also greatly reduced. If the content of the monohydroxy cyclic acetal in the cyclic acetal (meth) acrylate composition is adjusted so as not to exceed 0.8 mol% as in the present invention, the cyclic acetal (meth) having a high curing sensitivity. Since an acrylate composition is obtained, it is not necessary to remove as much monohydroxy cyclic acetal as possible from the composition. Therefore, according to the present invention, not only the labor and working time for removing the monohydroxy cyclic acetal from the composition can be reduced, but also the cyclic acetal (meth) acrylate composition can be obtained in a high yield.
なお、組成物中のモノヒドロキシ環式アセタールの含有量モル％は、組成物中の原料基質、主生成物である環式アセタール（メタ）アクリレート、及び副生成物の合計含有量を１００モル％としたときの含有量モル％である。 In addition, content mol% of monohydroxy cyclic acetal in a composition is 100 mol% in total content of the raw material substrate in a composition, cyclic acetal (meth) acrylate which is a main product, and a by-product. The content is mol%.
本発明においては、モノヒドロキシ環式アセタールが、トリメチロールプロパン環式ホルマールであることが好ましい。 In the present invention, the monohydroxy cyclic acetal is preferably trimethylolpropane cyclic formal.
また、紫外線による硬化感度を高めるために、環式アセタール（メタ）アクリレートの含有量は９９モル％以上であることが好ましい。 Moreover, in order to improve the curing sensitivity by ultraviolet rays, the content of cyclic acetal (meth) acrylate is preferably 99 mol% or more.
なお、組成物中の環式アセタール（メタ）アクリレートの含有量モル％は、組成物中の原料基質、主生成物である環式アセタール（メタ）アクリレート、及び副生成物の合計含有量を１００モル％としたときの含有量モル％である。 In addition, content mol% of the cyclic acetal (meth) acrylate in a composition is 100% of the total content of the raw material substrate in a composition, the cyclic acetal (meth) acrylate which is a main product, and a by-product. The content is mol% when the mol% is used.
また、本発明は、前記環式アセタール（メタ）アクリレート組成物を含む紫外線硬化型インクジェット用インク、に関する。 The present invention also relates to an ultraviolet curable inkjet ink comprising the cyclic acetal (meth) acrylate composition.
本発明の環式アセタール（メタ）アクリレート組成物は、従来のものに比べて紫外線による硬化感度が高く、硬化速度が大きいという特徴を有する。本発明の環式アセタール（メタ）アクリレート組成物は、特に紫外線硬化型インクジェット用インクに添加される紫外線重合性モノマーとして有用である。 The cyclic acetal (meth) acrylate composition of the present invention is characterized in that it has higher curing sensitivity by ultraviolet rays and a higher curing rate than conventional ones. The cyclic acetal (meth) acrylate composition of the present invention is particularly useful as an ultraviolet polymerizable monomer added to an ultraviolet curable inkjet ink.
本発明の環式アセタール（メタ）アクリレート組成物は、下記一般式（１）で表されるモノヒドロキシ環式アセタールと（メタ）アクリレートとのエステル交換反応によって得られる下記一般式（２）で表される環式アセタール（メタ）アクリレートを主成分として含み、モノヒドロキシ環式アセタールの含有量が０．８モル％以下である。
（式中、Ｒ１はメチル基又はエチル基であり、Ｒ２は水素、炭素数１〜３のアルキル基、又は炭素数１〜３のハロゲン化アルキル基である。）
（式中、Ｒ１はメチル基又はエチル基であり、Ｒ２は水素、炭素数１〜３のアルキル基又は炭素数１〜３のハロゲン化アルキル基であり、Ｒ３は水素又はメチル基である。）
The cyclic acetal (meth) acrylate composition of the present invention is represented by the following general formula (2) obtained by a transesterification reaction between a monohydroxy cyclic acetal represented by the following general formula (1) and (meth) acrylate. Cyclic acetal (meth) acrylate as a main component, and the content of monohydroxy cyclic acetal is 0.8 mol% or less.
(In the formula, R 1 is a methyl group or an ethyl group, and R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms.)
(In the formula, R 1 is a methyl group or an ethyl group, R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms, and R 3 is hydrogen or a methyl group. is there.)
モノヒドロキシ環式アセタールは、トリメチロールプロパン環式ホルマール（一般式（１）において、Ｒ１がエチル基、Ｒ２が水素）であることが好ましい。 The monohydroxy cyclic acetal is preferably trimethylolpropane cyclic formal (in the general formula (1), R 1 is an ethyl group and R 2 is hydrogen).
（メタ）アクリレートとは、アクリレート、メタクリレート、又はこれらの混合物を意味する。（メタ）アクリレートは特に制限されないが、炭素数１〜４のアルキル基を有するアルキル（メタ）アクリレートであることが好ましい。 (Meth) acrylate means acrylate, methacrylate, or a mixture thereof. The (meth) acrylate is not particularly limited, but is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms.
モノヒドロキシ環式アセタールと（メタ）アクリレートとのエステル交換反応は、公知の方法を採用できる。 A known method can be adopted for the transesterification reaction between the monohydroxy cyclic acetal and (meth) acrylate.
（メタ）アクリレートの使用量は特に制限されないが、モノヒドロキシ環式アセタール１モルあたり１．１〜３モルであることが好ましい。 The amount of (meth) acrylate used is not particularly limited, but is preferably 1.1 to 3 mol per mol of monohydroxy cyclic acetal.
エステル交換触媒は公知のものを特に制限なく使用することができ、具体的には、酸化カルシウム、酸化バリウム、酸化鉛、酸化亜鉛、酸化ジルコニウム等の酸化物；水酸化カリウム、水酸化ナトリウム、水酸化リチウム、水酸化カルシウム、水酸化タリウム、水酸化スズ、水酸化鉛、水酸化ニッケル等の水酸化物；塩化リチウム、塩化カルシウム、塩化スズ、塩化鉛、塩化ジルコニウム、塩化ニッケル等のハロゲン化物；炭酸カリウム、炭酸ルビジウム、炭酸セシウム、炭酸鉛、炭酸亜鉛、炭酸ニッケル等の炭酸塩；炭酸水素カリウム、炭酸水素ルビジウム、炭酸水素セシウム等の炭酸水素塩；リン酸ナトリウム、リン酸カリウム、リン酸ルビジウム、リン酸鉛、リン酸亜鉛、リン酸ニッケル等のリン酸塩；硝酸リチウム、硝酸カルシウム、硝酸鉛、硝酸亜鉛、硝酸ニッケル等の硝酸塩；酢酸リチウム、酢酸カルシウム、酢酸鉛、酢酸亜鉛、酢酸ニッケル等のカルボン酸塩；ナトリウムメトキシド、ナトリウムエトキシド、カリウムメトキシド、カリウムエトキシド、カリウムｔ−ブトキシド、カルシウムメトキシド、カルシウムエトキシド、バリウムメトキシド、バリウムエトキシド、テトラエトキシチタン、テトラブトキシチタン、テトラ（２−エチルヘキサノキシ）チタン等のアルコキシ化合物；リチウムアセチルアセトナート、ジルコニアアセチルアセトナート、亜鉛アセチルアセトナート、ジブトキシスズアセチルアセトナート、ジブトキシチタンアセチルアセトナート等のアセチルアセトナート錯体；テトラメチルアンモニウムメトキシド、テトラメチルアンモニウムｔ−ブトキシド、トリメチルベンジルアンモニウムエトキシド等の４級アンモニウムアルコキシド；ジメチルスズオキサイド、メチルブチルスズオキサイド、ジブチルスズオキサイド、ジオクチルスズオキサイド等のジアルキルスズ化合物；ビス（ジブチルスズアセテート）オキサイド、ビス（ジブチルスズラウレート）オキサイド等のジスタノキサン；ジブチルスズジアセテート、ジブチルスズジラウレート等のジアルキルスズジカルボン酸塩等が挙げられる。これらは、単独で用いてもよく２種類以上を併用してもよい。これらのうち、副生成物（高沸成分）の生成を抑制する観点からジブチルスズオキサイド、ジオクチルスズオキサイドを用いることが好ましい。 As the transesterification catalyst, known ones can be used without particular limitation. Specifically, oxides such as calcium oxide, barium oxide, lead oxide, zinc oxide, zirconium oxide; potassium hydroxide, sodium hydroxide, water Hydroxides such as lithium oxide, calcium hydroxide, thallium hydroxide, tin hydroxide, lead hydroxide, nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, nickel chloride; Carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, zinc carbonate, nickel carbonate; bicarbonates such as potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate; sodium phosphate, potassium phosphate, rubidium phosphate Phosphates such as lead phosphate, zinc phosphate, nickel phosphate; lithium nitrate, calcium nitrate Nitrates such as lead nitrate, zinc nitrate, nickel nitrate; carboxylates such as lithium acetate, calcium acetate, lead acetate, zinc acetate, nickel acetate; sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t -Alkoxy compounds such as butoxide, calcium methoxide, calcium ethoxide, barium methoxide, barium ethoxide, tetraethoxy titanium, tetrabutoxy titanium, tetra (2-ethylhexanoxy) titanium; lithium acetylacetonate, zirconia acetylacetate Acetylacetonate complexes such as narate, zinc acetylacetonate, dibutoxytin acetylacetonate, dibutoxytitanium acetylacetonate; tetramethylammonium methoxide, tetramethylammonium Quaternary ammonium alkoxides such as t-butoxide and trimethylbenzylammonium ethoxide; Dialkyltin compounds such as dimethyltin oxide, methylbutyltin oxide, dibutyltin oxide and dioctyltin oxide; bis (dibutyltin acetate) oxide, bis (dibutyltin laurate) oxide And distantin dicarboxylates such as dibutyltin diacetate and dibutyltin dilaurate. These may be used alone or in combination of two or more. Among these, it is preferable to use dibutyltin oxide and dioctyltin oxide from the viewpoint of suppressing generation of by-products (high boiling components).
エステル交換触媒の使用量は特に制限されないが、（メタ）アクリレート１モルあたり、０．０００１〜０．０１モルであることが好ましく、より好ましくは０．００２〜０．０１モルである。 Although the usage-amount of a transesterification catalyst is not restrict | limited in particular, It is preferable that it is 0.0001-0.01 mol per mol of (meth) acrylate, More preferably, it is 0.002-0.01 mol.
エステル交換反応は、（メタ）アクリレートが重合することを抑制する観点から、重合禁止剤（重合防止剤）の存在下で行うことが好ましい。 The transesterification reaction is preferably performed in the presence of a polymerization inhibitor (polymerization inhibitor) from the viewpoint of suppressing polymerization of (meth) acrylate.
重合禁止剤としては、例えば、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、４−アセトアミノ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、２，２，６，６−テトラメチルピペリジン−Ｎ−オキシルなどのＮ−オキシラジカル系化合物；４−メトキシフェノール、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−Ｎ，Ｎ−ジメチルアミノ−ｐ−クレゾール、２，４−ジメチル−６−ｔｅｒｔ−ブチルフェノール、４−ｔｅｒｔ−ブチルカテコール、４，４’−チオ−ビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−ブチリデン−ビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）などのフェノール系化合物；メトキノン、ハイドロキノン、２，５−ジ−ｔｅｒｔ−ブチルハイドロキノン、２，６−ジ−ｔｅｒｔ−ブチルハイドロキノン、ベンゾキノンなどのキノン系化合物；塩化第一銅；ジメチルジチオカルバミン酸銅などのジアルキルジチオカルバミン酸銅；フェノチアジン、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン、フェニル−β−ナフチルアミン，Ｎ，Ｎ’−ジ−β−ナフチル−ｐ−フェニレンジアミン、Ｎ−フェニル−Ｎ’−イソプロピル−ｐ−フェニレンジアミンなどのアミノ化合物；１，４−ジヒドロキシ−２，２，６，６−テトラメチルピペリジン、１−ヒドロキシ−２，２，６，６−テトラメチルピペリジン、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジンなどのヒドロキシアミン系化合物などが挙げられる。これらは、単独で用いてもよく２種類以上を併用してもよい。 Examples of the polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4- Benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine N-oxy radical compounds such as -N-oxyl; 4-methoxyphenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol 2,6-di-tert-butyl-N, N-dimethylamino-p-cresol, 2,4-dimethyl-6-tert-butylphenol, 4 phenolic compounds such as tert-butylcatechol, 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol); Quinone compounds such as methoquinone, hydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, benzoquinone; cuprous chloride; copper dialkyldithiocarbamate such as copper dimethyldithiocarbamate; phenothiazine N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, etc. Amino compounds; 1,4-dihydroxy-2 Examples include hydroxyamine compounds such as 2,6,6-tetramethylpiperidine, 1-hydroxy-2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine. It is done. These may be used alone or in combination of two or more.
重合禁止剤の使用量は特に制限されないが、（メタ）アクリレート１００重量部あたり０．００１〜５重量部であることが好ましく、より好ましくは０．００２〜０．０１重量部である。 The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 5 parts by weight, more preferably 0.002 to 0.01 parts by weight, per 100 parts by weight of (meth) acrylate.
エステル交換反応においては、有機溶媒を用いてもよい。 In the transesterification reaction, an organic solvent may be used.
有機溶媒は特に制限されないが、反応系内で不活性な有機溶媒であることが好ましい。有機溶媒としては、例えば、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタンなどの脂肪族炭化水素化合物；シクロヘキサン、メチルシクロヘキサンなどの脂環式炭化水素化合物；ベンゼン、トルエン、キシレンなどの芳香族炭化水素化合物；テトラヒドロフランなどのエーテル化合物；ジクロロメタン、１，１−ジクロロエタンなどの有機塩素化合物；ニトロベンゼンなどの芳香族ニトロ化合物；トリエチルホスフェートなどの有機リン化合物；ジメチルスルホキシドなどの有機硫黄化合物などが挙げられる。これらは、単独で用いてもよく２種類以上を併用してもよい。 The organic solvent is not particularly limited, but is preferably an inert organic solvent in the reaction system. Examples of the organic solvent include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, and n-octane; alicyclic hydrocarbon compounds such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene. Compounds: Ether compounds such as tetrahydrofuran; Organochlorine compounds such as dichloromethane and 1,1-dichloroethane; Aromatic nitro compounds such as nitrobenzene; Organophosphorus compounds such as triethyl phosphate; Organosulfur compounds such as dimethyl sulfoxide and the like. These may be used alone or in combination of two or more.
有機溶媒の使用量は特に制限されないが、通常、原料基質の合計量１００重量部あたり１〜１００重量部程度である。 The amount of the organic solvent used is not particularly limited, but is usually about 1 to 100 parts by weight per 100 parts by weight of the total amount of the raw material substrate.
エステル交換反応を行なう際の反応温度は特に制限されないが、反応速度を高める観点から、７０℃以上であることが好ましく、より好ましくは８０℃以上であり、生成物の重合を防止する観点から、１３０℃以下であることが好ましく、より好ましくは１１０℃以下である。 The reaction temperature during the transesterification reaction is not particularly limited, but from the viewpoint of increasing the reaction rate, it is preferably 70 ° C or higher, more preferably 80 ° C or higher, from the viewpoint of preventing polymerization of the product. It is preferable that it is 130 degrees C or less, More preferably, it is 110 degrees C or less.
エステル交換反応は、（メタ）アクリレートが重合することを抑制する観点から酸素を含有する雰囲気下で行うことが好ましい。また、雰囲気の圧力は、大気圧であってもよく、加圧又は減圧であってもよい。 The transesterification reaction is preferably performed in an atmosphere containing oxygen from the viewpoint of suppressing polymerization of (meth) acrylate. Moreover, atmospheric pressure may be atmospheric pressure, and pressurization or pressure reduction may be sufficient as it.
エステル交換反応の反応時間は、原料や反応温度などによって異なるので一概には決定できないが、通常、反応転換率が９９％以上になるまで行う。反応転換率は、例えば、ガスクロマトグラフィー、液体クロマトグラフィーなどによって確認できる。 The reaction time for the transesterification reaction varies depending on the raw materials and reaction temperature and cannot be determined unconditionally. However, it is usually carried out until the reaction conversion rate reaches 99% or more. The reaction conversion rate can be confirmed, for example, by gas chromatography, liquid chromatography or the like.
エステル交換反応は、例えば、精留塔、流動床、固定床、反応蒸留塔などを用いて行なうことかできる。また、流通式又は回分式のいずれの方式で行なってもよい。 The transesterification reaction can be performed using, for example, a rectification column, a fluidized bed, a fixed bed, a reactive distillation column, or the like. Moreover, you may carry out by any system of a circulation type or a batch type.
エステル交換反応の進行とともにアルコールが副生する。副生するアルコールは、反応を進行させるために反応系外に除去することが好ましい。 Alcohol is by-produced as the transesterification proceeds. The alcohol produced as a by-product is preferably removed from the reaction system in order to advance the reaction.
副生アルコールの除去方法としては、例えば、減圧下で反応を行う方法、共沸溶媒を用いて反応を行う方法、吸着剤の存在下で反応を行う方法などが挙げられる。これらの中で、共沸溶媒を用いて反応を行う方法が好ましい。 Examples of the method for removing the by-product alcohol include a method of performing the reaction under reduced pressure, a method of performing the reaction using an azeotropic solvent, and a method of performing the reaction in the presence of an adsorbent. Among these, a method of performing the reaction using an azeotropic solvent is preferable.
エステル交換反応の終了後、反応混合物から有機溶媒、未反応の原料、及び副生アルコールなどを精留により除去して、環式アセタール（メタ）アクリレートを主成分とし、モノヒドロキシ環式アセタールの含有量が０．８モル％以下である留分（環式アセタール（メタ）アクリレート組成物）を得る。 After completion of the transesterification reaction, organic solvent, unreacted raw materials, by-product alcohol, etc. are removed from the reaction mixture by rectification, and the main component is cyclic acetal (meth) acrylate, and monohydroxy cyclic acetal is contained. A fraction (cyclic acetal (meth) acrylate composition) having an amount of 0.8 mol% or less is obtained.
具体的には、反応混合物の精留は、精留塔を用いて行う。精留塔としては、充填塔を用いてもよく、棚段塔を用いてもよい。精留塔の理論段数は、有機溶媒、未反応の原料、及び副生アルコールの分離性の観点から３段以上であることが好ましい。また、還流比は、生産性及び分離性などを考慮して適宜調整することができるが、有機溶媒や副生アルコールを留出させる精留初期の還流比は０．１〜１であることが好ましく、未反応の原料を留出させる精留中期の還流比は１〜５であることが好ましく、目的物である環式アセタール（メタ）アクリレートを留出させる精留終期の還流比は０．１〜３であることが好ましい。また、精留時の減圧度は、例えば、有機溶媒や副生アルコールを留出させる精留初期の減圧度は４〜６０ｋＰａ程度であり、未反応の原料を留出させる精留中期の減圧度は０．３〜０．５ｋＰａ程度であり、目的物である環式アセタール（メタ）アクリレートを留出させる精留終期の減圧度は０．２〜０．３ｋＰａ程度である。また、精留時の温度は特に制限されないが、精留効率を上げるため、及び高沸成分の生成を抑制する観点から、１１０〜１３５℃程度である。 Specifically, the rectification of the reaction mixture is performed using a rectification column. As the rectifying column, a packed column may be used and a plate column may be used. The number of theoretical plates of the rectifying column is preferably 3 or more from the viewpoint of separability of the organic solvent, unreacted raw material, and by-product alcohol. In addition, the reflux ratio can be appropriately adjusted in consideration of productivity and separability, but the reflux ratio at the initial stage of rectification for distilling the organic solvent or by-product alcohol is 0.1 to 1. Preferably, the reflux ratio in the middle of rectification for distilling off the unreacted raw material is preferably 1 to 5, and the reflux ratio in the last stage of rectification for distilling the target cyclic acetal (meth) acrylate is 0.00. It is preferable that it is 1-3. The degree of vacuum during rectification is, for example, about 4 to 60 kPa in the initial stage of rectification for distilling out organic solvents and by-product alcohol, and the degree of vacuum in the middle of rectification for distilling out unreacted raw materials. Is about 0.3 to 0.5 kPa, and the degree of vacuum at the end of rectification for distilling the target cyclic acetal (meth) acrylate is about 0.2 to 0.3 kPa. The temperature during rectification is not particularly limited, but is about 110 to 135 ° C. from the viewpoint of increasing the rectification efficiency and suppressing the generation of high boiling components.
反応混合物を精留して得られる環式アセタール（メタ）アクリレート組成物は、環式アセタール（メタ）アクリレートを９９モル％以上で含有することが好ましい。また、環式アセタール（メタ）アクリレート組成物の収率は、８５％以上であることが好ましく、より好ましくは８８％以上であり、さらに好ましくは９０％以上であり、特に好ましくは９４％以上である。 The cyclic acetal (meth) acrylate composition obtained by rectifying the reaction mixture preferably contains 99 mol% or more of the cyclic acetal (meth) acrylate. The yield of the cyclic acetal (meth) acrylate composition is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 94% or more. is there.
本発明の環式アセタール（メタ）アクリレート組成物は、モノヒドロキシ環式アセタールの含有量が０．８モル％以下であり、従来のものに比べて紫外線による硬化感度が高く、硬化速度が大きいものである。 The cyclic acetal (meth) acrylate composition of the present invention has a monohydroxy cyclic acetal content of 0.8 mol% or less, and has a higher curing sensitivity by ultraviolet rays and a higher curing rate than the conventional one. It is.
以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で25時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率99.9%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が99%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率88.8%、粘度 10.0mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９９．９モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は０．１モル％であった。
Example 1
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g in a reaction kettle equipped with a rectifier equipped with a stirrer, thermometer, fractionation tower, and cooler , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The transesterification reaction was carried out under atmospheric pressure for 25 hours by heating to 0 ° C. and extracting methanol coming out from the top of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 99.9%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only the fraction having a target content of trimethylolpropane cyclic formal acrylate of 99% or more was obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 88.8%, a viscosity of 10.0 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 99.9 mol%, trimethylolpropane cyclic formal The content of (TMPCF) was 0.1 mol%.
実施例２
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で25時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率99.9%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が98.5%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率94.1%、粘度 10.0mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９９．７モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は０．３モル％であった。
Example 2
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g in a reaction kettle equipped with a rectifier equipped with a stirrer, thermometer, fractionation tower, and cooler , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The transesterification reaction was carried out under atmospheric pressure for 25 hours by heating to 0 ° C. and extracting methanol coming out from the top of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 99.9%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions with a target content of trimethylolpropane cyclic formal acrylate of 98.5% or more were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 94.1%, a viscosity of 10.0 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 99.7 mol%, and the trimethylolpropane cyclic formal was The content of (TMPCF) was 0.3 mol%.
実施例３
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で24時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率98%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が98.2%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率94.1%、粘度 10.0mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９９．５モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は０．５モル％であった。
Example 3
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g in a reaction kettle equipped with a rectifier equipped with a stirrer, thermometer, fractionation tower, and cooler , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The transesterification reaction was performed for 24 hours under atmospheric pressure by heating to 0 ° C. and extracting methanol coming out from the upper part of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 98%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions with a content of 98.2% or more of the target product, trimethylolpropane cyclic formal acrylate, were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 94.1%, a viscosity of 10.0 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 99.5 mol%, trimethylolpropane cyclic formal The content of (TMPCF) was 0.5 mol%.
実施例４
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で23時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率97.5%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が97.7%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率94.0%、粘度 10.0mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９９．２モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は０．８モル％であった。
Example 4
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g in a reaction kettle equipped with a rectifier equipped with a stirrer, thermometer, fractionation tower, and cooler , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The ester exchange reaction was carried out under atmospheric pressure for 23 hours by heating to 0 ° C. and extracting methanol coming out from the upper part of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 97.5%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions with a target content of trimethylolpropane cyclic formal acrylate of 97.7% or more were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 94.0%, a viscosity of 10.0 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 99.2 mol%, and trimethylolpropane cyclic formal. The content of (TMPCF) was 0.8 mol%.
比較例１
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で22時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率97%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が97.4%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率93.9%、粘度 10.1mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９９．０モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は１．０モル％であった。
Comparative Example 1
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g in a reaction kettle equipped with a rectifier equipped with a stirrer, thermometer, fractionation tower, and cooler , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The ester exchange reaction was carried out under atmospheric pressure for 22 hours by heating to 0 ° C. and extracting methanol coming out from the upper part of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 97%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions with a target content of 97.4% or more of the trimethylolpropane cyclic formal acrylate were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 93.9%, a viscosity of 10.1 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 99.0 mol%, and the trimethylolpropane cyclic formal was The content of (TMPCF) was 1.0 mol%.
比較例２
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で21時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率96.5%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が97%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率93.9%、粘度 10.2mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９８．８モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は１．２モル％であった。
Comparative Example 2
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g in a reaction kettle equipped with a rectifier equipped with a stirrer, thermometer, fractionation tower, and cooler , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The ester exchange reaction was carried out for 21 hours under atmospheric pressure by heating to 0 ° C. and extracting methanol coming out from the upper part of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 96.5%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only a fraction having a content of 97% or more of the target product, trimethylolpropane cyclic formal acrylate, was obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 93.9%, a viscosity of 10.2 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 98.8 mol%, trimethylolpropane cyclic formal The content of (TMPCF) was 1.2 mol%.
比較例３
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で20時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率95%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が96.5%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率93.8%、粘度 10.2mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９８．５モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は１．５モル％であった。
Comparative Example 3
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g in a reaction kettle equipped with a rectifier equipped with a stirrer, thermometer, fractionation tower, and cooler , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The transesterification reaction was carried out for 20 hours under atmospheric pressure by heating to 0 ° C. and extracting methanol coming out from the upper part of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 95%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions with a target content of 96.5% or more of the trimethylolpropane cyclic formal acrylate were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 93.8%, a viscosity of 10.2 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 98.5 mol%, trimethylolpropane cyclic formal. The content of (TMPCF) was 1.5 mol%.
比較例４
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で19時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率93%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が95%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率93.6%、粘度 10.5mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９７．０モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は３．０モル％であった。
Comparative Example 4
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The ester exchange reaction was performed for 19 hours under atmospheric pressure by heating to 0 ° C. and extracting methanol coming out from the top of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 93%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions with a content of 95% or more of the target product, trimethylolpropane cyclic formal acrylate, were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 93.6%, a viscosity of 10.5 mPa.s / 25 ° C., and a color number of APHA 7. As a result of GC analysis of the trimethylolpropane cyclic formal acrylate composition (measurement conditions will be described later), the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 97.0 mol%, trimethylolpropane cyclic formal The content of (TMPCF) was 3.0 mol%.
比較例５
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で18時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率92%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が93%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率93.4%、粘度 10.7mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９５．０モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は５．０モル％であった。
Comparative Example 5
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The ester exchange reaction was carried out for 18 hours under atmospheric pressure by heating to 0 ° C. and extracting methanol coming out from the upper part of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 92%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions having a content of 93% or more of the target product, trimethylolpropane cyclic formal acrylate, were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 93.4%, a viscosity of 10.7 mPa.s / 25 ° C., and a color number of APHA 7. As a result of GC analysis of the trimethylolpropane cyclic formal acrylate composition (measurement conditions will be described later), the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 95.0 mol%, trimethylolpropane cyclic formal. The content of (TMPCF) was 5.0 mol%.
比較例６
攪拌機、温度計、分留塔、冷却器を備える精留装置が配置された反応釜にトリメチロールプロパン環式ホルマール(TMPCF) 500g(3.42mol)とアクリル酸メチル 736g(8.55mol)、ノルマルヘキサン 80g、ジオクチル錫オキシド(触媒) 7.2g、重合禁止剤として4-メトキシフェノール(重合防止剤) 6.8gを仕込み、液中にエアーを5ml/min量で吹き込み、オイルバスにて反応液を75〜90℃まで加熱を行い、分留塔上部から出てくるメタノールを抜き出すエステル交換反応を大気圧下で18時間行った。反応液を一部抜き出しGC分析を行った結果、目的とするトリメチロールプロパン環式ホルマールアクリレート(TMPCFA)が反応転化率90%にて得られていることを確認した。次に減圧度を35kPaに設定し釜内温度を110℃まで加温し、分留塔上部より、ノルマルヘキサンを留去し、減圧度を徐々に280Paまで変更しアクリル酸メチルを留去後に、目的物であるトリメチロールプロパン環式ホルマールアクリレートの含量が91%以上の留分のみを取得した。結果としてトリメチロールプロパン環式ホルマールアクリレート組成物を収率92.8%、粘度 10.9mPa.s/25℃、色数APHA 7にて得た。トリメチロールプロパン環式ホルマールアクリレート組成物のGC分析（測定条件は後述する）を行った結果、トリメチロールプロパン環式ホルマールアクリレート(TMPCFA)の含有量は９３．０モル％、トリメチロールプロパン環式ホルマール(TMPCF)の含有量は７．０モル％であった。
Comparative Example 6
Trimethylolpropane cyclic formal (TMPCF) 500 g (3.42 mol), methyl acrylate 736 g (8.55 mol), normal hexane 80 g , Dioctyltin oxide (catalyst) 7.2g, 4-methoxyphenol (polymerization inhibitor) 6.8g as a polymerization inhibitor was charged, air was blown into the liquid at an amount of 5ml / min, and the reaction liquid was 75-90 in an oil bath. The ester exchange reaction was carried out for 18 hours under atmospheric pressure by heating to 0 ° C. and extracting methanol coming out from the upper part of the fractionation tower. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target trimethylolpropane cyclic formal acrylate (TMPCFA) was obtained at a reaction conversion rate of 90%. Next, the degree of vacuum was set to 35 kPa, the temperature in the kettle was heated to 110 ° C, normal hexane was distilled off from the upper part of the fractionation tower, the degree of vacuum was gradually changed to 280 Pa, and methyl acrylate was distilled off. Only fractions with a content of the trimethylolpropane cyclic formal acrylate, which was the target product, of 91% or more were obtained. As a result, a trimethylolpropane cyclic formal acrylate composition was obtained with a yield of 92.8%, a viscosity of 10.9 mPa.s / 25 ° C., and a color number of APHA 7. As a result of performing GC analysis (measurement conditions will be described later) of the trimethylolpropane cyclic formal acrylate composition, the content of trimethylolpropane cyclic formal acrylate (TMPCFA) was 93.0 mol%, trimethylolpropane cyclic formal. The content of (TMPCF) was 7.0 mol%.
〔測定方法〕
（硬化するまでの露光量の測定）
作製したトリメチロールプロパン環式ホルマールアクリレート組成物に、光重合開始剤として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サイド（チバ・スペシャリティ社製：ＤＡＲＯＣＵＲ ＴＰＯ）を、組成物と開始剤の総量に対して１０ｗｔ％を加え、スターラーで1時間撹拌して混合溶液を調合した。その後、洗浄処理を行ったガラス板上に、混合溶液をバーコーターＮＯ.１０を用いて塗布した。次に、アイグラフィックス社製のＵＶ露光機を用いて塗膜が硬化するまで露光を行い、硬化した時の露光量を測定した。
〔Measuring method〕
(Measurement of exposure until curing)
To the prepared trimethylolpropane cyclic formal acrylate composition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Specialty: DAROCUR TPO) as a photopolymerization initiator is added to the total amount of the composition and the initiator. On the other hand, 10 wt% was added and stirred with a stirrer for 1 hour to prepare a mixed solution. Thereafter, the mixed solution was applied onto the glass plate subjected to the cleaning treatment using a bar coater No. 10. Next, it exposed until the coating film hardened | cured using the UV exposure machine by an eye graphics company, and the exposure amount when it hardened was measured.
（ＧＣ分析の測定方法）
ＧＣ分析は、Agilent社製（６８５０型）を用いて、以下の測定条件で行った。
注入口は、ヒーター温度２８０℃、スプリット比５０：１、圧力５０ｋPaに設定した。検出器は、ＦＩＤを使用し、ヒーター温度２８０℃に設定した。ＧＣカラムは、Agilent社製のＨＰ−１（長さ30ｍ、内径０．３２ｍｍ、膜厚０．２５μｍ）を使用した。オーブンは、初期温度は７０℃で５分間保持し、その後毎分１０℃で昇温し、２８０℃に到達後１０分間保持した。打ち込み量は、０．２μｌとした。
(Measurement method of GC analysis)
The GC analysis was performed under the following measurement conditions using an Agilent (6850 type).
The inlet was set to a heater temperature of 280 ° C., a split ratio of 50: 1, and a pressure of 50 kPa. The detector used FID and set the heater temperature to 280 ° C. As the GC column, HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent was used. The oven was maintained at an initial temperature of 70 ° C. for 5 minutes, then heated at 10 ° C. per minute, and held for 10 minutes after reaching 280 ° C. The driving amount was 0.2 μl.
本発明の環式アセタール（メタ）アクリレート組成物は、紫外線硬化型インクジェット用インクに添加される紫外線重合性モノマーとして好適に用いられる。
The cyclic acetal (meth) acrylate composition of the present invention is suitably used as an ultraviolet polymerizable monomer added to an ultraviolet curable inkjet ink.
Claims (3)
（式中、Ｒ１はメチル基又はエチル基であり、Ｒ２は水素、炭素数１〜３のアルキル基、又は炭素数１〜３のハロゲン化アルキル基である。）
（式中、Ｒ１はメチル基又はエチル基であり、Ｒ２は水素、炭素数１〜３のアルキル基又は炭素数１〜３のハロゲン化アルキル基であり、Ｒ３は水素又はメチル基である。） The main component is a cyclic acetal (meth) acrylate represented by the following general formula (2) obtained by a transesterification reaction between a monohydroxy cyclic acetal represented by the following general formula (1) and (meth) acrylate. in a cyclic acetal (meth) acrylate compositions, the content of the monohydroxy cyclic acetal Ri der than 0.8 mol%, the content of the cyclic acetal (meth) acrylate is 99 mol% or more Oh cyclic acetal, wherein Rukoto (meth) acrylate composition.
(In the formula, R 1 is a methyl group or an ethyl group, and R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms.)
(In the formula, R 1 is a methyl group or an ethyl group, R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms, and R 3 is hydrogen or a methyl group. is there.)
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