JP6829958B2 - Cyclohexyl (meth) acrylate composition - Google Patents
Cyclohexyl (meth) acrylate composition Download PDFInfo
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- JP6829958B2 JP6829958B2 JP2016137101A JP2016137101A JP6829958B2 JP 6829958 B2 JP6829958 B2 JP 6829958B2 JP 2016137101 A JP2016137101 A JP 2016137101A JP 2016137101 A JP2016137101 A JP 2016137101A JP 6829958 B2 JP6829958 B2 JP 6829958B2
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- Prior art keywords
- meth
- acrylate
- cyclohexyl
- content
- mol
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 78
- 239000000203 mixture Substances 0.000 title claims description 66
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 title claims description 50
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 13
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 8
- -1 lead acetate Chemical compound 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 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 5
- 239000003112 inhibitor Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical group CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 238000004508 fractional distillation Methods 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
- 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
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 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
- XPEMPJFPRCHICU-UHFFFAOYSA-N (1-tert-butylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C(C)(C)C)CCCCC1 XPEMPJFPRCHICU-UHFFFAOYSA-N 0.000 description 1
- 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
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-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
- MOGAVOOFUGWHHE-UHFFFAOYSA-N 2,6-ditert-butyl-3-(dimethylamino)-4-methylphenol Chemical compound CN(C)C1=C(C)C=C(C(C)(C)C)C(O)=C1C(C)(C)C MOGAVOOFUGWHHE-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
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-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
- 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
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 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
- 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
- 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
- 229910019142 PO4 Inorganic materials 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
- 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- FVQARXYJIGSYRE-UHFFFAOYSA-N butyl-methyl-oxotin Chemical compound CCCC[Sn](C)=O FVQARXYJIGSYRE-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 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
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium 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
- 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 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
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 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
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-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
- 239000007788 liquid Substances 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
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 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
- 150000002823 nitrates Chemical class 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
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 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
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 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
- KBAHJOGZLVQNBH-UHFFFAOYSA-K rubidium(1+);phosphate Chemical compound [Rb+].[Rb+].[Rb+].[O-]P([O-])([O-])=O KBAHJOGZLVQNBH-UHFFFAOYSA-K 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium 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
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、シクロヘキシル（メタ）アクリレート組成物、及び当該シクロヘキシル（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、紫外線硬化型粘着剤、又は紫外線硬化型接着剤に関する。 The present invention relates to a cyclohexyl (meth) acrylate composition, and an ultraviolet curable inkjet ink containing the cyclohexyl (meth) acrylate composition, an ultraviolet curable pressure-sensitive adhesive, or an ultraviolet curable adhesive.
紫外線硬化型インクジェット用インク、紫外線硬化型粘着剤、又は紫外線硬化型接着剤に添加される紫外線重合性モノマーとして、脂環式炭化水素基を有するアクリレートが使用されている。 An acrylate having an alicyclic hydrocarbon group is used as an ultraviolet polymerizable monomer added to an ultraviolet curable inkjet ink, an ultraviolet curable pressure-sensitive adhesive, or an ultraviolet curable adhesive.
例えば、特許文献１には、（成分Ａ）Ｎ−ビニルカプロラクタム、（成分Ｂ）芳香環を有する単官能アクリレート、及び（成分Ｃ）脂肪族炭化水素環を有する単官能アクリレート等を含有するインクジェットインク組成物が開示されており、前記成分Ｃとして、例えば、３，３，５−トリメチルシクロヘキシルアクリレート及びｔ−ブチルシクロヘキシルアクリレートが記載されている。 For example, Patent Document 1 describes an inkjet ink containing (component A) N-vinylcaprolactam, (component B) a monofunctional acrylate having an aromatic ring, (component C) a monofunctional acrylate having an aliphatic hydrocarbon ring, and the like. The composition is disclosed, and as the component C, for example, 3,3,5-trimethylcyclohexyl acrylate and t-butylcyclohexyl acrylate are described.
しかし、市販されているシクロヘキシ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。 However, a commercially available composition containing cyclohexyl acrylate has a problem that it has low curing sensitivity due to ultraviolet rays and it takes time to cure.
本発明は、紫外線による硬化感度が高いシクロヘキシル（メタ）アクリレート組成物、及び当該シクロヘキシル（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、紫外線硬化型粘着剤、又は紫外線硬化型接着剤を提供するものである。 The present invention provides a cyclohexyl (meth) acrylate composition having high curing sensitivity by ultraviolet rays, and an ultraviolet curable inkjet ink containing the cyclohexyl (meth) acrylate composition, an ultraviolet curable pressure-sensitive adhesive, or an ultraviolet curable adhesive. It is something to do.
本発明は、下記一般式（１）で表されるシクロヘキシル（メタ）アクリレートを主成分とするシクロヘキシル（メタ）アクリレート組成物であって、
前記シクロヘキシル（メタ）アクリレートの原料である下記一般式（２）で表されるシクロヘキサノールの含有量が０．８モル％以下であることを特徴とするシクロヘキシル（メタ）アクリレート組成物、に関する。
（式中、Ｒ１は水素又はメチル基であり、Ｒ２〜Ｒ１１はそれぞれ独立に水素又は炭素数１〜４のアルキル基である。）
The present invention is a cyclohexyl (meth) acrylate composition containing a cyclohexyl (meth) acrylate as a main component represented by the following general formula (1).
The present invention relates to a cyclohexyl (meth) acrylate composition, wherein the content of cyclohexanol represented by the following general formula (2), which is a raw material of the cyclohexyl (meth) acrylate, is 0.8 mol% or less.
(In the formula, R 1 is a hydrogen or methyl group, and R 2 to R 11 are independently hydrogen or an alkyl group having 1 to 4 carbon atoms.)
通常、シクロヘキシル（メタ）アクリレート組成物は、シクロヘキサノールと（メタ）アクリレートとのエステル交換反応によって製造される。本発明者は、従来のシクロヘキシル（メタ）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シクロヘキサノ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（２）で表されるシクロヘキサノールと（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上記一般式（１）で表されるシクロヘキシル（メタ）アクリレートを主成分とするシクロヘキシル（メタ）アクリレート組成物においては、シクロヘキサノールが、シクロヘキシル（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。 Usually, the cyclohexyl (meth) acrylate composition is produced by a transesterification reaction between cyclohexanol and (meth) acrylate. The present inventor considered that the low curing sensitivity of the conventional cyclohexyl (meth) acrylate composition may be due to cyclohexanol contained in the composition. Then, as a result of repeated diligent studies, the cyclohexanol (meth) acrylate represented by the general formula (1) obtained by the transesterification reaction between cyclohexanol represented by the general formula (2) and the (meth) acrylate was obtained. In the cyclohexyl (meth) acrylate composition as a main component, cyclohexanol has been found to inhibit the curing sensitivity of the cyclohexyl (meth) acrylate composition.
また、本発明者は、シクロヘキサノールの含有量が閾値である０．８モル％を超えると、シクロヘキシル（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。シクロヘキシル（メタ）アクリレート組成物中のシクロヘキサノールの含有量は少ないほど好ましいが、組成物中からシクロヘキサノ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、シクロヘキシル（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、シクロヘキシル（メタ）アクリレート組成物中のシクロヘキサノールの含有量が０．８モル％を超えないように調整すれば、硬化感度が高いシクロヘキシル（メタ）アクリレート組成物が得られるため、組成物中からシクロヘキサノ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、組成物中からシクロヘキサノ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、収率よくシクロヘキシル（メタ）アクリレート組成物を得ることができる。 The present inventor has also found that when the content of cyclohexanol exceeds the threshold value of 0.8 mol%, the curing sensitivity of the cyclohexyl (meth) acrylate composition begins to decrease. The lower the content of cyclohexanol in the cyclohexanol (meth) acrylate composition, the better, but trying to remove cyclohexanol from the composition as much as possible requires not only a great deal of labor and a long working time, but also cyclohexanol. There is a demerit that the yield of the (meth) acrylate composition is also significantly reduced. If the content of cyclohexanol in the cyclohexanol (meth) acrylate composition is adjusted so as not to exceed 0.8 mol% as in the present invention, a cyclohexanol (meth) acrylate composition having high curing sensitivity can be obtained. , It is not necessary to remove cyclohexanol from the composition as much as possible. Therefore, according to the present invention, not only can the labor and working time for removing cyclohexanol from the composition be reduced, but also a cyclohexyl (meth) acrylate composition can be obtained in good yield.
なお、組成物中のシクロヘキサノールの含有量モル％は、組成物中の原料基質、主生成物であるシクロヘキシル（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。 The content of cyclohexanol in the composition in mol% is the content when the total content of the raw material substrate, the main product cyclohexanol (meth) acrylate, and the by-product in the composition is 100 mol%. The amount is mol%.
また、紫外線による硬化感度を高めるために、シクロヘキシル（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。 Further, in order to increase the curing sensitivity by ultraviolet rays, the content of cyclohexyl (meth) acrylate is preferably 99 mol% or more.
なお、組成物中のシクロヘキシル（メタ）アクリレートの含有量モル％は、組成物中の原料基質、主生成物であるシクロヘキシル（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。 The molar% of the cyclohexyl (meth) acrylate content in the composition was 100 mol%, which was the total content of the raw material substrate, the main product cyclohexyl (meth) acrylate, and the by-product in the composition. When the content is mol%.
また、本発明は、前記シクロヘキシル（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、紫外線硬化型粘着剤、又は紫外線硬化型接着剤に関する。 The present invention also relates to an ultraviolet curable inkjet ink containing the cyclohexyl (meth) acrylate composition, an ultraviolet curable pressure-sensitive adhesive, or an ultraviolet curable adhesive.
本発明のシクロヘキシル（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。本発明のシクロヘキシル（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、紫外線硬化型粘着剤、又は紫外線硬化型接着剤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 cyclohexyl (meth) acrylate composition of the present invention is characterized in that it has a higher curing sensitivity due to ultraviolet rays and a higher curing rate than conventional ones. The cyclohexyl (meth) acrylate composition of the present invention is particularly useful as an ultraviolet polymerizable monomer added to an ultraviolet curable inkjet ink, an ultraviolet curable pressure-sensitive adhesive, or an ultraviolet curable adhesive.
本発明のシクロヘキシル（メタ）アクリレート組成物は、下記一般式（１）で表されるシクロヘキシル（メタ）アクリレートを主成分としており、前記シクロヘキシル（メタ）アクリレートの原料である下記一般式（２）で表されるシクロヘキサノールの含有量（２種以上のシクロヘキサノールの含有する場合は合計含有量）が０．８モル％以下である。
（式中、Ｒ１は水素又はメチル基であり、Ｒ２〜Ｒ１１はそれぞれ独立に水素又は炭素数１〜４のアルキル基である。）
The cyclohexanol (meth) acrylate composition of the present invention contains cyclohexyl (meth) acrylate represented by the following general formula (1) as a main component, and is the raw material of the cyclohexyl (meth) acrylate according to the following general formula (2). The content of cyclohexanol represented (total content when two or more kinds of cyclohexanol are contained) is 0.8 mol% or less.
(In the formula, R 1 is a hydrogen or methyl group, and R 2 to R 11 are independently hydrogen or an alkyl group having 1 to 4 carbon atoms.)
前記シクロヘキシル（メタ）アクリレート組成物は、前記一般式（２）で表されるシクロヘキサノールと（メタ）アクリレートとのエステル交換反応によって製造される。（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。 The cyclohexyl (meth) acrylate composition is produced by a transesterification reaction between cyclohexanol represented by the general formula (2) and (meth) acrylate. (Meta) 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.
前記一般式（２）で表されるシクロヘキサノールのＲ２〜Ｒ１１は、それぞれ独立に水素又はメチル基であることが好ましく、具体的には、下記のシクロヘキサノールが挙げられる。これらは１種単独で用いてもよく、２種以上を併用してもよい。特に、式（２−１）で表される３，３，５−トリメチルシクロヘキサノールを用いることが好ましい。
R 2 to R 11 of the cyclohexanol represented by the general formula (2) are preferably hydrogen or methyl groups independently, and specific examples thereof include the following cyclohexanols. These may be used alone or in combination of two or more. In particular, it is preferable to use 3,3,5-trimethylcyclohexanol represented by the formula (2-1).
シクロヘキサノールと（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 cyclohexanol 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、シクロヘキサノール１モルあたり１．１〜３モルであることが好ましい。 The amount of the (meth) acrylate used is not particularly limited, but is preferably 1.1 to 1 mol per 1 mol of cyclohexanol.
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テトラエトキシチタン、テトラブトキシチタン、及びテトラ（２−エチルヘキサノキシ）チタン等のアルコキシチタンを用いることが好ましい。 Known ester exchange catalysts can be used without particular limitation. Specifically, oxides such as calcium oxide, barium oxide, lead oxide, zinc oxide and zirconium oxide; potassium hydroxide, sodium hydroxide and water. Hydroxides such as lithium oxide, calcium hydroxide, tallium hydroxide, tin hydroxide, lead hydroxide, nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, nickel chloride; Carbon dioxide such as potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, zinc carbonate, nickel carbonate; hydrogen carbonate such as potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate; sodium phosphate, potassium phosphate, rubidium phosphate , Phosphates such as lead phosphate, zinc phosphate, nickel phosphate; nitrates such as lithium nitrate, calcium nitrate, lead nitrate, zinc nitrate, nickel nitrate; lithium acetate, calcium acetate, lead acetate, zinc acetate, nickel acetate Oxides such as: sodium methoxydo, sodium ethoxide, potassium methoxydo, potassium ethoxide, potassium t-butoxide, calcium methoxyde, calcium ethoxide, barium methoxyde, barium ethoxyde, tetraethoxytitanium, tetrabutoxytitanium. , Tetra (2-ethylhexanoxy) titanium and other alkoxy compounds; lithium acetylacetonate, zirconia acetylacetonate, zinc acetylacetonate, dibutoxytin acetylacetonate, dibutoxytitanium acetylacetonate and other acetylacetonate complexes. Tertiary ammonium alkoxides such as tetramethylammonium methoxyde, tetramethylammonium t-butoxide, trimethylbenzylammonium ethoxide; dialkyltin compounds such as dimethyltin oxide, methylbutyltin oxide, dibutyltin oxide, dioctyltin oxide; bis (dibutyltin acetate) ) Oxide, distanoxane such as bis (dibutyltin laurate) oxide; dialkyltin dicarboxylate such as dibutyltin diacetate and dibutyltin dilaurate. These may be used alone or in combination of two or more. Of these, alkoxy titanium such as tetraethoxytitanium, tetrabutoxytitanium, and tetra (2-ethylhexanoxy) titanium is preferably used from the viewpoint of suppressing the formation 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。 The amount of the transesterification catalyst used is not particularly limited, but is preferably 0.0001 to 0.01 mol, more preferably 0.002 to 0.01 mol, per 1 mol of the (meth) acrylate.
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 carried out in the presence of a polymerization inhibitor (polymerization inhibitor) from the viewpoint of suppressing the polymerization of the (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-tert-butylcatechol, 4,4'-thio-bis ( Phenolic compounds such as 3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol); methquinone, hydroquinone, 2,5-di-tert-butylhydroquinone. , 2,6-di-tert-butylhydroquinone, quinone compounds such as benzoquinone; cuprous chloride; copper dialkyldithiocarbamate such as copper dimethyldithiocarbamate; phenothiazine, N, N'-diphenyl-p-phenylenediamine, phenyl Amino compounds such as -β-naphthylamine, N, N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine; 1,4-dihydroxy-2,2,6 , 6-Tetramethylpiperidin, 1-hydroxy-2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine and other hydroxyamine-based compounds. 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０．００２〜０．１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 0.1 parts by weight, per 100 parts by weight of the (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 organic solvent that is inert 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; organic chlorine compounds such as dichloromethane and 1,1-dichloroethane; aromatic nitro compounds such as nitrobenzene; organic phosphorus compounds such as triethyl phosphate; organic sulfur compounds such as dimethyl sulfoxide. 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 when the transesterification reaction is carried out is not particularly limited, but is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of increasing the reaction rate, and from the viewpoint of preventing polymerization of the product. The temperature is preferably 130 ° C. or lower, more preferably 110 ° C. or lower.
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 carried out in an oxygen-containing atmosphere from the viewpoint of suppressing the polymerization of the (meth) acrylate. Further, the pressure of the atmosphere may be atmospheric pressure, pressurization or depressurization.
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 of the transesterification reaction varies depending on the raw material, the reaction temperature, and the like and cannot be unconditionally determined, but is usually carried out until the reaction conversion rate reaches 99% or more. The reaction conversion rate can be confirmed by, for example, 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 carried out by using, for example, a rectification column, a fluidized bed, a fixed bed, a reaction distillation column or the like. Further, it may be carried out by either a distribution method or a batch method.
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 by-produces as the transesterification reaction progresses. By-produced alcohol is preferably removed from the reaction system in order to allow the reaction to proceed.
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 carrying out the reaction under reduced pressure, a method of carrying out the reaction using an azeotropic solvent, and a method of carrying out the reaction in the presence of an adsorbent. Among these, a method of carrying out 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、シクロヘキシル（メタ）アクリレートを主成分とし、シクロヘキサノールの含有量が０．８モル％以下である留分（シクロヘキシル（メタ）アクリレート組成物）を得る。 After the transesterification reaction is completed, the organic solvent, unreacted raw material, by-product alcohol, etc. are removed from the reaction mixture by rectification, and cyclohexanol (meth) acrylate is the main component, and the cyclohexanol content is 0.8. A fraction (cyclohexyl (meth) acrylate composition) of 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、目的物であるシクロヘキシル（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０．３〜０．６ｋＰａ程度であり、目的物であるシクロヘキシル（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、９５〜１２０℃程度である。 Specifically, the rectification of the reaction mixture is carried out using a rectification column. As the rectification tower, a filling tower may be used, or a shelf column may be used. The number of theoretical plates of the rectification column is preferably 3 or more from the viewpoint of separability of the organic solvent, the unreacted raw material, and the by-product alcohol. The reflux ratio can be appropriately adjusted in consideration of productivity, separability, etc., but the reflux ratio at the initial stage of rectification for distilling an organic solvent or by-product alcohol is 0.1 to 1. Preferably, the reflux ratio in the middle stage of rectification for distilling the unreacted raw material is preferably 1 to 5, and the reflux ratio in the final stage of rectification for distilling the target cyclohexyl (meth) acrylate is 0.1 to 1. It is preferably 3. The degree of decompression during rectification is, for example, about 4 to 60 kPa at the initial stage of rectification in which an organic solvent or by-product alcohol is distilled, and the degree of decompression in the middle stage of rectification in which unreacted raw materials are distilled. Is about 0.3 to 0.6 kPa, and the degree of decompression at the final stage of rectification for distilling the target cyclohexyl (meth) acrylate is about 0.2 to 0.3 kPa. The temperature at the time of rectification is not particularly limited, but is about 95 to 120 ° C. from the viewpoint of increasing the rectification efficiency and suppressing the formation of high boiling components.
反応混合物を精留して得られるシクロヘキシル（メタ）アクリレート組成物は、シクロヘキシル（メタ）アクリレートを９９モル％以上含有することが好ましい。また、シクロヘキシル（メタ）アクリレートの収率は、７０％以上であることが好ましく、より好ましくは７５％以上であり、さらに好ましくは８０％以上であり、特に好ましくは８５％以上である。 The cyclohexyl (meth) acrylate composition obtained by rectifying the reaction mixture preferably contains 99 mol% or more of cyclohexyl (meth) acrylate. The yield of cyclohexyl (meth) acrylate is preferably 70% or more, more preferably 75% or more, further preferably 80% or more, and particularly preferably 85% or more.
本発明のシクロヘキシル（メタ）アクリレート組成物は、シクロヘキサノールの含有量が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 cyclohexanol (meth) acrylate composition of the present invention has a cyclohexanol content of 0.8 mol% or less, has a higher curing sensitivity with ultraviolet rays than the conventional one, and has a high curing rate.
本発明の紫外線硬化型インクジェット用インク、紫外線硬化型粘着剤、又は紫外線硬化型接着剤は、少なくとも前記シクロヘキシル（メタ）アクリレート組成物を含むものであり、公知の他の成分を任意に含んでいてもよい。 The ultraviolet-curable inkjet ink, the ultraviolet-curable pressure-sensitive adhesive, or the ultraviolet-curable adhesive of the present invention contains at least the cyclohexyl (meth) acrylate composition, and optionally contains other known components. May be good.
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。 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３，３，５−トリメチルシクロヘキサノール（ＴＭＣＨ）３５０ｇ（２．４６ｍｏｌ）とアクリル酸メチル４２４ｇ（４．９２ｍｏｌ）、ノルマルヘキサン３５ｇ、テトラメトキシチタン（触媒）０．８５ｇ、重合防止剤として４−メトキシフェノール０．４８ｇとＮ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン（セイコーケミカル社製、オゾノン６Ｃ）０．４８ｇを仕込み、液中にエアーを３ｍｌ／ｍｉｎ量で吹き込み、オイルバスにて反応液を９０〜９６℃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１３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３，３，５−トリメチルシクロヘキシルアクリレート（ＴＭＣＨＡ）が反応転化率９９．７％で得られていることを確認した。次に減圧度を２７ｋＰａに設定し釜内温度を１１０℃まで加温して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４００Ｐａまで変更してアクリル酸メチルを留去し、その後、目的物であるＴＭＣＨＡの含量が９９．０％以上の留分のみを取得した。結果としてＴＭＣＨＡ組成物を収率７８％で得た。ＴＭＣＨＡ組成物のＧＣ分析（測定条件は後述する）を行った結果、ＴＭＣＨＡの含有量は９９．６モル％、ＴＭＣＨの含有量は０．０７モル％であった。
Example 1
350 g (2.46 mol) of 3,3,5-trimethylcyclohexanol (TMCH) and 424 g (4.92 mol) of methyl acrylate in a reaction vessel equipped with a rectifying device equipped with a stirrer, a thermometer, a fractional column, and a cooler. ), Normal hexane 35 g, tetramethoxytitanium (catalyst) 0.85 g, 4-methoxyphenol 0.48 g as a polymerization inhibitor and N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Seiko) 0.48 g of Ozonon 6C) manufactured by Chemical Co., Ltd. is charged, air is blown into the liquid at a rate of 3 ml / min, the reaction liquid is heated to 90 to 96 ° C. in an oil bath, and methanol comes out from the upper part of the fractional distillation tower. The transesterification reaction was carried out under atmospheric pressure for 13 hours. As a result of extracting a part of the reaction solution and performing GC analysis, it was confirmed that the target 3,3,5-trimethylcyclohexylacrylate (TMCHA) was obtained with a reaction conversion rate of 99.7%. Next, the degree of decompression was set to 27 kPa, the temperature inside the kettle was heated to 110 ° C., normal hexane was distilled off from the upper part of the fractional distillation tower, the degree of pressure reduction was gradually changed to 400 Pa, and methyl acrylate was distilled off. Then, only a fraction having a content of TMCHA, which is the target product, of 99.0% or more was obtained. As a result, the TMCHA composition was obtained in a yield of 78%. As a result of performing GC analysis of the TMCHA composition (measurement conditions will be described later), the content of TMCHA was 99.6 mol% and the content of TMCH was 0.07 mol%.
実施例２
実施例１において、目的物であるＴＭＣＨＡの含量が９８．５％以上の留分のみを取得した以外は実施例１と同様の方法でＴＭＣＨＡ組成物を収率７９％で得た。ＴＭＣＨＡ組成物のＧＣ分析（測定条件は後述する）を行った結果、ＴＭＣＨＡの含有量は９９．５モル％、ＴＭＣＨの含有量は０．０８モル％であった。
Example 2
In Example 1, a TMCHA composition was obtained in a yield of 79% in the same manner as in Example 1 except that only a fraction having a target TMCHA content of 98.5% or more was obtained. As a result of performing GC analysis of the TMCHA composition (measurement conditions will be described later), the content of TMCHA was 99.5 mol% and the content of TMCH was 0.08 mol%.
実施例３
実施例１において、目的物であるＴＭＣＨＡの含量が９２．０％以上の留分のみを取得した以外は実施例１と同様の方法でＴＭＣＨＡ組成物を収率８７％で得た。ＴＭＣＨＡ組成物のＧＣ分析（測定条件は後述する）を行った結果、ＴＭＣＨＡの含有量は９９．３モル％、ＴＭＣＨの含有量は０．３６モル％であった。
Example 3
In Example 1, a TMCHA composition was obtained in a yield of 87% by the same method as in Example 1 except that only a fraction having a TMCHA content of 92.0% or more, which was the target product, was obtained. As a result of performing GC analysis (measurement conditions will be described later) of the TMCHA composition, the content of TMCHA was 99.3 mol% and the content of TMCH was 0.36 mol%.
実施例４
実施例１において、目的物であるＴＭＣＨＡの含量が７８．０％以上の留分のみを取得した以外は実施例１と同様の方法でＴＭＣＨＡ組成物を収率８９％で得た。ＴＭＣＨＡ組成物のＧＣ分析（測定条件は後述する）を行った結果、ＴＭＣＨＡの含有量は９８．９モル％、ＴＭＣＨの含有量は０．８０モル％であった。
Example 4
In Example 1, a TMCHA composition was obtained in a yield of 89% in the same manner as in Example 1 except that only a fraction having a TMCHA content of 78.0% or more, which was the target product, was obtained. As a result of performing GC analysis (measurement conditions will be described later) of the TMCHA composition, the content of TMCHA was 98.9 mol% and the content of TMCH was 0.80 mol%.
比較例１
実施例１において、目的物であるＴＭＣＨＡの含量が７８．０％以上かつ９９．８％以下の留分のみを取得した以外は実施例１と同様の方法でＴＭＣＨＡ組成物を収率７２％で得た。ＴＭＣＨＡ組成物のＧＣ分析（測定条件は後述する）を行った結果、ＴＭＣＨＡの含有量は９８．７モル％、ＴＭＣＨの含有量は０．９５モル％であった。
Comparative Example 1
In Example 1, the TMCHA composition was obtained in a yield of 72% by the same method as in Example 1 except that only a fraction having a target TMCHA content of 78.0% or more and 99.8% or less was obtained. Obtained. As a result of performing GC analysis (measurement conditions will be described later) of the TMCHA composition, the content of TMCHA was 98.7 mol% and the content of TMCH was 0.95 mol%.
比較例２
実施例１において、目的物であるＴＭＣＨＡの含量が７８．０％以上かつ９９．６％以下の留分のみを取得した以外は実施例１と同様の方法でＴＭＣＨＡ組成物を収率４４％で得た。ＴＭＣＨＡ組成物のＧＣ分析（測定条件は後述する）を行った結果、ＴＭＣＨＡの含有量は９８．１モル％、ＴＭＣＨの含有量は１．５６モル％であった。
Comparative Example 2
In Example 1, the TMCHA composition was obtained in a yield of 44% in the same manner as in Example 1 except that only a fraction having a target TMCHA content of 78.0% or more and 99.6% or less was obtained. Obtained. As a result of GC analysis of the TMCHA composition (measurement conditions will be described later), the TMCHA content was 98.1 mol% and the TMCH content was 1.56 mol%.
比較例３
実施例１において、目的物であるＴＭＣＨＡの含量が７８．０％以上かつ９９．５％以下の留分のみを取得した以外は実施例１と同様の方法でＴＭＣＨＡ組成物を収率３３％で得た。ＴＭＣＨＡ組成物のＧＣ分析（測定条件は後述する）を行った結果、ＴＭＣＨＡの含有量は９７．７モル％、ＴＭＣＨの含有量は２．０７モル％であった。
Comparative Example 3
In Example 1, the TMCHA composition was obtained in a yield of 33% in the same manner as in Example 1 except that only a fraction having a target TMCHA content of 78.0% or more and 99.5% or less was obtained. Obtained. As a result of performing GC analysis (measurement conditions will be described later) of the TMCHA composition, the content of TMCHA was 97.7 mol% and the content of TMCH was 2.07 mol%.
〔測定方法〕
（硬化するまでの露光量の測定）
作製したＴＭＣＨＡ組成物に、光重合開始剤として２−ヒドロキシ−２−メチルプロピオフェノン（チバ・スペシャリティ社製、ＤＡＲＯＣＵＲ１１７３）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５分間撹拌して混合溶液を調合した。その後、ＰＥＴ基板上に、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 TMCHA composition, add 2-hydroxy-2-methylpropiophenone (manufactured by Ciba Specialty Co., Ltd., DAROCUR1173) as a photopolymerization initiator in an amount of 10 wt% based on the total amount of the composition and the initiator, and use a stirrer. The mixed solution was prepared by stirring for 5 minutes. Then, the mixed solution was applied onto the PET substrate using the bar coater No. 10. Next, exposure was performed using a UV exposure machine manufactured by Eye Graphics until the coating film was cured, and the exposure amount at the time of curing 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３００℃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２０℃で昇温し、３００℃に到達後３．５分間保持した。打ち込み量は、０．２μｌとした。
(Measurement method for GC analysis)
The GC analysis was performed using an Agilent (6850 type) under the following measurement conditions.
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 the heater temperature was set to 300 ° 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 held at an initial temperature of 70 ° C. for 5 minutes, then warmed at 20 ° C. per minute, and held for 3.5 minutes after reaching 300 ° C. The driving amount was 0.2 μl.
本発明のシクロヘキシル（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、紫外線硬化型粘着剤、又は紫外線硬化型接着剤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 cyclohexyl (meth) acrylate composition of the present invention is suitably used as an ultraviolet polymerizable monomer added to an ultraviolet curable inkjet ink, an ultraviolet curable pressure-sensitive adhesive, or an ultraviolet curable adhesive.
Claims (6)
前記シクロヘキシル（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用いられるものであり、
前記シクロヘキシル（メタ）アクリレートの含有量が９９モル％以上であり、
前記シクロヘキシル（メタ）アクリレートの原料である下記一般式（２−１）〜（２−４）で表されるシクロヘキサノールの含有量（２種以上の前記シクロヘキサノールを含有する場合は合計含有量）が０．８モル％以下であることを特徴とするシクロヘキシル（メタ）アクリレート組成物。
The cyclohexyl (meth) acrylate composition is used for an ultraviolet curable inkjet ink.
The content of the cyclohexyl (meth) acrylate is 99 mol% or more, and the content is 99 mol% or more.
The content of cyclohexanol represented by the following general formulas (2-1) to (2-4), which is the raw material of the cyclohexyl (meth) acrylate (total content when two or more of the cyclohexanols are contained). A cyclohexanol (meth) acrylate composition, which comprises 0.8 mol% or less.
前記シクロヘキシル（メタ）アクリレート組成物は、紫外線硬化型粘着剤に用いられるものであり、The cyclohexyl (meth) acrylate composition is used for an ultraviolet curable pressure-sensitive adhesive.
前記シクロヘキシル（メタ）アクリレートの含有量が９９モル％以上であり、The content of the cyclohexyl (meth) acrylate is 99 mol% or more, and the content is 99 mol% or more.
前記シクロヘキシル（メタ）アクリレートの原料である下記一般式（２−１）〜（２−４）で表されるシクロヘキサノールの含有量（２種以上の前記シクロヘキサノールを含有する場合は合計含有量）が０．８モル％以下であることを特徴とするシクロヘキシル（メタ）アクリレート組成物。The content of cyclohexanol represented by the following general formulas (2-1) to (2-4), which is the raw material of the cyclohexyl (meth) acrylate (total content when two or more of the cyclohexanols are contained). A cyclohexanol (meth) acrylate composition, which comprises 0.8 mol% or less.
前記シクロヘキシル（メタ）アクリレート組成物は、紫外線硬化型接着剤に用いられるものであり、The cyclohexyl (meth) acrylate composition is used for an ultraviolet curable adhesive.
前記シクロヘキシル（メタ）アクリレートの含有量が９９モル％以上であり、The content of the cyclohexyl (meth) acrylate is 99 mol% or more, and the content is 99 mol% or more.
前記シクロヘキシル（メタ）アクリレートの原料である下記一般式（２−１）〜（２−４）で表されるシクロヘキサノールの含有量（２種以上の前記シクロヘキサノールを含有する場合は合計含有量）が０．８モル％以下であることを特徴とするシクロヘキシル（メタ）アクリレート組成物。The content of cyclohexanol represented by the following general formulas (2-1) to (2-4), which is the raw material of the cyclohexyl (meth) acrylate (total content when two or more of the cyclohexanols are contained). A cyclohexanol (meth) acrylate composition, which comprises 0.8 mol% or less.
An ultraviolet curable adhesive containing the cyclohexyl (meth) acrylate composition according to claim 3 .
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