JP2018087315A - Cationic surfactant, method for producing the same and application thereof - Google Patents
Cationic surfactant, method for producing the same and application thereof Download PDFInfo
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- JP2018087315A JP2018087315A JP2017123552A JP2017123552A JP2018087315A JP 2018087315 A JP2018087315 A JP 2018087315A JP 2017123552 A JP2017123552 A JP 2017123552A JP 2017123552 A JP2017123552 A JP 2017123552A JP 2018087315 A JP2018087315 A JP 2018087315A
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- carbon atoms
- group
- cationic surfactant
- alkyl
- alkenyl
- Prior art date
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- 239000003093 cationic surfactant Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 239000011342 resin composition Substances 0.000 claims abstract description 20
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 5
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 4
- -1 amine compound Chemical class 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 29
- 239000013067 intermediate product Substances 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 21
- 238000005956 quaternization reaction Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 abstract description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 abstract 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 47
- 238000002360 preparation method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 12
- 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 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000002216 antistatic agent Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 5
- QXONIHMUSQFKJU-UHFFFAOYSA-N 2-(prop-1-enoxymethyl)oxirane Chemical compound CC=COCC1CO1 QXONIHMUSQFKJU-UHFFFAOYSA-N 0.000 description 5
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical group C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LJQFHDUFUVMPSP-UHFFFAOYSA-N 8-methylnonan-1-amine Chemical compound CC(C)CCCCCCCN LJQFHDUFUVMPSP-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000033999 Device damage Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N NC1CCCC1 Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006622 cycloheptylmethyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000006623 cyclooctylmethyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical group CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
Description
本発明はカチオン性界面活性剤に関し、特に、帯電防止性及び防曇・防露性を向上させることができるカチオン性界面活性剤、その製造方法及びその応用に関する。 The present invention relates to a cationic surfactant, and more particularly to a cationic surfactant capable of improving antistatic properties and antifogging / dewproof properties, a production method thereof, and an application thereof.
生活の質を重視する傾向が高まるにつれ、従来の電子製品は軽量・薄型化し、それに従って電子製品内部の光電素子がより小型化している。しかしながら、光電素子の体積が縮小するにつれ、その使用環境に対する要求も厳しくなっている。 As the tendency toward emphasizing the quality of life has increased, conventional electronic products have become lighter and thinner, and the photoelectric elements inside the electronic products have become smaller accordingly. However, as the volume of the photoelectric element is reduced, the requirements for the usage environment are becoming stricter.
光電素子が高温多湿の環境に使用される場合、水蒸気が素子表面に凝結しやすく、その機能に影響を及ぼし、ひいては素子損傷を引き起こす。特に、表示領域において、水蒸気がディスプレイの表示に影響を及ぼし、その機能を低下させる。 When the photoelectric device is used in a hot and humid environment, water vapor is likely to condense on the device surface, affecting its function and eventually causing device damage. In particular, in the display area, water vapor affects the display on the display, reducing its function.
次に、光電素子では主に電荷の伝導が素子の効率に影響するので、安定な電界環境は光電素子の性能の向上に寄与する。しかしながら、日常生活で発生する静電気が常に光電素子に影響を及ぼす。静電気は瞬間的に放電するが、高電圧を有するため、小型化の光電素子に対して常に極大の損傷を引き起こす。 Next, in the photoelectric element, charge conduction mainly affects the efficiency of the element, so that a stable electric field environment contributes to improvement of the performance of the photoelectric element. However, static electricity generated in daily life always affects the photoelectric element. Although static electricity is instantaneously discharged, since it has a high voltage, it always causes maximum damage to a miniaturized photoelectric device.
前記水蒸気又は静電気の光電素子に対する損傷を効果的に除去するために、光電素子の表面は防曇・防露材料又は帯電防止材料を設置することにより水蒸気の凝結を避けるか又は静電気を除去し、光電素子に対する損傷を避ける。 In order to effectively remove damage to the water vapor or static electricity photoelectric element, the surface of the photoelectric element avoids condensation of water vapor by removing anti-fogging / dew condensation material or antistatic material, or removes static electricity, Avoid damage to the photoelectric element.
一般に、上記の防曇・防露材料又は帯電防止材料は界面活性剤（例えば防曇・防露剤又は帯電防止剤等）を含む複合膜であってよく、これにより前記の効果を有する。 In general, the anti-fogging / dew-proofing material or antistatic material may be a composite film containing a surfactant (for example, an anti-fogging / dew-proofing agent or an antistatic agent), thereby having the above-described effects.
しかしながら、従来の防曇・防露剤又は帯電防止剤は物理的方法のみで保護膜の樹脂材料と均一に混合され、このため、環境温度湿度の変化又は時間の経過に従って、防曇・防露剤又は帯電防止剤は複合膜の表面に移動（マイグレーション：ｍｉｇｒａｔｉｏｎ）し、その防曇・防露性又は帯電防止効能を低下させる。 However, the conventional anti-fogging / dew-proofing agent or antistatic agent is uniformly mixed with the resin material of the protective film only by a physical method. The agent or antistatic agent migrates to the surface of the composite film (migration), and reduces its anti-fogging / dew-proofing property or antistatic effect.
次に、表面に移動した防曇・防露剤又は帯電防止剤はさらに複合膜表面のアフタータック（ａｆｔｅｒ−ｔａｃｋ）を引き起こし、その表面特性を低下させる。 Next, the anti-fogging / dew proofing agent or antistatic agent that has moved to the surface further causes after-tack on the surface of the composite membrane, thereby reducing its surface properties.
この点に鑑みれば、従来のカチオン性界面活性剤、その製造方法及びその応用の欠点を改良するためのカチオン性界面活性剤、その製造方法及びその応用を提供することは急務である。 In view of this point, it is an urgent need to provide a conventional cationic surfactant, a production method thereof and a cationic surfactant for improving the drawbacks of the application, a production method thereof and an application thereof.
このため、本発明の一様態は、反応物を利用することにより、特定な構造を有するとともに良好な帯電防止性及び防曇・防露性を有するカチオン性界面活性剤を製造する。 For this reason, according to one embodiment of the present invention, a cationic surfactant having a specific structure and good antistatic properties and antifogging / dewproofing properties is produced by utilizing a reactant.
本発明の他の一様態は、製造されたカチオン界面活性剤が前記の特定な構造を有するカチオン界面活性剤の製造方法を提供することにある。 Another aspect of the present invention is to provide a method for producing a cationic surfactant in which the produced cationic surfactant has the specific structure.
本発明の別の一様態は、前記のカチオン界面活性剤を含む光硬化性樹脂組成物を提供することにある。 Another aspect of the present invention is to provide a photocurable resin composition containing the cationic surfactant.
本発明の別の一様態は、前記光硬化性樹脂組成物で製造された光硬化膜からなる複合膜を提供することにある。 Another aspect of the present invention is to provide a composite film composed of a photocured film produced from the photocurable resin composition.
本発明の一様態によれば、下式（Ｉ）に示す構造を有するカチオン界面活性剤を提供する。
式（Ｉ）において、Ｒ１は炭素数が１〜３０のアルキル、炭素数が２〜３０のオレフィン基又は炭素数が３〜３０のシクロアルカン基を表し、Ｒ２は炭素数が１〜４のアルキル、アルキルアルコール基、アルカノイル基又はアルキルフェニルを表し、Ｒ３は炭素数が１〜５のアルキル、炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は−ＯＲ４を表し、Ｒ４は炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は
In Formula (I), R 1 represents an alkyl having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms, or a cycloalkane group having 3 to 30 carbon atoms, and R 2 has 1 to 4 carbon atoms. R 3 is alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, alkynyl having 2 to 5 carbons, aromatic group, alkyl Represents an aromatic group, an alkenyl aromatic group, or —OR 4 , wherein R 4 is alkenyl having 2 to 5 carbon atoms, alkynyl having 2 to 5 carbon atoms, aromatic group, alkyl aromatic group, alkenyl aromatic group, or
本発明の一実施例によれば、前記のアニオン親水基はＦ−、Ｃｌ−、Ｂｒ−、Ｉ−、（ＳＯ２ＣＦ３）２Ｎ−又は
を含み、且つＲ６はメチル又はエチルを表す。
According to one embodiment of the present invention, the anionic hydrophilic group is F − , Cl − , Br − , I − , (SO 2 CF 3 ) 2 N − or
And R 6 represents methyl or ethyl.
本発明の別の一様態によれば、カチオン性界面活性剤の製造方法を提供する。この方法は、まず混合物に対して前反応を行うことにより、中間生成物を形成し、この前反応は第１反応を含み、且つこの混合物は下式（Ｉ−１）に示すアミン化合物及び下式（Ｉ−２）に示すエポキシ化合物を含む。
Ｒ１−ＮＨ２ （Ｉ−１）
式（Ｉ−１）において、Ｒ１は炭素数が１〜３０のアルキル、炭素数が２〜３０のオレフィン基又は炭素数が３〜３０シクロアルカン基を表し、
式（Ｉ−２）において、Ｒ３は炭素数が１〜５のアルキル、炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は−ＯＲ４を表し、Ｒ４は炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は
R 1 —NH 2 (I-1)
In the formula (I-1), R1 represents an alkyl having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms, or a cycloalkane group having 3 to 30 carbon atoms,
In the formula (I-2), R 3 is alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, alkynyl having 2 to 5 carbons, aromatic group, alkyl aromatic group, alkenyl aromatic. represents a group or -OR 4, R 4 is alkenyl having 2 to 5 carbon atoms, alkynyl number of 2 to 5 carbon atoms, an aromatic group, an alkyl aromatic group, an alkenyl aromatic group, or
その後、前記得られた中間生成物及び下式（Ｉ−３）に示す化合物に対して四級化反応を行うと、カチオン性界面活性剤を製造することができる。このカチオン性界面活性剤は前記の構造を有し、且つｎ及びｍはそれぞれ０を表し、
Ｒ２−Ａ （Ｉ−３）
式（Ｉ−３）において、Ｒ２は炭素数が１〜４のアルキル、アルキルアルコール基、アルカノイル基又はアルキルフェニルを表し、且つＡは親水基である。
Then, when a quaternization reaction is performed on the obtained intermediate product and the compound represented by the following formula (I-3), a cationic surfactant can be produced. This cationic surfactant has the above structure, and n and m each represents 0,
R 2 -A (I-3)
In the formula (I-3), R 2 represents an alkyl having 1 to 4 carbon atoms, an alkyl alcohol group, an alkanoyl group or an alkylphenyl, and A is a hydrophilic group.
本発明の一実施例によれば、前記の第１反応を行った後、この前反応は第１反応の生成物及び炭素数が２〜４のエポキシアルキル化合物に対して第２反応を行うことを更に含む。 According to one embodiment of the present invention, after performing the first reaction, the pre-reaction is performed on the product of the first reaction and the epoxyalkyl compound having 2 to 4 carbon atoms. Is further included.
本発明の他の一実施例によれば、前記製造方法で製造されたカチオン性界面活性剤は前記の構造を有し、ｎ及びｍはそれぞれ０〜１００の整数を表し、且つｎとｍの和が０より大きい。 According to another embodiment of the present invention, the cationic surfactant produced by the production method has the above structure, n and m each represent an integer of 0 to 100, and n and m The sum is greater than zero.
本発明の別の一実施例によれば、前記の親水基はハロゲン原子、（ＳＯ２ＣＦ３）２Ｎ−又は
を含み、Ｒ６はメチル又はエチルを表し、且つ「＊」は結合位置を表す。
According to another embodiment of the present invention, the hydrophilic group is a halogen atom, (SO 2 CF 3 ) 2 N— or
R 6 represents methyl or ethyl, and “*” represents a bonding position.
本発明の別の一様態によれば、光硬化性樹脂組成物を提出する。この光硬化性樹脂組成物は光硬化可能な樹脂材料（Ｐｈｏｔｏｃｕｒａｂｌｅ ｒｅｓｉｎ ｍａｔｅｒｉａｌ）と前記のカチオン性界面活性剤とを含む。光硬化可能な樹脂材料１００重量部に対して、カチオン性界面活性剤の使用量は０．５重量部〜３０重量部である。 According to another aspect of the present invention, a photocurable resin composition is submitted. This photocurable resin composition contains a photocurable resin material (Photocurable resin material) and the above-mentioned cationic surfactant. The amount of the cationic surfactant used is 0.5 to 30 parts by weight with respect to 100 parts by weight of the photocurable resin material.
本発明の別の一様態によれば、複合膜を提出する。この複合膜は基材と光硬化膜とを含み、且つ、この光硬化膜は、前記の光硬化性樹脂組成物が光硬化プロセスによって形成されたものであり、基材の表面上に設けられ、且つ水に対する接触角が５０度を超えない。 According to another aspect of the invention, a composite membrane is submitted. The composite film includes a base material and a photocured film, and the photocured film is formed by photocuring process of the photocurable resin composition, and is provided on the surface of the base material. And the contact angle with respect to water does not exceed 50 degrees.
本発明の一実施例によれば、前記単位面積あたりの複合膜の第１インピーダンス値は１０１１オームより小さい。 According to an embodiment of the present invention, the first impedance value of the composite membrane per unit area is less than 10 11 ohms.
本発明の他の一実施例によれば、前記の複合膜を高温多湿環境に置いた後の、単位面積あたりの複合膜の第２インピーダンス値は１０１１オームより小さく、且つこの第２インピーダンス値と第１インピーダンス値の比は５０より小さく０より大きい。 According to another embodiment of the present invention, the second impedance value of the composite membrane per unit area is less than 10 11 ohms after the composite membrane is placed in a high temperature and humidity environment, and the second impedance value. And the ratio of the first impedance value is less than 50 and greater than 0.
本発明が応用されたカチオン性界面活性剤、その製造方法及びその応用は、カチオン性界面活性剤の不飽和基及び樹脂材料によって化学結合を形成し、良好な経時安定性を有する。 The cationic surfactant to which the present invention is applied, its production method and its application form a chemical bond with the unsaturated group of the cationic surfactant and the resin material, and have good stability over time.
本発明の実施例及びその利点をより完全に理解するために、以下の説明を参照して対応する図面を合わせる。強調する必要があるのは、各種の特徴は割合に従って描画されず、ただ例示のみを目的とすることである。関連図面の内容は以下のように説明する。
以下、本発明の実施例の製造及び使用を慎重に検討する。しかしながら、理解すべきことは、実施例は複数の応用可能な発明概念を提供し、様々な特定な内容に実施されることができる。検討された特定な実施例は説明するためのもののみであり、本発明の範囲を限定するためのものではない。 In the following, the manufacture and use of embodiments of the present invention will be carefully considered. However, it should be understood that the embodiments provide multiple applicable inventive concepts and can be implemented in a variety of specific contexts. The specific embodiments discussed are for illustrative purposes only and are not intended to limit the scope of the present invention.
本発明に呼ばれたアフタータック（ａｆｔｅｒ−ｔａｃｋ）とは、温度及び湿度、又は防曇・防露剤や帯電防止剤の複合膜の表面への移動（ｍｉｇｒａｔｉｏｎ）によるコーティングの表面粘着欠点により、コーティングの表面に汚染物を粘着しやすく、又はその表面の平坦度を低下させ、更にコーティングの表面特性を低下させる。 The after-tack referred to in the present invention is the temperature and humidity, or the surface adhesion defect of the coating due to migration of the anti-fogging / dew-proofing agent or antistatic agent to the surface of the composite film, It tends to stick contaminants to the surface of the coating, or reduces the flatness of the surface, further reducing the surface properties of the coating.
図１を参照されたい。図１は本発明の一実施例のカチオン性界面活性剤の製造方法のフローチャートである。一実施例において、ステップ１１０に示すように、この製造方法は、まず混合物を提供する。この混合物は下式（Ｉ−１）に示すアミン化合物及び下式（Ｉ−２）に示すエポキシ化合物を含む。
Ｒ１−ＮＨ２ （Ｉ−１）
式（Ｉ−１）において、Ｒ１は炭素数が１〜３０のアルキル、炭素数が２〜３０のオレフィン基又は炭素数が３〜３０のシクロアルカン基を表す。
Please refer to FIG. FIG. 1 is a flowchart of a method for producing a cationic surfactant according to one embodiment of the present invention. In one embodiment, as shown in
R 1 —NH 2 (I-1)
In the formula (I-1), R 1 represents an alkyl having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms, or a cycloalkane group having 3 to 30 carbon atoms.
式（Ｉ−１）において、Ｒ１は置換もしくは無置換の直鎖状基又は分岐鎖状基であってよい。一実施例において、Ｒ１は炭素数が１〜３０のアルキルを表す場合、Ｒ１はメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、エイコシル、ヘニコシル、ベヘニル、トリコシル、テトラコシル、ペンタデシル、イソペンチル、イソヘキシル、イソヘプチル、イソオクチル、イソノニル、イソデシル、イソウンデシル、イソドデシル、イソトリデシル、イソテトラデシル、イソペンタデシル、イソヘキサデシル、イソヘプタデシル、イソオクタデシル、エチルヘキシル、エチルヘプチル、エチルオクチル、エチルノニル、エチルデシル、プロピルヘキシル、プロピルヘプチル、プロピルオクチル、プロピルノニル、プロピルデシル、ブチルヘキシル、ブチルヘプチル、ブチルオクチル、ブチルノニル、ブチルデシル、第二級ヘキシル、第二級ヘプチル、第二級オクチル、第二級ノニル、第二級デシル、第二級ウンデシル、第二級ドデシル、第二級トリデシル、第二級テトラデシル、第二級ペンタデシル又は第二級ヘキサデシル等を含むがこれらに限定されない。Ｒ１は炭素数が２〜３０のオレフィン基を表す場合、Ｒ１はプロペニル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセン、ドデセニル、トリデセニル、テトラデセニル、ペンタデセニル、ヘキサデセニル、ヘプタデセニル又はオクタデセニル等を含むがこれらに限定されない。Ｒ１は炭素数が３〜３０のシクロアルカン基を表す場合、Ｒ１はシクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロペンチルメチル、シクロペンチルエチル、シクロペンチルプロピル、シクロペンチルブチル、シクロヘキシルメチル、シクロヘキシルエチル、シクロヘキシルプロピル、シクロヘキシルブチル、シクロヘプチルメチル、シクロヘプチルエチル、シクロヘプチルプロピル、シクロヘプチルブチル、シクロオクチルメチル、シクロオクチルエチル、シクロオクチルプロピル又はシクロオクチルブチル等を含むがこれらに限定されない。 In the formula (I-1), R 1 may be a substituted or unsubstituted linear group or branched chain group. In one embodiment, when R 1 represents alkyl having 1 to 30 carbon atoms, R 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl , Pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, behenyl, tricosyl, tetracosyl, pentadecyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, pentadecyl Hexadecyl, isoheptadecyl, isooctadecyl, ethylhexyl, ethylheptyl, ethyloctyl, ethylnonyl, ethyldecyl, propylhexyl, propiyl Heptyl, propyloctyl, propylnonyl, propyldecyl, butylhexyl, butylheptyl, butyloctyl, butylnonyl, butyldecyl, secondary hexyl, secondary heptyl, secondary octyl, secondary nonyl, secondary decyl, primary Examples include, but are not limited to, secondary undecyl, secondary dodecyl, secondary tridecyl, secondary tetradecyl, secondary pentadecyl or secondary hexadecyl. When R 1 represents an olefin group having 2 to 30 carbon atoms, R 1 is propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecene, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl or octadecenyl Including, but not limited to. When R 1 represents a cycloalkane group having 3 to 30 carbon atoms, R 1 is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl , Cyclohexylbutyl, cycloheptylmethyl, cycloheptylethyl, cycloheptylpropyl, cycloheptylbutyl, cyclooctylmethyl, cyclooctylethyl, cyclooctylpropyl, cyclooctylbutyl, and the like.
好ましくは、Ｒ１は炭素数が６〜２５のアルキル、炭素数が６〜２５のオレフィン基又は炭素数が６〜２５のシクロアルカン基を表す。上記式（Ｉ−１）に示すアミン化合物は単独に１種を使用するか又は複数種を混合して使用することができる。 Preferably, R 1 represents an alkyl having 6 to 25 carbon atoms, an olefin group having 6 to 25 carbon atoms, or a cycloalkane group having 6 to 25 carbon atoms. The amine compound shown by the said formula (I-1) can be used individually by 1 type or in mixture of multiple types.
式（Ｉ−２）において、Ｒ３は置換もしくは無置換の直鎖状基又は分岐鎖状基であってよい。一実施例において、Ｒ３の具体的な例は、好ましくは、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ペンチル、イソペンチル、ビニール、プロペニル、ブテニル、ペンテニル、エチニル、プロピニル、ブチニル、ペンチニル、フェニル、フェニルメチル、フェニルエチル、フェニルプロピル、ナフチル、ナフチルメチル、ナフチルエチル、ナフチルプロピル、ビフェニル、スチレン化フェニル、スチリル又はメチルスチリル等を含むがこれらに限定されない。式（Ｉ−２）に示すエポキシ化合物は単独に１種を使用するか又は複数種を混合して使用することができる。 In the formula (I-2), R 3 may be a substituted or unsubstituted linear group or branched chain group. In one example, specific examples of R 3 are preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, vinyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl, pentynyl, phenyl , Phenylmethyl, phenylethyl, phenylpropyl, naphthyl, naphthylmethyl, naphthylethyl, naphthylpropyl, biphenyl, styrenated phenyl, styryl, methylstyryl and the like. The epoxy compound shown to a formula (I-2) can be used individually by 1 type or can be used in mixture of multiple types.
その後、ステップ１２０に示すように、前記の混合物に対して前反応を行い、これにより中間生成物を形成する。前反応は第１反応を含むことができ、且つ製造された中間生成物は下式（Ｉ−４−１）に示す構造を有する。
式（Ｉ−１）に示すアミン化合物の総使用量１モルに対して、式（Ｉ−２）に示すエポキシ化合物の使用量は０．５モル〜４．０モルであってよく、好ましくは１．０モル〜３．０モルであり、より好ましくは１．５モル〜２．５モルである。 The usage amount of the epoxy compound represented by the formula (I-2) may be 0.5 mol to 4.0 mol with respect to 1 mol of the total usage amount of the amine compound represented by the formula (I-1), preferably It is 1.0 mol-3.0 mol, More preferably, it is 1.5 mol-2.5 mol.
一実施例において、第１反応の反応温度は７０℃〜１５０℃であってよく、好ましくは８０℃〜１４０℃であり、より好ましくは９０℃〜１２０℃である。第１反応の反応時間は２時間〜８時間であってよく、好ましくは２時間〜６時間であり、より好ましくは３時間〜５時間である。 In one example, the reaction temperature of the first reaction may be 70 ° C to 150 ° C, preferably 80 ° C to 140 ° C, more preferably 90 ° C to 120 ° C. The reaction time of the first reaction may be 2 hours to 8 hours, preferably 2 hours to 6 hours, and more preferably 3 hours to 5 hours.
ステップ１２０を行った後、ステップ１３０及びステップ１４０に示すように、前記の中間生成物及び下式（Ｉ−３）に示す化合物に対して四級化反応を行うと、下式（Ｉ´
−１）に示すカチオン界面活性剤を製造することができる。
After performing
The cationic surfactant shown to -1) can be manufactured.
Ｒ２−Ａ （Ｉ−３）
式（Ｉ−３）において、Ｒ２は炭素数が１〜４のアルキル、アルキルアルコール基、アルカノイル基又はアルキルフェニルを表し、且つＡは親水基である。
R 2 -A (I-3)
In the formula (I-3), R 2 represents an alkyl having 1 to 4 carbon atoms, an alkyl alcohol group, an alkanoyl group or an alkylphenyl, and A is a hydrophilic group.
式（Ｉ−３）において、Ｒ２は置換もしくは無置換の直鎖状基又は分岐鎖状基であってよい。一実施例において、Ｒ２は炭素数が１〜４のアルキルを表す場合、Ｒ２はメチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第三ブチルを含むがこれらに限定されない。Ｒ２はアルキルアルコール基を表す場合、Ｒ２はメタノール基、エタノール基、プロパノール基、ブタノール基、イソプロパノール基、イソブタノール基等を含むがこれらに限定されない。Ｒ２はアルカノイル基を表す場合、Ｒ２はアセチル基、プロピオニル基、ブチリル基等を含むがこれらに限定されない。Ｒ２はアルキルフェニルを表す場合、フェニルに結合されたアルキルは炭素数が１〜３の直鎖アルキル又は分岐鎖アルキルであってよく、且つＲ２はベンジル、フェニルエチル、フェニルプロピル又はフェニルブチル等を含むがこれらに限定されない。 In the formula (I-3), R 2 may be a substituted or unsubstituted linear group or branched chain group. In one embodiment, when R 2 represents alkyl having 1 to 4 carbon atoms, R 2 includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl. When R 2 represents an alkyl alcohol group, R 2 includes, but is not limited to, a methanol group, an ethanol group, a propanol group, a butanol group, an isopropanol group, an isobutanol group, and the like. When R 2 represents an alkanoyl group, R 2 includes, but is not limited to, an acetyl group, a propionyl group, a butyryl group, and the like. When R 2 represents alkylphenyl, the alkyl bonded to phenyl may be linear or branched alkyl having 1 to 3 carbon atoms, and R 2 is benzyl, phenylethyl, phenylpropyl, phenylbutyl, etc. Including, but not limited to.
式（Ｉ−３）における親水基はハロゲン原子、（ＳＯ２ＣＦ３）２Ｎ−、
前記の四級化反応を行う場合、式（Ｉ−３）に示す化合物の−Ｒ２基は中間生成物の窒素原子と結合して、第四級アンモニウム塩を生成し、本発明のカチオン性界面活性剤を製造する。 When the quaternization reaction is performed, the —R 2 group of the compound represented by the formula (I-3) is bonded to the nitrogen atom of the intermediate product to form a quaternary ammonium salt, and the cationic property of the present invention. A surfactant is produced.
一実施例において、前記中間生成物の総使用量１モルに対して式（Ｉ−３）に示す化合物の使用量は０．３モル〜２．０モルであってよく、好ましくは０．５モル〜１．５モルであり、より好ましくは０．６モル〜１．２モルである。 In one embodiment, the amount of the compound represented by formula (I-3) used may be 0.3 mol to 2.0 mol, preferably 0.5 mol, relative to 1 mol of the total amount of the intermediate product used. It is mol-1.5 mol, More preferably, it is 0.6 mol-1.2 mol.
前記四級化反応の反応温度は４０℃〜９０℃であってよく、好ましくは５０℃〜８０℃であり、より好ましくは６０℃〜７０℃である。四級化反応の反応時間は１時間〜５時間であってよく、好ましくは１．５時間〜４．５時間で、より好ましくは２時間〜４時間である。 The reaction temperature of the quaternization reaction may be 40 ° C to 90 ° C, preferably 50 ° C to 80 ° C, more preferably 60 ° C to 70 ° C. The reaction time of the quaternization reaction may be 1 hour to 5 hours, preferably 1.5 hours to 4.5 hours, more preferably 2 hours to 4 hours.
式（Ｉ´−１）において、Ｒ１、Ｒ２及びＲ３の定義はそれぞれ前述の通りであり、ここで繰り返して説明しない。Ａ−はアニオン親水基である。Ｒ１、Ｒ２及びＲ３の中の少なくとも一方は不飽和基を有する。
In formula (I′-1), the definitions of R 1 , R 2 and R 3 are as described above, and will not be repeated here. A - is an anion hydrophilic group. At least one of R 1 , R 2 and R 3 has an unsaturated group.
一実施例において、前記の前反応は第１反応の生成物及び炭素数が２〜４のエポキシアルキル化合物に対して第２反応を行うステップを選択的に含み、下式（Ｉ−４−２）に示す構造を有する中間生成物を製造する。
式（Ｉ−４−２）において、Ｒ１及びＲ３の定義はそれぞれ前述の通りであり、ここで繰り返して説明しない。Ｙ１及びＹ２はそれぞれ炭素数が２〜４のアルキリデンを表し、ｎ及びｍはそれぞれ０〜１００の整数を表し、且つｎとｍの和が０より大きい。
In one embodiment, the pre-reaction selectively includes a step of performing the second reaction on the product of the first reaction and the epoxyalkyl compound having 2 to 4 carbon atoms. An intermediate product having the structure shown in FIG.
In formula (I-4-2), the definitions of R 1 and R 3 are as described above, and will not be repeated here. Y 1 and Y 2 each represent an alkylidene having 2 to 4 carbon atoms, n and m each represent an integer of 0 to 100, and the sum of n and m is greater than 0.
一実施例において、ｎ及びｍは、好ましくは０〜５０の整数を表し、より好ましくは０〜３０の整数を表す。 In one Example, n and m preferably represent an integer of 0 to 50, more preferably an integer of 0 to 30.
ｎとｍの和は０より大きい場合、−Ｏ−Ｙ１−及び／又は−Ｏ−Ｙ２−セグメントにより製造されたカチオン性界面活性剤は親水性、防曇・防露性及び帯電防止性の効果を有する。 When the sum of n and m is greater than 0, the cationic surfactant produced by —O—Y 1 — and / or —O—Y 2 — segments is hydrophilic, anti-fogging / dew proof and antistatic It has the effect of.
ｎとｍの和は、好ましくは５〜５０であり、より好ましくは５〜３０である。 The sum of n and m is preferably 5 to 50, more preferably 5 to 30.
ｎとｍの和は５〜３０である場合、製造されたカチオン性剤界面活性剤はより良い親水性、防曇・防露性及び帯電防止性を有する。 When the sum of n and m is 5 to 30, the produced cationic surfactant has better hydrophilicity, antifogging / dewproofing property and antistatic property.
第１反応の生成物の総使用量１モルに対して、前記炭素数が２〜４のエポキシアルキル化合物の使用量は２．０モル〜５０．０モルであってよく、好ましくは５．０モル〜４０．０モルであり、より好ましくは５．０モル〜３０．０モルである。 The usage amount of the epoxy alkyl compound having 2 to 4 carbon atoms may be 2.0 mol to 50.0 mol, preferably 5.0 mol, with respect to 1 mol of the total usage amount of the product of the first reaction. It is mol-40.0 mol, More preferably, it is 5.0 mol-30.0 mol.
この実施例において、前記製造された中間生成物［式（Ｉ−４−２）に示す］と前記式（Ｉ−３）に示す化合物とは、さらに四級化反応を行うことができ、下式（Ｉ´−２）に示すカチオン性界面活性剤を製造する。
式（Ｉ´−２）において、Ｒ１、Ｒ２、Ｒ３、Ｙ１、Ｙ２、Ａ−、ｎ及びｍの定義はそれぞれ前述の通りであり、ここで繰り返して説明しない。Ｒ１、Ｒ２及びＲ３の中の少なくとも一方は不飽和基を有する。
In this example, the produced intermediate product [shown in formula (I-4-2)] and the compound shown in formula (I-3) can be further subjected to quaternization reaction. A cationic surfactant represented by the formula (I′-2) is produced.
In formula (I′-2), the definitions of R 1 , R 2 , R 3 , Y 1 , Y 2 , A − , n and m are as described above, and will not be repeated here. At least one of R 1 , R 2 and R 3 has an unsaturated group.
同様に、四級化反応を行う場合、式（Ｉ−３）に示す化合物の−Ｒ２基は中間生成物の窒素原子と結合して、第四級アンモニウム塩を生成し、本発明のカチオン性界面活性剤を製造する。 Similarly, when the quaternization reaction is performed, the —R 2 group of the compound represented by the formula (I-3) is bonded to the nitrogen atom of the intermediate product to form a quaternary ammonium salt, and the cation of the present invention. A surfactant is produced.
式（Ｉ−４−２）に示す中間生成物の総使用量１モルに対して、式（Ｉ−３）に示す化合物の使用量は０．３モル〜２．０モルであってよく、好ましくは０．５モル〜１．５モルであり、より好ましくは０．６モル〜１．２モルである。 The amount of the compound represented by the formula (I-3) used may be 0.3 mol to 2.0 mol with respect to 1 mol of the total amount of the intermediate product represented by the formula (I-4-2). Preferably it is 0.5 mol-1.5 mol, More preferably, it is 0.6 mol-1.2 mol.
この実施例において、四級化反応の反応パラメータ（例えば反応温度及び反応時間等）は前記ステップ１３０に記載の四級化反応の反応パラメータと同一であるか又は同一ではないようにすることができる。
In this embodiment, the reaction parameters of the quaternization reaction (for example, reaction temperature and reaction time) can be the same as or not the same as the reaction parameters of the quaternization reaction described in
前記の説明によれば、本発明の製造方法で製造されたカチオン性界面活性剤は下式（Ｉ）に示す構造を有する。
式（Ｉ）において、Ｒ１、Ｒ２、Ｒ３、Ｙ１、Ｙ２及びＡ−の定義はそれぞれ前述の通りであり、ここで繰り返して説明しないが、ｎ及びｍはそれぞれ０〜１００の整数を表す。同様に、Ｒ１、Ｒ２及びＲ３の中の少なくとも一方は不飽和基を有する。
According to the above description, the cationic surfactant produced by the production method of the present invention has a structure represented by the following formula (I).
In formula (I), the definitions of R 1 , R 2 , R 3 , Y 1 , Y 2 and A − are as described above, and will not be repeated here, but n and m are each from 0 to 100 Represents an integer. Similarly, at least one of R 1 , R 2 and R 3 has an unsaturated group.
一具体的な例において、本発明のカチオン性界面活性剤と光硬化可能な樹脂材料を混合して、光硬化性樹脂組成物を製造する。光硬化可能な樹脂材料の使用量１００重量部に対して、カチオン性界面活性剤の使用量は０．５重量部〜３０重量部であってよく、好ましくは２．５重量部〜２５重量部であり、より好ましくは５重量部〜２５重量部であり、最も好ましくは５重量部〜２０重量部である。 In one specific example, the cationic surfactant of the present invention and a photocurable resin material are mixed to produce a photocurable resin composition. The amount of the cationic surfactant used may be 0.5 to 30 parts by weight, preferably 2.5 to 25 parts by weight, based on 100 parts by weight of the photocurable resin material. More preferably, it is 5 to 25 parts by weight, and most preferably 5 to 20 parts by weight.
カチオン性界面活性剤の使用量が３０重量部より大きい場合、製造された光硬化性樹脂組成物が成膜された後で、アフタータックの欠点が発生しやすい。カチオン性界面活性剤の使用量が０．５重量部より小さい場合、カチオン性界面活性剤が少なすぎると効果的に光硬化性樹脂組成物の効能を向上させることができない。 When the amount of the cationic surfactant used is greater than 30 parts by weight, after-tack defects are likely to occur after the produced photocurable resin composition is formed. When the amount of the cationic surfactant used is less than 0.5 parts by weight, the effectiveness of the photocurable resin composition cannot be effectively improved if the amount of the cationic surfactant is too small.
具体的な例において、前記の光硬化性樹脂組成物に紫外線又はその他のエネルギー線が照射されると、光硬化可能な樹脂材料における二重結合を有する基は付加重合反応を行い、且つカチオン界面活性剤の有する二重結合を有する基［即ち前記式（Ｉ）において、不飽和基のＲ１、Ｒ２又はＲ３を有する］が、光硬化可能な樹脂材料の付加重合反応に加わることでカチオン界面活性剤と硬化可能な樹脂材料が化学結合を形成して、その経時安定性を向上させる。 In a specific example, when the photocurable resin composition is irradiated with ultraviolet rays or other energy rays, a group having a double bond in the photocurable resin material undergoes an addition polymerization reaction, and a cationic interface. A group having a double bond of the activator [that is, having the unsaturated group R 1 , R 2 or R 3 in the formula (I)] participates in the addition polymerization reaction of the photocurable resin material. The cationic surfactant and the curable resin material form a chemical bond and improve the stability over time.
他の具体的な例において、前記の光硬化性樹脂組成物を基材の表面に塗布し、且つ光硬化プロセスにより光硬化膜を形成し、複合膜を形成してもよい。換言すれば、この光硬化膜は前記光硬化性樹脂組成物の光硬化構造を含む。単位面積あたりの複合膜の第１インピーダンス値は１０１１オームより小さいので、製造された複合膜は良好な帯電防止性を有する。 In another specific example, the above-mentioned photocurable resin composition may be applied to the surface of a substrate, and a photocured film may be formed by a photocuring process to form a composite film. In other words, the photocured film includes a photocured structure of the photocurable resin composition. Since the first impedance value of the composite film per unit area is less than 10 11 ohms, the manufactured composite film has good antistatic properties.
この具体的な例において、前記の基材は光学フィルム、ガラス基材、プラスチック基材、紙基材、木板基材、太陽電池パネル、その他の適当な基材又は上記基材の任意の組み合わせからなるがこれらに限定されない。 In this specific example, the substrate is from an optical film, glass substrate, plastic substrate, paper substrate, wood board substrate, solar cell panel, other suitable substrate or any combination of the above substrates. However, it is not limited to these.
次に、カチオン性界面活性剤はカチオン親水性基を有するので、製造された光硬化膜は良い防曇・防露性を有し、複合膜の防曇・防露性を向上させることができる。一実施例において、本発明の光硬化膜の水に対する接触角は５０度を超えず、好ましくは３５度を超えず、より好ましくは２０度を超えない。光硬化膜の水に対する接触角は５０度を超える（即ちそれにより大きい）と、光硬化膜の防曇・防露性が低下する。 Next, since the cationic surfactant has a cationic hydrophilic group, the produced photocured film has good anti-fogging / dew-proofing properties and can improve the anti-fogging / dew-proofing properties of the composite film. . In one embodiment, the contact angle of the photocured film of the present invention with respect to water does not exceed 50 degrees, preferably does not exceed 35 degrees, and more preferably does not exceed 20 degrees. When the contact angle of the photocured film with respect to water exceeds 50 degrees (that is, greater than that), the antifogging and dewproof properties of the photocured film are deteriorated.
前記の説明から分かるように、本発明の光硬化性樹脂組成物に対して光硬化プロセスを行った場合、式（Ｉ）に示すカチオン性界面活性剤におけるＲ１、Ｒ２又はＲ３の不飽和基は光硬化可能な樹脂材料の二重結合を有する基と付加重合反応して、化学結合し、より優れた経時安定性を有する。 As can be seen from the above description, when the photocuring process is performed on the photocurable resin composition of the present invention, R 1 , R 2, or R 3 in the cationic surfactant represented by the formula (I) is not lost. The saturated group undergoes an addition polymerization reaction with a group having a double bond of the photocurable resin material, chemically bond, and has better stability over time.
このため、本発明の複合膜を長期間に高温多湿の環境に置いた後も、複合膜のインピーダンス値（第２インピーダンス値）は依然として１０１１オームより小さく、静電気変化も５０より小さく０より大きく、且つ良好な防曇・防露性を有する。これにより、本発明のカチオン性界面活性剤は良好な経時安定性を有する。 For this reason, even after the composite membrane of the present invention is placed in a hot and humid environment for a long time, the impedance value (second impedance value) of the composite membrane is still less than 10 11 ohms, and the electrostatic change is also less than 50 and greater than 0. And good anti-fogging and dew-proofing properties. Thereby, the cationic surfactant of the present invention has good temporal stability.
前記静電気変化は、好ましくは、１０より小さく０．１以上であり、より好ましくは、５以下０．１以上である。 The static change is preferably less than 10 and 0.1 or more, and more preferably 5 or less and 0.1 or more.
他の一実施例において、本発明の複合膜を長期間に高温多湿の環境に置いた後の、複合膜のインピーダンス値（第２インピーダンス値）は、置く前の複合膜のインピーダンス値（第１インピーダンス値）より小さい可能性がある。その原因は、長期間の高温多湿環境の影響により、複合膜は環境における湿気を吸収し、これにより複合膜における抵抗値を低下させることであると考えられる。 In another embodiment, the composite membrane impedance value (second impedance value) after the composite membrane of the present invention has been placed in a hot and humid environment for a long period of time is the impedance value (first impedance value) of the composite membrane before placement. Impedance value) may be smaller. The cause is considered to be that the composite film absorbs moisture in the environment due to the influence of the high-temperature and high-humidity environment for a long period of time, thereby reducing the resistance value in the composite film.
一応用例において、本発明の光硬化性樹脂組成物は塗料産業に応用することができる以外にも、任意の基材に塗布することができ、これにより良好な帯電防止性及び防曇・防露性を与えることができる。 In one application example, the photo-curable resin composition of the present invention can be applied to any substrate besides being applicable to the paint industry, thereby providing good antistatic properties and anti-fogging / dew-proofing. Can give sex.
以下、実施例を利用することにより本発明の応用を説明し、しかしながら、本発明を限定するためのものではなく、任意の当業者は、本発明の主旨及び範囲から逸脱しない限り、各種の変更及び修飾を行うことができる。 Hereinafter, the application of the present invention will be described by way of examples, but is not intended to limit the present invention, and any person skilled in the art can make various modifications without departing from the spirit and scope of the present invention. And modifications can be made.
〔光硬化可能な樹脂材料の調製〕
〔調製例Ｒ−１〕
まず、５５重量部〜６５重量部の脂肪族ウレタンジアクリレート（ａｌｉｐｈａｔｉｃ ｕｒｅｔｈａｎｅ ｄｉａｃｒｙｌａｔｅ、長興材料工業株式会社製、商品名が６１１Ｂ−８５である）、９重量部〜１６重量部のエトキシル化トリメチロールプロパントリアクリレート（Ｅｔｈｏｘｙｌａｔｅｄ ｔｒｉｍｅｔｈｙｌｏｌｐｒｏｐａｎｅ ｔｒｉａｃｒｙｌａｔｅ、Ｓａｔｏｍｅｒ会社製、商品名がＳＲ４１５である）、２５重量部〜３５重量部の２−（２−エトキシエトキシ）エチルアクリレート［２−（２−Ｅｔｈｏｘｙｅｔｈｏｘｙ）ｅｔｈｙｌ ａｃｒｙｌａｔｅ、Ｓａｔｏｍｅｒ会社製、商品名がＳＲ２５６である］、０重量部〜５重量部のテトラヒドロフルフリルアクリレート（Ｔｅｔｒａｈｙｄｒｏｆｕｒｆｕｒｙｌ ａｃｒｙｌａｔｅ、長興材料工業株式会社製、商品名がＥＭ２１４である）、１重量部〜５重量部の１−ヒドロキシシクロヘキシルフェニルケトン（１−Ｈｙｄｒｏｘｙｃｙｃｌｏｈｅｘｙｌ ｐｈｅｎｙｌ ｋｅｔｏｎｅ、光開始剤、ＢＡＳＦ社製、商品名がＩｒｇａｃｕｒｅ １８４である）及び１重量部〜２重量部のジフェニル(２，４，６−トリメチルベンゾイル)ホスフィンオキシド［Ｄｉｐｈｅｎｙｌ（２，４，６−ｔｒｉｍｅｔｈｙｌｂｅｎｚｏｙｌ）ｐｈｏｓｐｈｉｎｅ ｏｘｉｄｅ、光開始剤、ＢＡＳＦ社製、商品名がＤａｒｏｃｕｒ ＴＰＯである］をミキサーに添加し、且つ室温において、攪拌装置で持続的に攪拌混合し、調製例Ｒ−１の光硬化可能な樹脂材料を製造することができる。
[Preparation of photocurable resin material]
[Preparation Example R-1]
First, 55 parts by weight to 65 parts by weight of aliphatic urethane diacrylate (aliphatic urethane diacrylate, manufactured by Changxing Materials Co., Ltd., trade name is 611B-85), 9 parts by weight to 16 parts by weight of ethoxylated trimethylolpropane Triacrylate (Ethoxylated propylene triacrylate, manufactured by Satomer, trade name is SR415), 25 to 35 parts by weight of 2- (2-ethoxyethoxy) ethyl acrylate [2- (2-Ethoxyethyl) ethyl acrylate company, Manufactured under the trade name SR256], 0 to 5 parts by weight of tetrahydrofurfuryl acrylate (Tetrahhydrofurfuryl acr 1 to 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (photoinitiator, manufactured by BASF, trade name Irgacure, manufactured by Changxing Material Industries Co., Ltd., trade name is EM214) 184) and 1 to 2 parts by weight of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, photoinitiator, manufactured by BASF Corporation, trade name Is Darocur TPO] and is continuously stirred and mixed at room temperature with a stirrer to produce the photocurable resin material of Preparation Example R-1.
〔調製例Ｒ−２〕
まず、１５重量部〜２５重量部のビスフェノールＡエポキシジアクリレート（Ｂｉｓｐｈｅｎｏｌ Ａ ｅｐｏｘｙ ｄｉａｃｒｙｌａｔｅ、Ｓａｒｔｏｍｅｒ社製、商品名がＣＮ １０４である）、２０重量部〜３０重量部の２−フェノキシエチルアクリレート（２−Ｐｈｅｎｏｘｙｅｔｈｙｌ ａｃｒｙｌａｔｅ、Ｓａｔｏｍｅｒ社製、商品名がＳＲ ３３９である）、１５重量部〜２５重量部のエトキシ化ビスフェノールＡジアクリレート（Ｅｔｈｏｘｙｌａｔｅｄ ｂｉｓｐｈｅｎｏｌ Ａ ｄｉａｃｒｙｌａｔｅ、Ｓａｔｏｍｅｒ社製、商品名がＳＲ ３４９である）、２０重量部〜３０重量部のｏ−フェニルフェノキシエチルアクリレート［ｏ−Ｐｈｅｎｙｌ ｐｈｅｎｏｘｙ ｅｔｈｙｌ ａｃｒｙｌａｔｅ、長興材料工業株式会社製、且つ商品名がＥＭ２１０５である］、４重量部〜５重量部の１−ヒドロキシシクロヘキシルフェニルケトン（１−Ｈｙｄｒｏｘｙｃｙｃｌｏｈｅｘｙｌ ｐｈｅｎｙｌ ｋｅｔｏｎｅ、光開始剤、ＢＡＳＦ社製、商品名がＩｒｇａｃｕｒｅ １８４である）及び１重量部〜２重量部のジフェニル(２，４，６−トリメチルベンゾイル)ホスフィンオキシド［Ｄｉｐｈｅｎｙｌ（２，４，６−ｔｒｉｍｅｔｈｙｌｂｅｎｚｏｙｌ）ｐｈｏｓｐｈｉｎｅ ｏｘｉｄｅ、光開始剤、ＢＡＳＦ社製、商品名がＤａｒｏｃｕｒ ＴＰＯである］をミキサーに添加し、且つ室温において、攪拌装置で持続的に攪拌混合し、調製例Ｒ−２の光硬化可能な樹脂材料を製造することができる。
[Preparation Example R-2]
First, 15 to 25 parts by weight of bisphenol A epoxy diacrylate (Bisphenol A epoxy diacrylate, manufactured by Sartomer, trade name is CN 104), 20 to 30 parts by weight of 2-phenoxyethyl acrylate (2- Phenoxyethyl acrylate, manufactured by Satomer, trade name is SR 339), 15 to 25 parts by weight of ethoxylated bisphenol A diacrylate (Ethoxylated bisphenol A diacrylate, manufactured by Satomer, trade name is SR 349), 20 Parts by weight to 30 parts by weight of o-phenylphenoxyethyl acrylate [o-Phenylphenoxy ethyl acrylate, manufactured by Changxing Material Industries Co., Ltd. Name is EM2105] 4 parts by weight to 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (1-Hydroxycyclohexyl phenyl ketone, photoinitiator, manufactured by BASF, trade name is Irgacure 184) and 1 part by weight to 2 parts Add parts by weight of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, photoinitiator, manufactured by BASF, trade name is Darocur TPO] to the mixer In addition, the photocurable resin material of Preparation Example R-2 can be produced by continuously stirring and mixing with a stirring device at room temperature.
〔調製例Ｒ−３〕
まず、３０重量部〜４０重量部の２−フェノキシエチルアクリレート（２−Ｐｈｅｎｏｘｙｅｔｈｙｌ ａｃｒｙｌａｔｅ、Ｓａｔｏｍｅｒ社製、商品名がＳＲ ３３９である）、１５重量部〜２５重量部の１，６−ヘキサンジオールジアクリレート（１，６−ｈｅｘａｎｅｄｉｏｌ ｄｉａｃｒｙｌａｔｅ、Ｓａｔｏｍｅｒ社製、商品名がＳＲ ２３８である）、２５重量部〜３５重量部のエトキシ化ビスフェノールＡジアクリレート（Ｅｔｈｏｘｙｌａｔｅｄ ｂｉｓｐｈｅｎｏｌ Ａ ｄｉａｃｒｙｌａｔｅ、Ｓａｔｏｍｅｒ社製、商品名がＳＲ ３４９である）、２０重量部〜３０重量部のトリプロピレングリコールジアクリレート（Ｔｒｉｐｒｏｐｙｌｅｎｅ ｇｌｙｃｏｌ ｄｉａｃｒｙｌａｔｅ、新力美科技株式会社製、且つ商品名が２８１５である）、３重量部〜５重量部の１−ヒドロキシシクロヘキシルフェニルケトン（１−Ｈｙｄｒｏｘｙｃｙｃｌｏｈｅｘｙｌ ｐｈｅｎｙｌ ｋｅｔｏｎｅ、光開始剤、ＢＡＳＦ社製、商品名がＩｒｇａｃｕｒｅ １８４である）及び１重量部〜２重量部のジフェニル(２，４，６−トリメチルベンゾイル)ホスフィンオキシド［Ｄｉｐｈｅｎｙｌ（２，４，６−ｔｒｉｍｅｔｈｙｌｂｅｎｚｏｙｌ）ｐｈｏｓｐｈｉｎｅ ｏｘｉｄｅ、光開始剤、ＢＡＳＦ社製、商品名がＤａｒｏｃｕｒ ＴＰＯである］をミキサーに添加し、且つ室温において、攪拌装置で持続的に攪拌混合し、調製例Ｒ−３の光硬化可能な樹脂材料を製造することができる。
[Preparation Example R-3]
First, 30 to 40 parts by weight of 2-phenoxyethyl acrylate (2-Phenoxyethyl acrylate, manufactured by Satomer, trade name is SR 339), 15 to 25 parts by weight of 1,6-hexanediol diacrylate (1,6-hexanediacrylate, manufactured by Satomer, trade name is SR 238), 25 to 35 parts by weight of ethoxylated bisphenol A diacrylate (Ethoxylated bisphenol A diacrylate, manufactured by Satomer, trade name is SR 349) 20 parts by weight to 30 parts by weight of tripropylene glycol diacrylate (manufactured by Shinriki Science & Technology Co., Ltd.) and the trade name is 281 3) to 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (1-Hydroxycyclohexyl phenyl ketone, photoinitiator, manufactured by BASF, trade name is Irgacure 184) and 1 part to 2 parts by weight Of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, photoinitiator, manufactured by BASF, trade name is Darocur TPO], Further, at room temperature, the photocurable resin material of Preparation Example R-3 can be produced by continuously stirring and mixing with a stirring device.
〔カチオン性界面活性剤の調製〕
〔調製例Ｓ−１〕
まず、１モル（１２９ｇ）の２−エチルヘキシルアミンと２モル（２２８ｇ）のプロペニルグリシジルエーテルを反応フラスコに添加し、且つ１００℃〜１２０℃まで昇温し、これにより第１反応を行う。３時間反応した後、５モル（２２０ｇ）のエチレンオキサイドを導入し、且つ１５０℃まで昇温し、これにより第２反応を行う。２時間熟成した後、調製例Ｓ−１の中間生成物を製造することができる。次に、１モル（９２ｇ）の１−クロロブタンを前記の中間生成物に滴下し、且つ温度を１００℃に調整し、これにより四級化反応を行う。８時間反応した後、下式（ＩＩ−１）に示す調製例Ｓ−１のカチオン性界面活性剤（ただし、ｎ＋ｍ＝５）を製造することができる。
[Preparation Example S-1]
First, 1 mol (129 g) of 2-ethylhexylamine and 2 mol (228 g) of propenyl glycidyl ether are added to the reaction flask, and the temperature is raised to 100 ° C. to 120 ° C., thereby performing the first reaction. After reacting for 3 hours, 5 mol (220 g) of ethylene oxide is introduced, and the temperature is raised to 150 ° C., whereby the second reaction is performed. After aging for 2 hours, the intermediate product of Preparation Example S-1 can be produced. Next, 1 mol (92 g) of 1-chlorobutane is added dropwise to the intermediate product, and the temperature is adjusted to 100 ° C., thereby carrying out a quaternization reaction. After reacting for 8 hours, the cationic surfactant of Preparation Example S-1 represented by the following formula (II-1) (where n + m = 5) can be produced.
〔調製例Ｓ−２〕
１モル（１８６ｇ）のドデシルアミンと２モル（２２８ｇ）のプロペニルグリシジルエーテルを反応フラスコに添加し、且つ１００℃〜１２０℃まで昇温し、これにより第１反応を行う。３時間反応した後、１０モル（４４０ｇ）のエチレンオキサイドを導入し、且つ１５０℃まで昇温し、これにより第２反応を行う。２時間熟成した後、調製例Ｓ−２の中間生成物を製造することができる。次に、１モル（１５４ｇ）の硫酸ジエチルを前記の中間生成物に滴下し、且つ５０℃で四級化反応を行い、２時間反応した後、下式（ＩＩ−２）に示す調製例Ｓ−２のカチオン性界面活性剤（ただし、ｎ＋ｍ＝１０）を製造することができる。
1 mol (186 g) of dodecylamine and 2 mol (228 g) of propenyl glycidyl ether are added to the reaction flask and the temperature is raised to 100 ° C. to 120 ° C., thereby carrying out the first reaction. After reacting for 3 hours, 10 mol (440 g) of ethylene oxide is introduced, and the temperature is raised to 150 ° C., whereby the second reaction is performed. After aging for 2 hours, the intermediate product of Preparation Example S-2 can be produced. Next, 1 mol (154 g) of diethyl sulfate was added dropwise to the intermediate product, followed by a quaternization reaction at 50 ° C., followed by reaction for 2 hours, and then Preparation Example S shown in the following formula (II-2) -2 cationic surfactant (where n + m = 10) can be produced.
〔調製例Ｓ−３〕
１モル（２６９ｇ）のオクタデシルアミンと２モル（２２８ｇ）のプロペニルグリシジルエーテルを反応フラスコに添加し、且つ１００℃〜１２０℃まで昇温し、これにより第１反応を行う。３時間反応した後、３０モル（１３２０ｇ）のエチレンオキサイドを導入し、且つ１５０℃まで昇温し、これにより第２反応を行う。２時間熟成した後、調製例Ｓ−３の中間生成物を製造することができる。次に、１モル（１２６ｇ）の硫酸ジメチルを前記の中間生成物に滴下し、且つ５０℃で四級化反応を行う。２時間反応した後、下式（ＩＩ−３）に示す調製例Ｓ−３のカチオン性界面活性剤（ただし、ｎ＋ｍ＝３０）を製造することができる。
[Preparation Example S-3]
1 mol (269 g) of octadecylamine and 2 mol (228 g) of propenyl glycidyl ether are added to the reaction flask and the temperature is raised to 100 ° C. to 120 ° C., thereby carrying out the first reaction. After reacting for 3 hours, 30 mol (1320 g) of ethylene oxide is introduced, and the temperature is raised to 150 ° C., whereby the second reaction is performed. After aging for 2 hours, the intermediate product of Preparation Example S-3 can be produced. Next, 1 mol (126 g) of dimethyl sulfate is added dropwise to the intermediate product, and a quaternization reaction is performed at 50 ° C. After reacting for 2 hours, the cationic surfactant of Preparation Example S-3 represented by the following formula (II-3) (where n + m = 30) can be produced.
〔調製例Ｓ−４〕
１モル（９９ｇ）のシクロヘキシルアミンと２モル（２２８ｇ）のプロペニルグリシジルエーテルを反応フラスコに添加し、且つ１００℃〜１２０℃まで昇温し、これにより第１反応を行う。３時間反応した後、２０モル（８８０ｇ）のエチレンオキサイドを導入し、且つ１５０℃まで昇温し、これにより第２反応を行い、２時間熟成した後、調製例Ｓ−４の中間生成物を製造することができる。次に、１モル（１２６ｇ）の塩化ベンジルを前記の中間生成物に滴下し、８０℃で四級化反応を行い、８時間反応した後、下式（ＩＩ−４）に示す調製例Ｓ−４のカチオン性界面活性剤（ただし、ｎ＋ｍ＝２０）を製造することができる。
1 mol (99 g) of cyclohexylamine and 2 mol (228 g) of propenyl glycidyl ether are added to the reaction flask and the temperature is raised to 100 ° C. to 120 ° C., thereby carrying out the first reaction. After reacting for 3 hours, 20 mol (880 g) of ethylene oxide was introduced, and the temperature was raised to 150 ° C., whereby the second reaction was performed, and after aging for 2 hours, the intermediate product of Preparation Example S-4 was obtained. Can be manufactured. Next, 1 mol (126 g) of benzyl chloride was added dropwise to the intermediate product, subjected to a quaternization reaction at 80 ° C., reacted for 8 hours, and then, Preparation Example S- shown in the following formula (II-4) 4 cationic surfactants (where n + m = 20) can be produced.
〔調製例Ｓ−５〕
１モル（１５７ｇ）のイソデシルアミンと２モル（２２８ｇ）のプロペニルグリシジルエーテルを反応フラスコに添加し、且つ１００℃〜１２０℃まで昇温し、これにより第１反応を行う。３時間反応した後、調製例Ｓ−５の中間生成物を製造することができる。次に、１モル（１２６ｇ）の硫酸ジメチルを前記の中間生成物に滴下し、５０℃で四級化反応を行い、２時間反応した後、下式（ＩＩ−５）に示す調製例Ｓ−５のカチオン性界面活性剤を製造することができる。
1 mol (157 g) of isodecylamine and 2 mol (228 g) of propenyl glycidyl ether are added to the reaction flask and the temperature is raised to 100 ° C. to 120 ° C., thereby carrying out the first reaction. After reacting for 3 hours, the intermediate product of Preparation Example S-5 can be produced. Next, 1 mol (126 g) of dimethyl sulfate was added dropwise to the above intermediate product, a quaternization reaction was performed at 50 ° C., and after 2 hours of reaction, Preparation Example S- shown in the following formula (II-5) 5 cationic surfactants can be produced.
〔複合膜の調製〕
以下、表１及び表２に示すように実施例１〜２３及び比較例１〜９の複合膜を製作する。
(Preparation of composite membrane)
Hereinafter, as shown in Table 1 and Table 2, composite films of Examples 1 to 23 and Comparative Examples 1 to 9 are manufactured.
〔実施例１〕
１００重量部の光硬化可能な樹脂材料（調製例Ｒ−１）及び１０重量部のカチオン性界面活性剤（調製例Ｓ−１）をミキサーに添加し、且つ室温において、攪拌装置で持続的に攪拌混合し、実施例１の光硬化性樹脂組成物を製造することができる。
[Example 1]
100 parts by weight of a photocurable resin material (Preparation Example R-1) and 10 parts by weight of a cationic surfactant (Preparation Example S-1) are added to a mixer and continuously with a stirrer at room temperature. The photocurable resin composition of Example 1 can be produced by stirring and mixing.
その後、前記の光硬化性樹脂組成物を基材に塗布し、且つそれに対して紫外線を照射し、これにより光硬化膜を形成し、実施例１の複合膜を製造することができる。得られた複合膜は以下の表面特性、粘着性、帯電防止性、防曇・防露性及び環境試験等の評価方式で評価を行い、得られた結果を表１に示す。 Thereafter, the photocurable resin composition is applied to a substrate and irradiated with ultraviolet rays to form a photocured film, whereby the composite film of Example 1 can be manufactured. The obtained composite film was evaluated by the following evaluation methods such as surface characteristics, adhesiveness, antistatic property, anti-fogging / dew proof property and environmental test, and the obtained results are shown in Table 1.
〔実施例２〜２３及び比較例１〜９〕
実施例２〜２３及び比較例１〜９は、実施例１の複合膜の製作方法と同じ調製方法を使用する。相違点は、実施例２〜２３及び比較例１〜９が光硬化膜における光硬化可能な樹脂材料及びカチオン性界面活性剤の種類及び使用量を変更することであり、且つその評価結果はそれぞれ表１及び表２に示すとおりであり、ここでは繰り返し説明しない。
[Examples 2 to 23 and Comparative Examples 1 to 9]
Examples 2-23 and Comparative Examples 1-9 use the same preparation method as the fabrication method of the composite membrane of Example 1. The difference is that Examples 2 to 23 and Comparative Examples 1 to 9 change the type and amount of photocurable resin material and cationic surfactant in the photocured film, and the evaluation results are respectively It is as shown in Table 1 and Table 2, and will not be described repeatedly here.
〔評価項目〕
１．表面特性
前記実施例１〜２３及び比較例１〜９で製造された光硬化性樹脂組成物を＃４の塗布棒で均一にＰＥＴ膜に塗布して、１０μｍ厚さのコーティングを形成し、紫外線で硬化された後、手で光硬化膜を直接に触って乾燥であるかどうかを判定し、且つ以下の標準で評価する。
○：表面が完全に乾燥される。
△：表面が完全に乾燥されない。
×：表面
アフタータック。
〔Evaluation item〕
1. Surface characteristics The photo-curable resin compositions produced in Examples 1 to 23 and Comparative Examples 1 to 9 were uniformly applied to a PET film with an application stick of # 4 to form a coating having a thickness of 10 μm. After being cured, the photocured film is directly touched by hand to determine whether it is dry, and evaluated according to the following standards.
○: The surface is completely dried.
Δ: The surface is not completely dried.
X: Surface after tack.
２．外観
前記実施例１〜２３及び比較例１〜９で製造された光硬化性樹脂組成物を特定のパターンを有する基板に塗布する。紫外線で硬化された後、目視で光硬化膜を透過して特定のパターンを観察し、且つ以下の標準で評価する。
◎：特定のパターンはクリアである。
○：特定のパターンは少しぼやけている。
△：特定のパターンはぼやけている。
×：特定のパターンが観察されない。
2. Appearance The photocurable resin compositions produced in Examples 1 to 23 and Comparative Examples 1 to 9 are applied to a substrate having a specific pattern. After being cured with ultraviolet rays, a specific pattern is observed through the photocured film by visual observation, and evaluated according to the following standards.
A: The specific pattern is clear.
○: The specific pattern is slightly blurred.
Δ: The specific pattern is blurred.
X: A specific pattern is not observed.
３．粘着性
ＡＳＴＭ Ｄ３３５９試験標準により、上記実施例１〜２３及び比較例１〜９で製造された複合膜の光硬化膜を、クロスカットテスター又はナイフで１０×１０個（１００個）の１ｍｍ×１ｍｍサイズの小さな正方形に分割し、３Ｍ６００テープで粘着した後、手でテープの一端を把持し、垂直方向（９０°）で急速にテープを引き裂き、小さな正方形がテープで粘着された数を観察し、剥離領域の総面積に対する面積パーセンテージを計算し、且つ以下の基準で評価する。
○：５Ｂ
△：４Ｂ
×：３Ｂ〜０Ｂ
５Ｂは、切開部の交差点で滑らかで完全であり、コーティングが何ら剥離されない。
４Ｂは、切開部の交差点で小面積の剥離があり、剥離領域の面積パーセンテージ≦５％。
３Ｂは、切割辺縁及び交差点で剥離があり、剥離領域の面積パーセンテージが５％より大きく１５％以下。
２Ｂは、切割辺縁、交差点及び小さな正方形には剥離があり、剥離領域の面積パーセンテージが１５％より大きく３５％以下。
１Ｂは、切割辺縁、交差点及び小さな正方形には剥離があり、剥離領域の面積パーセンテージが３５％より大きく６５％以下。
０Ｂは、切割辺縁、交差点及び小さな正方形には剥離があり、剥離領域の面積パーセンテージが６５％より大きい。
3. Tackiness According to ASTM D3359 test standard, the photocured films of the composite films produced in Examples 1 to 23 and Comparative Examples 1 to 9 are 10 × 10 pieces (100 pieces) of 1 mm × 1 mm using a cross-cut tester or a knife. After dividing into small squares and sticking with 3M600 tape, grip one end of the tape by hand, tear the tape rapidly in the vertical direction (90 °), observe the number of small squares stuck with the tape, The area percentage with respect to the total area of the peeled area is calculated and evaluated according to the following criteria.
○: 5B
Δ: 4B
X: 3B to 0B
5B is smooth and complete at the intersection of the incision and no coating is peeled off.
4B has a small area peeling at the intersection of the incision, and the area percentage of the peeling area ≦ 5%.
3B has peeling at the cutting edge and the intersection, and the area percentage of the peeling region is larger than 5% and 15% or less.
In 2B, there are peeling at the cut edges, intersections and small squares, and the area percentage of the peeling region is greater than 15% and not more than 35%.
In 1B, there are separations at the cut edges, intersections, and small squares, and the area percentage of the separation region is greater than 35% and not more than 65%.
0B has delamination at the cut edges, intersections and small squares, and the area percentage of the delamination area is greater than 65%.
４．帯電防止性
表面インピーダンステスター（Ｓｔａｔｉｃ Ｓｏｌｕｔｉｏｎｓ Ｉｎｃ．社製、且つ型番がＲＴ−１０００である）で前記実施例１〜２３及び比較例１〜９で製造された複合膜のインピーダンス値を測定し、且つ以下の標準で評価を行い、また、インピーダンステスターの電圧を１１０ボルトに設定する。
◎：インピーダンス値≦１０１０。
○：１０１０＜インピーダンス値≦１０１１。
△：１０１１＜インピーダンス値≦１０１２。
×：１０１２＜インピーダンス値。
4). Antistatic property A surface impedance tester (manufactured by Static Solutions Inc., and model number is RT-1000) is used to measure impedance values of the composite membranes manufactured in Examples 1 to 23 and Comparative Examples 1 to 9, and Evaluation is performed according to the following standards, and the voltage of the impedance tester is set to 110 volts.
A: Impedance value ≦ 10 10 .
○: 10 10 <impedance value ≦ 10 11 .
Δ: 10 11 <impedance value ≦ 10 12 .
×: 10 12 <impedance value.
５．防曇・防露性
前記実施例１〜２３及び比較例１〜９で製造された複合膜を、８０℃の水が入ったビーカー口に設置する。光硬化膜はビーカー口に対向し、且つ光硬化膜の表面は水面から５センチメートル離れる。
5. Anti-fogging / dew-proof property The composite membranes produced in Examples 1 to 23 and Comparative Examples 1 to 9 are placed in a beaker opening containing water at 80 ° C. The photocured film faces the beaker mouth, and the surface of the photocured film is 5 cm away from the water surface.
１分間置いた後、目視で光硬化膜の表面上には水蒸気の凝結があるかどうかを判断し、且つ以下の標準により評価を行う。
◎：水蒸気の凝結がなく、且つ蒸発した水分子が光硬化膜上に付着し、且つ平坦な水膜（即ち連続的な水膜）が形成される。
○：水蒸気の凝結がなく、且つ蒸発した水分子が光硬化膜上に付着し、且つ不平坦な水膜に凝結される。
△：少し水蒸気の凝結がある。
×：水蒸気の凝結がある。
After leaving for 1 minute, it is visually judged whether or not there is condensation of water vapor on the surface of the photocured film, and evaluation is performed according to the following standards.
A: There is no condensation of water vapor, evaporated water molecules adhere to the photocured film, and a flat water film (that is, a continuous water film) is formed.
○: There is no condensation of water vapor, and evaporated water molecules adhere to the photocured film and are condensed to a non-flat water film.
Δ: There is a slight condensation of water vapor.
X: There is condensation of water vapor.
６．接触角
本発明で製造された光硬化膜の水に対する接触角は従来の技術方法と機器で測定され、このため、ここで繰り返して説明しない。
6). Contact angle The contact angle of the photocured film produced in the present invention with respect to water is measured by a conventional method and apparatus, and therefore will not be described again here.
７．環境試験
環境試験は、前記実施例１〜２３及び比較例１〜９で製造された複合膜を高温多湿環境（温度が６５℃であるとともに湿度が８０％である環境）に置いて、少なくとも５００時間経過した後、複合膜を取り出し、且つ順次に前記の評価項目を行う。そのうち、環境試験を行った後のインピーダンス値変化の評価方法は下式（ＩＩＩ）によって計算され、且つ以下の標準により評価する。
○：０＜インピーダンス値変化＜５０。
△：５０≦インピーダンス値変化。
7). Environmental test In the environmental test, the composite films produced in Examples 1 to 23 and Comparative Examples 1 to 9 were placed in a high-temperature and high-humidity environment (an environment where the temperature was 65 ° C and the humidity was 80%), and at least 500 After a lapse of time, the composite film is taken out and the evaluation items are sequentially performed. Among them, the evaluation method of the impedance value change after the environmental test is performed is calculated by the following formula (III), and is evaluated according to the following standard.
A: 0 <impedance value change <50.
Δ: 50 ≦ impedance value change.
表１及び表２の結果から分かるように、本発明のカチオン性界面活性剤と光硬化可能な樹脂材料で製造された光硬化膜は、良好な表面特性を有し、且つ環境試験を行った後も、本発明のカチオン性界面活性剤では従来のアフタータックの欠点が発生しない。 As can be seen from the results in Tables 1 and 2, the photocured film produced with the cationic surfactant of the present invention and a photocurable resin material had good surface properties and was subjected to an environmental test. Later, the cationic surfactant of the present invention does not have the disadvantages of conventional aftertacks.
次に、本発明で製造された光硬化膜も、良好な外観特性及び粘着性を有し、各種の基材に貼り付けることができ、且つその視覚評価に影響を及ぼさない。なお、本発明で製造された複合膜は良好な帯電防止性及び防曇・防露性を有し、更に従来の静電気及び／又は水蒸気による装置又は基材に対する損傷を抑制することができる。表２において、比較例１〜９の評価結果から分かるように、光硬化性樹脂組成物が本発明のカチオン性界面活性剤を含まない場合、製造された光硬化膜は、帯電防止性及び／又は防曇・防露性を有さず、又は、製造された光硬化膜の外観又は粘着性が応用要求を満たさない。 Next, the photocured film produced by the present invention also has good appearance characteristics and adhesiveness, can be attached to various base materials, and does not affect the visual evaluation. In addition, the composite film manufactured by this invention has favorable antistatic property, anti-fogging, and dew-proof property, and can suppress the damage to the apparatus or base material by the conventional static electricity and / or water vapor | steam. In Table 2, as can be seen from the evaluation results of Comparative Examples 1 to 9, when the photocurable resin composition does not contain the cationic surfactant of the present invention, the produced photocured film has antistatic properties and / or Or it does not have anti-fogging and dew-proof properties, or the appearance or adhesiveness of the produced photocured film does not satisfy the application requirements.
なお、本発明で製造された光硬化膜は環境試験を行った後、その表面特性、帯電防止性及び防曇・防露性等の効果が低下しない。これにより、本発明のカチオン性界面活性剤は良好な安定性を有する。 In addition, after carrying out an environmental test, the photocured film manufactured by this invention does not fall the effects, such as the surface characteristic, antistatic property, and antifogging and dew-proof property. Thereby, the cationic surfactant of the present invention has good stability.
本発明の実施例及び比較例から分かるように、本発明により製造されたカチオン性界面活性剤は、それを用いて製造した複合膜の帯電防止性及び防曇・防露性を効果的に向上させることができる。そのうち、カチオン性界面活性剤の二重結合を有する基と光硬化可能な樹脂材料は更に結合することができるので、本発明により製造されたカチオン性界面活性剤は、従来のカチオン性界面活性剤の移動（マイグレーション）の欠点を効果的に克服することができ、更にその経時安定性を向上させる。 As can be seen from the examples and comparative examples of the present invention, the cationic surfactant produced according to the present invention effectively improves the antistatic property and antifogging / dewproofing property of the composite membrane produced using the same. Can be made. Among them, the cationic surfactant produced according to the present invention is a conventional cationic surfactant because the photocurable resin material and the group having a double bond of the cationic surfactant can be further bonded. It is possible to effectively overcome the drawbacks of migration, and to improve the stability over time.
本発明は、実施形態として上記の通り開示したが、これは本発明を限定するものではない。当業者は、本発明の精神と範囲から逸脱しない限り、各種の変更や修飾を加えることができる。従って、本発明の保護範囲は、添付する特許請求の範囲に限定されるものを基準とする。 Although the present invention has been disclosed as the embodiment as described above, this does not limit the present invention. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Accordingly, the scope of protection of the present invention shall be based on what is limited to the appended claims.
１００：方法
１１０：混合物を提供するステップ
１２０：混合物に対して前反応を行うステップ
１３０：四級化反応を行うステップ
１４０：カチオン性界面活性剤を製造するステップ
Claims (10)
式（Ｉ）において、Ｒ１は炭素数が１〜３０のアルキル、炭素数が２〜３０のオレフィン基又は炭素数が３〜３０のシクロアルカン基を表し、Ｒ２は炭素数が１〜４のアルキル、アルキルアルコール基、アルカノイル基又はアルキルフェニルを表し、Ｒ３は炭素数が１〜５のアルキル、炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は−ＯＲ４を表し、Ｒ４は炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は
を表し、Ｒ５は炭素数が２〜５のアルケニルを表し、Ｒ１、Ｒ２及びＲ３の中の少なくとも一方は不飽和基を有し、Ｙ１及びＹ２はそれぞれ炭素数が２〜４のアルキリデンを表し、Ａ−はアニオン親水基であり、且つｎ及びｍはそれぞれ０〜１００の整数を表すことを特徴とするカチオン性界面活性剤。 Having the structure shown in the following formula (I):
In Formula (I), R 1 represents an alkyl having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms, or a cycloalkane group having 3 to 30 carbon atoms, and R 2 has 1 to 4 carbon atoms. R 3 is alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, alkynyl having 2 to 5 carbons, aromatic group, alkyl Represents an aromatic group, an alkenyl aromatic group, or —OR 4 , wherein R 4 is alkenyl having 2 to 5 carbon atoms, alkynyl having 2 to 5 carbon atoms, aromatic group, alkyl aromatic group, alkenyl aromatic group, or
R 5 represents alkenyl having 2 to 5 carbon atoms, at least one of R 1 , R 2 and R 3 has an unsaturated group, and Y 1 and Y 2 each have 2 to 2 carbon atoms. A cationic surfactant, wherein 4 represents an alkylidene, A − represents an anionic hydrophilic group, and n and m each represents an integer of 0 to 100.
を含み、且つＲ６はメチル又はエチルを表す請求項１に記載のカチオン性界面活性剤。 The anionic hydrophilic group is F − , Cl − , Br − , I − , (SO 2 CF 3 ) 2 N − or
The cationic surfactant according to claim 1, wherein R 6 represents methyl or ethyl.
Ｒ１−ＮＨ２ （Ｉ−１）
式（Ｉ−１）において、Ｒ１は炭素数が１〜３０のアルキル、炭素数が２〜３０のオレフィン基又は炭素数が３〜３０のシクロアルカン基を表し、
式（Ｉ−２）において、Ｒ３は炭素数が１〜５のアルキル、炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は−ＯＲ４を表し、Ｒ４は炭素数が２〜５のアルケニル、炭素数が２〜５のアルキニル、芳香族基、アルキル芳香族基、アルケニル芳香族基又は
前記中間生成物及び下式（Ｉ−３）に示す化合物に対して四級化反応を行うこれにより前記カチオン性界面活性剤を製造し、前記カチオン性界面活性剤は請求項１又は２に記載の構造を有し、且つｎ及びｍはそれぞれ０を表し、
Ｒ２−Ａ （Ｉ−３）
式（Ｉ−３）において、Ｒ２は炭素数が１〜４のアルキル、アルキルアルコール基、アルカノイル基又はアルキルフェニルを表し、且つＡは親水基である、カチオン性界面活性剤の製造方法。 By prereacting the mixture, an intermediate product is formed, the prereaction includes the first reaction, and the mixture is represented by the amine compound represented by the following formula (I-1) and the following formula (I-2): Including epoxy compounds,
R 1 —NH 2 (I-1)
In the formula (I-1), R 1 represents an alkyl having 1 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms, or a cycloalkane group having 3 to 30 carbon atoms,
In the formula (I-2), R 3 is alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, alkynyl having 2 to 5 carbons, aromatic group, alkyl aromatic group, alkenyl aromatic. represents a group or -OR 4, R 4 is alkenyl having 2 to 5 carbon atoms, alkynyl number of 2 to 5 carbon atoms, an aromatic group, an alkyl aromatic group, an alkenyl aromatic group, or
The cationic surfactant is produced by performing a quaternization reaction on the intermediate product and the compound represented by the following formula (I-3), and the cationic surfactant is according to claim 1 or 2. And n and m each represents 0,
R 2 -A (I-3)
In formula (I-3), R 2 represents an alkyl having 1 to 4 carbon atoms, an alkyl alcohol group, an alkanoyl group or an alkylphenyl, and A is a hydrophilic group, and a method for producing a cationic surfactant.
前記第１反応の生成物及び炭素数が２〜４のエポキシアルキル化合物に対して第２反応を行うことを更に含む請求項３に記載のカチオン性界面活性剤の製造方法。 After performing the first reaction, the pre-reaction is
The method for producing a cationic surfactant according to claim 3, further comprising performing a second reaction on the product of the first reaction and the epoxyalkyl compound having 2 to 4 carbon atoms.
であり、Ｒ６はメチル又はエチルを表し、且つ「＊」は結合位置を表す請求項３〜５のいずれか一項に記載のカチオン性界面活性剤の製造方法。 The hydrophilic group is a halogen atom, (SO 2 CF 3 ) 2 N— or
The method for producing a cationic surfactant according to any one of claims 3 to 5, wherein R 6 represents methyl or ethyl, and "*" represents a bonding position.
前記光硬化可能な樹脂材料１００重量部に対して、使用量は、０．５重量部〜３０重量部である請求項１又は２に記載のカチオン性界面活性剤と、を含む光硬化性樹脂組成物。 A photocurable resin material;
The photocurable resin containing the cationic surfactant according to claim 1 or 2, wherein the amount of use is 0.5 to 30 parts by weight with respect to 100 parts by weight of the photocurable resin material. Composition.
前記基材の一つの表面に設けられ、且つ請求項７に記載の光硬化性樹脂組成物の光硬化構造を有し、水に対する接触角が５０度を超えない光硬化膜と、からなる複合膜。 A substrate;
A composite comprising a photocured film provided on one surface of the substrate and having a photocured structure of the photocurable resin composition according to claim 7 and having a contact angle with water not exceeding 50 degrees. film.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10291967A (en) * | 1997-04-17 | 1998-11-04 | Asahi Denka Kogyo Kk | Modifier for compound having intramolecular si-h bond, amino-modified silicone and surfactant |
| JPH11165391A (en) * | 1997-12-03 | 1999-06-22 | Teijin Ltd | Antistatic polyester film |
| JP2001159084A (en) * | 1999-11-30 | 2001-06-12 | Sanyo Chem Ind Ltd | Auxiliary for removing hot-melt adhesive resin and method for producing regenerated pulp |
| JP2002161296A (en) * | 2000-09-14 | 2002-06-04 | Sanyo Chem Ind Ltd | Detergent |
| JP2002161491A (en) * | 2000-09-18 | 2002-06-04 | Oji Paper Co Ltd | Bleaching auxiliary for paper manufacturing pulp and method for bleaching the same |
| JP2004263008A (en) * | 2003-02-28 | 2004-09-24 | Toto Ltd | Anti-fogging agent composition and anti-fogging agent using the same and used for bathroom |
| JP2008019254A (en) * | 2006-06-14 | 2008-01-31 | Toho Chem Ind Co Ltd | Composition for hair |
| WO2012069639A2 (en) * | 2010-11-25 | 2012-05-31 | L'oreal | Composition for treating keratin fibres comprising a cationic surfactant comprising a hydroxylated chain |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10291967A (en) * | 1997-04-17 | 1998-11-04 | Asahi Denka Kogyo Kk | Modifier for compound having intramolecular si-h bond, amino-modified silicone and surfactant |
| JPH11165391A (en) * | 1997-12-03 | 1999-06-22 | Teijin Ltd | Antistatic polyester film |
| JP2001159084A (en) * | 1999-11-30 | 2001-06-12 | Sanyo Chem Ind Ltd | Auxiliary for removing hot-melt adhesive resin and method for producing regenerated pulp |
| JP2002161296A (en) * | 2000-09-14 | 2002-06-04 | Sanyo Chem Ind Ltd | Detergent |
| JP2002161491A (en) * | 2000-09-18 | 2002-06-04 | Oji Paper Co Ltd | Bleaching auxiliary for paper manufacturing pulp and method for bleaching the same |
| JP2004263008A (en) * | 2003-02-28 | 2004-09-24 | Toto Ltd | Anti-fogging agent composition and anti-fogging agent using the same and used for bathroom |
| JP2008019254A (en) * | 2006-06-14 | 2008-01-31 | Toho Chem Ind Co Ltd | Composition for hair |
| WO2012069639A2 (en) * | 2010-11-25 | 2012-05-31 | L'oreal | Composition for treating keratin fibres comprising a cationic surfactant comprising a hydroxylated chain |
Non-Patent Citations (1)
| Title |
|---|
| TETRAHEDRON LETTERS, vol. Vol.44, JPN6018028407, 2003, pages 4073 - 4075 * |
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