JP6524148B2 - 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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- JP6524148B2 JP6524148B2 JP2017123552A JP2017123552A JP6524148B2 JP 6524148 B2 JP6524148 B2 JP 6524148B2 JP 2017123552 A JP2017123552 A JP 2017123552A JP 2017123552 A JP2017123552 A JP 2017123552A JP 6524148 B2 JP6524148 B2 JP 6524148B2
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- cationic surfactant
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- alkyl
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- 239000003093 cationic surfactant Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- -1 amine compound Chemical class 0.000 claims description 53
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000002131 composite material Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000013067 intermediate product Substances 0.000 claims description 20
- 239000011342 resin composition Substances 0.000 claims description 19
- 238000005956 quaternization reaction Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 125000000304 alkynyl group Chemical group 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 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
- 150000001336 alkenes Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 51
- 238000002360 preparation method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 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
- 238000000034 method Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000002216 antistatic agent Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 6
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 6
- 206010040844 Skin exfoliation Diseases 0.000 description 6
- 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 6
- 230000008859 change Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- QXONIHMUSQFKJU-UHFFFAOYSA-N 2-(prop-1-enoxymethyl)oxirane Chemical compound CC=COCC1CO1 QXONIHMUSQFKJU-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 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
- 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 3
- 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
- 230000007547 defect Effects 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 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 3
- 125000002255 pentenyl group Chemical group C(=CCCC)* 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
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-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
- 230000003796 beauty Effects 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 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
- 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
- 238000002156 mixing Methods 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
- 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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000000016 photochemical curing Methods 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
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 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
- 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
- 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 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
- 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
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-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
- 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 150000001767 cationic compounds 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
- 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
- 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
- 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
- 230000007774 longterm Effects 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
- 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
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 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
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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 property and antifogging / dew resistance, a method for producing the same and its application.
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 emphasis on quality of life increases, conventional electronic products are becoming lighter and thinner, and accordingly, the photoelectric elements inside the electronic products are becoming smaller. However, as the volume of a photoelectric device shrinks, the requirements for its use environment also become severe.
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 tends to condense on the surface of the device, affecting its function and thus causing damage to the device. In particular, in the display area, water vapor affects the display of the display and degrades 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 device, the conduction of charge mainly affects the efficiency of the device, so the stable electric field environment contributes to the improvement of the performance of the photoelectric device. However, static electricity generated in daily life always affects the photoelectric element. Static electricity discharges momentarily, but has a high voltage, which always causes maximum damage to miniaturized photoelectric elements.
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 the damage to the photoelectric conversion element of water vapor or static electricity, the surface of the photoelectric conversion element avoids condensation of water vapor or removes static electricity by installing an anti-fogging / anti-deposition material or antistatic material. Avoid damage to photoelectric elements.
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 above-mentioned anti-fogging / dew-proof material or antistatic material may be a composite film containing a surfactant (for example, an anti-fogging / dew-proof agent or an antistatic agent), thereby having the aforementioned effect.
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 agent or anti-static agent is uniformly mixed with the resin material of the protective film only by physical method, and therefore, the anti-fogging agent or anti-fogging agent is The agent or antistatic agent migrates to the surface of the composite film (migration) to reduce its anti-fogging / anti-dew properties 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 antifogging agent or antistatic agent transferred to the surface further causes after-tack on the surface of the composite film to deteriorate 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 urgent to provide the conventional cationic surfactant, the method for producing the cationic surfactant, the cationic surfactant for improving the disadvantages of the application, the method for producing the cationic surfactant and the 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, one aspect of the present invention uses a reactant to produce a cationic surfactant having a specific structure and having good antistatic properties and antifogging and dewproof properties.
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 above 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 comprising the above-mentioned 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 comprising 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
According to one aspect of the present invention, there is provided a cationic surfactant having a structure shown in the following formula (I).
In formula (I), R 1 represents an alkyl having 1 to 30 carbons, an olefin group having 2 to 30 carbons, or a cycloalkane group having 3 to 30 carbons, and R 2 has 1 to 4 carbons R 3 represents an alkyl having 1 to 5 carbons, an alkenyl having 2 to 5 carbons, an alkynyl having 2 to 5 carbons, an aromatic group, an alkyl; Represents an aromatic group, an alkenyl aromatic group or -OR 4 , and R 4 represents an alkenyl having 2 to 5 carbon atoms, an alkynyl having 2 to 5 carbon atoms, an aromatic group, an alkyl aromatic group, an 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 an embodiment of the present invention, said 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 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 3 to 30 cycloalkane group having carbon atoms,
In formula (I-2), R 3 is an alkyl having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms, an alkynyl having 2 to 5 carbon atoms, an aromatic group, an alkyl aromatic group, an alkenyl aromatic group 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。
Thereafter, when the 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. The cationic surfactant has the above structure, and n and m each represent 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.
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 an embodiment of the present invention, after performing the first reaction, this pre-reaction performs a second reaction on the product of the first reaction and the epoxy alkyl compound having 2 to 4 carbon atoms. Further includes
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 above production method has the above-mentioned structure, n and m each represents an integer of 0 to 100, and n and m The sum is greater than 0.
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
And 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 presented. The photocurable resin composition comprises a 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 presented. The composite film includes a substrate and a photocurable film, and the photocurable film is formed by the photocuring process of the photocurable resin composition described above, and is provided on the surface of the substrate. And the contact angle with 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 smaller 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 film per unit area is less than 10 11 ohms after the composite film 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, the method for producing the same and the application thereof form a chemical bond by 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。 The following will carefully consider the manufacture and use of the embodiments of the present invention. However, it should be understood that the embodiments provide several applicable inventive concepts and can be implemented in various specific contexts. The particular embodiments discussed are for the purpose of illustration only, and not for the purpose of limiting the scope of the 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 refers to the surface adhesion defect of the coating due to temperature and humidity, or migration of the anti-fogging agent, anti-fogging 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 and further reduces 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。
See FIG. FIG. 1 is a flow chart of a method of producing a cationic surfactant according to an embodiment of the present invention. In one embodiment, as shown in
R 1 -NH 2 (I-1)
In 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 formula (I-1), R 1 may be a substituted or unsubstituted linear group or a branched group. In one embodiment, when R 1 represents alkyl having 1 to 30 carbons, R 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl , Pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, behenyl, tricosyl, tricosyl, tetracosyl, tetradecyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotetradecyl, isopentadecyl, isodecyl 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, secondary Examples include, but are not limited to, secondary undecyl, secondary dodecyl, secondary tridecyl, secondary tetradecyl, secondary pentadecyl or secondary hexadecyl and the like. When R 1 represents an olefin group having 2 to 30 carbon atoms, R 1 is propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, heptadecenyl or octadecenyl Etc. but not limited thereto. 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 And cyclohexylbutyl, cycloheptylmethyl, cycloheptylethyl, cycloheptylpropyl, cycloheptylbutyl, cyclooctylmethyl, cyclooctylethyl, cyclooctylpropyl, cyclooctylbutyl and the like, without being limited thereto.
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 to said Formula (I-1) can be used individually by 1 type, or it can be used 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 formula (I-2), R 3 may be a substituted or unsubstituted linear group or branched group. In one embodiment, specific examples of R 3 are preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, vinyl, propenyl, butenyl, pentenyl, pentenyl, propynyl, butynyl, pentynyl, phenyl Phenylmethyl, phenylethyl, phenylpropyl, naphthyl, naphthylmethyl, naphthylethyl, naphthylpropyl, biphenyl, styrenated phenyl, styryl or methylstyryl and the like, but not limited thereto. The epoxy compounds represented by the formula (I-2) can be used alone or in combination of two or more.
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 used amount of the epoxy compound represented by the formula (I-2) may be 0.5 mol to 4.0 mol, preferably 1 mol to the total used amount of the amine compound represented by the formula (I-1). It is 1.0 mol to 3.0 mol, more preferably 1.5 mol to 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 embodiment, 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
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 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 formula (I-3), R 2 may be a substituted or unsubstituted linear or branched 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 and 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 or 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 described above is carried out, 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 compound of the present invention Produce a surfactant.
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 the formula (I-3) used may be 0.3 mol to 2.0 mol, preferably 0.5 mol, per 1 mol of the total used amount of the intermediate product. It is a mole to 1.5 moles, more preferably 0.6 moles to 1.2 moles.
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, and 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 defined above, and will not be repeated here. A - is an anionic 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 optionally includes the step of performing a second reaction on the product of the first reaction and the epoxyalkyl compound having 2 to 4 carbon atoms, and the following formula (I-4-2): An intermediate product having the structure shown in 2.) is produced.
In formula (I-4-2), the definitions of R 1 and R 3 are as defined 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 embodiment, 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。 the sum of n and m is greater than 0, -O-Y 1 - and / or -O-Y 2 - cationic surfactants produced by segment hydrophilic, anti-fogging, anti-condensation properties and antistatic properties Have 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 agent surfactant has better hydrophilicity, anti-fogging, dew-proof and antistatic properties.
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 amount of the epoxy alkyl compound having 2 to 4 carbon atoms used may be 2.0 moles to 50.0 moles, preferably 5.0 moles to 1 mole of the total amount of the product of the first reaction. The molar amount is 40.0 mol, more preferably 5.0 mol to 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 represented by Formula (I-3) can be further subjected to a quaternization reaction, A cationic surfactant represented by 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 To prepare a cationic surfactant.
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 used amount of the compound represented by the formula (I-3) may be 0.3 mol to 2.0 mol with respect to 1 mol in total of the intermediate used amount represented by the formula (I-4-2). Preferably, it is 0.5 mol to 1.5 mol, more preferably 0.6 mol to 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 (such as reaction temperature and reaction time) may be identical or not identical to 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 the formula (I), R 1, R 2, R 3, Y 1, Y 2 and A - definitions are as defined above, respectively, will not be described again here, but, n and m are from 0 to 100, respectively 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 parts by weight to 25 parts by weight, and most preferably 5 parts by weight 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。 If the amount of the cationic surfactant used is greater than 30 parts by weight, after tacking of the produced photocurable resin composition, a defect of after tack tends to occur. When the amount of the cationic surfactant used is smaller than 0.5 parts by weight, if the amount of the cationic surfactant is too small, the efficacy of the photocurable resin composition can not be effectively improved.
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 above-mentioned photocurable resin composition is irradiated with ultraviolet rays or other energy rays, the group having a double bond in the photocurable resin material undergoes an addition polymerization reaction, and a cation interface A group having a double bond possessed by an activator [ie, having unsaturated group R 1 , R 2 or R 3 in the above-mentioned 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 to improve their temporal stability.
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 photocurable resin composition described above 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, this photocurable film contains a photocurable 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 produced 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 particular example, the substrate is an optical film, a glass substrate, a plastic substrate, a paper substrate, a wood board substrate, a solar panel, any other suitable substrate or any combination of the above substrates But not limited thereto.
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 light-cured film has good anti-fogging and dew-proof properties, and can improve the anti-fogging and dew-proof properties of the composite film. . In one embodiment, the contact angle to water of the photo-cured film of the present invention does not exceed 50 degrees, preferably 35 degrees, more preferably 20 degrees. When the contact angle to water of the photocurable film is more than 50 degrees (that is, it is larger), the anti-fogging / dew resistance of the photocurable film is reduced.
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 understood from the above description, when the photocurable process of the photocurable resin composition of the present invention is carried out, R 1 , R 2 or R 3 in the cationic surfactant shown in formula (I) is not The saturated group undergoes an addition polymerization reaction with the group having a double bond of the photocurable resin material, chemically bonds, 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。 Therefore, even after the composite film 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 film is still smaller than 10 11 ohms, and the electrostatic change is smaller than 50 and larger than 0. And good anti-fogging and dew-proofing properties. Thereby, the cationic surfactant of the present invention has good stability over time.
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 electrostatic change is preferably less than 10 and not less than 0.1, more preferably not more than 5 and not less than 0.1.
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, after placing the composite membrane of the present invention in a high temperature and humidity environment for a long time, the impedance value (second impedance value) of the composite membrane is the impedance value of the composite membrane before placement (first It may be smaller than the impedance value). It is considered that the cause is that the composite film absorbs moisture in the environment due to the influence of a long-term hot and humid environment, 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, the photocurable resin composition of the present invention can be applied to any substrate other than that it can be applied to the paint industry, thereby providing good antistatic properties, antifogging and anti-dew properties. 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。 The application of the present invention will now be described by means of examples but 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 Choxing Material Industries Co., Ltd., trade name: 611B-85), 9 parts by weight to 16 parts by weight of ethoxylated trimethylolpropane Triacrylate (Ethoxylated trimethylolpropane triacrylate, product of Satomer, trade name: SR415), 25 parts by weight to 35 parts by weight of 2- (2-ethoxyethoxy) ethyl acrylate [2- (2-Ethoxyethoxy) ethyl acrylate, Satomer company Manufactured by trade name SR 256], 0 to 5 parts by weight of tetrahydrofurfuryl acrylate (Tetrahydrofurfuryl acr late, manufactured by Changxing Materials Industry Co., Ltd., trade name EM214), 1 to 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone, photoinitiator, manufactured by BASF, trade name Irgacure And 1 part by weight to 2 parts by weight of diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, photoinitiator, manufactured by BASF, trade name Is a Darocur TPO] to the mixer and can be continuously stirred and mixed with a stirrer at room temperature 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 parts by weight to 25 parts by weight of bisphenol A epoxy diacrylate (Bisphenol A epoxy diacrylate (manufactured by Sartomer, trade name: CN 104), 20 parts by weight to 30 parts by weight of 2-phenoxyethyl acrylate (2- Phenoxyethyl acrylate, product of Satomer, trade name SR 339, 15 parts by weight to 25 parts by weight of ethoxylated bisphenol A diacrylate (Ethoxylated bisphenol A diacrylate, product Satomer, trade name SR 349), 20 Parts by weight to 30 parts by weight of o-phenyl phenoxy ethyl acrylate [Chang Hing Materials Industry Co., Ltd., and products Name is EM 2105], 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 by weight of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, photoinitiator, manufactured by BASF, trade name Darocur TPO] is added to the mixer The mixture can be continuously stirred and mixed at room temperature with a stirrer to produce the photocurable resin material of Preparation Example R-2.
〔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 parts by weight to 40 parts by weight of 2-phenoxyethyl acrylate (2-Phenoxyethyl acrylate, manufactured by Satomer, trade name: SR 339), 15 parts by weight to 25 parts by weight of 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate, product of Satomer, trade name is SR 238), 25 parts by weight to 35 parts by weight of ethoxylated bisphenol A diacrylate (Satomer, trade name is SR 349) 20 parts by weight to 30 parts by weight of tripropylene glycol diacrylate (manufactured by New Beauty & Beauty Co., Ltd., and the trade name is 281). 5), 3 to 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone, photoinitiator, manufactured by BASF, trade name Irgacure 184) and 1 to 2 parts by weight Of diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide [Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, photoinitiator, manufactured by BASF, trade name Darocur TPO] is added to the mixer, And at room temperature, stirring and mixing can be carried out continuously with a stirrer, and the photocurable resin material of Preparation Example R-3 can be produced.
〔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 mole (129 g) of 2-ethylhexylamine and 2 moles (228 g) of propenyl glycidyl ether are added to the reaction flask and the temperature is raised to 100 ° C. to 120 ° C. to perform the first reaction. After reacting for 3 hours, 5 moles (220 g) of ethylene oxide are introduced, and the temperature is raised to 150 ° C., thereby performing the second reaction. After aging for 2 hours, the intermediate product of Preparation Example S-1 can be prepared. Next, 1 mole (92 g) of 1-chlorobutane is added dropwise to the above intermediate product, and the temperature is adjusted to 100 ° C., thereby performing the quaternization reaction. After reacting for 8 hours, the cationic surfactant (where n + m = 5) of Preparation Example S-1 represented by the following formula (II-1) 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。
One mole (186 g) of dodecylamine and 2 moles (228 g) of propenyl glycidyl ether are added to the reaction flask and heated to 100 ° C. to 120 ° C. to perform the first reaction. After reacting for 3 hours, 10 moles (440 g) of ethylene oxide are introduced, and the temperature is raised to 150 ° C., thereby performing the second reaction. After aging for 2 hours, the intermediate product of Preparation Example S-2 can be prepared. Next, 1 mole (154 g) of diethyl sulfate is added dropwise to the above intermediate product, and after performing quaternization reaction at 50 ° C. and reacting for 2 hours, Preparation Example S shown in the following formula (II-2) A cationic surfactant of −2 (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
One mole (269 g) of octadecylamine and 2 moles (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, 30 moles (1320 g) of ethylene oxide is introduced, and the temperature is raised to 150 ° C., thereby performing the second reaction. After aging for 2 hours, the intermediate product of Preparation Example S-3 can be prepared. Next, 1 mole (126 g) of dimethyl sulfate is dropped to the above intermediate product, and the quaternization reaction is carried out at 50 ° C. After reacting for 2 hours, the cationic surfactant (where n + m = 30) of Preparation Example S-3 represented by the following formula (II-3) 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。
One mole (99 g) of cyclohexylamine and 2 moles (228 g) of propenyl glycidyl ether are added to the reaction flask and the temperature is raised to 100 ° C. to 120 ° C. to perform the first reaction. After reacting for 3 hours, 20 moles (880 g) of ethylene oxide was introduced, and the temperature was raised to 150 ° C., whereby a second reaction was carried out, and after aging for 2 hours, the intermediate product of Preparation Example S-4 was obtained It can be manufactured. Next, 1 mole (126 g) of benzyl chloride is added dropwise to the above intermediate product, and the quaternization reaction is carried out at 80 ° C., and after reaction for 8 hours, Preparation Example S-shown by the following formula (II-4) Four 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。
One mole (157 g) of isodecylamine and 2 moles (228 g) of propenyl glycidyl ether are added to the reaction flask and the temperature is raised to 100 ° C. to 120 ° C. to carry out the first reaction. After reacting for 3 hours, the intermediate product of Preparation Example S-5 can be prepared. Next, 1 mol (126 g) of dimethyl sulfate is added dropwise to the above intermediate product, and the quaternization reaction is carried out at 50 ° C., and after reaction for 2 hours, Preparation Example S shown in the following formula (II-5) Five 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 Tables 1 and 2, composite membranes 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 the mixer and kept continuously by means of a stirrer at room temperature. The photocurable resin composition of Example 1 can be manufactured 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 above-described photocurable resin composition is applied to a substrate, and ultraviolet light is irradiated thereto, whereby a photocured film can be formed, and the composite film of Example 1 can be manufactured. The obtained composite film was evaluated by the following evaluation methods such as surface characteristics, tackiness, antistatic property, antifogging / dew resistance 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 to 23 and Comparative Examples 1 to 9 use the same preparation method as the method of producing 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 the photocurable resin material and the cationic surfactant in the photocurable film, and the evaluation results are respectively As shown in Tables 1 and 2, they 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 Properties The photocurable resin compositions produced in Examples 1-23 and Comparative Examples 1-9 are uniformly applied to a PET film with a # 4 coating bar to form a 10 μm thick coating, and ultraviolet light is applied. After being cured, the photocured film is manually touched to determine if it is dry or not, and rated according to the following standard.
○: The surface is completely dried.
Δ: The surface is not completely dried.
×: Table Men'a Futatakku.
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 by ultraviolet light, a specific pattern is visually observed through the photocured film, and evaluated according to the following standard.
:: 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 film of the composite film produced in the above Examples 1-23 and Comparative Examples 1-9 is 10 × 10 (100) 1 mm × 1 mm with a cross cut tester or knife. After dividing into small squares and sticking with 3M600 tape, hold 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 to the total area of the exfoliated area is calculated and evaluated according to the following criteria.
○: 5 B
Δ: 4 B
X: 3B to 0B
5B is smooth and complete at the intersection of the incisions and no coating peels off.
4B has small area exfoliation at the intersection of the incisions, area percentage of exfoliated area ≦ 5%.
3B has exfoliation at the cut edges and at intersections, and the area percentage of the exfoliated area is more than 5% and not more than 15%.
In 2B, there are peelings in the cut edges, intersections and small squares, and the area percentage of the peeled area is more than 15% and 35% or less.
In 1B, there is peeling at the cutting edge, intersection and small square, and the area percentage of the peeling area is more than 35% and 65% or less.
0B has exfoliation at the cut edges, intersections and small squares, and the area percentage of the exfoliated 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 The impedance value of the composite membrane manufactured in the above Examples 1 to 23 and Comparative Examples 1 to 9 was measured with a surface impedance tester (manufactured by Static Solutions Inc., model number is RT-1000), and Evaluate with the following standard, and set the voltage of the impedance tester to 110 volts.
◎: 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. Antifogging / Dew Resistance The composite films produced in Examples 1 to 23 and Comparative Examples 1 to 9 are placed in a beaker port containing water at 80 ° C. The photocured film faces the beaker port, and the surface of the photocured film is 5 centimeters 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 one minute, it is visually judged whether or not there is condensation of water vapor on the surface of the photocured film, and evaluation is made according to the following standard.
◎: There is no condensation of water vapor, and evaporated water molecules adhere on the photo-cured film, and a flat water film (that is, a continuous water film) is formed.
Good: There is no condensation of water vapor, and the evaporated water molecules adhere to the photo-cured film and condense to an uneven water film.
Δ: 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 to water of the photocured film produced according to the present invention is measured by conventional prior art methods and equipment and is therefore not repeated 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 The environmental test is performed by placing the composite membrane manufactured in the above Examples 1 to 23 and Comparative Examples 1 to 9 in a high temperature and high humidity environment (in which the temperature is 65.degree. C. and the humidity is 80%). After a lapse of time, the composite membrane is taken out and the above evaluation items are sequentially performed. Among them, the evaluation method of the impedance value change after conducting the environmental test is calculated by the following formula (III), and is evaluated by the following standard.
: 0: 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 from the cationic surfactant of the present invention and the photocurable resin material had good surface characteristics and was subjected to an environmental test. After that, the cationic surfactants according to the invention do not suffer from the disadvantages of the conventional aftertack.
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 substrates, and does not affect the visual evaluation. The composite film produced according to the present invention has good antistatic properties, antifogging and dew proofing properties, and can further suppress damage to the device or substrate due to conventional static electricity and / or water vapor. As can be seen from the evaluation results of Comparative Examples 1 to 9 in Table 2, 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 light-cured film does not meet 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 conducting the environmental test, the photocurable film manufactured by this invention does not fall in effects, such as surface characteristics, antistatic property, anti-fogging 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 the antifogging / dew resistance of a composite film produced using it. It can be done. Among them, the cationic surfactant prepared according to the present invention is a conventional cationic surfactant because the group having the double bond of the cationic surfactant and the photocurable resin material can be further bonded. It can effectively overcome the defect of migration of (G) and further improve its 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 invention has been disclosed as an embodiment as described above, this is not a limitation of the invention. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is 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)
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、
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 pre-reacting the mixture, an intermediate is formed, the pre-reaction 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) Containing epoxy compounds,
R 1 -NH 2 (I-1)
In 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,
The said cationic surfactant is manufactured by performing the quaternization reaction with respect to the said intermediate product and the compound shown to a following Formula (I-3), and said cationic surfactant is described in Claim 1 or 2. And n and m each represent 0,
R 2 -A (I-3)
In the formula (I-3), a method for producing a cationic surfactant, wherein 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.
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 carrying out 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.
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。 Photocurable resin material,
A photocurable resin comprising the cationic surfactant according to claim 1 or 2, wherein the amount used is 0.5 parts by weight 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 photocurable film provided on one surface of the substrate and having a photocurable structure of the photocurable resin composition according to claim 7, wherein the contact angle with water does not exceed 50 degrees film.
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