JP6819152B2 - How to wash varnish containing amphipathic compounds - Google Patents
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- JP6819152B2 JP6819152B2 JP2016171909A JP2016171909A JP6819152B2 JP 6819152 B2 JP6819152 B2 JP 6819152B2 JP 2016171909 A JP2016171909 A JP 2016171909A JP 2016171909 A JP2016171909 A JP 2016171909A JP 6819152 B2 JP6819152 B2 JP 6819152B2
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- 239000002966 varnish Substances 0.000 title claims description 126
- 150000001875 compounds Chemical class 0.000 title claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 113
- -1 maleimide compound Chemical class 0.000 claims description 75
- 239000003921 oil Substances 0.000 claims description 70
- 238000005406 washing Methods 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 262
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 135
- 239000000243 solution Substances 0.000 description 78
- 239000012535 impurity Substances 0.000 description 39
- 239000002253 acid Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N heptyl methyl ketone Natural products CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical group CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWOIWTRRPFHBSI-UHFFFAOYSA-N 4-[2-[3-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=CC(C(C)(C)C=2C=CC(N)=CC=2)=CC=1C(C)(C)C1=CC=C(N)C=C1 KWOIWTRRPFHBSI-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical group C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VUKHQPGJNTXTPY-UHFFFAOYSA-N but-2-enylbenzene Chemical group CC=CCC1=CC=CC=C1 VUKHQPGJNTXTPY-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000005254 oxyacyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、両親媒性化合物を含有するワニスの水洗方法に関する。 The present invention relates to a method for washing a varnish containing an amphipathic compound with water.
プリント配線板、電子部品等に用いられる層間絶縁材料には、近年の環境意識の高まりから、鉛フリーはんだによる電子部品の搭載、及び、ハロゲンフリーによる難燃化の要求に対応できることが求められている。鉛フリーはんだは、従来のはんだよりも使用温度が高いため、層間絶縁材料にはより一層高い耐熱性が求められている。また、製品の安全性及び作業環境向上の観点から、層間絶縁材料は毒性の低い成分で構成されることが要求されており、それに伴い、毒性ガス等が発生しない樹脂が望まれている。 Interlayer insulation materials used for printed wiring boards, electronic components, etc. are required to be able to meet the demands of mounting electronic components with lead-free solder and flame retardancy with halogen-free due to the growing environmental awareness in recent years. There is. Since lead-free solder has a higher operating temperature than conventional solder, the interlayer insulating material is required to have even higher heat resistance. Further, from the viewpoint of product safety and improvement of working environment, the interlayer insulating material is required to be composed of components having low toxicity, and accordingly, a resin that does not generate toxic gas or the like is desired.
特許文献１に記載の少なくとも２つのイミド結合を有するマレイミド化合物は、優れた耐熱性、絶縁性及び低吸水性を発現し、加熱時に毒性ガスを発生しないという利点を有する。 The maleimide compound having at least two imide bonds described in Patent Document 1 has an advantage that it exhibits excellent heat resistance, insulating property and low water absorption, and does not generate toxic gas when heated.
特許文献１に記載の少なくとも２つのイミド結合を有するマレイミド化合物は、合成時に触媒として酸化合物を使用する他、マレイミド化反応時に過剰のマレイン酸化合物を使用する。そのため、合成終了後には、酸化合物と反応余りのマレイン酸化合物とを除去する必要がある。従来は、シリカゲルろ過による吸着処理が行われていたが、処理完了までの時間が長く、一度に処理できる量も少ないため、処理コストが高かった。 The maleimide compound having at least two imide bonds described in Patent Document 1 uses an acid compound as a catalyst during synthesis and an excess maleic acid compound during a maleimide formation reaction. Therefore, it is necessary to remove the acid compound and the maleic acid compound remaining in the reaction after the completion of the synthesis. In the past, adsorption treatment was performed by silica gel filtration, but the treatment cost was high because the time required to complete the treatment was long and the amount that could be treated at one time was small.
従来、疎水性の高い化合物を含有するワニスに水を添加すると、溶液は油層及び水層の２層に分離する。しかしながら、特許文献１に記載の少なくとも２つのイミド結合を有するマレイミド化合物は、両親媒性であるため、酸化合物及びマレイン酸化合物を除去するために水を添加しても乳化してしまい、２層に分離させることが困難であった。そこで、水の代わりに食塩水等のイオン性水溶液を添加すると、塩化された酸化合物及びマレイン酸化合物が選択的に水層に移行するため、油層及び水層の２層に分離させることができる。しかしながら、イオン性水溶液を添加すると、マレイミド化合物中にイオン性不純物が混入してしまい、層間絶縁材料として使用した場合に絶縁信頼性を低下させる恐れがあるとともに、マレイミド化合物の収率が低下するという問題がある。 Conventionally, when water is added to a varnish containing a highly hydrophobic compound, the solution is separated into two layers, an oil layer and an aqueous layer. However, since the maleimide compound having at least two imide bonds described in Patent Document 1 is amphipathic, it is emulsified even if water is added to remove the acid compound and the maleic acid compound, resulting in two layers. It was difficult to separate them into. Therefore, when an ionic aqueous solution such as a saline solution is added instead of water, the chlorinated acid compound and the maleic acid compound are selectively transferred to the aqueous layer, so that they can be separated into two layers, an oil layer and an aqueous layer. .. However, when an ionic aqueous solution is added, ionic impurities are mixed in the maleimide compound, which may lower the insulation reliability when used as an interlayer insulating material and lower the yield of the maleimide compound. There's a problem.
イオン性不純物が混入しない洗浄方法として、水の他に少量の水溶性アルコール又は水溶性ケトン類を混ぜて添加する方法がある。この方法を実施すると、溶液は油層、乳化層及び水層の３層に分離する。しかしながら、少なくとも２つのイミド結合を有するマレイミド化合物の一部がアルコール又はケトン類に溶解して乳化層に移行してしまうため、油層に残るマレイミド化合物の量が減少し、収率が低下するという問題がある。また、溶液を静置して３層に分離するまで時間がかかるため、処理コストも高かった。 As a cleaning method in which ionic impurities are not mixed, there is a method of adding a small amount of water-soluble alcohol or water-soluble ketones in addition to water. When this method is carried out, the solution is separated into three layers, an oil layer, an emulsified layer and an aqueous layer. However, since a part of the maleimide compound having at least two imide bonds is dissolved in alcohol or ketones and transferred to the emulsified layer, the amount of the maleimide compound remaining in the oil layer is reduced, and the yield is lowered. There is. In addition, since it takes time to allow the solution to stand and separate into three layers, the treatment cost is also high.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、少なくとも２つのイミド結合を有するマレイミド化合物等の両親媒性化合物を含有するワニスを水洗する方法であって、ワニスを短時間で収率高く水洗することができ、酸化合物の除去性に優れとともに、洗浄後のワニスのイオン性不純物濃度を十分に低減することができる水洗方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the prior art, and is a method of washing a varnish containing an amphoteric compound such as a maleimide compound having at least two imide bonds with water, in which the varnish is washed for a short time. It is an object of the present invention to provide a water washing method capable of washing with water in high yield, having excellent removability of acid compounds, and sufficiently reducing the concentration of ionic impurities in the varnish after washing.
本発明者らは上記の課題を解決すべく検討を進めた結果、下記の本発明により当該課題を解決できることを見出した。 As a result of studying to solve the above problems, the present inventors have found that the following problems can be solved by the present invention.
［１］両親媒性化合物を含有するワニスを水の中に添加して攪拌する工程と、攪拌後の混合溶液を水層と油層とに分離して水層を除去する、又は、水層と乳化層と油層とに分離して水層及び乳化層を除去する工程と、を有する、両親媒性化合物を含有するワニスの水洗方法。
［２］上記ワニスの質量をＡ、上記水の質量をＢとしたとき、０．１≦Ａ／Ｂ≦１．０を満たす、上記［１］に記載の方法。
［３］上記ワニスを添加する上記水の温度が５０〜１００℃である、上記［１］又は［２］に記載の方法。
［４］上記ワニスにおける上記両親媒性化合物の濃度が５〜９０質量％である、上記［１］〜［３］のいずれかに記載の方法。
［５］上記両親媒性化合物が、マレイミド基、少なくとも２つのイミド結合を有する２価の基、及び、飽和又は不飽和の２価の炭化水素基を有する化合物である、上記［１］〜［４］のいずれかに記載の方法。
［６］上記両親媒性化合物が、下記一般式（１）で表される少なくとも２つのイミド結合を有するマレイミド化合物である、上記［１］〜［５］のいずれかに記載の方法。
［式（１）中、Ｒ及びＱは各々独立に、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示し、ｎは１〜１００の整数を示す。］
[1] A step of adding a varnish containing an amphoteric compound to water and stirring the mixture, and separating the mixed solution after stirring into an aqueous layer and an oil layer to remove the aqueous layer, or using the aqueous layer. A method for washing a varnish containing an amphoteric compound, which comprises a step of separating an emulsified layer and an oil layer to remove the aqueous layer and the emulsified layer.
[2] The method according to [1] above, wherein 0.1 ≦ A / B ≦ 1.0 is satisfied when the mass of the varnish is A and the mass of water is B.
[3] The method according to [1] or [2] above, wherein the temperature of the water to which the varnish is added is 50 to 100 ° C.
[4] The method according to any one of [1] to [3] above, wherein the concentration of the amphipathic compound in the varnish is 5 to 90% by mass.
[5] The above-mentioned [1] to [5], wherein the amphoteric compound is a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group. 4] The method according to any one of.
[6] The method according to any one of [1] to [5] above, wherein the amphipathic compound is a maleimide compound having at least two imide bonds represented by the following general formula (1).
[In formula (1), R and Q are independently substituted or unsubstituted aliphatic groups having 1 to 100 carbon atoms, substituted or unsubstituted aromatic groups, substituted or unsubstituted heteroaromatic groups, or , Substituent or unsubstituted, indicates a siloxane moiety having 1 to 100 silicon numbers, and n indicates an integer of 1 to 100. ]
両親媒性化合物を含有するワニスの中に水を添加して攪拌した場合、添加した水の大部分が乳化してしまい、油層、乳化層及び水層の３層に分離するまでに長時間を要し、洗浄コストが上がり、また洗浄後の両親媒性化合物の収率も不十分であった。これに対し、上記本発明のワニスの水洗方法によれば、水の中に、両親媒性化合物を含有するワニスを添加して攪拌することで、驚くべきことに、ワニスの中に水を添加した場合と比べて水の乳化を大幅に抑制することができ、水とワニスとの混合溶液を短時間で油層、乳化層及び水層の３層、又は、油層及び水層の２層に分離することができる。加えて、乳化層が形成された場合でもその量は少なく、両親媒性化合物を効率的に油層に分離することができ、同時に酸化合物及びイオン性不純物を効率的に水層に分離することができるため、洗浄後の両親媒性化合物の収率を向上させることができ、且つ、酸化合物及びイオン性不純物を十分に除去することができる。また、ワニスの洗浄に水を用いているため、食塩水等のイオン性水溶液を用いた場合と比較して、洗浄後のワニスのイオン性不純物濃度を十分に低減することができる。 When water is added to a varnish containing an amphipathic compound and stirred, most of the added water is emulsified, and it takes a long time to separate into three layers: an oil layer, an emulsified layer and an aqueous layer. In addition, the washing cost was increased, and the yield of the amphipathic compound after washing was also insufficient. On the other hand, according to the method for washing the varnish of the present invention with water, by adding a varnish containing an amphoteric compound to water and stirring the varnish, surprisingly, water is added to the varnish. The emulsification of water can be significantly suppressed as compared with the case where the water is emulsified, and the mixed solution of water and varnish is separated into three layers of oil layer, emulsified layer and aqueous layer, or two layers of oil layer and aqueous layer in a short time. can do. In addition, even when an emulsified layer is formed, the amount is small, and the amphipathic compound can be efficiently separated into the oil layer, and at the same time, the acid compound and the ionic impurity can be efficiently separated into the aqueous layer. Therefore, the yield of the amphipathic compound after washing can be improved, and the acid compound and ionic impurities can be sufficiently removed. Further, since water is used for washing the varnish, the concentration of ionic impurities in the varnish after washing can be sufficiently reduced as compared with the case where an ionic aqueous solution such as a saline solution is used.
本発明によれば、両親媒性化合物を含有するワニスを水洗する方法であって、ワニスを短時間で収率高く水洗することができ、酸化合物の除去性に優れとともに、洗浄後のワニスのイオン性不純物濃度を十分に低減することができる水洗方法を提供することができる。 According to the present invention, it is a method of washing a varnish containing an amphipathic compound with water, and the varnish can be washed with water in a short time with a high yield, excellent in removing acid compounds, and of the varnish after washing. It is possible to provide a water washing method capable of sufficiently reducing the concentration of ionic impurities.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail according to its preferred embodiment.
本実施形態のワニスの水洗方法は、両親媒性化合物を含有するワニスを水の中に添加して攪拌する工程と、攪拌後の混合溶液を水層と油層とに分離して水層を除去する、又は、水層と乳化層と油層とに分離して水層及び乳化層を除去する工程と、を有する。 The method for washing the varnish of the present embodiment is a step of adding a varnish containing an amphoteric compound to water and stirring the mixture, and separating the mixed solution after stirring into an aqueous layer and an oil layer to remove the aqueous layer. Or, it has a step of separating the aqueous layer, the emulsified layer and the oil layer and removing the aqueous layer and the emulsified layer.
［両親媒性化合物］
本実施形態の両親媒性化合物とは、分子内に疎水性構造と親水性構造とを併せ持つ化合物である。両親媒性化合物としては、例えば、イミド化合物、アミド化合物、マレイミド化合物、エステル化合物、フェノール化合物、アクリル化合物、ウレタン化合物等が挙げられる。中でも、（ａ）マレイミド基、（ｂ）少なくとも２つのイミド結合を有する２価の基、及び、（ｃ）飽和又は不飽和の２価の炭化水素基を有する化合物（以下、「（Ａ１）成分」ということがある）は、当該化合物を含むワニスに水を添加すると乳化しやすく、分離が困難であるため、本実施形態の水洗方法により水洗することが好ましい。更に、下記一般式（１）で表される少なくとも２つのイミド結合を有するマレイミド化合物（以下、「（Ａ２）成分」ということがある）は、疎水性構造と親水性構造の繰り返し単位から構成されるため、当該化合物を含むワニスに水を添加すると乳化しやすく、分離が困難であるため、本実施形態の水洗方法により水洗することが好ましい。
［式（１）中、Ｒ及びＱは各々独立に、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示し、ｎは１〜１００の整数を示す。］
[Aphiphile]
The amphipathic compound of the present embodiment is a compound having both a hydrophobic structure and a hydrophilic structure in the molecule. Examples of the amphoteric compound include imide compounds, amide compounds, maleimide compounds, ester compounds, phenol compounds, acrylic compounds, urethane compounds and the like. Among them, a compound having (a) a maleimide group, (b) a divalent group having at least two imide bonds, and (c) a saturated or unsaturated divalent hydrocarbon group (hereinafter, "(A1) component" When water is added to the varnish containing the compound, it is easy to emulsify and separation is difficult. Therefore, it is preferable to wash with water by the water washing method of the present embodiment. Further, the maleimide compound having at least two imide bonds represented by the following general formula (1) (hereinafter, may be referred to as “component (A2)”) is composed of repeating units of a hydrophobic structure and a hydrophilic structure. Therefore, when water is added to the varnish containing the compound, it is easy to emulsify and separation is difficult. Therefore, it is preferable to wash with water by the water washing method of the present embodiment.
[In formula (1), R and Q are independently substituted or unsubstituted aliphatic groups having 1 to 100 carbon atoms, substituted or unsubstituted aromatic groups, substituted or unsubstituted heteroaromatic groups, or , Substituent or unsubstituted, indicates a siloxane moiety having a silicon number of 1 to 100, and n indicates an integer of 1 to 100. ]
以下、（Ａ１）成分について説明する。なお、（Ａ１）成分を構成する（ａ）マレイミド基を構造（ａ）、（ｂ）少なくとも２つのイミド結合を有する２価の基を構造（ｂ）、（ｃ）飽和又は不飽和の２価の炭化水素基を構造（ｃ）ということがある。 Hereinafter, the component (A1) will be described. It should be noted that (a) a maleimide group constituting the component (A1) is a structure (a), (b) a divalent group having at least two imide bonds is a structure (b), (c) a saturated or unsaturated divalent group. The hydrocarbon group of is sometimes referred to as structure (c).
（ａ）マレイミド基は特に限定されず、一般的なマレイミド基である。（ａ）マレイミド基は芳香環に結合していても、脂肪族鎖に結合していてもよいが、脂肪族鎖に結合していてもよい。 (A) The maleimide group is not particularly limited and is a general maleimide group. (A) The maleimide group may be bonded to an aromatic ring or an aliphatic chain, or may be bonded to an aliphatic chain.
（ｂ）少なくとも２つのイミド結合を有する２価の基としては特に限定されないが、例えば、下記式（Ｉ）で表される基が挙げられる。 (B) The divalent group having at least two imide bonds is not particularly limited, and examples thereof include a group represented by the following formula (I).
式（Ｉ）中、Ｒ１は４価の有機基を示す。Ｒ１は４価の有機基であれば特に限定されないが、例えば、炭素数１〜１００の炭化水素基であってもよく、炭素数２〜５０の炭化水素基であってもよく、炭素数４〜３０の炭化水素基であってもよい。 In formula (I), R 1 represents a tetravalent organic group. R 1 is not particularly limited as long as it is a tetravalent organic group, but may be, for example, a hydrocarbon group having 1 to 100 carbon atoms, a hydrocarbon group having 2 to 50 carbon atoms, or a hydrocarbon group having 2 to 50 carbon atoms. It may be 4 to 30 hydrocarbon groups.
Ｒ１は、置換又は非置換のシロキサン部位であってもよい。シロキサン部位としては、例えば、ジメチルシロキサン、メチルフェニルシロキサン、ジフェニルシロキサン等に由来する構造が挙げられる。 R 1 may be a substituted or unsubstituted siloxane moiety. Examples of the siloxane moiety include structures derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and the like.
Ｒ１が置換されている場合、置換基としては、例えば、アルキル基、アルケニル基、アルキニル基、水酸基、アルコキシ基、メルカプト基、シクロアルキル基、置換シクロアルキル基、ヘテロ環基、置換ヘテロ環基、アリール基、置換アリール基、ヘテロアリール基、置換ヘテロアリール基、アリールオキシ基、置換アリールオキシ基、ハロゲン原子、ハロアルキル基、シアノ基、ニトロ基、ニトロソ基、アミノ基、アミド基、−Ｃ（Ｏ）Ｈ、−ＮＲｘＣ（Ｏ）−Ｎ（Ｒｘ）２、−ＯＣ（Ｏ）−Ｎ（Ｒｘ）２、アシル基、オキシアシル基、カルボキシル基、カルバメート基、スルホンアミド基等が挙げられる。ここで、Ｒｘは水素原子又はアルキル基を示す。これらの置換基は目的、用途等に合わせて、１種類又は２種類以上を選択できる。 When R 1 is substituted, the substituents include, for example, an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, an alkoxy group, a mercapto group, a cycloalkyl group, a substituted cycloalkyl group, a heterocyclic group, a substituted heterocyclic group. , Aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, aryloxy group, substituted aryloxy group, halogen atom, haloalkyl group, cyano group, nitro group, nitroso group, amino group, amide group, -C ( O) H, -NR x C (O) -N (R x ) 2 , -OC (O) -N (R x ) 2 , acyl group, oxyacyl group, carboxyl group, carbamate group, sulfonamide group, etc. Be done. Here, R x represents a hydrogen atom or an alkyl group. One type or two or more types of these substituents can be selected according to the purpose, application and the like.
Ｒ１としては、例えば、１分子中に２個以上の無水物環を有する酸無水物の４価の残基、すなわち、酸無水物から酸無水物基（−Ｃ（＝Ｏ）ＯＣ（＝Ｏ）−）を２個除いた４価の基が好ましい。酸無水物としては、後述するような化合物が例示できる。 As R 1 , for example, a tetravalent residue of an acid anhydride having two or more anhydride rings in one molecule, that is, an acid anhydride group (-C (= O) OC (=) A tetravalent group excluding two O)-) is preferable. Examples of the acid anhydride include compounds described below.
Ｒ１は芳香族であってもよく、無水ピロメリット酸から２つの酸無水物基を取り除いた基であってもよい。すなわち、構造（ｂ）は下記式（ＩＩＩ）で表される基であってもよい。 R 1 may be aromatic, or may be a group obtained by removing two acid anhydride groups from pyromellitic anhydride. That is, the structure (b) may be a group represented by the following formula (III).
構造（ｂ）は、（Ａ１）成分中に複数存在してもよい。その場合、構造（ｂ）は、それぞれ同一であってもよく、異なっていてもよい。（Ａ１）成分中の構造（ｂ）の数は、２〜４０であってもよく、２〜２０であってもよく、２〜１０であってもよい。 A plurality of structures (b) may be present in the component (A1). In that case, the structures (b) may be the same or different. The number of structures (b) in the component (A1) may be 2 to 40, 2 to 20, or 2 to 10.
構造（ｂ）は、下記式（ＩＶ）又は下記式（Ｖ）で表される基であってもよい。 The structure (b) may be a group represented by the following formula (IV) or the following formula (V).
構造（ｃ）は特に限定されず、直鎖状、分岐状、環状のいずれであってもよい。また、飽和又は不飽和の２価の炭化水素基の炭素数は、８〜１００であってもよい。構造（ｃ）は、炭素数８〜１００の分岐を有していてもよいアルキレン基であってもよく、炭素数１０〜７０の分岐を有していてもよいアルキレン基であってもよく、炭素数１５〜５０の分岐を有していてもよいアルキレン基であってもよい。 The structure (c) is not particularly limited, and may be linear, branched, or cyclic. Further, the saturated or unsaturated divalent hydrocarbon group may have 8 to 100 carbon atoms. The structure (c) may be an alkylene group which may have a branch having 8 to 100 carbon atoms, or an alkylene group which may have a branch having 10 to 70 carbon atoms. It may be an alkylene group which may have a branch having 15 to 50 carbon atoms.
構造（ｃ）としては、例えば、ノニレン基、デシレン基、ウンデシレン基、ドデシレン基、テトラデシレン基、ヘキサデシレン基、オクタデシレン基、ノナデシレン基等のアルキレン基；ベンジレン基、フェニレン基、ナフチレン基等のアリーレン基；フェニレンメチレン基、フェニレンエチレン基、ベンジルプロピレン基、ナフチレンメチレン基、ナフチレンエチレン基等のアリーレンアルキレン基；フェニレンジメチレン基、フェニレンジエチレン基等のアリーレンジアルキレン基などが挙げられる。 The structure (c) includes, for example, an alkylene group such as a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group and a nonadesilene group; an arylene group such as a benzylene group, a phenylene group and a naphthylene group; Aliren alkylene groups such as phenylene methylene group, phenylene ethylene group, benzyl propylene group, naphthylene methylene group and naphthylene ethylene group; allylene alkylene groups such as phenylenedi methylene group and phenylenedi ethylene group can be mentioned.
構造（ｃ）は、下記式（ＩＩ）で表される基であってもよい。 The structure (c) may be a group represented by the following formula (II).
式（ＩＩ）中、Ｒ２及びＲ３は各々独立に炭素数４〜５０のアルキレン基を示す。Ｒ２及びＲ３は各々独立に、炭素数５〜２５のアルキレン基であってもよく、炭素数６〜１０のアルキレン基であってもよく、炭素数７〜１０のアルキレン基であってもよい。 In formula (II), R 2 and R 3 each independently represent an alkylene group having 4 to 50 carbon atoms. R 2 and R 3 may be independently alkylene groups having 5 to 25 carbon atoms, alkylene groups having 6 to 10 carbon atoms, or alkylene groups having 7 to 10 carbon atoms. Good.
式（ＩＩ）中、Ｒ４は炭素数４〜５０のアルキル基を示す。Ｒ４は炭素数５〜２５のアルキル基であってもよく、炭素数６〜１０のアルキル基であってもよく、炭素数７〜１０のアルキル基であってもよい。 In formula (II), R 4 represents an alkyl group having 4 to 50 carbon atoms. R 4 may be an alkyl group having 5 to 25 carbon atoms, an alkyl group having 6 to 10 carbon atoms, or an alkyl group having 7 to 10 carbon atoms.
式（ＩＩ）中、Ｒ５は炭素数２〜５０のアルキル基を示す。Ｒ５は炭素数３〜２５のアルキル基であってもよく、炭素数４〜１０のアルキル基であってもよく、炭素数５〜８のアルキル基であってもよい。 In formula (II), R 5 represents an alkyl group having 2 to 50 carbon atoms. R 5 may be an alkyl group having 3 to 25 carbon atoms, an alkyl group having 4 to 10 carbon atoms, or an alkyl group having 5 to 8 carbon atoms.
構造（ｃ）は、（Ａ１）成分中に複数存在してもよい。その場合、構造（ｃ）はそれぞれ同一であってもよく、異なっていてもよい。例えば、（Ａ１）成分中に２〜４０の構造（ｃ）が存在してもよく、２〜２０の構造（ｃ）が存在してもよく、２〜１０の構造（ｃ）が存在してもよい。 A plurality of structures (c) may be present in the component (A1). In that case, the structures (c) may be the same or different. For example, 2 to 40 structures (c) may be present in the component (A1), 2 to 20 structures (c) may be present, and 2 to 10 structures (c) are present. May be good.
次に、（Ａ２）成分について説明する。（Ａ２）成分は上記一般式（１）で表されるマレイミド化合物であり、分子内に少なくとも２つのイミド結合を有する。式（１）中、Ｒ及びＱは各々独立に、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示すが、Ｒは上述の構造（ｃ）と同じものであってもよく、Ｑは上述のＲ１と同じものであってもよい。また、ｎは１〜１０の整数であってもよい。 Next, the component (A2) will be described. The component (A2) is a maleimide compound represented by the above general formula (1) and has at least two imide bonds in the molecule. In formula (1), R and Q are independently substituted or unsubstituted aliphatic groups having 1 to 100 carbon atoms, substituted or unsubstituted aromatic groups, substituted or unsubstituted heteroaromatic groups, or Although the substituted or unsubstituted siloxane moiety having 1 to 100 silicon numbers is shown, R may be the same as the above-mentioned structure (c), and Q may be the same as the above-mentioned R 1 . Further, n may be an integer of 1 to 10.
（Ａ１）成分及び（Ａ２）成分としてより具体的には、下記式（ＸＩＩ−１）〜（ＸＩＩ−３）で表される化合物が挙げられる。式（ＸＩＩ−１）〜（ＸＩＩ−３）において、ｎは１〜１０の整数を示す。 More specific examples of the component (A1) and the component (A2) include compounds represented by the following formulas (XII-1) to (XII-3). In formulas (XII-1) to (XII-3), n represents an integer of 1-10.
（Ａ１）成分及び（Ａ２）成分の分子量は特に限定されない。（Ａ１）成分及び（Ａ２）成分の重量平均分子量（Ｍｗ）の下限値は、５００、１０００、１５００又は１７００であってもよい。また、（Ａ１）成分及び（Ａ２）成分のＭｗの上限値は、１００００、９０００、７０００又は５０００であってもよい。（Ａ１）成分及び（Ａ２）成分のＭｗは、５００〜１００００であってもよく、１０００〜９０００であってもよく、１５００〜９０００であってもよく、１５００〜７０００であってもよく、１７００〜５０００であってもよい。 The molecular weights of the component (A1) and the component (A2) are not particularly limited. The lower limit of the weight average molecular weight (Mw) of the component (A1) and the component (A2) may be 500, 1000, 1500 or 1700. Further, the upper limit of Mw of the component (A1) and the component (A2) may be 10000, 9000, 7000 or 5000. The Mw of the component (A1) and the component (A2) may be 500 to 10000, 1000 to 9000, 1500 to 9000, 1500 to 7000, and 1700. It may be ~ 5000.
（Ａ１）成分及び（Ａ２）成分のＭｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定することができる。 The Mw of the component (A1) and the component (A2) can be measured by a gel permeation chromatography (GPC) method.
なお、ＧＰＣの測定条件は下記のとおりである。
ポンプ：Ｌ−６２００型［株式会社日立ハイテクノロジーズ製］
検出器：Ｌ−３３００型ＲＩ［株式会社日立ハイテクノロジーズ製］
カラムオーブン：Ｌ−６５５Ａ−５２［株式会社日立ハイテクノロジーズ製］
ガードカラム及びカラム：ＴＳＫ Ｇｕａｒｄｃｏｌｕｍｎ ＨＨＲ−Ｌ＋ＴＳＫｇｅｌ Ｇ４０００ＨＨＲ＋ＴＳＫｇｅｌ Ｇ２０００ＨＨＲ［すべて東ソー株式会社製、商品名］
カラムサイズ：６．０×４０ｍｍ（ガードカラム）、７．８×３００ｍｍ（カラム）
溶離液：テトラヒドロフラン
試料濃度：３０ｍｇ／５ｍＬ
注入量：２０μＬ
流量：１．００ｍＬ／分
測定温度：４０℃
The GPC measurement conditions are as follows.
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolum HHR-L + TSKgel G4000HHR + TSKgel G2000HHR [All manufactured by Tosoh Corporation, product name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C
（Ａ１）成分及び（Ａ２）成分を製造する方法は限定されない。（Ａ１）成分及び（Ａ２）成分は、例えば、酸無水物とジアミンとを反応させてアミン末端化合物を合成した後、該アミン末端化合物を過剰の無水マレイン酸と反応させることで作製してもよい。 The method for producing the component (A1) and the component (A2) is not limited. The component (A1) and the component (A2) may be prepared, for example, by reacting an acid anhydride with a diamine to synthesize an amine-terminated compound, and then reacting the amine-terminated compound with an excess of maleic anhydride. Good.
酸無水物としては、例えば、無水ピロメリット酸、無水マレイン酸、無水コハク酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物等が挙げられる。これらの酸無水物は目的、用途等に合わせて、１種類を単独で用いても、２種類以上を併用してもよい。なお、前述のとおり、上記式（Ｉ）のＲ１として、上記に挙げられるような酸無水物に由来する４価の有機基を用いることができる。酸無水物は、無水ピロメリット酸であってもよい。 Examples of the acid anhydride include pyromellitic anhydride, maleic anhydride, succinic anhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl. Examples thereof include tetracarboxylic dianhydride and 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride. These acid anhydrides may be used alone or in combination of two or more, depending on the purpose, application and the like. As described above, as R 1 of the above formula (I), a tetravalent organic group derived from the acid anhydride as described above can be used. The acid anhydride may be pyromellitic anhydride.
ジアミンとしては、例えば、ダイマージアミン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、１，３−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ジアミノ−３，３’−ジヒドロキシビフェニル、１，３−ビス［２−（４−アミノフェニル）−２−プロピル］ベンゼン、１，４−ビス［２−（４−アミノフェニル）−２−プロピル］ベンゼン、ポリオキシアルキレンジアミン、［３，４−ビス（１−アミノヘプチル）−６−ヘキシル−５−（１−オクテニル）］シクロヘキセン等が挙げられる。これらは目的、用途等に合わせて、１種類を単独で用いても、２種類以上を併用してもよい。 Examples of the diamine include diamine diamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (4-aminophenoxy) benzene, and 4,4'-bis (4-amino). Phenoxy) biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4) -Aminophenyl) -2-propyl] benzene, polyoxyalkylenediamine, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene and the like. These may be used alone or in combination of two or more depending on the purpose, application and the like.
（Ａ１）成分及び（Ａ２）成分の合成は、通常、溶媒中で触媒として酸を用いて行われる。溶媒としては、後述するワニス溶媒と同様の溶媒が用いられる。酸としては、メタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、１０−カンファースルホン酸、蟻酸、酢酸、無水酢酸、マレイン酸、塩酸等が挙げられる。これらの中でも、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、１０−カンファースルホン酸、塩酸等の強酸が好適に用いられる。 The synthesis of the component (A1) and the component (A2) is usually carried out using an acid as a catalyst in a solvent. As the solvent, the same solvent as the varnish solvent described later is used. Examples of the acid include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 10-camparsulfonic acid, formic acid, acetic anhydride, acetic anhydride, maleic acid, hydrochloric acid and the like. Among these, strong acids such as trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 10-camphorsulfonic acid and hydrochloric acid are preferably used.
触媒として用いられる酸（酸化合物）は、合成終了後、洗浄により除去する必要がある。本実施形態の水洗方法によれば、合成終了後に残存する上記酸を十分に且つ効率的に除去することができる。また、（Ａ１）成分及び（Ａ２）成分の合成時に過剰な無水マレイン酸を使用するが、本実施形態の水洗方法によれば、反応余りの無水マレイン酸（マレイン酸化合物）を十分に且つ効率的に除去することができる。 The acid (acid compound) used as a catalyst needs to be removed by washing after the synthesis is completed. According to the water washing method of the present embodiment, the acid remaining after the completion of synthesis can be sufficiently and efficiently removed. Further, although excess maleic anhydride is used during the synthesis of the component (A1) and the component (A2), according to the water washing method of the present embodiment, the maleic anhydride (maleic acid compound) remaining in the reaction is sufficiently and efficiently used. Can be removed as a target.
［ワニス溶媒］
本実施形態の水洗方法において、両親媒性化合物を含有するワニスに使用する溶媒としては、例えば、トルエン、キシレン、メシチレン等の芳香族系溶媒、ヘキサン、シクロヘキサン等の飽和炭化水素系溶媒、シクロペンタノン、シクロヘキサノン等の疎水性ケトン類、及び、原油蒸留時に得られる石油系溶媒などが挙げられる。これらの中でも、分離時間、及び脱溶の容易さの観点から、トルエン、キシレンを使用することが好ましい。
[Varnish solvent]
In the water washing method of the present embodiment, examples of the solvent used for the varnish containing the amphoteric compound include aromatic solvents such as toluene, xylene and mesitylene, saturated hydrocarbon solvents such as hexane and cyclohexane, and cyclopenta. Examples thereof include hydrophobic ketones such as non- and cyclohexanone, and petroleum-based solvents obtained during crude oil distillation. Among these, toluene and xylene are preferably used from the viewpoint of separation time and ease of desolubilization.
［ワニス濃度］
本実施形態の水洗方法において、両親媒性化合物を含有するワニス中の両親媒性化合物の濃度は、ワニス全量を基準として５〜９０質量％であることが好ましい。ワニス濃度が５質量％以上であると、溶媒の必要量が大きくなり過ぎず、溶媒コストを抑制することができる。ワニス濃度が９０質量％以下であると、酸化合物及びイオン性不純物の除去効率が向上する傾向がある。酸化合物及びイオン性不純物の除去効率、及びコストの観点から、ワニス濃度は、２０〜８０質量％であることがより好ましく、３０〜７０質量％であることが更に好ましい。
[Varnish concentration]
In the water washing method of the present embodiment, the concentration of the amphipathic compound in the varnish containing the amphipathic compound is preferably 5 to 90% by mass based on the total amount of the varnish. When the varnish concentration is 5% by mass or more, the required amount of the solvent does not become too large, and the solvent cost can be suppressed. When the varnish concentration is 90% by mass or less, the efficiency of removing acid compounds and ionic impurities tends to be improved. From the viewpoint of removal efficiency of acid compounds and ionic impurities and cost, the varnish concentration is more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass.
ワニス中の両親媒性化合物の濃度は、加熱等によりワニスから溶媒を除去する前後の質量を比較することで算出することができる。例えば、両親媒性化合物を含有するワニス１ｇを重さＺ１ｇのアルミシャーレにとり、所定の温度で所定の時間加熱後のアルミシャーレ（残存した両親媒性化合物を含む）の重さがＺ２ｇであったとき、ワニスの濃度は下記の式で求められる。
ワニス濃度＝（Ｚ１＋１−Ｚ２）×１００ （質量％）
ここで、加熱温度及び加熱時間は、両親媒性化合物を残存させたまま溶媒を十分に除去できる温度及び時間であればよい。
The concentration of the amphipathic compound in the varnish can be calculated by comparing the mass before and after removing the solvent from the varnish by heating or the like. For example, 1 g of a varnish containing an amphipathic compound is placed in an aluminum petri dish weighing Z 1 g, and the weight of the aluminum petri dish (including the remaining amphipathic compound) after heating at a predetermined temperature for a predetermined time is Z 2. When it is g, the concentration of the varnish is calculated by the following formula.
Varnish concentration = (Z 1 + 1-Z 2 ) x 100 (mass%)
Here, the heating temperature and heating time may be any temperature and time at which the solvent can be sufficiently removed while the amphipathic compound remains.
［ワニスのイオン性不純物濃度］
本実施形態の水洗方法において、洗浄前のワニスのイオン性不純物濃度は、１０００質量ｐｐｍを上回っていてもよい。１０００質量ｐｐｍを上回るイオン性不純物を含有するワニスを本実施形態の水洗方法により水洗することで、イオン性不純物濃度を大幅に低減することができる。ここで、イオン性不純物としては、両親媒性化合物の合成時に使用される触媒に由来するイオンが挙げられ、例えば、硫黄（Ｓ）イオン、フッ素（Ｆ）イオン、塩素（Ｃｌ）イオン等が挙げられる。また、ワニスの洗浄に食塩水等のイオン性水溶液を用いた場合、洗浄後のワニスには、ナトリウム（Ｎａ）イオン、塩素（Ｃｌ）イオン等のイオン性水溶液に由来するイオン性不純物が混入しやすい。本実施形態の水洗方法においては、ワニスの洗浄に水を用いているため、イオン性不純物の混入を抑制でき、洗浄後のワニスのイオン性不純物濃度を十分に低減することができる。
[Varnish ionic impurity concentration]
In the water washing method of the present embodiment, the concentration of ionic impurities in the varnish before washing may exceed 1000 mass ppm. By washing the varnish containing ionic impurities exceeding 1000 mass ppm with water by the water washing method of the present embodiment, the concentration of ionic impurities can be significantly reduced. Here, examples of the ionic impurities include ions derived from a catalyst used in the synthesis of amphipathic compounds, and examples thereof include sulfur (S) ion, fluorine (F) ion, and chlorine (Cl) ion. Be done. When an ionic aqueous solution such as a saline solution is used for washing the varnish, ionic impurities derived from the ionic aqueous solution such as sodium (Na) ion and chlorine (Cl) ion are mixed in the washed varnish. Cheap. In the water washing method of the present embodiment, since water is used for washing the varnish, it is possible to suppress the mixing of ionic impurities and sufficiently reduce the concentration of ionic impurities in the varnish after washing.
洗浄後のワニスのイオン性不純物濃度は、５０質量ｐｐｍ以下であることが好ましく、３０質量ｐｐｍ以下であることがより好ましく、１０質量ｐｐｍ未満であることが特に好ましい。洗浄後のワニスのイオン性不純物濃度が５０質量ｐｐｍ以下であることで、当該ワニスを層間絶縁材料に用いた場合の絶縁信頼性の低下を抑制することができる。 The concentration of ionic impurities in the varnish after washing is preferably 50 mass ppm or less, more preferably 30 mass ppm or less, and particularly preferably less than 10 mass ppm. When the concentration of ionic impurities in the varnish after cleaning is 50 mass ppm or less, it is possible to suppress a decrease in insulation reliability when the varnish is used as an interlayer insulating material.
ワニスのイオン性不純物濃度は、ワニスを脱溶して、得られた両親媒性化合物を酸分解（マイクロウェーブ法）により前処理し、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＯＥＳ）にて、両親媒性化合物中のイオン濃度を測定することで求めることができる。 The concentration of ionic impurities in the varnish is determined by dedissolving the varnish, pretreating the obtained amphipathic compound by acid decomposition (microwave method), and using an inductively coupled plasma emission spectrophotometer (ICP-OES). It can be determined by measuring the ion concentration in the amphipathic compound.
［ワニスと水の使用量］
本実施形態の水洗方法において、両親媒性化合物を含有するワニスの量をＡ（単位：質量部）、水の量をＢ（単位：質量部）としたとき、０．１≦Ａ／Ｂ≦１．０を満たすことが好ましい。Ａ／Ｂ≦１．０とすることで、ワニスを添加した水が乳化し過ぎることを防ぎ、混合溶液を油層、乳化層及び水層、又は、油層及び水層に分離するまでに要する時間を短縮（例えば静置時間を３時間以下に短縮）することができる。そのため、製造コストを抑制し、また収率も向上させることができる。Ａ／Ｂ≧０．１とすることで、水の必要量を抑制し、廃水コストを低減することができる。分離時間、及び廃水コストの観点から、Ａ／Ｂは、０．３≦Ａ／Ｂ≦０．８を満たすことがより好ましく、０．５≦Ａ／Ｂ≦０．７を満たすことが更に好ましい。
[Varnish and water usage]
In the water washing method of the present embodiment, when the amount of varnish containing an amphipathic compound is A (unit: parts by mass) and the amount of water is B (unit: parts by mass), 0.1 ≦ A / B ≦ It is preferable to satisfy 1.0. By setting A / B ≦ 1.0, it is possible to prevent the water to which the varnish is added from being over-emulsified, and the time required for the mixed solution to be separated into an oil layer, an emulsified layer and an aqueous layer, or an oil layer and an aqueous layer. It can be shortened (for example, the standing time can be shortened to 3 hours or less). Therefore, the production cost can be suppressed and the yield can be improved. By setting A / B ≧ 0.1, the required amount of water can be suppressed and the wastewater cost can be reduced. From the viewpoint of separation time and wastewater cost, A / B more preferably satisfies 0.3 ≦ A / B ≦ 0.8, and further preferably 0.5 ≦ A / B ≦ 0.7. ..
［水の種類］
本実施形態の水洗方法に使用する水としては特に限定されないが、例えば、イオン交換水、蒸留水、純水、超純水、水道水、工業用水等を用いることができる。これらの中でも、洗浄後のワニスのイオン性不純物濃度をより低減する観点から、イオン交換水、蒸留水、純水、超純水を用いることが好ましい。
[Type of water]
The water used in the water washing method of the present embodiment is not particularly limited, and for example, ion-exchanged water, distilled water, pure water, ultrapure water, tap water, industrial water and the like can be used. Among these, ion-exchanged water, distilled water, pure water, and ultrapure water are preferably used from the viewpoint of further reducing the concentration of ionic impurities in the varnish after washing.
また、本実施形態の水洗方法に使用する水のイオン性不純物濃度は、３００質量ｐｐｍ以下であることが好ましく、１００質量ｐｐｍ以下であることがより好ましい。イオン性不純物濃度が上記上限値以下である水を用いることで、洗浄後のワニスのイオン性不純物濃度をより低減することができる。水のイオン性不純物濃度は、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＯＥＳ）にて、水中のイオン濃度を測定することで求めることができる。 The concentration of ionic impurities in the water used in the washing method of the present embodiment is preferably 300 mass ppm or less, and more preferably 100 mass ppm or less. By using water having an ionic impurity concentration of not more than the above upper limit value, the ionic impurity concentration of the varnish after washing can be further reduced. The ionic impurity concentration of water can be determined by measuring the ionic concentration in water with an inductively coupled plasma emission spectrophotometer (ICP-OES).
［水の温度］
本実施形態の水洗方法において、ワニスを添加する際の水の温度は、５０〜１００℃であることが好ましい。水の温度が５０℃以上であると、酸化合物及びイオン性不純物の除去効率が向上し、収率も向上する傾向がある。酸化合物及びイオン性不純物の除去効率の観点から、水の温度は７０〜１００℃であることがより好ましい。
[Water temperature]
In the water washing method of the present embodiment, the temperature of water when adding the varnish is preferably 50 to 100 ° C. When the temperature of water is 50 ° C. or higher, the efficiency of removing acid compounds and ionic impurities tends to be improved, and the yield tends to be improved. From the viewpoint of the efficiency of removing acid compounds and ionic impurities, the temperature of water is more preferably 70 to 100 ° C.
水の温度は、ワニスを添加した後も上記範囲内の温度を維持することが好ましい。すなわち、ワニスを水の中に添加後、上記範囲内の温度を維持して混合溶液を攪拌することが好ましい。混合溶液を静置して、油層、乳化層及び水層、又は、油層及び水層に分離する際には、混合溶液の温度は５０〜１００℃とすることが好ましい。 The temperature of the water is preferably maintained within the above range even after the addition of the varnish. That is, it is preferable to add the varnish to water and then stir the mixed solution while maintaining the temperature within the above range. When the mixed solution is allowed to stand and separated into an oil layer, an emulsified layer and an aqueous layer, or an oil layer and an aqueous layer, the temperature of the mixed solution is preferably 50 to 100 ° C.
［ワニスと水の添加順序］
本実施形態の水洗方法は、水の中に、両親媒性化合物を含有するワニスを添加することで実施する。ワニスを添加する際に、水は攪拌していることが好ましい。攪拌中のワニスの中に水を添加してしまうと、水の全て又は大部分が乳化してしまい、水とワニスとの混合溶液を油層、乳化層及び水層に分離するまでに長時間（例えば３時間を超える静置時間）を要してしまうため、製造コストが上がり、また収率も低下する恐れがある。これに対し、攪拌中の水の中にワニスを添加した場合、水の乳化を大幅に抑制することができ、水とワニスとの混合溶液を短時間で油層、乳化層及び水層の３層、又は、油層及び水層の２層に分離することができる。
[Varnish and water addition order]
The washing method of the present embodiment is carried out by adding a varnish containing an amphipathic compound to water. When adding the varnish, it is preferable that the water is agitated. If water is added to the varnish during stirring, all or most of the water will be emulsified, and it will take a long time to separate the mixed solution of water and varnish into an oil layer, an emulsified layer and an aqueous layer ( For example, a standing time of more than 3 hours) is required, so that the manufacturing cost may increase and the yield may decrease. On the other hand, when varnish is added to the water being stirred, emulsification of water can be significantly suppressed, and a mixed solution of water and varnish can be quickly prepared into three layers of an oil layer, an emulsified layer and an aqueous layer. , Or it can be separated into two layers, an oil layer and an aqueous layer.
［ワニスと水の混合攪拌時間］
本実施形態の水洗方法において、水の中に、両親媒性化合物を含有するワニスを添加した後、酸化合物及びイオン性不純物の水層及び／又は乳化層への移行を促進するため、５分〜２時間攪拌することが好ましい。攪拌時間を５分以上とすることで、酸化合物及びイオン性不純物の除去効率を向上させることができる。攪拌時間を２時間以下とすることで、工程時間が長くなることを防ぎ、製造コストを低減することができる。酸化合物及びイオン性不純物の除去効率、及びコストの観点から、攪拌時間は２０分〜１時間であることがより好ましい。
[Mixing and stirring time of varnish and water]
In the water washing method of the present embodiment, after adding the varnish containing the amphipathic compound to the water, 5 minutes to promote the transfer of the acid compound and the ionic impurity to the aqueous layer and / or the emulsified layer. It is preferable to stir for ~ 2 hours. By setting the stirring time to 5 minutes or more, the efficiency of removing acid compounds and ionic impurities can be improved. By setting the stirring time to 2 hours or less, it is possible to prevent the process time from becoming long and reduce the manufacturing cost. From the viewpoint of removal efficiency of acid compounds and ionic impurities and cost, the stirring time is more preferably 20 minutes to 1 hour.
［攪拌条件］
本実施形態の水洗方法において、ワニスを添加する前の水の攪拌、及び、添加後の水とワニスとの混合溶液の攪拌は、平羽根タービン、パドル翼、プロペラ翼、アンカー翼等を用いて行うことができる。攪拌は、回転数１０ｒｐｍ以上の条件で行うことが好ましい。回転数を１０ｒｐｍ以上とすることで、混合溶液を油層、乳化層及び水層、又は、油層及び水層に分離するまでに要する時間を短縮（例えば静置時間を３時間以下に短縮）することができる。そのため、製造コストを抑制し、また、収率を向上させることができる。分離時間、及び廃水コストの観点から、回転数２０ｒｐｍ以上の条件で行うことがより好ましい。
[Stirring conditions]
In the water washing method of the present embodiment, the water before adding the varnish and the mixed solution of the water and the varnish after the addition are stirred by using a flat blade turbine, a paddle blade, a propeller blade, an anchor blade, or the like. It can be carried out. Stirring is preferably performed under the condition of a rotation speed of 10 rpm or more. By setting the rotation speed to 10 rpm or more, the time required to separate the mixed solution into the oil layer, the emulsified layer and the aqueous layer, or the oil layer and the aqueous layer is shortened (for example, the standing time is shortened to 3 hours or less). Can be done. Therefore, the manufacturing cost can be suppressed and the yield can be improved. From the viewpoint of separation time and wastewater cost, it is more preferable to carry out under the condition of rotation speed of 20 rpm or more.
［ワニスと水の混合溶液の静置時間］
本実施形態の水洗方法では、両親媒性化合物を含有するワニスと水とを攪拌した後、混合溶液を静置して、水層、乳化層及び油層の３層、又は、水層及び油層の２層に分離させる必要がある。静置時間は５分〜２時間であることが好ましい。静置時間を５分以上とすることで、十分に分離させることができ、収率の低下を抑制することができる。静置時間を２時間以下とすることで、工程時間が長くなることを防ぎ、製造コストを低減することができる。収率、及びコストの観点から、静置時間は２０分〜１時間であることがより好ましい。
[Standing time of mixed solution of varnish and water]
In the water washing method of the present embodiment, after stirring the varnish containing the amphipathic compound and water, the mixed solution is allowed to stand to form three layers of an aqueous layer, an emulsified layer and an oil layer, or an aqueous layer and an oil layer. It needs to be separated into two layers. The standing time is preferably 5 minutes to 2 hours. By setting the standing time to 5 minutes or more, sufficient separation can be achieved and a decrease in yield can be suppressed. By setting the standing time to 2 hours or less, it is possible to prevent the process time from becoming long and reduce the manufacturing cost. From the viewpoint of yield and cost, the standing time is more preferably 20 minutes to 1 hour.
［酸化合物及びイオン性不純物の除去］
水とワニスの混合溶液を静置して水層、乳化層及び油層の３層、又は、水層及び油層の２層に分離させた後、３層に分離した場合は水層及び乳化層を、２層に分離した場合は水層を除去することで、ワニス中の酸化合物及びイオン性不純物を除去することができる。分離した水層及び乳化層、又は水層は、容器下に抜き出し弁が付いている場合は、そこから除去することができる。また、抜き出し弁が付いていない場合は、容器底から、ポンプにより、水層及び乳化層、又は水層を汲み上げることにより、それらを除去することができる。
[Removal of acid compounds and ionic impurities]
The mixed solution of water and varnish is allowed to stand to separate into three layers of water layer, emulsified layer and oil layer, or two layers of water layer and oil layer, and when separated into three layers, the water layer and emulsified layer are separated. When separated into two layers, the acid compound and ionic impurities in the varnish can be removed by removing the aqueous layer. The separated aqueous layer and emulsified layer, or aqueous layer can be removed from the outlet valve if it is provided under the container. If the outlet valve is not provided, it can be removed by pumping the aqueous layer and the emulsified layer or the aqueous layer from the bottom of the container.
［洗浄回数］
両親媒性化合物を含有するワニスを水の中に添加して攪拌する工程、並びに、攪拌後の混合溶液を水層と油層とに分離して水層を除去する、又は、水層と乳化層と油層とに分離して水層及び乳化層を除去する工程を含む一連の洗浄工程は、複数回繰り返し行うことができる。一連の洗浄工程の繰り返し回数（洗浄回数）は、２〜５回であることが好ましく、２〜３回であることがより好ましい。洗浄回数が２回以上であることで、酸化合物及びイオン性不純物の除去効率を向上させることができる。洗浄回数が５回以下であることで、収率の低下を抑制し、またコストを低減することができる。
[Number of washings]
A step of adding a varnish containing an amphoteric compound to water and stirring, and separating the mixed solution after stirring into an aqueous layer and an oil layer to remove the aqueous layer, or an aqueous layer and an emulsified layer. A series of washing steps including a step of separating the water layer and the oil layer and removing the aqueous layer and the emulsified layer can be repeated a plurality of times. The number of repetitions (number of washings) of the series of washing steps is preferably 2 to 5 times, and more preferably 2 to 3 times. When the number of washings is 2 or more, the efficiency of removing acid compounds and ionic impurities can be improved. When the number of washings is 5 or less, the decrease in yield can be suppressed and the cost can be reduced.
一連の洗浄工程を繰り返し行う場合、各洗浄工程における上記Ａ／Ｂの値は、０．１≦Ａ／Ｂ≦１．０を常に満たすことが好ましく、０．３≦Ａ／Ｂ≦０．８を常に満たすことがより好ましく、０．５≦Ａ／Ｂ≦０．７を常に満たすことが更に好ましい。上記条件を満たすように、各洗浄工程において毎回濃度調整を行うことが好ましい。 When a series of cleaning steps are repeated, the value of A / B in each cleaning step preferably always satisfies 0.1 ≦ A / B ≦ 1.0, and 0.3 ≦ A / B ≦ 0.8. Is more preferable, and 0.5 ≦ A / B ≦ 0.7 is more preferable. It is preferable to adjust the concentration each time in each cleaning step so as to satisfy the above conditions.
［洗浄総時間］
本実施形態の水洗方法において、全ての洗浄工程に要する時間を合計した洗浄総時間は、１〜１０時間であることが好ましく、１〜５時間であることがより好ましい。本実施形態の水洗方法によれば、洗浄総時間を短縮しつつ、十分な酸化合物及びイオン性不純物の除去効率を得ることができる。
[Total cleaning time]
In the water washing method of the present embodiment, the total washing time, which is the total time required for all the washing steps, is preferably 1 to 10 hours, more preferably 1 to 5 hours. According to the water washing method of the present embodiment, it is possible to obtain sufficient removal efficiency of acid compounds and ionic impurities while shortening the total washing time.
［樹脂酸価］
本実施形態の水洗方法により洗浄した後の両親媒性化合物は、樹脂酸価が０〜１０ｍｇＫＯＨ／ｇとなっていることが好ましく、０〜８ｍｇＫＯＨ／ｇとなっていることがより好ましい。樹脂酸価が１０ｍｇＫＯＨ／ｇ以下であることで、酸化合物が十分に除去されているといえる。
[Resin acid value]
The amphipathic compound washed by the water washing method of the present embodiment preferably has a resin acid value of 0 to 10 mgKOH / g, and more preferably 0 to 8 mgKOH / g. When the resin acid value is 10 mgKOH / g or less, it can be said that the acid compound is sufficiently removed.
樹脂酸価は、洗浄後のワニスにフェノールフタレイン溶液を加え、水酸化カリウムエタノール溶液を、溶液が赤くなるまで滴下した時の滴下量から求めることができる。 The resin acid value can be determined from the amount of the phenolphthalein solution added to the washed varnish and the potassium hydroxide ethanol solution added dropwise until the solution turns red.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
（実施例１〜４）
還流冷却器、水分捕捉器付きの５Ｌフラスコに、トルエン（和光純薬（株）製）２２８０．０ｇ、Ｐｒｉａｍｉｎｅ １０７５（商品名、クローダジャパン（株）製、ダイマージアミン）５１６．６ｇを加え、攪拌羽根で攪拌させた。そこにメタンスルホン酸４６．３ｇ（和光純薬（株）製）を少しずつ添加した。オイルバスを使用して、フラスコ内を５０℃に加熱した後、無水ピロメリット酸（和光純薬（株）製）１３６．６ｇを添加した。フラスコ内を１１５℃に加熱し、トルエンを１０時間還流させた。イミド基の脱水閉環反応により、水２２．６ｇが回収された。フラスコ内温度を４０℃まで空冷し、無水マレイン酸（和光純薬（株）製）７９．４ｇを添加した。フラスコ内を１１５℃に加熱し、トルエンを２０時間還流させた。マレイミド基の脱水閉環反応により、水１２．１ｇが回収された。フラスコ内温度を４０℃まで空冷し、両親媒性化合物として下記一般式（２）で表される少なくとも２つのイミド結合を有するマレイミド化合物を含有するワニスを得た。ワニス中のイオン性不純物（Ｓイオン）の含有量は１０００質量ｐｐｍ（検出上限）を超えていた。
［式中、ｎは１〜１０の整数を示す。］
(Examples 1 to 4)
To a 5L flask equipped with a reflux condenser and a water trap, add 2280.0 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 516.6 g of Priamine 1075 (trade name, manufactured by Crowder Japan Co., Ltd., diamine diamine) and stir. It was stirred with a blade. 46.3 g of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little. After heating the inside of the flask to 50 ° C. using an oil bath, 136.6 g of pyromellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The inside of the flask was heated to 115 ° C., and toluene was refluxed for 10 hours. 22.6 g of water was recovered by the dehydration ring closure reaction of the imide group. The temperature inside the flask was air-cooled to 40 ° C., and 79.4 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The inside of the flask was heated to 115 ° C., and toluene was refluxed for 20 hours. 12.1 g of water was recovered by the dehydration ring closure reaction of the maleimide group. The temperature inside the flask was air-cooled to 40 ° C. to obtain a varnish containing a maleimide compound having at least two imide bonds represented by the following general formula (2) as an amphipathic compound. The content of ionic impurities (S ions) in the varnish exceeded 1000 mass ppm (detection upper limit).
[In the formula, n represents an integer of 1-10. ]
合成終了後のワニスをトルエンで希釈又は還流により濃縮し、上記マレイミド化合物の濃度を３０質量％又は７０質量％に調整した。濃度調整後のワニス１ｋｇを、回転数３５ｒｐｍで攪拌中の純水（１．５ｋｇ又は２．０ｋｇ、温度：７０℃又は９０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２〜０．４時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層（上層）であるトルエン溶液のみを回収した。その後、得られたトルエン溶液０．９７ｋｇ（上記マレイミド化合物の濃度を３０．０質量％又は７０．０質量％に調整したもの）を、回転数３５ｒｐｍで攪拌中の純水（１．５ｋｇ又は２．０ｋｇ、温度：７０℃又は９０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２〜０．４時間静置させ、水層、乳化層及び油層の３層に分離させた。水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。再び、得られたトルエン溶液０．９５ｋｇ（上記マレイミド化合物の濃度を３０．０質量％又は７０．０質量％に調整したもの）を、回転数３５ｒｐｍで攪拌中の純水（１．５ｋｇ又は２．０ｋｇ、温度：７０℃又は９０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２〜０．４時間静置させ、水層、乳化層及び油層の３層に分離させた。水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。これにより、洗浄されたワニスを得た。洗浄回数は合計３回であった。各実施例の洗浄時の具体的条件は表１に示す。 After completion of the synthesis, the varnish was diluted with toluene or concentrated by reflux to adjust the concentration of the maleimide compound to 30% by mass or 70% by mass. 1 kg of the varnish after adjusting the concentration is added to pure water (1.5 kg or 2.0 kg, temperature: 70 ° C. or 90 ° C.) being stirred at a rotation speed of 35 rpm, and the stirring rotation speed and the solution temperature are maintained. , Stirred for 0.3 hours. Then, the mixed solution was allowed to stand for 0.2 to 0.4 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer (upper layer), was recovered. Then, 0.97 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass or 70.0% by mass) was stirred with pure water (1.5 kg or 2) at a rotation speed of 35 rpm. It was added to 0.0 kg, temperature: 70 ° C. or 90 ° C.), and the mixture was stirred for 0.3 hours while maintaining the stirring speed and the solution temperature. Then, the mixed solution was allowed to stand for 0.2 to 0.4 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. The aqueous layer and the emulsified layer were removed, and only the toluene solution, which was an oil layer, was recovered. Again, 0.95 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass or 70.0% by mass) was stirred with pure water (1.5 kg or 2) at a rotation speed of 35 rpm. It was added to 0.0 kg, temperature: 70 ° C. or 90 ° C.), and the mixture was stirred for 0.3 hours while maintaining the stirring speed and the solution temperature. Then, the mixed solution was allowed to stand for 0.2 to 0.4 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. The aqueous layer and the emulsified layer were removed, and only the toluene solution, which was an oil layer, was recovered. This gave a washed varnish. The total number of washes was three. Table 1 shows specific conditions for cleaning each example.
（実施例５）
還流冷却器、水分捕捉器付きの５Ｌフラスコに、トルエン（和光純薬（株）製）２２８０．０ｇ、２，２，４−トリメチルヘキサン−１，６−ジアミン（Ｂｏｃ Ｓｃｉｅｎｃｅｓ社製）６０９．５ｇを加え、攪拌羽根で攪拌させた。そこにメタンスルホン酸５０．０ｇ（和光純薬（株）製）を少しずつ添加した。フラスコ内温度を４０℃まで空冷し、無水マレイン酸（和光純薬（株）製）９０６．１ｇを添加した。フラスコ内を１１５℃に加熱し、トルエンを２０時間還流させた。マレイミド基の脱水閉環反応により、水１３８．６ｇが回収された。フラスコ内温度を４０℃まで空冷し、両親媒性化合物として下記一般式（３）で表される脂肪族マレイミド化合物を含有するワニスを得た。ワニス中のイオン性不純物（Ｓイオン）の含有量は１０００質量ｐｐｍ（検出上限）を超えていた。
Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 2280.0 g, 2,2,4-trimethylhexane-1,6-diamine (manufactured by Boc Sciences) 609.5 g in a 5 L flask equipped with a reflux condenser and a water trap. Was added, and the mixture was stirred with a stirring blade. To this, 50.0 g of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little. The temperature inside the flask was air-cooled to 40 ° C., and 906.1 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The inside of the flask was heated to 115 ° C., and toluene was refluxed for 20 hours. 138.6 g of water was recovered by the dehydration ring closure reaction of the maleimide group. The temperature inside the flask was air-cooled to 40 ° C. to obtain a varnish containing an aliphatic maleimide compound represented by the following general formula (3) as an amphipathic compound. The content of ionic impurities (S ions) in the varnish exceeded 1000 mass ppm (detection upper limit).
合成終了後のワニスをトルエンで希釈し、上記マレイミド化合物の濃度を３０質量％に調整した。濃度調整後のワニス１ｋｇを、回転数３５ｒｐｍで攪拌中の純水（２．０ｋｇ、温度：９０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層（上層）であるトルエン溶液のみを回収した。その後、得られたトルエン溶液０．９８ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を、回転数３５ｒｐｍで攪拌中の純水（１．９６ｋｇ、温度：９０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２時間静置させ、水層、乳化層及び油層の３層に分離させた。水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。再び、得られたトルエン溶液０．９６ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を、回転数３５ｒｐｍで攪拌中の純水（１．９２ｋｇ、温度：９０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２時間静置させ、水層、乳化層及び油層の３層に分離させた。水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。これにより、洗浄されたワニスを得た。洗浄回数は合計３回であった。 The varnish after completion of the synthesis was diluted with toluene to adjust the concentration of the maleimide compound to 30% by mass. 1 kg of the varnish after adjusting the concentration was added to pure water (2.0 kg, temperature: 90 ° C.) being stirred at a rotation speed of 35 rpm, and the mixture was stirred for 0.3 hours while maintaining the stirring rotation speed and the solution temperature. .. Then, the mixed solution was allowed to stand for 0.2 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer (upper layer), was recovered. Then, 0.98 kg of the obtained toluene solution (the concentration of the maleimide compound adjusted to 30.0% by mass) was stirred in pure water (1.96 kg, temperature: 90 ° C.) at a rotation speed of 35 rpm. Was added to the mixture, and the mixture was stirred for 0.3 hours while maintaining the stirring rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 0.2 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. The aqueous layer and the emulsified layer were removed, and only the toluene solution, which was an oil layer, was recovered. Again, 0.96 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass) was stirred in pure water (1.92 kg, temperature: 90 ° C.) at a rotation speed of 35 rpm. Was added to the mixture, and the mixture was stirred for 0.3 hours while maintaining the stirring rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 0.2 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. The aqueous layer and the emulsified layer were removed, and only the toluene solution, which was an oil layer, was recovered. This gave a washed varnish. The total number of washes was three.
（比較例１）
実施例１〜４と同様の方法で、上記一般式（２）で表される少なくとも２つのイミド結合を有するマレイミド化合物を含有するワニスを得た。このワニスをトルエンで希釈し、上記マレイミド化合物の濃度を３０質量％に調整した。濃度調整後のワニス１ｋｇを、１２０ｇのシリカゲルを充填したガラスフリット漏斗でろ過した。これにより、洗浄されたワニスを得た。溶液のろ過が完全に完了するまでに２４時間を要した。
(Comparative Example 1)
A varnish containing a maleimide compound having at least two imide bonds represented by the above general formula (2) was obtained by the same method as in Examples 1 to 4. The varnish was diluted with toluene to adjust the concentration of the maleimide compound to 30% by mass. After adjusting the concentration, 1 kg of the varnish was filtered through a glass frit funnel filled with 120 g of silica gel. This gave a washed varnish. It took 24 hours to complete the filtration of the solution.
（比較例２）
実施例１〜４と同様の方法で、上記一般式（２）で表される少なくとも２つのイミド結合を有するマレイミド化合物を含有するワニスを得た。このワニスをトルエンで希釈し、上記マレイミド化合物の濃度を３０質量％に調整した。回転数３５ｒｐｍで攪拌中のワニス１ｋｇ（温度：９０℃）に、飽和食塩水２．０ｋｇ（温度：９０℃）を添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２時間静置させ、水層及び油層の２層に分離させた。２層の内、下層の水層を除去し、油層（上層）であるトルエン溶液のみを回収した。その後、得られたトルエン溶液０．９７ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を回転数３５ｒｐｍで攪拌させ、そこに９０℃の飽和食塩水２．０ｋｇ（温度：９０℃）を添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２時間静置させ、水層及び油層の２層に分離させた。２層の内、下層の水層を除去し、油層であるトルエン溶液のみを回収した。再び、得られたトルエン溶液０．９７ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を回転数３５ｒｐｍで攪拌させ、そこに９０℃の飽和食塩水２．０ｋｇ（温度：９０℃）を添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を０．２時間静置させ、水層及び油層の２層に分離させた。２層の内、下層の水層を除去し、油層であるトルエン溶液のみを回収した。これにより、洗浄されたワニスを得た。洗浄回数は合計３回であった。
(Comparative Example 2)
A varnish containing a maleimide compound having at least two imide bonds represented by the above general formula (2) was obtained by the same method as in Examples 1 to 4. The varnish was diluted with toluene to adjust the concentration of the maleimide compound to 30% by mass. 2.0 kg of saturated saline (temperature: 90 ° C.) was added to 1 kg of varnish (temperature: 90 ° C.) being stirred at a rotation speed of 35 rpm, and the mixture was stirred for 0.3 hours while maintaining the stirring rotation speed and solution temperature. .. Then, the mixed solution was allowed to stand for 0.2 hours while maintaining the solution temperature, and separated into two layers, an aqueous layer and an oil layer. Of the two layers, the lower aqueous layer was removed, and only the toluene solution, which was the oil layer (upper layer), was recovered. Then, 0.97 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm, and 2.0 kg of saturated saline solution at 90 ° C. (temperature: 90) was stirred therein. ° C.) was added, and the mixture was stirred for 0.3 hours while maintaining the stirring speed and the solution temperature. Then, the mixed solution was allowed to stand for 0.2 hours while maintaining the solution temperature, and separated into two layers, an aqueous layer and an oil layer. Of the two layers, the lower aqueous layer was removed, and only the toluene solution, which was an oil layer, was recovered. Again, 0.97 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm, and 2.0 kg of saturated saline solution at 90 ° C. (temperature: 90) was stirred there. ° C.) was added, and the mixture was stirred for 0.3 hours while maintaining the stirring speed and the solution temperature. Then, the mixed solution was allowed to stand for 0.2 hours while maintaining the solution temperature, and separated into two layers, an aqueous layer and an oil layer. Of the two layers, the lower aqueous layer was removed, and only the toluene solution, which was an oil layer, was recovered. This gave a washed varnish. The total number of washes was three.
（比較例３）
実施例１〜４と同様の方法で、上記一般式（２）で表される少なくとも２つのイミド結合を有するマレイミド化合物を含有するワニスを得た。このワニスをトルエンで希釈し、上記マレイミド化合物の濃度を３０質量％に調整した。濃度調整後のワニス１ｋｇを、回転数３５ｒｐｍで攪拌中のエタノール水溶液２．０ｋｇ（濃度：３０質量％、温度：８０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層（上層）であるトルエン溶液のみを回収した。その後、得られたトルエン溶液０．８９ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を、回転数３５ｒｐｍで攪拌中のエタノール水溶液２．０ｋｇ（濃度：３０質量％、温度：８０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。再び、得られたトルエン溶液０．７７ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を、回転数３５ｒｐｍで攪拌中のエタノール水溶液２．０ｋｇ（濃度：３０質量％、温度：８０℃）の中に添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。これにより、洗浄されたワニスを得た。洗浄回数は合計３回であった。
(Comparative Example 3)
A varnish containing a maleimide compound having at least two imide bonds represented by the above general formula (2) was obtained by the same method as in Examples 1 to 4. The varnish was diluted with toluene to adjust the concentration of the maleimide compound to 30% by mass. 1 kg of the varnish after adjusting the concentration was added to 2.0 kg of an aqueous ethanol solution (concentration: 30% by mass, temperature: 80 ° C.) being stirred at a rotation speed of 35 rpm, and 0 while maintaining the stirring rotation speed and the solution temperature. . Stirred for 3 hours. Then, the mixed solution was allowed to stand for 1 hour while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer (upper layer), was recovered. Then, 0.89 kg of the obtained toluene solution (concentration of the maleimide compound adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm to 2.0 kg of an aqueous ethanol solution (concentration: 30% by mass, temperature: It was added to 80 ° C.), and the mixture was stirred for 0.3 hours while maintaining the stirring speed and the solution temperature. Then, the mixed solution was allowed to stand for 1 hour while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer, was recovered. Again, 0.77 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm with 2.0 kg of an aqueous ethanol solution (concentration: 30% by mass, temperature:). It was added to 80 ° C.), and the mixture was stirred for 0.3 hours while maintaining the stirring speed and the solution temperature. Then, the mixed solution was allowed to stand for 1 hour while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer, was recovered. This gave a washed varnish. The total number of washes was three.
（比較例４）
実施例１〜４と同様の方法で、上記一般式（２）で表される少なくとも２つのイミド結合を有するマレイミド化合物を含有するワニスを得た。このワニスをトルエンで希釈し、上記マレイミド化合物の濃度を３０質量％に調整した。回転数３５ｒｐｍで攪拌中のワニス１ｋｇに、９０℃の純水２．０ｋｇを添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１２時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層（上層）であるトルエン溶液のみを回収した。その後、得られたトルエン溶液０．８８ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を回転数３５ｒｐｍで攪拌させ、そこに９０℃の純水２．０ｋｇを添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１２時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。再び、得られたトルエン溶液０．７６ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を回転数３５ｒｐｍで攪拌させ、そこに９０℃の純水２．０ｋｇを添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１２時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。これにより、洗浄されたワニスを得た。洗浄回数は合計３回であった。
(Comparative Example 4)
A varnish containing a maleimide compound having at least two imide bonds represented by the above general formula (2) was obtained by the same method as in Examples 1 to 4. The varnish was diluted with toluene to adjust the concentration of the maleimide compound to 30% by mass. To 1 kg of the varnish being stirred at a rotation speed of 35 rpm, 2.0 kg of pure water at 90 ° C. was added, and the mixture was stirred for 0.3 hours while maintaining the stirring rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 12 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer (upper layer), was recovered. Then, 0.88 kg of the obtained toluene solution (the concentration of the maleimide compound adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm, 2.0 kg of pure water at 90 ° C. was added thereto, and the mixture was stirred. The mixture was stirred for 0.3 hours while maintaining the rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 12 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer, was recovered. Again, 0.76 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm, 2.0 kg of pure water at 90 ° C. was added thereto, and the mixture was stirred. The mixture was stirred for 0.3 hours while maintaining the rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 12 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer, was recovered. This gave a washed varnish. The total number of washes was three.
（比較例５）
実施例５と同様の方法で、上記一般式（３）で表される脂肪族マレイミド化合物を含有するワニスを得た。このワニスをトルエンで希釈し、上記マレイミド化合物の濃度を３０質量％に調整した。回転数３５ｒｐｍで攪拌中のワニス１ｋｇに、９０℃の純水２．０ｋｇを添加し、攪拌回転数及び溶液温度を維持したまま、０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１２時間静置させ、水層、乳化層及び油層の３層に分離させた。３層の内、下層及び中間層である水層及び乳化層を除去し、油層（上層）であるトルエン溶液のみを回収した。その後、得られたトルエン溶液０．８８ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を回転数３５ｒｐｍで攪拌させ、そこに９０℃の純水２．０ｋｇを添加し、攪拌回転数及び溶液温度を維持したまま０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１２時間静置させ、水層、乳化層及び油層の３層に分離させた。水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。再び、得られたトルエン溶液０．７６ｋｇ（上記マレイミド化合物の濃度を３０．０質量％に調整したもの）を回転数３５ｒｐｍで攪拌させ、そこに９０℃の純水２．０ｋｇを添加し、攪拌回転数及び溶液温度を維持したまま０．３時間攪拌した。その後、溶液温度を維持したまま、混合溶液を１２時間静置させ、水層、乳化層及び油層の３層に分離させた。水層及び乳化層を除去し、油層であるトルエン溶液のみを回収した。これにより、洗浄されたワニスを得た。洗浄回数は合計３回であった。
(Comparative Example 5)
A varnish containing an aliphatic maleimide compound represented by the above general formula (3) was obtained by the same method as in Example 5. The varnish was diluted with toluene to adjust the concentration of the maleimide compound to 30% by mass. To 1 kg of the varnish being stirred at a rotation speed of 35 rpm, 2.0 kg of pure water at 90 ° C. was added, and the mixture was stirred for 0.3 hours while maintaining the stirring rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 12 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. Of the three layers, the lower layer and the intermediate layer, the aqueous layer and the emulsified layer, were removed, and only the toluene solution, which was the oil layer (upper layer), was recovered. Then, 0.88 kg of the obtained toluene solution (the concentration of the maleimide compound adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm, 2.0 kg of pure water at 90 ° C. was added thereto, and the mixture was stirred. The mixture was stirred for 0.3 hours while maintaining the rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 12 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. The aqueous layer and the emulsified layer were removed, and only the toluene solution, which was an oil layer, was recovered. Again, 0.76 kg of the obtained toluene solution (the concentration of the maleimide compound was adjusted to 30.0% by mass) was stirred at a rotation speed of 35 rpm, 2.0 kg of pure water at 90 ° C. was added thereto, and the mixture was stirred. The mixture was stirred for 0.3 hours while maintaining the rotation speed and the solution temperature. Then, the mixed solution was allowed to stand for 12 hours while maintaining the solution temperature, and separated into three layers of an aqueous layer, an emulsified layer and an oil layer. The aqueous layer and the emulsified layer were removed, and only the toluene solution, which was an oil layer, was recovered. This gave a washed varnish. The total number of washes was three.
＜評価方法＞
（ワニスの濃度測定方法）
両親媒性化合物を含有するワニス１ｇを重さＺ１ｇのアルミシャーレにとり、１５５℃で１時間加熱後のアルミシャーレ（残存した両親媒性化合物を含む）の重さがＺ２ｇであったとき、ワニスの濃度は下記の式で求められる。結果を表１及び表２に示す。
ワニス濃度＝（Ｚ１＋１−Ｚ２）×１００ （質量％）
<Evaluation method>
(Varnish concentration measurement method)
1 g of a varnish containing an amphipathic compound was placed in an aluminum petri dish weighing Z 1 g, and the weight of the aluminum petri dish (including the remaining amphipathic compound) after heating at 155 ° C. for 1 hour was Z 2 g. Then, the concentration of the varnish is calculated by the following formula. The results are shown in Tables 1 and 2.
Varnish concentration = (Z 1 + 1-Z 2 ) x 100 (mass%)
（樹脂酸価の測定方法）
両親媒性化合物の濃度を３０質量％に調整したワニス１ｇに、トルエン１ｇ及び２−プロパノール１ｇを加え、攪拌した。そこにフェノールフタレイン溶液を１滴加え、濃度０．１ｍｏｌ／Ｌの水酸化カリウムエタノール溶液を、溶液が赤くなるまで滴下した。滴下量がＸｍＬのとき、樹脂酸価は下記の式で求められる。結果を表１及び表２に示す。
樹脂酸価＝（Ｘ×５．６１）／０．３ （ｍｇＫＯＨ／ｇ）
(Measuring method of resin acid value)
To 1 g of a varnish having an amphipathic compound concentration adjusted to 30% by mass, 1 g of toluene and 1 g of 2-propanol were added and stirred. One drop of a phenolphthalein solution was added thereto, and a potassium hydroxide ethanol solution having a concentration of 0.1 mol / L was added dropwise until the solution turned red. When the dropping amount is XmL, the resin acid value is calculated by the following formula. The results are shown in Tables 1 and 2.
Resin acid value = (X × 5.61) /0.3 (mgKOH / g)
（収率の算出方法）
洗浄前の両親媒性化合物を含有するワニスの量がＸ１ｇ、濃度がＹ１質量％で、洗浄後に得られた両親媒性化合物を含有するワニスの量がＸ２ｇ、濃度がＹ２質量％のとき、収率は下記の式で求められる。結果を表１及び表２に示す。
収率＝｛（Ｘ２×Ｙ２）／（Ｘ１×Ｙ１）｝×１００ （％）
(Yield calculation method)
The amount of varnish containing the amphipathic compound before washing was X 1 g and the concentration was Y 1 % by mass, and the amount of varnish containing the amphipathic compound obtained after washing was X 2 g and the concentration was Y 2. When it is mass%, the yield is calculated by the following formula. The results are shown in Tables 1 and 2.
Yield = {(X 2 x Y 2 ) / (X 1 x Y 1 )} x 100 (%)
（イオン性不純物濃度の測定）
洗浄後に得られたマレイミド化合物を含有するワニスを脱溶して、得られたマレイミド化合物を酸分解（マイクロウェーブ法）により前処理し、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＯＥＳ）にて、マレイミド化合物中のイオン濃度を測定した。測定器には日立ハイテクサイエンス製ＳＰＳ５１００を用いた。結果を表１及び表２に示す。
(Measurement of ionic impurity concentration)
The varnish containing the maleimide compound obtained after washing is desolubilized, the obtained maleimide compound is pretreated by acid decomposition (microwave method), and an inductively coupled plasma emission spectrophotometer (ICP-OES) is used. The ion concentration in the maleimide compound was measured. As a measuring instrument, SPS5100 manufactured by Hitachi High-Tech Science was used. The results are shown in Tables 1 and 2.
表１及び表２中、Ａ、Ｂ、Ｂ２及びＢ３の意味はそれぞれ以下の通りである。
Ａ：両親媒性化合物を含有するワニスの質量
Ｂ：水の質量
Ｂ２：飽和食塩水の質量
Ｂ３：エタノール水溶液（濃度３０質量％）の質量
In Table 1 and Table 2, the meanings of A, B, B2 and B3 are as follows.
A: Mass of varnish containing amphipathic compound B: Mass of water B2: Mass of saturated saline solution B3: Mass of aqueous ethanol solution (concentration 30% by mass)
比較例１、４及び５は、洗浄総時間が２４時間以上となった。比較例１及び２は、洗浄後のワニスのイオン性不純物濃度が低減できていなかった。比較例３は、エタノールにマレイミド化合物の一部が溶解してしまったため、収率が７０％を下回った。また、比較例１及び３〜５はいずれも、洗浄後の樹脂酸価が１０．０ｍｇＫＯＨ／ｇを上回っており、収率も比較例３〜５では７０％を下回っていた。これらに対して、実施例１〜５はいずれも、洗浄総時間が３時間以内と短く、洗浄後の樹脂酸価が７．０ｍｇＫＯＨ／ｇを下回っており、収率も７０％を上回っており、イオン性不純物の混入が観測されなかった。
In Comparative Examples 1, 4 and 5, the total cleaning time was 24 hours or more. In Comparative Examples 1 and 2, the concentration of ionic impurities in the varnish after washing could not be reduced. In Comparative Example 3, the yield was less than 70% because a part of the maleimide compound was dissolved in ethanol. Further, in both Comparative Examples 1 and 3 to 5, the resin acid value after washing was higher than 10.0 mgKOH / g, and the yield was also lower than 70% in Comparative Examples 3 to 5. On the other hand, in all of Examples 1 to 5, the total cleaning time was as short as 3 hours or less, the resin acid value after cleaning was lower than 7.0 mgKOH / g, and the yield was also higher than 70%. , No ionic impurities were observed.
Claims (7)
攪拌後の混合溶液を水層と油層とに分離して水層を除去する、又は、水層と乳化層と油層とに分離して水層及び乳化層を除去する工程と、
を有し、
前記両親媒性化合物が、マレイミド基、少なくとも２つのイミド結合を有する２価の基、及び、飽和又は不飽和の２価の炭化水素基を有する化合物である、両親媒性化合物を含有するワニスの水洗方法。 A step of adding a varnish containing an amphipathic compound to water and stirring it,
A step of separating the mixed solution after stirring into an aqueous layer and an oil layer to remove the aqueous layer, or separating the mixed solution into an aqueous layer, an emulsified layer and an oil layer to remove the aqueous layer and the emulsified layer.
Have a,
A varnish containing an amphoteric compound, wherein the amphoteric compound is a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group . Washing method.
［式（１）中、Ｒ及びＱは各々独立に、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示し、ｎは１〜１００の整数を示す。］[In formula (1), R and Q are independently substituted or unsubstituted aliphatic groups having 1 to 100 carbon atoms, substituted or unsubstituted aromatic groups, substituted or unsubstituted heteroaromatic groups, or , Substituent or unsubstituted, indicates a siloxane moiety having a silicon number of 1 to 100, and n indicates an integer of 1 to 100. ]
攪拌後の混合溶液を水層と油層とに分離して水層を除去する、又は、水層と乳化層と油層とに分離して水層及び乳化層を除去する工程と、
を有し、
前記両親媒性化合物が、下記一般式（１）で表される少なくとも２つのイミド結合を有するマレイミド化合物である、両親媒性化合物を含有するワニスの水洗方法。
［式（１）中、Ｒ及びＱは各々独立に、置換又は非置換の炭素数１〜１００の脂肪族基、置換又は非置換の芳香族基、置換又は非置換のヘテロ芳香族基、或いは、置換又は非置換のケイ素数１〜１００のシロキサン部位を示し、ｎは１〜１００の整数を示す。］ A step of adding a varnish containing an amphipathic compound to water and stirring it,
A step of separating the mixed solution after stirring into an aqueous layer and an oil layer to remove the aqueous layer, or separating the mixed solution into an aqueous layer, an emulsified layer and an oil layer to remove the aqueous layer and the emulsified layer.
Have a,
A method for washing a varnish containing an amphipathic compound, wherein the amphipathic compound is a maleimide compound having at least two imide bonds represented by the following general formula (1) .
[In formula (1), R and Q are independently substituted or unsubstituted aliphatic groups having 1 to 100 carbon atoms, substituted or unsubstituted aromatic groups, substituted or unsubstituted heteroaromatic groups, or , Substituent or unsubstituted, indicates a siloxane moiety having a silicon number of 1 to 100, and n indicates an integer of 1 to 100. ]
攪拌後の混合溶液を水層と油層とに分離して水層を除去する、又は、水層と乳化層と油層とに分離して水層及び乳化層を除去する工程と、
を有し、
前記両親媒性化合物が、下記一般式（３）で表される脂肪族マレイミド化合物である、両親媒性化合物を含有するワニスの水洗方法。
A step of separating the mixed solution after stirring into an aqueous layer and an oil layer to remove the aqueous layer, or separating the mixed solution into an aqueous layer, an emulsified layer and an oil layer to remove the aqueous layer and the emulsified layer.
Have a,
A method for washing a varnish containing an amphipathic compound, wherein the amphipathic compound is an aliphatic maleimide compound represented by the following general formula (3) .
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