JPS6256779B2 - - Google Patents
Info
- Publication number
- JPS6256779B2 JPS6256779B2 JP58118022A JP11802283A JPS6256779B2 JP S6256779 B2 JPS6256779 B2 JP S6256779B2 JP 58118022 A JP58118022 A JP 58118022A JP 11802283 A JP11802283 A JP 11802283A JP S6256779 B2 JPS6256779 B2 JP S6256779B2
- Authority
- JP
- Japan
- Prior art keywords
- initial condensate
- parts
- formaldehyde
- hydrophobic
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 230000002209 hydrophobic effect Effects 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 31
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003094 microcapsule Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 4
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000002775 capsule Substances 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 28
- 239000011162 core material Substances 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- -1 alkyl urea Chemical compound 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920001059 synthetic polymer Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000010386 dodecyl gallate Nutrition 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 2
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229940100445 wheat starch Drugs 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- VSKCCZIUZNTICH-ZPYUXNTASA-N (e)-but-2-enoic acid;ethenyl acetate Chemical compound C\C=C\C(O)=O.CC(=O)OC=C VSKCCZIUZNTICH-ZPYUXNTASA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- SMNNDVUKAKPGDD-UHFFFAOYSA-N 2-butylbenzoic acid Chemical compound CCCCC1=CC=CC=C1C(O)=O SMNNDVUKAKPGDD-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- BUMWKRFSDWYKQH-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid;methyl prop-2-enoate Chemical compound COC(=O)C=C.OS(=O)(=O)C1=CC=CC=C1C=C BUMWKRFSDWYKQH-UHFFFAOYSA-N 0.000 description 1
- NORSCOJMIBLOFM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(=O)OCCO NORSCOJMIBLOFM-UHFFFAOYSA-N 0.000 description 1
- QBQSKYIIEGLPJT-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOC(=O)C=C QBQSKYIIEGLPJT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CUKVGYQSIHWKAV-UHFFFAOYSA-N 2-methylprop-2-enamide;2-methylprop-2-enoic acid Chemical compound CC(=C)C(N)=O.CC(=C)C(O)=O CUKVGYQSIHWKAV-UHFFFAOYSA-N 0.000 description 1
- JJLGDPNMAWKKAU-UHFFFAOYSA-N 2-methylprop-2-enamide;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(N)=O JJLGDPNMAWKKAU-UHFFFAOYSA-N 0.000 description 1
- YPEMKASELPCGPB-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(=C)C(O)=O YPEMKASELPCGPB-UHFFFAOYSA-N 0.000 description 1
- KFCDDRTYJQZGKK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enenitrile Chemical compound C=CC#N.CC(=C)C(O)=O KFCDDRTYJQZGKK-UHFFFAOYSA-N 0.000 description 1
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-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
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-IGMARMGPSA-N Calcium-40 Chemical compound [40Ca] OYPRJOBELJOOCE-IGMARMGPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
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- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- NKOUWLLFHNBUDW-UHFFFAOYSA-N Dipropyl hexanedioate Chemical compound CCCOC(=O)CCCCC(=O)OCCC NKOUWLLFHNBUDW-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 229920002230 Pectic acid Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
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- 229920001615 Tragacanth Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- DPZOGEBRVILXDK-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol;formaldehyde Chemical class O=C.NC1=NC(N)=NC(NCO)=N1 DPZOGEBRVILXDK-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XWPWZOJBTOJEGW-UHFFFAOYSA-L disodium;benzene-1,3-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(S([O-])(=O)=O)=C1 XWPWZOJBTOJEGW-UHFFFAOYSA-L 0.000 description 1
- VCFILMCOJAQDAY-UHFFFAOYSA-L disodium;butyl phosphate Chemical compound [Na+].[Na+].CCCCOP([O-])([O-])=O VCFILMCOJAQDAY-UHFFFAOYSA-L 0.000 description 1
- JOQAMSDLZYQHMX-UHFFFAOYSA-L disodium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Na+].[Na+].[O-]P([O-])(=O)C1=CC=CC=C1 JOQAMSDLZYQHMX-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RZBXSLICNMYVAJ-UHFFFAOYSA-N ethenyl acetate;2-methylprop-2-enoic acid Chemical compound CC(=O)OC=C.CC(=C)C(O)=O RZBXSLICNMYVAJ-UHFFFAOYSA-N 0.000 description 1
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- XHIOOWRNEXFQFM-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(=O)C=C XHIOOWRNEXFQFM-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- IWVKTOUOPHGZRX-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(=O)C(C)=C IWVKTOUOPHGZRX-UHFFFAOYSA-N 0.000 description 1
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- IQSHMXAZFHORGY-UHFFFAOYSA-N methyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound COC(=O)C=C.CC(=C)C(O)=O IQSHMXAZFHORGY-UHFFFAOYSA-N 0.000 description 1
- OOJJKUUUQUATPH-UHFFFAOYSA-N methyl prop-2-enoate;prop-2-enamide;prop-2-enoic acid Chemical compound NC(=O)C=C.OC(=O)C=C.COC(=O)C=C OOJJKUUUQUATPH-UHFFFAOYSA-N 0.000 description 1
- MYSWGNHLJGOCPT-UHFFFAOYSA-N methyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C=C MYSWGNHLJGOCPT-UHFFFAOYSA-N 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- LKWRQEMYZRVHNW-UHFFFAOYSA-M sodium;3,7-dimethylnaphthalene-2-sulfonate Chemical compound [Na+].C1=C(C)C(S([O-])(=O)=O)=CC2=CC(C)=CC=C21 LKWRQEMYZRVHNW-UHFFFAOYSA-M 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- WCUGDZILGGPIEZ-UHFFFAOYSA-M sodium;6-methylnaphthalene-2-sulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C=CC2=CC(C)=CC=C21 WCUGDZILGGPIEZ-UHFFFAOYSA-M 0.000 description 1
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- FVOMJWZIGNBHOA-UHFFFAOYSA-M sodium;diphenyl phosphate Chemical compound [Na+].C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 FVOMJWZIGNBHOA-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Color Printing (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Description
【発明の詳細な説明】
本発明は疎水性芯物質を包含するマイクロカプ
セルの新規な製造方法に関する。特にカプセル芯
物質の保持性に優れたカプセルを、カプセル膜の
厚さを自由にコントロールしながら、容易にしか
も高濃度で製造し得る方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing microcapsules containing a hydrophobic core material. In particular, the present invention relates to a method for easily producing capsules with excellent retention of capsule core substances at a high concentration while freely controlling the thickness of the capsule membrane.
近年、マイクロカプセル化技術の進歩は著し
く、それらマイクロカプセル化物の使用分野も感
圧複写紙を始めとして極めて広範囲、多方面にわ
たつている。 In recent years, microencapsulation technology has made remarkable progress, and the fields of use of these microencapsulated products are extremely wide and diverse, including pressure-sensitive copying paper.
マイクロカプセルの製造法としては、コアセル
ベーシヨン法、界面重合法、in―situ重合法など
各種の方法が知られているが、中でもアルデヒド
重縮合樹脂を壁膜として有するマイクロカプセル
は一般に耐水性、耐溶剤性等において優れている
ため、各種のカプセル化法が提案されており、例
えば水或いは親水性媒体中に存在するアルデヒド
重縮合系膜材を疎水性芯物質のまわりに堆積させ
る方法に関し米国特許3016308号、特公昭47−
51714号、特開昭48−57892号、特開昭51−9079
号、特開昭52−66878号、特開昭53−84881号、特
開昭53−84882号、特開昭53−84883号、特開昭54
−25277号、特開昭54−49984号、特開昭54−
53679号、特開昭54−85184号、特開昭54−85185
号、特開昭54−107881号、特開昭55−8856号、特
開昭55−15660号、特開昭55−47139号、特開昭55
−51431号、特開昭55−67329号、特開昭55−
92135号、特開昭55−132631号、特開昭55−
152546号、特開昭56−51238号、特開昭56−78626
号、特開昭56−102934号、特開昭56−115634号、
特開昭56−155636号、特開昭57−110332号、特開
昭57−135038号、特開昭57−147429号、等が挙げ
られる。 Various methods are known for manufacturing microcapsules, such as coacervation method, interfacial polymerization method, and in-situ polymerization method.Among them, microcapsules with aldehyde polycondensation resin as a wall film are generally water-resistant. Because of its excellent solvent resistance, various encapsulation methods have been proposed, including a method in which an aldehyde polycondensation membrane material present in water or a hydrophilic medium is deposited around a hydrophobic core substance. U.S. Patent No. 3016308, Special Publication No. 47-
No. 51714, JP-A-48-57892, JP-A-51-9079
No., JP 52-66878, JP 53-84881, JP 53-84882, JP 53-84883, JP 54
−25277, JP-A-54-49984, JP-A-54-
No. 53679, JP-A-54-85184, JP-A-54-85185
No., JP-A-54-107881, JP-A-55-8856, JP-A-55-15660, JP-A-55-47139, JP-A-55
−51431, JP-A-55-67329, JP-A-55-
No. 92135, JP-A-55-132631, JP-A-55-
No. 152546, JP-A-56-51238, JP-A-56-78626
No., JP-A-56-102934, JP-A-56-115634,
Examples include JP-A-56-155636, JP-A-57-110332, JP-A-57-135038, and JP-A-57-147429.
一方、アルデヒド重縮合樹脂材料を疎水性芯物
質に含有させ、乳化後、重縮合させてカプセル膜
を形成させる方法も提案されており、これに関す
る特許として特公昭44−27257号、特公昭45−
20885号、特公昭52−18671号等が挙げられる。 On the other hand, a method has also been proposed in which a hydrophobic core material contains an aldehyde polycondensation resin material, and after emulsification, polycondensation is performed to form a capsule membrane.
Examples include No. 20885 and Special Publication No. 52-18671.
しかし、上記の如く多数開発されたこれらカプ
セル化法も次なる欠点を有する。例えば、水或い
は親水性媒体中に存在するアルデヒド系重縮合膜
材を疎水性芯物質のまわりに堆積させる方法の場
合、カプセル膜が厚く芯物質保持性の良好なるカ
プセルを得るために膜材の配合量を増やしてカプ
セル調製を行うと、調製系の増粘傾向が顕著にな
り、系の濃度を低くしなければ調製が困難とな
る。又、これによつて得られるカプセル分散液の
粘度は濃度が低い割に高く、これを用いて調製し
た塗液の塗工適性は極めて悪い。又、カプセル膜
は上記の如く膜材を増やすことでやや厚くするこ
とができるものの、芯物質表面への堆積効率が膜
材の配合量に比例して除々に低下する為、あまり
厚い膜を有するカプセルが得られない。又、膜材
の配合量が増えると樹脂が芯物質表面へ不均一に
堆積するようになる為、保持性の改良効果は低く
なる。 However, these encapsulation methods, which have been developed in large numbers as described above, also have the following drawbacks. For example, in the case of a method in which an aldehyde-based polycondensation membrane material existing in water or a hydrophilic medium is deposited around a hydrophobic core substance, the membrane material is When capsules are prepared by increasing the blended amount, the tendency of the preparation system to increase in viscosity becomes significant, and preparation becomes difficult unless the concentration of the system is lowered. Furthermore, the viscosity of the capsule dispersion obtained thereby is high despite its low concentration, and the coating suitability of a coating liquid prepared using the same is extremely poor. In addition, although the capsule membrane can be made somewhat thicker by increasing the membrane material as described above, the deposition efficiency on the core material surface gradually decreases in proportion to the amount of membrane material blended, so the membrane cannot be made too thick. I can't get the capsule. Furthermore, as the amount of the membrane material increases, the resin will be deposited non-uniformly on the surface of the core material, resulting in a lower retention improvement effect.
一方、疎水性のアルデヒド重縮合樹脂材料を疎
水性芯物質に含有させ、乳化後重縮合させてカプ
セル膜を形成させる方法の場合、厚い壁膜を有す
るカプセルが高濃度、低粘度で得られるものの、
反応速度が遅く架橋が進み難い為、膜の厚さのわ
りに内包物保持性が劣るものとなりがちである。
又、厚い壁膜を有し、しかも内包物保持性の良好
なるカプセルを得ようとして、疎水性のアルデヒ
ド重縮合材料を多量に配合し、厳しい条件下で反
応を進めても芯物質表面に堆積して壁膜を形成す
る樹脂以外に芯物質中に溶解した状態で重縮合樹
脂オリゴマーが形成され、芯物質の粘度を上昇せ
しめる原因となる。これを感圧複写紙用カプセル
として適用した場合、転移性のはなはだ悪いもの
となる。 On the other hand, in the case of a method in which a hydrophobic aldehyde polycondensation resin material is contained in a hydrophobic core substance and polycondensed after emulsification to form a capsule membrane, capsules with a thick wall membrane can be obtained at high concentration and low viscosity. ,
Since the reaction rate is slow and crosslinking is difficult to proceed, the inclusion retention property tends to be poor in relation to the film thickness.
In addition, in an attempt to obtain capsules with thick wall membranes and good retention of inclusions, a large amount of hydrophobic aldehyde polycondensation material was blended, and even if the reaction proceeded under severe conditions, it would not accumulate on the surface of the core substance. In addition to the resin forming the wall film, polycondensation resin oligomers are formed dissolved in the core material, which causes an increase in the viscosity of the core material. When this is applied as a capsule for pressure-sensitive copying paper, the transferability is extremely poor.
本発明者らは、かかる現状に鑑み、鋭意研究し
た結果、芯物質保持性の優れたカプセルを、カプ
セル膜の厚さを自由にコントロールしながら、容
易にしかも高濃度で製造し得る方法を見出すこと
に成功した。 In view of the current situation, the present inventors conducted intensive research and found a method that allows capsules with excellent core substance retention to be easily produced at high concentration while freely controlling the thickness of the capsule membrane. It was very successful.
本発明は、水或いは親水性媒体中に含有せしめ
た親水性のアルデヒド系樹脂形成材料を重縮合せ
しめて疎水性芯物質を被覆するマイクロカプセル
の製造方法において、該疎水性芯物質中に疎水性
のアルデヒド系樹脂初期縮合物を含有せしめるこ
とを特徴とするマイクロカプセルの製造方法であ
る。 The present invention provides a method for producing microcapsules in which a hydrophilic aldehyde resin-forming material contained in water or a hydrophilic medium is polycondensed to cover a hydrophobic core material, and in which a hydrophobic core material is coated with a hydrophobic core material. This is a method for producing microcapsules, characterized by containing an initial condensate of an aldehyde resin.
本発明において用いられる疎水性のアルデヒド
系樹脂初期縮合物としては、例えば、フエノール
ホルムアルデヒド樹脂初期縮合物、アミノアルデ
ヒド樹脂初期縮合物等が挙げられる。フエノール
ホルムアルデヒド樹脂初期縮合物としては例え
ば、フエノール、クレゾール、キシレノール、レ
ゾルシノール、ハイドロキノン、ピロカテコー
ル、ピロガロール等の少なくとも一種のフエノー
ル類とホルムアルデヒドが縮合して得られる初期
縮合物が挙げられる。アミノアルデヒド樹脂初期
縮合物としては、例えば尿素、チオ尿素、アルキ
ル尿素、エチレン尿素、アセトグアナミン、ベン
ゾグアナミン、メラミン、グアニジン、ジシアン
ジアミド、ビウレツト、シアナミド等の少なくと
も一種のアミン類と例えばホルムアルデヒド、ア
セトアルデヒド、パラホルムアルデヒド、ヘキサ
メチレンテトラミン、グルタールアルデヒド、グ
リオキザール、フルフラール等の少なくとも一種
のアルデヒド類を縮合して得られる初期縮合物或
いはそのアルキル化物やその部分アルキル化物さ
らにはそれらのアニオン、カチオン又はノニオン
変性物等の内、疎水性のものが単独或いは併用さ
れる。エーテル化に用いられるアルキル基として
はこれに限定されるものではないが、調製の容易
さの点で炭素数１から８の範囲のものが好まし
い。又、アニオン変性剤としては、例えば、スル
フアミン酸、スルフアニル酸、グリコール酸、グ
リシン、酸性亜硫酸塩、スルホン酸フエノール、
タウリン等、カチオン変性剤としてはジエチレン
トリアミン、トリエチレンテトラミン、テトラエ
チレンペンタミン、ジメチルアミノエタノール
等、ノニオン変性剤としてはエチレングリコー
ル、ジエチレングリコール等が挙げられ、これら
は初期縮合物が疎水性を失わない程度に使用され
る。本発明における初期縮合物としてはそれが疎
水性であれば上記の如く各種のものを用いること
が出来るが、中でもメラミン―ホルムアルデヒド
初期縮合物のアルキル化物、尿素―メラミン―ホ
ルムアルデヒド初期縮合物のアルキル化物、尿素
―ホルムアルデヒド初期縮合物のアルキル化物は
緻密な膜が得られる点で好ましい。 Examples of the hydrophobic aldehyde resin initial condensate used in the present invention include a phenol formaldehyde resin initial condensate, an aminoaldehyde resin initial condensate, and the like. Examples of the phenol formaldehyde resin initial condensate include initial condensates obtained by condensing formaldehyde with at least one phenol such as phenol, cresol, xylenol, resorcinol, hydroquinone, pyrocatechol, and pyrogallol. Examples of the aminoaldehyde resin initial condensate include at least one amine such as urea, thiourea, alkyl urea, ethylene urea, acetoguanamine, benzoguanamine, melamine, guanidine, dicyandiamide, biuret, and cyanamide, and formaldehyde, acetaldehyde, and paraformaldehyde. , hexamethylenetetramine, glutaraldehyde, glyoxal, an initial condensate obtained by condensing at least one aldehyde such as glyoxal, furfural, or an alkylated product thereof, a partially alkylated product thereof, or an anion, cation, or nonionic modified product thereof. Among them, hydrophobic ones are used alone or in combination. Although the alkyl group used for etherification is not limited to these, those having 1 to 8 carbon atoms are preferred from the viewpoint of ease of preparation. In addition, examples of anion modifiers include sulfamic acid, sulfanilic acid, glycolic acid, glycine, acidic sulfites, phenol sulfonate,
Cationic modifiers such as taurine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminoethanol, etc., and nonionic modifiers include ethylene glycol, diethylene glycol, etc. These are used to the extent that the initial condensate does not lose its hydrophobicity. used for. As the initial condensate in the present invention, as long as it is hydrophobic, various products can be used as mentioned above, among which are alkylated products of melamine-formaldehyde initial condensate, and alkylated products of urea-melamine-formaldehyde initial condensate. , an alkylated product of a urea-formaldehyde initial condensate is preferred in that a dense film can be obtained.
又、これらのアルデヒド系樹脂初期縮合物を疎
水性芯物質に溶解せしめる場合、用いる初期縮合
物の溶解性が不足する場合や高い粘度を有する場
合、さらには初期縮合物を溶解した疎水性芯物質
の粘度が高い場合には極性溶剤や低沸点溶剤を併
用することが可能であり、これに用いる低沸点溶
剤としては例えばｎ―ペンタン、メチレンクロラ
イド、エチレンクロライド、二流化炭素、アセト
ン、酢酸メチル、クロロホルム、メチルアルコー
ル、テトラヒドロフラン、ｎ―ヘキサン、四塩化
炭素、酢酸エチル、エチルアルコール、ｎ―プロ
ピルアルコール、iso―プロピルアルコール、ｎ
―ブチルアルコール、iso―ブチルアルコール、
ｔ―ブチルアルコール、ｎ―ペンチルアルコー
ル、メチルエチルケトン、ベンゼン、トルエン、
キシレン、エチルエーテル及び石油エーテル等が
挙げられる。 In addition, when these aldehyde-based resin initial condensates are dissolved in a hydrophobic core material, when the initial condensate used has insufficient solubility or has a high viscosity, and when the initial condensate is dissolved in a hydrophobic core material, When the viscosity of is high, it is possible to use a polar solvent or a low boiling point solvent in combination. Examples of low boiling point solvents used for this include n-pentane, methylene chloride, ethylene chloride, carbon disulfide, acetone, methyl acetate, Chloroform, methyl alcohol, tetrahydrofuran, n-hexane, carbon tetrachloride, ethyl acetate, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n
-butyl alcohol, iso-butyl alcohol,
t-butyl alcohol, n-pentyl alcohol, methyl ethyl ketone, benzene, toluene,
Examples include xylene, ethyl ether and petroleum ether.
極性溶剤としては、ジオキサン、シクロヘキサ
ノン、メチルイソブチルケトン、ジメチルホルム
アミド等が用いられる。 As the polar solvent, dioxane, cyclohexanone, methyl isobutyl ketone, dimethylformamide, etc. are used.
又、本発明においては疎水性の初期縮合物は疎
水性芯物質に溶解して使用されるのが望ましい
が、分散状態でも使用可能である。 Further, in the present invention, it is preferable that the hydrophobic initial condensate is used dissolved in the hydrophobic core material, but it can also be used in a dispersed state.
尚、疎水性のアルデヒド系樹脂初期縮合物の配
合量は、用いる疎水性芯物質及び疎水性のアルデ
ヒド系樹脂初期縮合物の種類、水或いは親水性媒
体中に含有させるアルデヒド系樹脂形成材料の種
類及び配合量、カプセルの粒径やその使用用途等
によつて異なり、一概には決められないが、疎水
性芯物質100重量部に対してアミノ化合物或いは
フエノール化合物換算で0.5重量部以上50重量部
以下が好ましく、特に２重量部以上30重量部以下
がより好ましい。 The blending amount of the hydrophobic aldehyde resin initial condensate depends on the type of hydrophobic core material and hydrophobic aldehyde resin initial condensate used, and the type of aldehyde resin forming material contained in water or the hydrophilic medium. It varies depending on the blending amount, the particle size of the capsule, its intended use, etc., and cannot be determined unconditionally, but 0.5 parts by weight or more in terms of amino compound or phenol compound and 50 parts by weight per 100 parts by weight of the hydrophobic core material. The following is preferable, particularly 2 parts by weight or more and 30 parts by weight or less.
尚、用いられる疎水性芯物質が固体である場合
には、初期縮合物或いは初期縮合物を溶解した低
沸点溶剤にこの固体を分散し、それを水或いは親
水性媒体中に乳化する形で用いられる。 In addition, when the hydrophobic core substance used is a solid, this solid is dispersed in the initial condensate or a low boiling point solvent in which the initial condensate is dissolved, and then used in the form of emulsification in water or a hydrophilic medium. It will be done.
本発明において用いられる親水性のアルデヒド
系樹脂形成材料としては、例えば、アミン類或い
はフエノール類に属する少なくとも一種とアルデ
ヒド類の少なくとも一種の組合せが挙げられ、こ
れらを適当に選択し、モノマー或いは初期縮合物
のかたちで添加される。 Examples of the hydrophilic aldehyde-based resin forming material used in the present invention include a combination of at least one member of amines or phenols and at least one member of aldehydes. It is added in the form of a substance.
このアミン類、フエノール類、アルデヒド類と
しては、具体的には疎水性のアルデヒド系樹脂初
期縮合物の形成材料として上記した如きものが挙
げられ、又、この初期縮合物としては上記の如き
アミン類或いはフエノール類に属する化合物の少
なくとも一種とアルデヒド類の少なくとも一種の
初期縮合物の他、そのメチル化物等のアルキル化
物、部分アルキル化物或いはそれらのアニオン、
カチオン又はノニオン変性物等、親水性のものが
選択される。尚、これらアニオン、カチオン、ノ
ニオンの各変性剤としては疎水性のアルデヒド系
樹脂初期縮合物において記載した如きものを挙げ
ることが出来る。 Specific examples of the amines, phenols, and aldehydes include those mentioned above as materials for forming hydrophobic aldehyde-based resin initial condensates; Alternatively, in addition to the initial condensate of at least one compound belonging to phenols and at least one aldehyde, alkylated products such as methylated products, partially alkylated products, or anions thereof,
Hydrophilic ones such as cationic or nonionic modified products are selected. As these anionic, cationic, and nonionic modifiers, those described in connection with the hydrophobic aldehyde resin initial condensate can be mentioned.
親水性のアルデヒド系樹脂形成材料としては、
上記の如く各種のものを用いることが出来るが、
中でも性能の優れた尿素―ホルムアルデヒド樹
脂、メラミン―ホルムアルデヒド樹脂、尿素―メ
ラミン―ホルムアルデヒド樹脂の素材となる尿素
及びホルムアルデヒド、尿素―ホルムアルデヒド
初期縮合物、メラミン―ホルムアルデヒド初期縮
合物、尿素―メラミン―ホルムアルデヒド初期縮
合物が好ましく、単独或いは混合して使用され
る。又、前記ホルムアルデヒド系樹脂初期縮合物
を用いる場合には、この初期縮合物と前記アルデ
ヒド類を併用することがより良好なる膜が得られ
る点で好ましい。 As a hydrophilic aldehyde resin forming material,
As mentioned above, various types can be used, but
Urea and formaldehyde, which are the raw materials for urea-formaldehyde resin, melamine-formaldehyde resin, and urea-melamine-formaldehyde resin, which have excellent performance among others, urea-formaldehyde initial condensate, melamine-formaldehyde initial condensate, and urea-melamine-formaldehyde initial condensate They are preferably used alone or in combination. Further, when the formaldehyde-based resin initial condensate is used, it is preferable to use the initial condensate and the aldehydes together, since a better film can be obtained.
尚、親水性のアルデヒド系樹脂形成材料の配合
量は、用いる疎水性芯物質の種類、カプセルの使
用用途或いは疎水性のアルデヒド系樹脂初期縮合
物の種類及び配合量等によつてかわり、一概に決
められるものではないが、疎水性芯物質100重量
部に対して、アミン化合物或いはフエノール化合
物換算で0.5重量部以上40重量部以下が好まし
く、特に２重量部以上20重量部以下が好ましい。 The amount of the hydrophilic aldehyde-based resin forming material varies depending on the type of hydrophobic core substance used, the intended use of the capsule, the type and amount of the hydrophobic aldehyde-based resin initial condensate, etc. Although not determined, it is preferably 0.5 parts by weight or more and 40 parts by weight or less in terms of amine compound or phenol compound, particularly preferably 2 parts by weight or more and 20 parts by weight or less, based on 100 parts by weight of the hydrophobic core material.
本発明においては、疎水性のアルデヒド系樹脂
初期縮合物を含有する疎水性芯物質が水或いは親
水性媒体中に乳化出来れば、特に乳化剤を用いる
必要はないが、乳化を容易に行う意味において乳
化剤を用いることが好ましく、その乳化剤として
は、アニオン性、ノニオン性、カチオン性、両性
の高分子や低分子乳化剤を用いることが出来る。 In the present invention, as long as the hydrophobic core material containing the hydrophobic aldehyde resin initial condensate can be emulsified in water or a hydrophilic medium, it is not necessary to use an emulsifier. It is preferable to use the emulsifier, and anionic, nonionic, cationic, or amphoteric polymer or low-molecular emulsifiers can be used.
アニオン性高分子としては、天然のものでも合
成のものでも用いることができ、例えば―
COO-，―SO− ３，―OPO２− ３基等を有するものが挙
げられ、具体的にはアラビアガム、カラジーナ
ン、アルギン酸ソーダ、ペクチン酸、トラガカン
トガム、アーモンドガム、寒天等の天然高分子、
カルボキシメチルセルロース、硫酸化セルロー
ス、硫酸化メチルセルロース、カルボキシメチル
澱粉、リン酸化澱粉、リグニンスルホン酸等の半
合成高分子、無水マレイン酸系（加水分解したも
のも含む）共重合体、アクリル酸系、メタクリル
酸系或いはクロトン酸系の重合体及び共重合体、
ビニルベンゼンスルホン酸系或いは２―アクリル
アミド―２―メチル―プロパンスルホン酸系の重
合体及び共重合体、およびかかる重合体、共重合
体の部分アミドまたは部分エステル化物、カルボ
キシ変性ポリビニルアルコール、スルホン酸変性
ポリビニルアルコール、リン酸変性ポリビニルア
ルコール等の合成高分子等が挙げられる。 Both natural and synthetic anionic polymers can be used, such as -
Examples include those having COO - , -SO - 3 , -OPO 2- 3 groups, etc., and specific examples include natural polymers such as gum arabic, carrageenan, sodium alginate, pectic acid, gum tragacanth, almond gum, agar, etc.
Carboxymethylcellulose, sulfated cellulose, sulfated methylcellulose, carboxymethyl starch, phosphorylated starch, semi-synthetic polymers such as lignin sulfonic acid, maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based, methacrylate Acid-based or crotonic acid-based polymers and copolymers,
Vinylbenzenesulfonic acid-based or 2-acrylamido-2-methyl-propanesulfonic acid-based polymers and copolymers, partial amides or partial esters of such polymers and copolymers, carboxy-modified polyvinyl alcohol, sulfonic acid-modified Examples include synthetic polymers such as polyvinyl alcohol and phosphoric acid-modified polyvinyl alcohol.
更に具体的には、無水マレイン酸系（加水分解
したものも含む）共重合体としてはメチルビニル
エーテル―無水マレイン酸共重合体、エチレン、
無水マレイン酸共重合体、酢酸ビニル―無水マレ
イン酸共重合体、メタクリルアミド―無水マレイ
ン酸共重合体、イソブチレン―無水マレイン酸共
重合体などが挙げられる。 More specifically, maleic anhydride copolymers (including hydrolyzed ones) include methyl vinyl ether-maleic anhydride copolymers, ethylene,
Examples include maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, methacrylamide-maleic anhydride copolymer, and isobutylene-maleic anhydride copolymer.
アクリル酸系共重合体、メタクリル酸系共重合
体或いはクロトン酸系共重合体としては、アクリ
ル酸メチル―アクリル酸共重合体（以下、“共重
合体”は略する）アクリル酸エチル―アクリル
酸、アクリル酸メチル―メタクリル酸、メタクリ
ル酸メチル―アクリル酸、メタクリル酸メチル―
メタクリル酸、アクリル酸メチル―アクリルアミ
ド―アクリル酸、アクリロニトリル―アクリル
酸、アクリロニトリル―メタクリル酸、ヒドロキ
シエチルアクリレート―アクリル酸、ヒドロキシ
エチルメタクリレート―メタクリル酸、酢酸ビニ
ル―アクリル酸、酢酸ビニル―メクタリル酸、ア
クリルアミド―アクリル酸、アクリルアミド―メ
タクリル酸、メタクリルアミド―アクリル酸、メ
タクリルアミド―メタクリル酸、酢酸ビニル―ク
ロトン酸等の共重合体が挙げられる。 Examples of the acrylic acid copolymer, methacrylic acid copolymer, or crotonic acid copolymer include methyl acrylate-acrylic acid copolymer (hereinafter referred to as "copolymer"), ethyl acrylate-acrylic acid , methyl acrylate - methacrylic acid, methyl methacrylate - acrylic acid, methyl methacrylate -
Methacrylic acid, methyl acrylate-acrylamide-acrylic acid, acrylonitrile-acrylic acid, acrylonitrile-methacrylic acid, hydroxyethyl acrylate-acrylic acid, hydroxyethyl methacrylate-methacrylic acid, vinyl acetate-acrylic acid, vinyl acetate-methacrylic acid, acrylamide- Examples include copolymers of acrylic acid, acrylamide-methacrylic acid, methacrylamide-acrylic acid, methacrylamide-methacrylic acid, vinyl acetate-crotonic acid, and the like.
ビニルベンゼンスルホン酸系、或いは２―アク
リルアミド―２―メチル―プロパンスルホン酸系
共重合体としては、アクリル酸メチル―ビニルベ
ンゼンスルホン酸（又はその塩）共重合体、酢酸
ビニル―ビニルベンゼンスルホン酸共重合体、ア
クリルアミド―ビニルベンゼンスルホン酸共重合
体、アクリロイルホルモリン―ビニルベンゼンス
ルホン酸共重合体、ビニルピロリドン―ビニルベ
ンゼンスルホン酸共重合体、ビニルピロリドン―
２―アクリルアミド―２―メチル―プロパンスル
ホン酸共重合体等が挙げられる。 Examples of vinylbenzenesulfonic acid copolymers or 2-acrylamido-2-methyl-propanesulfonic acid copolymers include methyl acrylate-vinylbenzenesulfonic acid (or salts thereof) copolymers, and vinyl acetate-vinylbenzenesulfonic acid copolymers. Polymer, acrylamide-vinylbenzenesulfonic acid copolymer, acryloylformoline-vinylbenzenesulfonic acid copolymer, vinylpyrrolidone-vinylbenzenesulfonic acid copolymer, vinylpyrrolidone-
Examples include 2-acrylamide-2-methyl-propanesulfonic acid copolymer.
ノニオン性高分子としては、天然のものでも合
成のものでも用いることができ、例えば―OH基
を有するものが挙げられる。 As the nonionic polymer, both natural and synthetic polymers can be used, including those having an --OH group.
具体的なノニオン性の半合成高分子としては、
ヒドロキシエチルセルロース、メチルセルロー
ス、プルラン（澱粉を原料として微生物発酵法に
よつて作られた非結晶性、易水溶性高分子多糖
類）、可溶性デンプン、酸化デンプンなどが挙げ
られる。 Specific nonionic semi-synthetic polymers include:
Examples include hydroxyethylcellulose, methylcellulose, pullulan (an amorphous, easily water-soluble polymeric polysaccharide made from starch by microbial fermentation), soluble starch, and oxidized starch.
又、合成品としては、ポリビニルアルコールが
挙げられる。 Further, as a synthetic product, polyvinyl alcohol can be mentioned.
カチオン性高分子としては例えば、カチオン変
性ポリビニルアルコール、又、両性高分子として
は、例えば、ゼラチン等が挙げられる。 Examples of cationic polymers include cation-modified polyvinyl alcohol, and examples of amphoteric polymers include gelatin.
低分子乳化剤としては、アニオン性、カチオン
性、ノニオン性、両性のものを挙げることが出来
るが、中でもアニオン性のものが好ましく、その
中でも、取分総炭素数１から14の範囲の有機イオ
ウ酸或いは有機リン酸のLi+，Na+，K+，NH4 +塩
が好ましく具体的には、ビニルスルホン酸ナトリ
ウム、ベンゼンスルホン酸ナトリウム、ベンゼン
スルフイン酸ナトリウム、ｐ―トルエンスルホン
酸ナトリウム、ｐ―トルエンスルフイン酸ナトリ
ウム、ｐ―ビニルベンゼンスルホン酸ナトリウ
ム、ｐ―ｉ―アミルベンゼンスルホン酸ナトリウ
ム、ナフタレン―α―スルホン酸ソーダー、ナフ
タレン―β―スルホン酸ソーダー、２―メチルナ
フタレン―６―スルホン酸ナトリウム、２，６―
ジメチルナフタレン―８―スルホン酸ナトリウ
ム、２，６―ジメチルナフタレン―３―スルホン
酸ナトリウム、１―ナフトール―４―スルホン酸
ナトリウム、ベンゼン―ｍ―ジスルホン酸ナトリ
ウム、ジフエニルリン酸ナトリウム、フエニルホ
スホン酸ナトリウム、ジ―ｎ―ブチルリン酸ナト
リウム、ジ―ｉ―アミルリン酸ナトリウム等が挙
げられる。 Examples of low-molecular emulsifiers include anionic, cationic, nonionic, and amphoteric ones, but anionic ones are preferred, and among them, organic sulfuric acids having a total carbon number of 1 to 14 are preferable. Alternatively, Li + , Na + , K + , NH 4 + salts of organic phosphoric acids are preferred, and specifically, sodium vinylsulfonate, sodium benzenesulfonate, sodium benzenesulfinate, sodium p-toluenesulfonate, p- Sodium toluenesulfinate, sodium p-vinylbenzenesulfonate, sodium p-i-amylbenzenesulfonate, sodium naphthalene-α-sulfonate, sodium naphthalene-β-sulfonate, sodium 2-methylnaphthalene-6-sulfonate ,2,6-
Sodium dimethylnaphthalene-8-sulfonate, sodium 2,6-dimethylnaphthalene-3-sulfonate, sodium 1-naphthol-4-sulfonate, sodium benzene-m-disulfonate, sodium diphenyl phosphate, sodium phenylphosphonate, di- Examples include sodium n-butyl phosphate and sodium di-i-amyl phosphate.
本発明においては、上記の如き高分子或いは低
分子乳化剤を単独又は併用してもよいが、この中
で好ましいのは高分子乳化剤であり、その中でも
アニオン性モノマーユニツトからなる重合体或い
は共重合体、アニオン性モノマーユニツトと疎水
性モノマーユニツトとの共重合体、ポリビニルア
ルコール或いはカチオン変性、アニオン変性、ノ
ニオン変性のポリビニルアルコールが好ましく、
特に無水マレイン酸系（加水分解したものも含
む）共重合体、アクリル酸系、メタクリル酸系或
いはクロトン酸系の重合体及び共重合体が好まし
い。 In the present invention, the above-mentioned high-molecular or low-molecular emulsifiers may be used alone or in combination, but preferred are high-molecular emulsifiers, and among these, polymers or copolymers composed of anionic monomer units are preferred. , a copolymer of an anionic monomer unit and a hydrophobic monomer unit, polyvinyl alcohol, or cationically modified, anionically modified or nonionically modified polyvinyl alcohol,
Particularly preferred are maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based, methacrylic acid-based, or crotonic acid-based polymers and copolymers.
尚、上記の如き乳化剤は水或いは親水性媒体中
に0.5％以上含有させるのが好ましく、乳化液調
製の容易さ、及び乳化液の安定化等の点から２％
以上含有させるのがより好ましい。使用量の上限
は系の粘度あるいはカプセル調製装置等により決
定されるが、一般的には20％以下にとどめられ
る。 The above emulsifier is preferably contained in water or a hydrophilic medium in an amount of 0.5% or more, and from the viewpoint of ease of emulsion preparation and stabilization of the emulsion, the content is preferably 2% or more.
It is more preferable to contain the above amount. The upper limit of the amount used is determined by the viscosity of the system, the capsule preparation equipment, etc., but is generally kept at 20% or less.
本発明において反応系を酸性に維持するため
に、例えばギ酸、酢酸、クエン酸、シユウ酸、パ
ラトルエンスルフオン酸、塩酸、硫酸などの如き
アミノアルデヒド樹脂製造分野で一般に用いられ
る所謂酸触媒が用いられる。 In the present invention, so-called acid catalysts commonly used in the field of aminoaldehyde resin production, such as formic acid, acetic acid, citric acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, and sulfuric acid, are used to maintain the reaction system acidic. It will be done.
尚、本発明における反応条件は、形成される膜
の種類等によつて変わり、これに限定されるもの
ではないが好ましくはPH5.0以下、50℃以上特に
好ましくはPH4.5以下、70℃以上であり、その条
件において１時間以上特に３時間以上維持するの
が好ましい。 The reaction conditions in the present invention vary depending on the type of film to be formed, and are not limited to these, but are preferably PH5.0 or lower, 50°C or higher, particularly preferably PH4.5 or lower, and 70°C. The above conditions are preferably maintained for 1 hour or more, particularly 3 hours or more.
本発明においてマイクロカプセル中に内包され
る疎水性芯物質としては、特に限定するものでは
ないが以下の如き物質が例示される。 In the present invention, the hydrophobic core substance to be encapsulated in the microcapsules is not particularly limited, but the following substances are exemplified.
魚油、ラード油などの如き動物油類、オリーブ
油、落花生油、亜麻仁油、大豆油、ひまし油など
の如き植物油類、石油、ケロシン、キシレン、ト
ルエンなどの如き鉱物油類、アルキル置換ジフエ
ニールアルカン、アルキル置換ナフタリン、ビフ
エニールエタン、サリチル酸メチル、アジピン酸
ジエチル、アジピン酸ジ―ｎ―プロピル、アジピ
ン酸ジ―ｎ―ブチル、フタル酸ジ―メチル、フタ
ル酸ジエチル、フタル酸ジ―ｎ―プロピル、フタ
ル酸ジ―ｎ―ブチル、フタル酸ジ―ｎ―オクチル
などの如き合成油類のように水に不溶性または実
質的に水に不溶性の液体或いは上記合成油に電子
供与性発色剤、電子受容性顕色剤、配位子化合
物、有機金属塩等を溶解した溶液、水に不溶性の
金属の酸化物および塩類、セルロースあるいはア
スベストの如き繊維様物質、水に不溶性の合成重
合体物質、鉱物類、顔料類、ガラス類、香料類、
香味料類、殺菌組成物類、生理学的組成物類、肥
料組成物類。 Animal oils such as fish oil, lard oil, etc., vegetable oils such as olive oil, peanut oil, linseed oil, soybean oil, castor oil, etc., mineral oils such as petroleum, kerosene, xylene, toluene, etc., alkyl-substituted diphenylalkanes, alkyl Substituted naphthalene, biphenylethane, methyl salicylate, diethyl adipate, di-n-propyl adipate, di-n-butyl adipate, di-methyl phthalate, diethyl phthalate, di-n-propyl phthalate, phthalate Liquids that are insoluble or substantially insoluble in water such as synthetic oils such as di-n-butyl acid and di-n-octyl phthalate, or the above synthetic oils are treated with an electron-donating coloring agent or an electron-accepting developer. Colorants, ligand compounds, solutions containing organic metal salts, water-insoluble metal oxides and salts, fibrous substances such as cellulose or asbestos, water-insoluble synthetic polymer substances, minerals, pigments glass, fragrances,
Flavorings, fungicidal compositions, physiological compositions, fertilizer compositions.
以下に本発明の方法をより具体的に説明するた
めに、感圧複写紙の分野へ応用した場合について
実施例を記載するが、勿論これに限定されるもの
ではない。また特に断らない限り例中の部および
％はそれぞれ重量部および重量％を表わす。 In order to more specifically explain the method of the present invention, examples will be described below in which the method is applied to the field of pressure-sensitive copying paper, but the present invention is of course not limited thereto. Further, unless otherwise specified, parts and % in the examples represent parts by weight and % by weight, respectively.
実施例 １
配位子化合物含有マイクロカプセル塗液の調製
及び塗布紙の作成
没食子酸ラウリル20部をアジピン酸ジエチル50
部とアジピン酸ジ―ｎ―ブチル50部との混合液に
加熱溶解し放冷後、ｎ―ブチル化メチロールメラ
ミン・ホルムアルデヒド初期縮合物（商品名メラ
ン27、日立化成社製）をメラミン換算で10部にな
る様添加して、内相油を得た。エチレン・無水マ
レイン酸共重合体（商品名EMA―31、モンサン
ト社製）の3.0％水溶液200部に20％苛性ソーダ水
溶液を添加してPHを5.0とした液にこの内相油を
乳化し、平均粒径５μとした後この系を55℃に昇
温した。Example 1 Preparation of microcapsule coating liquid containing a ligand compound and preparation of coated paper 20 parts of lauryl gallate was mixed with 50 parts of diethyl adipate.
After heating and dissolving in a mixture of 50 parts of di-n-butyl adipate and 50 parts of di-n-butyl adipate, the initial condensate of n-butylated methylolmelamine/formaldehyde (trade name Melan 27, manufactured by Hitachi Chemical Co., Ltd.) was dissolved in melamine equivalent to 10 parts. % to obtain an internal phase oil. This internal phase oil was emulsified in a solution in which 20% caustic soda aqueous solution was added to 200 parts of a 3.0% aqueous solution of ethylene/maleic anhydride copolymer (trade name EMA-31, manufactured by Monsanto) to adjust the pH to 5.0. After adjusting the particle size to 5μ, the system was heated to 55°C.
別に、37％ホルムアルデヒド水溶液30部にメラ
ミン10部を加え、60℃で15分間反応させてプレポ
リマー水溶液を調製した。 Separately, 10 parts of melamine was added to 30 parts of a 37% formaldehyde aqueous solution and reacted at 60°C for 15 minutes to prepare a prepolymer aqueous solution.
このプレポリマー水溶液を前記乳化液中に滴下
し、更に撹拌しながら0.5N―塩酸を滴下してPH
を4.5とした後、80℃まで加温し、その温度で１
時間保持後、1N―塩酸でPHを3.5に下げ、更に３
時間保温した後放冷して乳白色のカプセル分散液
を得た。 This prepolymer aqueous solution was dropped into the emulsion, and while stirring, 0.5N-hydrochloric acid was added dropwise to adjust the pH.
After setting the temperature to 4.5, heat it to 80℃, and at that temperature
After holding for a period of time, lower the pH to 3.5 with 1N hydrochloric acid, and then
After keeping warm for an hour, the mixture was allowed to cool to obtain a milky white capsule dispersion.
ついでこの分散液に小麦デンプン粉末20部、パ
ルプ粉末10部を添加混合し、固型分濃度が25％に
なるよう水を加えてカプセル塗液を得た。 Next, 20 parts of wheat starch powder and 10 parts of pulp powder were added to and mixed with this dispersion, and water was added so that the solid content concentration was 25% to obtain a capsule coating liquid.
尚、得られたカプセル塗液の粘度はブロツクフ
イールド型粘度計での測定の結果、12cps（25
℃）であり、この塗液をエアーナイフコーターを
使用して40ｇ／m2の原紙に固型分が５ｇ／m2にな
るよう塗布したが、500ｍ／minのスピードで塗
布することが出来た。 The viscosity of the obtained capsule coating liquid was measured using a block field viscometer and was found to be 12 cps (25 cps).
℃), and this coating liquid was applied to base paper of 40 g/m 2 using an air knife coater so that the solid content was 5 g/m 2 , and it was possible to apply at a speed of 500 m/min. .
単体感圧複写紙の作成
５％の苛性ソーダ水溶液1200部にジフエニルリ
ン酸エステル188部とtert―ブチル安息香酸134部
を添加して調製した水溶液に、水1000部に塩化第
二鉄135部を溶解した水溶液を撹拌下で添加し、
沈澱物であるジフエニルリン酸エステルとtert―
ブチル安息香酸の複合鉄塩を生成させ、濾過・洗
浄・風乾して淡く着色した微粉末を得た。Preparation of single pressure-sensitive copying paper 135 parts of ferric chloride was dissolved in 1000 parts of water to an aqueous solution prepared by adding 188 parts of diphenyl phosphate and 134 parts of tert-butylbenzoic acid to 1200 parts of a 5% aqueous solution of caustic soda. adding the aqueous solution under stirring;
Precipitated diphenyl phosphate and tert-
A complex iron salt of butylbenzoic acid was produced, and a pale colored fine powder was obtained by filtration, washing, and air drying.
次いで、水150部にポリリン酸ソーダ１部、上
記複合鉄塩粉末15部、酸化チタン35部、軽質炭酸
カルシウム50部、40％のパラフインワツクスエマ
ルジヨン（商品名セロゾールＡ、中京油脂〓製）
15部を添加し、強力に分散した後、この分散液に
スチレン―ブタジエン共重合体ラテツクス（50％
濃度）を16部加えて塗液を得た。 Next, to 150 parts of water, 1 part of sodium polyphosphate, 15 parts of the above composite iron salt powder, 35 parts of titanium oxide, 50 parts of light calcium carbonate, and 40% paraffin wax emulsion (trade name: Cellosol A, manufactured by Chukyo Yushi Co., Ltd.) were added.
After adding 15 parts of styrene-butadiene copolymer latex (50%
A coating liquid was obtained by adding 16 parts of
次いで、この塗液を上記の配位子化合物含有マ
イクロカプセル塗布紙の塗布面上に固型分で５
ｇ／m2になる様にエアーナイフコーターを使用し
て塗布し、単体感圧複写紙を得た。 Next, this coating liquid was applied to the coated surface of the above-mentioned ligand compound-containing microcapsule coated paper in a solid content of 5.
A single pressure-sensitive copying paper was obtained by applying the coating using an air knife coater to give a coating weight of g/m 2 .
評 価
上記の如くして得た単体感圧複写紙にリボン無
しタイプライターで印字したところ鮮明なる発色
像が得られた。又、この複写紙を100℃条件下で
３時間処理したが、塗布面にほとんど汚れを生じ
なかつた。Evaluation When the single pressure-sensitive copying paper obtained as described above was printed using a ribbonless typewriter, a clear colored image was obtained. Furthermore, when this copy paper was treated at 100° C. for 3 hours, almost no staining occurred on the coated surface.
比較例 １
配位子化合物含有マイクロカプセル塗液の調製
及び塗布紙の作成
没食子酸ラウリル20部をアジピン酸ジエチル50
部とアジピン酸ジ―ｎ―ブチル50部との混合液に
加熱溶解し、内相油を得た。Comparative Example 1 Preparation of microcapsule coating liquid containing a ligand compound and preparation of coated paper 20 parts of lauryl gallate was mixed with 50 parts of diethyl adipate.
and 50 parts of di-n-butyl adipate were heated and dissolved to obtain an internal phase oil.
EMA―31の3.0％水溶液200部に20％苛性ソー
ダ水溶液を添加してPHを5.0とした液にこの内相
油を乳化し、平均粒子径５μとした後この系を55
℃に昇温した。 This internal phase oil was emulsified in a solution with a pH of 5.0 by adding a 20% aqueous solution of caustic soda to 200 parts of a 3.0% aqueous solution of EMA-31, and the average particle size was adjusted to 5μ.
The temperature was raised to ℃.
別に、37％ホルムアルデヒド水溶液60部にメラ
ミン20部を加え、60℃で15分間反応させてプレポ
リマー水溶液を調製した。 Separately, 20 parts of melamine was added to 60 parts of a 37% formaldehyde aqueous solution and reacted at 60°C for 15 minutes to prepare a prepolymer aqueous solution.
このプレポリマー水溶液を前記乳化液中に滴下
し、更に撹拌しながら0.5N―塩酸を滴下してPH
を4.5とした後、80℃まで加温し、その温度で１
時間保持後、1N―塩酸でPHを3.5に下げ、更に３
時間保温した後放冷して乳白色のカプセル分散液
を得た。 This prepolymer aqueous solution was dropped into the emulsion, and while stirring, 0.5N-hydrochloric acid was added dropwise to adjust the pH.
After setting the temperature to 4.5, heat it to 80℃, and at that temperature
After holding for a period of time, lower the pH to 3.5 with 1N hydrochloric acid, and then
After keeping warm for an hour, the mixture was allowed to cool to obtain a milky white capsule dispersion.
ついで、この分散液を実施例１と同様にしてカ
プセル塗液とし、粘度を測定したが40cps（25
℃）であり、この塗液をエアーナイフコーターを
使用して40ｇ／m2の原紙に固型分が５ｇ／m2にな
るよう塗布したが、350ｍ／minのスピードしか
塗布出来なかつた。 Next, this dispersion was used as a capsule coating liquid in the same manner as in Example 1, and the viscosity was measured, and the viscosity was 40 cps (25 cps).
℃), and this coating liquid was applied to a base paper of 40 g/m 2 using an air knife coater so that the solid content was 5 g/m 2 , but it could only be applied at a speed of 350 m/min.
単体感圧複写紙の作成と評価
上記の配位子化合物含有マイクロカプセル塗布
紙の塗布面上に実施例１と同様にして調製した有
機鉄（）化合物含有塗液を固型分で５ｇ／m2に
なる様にエアーナイフコーターを使用して塗布
し、単体感圧複写紙を得た。Preparation and Evaluation of Single Pressure-Sensitive Copying Paper A coating solution containing an organic iron compound prepared in the same manner as in Example 1 was applied to the coated surface of the above-mentioned ligand compound-containing microcapsule coated paper at a solid content of 5 g/m2. 2 using an air knife coater to obtain a single pressure-sensitive copying paper.
上記の如くして得た単体感圧複写紙にリボン無
しタイプライターで印字したところ鮮明なる発色
像が得られた。又、この複写紙を100℃条件下で
３時間処理したが、実施例１と比べやや劣るもの
のほとんど汚れを生じなかつた。 When the single pressure-sensitive copying paper obtained as described above was printed with a ribbonless typewriter, a clear colored image was obtained. Further, this copy paper was treated at 100° C. for 3 hours, and although it was slightly inferior to Example 1, almost no staining occurred.
比較例 ２
配位子化合物含有マイクロカプセル塗液の調製
及び塗布紙の作成
没食子酸ラウリル20部をアジピン酸ジエチル50
部とアジピン酸ジ―ｎ―ブチル50部との混合液に
加熱溶解し、放冷後、メラン27をメラミン換算で
20部になる様添加して、内相油を得た。EMA―
31の3.0％水溶液200部に20％苛性ソーダ水溶液を
添加してPHを5.0とした液にこの内相油を乳化
し、平均粒径５μとした後この系を55℃に昇温
し、更に撹拌しながら0.5N―塩酸を滴下してPH
を4.5とした後、80℃まで加温し、その温度で１
時間保持後、1N―塩酸でPHを3.5に下げ、更に３
時間保温した後、放冷して乳白色のカプセル分散
液を得た。Comparative Example 2 Preparation of microcapsule coating liquid containing a ligand compound and preparation of coated paper 20 parts of lauryl gallate was mixed with 50 parts of diethyl adipate.
Melan 27 is dissolved in a mixed solution of 50 parts of di-n-butyl adipate and 50 parts of di-n-butyl adipate.
The mixture was added to 20 parts to obtain an internal phase oil. EMA―
The internal phase oil was emulsified in a solution with a pH of 5.0 by adding 20% aqueous sodium hydroxide solution to 200 parts of a 3.0% aqueous solution of No. While doing so, add 0.5N hydrochloric acid dropwise to adjust the pH.
After setting the temperature to 4.5, heat it to 80℃, and at that temperature
After holding for a period of time, lower the pH to 3.5 with 1N hydrochloric acid, and then
After being kept warm for an hour, the mixture was allowed to cool to obtain a milky white capsule dispersion.
次いでこの分散液を実施例１と同様にしてカプ
セル塗液とし、粘度を測定したが、9cps（25
℃）であり、この塗液をエアーナイフコーターを
使用して40ｇ／m2の原紙に固型分が５ｇ／m2にな
る様塗布したが、500ｍ／minのスピードで塗布
することが出来た。 Next, this dispersion was used as a capsule coating liquid in the same manner as in Example 1, and the viscosity was measured.
℃), and this coating liquid was applied to base paper of 40 g/m 2 using an air knife coater so that the solid content was 5 g/m 2 , and it was possible to apply at a speed of 500 m/min. .
単体感圧複写紙の作成と評価
上記の配位子化合物含有マイクロカプセル塗布
紙の塗布面上に実施例１と同様にして調製した有
機鉄（）化合物含有塗液を固型分で５ｇ／m2に
なる様にエアーナイフコーターを使用して塗布
し、単体感圧複写紙を得た。Preparation and Evaluation of Single Pressure-Sensitive Copying Paper A coating solution containing an organic iron compound prepared in the same manner as in Example 1 was applied to the coated surface of the above-mentioned ligand compound-containing microcapsule coated paper at a solid content of 5 g/m2. 2 using an air knife coater to obtain a single pressure-sensitive copying paper.
上記の如くして得た単体感圧複写紙にリボン無
しタイプライターで印字したところ、実施例１及
び比較例２と比べやや鮮明さに欠ける発色像が得
られた。又、この複写紙を100℃条件下で３時間
処理したところ、全面に黒色の汚れが生じた。 When the single pressure-sensitive copying paper obtained as described above was printed using a ribbonless typewriter, a colored image was obtained that was slightly less sharp than in Example 1 and Comparative Example 2. Further, when this copy paper was treated at 100° C. for 3 hours, black stains appeared on the entire surface.
実施例 ２
加熱装置を備えた撹拌混合容器中にアニオン変
性ポリビニルアルコール（商品名ゴーセナールＴ
―350、日本合成化学〓製）の３％水溶液150部を
加えてカプセル製造用水性媒体とした。Example 2 Anion-modified polyvinyl alcohol (trade name Gosenal T) was placed in a stirring mixing container equipped with a heating device.
150 parts of a 3% aqueous solution of Nippon Gosei Kagaku Co., Ltd.) was added to prepare an aqueous medium for capsule production.
別にアジピン酸ジ―ｎ―ブチル50部とアジピン
酸ジエチル50部との混合溶媒に没食子酸ラウリル
20部を加熱溶解し、放冷後メラン27をメラミン換
算で10部にになる様添加して、内相油とした。 Separately, add lauryl gallate to a mixed solvent of 50 parts of di-n-butyl adipate and 50 parts of diethyl adipate.
20 parts were heated and dissolved, and after being left to cool, Melan 27 was added so that the amount was 10 parts in terms of melamine, to obtain an internal phase oil.
この内相油を上記水性媒体中に平均粒径が5.0
μになるように乳化分散した後この系を60℃に昇
温した。 This internal phase oil was added to the above aqueous medium with an average particle size of 5.0.
After emulsifying and dispersing the mixture so as to have a particle size of μ, the temperature of this system was raised to 60°C.
別に、37％ホルムアルデヒド水溶液15部にメラ
ミン５部を加え、60℃で15分間反応させ、その後
更にグリシン0.5部を加え、１分間反応させて調
製したプレポリマー水溶液をPH5.5に調製したエ
チレン―無水マレイン酸共重合体（商品名EMA
―31、モンサント社製）の５％水溶液50部と混合
した。 Separately, 5 parts of melamine was added to 15 parts of a 37% formaldehyde aqueous solution and reacted at 60°C for 15 minutes. After that, 0.5 part of glycine was further added and reacted for 1 minute to prepare an aqueous prepolymer solution. Maleic anhydride copolymer (trade name: EMA)
-31, manufactured by Monsanto) and mixed with 50 parts of a 5% aqueous solution.
この混合液を撹拌下の前記乳化液中に滴下した
後、その条件下で、３時間反応させ、更に1.0N
―塩酸を滴下して系のPHを4.5に調整し、系を70
℃に昇温し、その条件下で３時間反応させた後、
放冷して乳白色のカプセル分散液を得た。 This mixed solution was dropped into the emulsion while stirring, and then reacted under the same conditions for 3 hours, and then 1.0N
- Add hydrochloric acid dropwise to adjust the pH of the system to 4.5, and bring the system to 70
After raising the temperature to ℃ and reacting under that condition for 3 hours,
The mixture was allowed to cool to obtain a milky white capsule dispersion.
次いで、この分散液を実施例１と同様にしてカ
プセル塗液とし、粘度を測定したが15cps（25
℃）であり、この塗液をエアーナイフコーターを
使用して40ｇ／m2の原紙に固型分が５ｇ／m2にな
るよう塗布したが、480ｍ／minのスピードで塗
布することが出来た。 Next, this dispersion was used as a capsule coating liquid in the same manner as in Example 1, and the viscosity was measured, and the viscosity was 15 cps (25 cps).
℃), and this coating liquid was applied to a base paper of 40 g/m 2 using an air knife coater so that the solid content was 5 g/m 2 , and it was possible to apply at a speed of 480 m/min. .
続いて、この塗布面上に実施例１と同様にして
調製した有機鉄（）化合物含有塗液を固型分で
５ｇ／m2になる様にエアーナイフコーターを使用
して塗布し、単体感圧複写紙を得た。 Subsequently, a coating liquid containing an organic iron () compound prepared in the same manner as in Example 1 was applied onto this coated surface using an air knife coater so that the solid content was 5 g/m 2 . Pressure copy paper was obtained.
上記の如くして得た単体感圧複写紙にリボン無
しタイプライターで印字したところ、実施例１と
同様鮮明なる発色像が得られ、又この複写紙を
100℃条件下で３時間処理してもほとんど汚れは
生じなかつた。 When the single pressure-sensitive copying paper obtained as described above was printed using a typewriter without ribbon, a clear colored image was obtained as in Example 1.
Almost no staining occurred even after treatment at 100°C for 3 hours.
実施例 ３
電子供与性発色剤含有マイクロカプセル塗液の
調製及び塗布紙の作成
クリスタルバイオレツトラクトン５部をジイソ
プロピルナフタレン100部に加熱溶解し放冷後、
ｎ―ブチル化メチロールメラミン―ホルムアルデ
ヒド初期縮合物（商品名ユーバン120、三井東圧
化学社製）をメラミン換算で10部になる様添加し
て、内相油を得た。別に、尿素10部とレゾルシン
１部を溶解した210部の水溶液と10％エチレン―
無水マレイン酸共重合体水溶液100部の混合溶液
に20％の苛性ソーダ水溶液を添加してPH3.5とし
た。次いで、この水溶液に上記内相油を乳化して
平均粒径５μとし、さらに37％ホルムアルデヒド
水溶液25部を加えた後、系の温度を70℃とし４時
間撹拌してカプセル分散液を得た。Example 3 Preparation of microcapsule coating liquid containing an electron-donating color former and preparation of coated paper 5 parts of crystal violet lactone was dissolved in 100 parts of diisopropylnaphthalene by heating, and after cooling,
An internal phase oil was obtained by adding n-butylated methylol melamine-formaldehyde initial condensate (trade name: Yuban 120, manufactured by Mitsui Toatsu Chemical Co., Ltd.) in an amount of 10 parts in terms of melamine. Separately, prepare 210 parts of an aqueous solution containing 10 parts of urea and 1 part of resorcinol, and 10% ethylene.
A 20% aqueous solution of caustic soda was added to a mixed solution of 100 parts of an aqueous maleic anhydride copolymer solution to adjust the pH to 3.5. Next, the internal phase oil was emulsified in this aqueous solution to give an average particle size of 5 μm, and 25 parts of a 37% formaldehyde aqueous solution was added thereto, and the system was heated to 70° C. and stirred for 4 hours to obtain a capsule dispersion.
次いで、この分散液に小麦デンプン粉末20部、
パルプ粉末10部を添加混合し、固型分濃度が25％
になるよう水を加えてカプセル塗液を得た。 Next, 20 parts of wheat starch powder was added to this dispersion,
Add and mix 10 parts of pulp powder, solid content concentration is 25%
Water was added to obtain a capsule coating solution.
尚、得られたカプセル塗液の粘度は、10cps
（20℃）であり、この塗液をエアーナイフコータ
ーを使用して40ｇ／m2の原紙に固型分が５ｇ／m2
になるよう塗布したが、500ｍ／minのスピード
で塗布することが出来た。 The viscosity of the obtained capsule coating liquid is 10 cps.
(20°C), and this coating liquid was coated on 40g/ m2 base paper using an air knife coater so that the solid content was 5g/ m2.
The coating was applied at a speed of 500 m/min.
単体感圧複写紙の作成
水酸化アルミニウム65部、酸化亜鉛20部、３，
５―ジ（α―メチルベンジル）サリチル酸亜鉛と
α―メチルスチレン・スチレン共重合体との混融
物（混融比80／20）15部、ポリビニルアルコール
水溶液５部（固型分）及び水300部をボールミル
で24時間粉砕して得た分散液に、カルボキシ変性
スチレン・ブタジエン共重合体ラテツクス20部
（固型分）を加えて調製した顕色剤塗液を上記塗
布紙の塗布面上にエアーナイフコーターで固型分
５ｇ／m2になるように塗抹して単体感圧複写紙を
作成した。Preparation of single pressure sensitive copying paper 65 parts of aluminum hydroxide, 20 parts of zinc oxide, 3.
15 parts of a blend of zinc 5-di(α-methylbenzyl)salicylate and α-methylstyrene/styrene copolymer (melt ratio 80/20), 5 parts of polyvinyl alcohol aqueous solution (solid content), and 300 parts of water A color developer coating solution prepared by adding 20 parts (solid content) of carboxy-modified styrene-butadiene copolymer latex to a dispersion obtained by grinding 1 part in a ball mill for 24 hours was applied onto the coated surface of the above-mentioned coated paper. A single pressure-sensitive copying paper was prepared by coating with an air knife coater so that the solid content was 5 g/m 2 .
評 価
上記の如くして得た単体感圧複写紙にリボン無
しタイプライターで印字したところ、鮮明なる発
色像が得られた。又、この複写紙を100℃条件下
で３時間処理したが、塗布面にほどんど汚れを生
じなかつた。Evaluation When the single pressure-sensitive copying paper obtained as described above was printed using a ribbonless typewriter, a clear colored image was obtained. Furthermore, when this copy paper was treated at 100° C. for 3 hours, almost no staining occurred on the coated surface.
Claims (1)
のアルデヒド系樹脂形成材料を重縮合せしめて疎
水性芯物質を被覆するマイクロカプセルの製造方
法において、該疎水性芯物質中に疎水性のアルデ
ヒド系樹脂初期縮合物を含有せしめることを特徴
とするマイクロカプセルの製造方法。 ２ 親水性のアルデヒド系樹脂形成材料がアミン
類とアルデヒド類及び／又はアミノアルデヒド樹
脂初期縮合物である請求の範囲第１項記載の製造
方法。 ３ 親水性のアルデヒド系樹脂形成材料が尿素及
びホルムアルデヒド或いは尿素―ホルムアルデヒ
ド初期縮合物、メラミン―ホルムアルデヒド初期
縮合物、尿素―メラミン―ホルムアルデヒド初期
縮合物の少なくとも一種である請求の範囲第２項
記載の製造方法。 ４ 疎水性のアルデヒド系樹脂初期縮合物がアミ
ノアルデヒド樹脂初期縮合物のアルキル化物であ
る請求の範囲第１〜３項記載の製造方法。 ５ 疎水性のアルデヒド系樹脂初期縮合物が尿素
―ホルムアルデヒド初期縮合物のアルキル化物、
メラミン―ホルムアルデヒド初期縮合物のアルキ
ル化物、尿素―メラミン―ホルムアルデヒド初期
縮合物のアルキル化物である請求の範囲第４項記
載の製造方法。 ６ 水或いは親水性媒体が乳化剤としてアニオン
性モノマーユニツトからなる重合体或いは共重合
体、アニオン性モノマーユニツトと疎水性モノマ
ーユニツトとの共重合体、ポリビニルアルコー
ル、変性ポリビニルアルコールの少なくとも一種
を含有する請求の範囲第１〜５項記載の製造方
法。 ７ 反応条件がPH5.0以下、温度50℃以上である
請求の範囲第１〜６項記載の製造方法。[Scope of Claims] 1. A method for producing microcapsules in which a hydrophilic aldehyde resin-forming material contained in water or a hydrophilic medium is polycondensed to cover a hydrophobic core substance, the method comprising: 1. A method for producing microcapsules, comprising: containing a hydrophobic aldehyde resin initial condensate. 2. The production method according to claim 1, wherein the hydrophilic aldehyde resin forming material is an initial condensate of amines, aldehydes and/or aminoaldehyde resins. 3. The production according to claim 2, wherein the hydrophilic aldehyde resin forming material is at least one of urea and formaldehyde, or a urea-formaldehyde initial condensate, a melamine-formaldehyde initial condensate, or a urea-melamine-formaldehyde initial condensate. Method. 4. The manufacturing method according to any one of claims 1 to 3, wherein the hydrophobic aldehyde resin initial condensate is an alkylated product of an aminoaldehyde resin initial condensate. 5 The hydrophobic aldehyde resin initial condensate is an alkylated product of a urea-formaldehyde initial condensate,
The method according to claim 4, which is an alkylated product of a melamine-formaldehyde initial condensate or an alkylated product of a urea-melamine-formaldehyde initial condensate. 6. Claims in which water or a hydrophilic medium contains as an emulsifier at least one of a polymer or copolymer composed of anionic monomer units, a copolymer of anionic monomer units and hydrophobic monomer units, polyvinyl alcohol, and modified polyvinyl alcohol. The manufacturing method according to items 1 to 5. 7. The manufacturing method according to claims 1 to 6, wherein the reaction conditions are a pH of 5.0 or lower and a temperature of 50°C or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58118022A JPS607935A (en) | 1983-06-28 | 1983-06-28 | Preparation of microcapsule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58118022A JPS607935A (en) | 1983-06-28 | 1983-06-28 | Preparation of microcapsule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS607935A JPS607935A (en) | 1985-01-16 |
| JPS6256779B2 true JPS6256779B2 (en) | 1987-11-27 |
Family
ID=14726126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58118022A Granted JPS607935A (en) | 1983-06-28 | 1983-06-28 | Preparation of microcapsule |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS607935A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61118133A (en) * | 1984-11-13 | 1986-06-05 | Kanzaki Paper Mfg Co Ltd | Manufacture of microcapsule |
| JPS61174941A (en) * | 1985-01-28 | 1986-08-06 | Kanzaki Paper Mfg Co Ltd | Preparation of microcapsule |
| JPS6297638A (en) * | 1985-10-25 | 1987-05-07 | Kanzaki Paper Mfg Co Ltd | Preparation of microcapsule |
| BR0111465B1 (en) * | 2000-06-03 | 2012-12-11 | microcapsule, modified process for encapsulating a dispersed material within a solid permeable shell of a polymeric resin, reaction product, and method for modifying the soil mobility of an agrochemical product. | |
| JP5421141B2 (en) * | 2009-03-24 | 2014-02-19 | 株式会社日本触媒 | Amino resin crosslinked particles and process for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5028484A (en) * | 1973-07-17 | 1975-03-24 | ||
| JPS5218671A (en) * | 1975-08-04 | 1977-02-12 | Seiken Kogyo Kk | Safety device for concentrically contrlling address |
-
1983
- 1983-06-28 JP JP58118022A patent/JPS607935A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5028484A (en) * | 1973-07-17 | 1975-03-24 | ||
| JPS5218671A (en) * | 1975-08-04 | 1977-02-12 | Seiken Kogyo Kk | Safety device for concentrically contrlling address |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS607935A (en) | 1985-01-16 |
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