JPH0233415B2 - - Google Patents
Info
- Publication number
- JPH0233415B2 JPH0233415B2 JP59003274A JP327484A JPH0233415B2 JP H0233415 B2 JPH0233415 B2 JP H0233415B2 JP 59003274 A JP59003274 A JP 59003274A JP 327484 A JP327484 A JP 327484A JP H0233415 B2 JPH0233415 B2 JP H0233415B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- acid
- initial condensate
- mono
- melamine
- 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 - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 claims description 28
- 239000011162 core material Substances 0.000 claims description 27
- 239000002775 capsule Substances 0.000 claims description 26
- 229920000877 Melamine resin Polymers 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000002209 hydrophobic effect Effects 0.000 claims description 17
- 239000003094 microcapsule Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000004640 Melamine resin Substances 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- -1 di-ethoxytrimethylol melamine Chemical compound 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- OQVXXNURRJNPIF-UHFFFAOYSA-N C(C)ON(C1=NC(=NC(=N1)N(CO)OCC)N(CO)OCC)CO Chemical compound C(C)ON(C1=NC(=NC(=N1)N(CO)OCC)N(CO)OCC)CO OQVXXNURRJNPIF-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- SXCFTHZSHLAXMF-UHFFFAOYSA-N CON(C1=NC(=NC(=N1)N(CO)OC(C)C)N(CO)OC)CO Chemical compound CON(C1=NC(=NC(=N1)N(CO)OC(C)C)N(CO)OC)CO SXCFTHZSHLAXMF-UHFFFAOYSA-N 0.000 claims description 4
- KCPJQXWQMYHZQH-UHFFFAOYSA-N [[4,6-bis[hydroxymethyl(propan-2-yloxy)amino]-1,3,5-triazin-2-yl]-ethoxyamino]methanol Chemical compound C(C)ON(C1=NC(=NC(=N1)N(CO)OC(C)C)N(CO)OC(C)C)CO KCPJQXWQMYHZQH-UHFFFAOYSA-N 0.000 claims description 4
- VRHMDTITFAIAKN-UHFFFAOYSA-N [ethoxy-[4-[ethoxy(hydroxymethyl)amino]-6-[hydroxymethyl(propan-2-yloxy)amino]-1,3,5-triazin-2-yl]amino]methanol Chemical compound C(C)ON(C1=NC(=NC(=N1)N(CO)OC(C)C)N(CO)OCC)CO VRHMDTITFAIAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920006318 anionic polymer Polymers 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 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 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 12
- 239000008096 xylene Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 239000003995 emulsifying agent Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000005538 encapsulation Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 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 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229960004592 isopropanol Drugs 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 229920001059 synthetic polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 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
- 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
- RVIJLMKZYPINER-UHFFFAOYSA-N [[4,6-bis[ethoxy(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CON(C1=NC(=NC(=N1)N(CO)OCC)N(CO)OCC)CO RVIJLMKZYPINER-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000002091 cationic group Chemical group 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000151 deposition Methods 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
- 239000010419 fine particle Substances 0.000 description 3
- 239000003607 modifier 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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
- 244000215068 Acacia senegal Species 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 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
- 229920000084 Gum arabic Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 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 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 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
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-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
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000006467 substitution reaction Methods 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
- 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
- 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
- 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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-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
- 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
- PTLRZUJHHRZSNK-UHFFFAOYSA-N C(CCC)OC1(N(C(N(C(N1OCCCC)(N(CO)CO)OCCCC)OCCCC)(N(CO)CO)OCCCC)OCCCC)N(CO)CO Chemical compound C(CCC)OC1(N(C(N(C(N1OCCCC)(N(CO)CO)OCCCC)OCCCC)(N(CO)CO)OCCCC)OCCCC)N(CO)CO PTLRZUJHHRZSNK-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 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
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 1
- FANBESOFXBDQSH-UHFFFAOYSA-N Ethyladipic acid Chemical compound CCC(C(O)=O)CCCC(O)=O FANBESOFXBDQSH-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-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
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 238000012695 Interfacial polymerization Methods 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
- 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
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 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
- 150000007513 acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000001450 anions Chemical class 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
- 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
- 235000019438 castor oil Nutrition 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction 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
- 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
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 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
- 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000010386 dodecyl gallate Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 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
- 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
- 229940015043 glyoxal Drugs 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000003446 ligand Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer 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
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 229920005615 natural polymer Polymers 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
- 239000003973 paint Substances 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000001737 promoting effect Effects 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
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- PDGBYPZJHBOOIC-UHFFFAOYSA-M sodium;2-tert-butylbenzoate Chemical compound [Na+].CC(C)(C)C1=CC=CC=C1C([O-])=O PDGBYPZJHBOOIC-UHFFFAOYSA-M 0.000 description 1
- ZDLGDUOCAJRZRN-UHFFFAOYSA-M sodium;3,7-dimethylnaphthalene-1-sulfonate Chemical compound [Na+].C1=C(C)C=C(S([O-])(=O)=O)C2=CC(C)=CC=C21 ZDLGDUOCAJRZRN-UHFFFAOYSA-M 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
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-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
- YEQCNBCFZFWPKX-UHFFFAOYSA-M sodium;dibutyl phosphate Chemical compound [Na+].CCCCOP([O-])(=O)OCCCC YEQCNBCFZFWPKX-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
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229950000244 sulfanilic acid Drugs 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
- 230000008719 thickening Effects 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 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
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
セルの製造方法に関する。特に、芯物質保持性に
優れたカプセルが、極めて容易に製造でき、その
適用範囲が極めて広いカプセル製造方法を提供す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing microcapsules containing a hydrophobic core material. In particular, it is an object of the present invention to provide a capsule manufacturing method that allows capsules with excellent core material retention properties to be manufactured extremely easily and has an extremely wide range of applicability.
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 having aldehyde polycondensation resin as a wall film are water resistant, Due to its excellent solvent resistance,
Various encapsulation methods have been proposed; for example, U.S. Pat. ,
JP-A-48-57892, JP-A-51-9079, JP-A-Sho
No. 52-66878, JP-A-53-84881, JP-A-53-
No. 84882, JP-A-53-84883, JP-A-54-25277
No., JP-A-54-49984, JP-A-54-53679, JP-A-54-85184, JP-A-54-85185, JP-A-54
-107881, JP-A-55-8856, JP-A-55-
No. 15660, JP-A-55-47139, JP-A-55-51431
No., JP-A-55-67329, JP-A-55-92135, JP-A-55-132631, JP-A-55-152546, JP-A-Sho.
No. 56-51238, JP-A-56-78626, JP-A-56-
No. 102934, JP-A-56-115634, JP-A-56-
No. 155636, JP-A-57-110332, JP-A-57-
135038, JP-A-57-147429, etc.
しかし、このように数多くのカプセル化法が開
発提案されいるにもかかわらず、これらの方法に
は次に挙げるが如き短所のいずれかが付随するた
め、まだ改良の必要がある。 However, even though a large number of encapsulation methods have been developed and proposed, there is still a need for improvement because these methods are associated with one of the following disadvantages.
芯物質の乳化剤として用いられる水溶性水高
分子の物性、例えば重合度、分子量分布、共重
合比率、変性度等の微妙な変化の影響を受け易
く、ロツトの異なる材料を用いる工業スケール
での調製において膜強度等の品質上のバラツキ
を生じ易い。 The physical properties of the water-soluble water polymer used as an emulsifier for the core material are susceptible to subtle changes in the degree of polymerization, molecular weight distribution, copolymerization ratio, degree of modification, etc., and preparation is carried out on an industrial scale using materials from different lots. This tends to cause variations in quality such as film strength.
カプセル調製条件の微妙な違いによりカプセ
ルの出来に差を生じ易い為、工業化に際し、そ
れを制御する為の高精度の装置を必要とする。 Subtle differences in capsule preparation conditions tend to cause differences in the quality of the capsules, so a highly accurate device is required to control this for industrialization.
工程が繁雑である。 The process is complicated.
膜形成時のカプセル粒子凝集を防ぐ為、一定
以上の強力撹拌が必要であり、疎水性芯物質が
低撹拌で容易に剪断される性質を有する場合、
乳化粒径を維持したままカプセル化することが
困難である。 In order to prevent capsule particles from agglomerating during film formation, strong stirring above a certain level is required, and if the hydrophobic core material has the property of being easily sheared with low stirring,
It is difficult to encapsulate while maintaining the emulsion particle size.
用いられる乳化剤の乳化安定性が悪い場合、
巨大油滴が生成し易く、これを感圧複写紙に適
用する場合、スポツト汚れの原因となる。 If the emulsifier used has poor emulsion stability,
Huge oil droplets are likely to be generated, and when applied to pressure-sensitive copying paper, they cause spot stains.
膜形成中に系が増粘する傾向があり、かつ膜
材料の芯物質表面への堆積の性質も弱いため、
堆積を促進する為にも希水を多量に用いる必要
があり、高濃度塗料が得られない。 The system tends to thicken during film formation, and the film material tends to be less likely to deposit on the surface of the core material.
It is necessary to use a large amount of diluted water to promote deposition, making it impossible to obtain a highly concentrated paint.
膜剤の芯物質表面への堆積効率が悪く内包物
保持性の充分なものが得られない。 The deposition efficiency of the film agent on the surface of the core material is poor, and sufficient inclusion retention properties cannot be obtained.
芯物質表面へ堆積する膜材が耐水性を有する
アルデヒド重縮合樹脂と耐水性の劣る高分子化
合物との混合物の形である場合、耐水性の劣る
カプセルしか得られない。 If the membrane material deposited on the surface of the core substance is in the form of a mixture of an aldehyde polycondensation resin having water resistance and a polymer compound having poor water resistance, only capsules with poor water resistance can be obtained.
これらを具体的に示すと、例えば特開昭51−
9079号、特開昭53−84882号、特開昭53−84883
号、特開昭54−53679号及び特開昭54−85184号や
特開昭53−84881号及び特開昭54−49984号に示さ
れるが如き疎水性モノマーユニツトと無水マレイ
ン酸或いはポリアクリル酸中で尿素ホルムアルデ
ヒド樹脂膜やメラミンホルムアルデヒド樹脂膜を
形成する方法では上記、、の欠点が付随す
る。又、特開昭54−85185号、特開昭54−107881
号及び特開昭55−132631号に示されるが如きカル
ボキシ変性ポリビニルアルコール、アラビアガ
ム、ケン化度95％以上のポリビニルアルコール中
で尿素ホルムアルデヒド樹脂膜を形成する方法や
特開昭55−92135号、特開昭57−110332号に示さ
れるが如きアニオン変性ポリビニルアルコール、
カチオン変性ポリビニルアルコール中でアミノア
ルデヒド樹脂膜を形成する方法では上記、、
、、の欠点が付随する。 To specifically show these, for example, JP-A-51-
No. 9079, JP-A-53-84882, JP-A-53-84883
Hydrophobic monomer units and maleic anhydride or polyacrylic acid as shown in JP-A-54-53679 and JP-A-54-85184, JP-A-53-84881 and JP-A-54-49984. Among them, the method of forming a urea formaldehyde resin film or a melamine formaldehyde resin film has the above-mentioned drawbacks. Also, JP-A-54-85185, JP-A-54-107881
A method of forming a urea formaldehyde resin film in carboxy-modified polyvinyl alcohol, gum arabic, polyvinyl alcohol with a degree of saponification of 95% or more as shown in JP-A No. 55-92135, anion-modified polyvinyl alcohol as shown in JP-A-57-110332;
In the method of forming an aminoaldehyde resin film in cation-modified polyvinyl alcohol,
, , are associated with disadvantages.
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.
これらのカプセル化法では、前記の如き〜
の欠点が付随することはほとんどないが、水或い
は親水性媒体より膜材を重合堆積させる方法によ
つて得られるカプセルに比較して、内包物保持性
がかなり劣つており、特に良好なる保持性が要求
される感圧複写紙用マイクロカプセルとしては全
く実用性に乏しいものであつた。 In these encapsulation methods, as mentioned above, ~
However, compared to capsules obtained by polymerizing and depositing a membrane material from water or a hydrophilic medium, the retention property of the inclusions is considerably inferior, and the retention property is particularly good. This was completely impractical as a microcapsule for pressure-sensitive copying paper, which requires the following properties.
かかる現状に鑑み、本発明者等はアルデヒド重
縮合樹脂を壁膜として有するマイクロカプセルの
製造方法において、カプセル芯物質の保持性に優
れたカプセルを容易にかつ、安定して製造し得る
方法について鋭意研究した結果、疎水性芯物質に
含有させたアルデヒド系樹脂初期縮合物を重合さ
せ、疎水性芯物質微粒子の表面に樹脂を堆積させ
るカプセル化法において、該アルデヒド系樹脂初
期縮合物として特定のものを選択することによつ
て、隠やかなる条件での反応によつても良好なる
内包物保持性を有するマイクロカプセルが得られ
ることを見出し、本発明を達成するに至つた。 In view of the current situation, the present inventors have made efforts to develop a method for easily and stably producing capsules with excellent retention of capsule core substances in a method for producing microcapsules having an aldehyde polycondensation resin as a wall film. As a result of research, in the encapsulation method in which an initial condensate of aldehyde resin contained in a hydrophobic core material is polymerized and the resin is deposited on the surface of fine particles of the hydrophobic core material, a specific initial condensate of aldehyde resin is used. The present inventors have discovered that microcapsules having good inclusion retention properties can be obtained even by secret reaction under certain conditions by selecting the following, and have achieved the present invention.
本発明は油溶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を水或いは親水性媒体中
に乳化し、重縮合を促進する条件下でカプセル膜
を形成せしめるマイクロカプセル化法において、
該初期縮合物として、トリエトキシトリメチロー
ルメラミン、ジ−エトキシ−モノ−イソプロポキ
シトリメチロールメラミン、ジ−メトキシ−モノ
−イソプロポキシトリメチロールメラミン、モノ
−エトキシ−ジ−イソプロポキシトリメチロール
メラミン、モノ−メトキシ−ジ−エトキシトリメ
チロールメラミンより選ばれる少なくとも１種の
メラミン樹脂初期縮合物を用い、且つ得られたマ
イクロカプセル分散液から濾過、乾燥することに
より水或いは親水性媒体を除去しないことを特徴
とするマイクロカプセルの製造方法である。 The present invention relates to a microencapsulation method in which a hydrophobic core material containing an oil-soluble aldehyde resin initial condensate is emulsified in water or a hydrophilic medium to form a capsule membrane under conditions that promote polycondensation.
The initial condensate includes triethoxytrimethylolmelamine, di-ethoxy-mono-isopropoxytrimethylolmelamine, di-methoxy-mono-isopropoxytrimethylolmelamine, mono-ethoxy-di-isopropoxytrimethylolmelamine, mono- A melamine resin initial condensate of at least one selected from methoxy-di-ethoxytrimethylolmelamine is used, and water or a hydrophilic medium is not removed from the resulting microcapsule dispersion by filtration and drying. This is a method for producing microcapsules.
尚、以前に本発明者らは、特願昭58−54779号
において、アルデヒド系樹脂初期縮合物を厳しい
反応条件下で重縮合させて極めて優れた内包物保
持性を有するマイクロカプセルが得られることを
報告しているが、本発明のカプセル化法は、その
反応条件よりもかなり穏やかな条件下でもカプセ
ル化が可能である為、熱及び酸に対してやや不安
定な物質をカプセル化する場合にも良好なるカプ
セルを得ることが出来、より適用範囲の広いカプ
セル化法と言える。 In addition, the present inventors have previously reported in Japanese Patent Application No. 58-54779 that microcapsules having extremely excellent inclusion retention properties can be obtained by polycondensing an aldehyde resin initial condensate under severe reaction conditions. However, the encapsulation method of the present invention allows encapsulation under much milder conditions than the reaction conditions, so it is useful when encapsulating substances that are somewhat unstable to heat and acids. However, it is also possible to obtain good capsules, and it can be said that this encapsulation method has a wider range of applications.
また、本発明におけるホルムアルデヒド置換度
はメラミンのアミノ基が有する活性水素の内、メ
チロール基、アルコキシメチロール基及びメチレ
ン基によつて何％が置換されているかを示す値で
次式によつて表される。 In addition, the degree of formaldehyde substitution in the present invention is a value indicating the percentage of active hydrogen possessed by the amino group of melamine that is substituted by methylol group, alkoxymethylol group, and methylene group, and is expressed by the following formula. Ru.
ホルムアルデヒド置換度＝メチロール基数＋アルコキ
シメチロール基数＋メチレン基数×２／メラミン個数×
６×100
又、アルキル化度はメチロール基の内、何％が
アルコキシ化されているかを示す値で次式によつ
て表わされる。 Formaldehyde substitution degree = number of methylol groups + number of alkoxymethylol groups + number of methylene groups x 2 / number of melamine x
6×100 Further, the degree of alkylation is a value indicating what percentage of the methylol group is alkoxylated and is expressed by the following formula.
アルキル化度＝アルコキシメチロール基数／メチロー
ル基数＋アルコキシメチロール基数×100
又、疎水化度はメラミン残基１ケ当りの全アル
キル基の総炭素数である。 Degree of alkylation=Number of alkoxymethylol groups/Number of methylol groups+Number of alkoxymethylol groups×100 Furthermore, the degree of hydrophobicity is the total number of carbon atoms of all alkyl groups per one melamine residue.
なお、本発明においては、初期縮合物１分子に
含まれるメラミン残基の平均個数で表される平均
核体数が１〜10、より好ましくは１〜５である初
期縮合物がより望ましく用いられる。 In the present invention, it is more desirable to use an initial condensate in which the average number of nuclei, expressed as the average number of melamine residues contained in one molecule of the initial condensate, is 1 to 10, more preferably 1 to 5. .
さらに、本発明においては膜材の性能を変える
等の目的で、メラミン樹脂初期縮合物と併用の形
で他のアルデヒド系樹脂初期縮合物を使用するこ
とが出来るが、こ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１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１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。 Furthermore, in the present invention, other aldehyde resin initial condensates can be used in combination with the melamine resin initial condensate for the purpose of changing the performance of the membrane material. Examples include phenol formaldehyde resin initial condensates, aminoaldehyde resin initial condensates, 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, para Initial condensate obtained by condensing at least one aldehyde such as formaldehyde, hexamethylenetetramine, glutaraldehyde, glyoxal, furfural, etc., or an alkylated product thereof, a partially alkylated product thereof, an anion, cation, or nonionic modified product thereof, etc. Among these, hydrophobic ones are used alone or in combination. Alkyl groups used for etherification are not limited to these, but from the viewpoint of ease of preparation, those having 1 carbon number
A range of from 8 to 8 is preferred. Examples of anionic modifiers include sulfamic acid, sulfanilic acid, glycolic acid, glycine, acidic sulfite, phenol sulfonate, and taurine, and cationic modifiers include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and dimethylaminoethanol. Examples of nonionic modifiers include ethylene glycol, diethylene glycol, etc., and these are used to the extent that the initial condensate does not lose its hydrophobicity.
本発明において、メラミン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、エチレンクロラ
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 the present invention, when a melamine resin initial condensate is dissolved in a hydrophobic core material, when the initial condensate used has insufficient solubility or has a high viscosity, or when the hydrophobic core material in which the initial condensate is dissolved, When the viscosity 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, ethylene chloride, ethylene chloride, carbon disulfide, acetone, methyl acetate, and 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、本発明においてはメラミン樹脂初期縮合物
は疎水性芯物質に完全に溶解して使用されるのが
望ましいが、部分的に溶解した状態でも使用可能
である。 Further, in the present invention, it is desirable that the melamine resin initial condensate be used in a completely dissolved state in the hydrophobic core material, but it can also be used in a partially dissolved state.
尚、本発明におけるメラミン樹脂初期縮合物の
配合量は、用いる初期縮合物の種類或いは、用い
る疎水性芯物質及び併用される他のアルデヒド系
樹脂の種類及び配合量、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重量部に対してメラミン換
算で２重量部以上50重量部以下が好ましく、特に
４重量部以上30重量部以下がより好ましい。 The amount of the melamine resin initial condensate used in the present invention depends on the type of initial condensate used, the type and amount of the hydrophobic core material used and other aldehyde resins used in combination, the particle size of the capsule, and its use. Although it varies depending on the application and cannot be determined unconditionally, it is preferably 2 parts by weight or more and 50 parts by weight or less in terms of melamine, particularly 4 parts by weight or more and 30 parts by weight or less, based on 100 parts by weight of the hydrophobic core material. preferable.
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.
本発明における重縮合促進条件は、用いるメラ
ミン樹脂初期縮合物の種類及びカプセルの使用用
途によつて変わり、一概に決められないが、40℃
以上で１時間以上、特に好ましくは、60℃以上の
条件下で１時間以上、特に３時間以上維持するの
が好ましく、取分、これを感圧複写紙用マイクロ
カプセルとして用いる場合には、70℃以上の条件
或いはPH5.0以下、60℃以上の条件で２時間以上
維持することが好ましい。 The conditions for promoting polycondensation in the present invention vary depending on the type of the melamine resin initial condensate used and the intended use of the capsules, and cannot be determined unconditionally.
It is preferable to maintain the temperature above for 1 hour or more, particularly preferably for 1 hour or more, especially for 3 hours or more under conditions of 60°C or higher. It is preferable to maintain the temperature at 2 hours or more at a temperature of 60°C or higher, or at a pH of 5.0 or lower.
本発明においては、メラミン樹脂初期縮合物を
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、この乳化剤としては、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, if the hydrophobic core material containing the melamine resin initial condensate can be emulsified in water or a hydrophilic medium, it is not necessary to use an emulsifier, but it is preferable to use an emulsifier in order to facilitate emulsification. Preferably, as the emulsifier, an anionic, nonionic, cationic, or amphoteric polymer or low-molecular emulsifier 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., specifically gum arabic, carrageenan,
Natural polymers such as sodium alginate, pectic acid, gum tragacanth, almond gum, agar, carboxymethylcellulose, sulfated cellulose, sulfated methylcellulose, carboxymethyl starch,
Phosphated starch, semi-synthetic polymers such as ligninsulfonic acid, maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based, methacrylic acid-based, or crotonic acid-based polymers and copolymers, vinyl Benzene sulfonic 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 polyvinyl Examples include synthetic polymers such as 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
したものを含む）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、スチレン−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-maleic anhydride copolymers,
Examples include maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, methacrylamide-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, and styrene-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−メタクリル酸、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、アクリロイルモルホリン−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, acryloylmorpholine-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。 Both natural and synthetic nonionic polymers can be used; for example, -OH
Examples include those having a 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+、NH+ 4
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、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、ロート油、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. Or organic phosphoric acid Li + , Na + , K + , NH + 4
Preferred salts include sodium vinylsulfonate, sodium benzenesulfonate, sodium benzenesulfinate, sodium p-toluenesulfonate, sodium p-toluenesulfinate, sodium p-vinylbenzenesulfonate, p-i - Sodium amylbenzenesulfonate, sodium naphthalene-α-sulfonate, sodium naphthalene-β-sulfonate, sodium 2-methylnaphthalene-6-sulfonate, sodium 2,6-dimethylnaphthalene-8-sulfonate,
Sodium 2,6-dimethylnaphthalene-3-sulfonate, sodium 1-naphthol-4-sulfonate, sodium benzene-m-disulfonate, funnel oil, sodium diphenyl phosphate, sodium phenylphosphonate, sodium di-n-butyl phosphate, Examples include 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
アニオン性高分子が好ましく、とりわけメラミン
樹脂初期縮合物と殆ど架橋反応をせずしかも乳化
力の優れている水酸基或いはアミド基を有するこ
とのない無水マレイン酸系共重合体、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
及び共重合体に属する高分子は、本発明の如き厳
しい条件下での調製では起りがちであつた増粘が
ほとんど起らず、乳化粒子が安定化し易い等の点
で好ましく。その中でもエチレン−無水マレイン
酸共重合体が特に好ましい。 In the present invention, the above-mentioned high-molecular or low-molecular emulsifiers may be used alone or in combination, but among these, preferred are high-molecular emulsifiers, and among these, anionic polymers are preferred, especially melamine resin initial condensation Maleic anhydride-based copolymers, acrylic acid-based, methacrylic acid-based, or crotonic acid-based polymers and copolymers that have no hydroxyl or amide groups and have almost no crosslinking reaction with substances and have excellent emulsifying power. Polymers belonging to the above group are preferable because they hardly cause the thickening that tends to occur in preparation under severe conditions such as those used in the present invention, and the emulsified particles are easily stabilized. Among these, ethylene-maleic anhydride copolymer is particularly preferred.
尚、上記の如き乳化剤は水或いは親水性媒体中
に0.1％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 0.1% 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.
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 fluoride, or the above synthetic oils may be treated with an electron-donating coloring agent or an electron-accepting developer. Colorants, ligand compounds,
Solutions of organic metal salts, water-insoluble metal oxides and salts, fiber-like substances such as cellulose or asbestos, water-insoluble synthetic polymer substances, minerals, pigments, glasses, 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、勿論これらに限定されるも
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
トリメチロールメラミンの調製
37％ホルマリン水溶液14.9部を水で稀釈し100
部とした後、0.1N−NaOH水溶液でPH6.5〜6.8に
調整し、更にメラミン23.1部を添加し、撹拌しな
がら徐々に75℃迄昇温し、メラミンを完全に溶解
させた。次いで、75℃で５分間保持した後、急速
に０℃に冷却し、撹拌を停止して１昼夜静置した
ところ白色の結晶が析出した。Example 1 Preparation of trimethylolmelamine Dilute 14.9 parts of 37% formalin aqueous solution with water to 100%
After adjusting the pH to 6.5 to 6.8 with a 0.1N NaOH aqueous solution, 23.1 parts of melamine was added, and the temperature was gradually raised to 75° C. with stirring to completely dissolve the melamine. Next, after being held at 75°C for 5 minutes, it was rapidly cooled to 0°C, stirring was stopped, and the mixture was allowed to stand for one day and night, and white crystals were precipitated.
この結晶を濾過し、メタノールで数回洗浄し、
風乾してトリメチロールメラミンの結晶24.7部を
得た。 The crystals were filtered, washed several times with methanol,
It was air-dried to obtain 24.7 parts of trimethylolmelamine crystals.
トリエトキシトリメチロールメラミンの調製
トリメチロールメラミン25.7部とエタノール
300部を還流冷却管を付けたパラブルフラスコ内
に添加し、78℃で撹拌しながら1N−HCl5部を加
え、トリメチロールメラミンの結晶を溶解させ
た。溶解後30分間78℃に保つた後、1N−NaOH
水溶液５部を添加した。 Preparation of triethoxytrimethylolmelamine 25.7 parts of trimethylolmelamine and ethanol
300 parts of the mixture was added to a parable flask equipped with a reflux condenser, and while stirring at 78°C, 5 parts of 1N HCl was added to dissolve the trimethylolmelamine crystals. After dissolving and keeping at 78℃ for 30 minutes, 1N−NaOH
5 parts of aqueous solution were added.
次いで、これを冷却し、濾過して微量の不純物
を除去した後、55℃の温度で60部迄減圧濃縮し、
これにキシレン30部を加えて更に40部迄減圧濃縮
し、トリエトキシトリメチロールメラミンを主成
分する初期縮合物のキシレン溶液を得た。 Next, this was cooled, filtered to remove trace impurities, and concentrated under reduced pressure at a temperature of 55°C to 60 parts.
To this was added 30 parts of xylene and further concentrated under reduced pressure to 40 parts to obtain a xylene solution of the initial condensate containing triethoxytrimethylolmelamine as a main component.
マイクロカプセルの調製
没食子酸ラウリル20部及びトリベンジルアミン
５部をアジビン酸−エチル50部とアジピン酸ジ−
ｎ−ブチル50部との混合液に溶解して得た溶液に
上記のメラミン初期縮合物を添加混合して内相液
を得た。 Preparation of microcapsules 20 parts of lauryl gallate and 5 parts of tribenzylamine were mixed with 50 parts of ethyl adipic acid and di-adipate.
The above melamine initial condensate was added and mixed to a solution obtained by dissolving it in a mixture with 50 parts of n-butyl to obtain an internal phase liquid.
別に、加熱装置を備えた撹拌混合容器中にエチ
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）3.0％水溶液200部を加え、
これに20％苛性ソーダ水溶液を添加してPHを5.0
に調節しカプセル製造用水性媒体とした。この水
性媒体中に上記内相液を平均粒径が4.0μになるよ
うに乳化分散した後、この系を７℃に昇温し、こ
の温度下で２時間保持した。 Separately, in a stirring mixing vessel equipped with a heating device, ethylene-maleic anhydride copolymer (trade name EMA-
31, manufactured by Monsanto), add 200 parts of a 3.0% aqueous solution,
Add 20% caustic soda aqueous solution to this to raise the pH to 5.0.
It was adjusted to be an aqueous medium for capsule production. After the internal phase liquid was emulsified and dispersed in this aqueous medium so that the average particle size was 4.0 μm, the system was heated to 7° C. and maintained at this temperature for 2 hours.
次いで、この系に撹拌下0.5N−塩酸を徐々に
添加して、系のPHを3.5に調整し、続いて系の温
度を徐々に80℃迄昇温し、更に80℃下で５時間反
応させて乳白色のカプセル分散液を得た。得られ
たカプセル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、固形分濃度が25％にな
るよう水を加えてカプセル塗液とし、40ｇ/m2の
紙にエアーナイフコーターで固形分５ｇ/m2にな
る様に塗抹した。 Next, 0.5N hydrochloric acid was gradually added to this system with stirring to adjust the pH of the system to 3.5, and then the temperature of the system was gradually raised to 80°C, and the reaction was further continued at 80°C for 5 hours. A milky white capsule dispersion was obtained. Add and mix 20 parts of wheat starch powder and 10 parts of pulp powder to the obtained capsule dispersion, add water to make a solid content concentration of 25% to make a capsule coating liquid, and apply it to 40 g/m 2 paper using an air knife coater. It was smeared to a solid content of 5 g/m 2 .
単体感圧複写紙の作成
５％の苛性ソーダ水溶液800部にｔ−ブチル安
息香酸89部とリン酸ジフエニル125部とラウリル
ベンゼンスルホン酸ソーダ70部を添加して調製し
た水溶液に、水500部に塩化第二鉄108部を溶解し
た水溶液を強力撹拌下で添加し、黄色の微粒子を
形成させた後、この分散液に20％のｔ−ブチル安
息香酸ナトリウムの水溶液500部を添加し、次い
で強力な撹拌下でこの分散液にTiCl25部を徐々
に添加して淡黄色の微粒子分散物てし、濾過、洗
浄してスラリーを得た。 Preparation of single-piece pressure-sensitive copying paper To an aqueous solution prepared by adding 89 parts of t-butylbenzoic acid, 125 parts of diphenyl phosphate, and 70 parts of sodium laurylbenzenesulfonate to 800 parts of a 5% aqueous solution of caustic soda, add chloride to 500 parts of water. An aqueous solution containing 108 parts of ferric iron was added under strong stirring to form yellow fine particles, and then 500 parts of a 20% aqueous solution of sodium t-butylbenzoate was added to the dispersion, followed by strong stirring. 25 parts of TiCl was gradually added to this dispersion under stirring to form a pale yellow fine particle dispersion, which was then filtered and washed to obtain a slurry.
次いで水200部にポリアクリル酸ソーダ１部、
ヒドロキシエチルセルロース１部を溶解し、これ
に上記スラリーを固形分で20部、酸化チタン20
部、水酸化アルミニウム60部を添加し、強力に分
散した後、その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（固型分濃度50
％）を15部加えて塗液を得た。 Next, add 1 part of sodium polyacrylate to 200 parts of water.
Dissolve 1 part of hydroxyethylcellulose, add 20 parts of the above slurry in solids, and 20 parts of titanium oxide.
After adding 60 parts of aluminum hydroxide and strongly dispersing, add carboxy-modified styrene-butadiene copolymer latex (solid content concentration 50 parts) to the dispersion.
%) was added to obtain a coating liquid.
得られた塗液を上記カプセル塗布紙の塗布面上
に乾燥重量で５ｇ/m2となるようにエアーナイフ
コーターで塗布して単体感圧複写紙を得た。 The resulting coating liquid was applied onto the coated surface of the capsule coated paper using an air knife coater to give a dry weight of 5 g/m 2 to obtain a single pressure-sensitive copying paper.
評 価
上記の如く作成した単体感圧複写紙をリボン無
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、別にこの複写紙を100℃条件
下で３時間処理したが、シートに全く汚れは見ら
れず、良好なる芯物質保持性を有することが分つ
た。Evaluation When the single pressure-sensitive copying paper prepared as described above was printed using a ribbonless typewriter, a clear colored image was obtained. Separately, this copy paper was treated at 100° C. for 3 hours, and no stains were observed on the sheet, indicating that it had good core material retention.
実施例 ２
ジ−エトキシ−モノ−イソプロポキシトリメチ
ロールメラミンの調製
トリメチロールメラミン25.7部とエタノール11
部とイソプロピルアルコール300部を還流冷却管
を付けたセパラブルフラスコ内に添加し、78℃下
で撹拌しながら1N−HCl10部を加え、トリメチ
ロールメラミンの結晶を溶解させた。溶解後２時
間78℃に保つた後、1N−NaOH水溶液10部を添
加した。Example 2 Preparation of di-ethoxy-mono-isopropoxytrimethylolmelamine 25.7 parts of trimethylolmelamine and 11 parts of ethanol
and 300 parts of isopropyl alcohol were added to a separable flask equipped with a reflux condenser, and while stirring at 78°C, 10 parts of 1N HCl was added to dissolve the trimethylolmelamine crystals. After dissolution, the temperature was maintained at 78°C for 2 hours, and then 10 parts of a 1N-NaOH aqueous solution was added.
次いで、これを冷却し、濾過して微量の不純物
を除去した後、70℃の温度で80部迄減圧濃縮し、
これにキシレン30部を加えて更に40部迄減圧濃縮
し、ジ−エトキシ−モノ−イソプロポキシトリメ
チロールメラミンを主成分とする初期縮合物のキ
シレン溶液を得た。 Next, this was cooled, filtered to remove trace impurities, and concentrated under reduced pressure at a temperature of 70°C to 80 parts.
To this was added 30 parts of xylene, and the mixture was further concentrated under reduced pressure to 40 parts to obtain a xylene solution of an initial condensate containing di-ethoxy-mono-isopropoxytrimethylolmelamine as a main component.
評 価
上記メラミン初期縮合物を用いた以外、実施例
１と全く同様にしてカプセル調製し、単体感圧複
写紙を作成した。次いで実施例１と同様な評価を
行なつたところ良好なる芯物質保持性を有するこ
とが分つた。Evaluation Capsules were prepared in exactly the same manner as in Example 1, except that the above melamine initial condensate was used, and a single pressure-sensitive copying paper was produced. Subsequently, the same evaluation as in Example 1 was carried out, and it was found that it had good core material retention properties.
実施例 ３
ジ−メトキシ−モノ−イソプロポキシトリメチ
ロールメラミンの調製
トリメチロールメラミン25.7部とメタノール
7.6部とイソプロピルアルコール300部を還流冷却
管を付けたセパラブルフラスコ内に添加し、64℃
下で撹拌しながら1N−HCl10部を加え、トリメ
チロールメラミンの結晶を溶解させた。溶解後１
時間64℃に保つた後、1N−NaOH水溶液10部を
添加した。Example 3 Preparation of di-methoxy-mono-isopropoxytrimethylolmelamine 25.7 parts of trimethylolmelamine and methanol
Add 7.6 parts and 300 parts of isopropyl alcohol into a separable flask equipped with a reflux condenser, and heat to 64°C.
While stirring, 10 parts of 1N HCl was added to dissolve the trimethylolmelamine crystals. After dissolving 1
After maintaining the temperature at 64°C for an hour, 10 parts of a 1N NaOH aqueous solution was added.
次いで、これを冷却し、濾過して微量の不純物
を除去した後、50℃の温度で80部迄減圧濃縮し、
これにキシレン30部を加えて更に40部迄減圧濃縮
し、ジ−メトキシ−モノ−イソプロポキシトリメ
チロールメラミンを主成分とする初期縮合物のキ
シレン溶液を得た。 Next, this was cooled, filtered to remove trace impurities, and concentrated under reduced pressure at a temperature of 50°C to 80 parts.
To this was added 30 parts of xylene and further concentrated under reduced pressure to 40 parts to obtain a xylene solution of the initial condensate containing di-methoxy-mono-isopropoxytrimethylolmelamine as the main component.
評 価
上記メラミン初期縮合物を用いた以外、実施例
１と全く同様にしてカプセルを調製し、単体感圧
複写紙を作成した。次いで実施例１と同様な評価
を行なつたところ良好なる芯物質保持性を有する
ことが分つた。Evaluation A capsule was prepared in exactly the same manner as in Example 1, except that the above melamine initial condensate was used, and a single pressure-sensitive copying paper was produced. Subsequently, the same evaluation as in Example 1 was carried out, and it was found that it had good core material retention properties.
実施例 ４
モノ−エトキシ−ジ−イソプロポキシトリメチ
ロールメラミンの調製
トリメチロールメラミン25.7部とエタノール
5.5部とイソプロピルアルコール300部を還流冷却
管を付けたセパラブルフラスコ内に添加し、78℃
下で撹拌しながら1N−HCl10部を加え、トリメ
チロールメラミンの結晶を溶解させた。溶解後２
時間78℃に保つた後、1N−NaOH水溶液10部を
添加した。Example 4 Preparation of mono-ethoxy-di-isopropoxytrimethylolmelamine 25.7 parts of trimethylolmelamine and ethanol
Add 5.5 parts and 300 parts of isopropyl alcohol into a separable flask equipped with a reflux condenser, and heat to 78°C.
While stirring, 10 parts of 1N HCl was added to dissolve the trimethylolmelamine crystals. After dissolving 2
After maintaining the temperature at 78°C for an hour, 10 parts of a 1N-NaOH aqueous solution was added.
次いで、これを冷却し、濾過して微量の不純物
を除去した後、70℃の温度で80部迄減圧濃縮し、
これにキシレン30部を加えて更に40部迄減圧濃縮
し、モノ−エトキシ−ジ−イソプロポキシトリメ
チロールメラミンを主成分とする初期縮合物のキ
シレン溶液を得た。 Next, this was cooled, filtered to remove trace impurities, and concentrated under reduced pressure at a temperature of 70°C to 80 parts.
To this was added 30 parts of xylene and further concentrated under reduced pressure to 40 parts to obtain a xylene solution of the initial condensate containing mono-ethoxy-di-isopropoxytrimethylolmelamine as the main component.
評 価
上記メラミン初期縮合物を用いた以外、実施例
１と全く同様にしてカプセルを調製し、単体感圧
複写紙を作成した。次いで実施例１と同様な評価
を行なつたところ良好なる芯物質保持性を有する
ことが分つた。Evaluation A capsule was prepared in exactly the same manner as in Example 1, except that the above melamine initial condensate was used, and a single pressure-sensitive copying paper was produced. Subsequently, the same evaluation as in Example 1 was carried out, and it was found that it had good core material retention properties.
実施例 ５
モノ−メトキシ−ジ−エトキシトリメチロール
メラミンの調製
トリメチロールメラミン25.7部とメタノール
3.8部とエタノール300部を還流冷却管を付けたセ
パラブルフラスコ内に添加し、64℃下で撹拌しな
がら1N−HCl5部を加え、トリメチロールメラミ
ンの結晶を溶解させた。溶解後30分間64℃に保つ
た後、1N−NaOH水溶液５部を添加した。Example 5 Preparation of mono-methoxy-di-ethoxytrimethylolmelamine 25.7 parts of trimethylolmelamine and methanol
3.8 parts and 300 parts of ethanol were added into a separable flask equipped with a reflux condenser, and 5 parts of 1N HCl was added while stirring at 64°C to dissolve the trimethylolmelamine crystals. After dissolving and maintaining at 64°C for 30 minutes, 5 parts of 1N-NaOH aqueous solution was added.
次いで、これを冷却し、濾過して微量の不純物
を除去した後、50℃の温度で80部迄減圧濃縮し、
これにキシレン30部を加えて更に40部迄減圧濃縮
し、モノ−メトキシ−ジ−エトキシトリメチロー
ルメラミンを主成分とする初期縮合物のキシレン
溶液を得た。 Next, this was cooled, filtered to remove trace impurities, and concentrated under reduced pressure at a temperature of 50°C to 80 parts.
To this was added 30 parts of xylene and further concentrated under reduced pressure to 40 parts to obtain a xylene solution of the initial condensate containing mono-methoxy-di-ethoxytrimethylolmelamine as the main component.
評 価
上記メラミン初期縮合物を用いた以外、実施例
１と全く同様にしてカプセルを調製し、単体感圧
複写紙を作成した。次いで実施例１と同様な評価
を行なつたところ良好なる芯物質保持性を有する
ことが分つた。Evaluation A capsule was prepared in exactly the same manner as in Example 1, except that the above melamine initial condensate was used, and a single pressure-sensitive copying paper was produced. Subsequently, the same evaluation as in Example 1 was carried out, and it was found that it had good core material retention properties.
比較例 １
ヘキサ−ｎ−ブトキシヘキサメチロールメラミ
ンを主成分とするユーバン120（三井東圧化学社
製）を固型分で36部用いた以外、実施例１と全く
同様にしてカプセル調製し、単体感圧複写紙を作
成した。次いで、実施例１と同様な評価を行なつ
たところ、100℃条件下、３時間の処理でシート
に汚れが発生し、芯物質保持性の劣ることが分つ
た。Comparative Example 1 Capsules were prepared in exactly the same manner as in Example 1, except that 36 parts of Yuban 120 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) containing hexa-n-butoxyhexamethylolmelamine as the main component was used in solid form. Created pressure-sensitive copy paper. Next, when the same evaluation as in Example 1 was carried out, it was found that the sheet became stained after being treated at 100° C. for 3 hours, and the core material retention was poor.
Claims (1)
有する疎水性芯物質を水或いは親水性媒体中に乳
化した後、重縮合を促進させて壁膜を形成せしめ
るマイクロカプセル化法において、該初期縮合物
としてトリエトキシトリメチロールメラミン、ジ
−エトキシ−モノ−イソプロポキシトリメチロー
ルメラミン、ジ−メトキシ−モノ−イソプロポキ
シトリメチロールメラミン、モノ−エトキシ−ジ
−イソプロポキシトリメチロールメラミン、モノ
−メトキシ−ジ−エトキシトリメチロールメラミ
ンより選ばれる少なくとも１種のメラミン樹脂初
期縮合物を用い、且つ得られたマイクロカプセル
分散液から濾過、乾燥することにより水或いは親
水性媒体を除去しないことを特徴とするマイクロ
カプセルの製造方法。 ２ 該メラミン樹脂初期縮合物が、トリエトキシ
トリメチロールメラミンである請求の範囲第１項
記載の製造方法。 ３ 縮重合を70℃以上の条件下或いはPH5.0以下、
60℃以下の条件下で２時間以上維持することによ
つて行わしめる請求の範囲第１項又は２項記載の
製造方法。 ４ 水或いは親水性媒体が水酸基或いはアミド基
を有することのないアニオン性高分子を含有する
請求の範囲第１項乃至第(3)項記載の製造方法。 ５ 該アニオン性高分子が無水マレイン酸系共重
合体、アクリル酸系、メタクリル酸系或いはクロ
トン酸系の重合体或いは共重合体である請求の範
囲第４項記載の製造方法。[Scope of Claims] 1. In a microencapsulation method in which a hydrophobic core material containing a melamine-formaldehyde initial condensate is emulsified in water or a hydrophilic medium, and then polycondensation is promoted to form a wall film. Initial condensates include triethoxytrimethylolmelamine, di-ethoxy-mono-isopropoxytrimethylolmelamine, di-methoxy-mono-isopropoxytrimethylolmelamine, mono-ethoxy-di-isopropoxytrimethylolmelamine, mono-methoxy- A micro capsule characterized by using at least one melamine resin initial condensate selected from di-ethoxytrimethylol melamine and not removing water or a hydrophilic medium from the obtained microcapsule dispersion by filtration and drying. Method of manufacturing capsules. 2. The manufacturing method according to claim 1, wherein the melamine resin initial condensate is triethoxytrimethylolmelamine. 3 Polycondensation is carried out at a temperature of 70°C or higher or at a pH of 5.0 or lower.
3. The manufacturing method according to claim 1 or 2, which is carried out by maintaining the temperature at 60° C. or lower for 2 hours or more. 4. The manufacturing method according to claims 1 to 3, wherein the water or the hydrophilic medium contains an anionic polymer having no hydroxyl group or amide group. 5. The production method according to claim 4, wherein the anionic polymer is a maleic anhydride-based copolymer, an acrylic acid-based, a methacrylic acid-based, or a crotonic acid-based polymer or copolymer.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59003274A JPS60147235A (en) | 1984-01-09 | 1984-01-09 | Preparation of microcapsule |
| US06/592,553 US4525520A (en) | 1983-03-28 | 1984-03-23 | Method of preparing microcapsules |
| DE8484103448T DE3461018D1 (en) | 1983-03-28 | 1984-03-28 | Method of preparing microcapsules |
| EP84103448A EP0120504B1 (en) | 1983-03-28 | 1984-03-28 | Method of preparing microcapsules |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59003274A JPS60147235A (en) | 1984-01-09 | 1984-01-09 | Preparation of microcapsule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60147235A JPS60147235A (en) | 1985-08-03 |
| JPH0233415B2 true JPH0233415B2 (en) | 1990-07-27 |
Family
ID=11552859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59003274A Granted JPS60147235A (en) | 1983-03-28 | 1984-01-09 | Preparation of microcapsule |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60147235A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166027A (en) * | 1984-02-09 | 1985-08-29 | Kanzaki Paper Mfg Co Ltd | Preparation of powdery capsule |
| KR100348363B1 (en) * | 2000-08-28 | 2002-08-10 | 김중현 | Preparation of monodispersed Melamine Formaldehyde Beads |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5218671A (en) * | 1975-08-04 | 1977-02-12 | Seiken Kogyo Kk | Safety device for concentrically contrlling address |
| JPS6256778A (en) * | 1985-09-04 | 1987-03-12 | 大同特殊鋼株式会社 | Melting furnace |
-
1984
- 1984-01-09 JP JP59003274A patent/JPS60147235A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5218671A (en) * | 1975-08-04 | 1977-02-12 | Seiken Kogyo Kk | Safety device for concentrically contrlling address |
| JPS6256778A (en) * | 1985-09-04 | 1987-03-12 | 大同特殊鋼株式会社 | Melting furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60147235A (en) | 1985-08-03 |
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