JPS6365944A - Preparation of microcapsule - Google Patents
Preparation of microcapsuleInfo
- Publication number
- JPS6365944A JPS6365944A JP61209997A JP20999786A JPS6365944A JP S6365944 A JPS6365944 A JP S6365944A JP 61209997 A JP61209997 A JP 61209997A JP 20999786 A JP20999786 A JP 20999786A JP S6365944 A JPS6365944 A JP S6365944A
- Authority
- JP
- Japan
- Prior art keywords
- melamine
- acid
- capsule
- wall film
- formaldehyde
- 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.)
- Granted
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 4
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- CBQFBEBEBCHTBK-UHFFFAOYSA-N 1-phenylprop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C(C=C)C1=CC=CC=C1 CBQFBEBEBCHTBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 5
- 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 abstract description 5
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000006068 polycondensation reaction Methods 0.000 abstract description 9
- 159000000000 sodium salts Chemical class 0.000 abstract description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 abstract 1
- 125000001174 sulfone group Chemical group 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000002775 capsule Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 25
- 239000011162 core material Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- -1 acrylic ester Chemical class 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 229920001577 copolymer Polymers 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
- 238000005538 encapsulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005354 coacervation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 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
- 239000012528 membrane Substances 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
- 238000002156 mixing Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 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
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- NKOUWLLFHNBUDW-UHFFFAOYSA-N Dipropyl hexanedioate Chemical compound CCCOC(=O)CCCCC(=O)OCCC NKOUWLLFHNBUDW-UHFFFAOYSA-N 0.000 description 1
- 206010068516 Encapsulation reaction Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013355 food flavoring agent 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
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 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
- 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
- 238000000227 grinding 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
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 235000011007 phosphoric acid Nutrition 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
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XTUPUYCJWKHGSW-UHFFFAOYSA-L zinc;2-carboxy-4,6-bis(1-phenylethyl)phenolate Chemical compound [Zn+2].C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C([O-])=O)=CC=1C(C)C1=CC=CC=C1.C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C([O-])=O)=CC=1C(C)C1=CC=CC=C1 XTUPUYCJWKHGSW-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
-
- 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)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、疎水性芯物質を内包するマイクロカプセルの
製造方法に関し、特に芯物質の保持性に優れたカプセル
を極めて容易に製造し得る方法に関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for manufacturing microcapsules containing a hydrophobic core substance, and in particular a method for extremely easily manufacturing capsules that have excellent core substance retention properties. It is related to.
「従来の技術」
近年、マイクロカプセル化技術の進歩は著しく、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、多方面にわたっている。"Prior Art" In recent years, microencapsulation technology has made remarkable progress, and the fields of use of encapsulated products are extremely wide and diverse, including pressure-sensitive copying paper.
マイクロカプセルの製造方法としては、コアセルベーシ
ョン法、界面重合法、1n−situ重合法等各種の方
法が知られている。コアセルベーション法では膜材とし
て主にゼラチンが使用されるため、価格が高い、高濃度
のカプセル液が得難い、微生物による攻撃を受は易い、
耐水性が悪い等の欠点があり、しかもカプセル化工程が
複雑であるという難点が付随する。Various methods are known for producing microcapsules, such as coacervation, interfacial polymerization, and 1n-situ polymerization. Since gelatin is mainly used as the membrane material in the coacervation method, it is expensive, it is difficult to obtain a highly concentrated capsule liquid, and it is easily attacked by microorganisms.
It has disadvantages such as poor water resistance, and also has the disadvantage that the encapsulation process is complicated.
また、界面重合法は芯物質の界面において疎水性上ツマ
−と親水性モノマーを重合反応させて壁膜を形成させる
方法であるが、疎水性モノマーとして酸クロライド、イ
ソシアネート、エポキシ化合物等の如く反応性が高く、
しかも毒性を有する物質を使用するため、取り扱い上の
制約が有り、例えば活性水素を有する芯物質は使用出来
ない。In addition, the interfacial polymerization method is a method in which a hydrophobic upper layer and a hydrophilic monomer are polymerized at the interface of a core material to form a wall film. Highly sexual,
Moreover, since a toxic substance is used, there are restrictions on handling, for example, a core material containing active hydrogen cannot be used.
さらに材料の価格が高いという欠点もある。Another disadvantage is that the materials are expensive.
in 5itu重合法には、芯物質の内部からモノマ
ーを重合させて壁膜を形成させる方法と、芯物質の外部
から壁膜を形成させる方法がある。前者の方法では疎水
性上ツマ−としてイソシアネート等を用いるため、界面
重合法と同様に芯物質の使用に制約を受ける。一方、後
者の方法では一般に尿素−ホルムアルデヒド樹脂、メラ
ミン−ホルムアルデヒド樹脂等のアミノ樹脂が壁膜材と
して使用される。The in-5-itu polymerization method includes a method in which a wall film is formed by polymerizing monomers from inside the core material, and a method in which a wall film is formed from the outside of the core material. In the former method, since isocyanate or the like is used as a hydrophobic polymer, there are restrictions on the use of a core material, similar to the interfacial polymerization method. On the other hand, in the latter method, amino resins such as urea-formaldehyde resins and melamine-formaldehyde resins are generally used as wall membrane materials.
メラミン−ホルムアルデヒド樹脂を壁膜材とするカプセ
ルは疎水性、耐溶剤性等において優れているため、多数
のカプセル化法が提案されており、例えば水や親水性媒
体中に存在するメラミン−ホルムアルデヒド樹脂初期縮
合物を疎水性芯物質の周りに堆積させる方法に関し、特
開昭55−15660号、特開昭55−47139号、
特開昭55−51431号、特開昭56−51238号
、特開昭56−58536号、特開昭56−10062
9号、特開昭56−121628号、特開昭57−10
3891号、特開昭58−14942号、特開昭58−
112041号、特開昭59=177129号、特開昭
60−28819号、特開昭60−190227号、特
開昭61−25635号等が提案されている。Capsules whose wall material is melamine-formaldehyde resin have excellent hydrophobicity and solvent resistance, and many encapsulation methods have been proposed. JP-A-55-15660, JP-A-55-47139, regarding a method of depositing an initial condensate around a hydrophobic core substance,
JP-A-55-51431, JP-A-56-51238, JP-A-56-58536, JP-A-56-10062
No. 9, JP-A-56-121628, JP-A-57-10
No. 3891, JP-A-58-14942, JP-A-58-
112041, JP 59-177129, JP 60-28819, JP 60-190227, JP 61-25635, etc. have been proposed.
「発明が解決しようとする問題点」
しかし、このように数多くのカプセル化法が開発提案さ
れているにもかかわらず、これらの方法には次に挙げる
如き短所のいずれかが付随するため未だ改良の必要が残
されている。"Problems to be Solved by the Invention" However, despite the fact that many encapsulation methods have been developed and proposed, these methods are still subject to improvement because they have one of the following disadvantages: The need remains.
■ 反応中にカプセル粒子の凝集やカプセル液の粘度上
昇が起こり易い。■ Agglomeration of capsule particles and increase in viscosity of capsule liquid are likely to occur during the reaction.
■ ■の現象を回避するために、カプセルの製造を低濃
度、低温度で行う必要があり、結果的に反応時間が長く
なる。(2) In order to avoid the phenomenon (2), it is necessary to manufacture capsules at a low concentration and at a low temperature, which results in a long reaction time.
■ 乳化剤の乳化力が不充分なため微小なカプセルが得
難く、これを感圧複写紙に適用すると、極めて汚れ易い
複写紙となってしまう。(2) It is difficult to obtain minute capsules because the emulsifying power of the emulsifier is insufficient, and when this is applied to pressure-sensitive copying paper, the copying paper becomes extremely smudged.
■ 乳化剤の乳化安定性が悪いため巨大油滴が発生し易
く、これを感圧複写紙に適用すると、スポット汚れが発
生する。■ Due to the poor emulsification stability of the emulsifier, giant oil droplets are likely to occur, and when this is applied to pressure-sensitive copying paper, spot stains occur.
■ 芯物質表面への壁膜材の堆積効率が悪く、カプセル
の芯物質保持性が低下する。■ The deposition efficiency of the wall film material on the surface of the core material is poor, and the ability of the capsule to retain the core material is reduced.
本発明者等はかかる現状に鑑み、特にメラミン−ホルム
アルデヒド樹脂を壁膜として有するマイクロカプセルの
製造方法について鋭意研究した結果、特定のアニオン性
高分子電解質の存在下で、メラミン−ホルムアルデヒド
樹脂を重縮合させると、芯物質表面への重縮合樹脂の堆
積が極めて効率化され、結果的に極めて優れた特性を有
するカプセル壁膜が形成されることを見出し、本発明を
完成するに至った。In view of the current situation, the present inventors conducted intensive research on a method for manufacturing microcapsules having melamine-formaldehyde resin as a wall film, and found that melamine-formaldehyde resin is polycondensed in the presence of a specific anionic polymer electrolyte. The present inventors have discovered that, by doing so, the deposition of the polycondensation resin on the surface of the core material becomes extremely efficient, resulting in the formation of a capsule wall film with extremely excellent properties, and the present invention has been completed.
「問題点を解決するための手段」
本発明はアニオン性高分子電解質の存在下、メラミン−
ホルムアルデヒド重縮合樹脂壁膜で疎水性芯物質を包被
するマイクロカプセルの製造方法において、該アニオン
性高分子電解質としてビニルトルエンスルホン酸系ポリ
マーを使用す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。"Means for Solving the Problems" The present invention proposes that melamine-
A method for producing microcapsules in which a hydrophobic core material is covered with a formaldehyde polycondensation resin wall film, characterized in that a vinyltoluenesulfonic acid-based polymer is used as the anionic polymer electrolyte. .
「作用」
本発明の方法で使用されるビニルトルエンスルホン酸系
ポリマーとしては、ポリビニルトルエンスルホン酸が好
ましく用いられるが、例えば無水マレイン酸、マレイン
酸エステル、アクリル酸、アクリル酸エステル、アクリ
ルアミド、アクリロニトリル、メタクリル酸、メタクリ
ル酸エステル、メタクリルアミド、メタクリロニトリル
、エチレン、プロピレン、スチレン、スチレンスルホン
酸、α−メチルスチレン、ビニルトルエン、ビニルスル
ホン酸、2−アクリルアミド−2メチルプロパンスルホ
ン酸、ビニルピロリドン等のモノマーとの共重合体であ
ってもよい。"Function" As the vinyltoluenesulfonic acid polymer used in the method of the present invention, polyvinyltoluenesulfonic acid is preferably used, but examples include maleic anhydride, maleic ester, acrylic acid, acrylic ester, acrylamide, acrylonitrile, Methacrylic acid, methacrylic acid ester, methacrylamide, methacrylonitrile, ethylene, propylene, styrene, styrene sulfonic acid, α-methylstyrene, vinyltoluene, vinylsulfonic acid, 2-acrylamido-2methylpropanesulfonic acid, vinylpyrrolidone, etc. It may also be a copolymer with a monomer.
ビニルトルエンスルホン酸系ポリマーは、スルホン基の
一部又は全部を例えばナトリウム塩、カリウム塩、アン
モニウム塩等の塩とすることによって水溶性となし水性
媒体中に溶解されるが、特にナトリウム塩が好ましく用
いられる。なお、分子量10,000〜2,000,0
00程度のポリマーが好ましく、より好ましくは200
、000〜1,000,000程度の分子量を有する
ポリマーが使用される。分子量が10.000未満のポ
リマーでは充分な乳化分散力が得られず、2,000,
000を越えるとポリマーの取り扱いが難しくなる。Vinyltoluenesulfonic acid-based polymers can be made water-soluble by converting some or all of the sulfonic groups into salts such as sodium salts, potassium salts, ammonium salts, etc., and can be dissolved in an aqueous medium, but sodium salts are particularly preferred. used. In addition, the molecular weight is 10,000 to 2,000,0
A polymer with a molecular weight of about 00 is preferable, more preferably a polymer with a molecular weight of about 200
, 000 to 1,000,000. Polymers with a molecular weight of less than 10,000 cannot provide sufficient emulsifying and dispersing power;
If it exceeds 000, handling of the polymer becomes difficult.
本発明の方法では、かかるビニルトルエンスルホン酸系
ポリマーをカプセル製造用の親水性媒体中に含有せしめ
るものであるが、カプセル調製の容易さ、得られるカプ
セル品質等を考慮すると、親水性媒体中に0.3重量%
以上、より好ましくは1重量%以上含有させるのが望ま
しい。含有量の上限は一般に系の粘度や用いられるカプ
セル調製装置等によって決定されるが、20重世%以下
に留めるのが望ましい。In the method of the present invention, such a vinyltoluenesulfonic acid-based polymer is contained in a hydrophilic medium for manufacturing capsules. 0.3% by weight
As mentioned above, it is more preferable to contain 1% by weight or more. The upper limit of the content is generally determined by the viscosity of the system, the capsule preparation device used, etc., but it is desirable to keep it below 20%.
本発明の方法では、上記の如くビニルトルエンスルホン
酸系ポリマーを含有する親水性媒体中でメラミン−ホル
ムアルデヒド重縮合樹脂壁膜を形成せしめるものである
が、かかる樹脂壁膜は一般に親水性のメラミン−ホルム
アルデヒド系樹脂初期縮合物によって形成される。また
、樹脂初期縮合物のメチル化物、さらには他のアミン類
、フェノール類、アルデヒド類やアニオン、カチオン、
ノニオン変性剤等で一部変性したものも使用される。In the method of the present invention, a melamine-formaldehyde polycondensation resin wall film is formed in a hydrophilic medium containing a vinyltoluenesulfonic acid polymer as described above, but such a resin wall film is generally made of hydrophilic melamine- Formed by formaldehyde resin initial condensate. In addition, methylated products of resin initial condensates, other amines, phenols, aldehydes, anions, cations,
Partially modified materials such as nonionic modifiers are also used.
アミン類としては、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、ジシンアジアミド、ビウレ
ット、シアナミド等:フェノール類としては、例えばフ
ェノール、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;
アルデヒド類としては、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、ゲルタールアルデヒド、グリオキサール、
フルフラール等;アニオン変性剤としては、例えばスル
アアミン酸、スルアアニル酸、グリコール酸、グリシン
、酸性亜硫酸塩、スルホン酸フェノール、タウリン等;
カチオン変性剤としては、例えば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;さらにノニオン変性剤
としては、例えば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る。Examples of amines include urea, thiourea, alkyl urea, ethylene urea, acetoguanamine, benzoguanamine, melamine, guanidine, dicinediamide, biuret, cyanamide, etc.; examples of phenols include phenol, cresol, xylenol, resorcinol, and hydroquinone. , pyrocatechol, pyrogallol, etc.;
Examples of aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, hexamethylenetetramine, geltaraldehyde, glyoxal,
Furfural, etc.; Examples of anion modifiers include sulamic acid, sulanilic acid, glycolic acid, glycine, acidic sulfite, phenol sulfonate, taurine, etc.;
Examples of cationic modifiers include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminoethanol, and the like; further examples of nonionic modifiers include ethylene glycol, diethylene glycol, and the like.
親水性のメラミン−ホルムアルデヒド系樹脂初期縮合物
としては、上記の如き各種のものが使用できるが、中で
もメラミン−ホルムアルデヒド樹脂初期縮合物及びその
メチル化物は、緻密な膜が得られるため最も好ましく用
いられる。As the hydrophilic melamine-formaldehyde resin initial condensate, various products such as those mentioned above can be used, but among them, the melamine-formaldehyde resin initial condensate and its methylated product are most preferably used because a dense film can be obtained. .
親水性メラミン−ホルムアルデヒド樹脂初期縮合物の配
合量は、用いる疎水性芯物質の種類、カプセルの用途等
に応じて適宜調節されるが、一般に疎水性芯物質100
重量部に対して、メラミン換算で2〜40重量部、より
好ましくは6〜20重量部重量部台される。The blending amount of the hydrophilic melamine-formaldehyde resin initial condensate is adjusted as appropriate depending on the type of hydrophobic core material used, the use of the capsule, etc., but generally 100% of the hydrophobic core material is used.
The amount is 2 to 40 parts by weight, more preferably 6 to 20 parts by weight in terms of melamine.
本発明におけるカプセル製造系は、−aに4〜7のpH
領域、より好ましくは5〜6のpH領域に調節され、メ
ラミン−ホルムアルデヒド樹脂の重縮合反応が進められ
る。その際、カプセル製造系を酸性に維持するために、
例えばギ酸、酢酸、クエン酸、シュウ酸、パラトルエン
スルフォン酸、塩酸、硫酸、硝酸、リン酸、塩化アンモ
ニウム、硫酸アンモニウム等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 capsule manufacturing system of the present invention, -a has a pH of 4 to 7.
The polycondensation reaction of the melamine-formaldehyde resin is carried out by adjusting the pH to a pH range of 5 to 6, preferably 5 to 6. At that time, in order to maintain the capsule manufacturing system acidic,
For example, so-called acid catalysts commonly used in the field of producing aminoaldehyde resins such as formic acid, acetic acid, citric acid, oxalic acid, para-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, ammonium chloride, ammonium sulfate, etc. are used.
なお、メラミン−ホルムアルデヒド樹脂の重縮合反応は
、系を加熱することにより促進され、結果的に安定した
品質を有するカプセルが比較的短時間で形成されるため
、系の温度は60℃以上、より好ましくは80℃以上に
加熱するのが望ましい。The polycondensation reaction of melamine-formaldehyde resin is accelerated by heating the system, and as a result, capsules with stable quality are formed in a relatively short time. Preferably, it is desirable to heat to 80°C or higher.
本発明の方法では、カプセル調製条件を過度に注意深く
操作する必要はなく、単にカプセル形成材料を混合して
簡単な重縮合条件を与えるのみで重縮合樹脂が効率よく
疎水性芯物質表面に堆積し、芯物質保持性等のカプセル
品質において極めて優れた特性を有するカプセルが容易
に形成されるものである。In the method of the present invention, there is no need to overly carefully manipulate the capsule preparation conditions, and the polycondensation resin is efficiently deposited on the surface of the hydrophobic core material by simply mixing the capsule-forming materials and providing simple polycondensation conditions. , capsules having extremely excellent properties in terms of capsule quality such as core material retention can be easily formed.
カプセル中に内包される疎水性芯物質については特に限
定されず、例えば魚油、ラード油等の動物油類、オリー
ブ油、落花生油、亜麻仁油、大豆油、ひまし油等の植物
油類、石油、ケロシン、キシレン、トルエン等の鉱物油
類、アルキル置換ジフェニールアルカン、アルキル置換
ナフタレン、ビフェニールエタン、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、フタル酸ジーn
−ブチル、フクル酸ジーn−オクチル等の合成油類の如
(水に不溶ないしは実質的に不溶な液体、さらには上記
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
属の酸化物やEAR、セルロースや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、肥料組成物頚、難燃剤、示温材料、液晶
、トナー材料等が例示される。The hydrophobic core substance contained in the capsule is not particularly limited, and includes, for example, animal oils such as fish oil and lard oil, vegetable oils such as olive oil, peanut oil, linseed oil, soybean oil, and castor oil, petroleum, kerosene, xylene, Mineral oils such as toluene, alkyl-substituted diphenylalkanes, alkyl-substituted naphthalenes, biphenylethanes, methyl salicylate,
Diethyl adipate, di-n-propyl adipate, di-n-butyl adipate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-n phthalate
- Synthetic oils such as butyl, di-n-octyl fuculate, etc. (liquids that are insoluble or substantially insoluble in water, and the synthetic oils that contain electron-donating color formers, electron-accepting color developers, and ligands) Solutions of compounds, organic metal salts, etc., water-insoluble metal oxides and EAR, fiber-like substances such as cellulose and asbestos, water-insoluble synthetic polymer substances, minerals, pigments, glasses, fragrances. Examples include flavoring agents, fungicidal compositions, physiological compositions, fertilizer compositions, flame retardants, temperature indicating materials, liquid crystals, toner materials, and the like.
「実施例」
以下に本発明の方法をより具体的に説明するために、感
圧複写紙分野に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%を表す。"Example" In order to more specifically explain the method of the present invention, examples will be described below regarding the case where the method is applied to the field of pressure-sensitive copying paper, but of course the present invention is not limited thereto. Further, unless otherwise specified, parts and % in the examples represent parts by weight and % by weight, respectively.
実施例1
ポリビニルトルエンスルホン酸の一部ナトリウム塩(ナ
ショナルスターチ・アンド・ケミカル社製、 VERS
A −Tl6O00)の3.3%水溶液150部を20
%酢酸溶液でp H4,5に調節してカプセル製造用の
親水性媒体とした。Example 1 Partial sodium salt of polyvinyltoluenesulfonic acid (manufactured by National Starch and Chemical Co., Ltd., VERS
150 parts of a 3.3% aqueous solution of A-Tl6O00) was added to 20
The pH was adjusted to 4.5 with a % acetic acid solution to provide a hydrophilic medium for capsule production.
別に、カプセル芯物質としてクリスタルバイオレットラ
クトン4部をアルキルナフタレン(クレハ化学社製、K
MC−113) 100部中に加熱溶解し、これを平
均粒径が3.5μになるように上記カプセル製造用の親
水性媒体中に乳化分散した。Separately, 4 parts of crystal violet lactone was added as a capsule core material to alkylnaphthalene (manufactured by Kureha Chemical Co., Ltd., K
MC-113) was heated and dissolved in 100 parts of MC-113), and this was emulsified and dispersed in the above-mentioned hydrophilic medium for capsule production so that the average particle size was 3.5 μm.
次に、メラミン10部、37%ホルムアルデヒド水溶液
30部を60℃で10分間加熱撹拌して調製したメラミ
ン−ホルムアルデヒド初期縮合物水溶液を上記乳化液中
に添加し、攪拌しながら20%水酸化ナトリウム水溶液
で系のpHを6.0に調節し、液温を90℃に上げて1
時間攪拌し続けてカプセル分散液を得た。Next, a melamine-formaldehyde initial condensate aqueous solution prepared by heating and stirring 10 parts of melamine and 30 parts of a 37% formaldehyde aqueous solution at 60°C for 10 minutes was added to the above emulsion, and while stirring, a 20% aqueous sodium hydroxide solution was added. Adjust the pH of the system to 6.0, raise the liquid temperature to 90°C, and
Stirring was continued for hours to obtain a capsule dispersion.
比較例1
カプセル製造用の親水性媒体として、20%水酸化ナト
リウム水溶液でp H4,5に調節したエチレン−無水
マレイン酸共重合体(モンサント社製。Comparative Example 1 As a hydrophilic medium for capsule production, an ethylene-maleic anhydride copolymer (manufactured by Monsanto) adjusted to pH 4.5 with a 20% aqueous sodium hydroxide solution.
EMA31)の3.3%水溶液150部を使用した以外
は実施例1と同様にしてカプセル分散液を得た。A capsule dispersion was obtained in the same manner as in Example 1, except that 150 parts of a 3.3% aqueous solution of EMA31) was used.
比較例2
カプセル製造用の親水性媒体として、20%水酸化ナト
リウム水溶液でp H4,5に調節したスチレン−無水
マレイン酸共重合体(モンサンド社製。Comparative Example 2 A styrene-maleic anhydride copolymer (manufactured by Monsando) adjusted to pH 4.5 with a 20% aqueous sodium hydroxide solution was used as a hydrophilic medium for capsule production.
スフリプセット520)の3.3%水溶液150部を使
用した以外は実施例1と同様にしてカプセル化反応を行
ったが、反応中に著しい泡立ちがありカプセル調製が相
当困難であった。The encapsulation reaction was carried out in the same manner as in Example 1, except that 150 parts of a 3.3% aqueous solution of Suflipset 520) was used, but there was significant foaming during the reaction, making capsule preparation quite difficult.
比較例3
カプセル製造用の親水性媒体として、20%水酸化ナト
リウム水溶液でI) H4,5に調節したポリビニルヘ
ンゼンスルホン酸の一部ナトリウム塩(ナショナルスタ
ーチ・アンド・ケミカル社製、 VERSA −Tl2
O3)の3.3%水溶液150部を使用した以外は実施
例1と同様にしてカプセル分散液を得たが、油滴同志の
合一によって50μm以上の粒子径を有する巨大カプセ
ルであった。Comparative Example 3 Partial sodium salt of polyvinylhenzenesulfonic acid (manufactured by National Starch and Chemical Co., Ltd., VERSA-Tl2) adjusted to H4,5 with 20% aqueous sodium hydroxide solution as a hydrophilic medium for capsule production.
A capsule dispersion was obtained in the same manner as in Example 1 except that 150 parts of a 3.3% aqueous solution of O3) was used, but the capsules were giant capsules having a particle size of 50 μm or more due to coalescence of oil droplets.
かくして得られた4種類のカプセル分散液の性能を試験
するために、以下の比較試験を行った。In order to test the performance of the four types of capsule dispersions thus obtained, the following comparative tests were conducted.
即ち、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
(固形分)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−ブタジェ
ン共重合体ラテックス20部(固形分)を加え調製した
顕色剤塗液を40 g/rdの原紙に乾燥重量が5g/
dになるように塗布して感圧複写紙用下用紙を作成した
。That is, 65 parts of aluminum hydroxide, 20 parts of zinc oxide, 3
, 5-di(α-methylbenzyl)salicylate zinc and α-
A dispersion obtained by grinding 15 parts of a mixed melt with methylstyrene-styrene copolymer (melt ratio 80/20), 5 parts of polyvinyl alcohol aqueous solution (solid content) and 300 parts of water in a ball mill for 24 hours, A developer coating solution prepared by adding 20 parts (solid content) of carboxy-modified styrene-butadiene copolymer latex was applied to 40 g/rd base paper to a dry weight of 5 g/rd.
A base paper for pressure-sensitive copying paper was prepared by applying the following coating to give the following properties.
得られた感圧複写紙用下用紙の顕色剤塗布面に実施例お
よび比較例で得られた4種類のカプセル分散液をそれぞ
れ乾燥重量が5 g/n?になるように塗布し、120
℃で30秒間乾燥させて比較試験紙とした。The four types of capsule dispersions obtained in Examples and Comparative Examples were applied to the developer-coated surface of the obtained pressure-sensitive copying paper bottom paper, each with a dry weight of 5 g/n? Apply it so that it becomes 120
It was dried at ℃ for 30 seconds to prepare a comparative test paper.
比較試験紙の塗布面の白色度をJIS l’8123に
従って測定して第1表に記載した。また、120℃で6
0分間熱処理した後の比較試験紙の塗布面の白色度を同
様に測定して第1表に記載した。The whiteness of the coated surface of the comparative test paper was measured according to JIS l'8123 and is listed in Table 1. Also, 6 at 120℃
The whiteness of the coated surface of the comparative test paper after heat treatment for 0 minutes was measured in the same manner and is listed in Table 1.
第1表
「効果」
第1表の結果からも明らかなように、本発明の方法で得
られたマイクロカプセルは極めて芯物質の保持性に優れ
ていた。Table 1 "Effects" As is clear from the results in Table 1, the microcapsules obtained by the method of the present invention had extremely excellent core substance retention.
Claims (1)
ルデヒド重縮合樹脂壁膜で疎水性芯物質を包被するマイ
クロカプセルの製造方法において、該アニオン性高分子
電解質としてビニルトルエンスルホン酸系ポリマーを使
用することを特徴とするマイクロカプセルの製造方法。In a method for producing microcapsules in which a hydrophobic core substance is covered with a melamine-formaldehyde polycondensed resin wall film in the presence of an anionic polymer electrolyte, a vinyltoluenesulfonic acid-based polymer is used as the anionic polymer electrolyte. A method for producing microcapsules characterized by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61209997A JPH0829247B2 (en) | 1986-09-05 | 1986-09-05 | Microcapsule manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61209997A JPH0829247B2 (en) | 1986-09-05 | 1986-09-05 | Microcapsule manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6365944A true JPS6365944A (en) | 1988-03-24 |
JPH0829247B2 JPH0829247B2 (en) | 1996-03-27 |
Family
ID=16582145
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61209997A Expired - Fee Related JPH0829247B2 (en) | 1986-09-05 | 1986-09-05 | Microcapsule manufacturing method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0829247B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10663841B2 (en) | 2017-12-22 | 2020-05-26 | Subaru Corporation | Image projection apparatus |
-
1986
- 1986-09-05 JP JP61209997A patent/JPH0829247B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10663841B2 (en) | 2017-12-22 | 2020-05-26 | Subaru Corporation | Image projection apparatus |
Also Published As
Publication number | Publication date |
---|---|
JPH0829247B2 (en) | 1996-03-27 |
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