CN103506059A - Manufacturing method of melamine microcapsule - Google Patents
Manufacturing method of melamine microcapsule Download PDFInfo
- Publication number
- CN103506059A CN103506059A CN201310241388.XA CN201310241388A CN103506059A CN 103506059 A CN103506059 A CN 103506059A CN 201310241388 A CN201310241388 A CN 201310241388A CN 103506059 A CN103506059 A CN 103506059A
- Authority
- CN
- China
- Prior art keywords
- melamine
- formaldehyde
- weight
- manufacture method
- compound
- 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
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 115
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000003094 microcapsule Substances 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 298
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 229920000768 polyamine Polymers 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 10
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 106
- 239000004202 carbamide Substances 0.000 claims description 53
- 235000013877 carbamide Nutrition 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000011162 core material Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 29
- 229910000765 intermetallic Inorganic materials 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000004009 herbicide Substances 0.000 claims description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 12
- WVKHCAOZIFYQEG-ODZAUARKSA-N (z)-but-2-enedioic acid;ethene Chemical compound C=C.OC(=O)\C=C/C(O)=O WVKHCAOZIFYQEG-ODZAUARKSA-N 0.000 claims description 12
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 12
- 235000005487 catechin Nutrition 0.000 claims description 12
- 229950001002 cianidanol Drugs 0.000 claims description 12
- -1 pentamethylene diethylenediamine Chemical compound 0.000 claims description 12
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 claims description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052900 illite Inorganic materials 0.000 claims description 7
- KFDIDIIKNMZLRZ-UHFFFAOYSA-N n'-propan-2-ylpropane-1,3-diamine Chemical compound CC(C)NCCCN KFDIDIIKNMZLRZ-UHFFFAOYSA-N 0.000 claims description 7
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 150000002171 ethylene diamines Chemical class 0.000 claims description 4
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- KDRUIMNNZBMLJR-UHFFFAOYSA-N 2-isopropylaminoethylamine Chemical compound CC(C)NCCN KDRUIMNNZBMLJR-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 abstract description 79
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 2
- MRAKLTZPBIBWFH-ARJAWSKDSA-N (z)-2-ethenylbut-2-enedioic acid Chemical compound OC(=O)\C=C(\C=C)C(O)=O MRAKLTZPBIBWFH-ARJAWSKDSA-N 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 239000002775 capsule Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 17
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- 241000220317 Rosa Species 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 6
- 208000034189 Sclerosis Diseases 0.000 description 5
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MACBSXIPRLPFDJ-UHFFFAOYSA-N oxygen(2-) platinum(2+) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Pt+2] MACBSXIPRLPFDJ-UHFFFAOYSA-N 0.000 description 4
- 239000012782 phase change material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 3
- DHFROBDVWAHIED-UHFFFAOYSA-N CC(C)NCCN.CC(C)NCCN Chemical compound CC(C)NCCN.CC(C)NCCN DHFROBDVWAHIED-UHFFFAOYSA-N 0.000 description 3
- KVACGDQKHPHZTN-UHFFFAOYSA-N N',N'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN.CN(C)CCN KVACGDQKHPHZTN-UHFFFAOYSA-N 0.000 description 3
- JORMWXRVEMNNET-UHFFFAOYSA-N NCCNCCNCCNCCNCCN.C=CCCC Chemical compound NCCNCCNCCNCCNCCN.C=CCCC JORMWXRVEMNNET-UHFFFAOYSA-N 0.000 description 3
- SJSOWFHBJSVQDL-UHFFFAOYSA-N O=C1NCCN1.O=C1NCCN1 Chemical compound O=C1NCCN1.O=C1NCCN1 SJSOWFHBJSVQDL-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XAHAOEIIQYSRHJ-UHFFFAOYSA-N benzene-1,2-diamine Chemical compound NC1=CC=CC=C1N.NC1=CC=CC=C1N XAHAOEIIQYSRHJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- RMVOECKULIHOQG-UHFFFAOYSA-N ethene;imidazolidine-2-thione;thiourea Chemical compound C=C.NC(N)=S.S=C1NCCN1 RMVOECKULIHOQG-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical group C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005354 coacervation Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VIJMMQUAJQEELS-UHFFFAOYSA-N n,n-bis(ethenyl)ethenamine Chemical compound C=CN(C=C)C=C VIJMMQUAJQEELS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008717 functional decline Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013097 stability assessment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5089—Processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5015—Organic compounds, e.g. fats, sugars
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5031—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poly(lactide-co-glycolide)
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a manufacturing method of melamine microcapsule, comprising the following steps: adding melamine, formalin and basic hydroxide and adjusting the pH to 8 to 10, and adding polyamine compound having at least two amine groups for reaction to form a melamine-methyl aldehyde prepolymer; using the basic hydroxide to basify more than one resin selected from an ethylene-maleic acid copolymer resin and a styrene-maleic acid copolymer resin to form an emulgator; putting a sac core substance into the emulgator for stirring to form an oily/aquiform emulsion; mixing the melamine-methyl aldehyde prepolymer with oily/aquiform emulsion and reacting under 40 to 80 DEG C; putting into a product of the abovementioned reaction a compound that reacts with methyl aldehyde and reacting under 40 to 80 DEG C; and putting into the product of the abovementioned reaction a metal or a metal compound that reacts with methyl aldehyde and reacting under 40 to 80 DEG C.
Description
Technical field
The present invention relates to a kind of manufacture method of microcapsules, when relating in particular to a kind of core material effect that can keep in capsule, can make residual formaldehyde obtain the manufacture method of minimized melamine system microcapsule.
Background technology
For Microencapsulation Method, according to the kind of the core material that will protect and the required physical property of microcapsules, determine the kind of capsule wall material (or capsule wall material) from external environment, and adopt the encapsulated method that is suitable for this.
As the core material that can manufacture microcapsules, there are the spices of comprising, medicine, resin, ink, oil, phase change material (phasechange material; PCM), phytocide, dyestuff, agrochemical are at interior a variety of functional materials.
As the coating material of microcapsules, conventionally use the function revealing according to the kind of core material and microcapsules desired body to use melamine (Melamine), gelatin (Gelatin), polyurethane (Urethane), urea (Urea), shitosan (Chitosan), epoxy (Epoxy) class material, polymethyl methacrylate (polymethylmethacrylate; PMMA) etc., can therefrom select the most suitable using.
The microcapsules of industrial extensive use are a kind of melamine microcapsules that use melamine formaldehyde resin as capsule wall material.Because melamine microcapsules have not only even particle size distribution, mechanical strength and so on physical property and reappearance excellence, and be conducive to the advantage of volume production, therefore industrial, be widely used.
Although there are this many advantages, yet removing residue formaldehyde after cannot avoiding manufacturing when application melamine microcapsules, and these formaldehyde impose intense stimulus and are harmful to health all multiple locations of human body, and can cause environmental pollution, therefore all dark with day to its use and remaining quantitative limitation.
Korean granted patent discloses a kind of microcapsules that reduced residual formaldehyde for No. 10-0634492 and with the raw material of its manufacture, disclosed residual formaldehyde minimizing method is characterised in that, after melamine microcapsules are cooled to room temperature, the compound only by adding simply with amido or alcohol hydroxyl group carries out post processing.
Yet, if excessive interpolation has the compound of amido or alcohol hydroxyl group after producing melamine microcapsules, due to the concentration step-down of the microcapsules of equivalent contrast, make to play the functional decline of the core material of microcapsules Core Feature, so only have again melamine microcapsules are additionally dropped in order to embody identical effect.Result weakens the effect that reduces residual formaldehyde, yet does not but mention completely the effect of the core material of microcapsules in No. 10-0634492nd, described Korean granted patent.
And, in order to reduce the harmful substance formaldehyde in melamine micro-capsule dispersion liquid, the very large Porous hydrophilic inorganic particle of specific area such as active carbon, silica gel (Silica-gel), zeolite (Zeolite), diatomite, calcination of talc in the JP 2005-95775 of Japanese Laid-Open Patent Publication, as methanal trapping agent, have been used, if yet in accordance with this, implement, due to and melamine micro-capsule dispersion liquid between larger specific gravity poor and will cause betiding the bad problem of stability that produces the capsule dispersant liquid of deposited phenomenon etc. in a few days.
Prior art document
Patent documentation:
No. 10-0634492nd, Korean granted patent
Japanese Laid-Open Patent Publication JP 2005-95775
Summary of the invention
Can be minimized for reducing the interpolation amount of substance of residual formaldehyde when the object of the present invention is to provide a kind of unlikely generation precipitation, and can also keep the core material effect in capsule and make residual formaldehyde obtain the manufacture method of minimized melamine system microcapsule.
The invention provides a kind of manufacture method of melamine system microcapsule, comprise the steps: that described melamine that (a) adds melamine, relative 100 weight portions is that the described melamine of the formalin of 50～300 weight portions, relative 100 weight portions is the alkaline hydrated oxide of 0.01～10 weight portion and pH is adjusted into 8～10, and after the described melamine of relative 100 weight portions adds the polyamine compounds with at least two amidos of 100～400 weight portions, react and form carbamide prepolymer; (b) more than one the resin of selecting in ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin is alkalized with alkaline hydrated oxide and forms emulsifying agent; (c) in described emulsifying agent, drop into core material and stir and form oily/watery emulsion; (d) described carbamide prepolymer is mixed to be incorporated at 40～80 ℃ with described oily/watery emulsion react; (e) in the product of above-mentioned steps (d), drop into the aitiogenic compound of formaldehyde and react at 40～80 ℃; (f) in the product of above-mentioned steps (e), drop into the aitiogenic metal of formaldehyde or metallic compound and react at 40～80 ℃.
Described polyamine compounds can be from ethylenediamine (ethylene diamine), tetra-methylenedimine (tetramethylene diamine), four ethylene diamines (tetraethylene diamine), hexamethylene diamine (hexamethylene diamine), phenylenediamine (phenylene diamine), pentamethylene diethylenediamine (pentamethylene diethylene diamine), IPD (isophorone diamine), triethylene glycol diamine (triethylene glycol diamine), Toluene-2,4-diisocyanate, 4-diamines (toluene-2,4-diamine), N, N-dimethyl-ethylenediamine (N, N-dimethyl ethylene diamine), N, N diethyl ethylenediamine (N, N-diethyl ethylene diamine), N-isopropyl ethylenediamine (N-isopropyl ethylene diamine), N-isopropyl-1,3-propane diamine (N-isopropyl-1,3-propane diamine), diethylenetriamines (diethylene triamine), diethylene tetramine (diethylene tetraamine), trien (triethylene tetraamine), hexa (hexamethylene tetraamine), tetren (tetraethylene pentaamine), penten (pentaethylene hexaamine), 2-imidazolidinone (2-imidazolidinone), ethylene thiourea (2-imidazolidinethione), the material of more than one that select in urea (urea).
In above-mentioned steps (e), can be more than one the material of selecting from phytocide (phytoncide), catechin (catechin), melamine with the aitiogenic described compound of formaldehyde.
Described metal or metallic compound can be from illite, platinum-titanium dioxide (Pt-TiO
2) be compound, silver (Ag), calcium hydroxide (Ca (OH)
2) in more than one the material selected.
Preferably, described alkaline hydrated oxide NaOH or potassium hydroxide.
Preferably, more than one the resin of selecting from ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin that contains 1～15 % by weight with respect to the emulsifying agent of 100 % by weight in described emulsifying agent.
Preferably, the aqueous solution that described formalin is the formaldehyde that contains 5～50 % by weight with respect to the formalin of 100 % by weight.
Preferably, described emulsifying agent is mixed with the weight ratio of 1:0.1～2 with described core material.
Preferably, described carbamide prepolymer is mixed with the weight ratio of 1:1～15 with described oily/watery emulsion.
Preferably, in above-mentioned steps (e), the product of above-mentioned steps (d) is mixed with the weight ratio of 1:0.001～0.2 with following the aitiogenic compound of described formaldehyde.
Preferably, in above-mentioned steps (f), the product of above-mentioned steps (e) is mixed with the weight ratio of 1:0.001～0.2 with described metal or metallic compound.
According to the present invention, can be used to form in the reacting of carbamide prepolymer (Prepolymer) by the much higher amines of the reactivity with formaldehyde is once devoted, and after forming microcapsules, another kind and the aitiogenic material of formaldehyde are separated to time difference secondary, drop into, thereby when can produce the effect that can keep the core material in microcapsules, can make residual formaldehyde obtain minimized melamine system microcapsule for three times.
According to the present invention, not only in initial reaction stage, drop into the much higher amines of reactivity of formaldehyde and remove unreacting acetal, but also reduce residual formaldehyde by the encapsulated reaction that participation forms capsule wall, and also drop into the aitiogenic material of formaldehyde and remove unreacted residual formaldehyde after forming capsule wall, can make accordingly to form microcapsules residual formaldehyde afterwards and measure minimized.
According to the present invention, not only do not produce precipitation, and can make for reduce residual formaldehyde interpolation material measure minimizedly, simultaneously can keep the core material effect in capsule and residual formaldehyde is obtained minimized.
The specific embodiment
Below, describe in detail according to a preferred embodiment of the invention.Yet following examples, in order to make the personnel in the art with general knowledge can fully understand that the present invention provides, can be deformed into many other forms, and scope of the present invention is not limited to following embodiment.
Below, so-called micro-represents the size of micron (μ m) magnitude, is specially the size of 1～1000 μ m scope, and so-called " microcapsules " represent to have the capsule of 1～1000 μ m range size.
The manufacture method of melamine system microcapsule comprises the steps: that the described melamine that (a) adds melamine, relative 100 weight portions is that the described melamine of the formalin of 50～300 weight portions, relative 100 weight portions is the alkaline hydrated oxide of 0.01～10 weight portion and pH is adjusted into 8～10 according to the preferred embodiment of the invention, and after the melamine of relatively described 100 weight portions adds the polyamine compounds with at least two amidos of 100～400 weight portions, react and form carbamide prepolymer; (b) more than one the resin of selecting in ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin is alkalized with alkaline hydrated oxide and forms emulsifying agent; (c) in described emulsifying agent, drop into core material and stir and form oily/watery emulsion (emulsion); (d) described carbamide prepolymer is mixed to be incorporated at 40～80 ℃ with described oily/watery emulsion react; (e) in the product of above-mentioned steps (d), drop into the aitiogenic compound of formaldehyde and react at 40～80 ℃; (f) in the product of above-mentioned steps (e), drop into the aitiogenic metal of formaldehyde or metallic compound and react at 40～80 ℃.
Described polyamine compounds can be from ethylenediamine (ethylene diamine), tetra-methylenedimine (tetramethylene diamine), four ethylene diamines (tetraethylene diamine), hexamethylene diamine (hexamethylene diamine), phenylenediamine (phenylene diamine), pentamethylene diethylenediamine (pentamethylene diethylene diamine), IPD (isophorone diamine), triethylene glycol diamine (triethylene glycol diamine), Toluene-2,4-diisocyanate, 4-diamines (toluene-2,4-diamine), N, N-dimethyl-ethylenediamine (N, N-dimethyl ethylene diamine), N, N diethyl ethylenediamine (N, N-diethyl ethylene diamine), N-isopropyl ethylenediamine (N-isopropyl ethylene diamine), N-isopropyl-1,3-propane diamine (N-isopropyl-1,3-propane diamine), diethylenetriamines (diethylene triamine), diethylene tetramine (diethylene tetraamine), trien (triethylene tetraamine), hexa (hexamethylene tetraamine), tetren (tetraethylene pentaamine), penten (pentaethylene hexaamine), 2-imidazolidinone (2-imidazolidinone), ethylene thiourea (2-imidazolidinethione), the material of more than one that select in urea (urea).
In above-mentioned steps (e), can be more than one the material of selecting from phytocide (phytoncide), catechin (catechin), melamine with the aitiogenic described compound of formaldehyde.
Described metal or metallic compound can be from illite, platinum-titanium dioxide (Pt-TiO
2) be compound, silver (Ag), calcium hydroxide (Ca (OH)
2) in more than one the material selected.
Preferably, described alkaline hydrated oxide is NaOH or potassium hydroxide.
Preferably, more than one the resin of selecting from ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin that contains 1～15 % by weight with respect to 100 % by weight emulsifying agents in described emulsifying agent.
Preferably, the aqueous solution that described formalin is the formaldehyde that contains 5～50 % by weight with respect to the formalin of 100 % by weight.
Preferably, described emulsifying agent is mixed with the weight ratio of 1:0.1～2 with described core material.
Preferably, described carbamide prepolymer is mixed with the weight ratio of 1:1～15 with described oily/watery emulsion.
Preferably, in above-mentioned steps (e), the product of above-mentioned steps (d) is mixed with the weight ratio of 1:0.001～0.2 with following the aitiogenic compound of described formaldehyde.
Preferably, in above-mentioned steps (f), the product of above-mentioned steps (e) is mixed with the weight ratio of 1:0.001～0.2 with described metal or metallic compound.
Below the manufacture method of melamine system microcapsule is according to the preferred embodiment of the invention carried out to more specific detail.
As Microencapsulation Method, there are coacervation, interfacial polymerization, situ aggregation method.
Coacervation is a kind of by the water-soluble polymer aqueous solution of core material fine dispersion being mixed with the solvent of polymer indissoluble or changing the pH etc. of the described water-soluble polymer aqueous solution and change the described water-soluble polymer aqueous solution into polymer and be difficult to the condition of dissolving, so that polymer surfaces condenses, then add hardener, on the surface of described core material, form accordingly the method for the sclerosis capsule wall being formed by polymer.
Interfacial polymerization is a kind of by the hydrophobicity core material solution that includes polymerisable hydrophobic monomer is fine scattered in water, manufactures the method for microcapsules thereby the contact area between water-soluble liquid phase and lyophobic dust causes monomer polymerization.
Situ aggregation method is a kind of core material to be imported in decentralized medium with the state of fine dispersion, and the polymerisable monomer that makes to be contained in core material and one of decentralized medium in the phase of dispersion and the contact area between medium, polymerization occurs and forms the method for capsule wall.For example, as decentralized medium, adopt the interfacial agent aqueous solution, as core material, adopt paraffin oil, and by paraffin oil emulsion dispersion in the interfacial agent aqueous solution, then devoted in the urea-formaldehyde resin that uses as polymer or melamine-formaldehyde resin solution and formed capsule.
In the present invention, in order to manufacture the residual minimum melamine system microcapsule of formaldehyde (HCHO), import following operation.
By being reacted with formaldehyde, melamine obtains, as the high molecular carbamide prepolymer (prepolymer) that forms the capsule wall of melamine system microcapsule, wherein in the process that melamine is reacted with formaldehyde, dropping into and the aitiogenic polyamine compounds of formaldehyde.A part for described polyamine compounds participates in forming the reaction of carbamide prepolymer, and a part is hardened by encapsulated reaction under high temperature at carbamide prepolymer to form in the process of capsule wall and participated in encapsulated reaction, thereby the residual formaldehyde that makes to be present in melamine system microcapsule reduces.
Preferably, described carbamide prepolymer is that the described melamine of the formalin of 50～300 weight portions, relative 100 weight portions is the alkaline hydrated oxide of 0.01～10 weight portion and pH is adjusted into 8～10 by adding the described melamine of melamine, relative 100 weight portions, and the melamine of relatively described 100 weight portions reacts and forms after adding the polyamine compounds with at least two amidos of 100～400 weight portions.
The melamine that drop into and the amount aitiogenic polyamine compounds of formaldehyde should relative 100 weight portions in initial reaction stage adds 100～400 weight portions left and right.If the amount of polyamine compounds is with respect to melamine less than 100 weight portions of 100 weight portions, the effect that may make to reduce formaldehyde is faint, if and surpass 400 weight portions, the carbamide condensation reaction that may be hardened and make to be used to form capsule wall is carried out not thorough, thereby makes encapsulatedly become unstable and be difficult to overcome the function that external environment maintains core material.
Preferably, Yi Bian to be used to form the reaction of described carbamide prepolymer be to stir to carry out 30 minutes～1 hour at the temperature of 40～90 ℃ of left and right.Preferably, described stirring is carried out with the speed of 100～300rpm.
Preferably, the aqueous solution that described formalin is the formaldehyde that contains 5～50 % by weight with respect to the formalin of 100 % by weight.
In order to form described carbamide prepolymer, can also add distilled water, for example, the distilled water of 50～500 weight portions can be added in the lump.
The compound adding in the process that melamine is reacted in order to form described carbamide prepolymer with formaldehyde is aminated compounds, than the lower monoamine of the reactivity with formaldehyde, described aminated compounds preferably has the polyamine compounds of two above amidos.
The described polyamine compounds with at least two amidos can be from ethylenediamine (ethylene diamine), tetra-methylenedimine (tetramethylene diamine), four ethylene diamines (tetraethylene diamine), hexamethylene diamine (hexamethylene diamine), phenylenediamine (phenylene diamine), pentamethylene diethylenediamine (pentamethylene diethylene diamine), IPD (isophorone diamine), triethylene glycol diamine (triethylene glycol diamine), Toluene-2,4-diisocyanate, 4-diamines (toluene-2,4-diamine), N, N-dimethyl-ethylenediamine (N, N-dimethyl ethylene diamine), N, N diethyl ethylenediamine (N, N-diethyl ethylene diamine), N-isopropyl ethylenediamine (N-isopropyl ethylene diamine), N-isopropyl-1,3-propane diamine (N-isopropyl-1,3-propane diamine), diethylenetriamines (diethylene triamine), diethylene tetramine (diethylene tetraamine), trien (triethylene tetraamine), hexa (hexamethylene tetraamine), tetren (tetraethylene pentaamine), penten (pentaethylene hexaamine), 2-imidazolidinone (2-imidazolidinone), ethylene thiourea (2-imidazolidinethione), the material of more than one that select in urea (urea).
Preferably, described alkaline hydrated oxide is NaOH or potassium hydroxide.
By maleic acid acrylic copolymer resin is formed to the emulsifying agent that plays teepol effect with alkaline hydrated oxide alkalization, preferably, more than one the resin of described maleic acid acrylic copolymer resin for selecting from ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin.
Preferably, more than one the resin of selecting from ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin that contains 1～15 % by weight with respect to the emulsifying agent of 100 % by weight in described emulsifying agent.
Preferably, the described alkaline hydrated oxide that is used to form emulsifying agent is NaOH or potassium hydroxide.
In described emulsifying agent, drop into core material and stir and form oily/watery (Oil/Water or O/W) emulsion.
Preferably, in order to form the stirring of described oily/watery emulsion, be to carry out 10 minutes～1 hour with the speed of 500～10,000rpm.
Preferably, described emulsifying agent is to mix with the weight ratio of 1:0.1～2 with described core material.
As core material, comprise such as spices, medicine, resin, ink, oil, phase change material (phase change material; PCM), phytocide, dyestuff, agrochemical, so long as can all can by encapsulated functional materials.
Described carbamide prepolymer is mixed with described oily/watery emulsion, and react at 40～80 ℃ of temperature, be preferably at 50～80 ℃ and react.
Preferably, by described carbamide prepolymer and described oily/watery emulsion with 1:1～15(carbamide prepolymer: weight ratio oily/watery emulsion) is mixed.
If described carbamide prepolymer is mixed and is reacted with described oily/watery emulsion, hardened as time goes by and formed capsule wall, finally according to described carbamide prepolymer and reacting of described oily/watery emulsion, being formed melamine system microcapsule (or melamine system microcapsule aqueous liquid dispersion).
A part in described polyamine compounds will participate in forming the reaction of carbamide prepolymer, yet the residue polyamine compounds that has neither part nor lot in the reaction that forms carbamide prepolymer is formed hardening by encapsulated reaction under high temperature at carbamide prepolymer in the process of capsule wall and participates in encapsulated reaction, reduces accordingly the residual formaldehyde existing in melamine system microcapsule.
In order further to reduce the residual quantity of the formaldehyde existing in melamine system microcapsule, in the product of described carbamide prepolymer and described oily/watery emulsion, drop into and react with the aitiogenic compound of formaldehyde and at 40～80 ℃ of temperature, be preferably at 50～70 ℃ of temperature and react.Preferably, devote selecting and being different from the polyamine compounds dropping in being used to form the reacting of carbamide prepolymer with the aitiogenic compound of formaldehyde in the product of carbamide prepolymer and oily/watery emulsion.The described reaction time is 10 minutes～24 hours, be preferably 2～3 hours, if input is shorter than the described reaction time with the reaction time after the aitiogenic compound of formaldehyde, the effect that reduces formaldehyde declines, if and longer than the described reaction time, production variation and make manufacturing expense increase.
Devote described compound in the product of carbamide prepolymer and oily/watery emulsion for can with the aitiogenic material of formaldehyde, it can be more than one the material of selecting in the phytocide that belongs to terpenoid (terpenoid), the catechin that belongs to Polyphenols and melamine.Preferably, by the product of carbamide prepolymer and oily/watery emulsion and with the aitiogenic compound of described formaldehyde with 1:0.001～0.2(product: with the aitiogenic compound of formaldehyde) weight ratio mix.If surpass 20 weight portions with the amount of the aitiogenic compound of described formaldehyde with respect to the carbamide prepolymer of 100 weight portions and the product of oily/watery emulsion, because capsule concentration step-down makes the functional of core material, weaken, and may make the dispersion stabilization of melamine system microcapsule and bin stability poor.
By causing and the reacting of formaldehyde with the aitiogenic compound of formaldehyde of dropping into phytocide, catechin or melamine and so on, thereby the residual formaldehyde secondary in melamine system microcapsule can be reduced.
In order further to reduce the residual formaldehyde existing in melamine system microcapsule, in the product forming with the aitiogenic compound of formaldehyde by input phytocide, catechin or melamine and so on, drop into the aitiogenic metal of formaldehyde or metallic compound and react at 40～80 ℃ of temperature, being preferably at 50～70 ℃ of temperature and reacting.The described reaction time is 10 minutes～24 hours, be preferably 2～3 hours, if drop into the aitiogenic metal of formaldehyde or metallic compound reaction time afterwards shorter than the described reaction time, cause the effect that reduces formaldehyde to decline, if and longer than the described reaction time, cause production variation and make manufacturing expense increase.
Described metal or metallic compound can be from illite (illite), platinum-titanium dioxide (Pt-TiO
2) be compound, silver (Ag), calcium hydroxide (Ca (OH)
2) in more than one the material selected.This metal or metallic compound play with formolite reaction the effect of Formaldehyde decomposition.Preferably, the product forming with the aitiogenic compound of formaldehyde that drops into phytocide, catechin or melamine and so on and described metal or metallic compound are with 1:0.001～0.2(product: metal or metallic compound) weight ratio mix.If the amount of described metal or metallic compound surpasses 20 weight portions with respect to the product that the compound with the aitiogenic phytocide of formaldehyde, catechin or melamine and so on forms of passing through to drop into of 100 weight portions, because capsule concentration step-down makes the functional of core material, weaken, and may make dispersion stabilization and the bin stability variation of melamine system microcapsule.
By dropping into illite (illite), platinum-titanium dioxide (Pt-TiO
2) be compound, silver (Ag), calcium hydroxide (Ca (OH)
2) and so on cause with the aitiogenic metal of formaldehyde or metallic compound and the reacting of formaldehyde, thereby the residual formaldehyde in melamine system microcapsule can be reduced for three times.
In above-mentioned example, to first dropping into and the aitiogenic phytocide of formaldehyde, the compound of catechin or melamine and so on and drop into again the operation of reacting with the aitiogenic metal of formaldehyde or metallic compound after reacting and be illustrated, yet also can by the product to described carbamide prepolymer and described oily/watery emulsion, drop into react with the aitiogenic metal of formaldehyde or metallic compound after input and the aitiogenic phytocide of formaldehyde, the compounds of catechin or melamine and the operation of reacting realizes.
As, in order to manufacture melamine system microcapsule, in the initial operation of reaction (forming the operation of carbamide prepolymer), utilize and the aitiogenic polyamine compounds of formaldehyde, and after the product that obtains carbamide prepolymer and oily/watery emulsion will with the aitiogenic compound of formaldehyde and metal or metal oxide secondary, utilize for three times, compared with producing the situation of disposable a large amount of inputs after melamine system microcapsule, can reduce interpolation amount of substance, thereby can be by the due efficacy exertion of melamine system microcapsule self to the highest limit.And, owing to starting just can reduce formaldehyde from reaction initial step (forming the operation of carbamide prepolymer), thereby can manufacture safer microcapsules, and owing at least dropping into once with the aitiogenic material of formaldehyde in each step, so it is minimized to make content of formaldehyde residual in melamine system microcapsule obtain.
Situation than the disposable input of material (with the aitiogenic material of formaldehyde) that secondary, three times are dropped into, if dropped into every a little time differences as above-mentioned operation, can improve the reaction efficiency with formaldehyde, therefore than the situation of disposable input, the residual quantity of formaldehyde can be reduced to 1/3～1/2.
By operation as above, can produce melamine system microcapsule and can make residual formaldehyde content residual in melamine system microcapsule minimized, in the melamine system microcapsule of manufacturing like this, contain the formaldehyde that concentration is the minute quantity below 20ppm.
And the melamine system microcapsule of manufacturing is like this physical property and the reappearance excellence of even particle size distribution, mechanical strength and so on not only, also helps volume production.
Below, concrete open according to experimental example of the present invention, however the present invention is not limited to each experimental example of following discloses.
<experimental example 1>
In the four-hole boiling flask of 1L, add 10g melamine, 40g distilled water, 20g formalin, 0.05g NaOH and pH is adjusted into 9, and add 21g diethylene tetramine (polyamines) at 80 ℃ of temperature, to stir 30 minutes afterwards and manufactured carbamide prepolymer (Prepolymer).The aqueous solution that described formalin has been used the formalin with respect to 100 % by weight to contain 35 % by weight formaldehyde.
In other 1L beaker by NaOH ethene-maleic acid copolymerized resin (trade name: EMA-31 that alkalizes, Monsanto company product) manufactured the emulsifying agent 200g that plays teepol effect, drop into wherein again as the 100g attar of rose of core material and use homogenizer with the speed stir about 10 minutes of 3,000rpm, to manufacture oily/watery (O/W) emulsion.Ethene-maleic acid copolymerized the resin that contains 5 % by weight with respect to the emulsifying agent of 100 % by weight in described emulsifying agent.
And after the carbamide prepolymer (Prepolymer) of so manufacturing is mixed with O/W emulsion, at 70 ℃, stir about makes its sclerosis in 2 hours and forms capsule wall, has manufactured thus melamine system microcapsule.Described stirring is to carry out with the speed of 100rpm.
<experimental example 2>
In the four-hole boiling flask of 1L, add 10g melamine, 40g distilled water, 20g formalin, 0.05g NaOH and pH is adjusted into 9, and add 7g diethylene tetramine (polyamines) at 80 ℃ of temperature, to stir 30 minutes afterwards and manufactured carbamide prepolymer (Prepolymer).The aqueous solution that described formalin has been used the formalin with respect to 100 % by weight to contain 35 % by weight formaldehyde.Described stirring is to carry out with the speed of 100rpm.
In other 1L beaker by NaOH ethene-maleic acid copolymerized resin (trade name: EMA-31 that alkalizes, Monsanto company product) manufactured the emulsifying agent 200g that plays teepol effect, drop into wherein again as the 100g attar of rose of core material and use homogenizer with the speed stir about 10 minutes of 3,000rpm, to manufacture oily/watery (O/W) emulsion.Ethene-maleic acid copolymerized the resin that contains 5 % by weight with respect to the emulsifying agent of 100 % by weight in described emulsifying agent.
And after the carbamide prepolymer (Prepolymer) of so manufacturing is mixed with O/W emulsion, at 70 ℃, stir about makes its sclerosis in 2 hours and forms capsule wall, has manufactured thus melamine system microcapsule.Described stirring is to carry out with the speed of 100rpm.
In melamine system microcapsule, drop into 14g phytocide, and at 50 ℃, react 3 hours and manufactured melamine system microcapsule.
<experimental example 3>
In the four-hole boiling flask of 1L, add 10g melamine, 40g distilled water, 20g formalin, 0.05g NaOH and pH is adjusted into 9, and add 7g diethylene tetramine (polyamines) at 80 ℃ of temperature, to stir 30 minutes afterwards and manufactured carbamide prepolymer (Prepolymer).The aqueous solution that described formalin has been used the formalin with respect to 100 % by weight to contain 35 % by weight formaldehyde.Described stirring is to carry out with the speed of 100rpm.
In other 1L beaker by NaOH ethene-maleic acid copolymerized resin (trade name: EMA-31 that alkalizes, Monsanto company product) with NaOH alkalization, manufactured the emulsifying agent 200g that plays teepol effect, drop into wherein again as the 100g attar of rose of core material and use homogenizer with the speed stir about 10 minutes of 3,000rpm, to manufacture oily/watery (O/W) emulsion.Ethene-maleic acid copolymerized the resin that contains 5 % by weight with respect to the emulsifying agent of 100 % by weight in described emulsifying agent.
And after the carbamide prepolymer (Prepolymer) of so manufacturing is mixed with O/W emulsion, at 70 ℃, stir about makes its sclerosis in 2 hours and forms capsule wall, has manufactured thus melamine system microcapsule.Described stirring is to carry out with the speed of 100rpm.
After dropping into 14g phytocide and react 3 hours at 50 ℃ in melamine system microcapsule, drop into 5% silver sol (Ag-Sol) of 7g and at 50 ℃, react 3 hours and manufactured melamine system microcapsule.
Openly can be for the reference examples comparing with each experimental example for making to grasp more easily above-mentioned experimental example 1 to the characteristic of experimental example 3.Reference examples 1 described later to reference examples 3 is disclosed for the characteristic with each experimental example compares purely, and it is not the prior art in field under the present invention.
<reference examples 1>
In the four-hole boiling flask of 1L, add 10g melamine, 40g distilled water, 20g formalin, 0.05g NaOH and pH is adjusted into 9, and at 80 ℃ of temperature, stir 30 minutes and manufactured carbamide prepolymer (Prepolymer).The aqueous solution that described formalin has been used the formalin with respect to 100 % by weight to contain 35 % by weight formaldehyde.Described stirring is to carry out with the speed of 100rpm.
In other 1L beaker by NaOH ethene-maleic acid copolymerized resin (trade name: EMA-31 that alkalizes, Monsanto company product) manufactured the emulsifying agent 200g that plays teepol effect, drop into wherein again as the 100g attar of rose of core material and use homogenizer with the speed stir about 10 minutes of 3,000rpm, to manufacture oily/watery (O/W) emulsion.Ethene-maleic acid copolymerized the resin that contains 5 % by weight with respect to the emulsifying agent of 100 % by weight in described emulsifying agent.
And after the carbamide prepolymer (Prepolymer) of so manufacturing is mixed with O/W emulsion, at 70 ℃, stir about makes its sclerosis in 2 hours and forms capsule wall, has manufactured thus melamine system microcapsule.Described stirring is to carry out with the speed of 100rpm.
<reference examples 2>
After adopting the method manufacture melamine system microcapsule identical with above-mentioned reference examples 1, devote microcapsules and at 50 ℃, react 3 hours and manufactured melamine system microcapsule 21g triethylene amine (Tri ethyleneamine, a kind of monoamine) is disposable.
<reference examples 3>
After adopting the method manufacture melamine system microcapsule identical with above-mentioned reference examples 1, devote microcapsules and at 50 ℃, react 3 hours and manufactured melamine system microcapsule 21g diethylene tetramine (diethylene tetraamine, a polyamine species) is disposable.
Following check experiment example is more easily to grasp in order to contribute to the situation that experimental example 1 is represented to the characteristic of experimental example 3 experimental result that the characteristic of experimental example and reference examples is compared.
<check experiment example 1>mensuration residual formaldehyde content
For attar of rose being used in above-mentioned reference examples 1～3 and experimental example 1～3, be the melamine system microcapsule that core material is manufactured, by distilled water extraction method (KS K ISO14184-1), measured residual formaldehyde concentration.
[table 1]
| Classification | Residual formaldehyde concentration (ppm) | Slip (comparing with reference examples 1) |
| Reference examples 1 | 920 | - |
| Reference examples 2 | 718 | 22% |
| Reference examples 3 | 524 | 43% |
| Experimental example 1 | 312 | 66% |
| Experimental example 2 | 147 | 84% |
| Experimental example 3 | 18 | 98% |
From table 1 above, than monoamine compound is used as and produces the situation (situation of reference examples 2) of melamine system microcapsule with the aitiogenic compound of formaldehyde, under the situation (situation of experimental example 1～3) of using polyamine compounds manufacture melamine system microcapsule, detected residual formaldehyde content still less, and than after producing melamine system microcapsule only by a kind of and situation (reference examples 2～3 disposable input of the aitiogenic material of formaldehyde, the situation of experimental example 2), in the situation (situation of experimental example 3) that different materials is divided into twice input, can make residual formaldehyde content obtain down minimized.
<check experiment example 2>fragrance protectiveness of melamine system microcapsule can assess
For the melamine system microcapsule of in above-mentioned reference examples 1～3 and experimental example 1～3, attar of rose being manufactured as core material, in water, drop into melamine system microcapsule and after making the dilution that melamine system microcapsule is 0.5 % by weight, towel is soaked in this dilution to take out again and twists later in the oven dry baking box (Dry Oven) of 50 ℃ oven dry approximately 30 minutes, with fragrance protectiveness, can assess accordingly the effect of the core material in melamine system microcapsule.
[table 2]
| Classification | Fragrance protectiveness energy (comparing with reference examples 1) |
| Reference examples 1 | - |
| Reference examples 2 | △ |
| Reference examples 3 | △ |
| Experimental example 1 | ○ |
| Experimental example 2 | ○ |
| Experimental example 3 | ◎ |
Fragrance protectiveness can assessment be, by choosing 50 people, each towel of each reference examples and experimental example is implemented respectively to subjective appreciation, and according to thinking that fragrance protectiveness compares as a rule the equally matched or better personnel's number of 1 melamine system microcapsule and assesses.
40～50: ◎ (very good)
30～40: zero (well)
20～30: △ (generally)
Below 20: X (poor)
From table 2 above, than will with the aitiogenic material of formaldehyde disposable situation (situation of reference examples 2 and reference examples 3) after producing melamine system microcapsule, by each encapsulated reaction process, be divided at least twice interpolation and the fragrance protectiveness of the melamine system microcapsule (situation of experimental example 2 and experimental example 3) manufactured can be more excellent.
<check experiment example 3>stability assessment of melamine system microcapsule
Prepare respectively the melamine system microcapsule 200ml in above-mentioned reference examples 1～3 and experimental example 1～3, attar of rose being manufactured as core material, and put it into PET (polyethylene terephthalate; PET) after reagent bottle, in 50 ℃ of thermostats, place 4 time-of-weeks, and visually observed its stability status.
[table 3]
Visually observe: confirm foreign matter and sediment
Zero: good
X: produce foreign matter or sediment
From table 3 above, by be chosen as mutually different material with the aitiogenic material of formaldehyde (polyamine compounds that initial reaction stage drops into, react compound, metal or metallic compound that end stage drops into) and be divided into drop into for 2～3 times and the stability of the melamine system microcapsule (situation of experimental example 2 and experimental example 3) of manufacture than more excellent.
Above, enumerated the preferred embodiments of the present invention and had been described in detail, yet the present invention is not limited to the various embodiments described above, the personnel that possess O-level knowledge in this area all can carry out diversified distortion in the scope of the technology of the present invention thought.
Claims (11)
1. a manufacture method for melamine system microcapsule, is characterized in that, comprises the steps:
(a) the described melamine that adds melamine, relative 100 weight portions is that the described melamine of the formalin of 50～300 weight portions, relative 100 weight portions is the alkaline hydrated oxide of 0.01～10 weight portion and pH is adjusted into 8～10, and after the described melamine of relative 100 weight portions adds the polyamine compounds with at least two amidos of 100～400 weight portions, react and form carbamide prepolymer;
(b) more than one the resin of selecting in ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin is alkalized with alkaline hydrated oxide and forms emulsifying agent;
(c) in described emulsifying agent, drop into core material and stir and form oily/watery emulsion;
(d) described carbamide prepolymer is mixed to be incorporated at 40～80 ℃ with described oily/watery emulsion react;
(e) in the product of above-mentioned steps (d), drop into the aitiogenic compound of formaldehyde and react at 40～80 ℃;
(f) in the product of above-mentioned steps (e), drop into the aitiogenic metal of formaldehyde or metallic compound and react at 40～80 ℃.
2. the manufacture method of melamine system microcapsule as claimed in claim 1, it is characterized in that, described polyamine compounds is from ethylenediamine, tetra-methylenedimine, four ethylene diamines, hexamethylene diamine, phenylenediamine, pentamethylene diethylenediamine, IPD, triethylene glycol diamine, Toluene-2,4-diisocyanate, 4-diamines, N, N-dimethyl-ethylenediamine, N, N diethyl ethylenediamine, N-isopropyl ethylenediamine, N-isopropyl-1, 3-propane diamine, diethylenetriamines, diethylene tetramine, trien, hexa, tetren, penten, 2-imidazolidinone, ethylene thiourea, the material of more than one that select in urea.
3. the manufacture method of melamine system microcapsule as claimed in claim 1, is characterized in that, in above-mentioned steps (e), is more than one the material of selecting from phytocide, catechin, melamine with the aitiogenic described compound of formaldehyde.
4. the manufacture method of melamine system microcapsule as claimed in claim 1, is characterized in that, described metal or metallic compound are more than one the materials of selecting from illite, platinum-TiO 2 series compound, silver, calcium hydroxide.
5. the manufacture method of melamine system microcapsule as claimed in claim 1, is characterized in that, described alkaline hydrated oxide is NaOH or potassium hydroxide.
6. the manufacture method of melamine system microcapsule as claimed in claim 1, it is characterized in that more than one the resin of selecting that contains 1～15 % by weight with respect to the emulsifying agent of 100 % by weight in described emulsifying agent from ethene-maleic acid copolymerized resin and styrene-maleic acid copolymer resin.
7. the manufacture method of melamine system microcapsule as claimed in claim 1, is characterized in that, the aqueous solution that described formalin is the formaldehyde that contains 5～50 % by weight with respect to the formalin of 100 % by weight.
8. the manufacture method of melamine system microcapsule as claimed in claim 1, is characterized in that, described emulsifying agent is mixed with the weight ratio of 1:0.1～2 with described core material.
9. the manufacture method of melamine system microcapsule as claimed in claim 1, is characterized in that, described carbamide prepolymer is mixed with the weight ratio of 1:1～15 with described oily/watery emulsion.
10. the manufacture method of melamine system microcapsule as claimed in claim 1, it is characterized in that, in above-mentioned steps (e), the product of above-mentioned steps (d) is mixed with the weight ratio of 1:0.001～0.2 with following the aitiogenic compound of described formaldehyde.
The manufacture method of 11. melamine system microcapsules as claimed in claim 1, is characterized in that, in above-mentioned steps (f), the product of above-mentioned steps (e) is mixed with the weight ratio of 1:0.001～0.2 with described metal or metallic compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120065336A KR101366307B1 (en) | 2012-06-19 | 2012-06-19 | Manufacturing method of melamine microcapsule |
| KR10-2012-0065336 | 2012-06-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103506059A true CN103506059A (en) | 2014-01-15 |
| CN103506059B CN103506059B (en) | 2016-01-20 |
Family
ID=49889797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310241388.XA Expired - Fee Related CN103506059B (en) | 2012-06-19 | 2013-06-18 | The manufacture method of melamine system microcapsule |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101366307B1 (en) |
| CN (1) | CN103506059B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104452277A (en) * | 2014-11-28 | 2015-03-25 | 东华大学 | Microcapsule capable of cladding 2,4-dichloro-3,5-dimethylphenol, as well as preparation and application of microcapsule |
| CN107027312A (en) * | 2014-11-14 | 2017-08-08 | Posco公司 | Environmental hormone degradation composition, coated steel sheet and its manufacture method using it |
| CN107243305A (en) * | 2017-04-26 | 2017-10-13 | 中国林业科学研究院木材工业研究所 | A kind of preparation method of nano cellulose crystal modified aminoresin microcapsules |
| CN109304135A (en) * | 2017-07-28 | 2019-02-05 | 捷恩智株式会社 | Liquid crystal capsule and method for producing the same |
| CN109420281A (en) * | 2017-09-04 | 2019-03-05 | 西安威西特消防科技有限责任公司 | A kind of microcapsules self-extinguishing agent |
| CN112566717A (en) * | 2018-08-24 | 2021-03-26 | 株式会社Lg生活健康 | Method for preparing microcapsules |
| CN112774588A (en) * | 2020-12-19 | 2021-05-11 | 江西善纳新材料科技有限公司 | Preparation method of noble metal @ melamine core-shell nanostructure |
| CN116102905A (en) * | 2022-12-27 | 2023-05-12 | 安徽美佳新材料股份有限公司 | Melamine-formaldehyde resin coated nano titanium dioxide and preparation method and application thereof |
| CN117430772A (en) * | 2023-07-25 | 2024-01-23 | 江苏佳饰家新材料集团股份有限公司 | Low-formaldehyde high-fluidity impregnating resin and preparation method thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101940705B1 (en) * | 2015-06-09 | 2019-01-21 | 문환업 | Adhesive Composition and Tape Cleaner Comprising the Same |
| GB201511605D0 (en) * | 2015-07-02 | 2015-08-19 | Givaudan Sa | Microcapsules |
| KR20190023697A (en) | 2017-08-30 | 2019-03-08 | 주식회사 대하맨텍 | Biodegradable functional capsule and manufacturing method of the same |
| WO2020040608A1 (en) * | 2018-08-24 | 2020-02-27 | 주식회사 엘지생활건강 | Microcapsule production method |
| KR102272566B1 (en) | 2019-01-18 | 2021-07-05 | 주식회사 대하맨텍 | Biodegradable capsule without irritation to human body and manufacturing method of the same |
| WO2020149684A2 (en) | 2019-01-18 | 2020-07-23 | 주식회사 대하맨텍 | Biodegradable capsule with safety due to no irritation to human body and manufacturing method therefor |
| KR20210148523A (en) | 2020-05-29 | 2021-12-08 | 주식회사 대하맨텍 | Biodegradable capsules for households and manufacturing method of the same |
| KR20230056879A (en) | 2021-10-21 | 2023-04-28 | 주식회사 대하맨텍 | Biodegradable microcapsules and manufacturing method of the same |
| CN116063929A (en) * | 2023-01-03 | 2023-05-05 | 广东粤港澳大湾区黄埔材料研究院 | A-direction sapphire substrate polishing solution and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513938A (en) * | 2003-08-21 | 2004-07-21 | 河北工业大学 | A kind of microcapsule coated phase change material and preparation method thereof |
| US20070138671A1 (en) * | 2005-12-15 | 2007-06-21 | Anastasiou Theodore J | Encapsulated active material with reduced formaldehyde potential |
| CN101116806A (en) * | 2007-08-30 | 2008-02-06 | 中山大学 | A kind of polythiol microcapsule and preparation method thereof |
| CN101376800A (en) * | 2008-10-07 | 2009-03-04 | 山东省科学院新材料研究所 | High temperature resistant type phase-change material micro-capsule and preparation thereof |
| WO2009028821A2 (en) * | 2007-08-31 | 2009-03-05 | Korea Research Institute Of Chemical Technology | Preparation of microcapsule with double layered structure |
| CN102438740A (en) * | 2009-03-12 | 2012-05-02 | 福尔曼化工原料及工艺技术有限公司及两合公司 | Improved microcapsules and their preparation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR910004435B1 (en) * | 1988-11-26 | 1991-06-27 | 전주제지 주식회사 | Manufacturing method of microcapsule for pressure-sensitive recording paper |
| KR920009491B1 (en) * | 1988-12-30 | 1992-10-17 | 전주제지 주식회사 | Preparation method of microcapsules for pressure-sensitive recording paper |
| KR100634492B1 (en) * | 2004-03-30 | 2006-10-17 | 임대우 | Microcapsules with reduced residual formaldehyde and fabrics produced using the same |
| KR20070096097A (en) * | 2005-12-21 | 2007-10-02 | 임대우 | Electrophoretic display using microencapsulated organic solvent-soluble polyaniline |
-
2012
- 2012-06-19 KR KR1020120065336A patent/KR101366307B1/en active Active
-
2013
- 2013-06-18 CN CN201310241388.XA patent/CN103506059B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513938A (en) * | 2003-08-21 | 2004-07-21 | 河北工业大学 | A kind of microcapsule coated phase change material and preparation method thereof |
| US20070138671A1 (en) * | 2005-12-15 | 2007-06-21 | Anastasiou Theodore J | Encapsulated active material with reduced formaldehyde potential |
| CN101116806A (en) * | 2007-08-30 | 2008-02-06 | 中山大学 | A kind of polythiol microcapsule and preparation method thereof |
| WO2009028821A2 (en) * | 2007-08-31 | 2009-03-05 | Korea Research Institute Of Chemical Technology | Preparation of microcapsule with double layered structure |
| CN101376800A (en) * | 2008-10-07 | 2009-03-04 | 山东省科学院新材料研究所 | High temperature resistant type phase-change material micro-capsule and preparation thereof |
| CN102438740A (en) * | 2009-03-12 | 2012-05-02 | 福尔曼化工原料及工艺技术有限公司及两合公司 | Improved microcapsules and their preparation |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107027312A (en) * | 2014-11-14 | 2017-08-08 | Posco公司 | Environmental hormone degradation composition, coated steel sheet and its manufacture method using it |
| CN104452277A (en) * | 2014-11-28 | 2015-03-25 | 东华大学 | Microcapsule capable of cladding 2,4-dichloro-3,5-dimethylphenol, as well as preparation and application of microcapsule |
| CN107243305A (en) * | 2017-04-26 | 2017-10-13 | 中国林业科学研究院木材工业研究所 | A kind of preparation method of nano cellulose crystal modified aminoresin microcapsules |
| CN109304135A (en) * | 2017-07-28 | 2019-02-05 | 捷恩智株式会社 | Liquid crystal capsule and method for producing the same |
| CN109420281A (en) * | 2017-09-04 | 2019-03-05 | 西安威西特消防科技有限责任公司 | A kind of microcapsules self-extinguishing agent |
| CN112566717A (en) * | 2018-08-24 | 2021-03-26 | 株式会社Lg生活健康 | Method for preparing microcapsules |
| CN112566717B (en) * | 2018-08-24 | 2023-03-10 | 株式会社Lg生活健康 | Method for preparing microcapsules |
| CN112774588A (en) * | 2020-12-19 | 2021-05-11 | 江西善纳新材料科技有限公司 | Preparation method of noble metal @ melamine core-shell nanostructure |
| CN116102905A (en) * | 2022-12-27 | 2023-05-12 | 安徽美佳新材料股份有限公司 | Melamine-formaldehyde resin coated nano titanium dioxide and preparation method and application thereof |
| CN117430772A (en) * | 2023-07-25 | 2024-01-23 | 江苏佳饰家新材料集团股份有限公司 | Low-formaldehyde high-fluidity impregnating resin and preparation method thereof |
| CN117430772B (en) * | 2023-07-25 | 2024-04-02 | 江苏佳饰家新材料集团股份有限公司 | Low-formaldehyde high-fluidity impregnating resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101366307B1 (en) | 2014-02-21 |
| CN103506059B (en) | 2016-01-20 |
| KR20130142268A (en) | 2013-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103506059A (en) | Manufacturing method of melamine microcapsule | |
| Nguon et al. | Microencapsulation by in situ polymerization of amino resins | |
| CN111836668B (en) | Improvements in or relating to organic compounds | |
| EP2544812A2 (en) | Improved microcapsules and production thereof | |
| WO2013173748A1 (en) | Dust suppressing aggregate | |
| EP2714014A2 (en) | Encapsulated polar materials and methods of preparation | |
| Zhu et al. | A facile ion imprinted synthesis of selective biosorbent for Cu2+ via microfluidic technology | |
| KR101781802B1 (en) | Manufacturing method aqueous dispersion of urethane microcapsule | |
| EP2732803B1 (en) | Thermally opening stable core/shell micro capsules | |
| CN116171293A (en) | Amine-modified polysaccharide carbamate/urea microcapsules | |
| EP3380446B1 (en) | Urea-containing fertilizers and process for production thereof | |
| He et al. | H2O2-triggered rapid deposition of poly (caffeic acid) coatings: a mechanism-based entry to versatile and high-efficient molecular separation | |
| DE102006005165A1 (en) | Process for the preparation of lithium molybdate nanoparticles | |
| WO2015193377A1 (en) | Urea composition and method for producing same | |
| Gunasegaran et al. | Kinetic studies of reactive orange 16 (RO16) dye removal from aqueous solution using PIMs | |
| JP6980007B2 (en) | Use of amphoteric electrolyte copolymer as a colloidal stabilizer in the method of encapsulating fragrances | |
| EP3251507A1 (en) | Improved insecticide formulations | |
| US9656233B2 (en) | Reversible microcapsule filter cake | |
| HUE031703T2 (en) | Antimicrobial chemical compositions | |
| JP2012512144A (en) | Process for preparing a readily dispersible solid N'-hydroxy-N-cyclohexyldiazenium oxide salt | |
| KR102798497B1 (en) | Improvement of organic compounds or improvements related thereto | |
| Zanino | Synthesis and characterization of organic bijel-like structures for the controlled release of a pesticide-fertilizer system | |
| JPS62277146A (en) | Production of microcapsule | |
| JP5201783B2 (en) | Micro capsule | |
| WO2018011327A1 (en) | Use of a urea composition to produce diesel exhaust fluid (aus 32) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |