CN116786044A - Composite core wall microcapsule and preparation method and application thereof - Google Patents
Composite core wall microcapsule and preparation method and application thereof Download PDFInfo
- Publication number
- CN116786044A CN116786044A CN202310745017.9A CN202310745017A CN116786044A CN 116786044 A CN116786044 A CN 116786044A CN 202310745017 A CN202310745017 A CN 202310745017A CN 116786044 A CN116786044 A CN 116786044A
- Authority
- CN
- China
- Prior art keywords
- polymer
- wall
- composite core
- polycondensation
- microcapsule
- 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.)
- Pending
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 100
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011162 core material Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 64
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 41
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 27
- 229920002396 Polyurea Polymers 0.000 claims abstract description 26
- 239000003599 detergent Substances 0.000 claims abstract description 23
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 38
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 38
- 239000012071 phase Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000006068 polycondensation reaction Methods 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000005056 polyisocyanate Substances 0.000 claims description 17
- 229920001228 polyisocyanate Polymers 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 12
- 238000006136 alcoholysis reaction Methods 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 239000008406 cosmetic ingredient Substances 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- HHPPHUYKUOAWJV-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCC1CO1 HHPPHUYKUOAWJV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000002537 cosmetic Substances 0.000 abstract description 7
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 34
- 235000019198 oils Nutrition 0.000 description 34
- 239000000047 product Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000003205 fragrance Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 229920002873 Polyethylenimine Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical group C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000162 poly(ureaurethane) Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 230000003578 releasing effect Effects 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XSNQECSCDATQEL-SECBINFHSA-N 2,6-dimethyl-7-octen-2-ol Chemical compound C=C[C@@H](C)CCCC(C)(C)O XSNQECSCDATQEL-SECBINFHSA-N 0.000 description 2
- NOWXSWMFTGXVSR-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-2-methylpropanal Chemical compound CC(C)(C)C1=CC=C(C(C)(C)C=O)C=C1 NOWXSWMFTGXVSR-UHFFFAOYSA-N 0.000 description 2
- DLHQZZUEERVIGQ-UHFFFAOYSA-N 3,7-dimethyl-3-octanol Chemical compound CCC(C)(O)CCCC(C)C DLHQZZUEERVIGQ-UHFFFAOYSA-N 0.000 description 2
- WXCMHFPAUCOJIG-UHFFFAOYSA-N 4'-tert-Butyl-2',6'-dimethyl-3',5'-dinitroacetophenone Chemical compound CC(=O)C1=C(C)C([N+]([O-])=O)=C(C(C)(C)C)C([N+]([O-])=O)=C1C WXCMHFPAUCOJIG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- UUQHKWMIDYRWHH-UHFFFAOYSA-N Methyl beta-orcinolcarboxylate Chemical compound COC(=O)C1=C(C)C=C(O)C(C)=C1O UUQHKWMIDYRWHH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- KMPQYAYAQWNLME-UHFFFAOYSA-N undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
- VIINAUVGZZLXGK-WPZRUTIUSA-N (2z)-3,7-dimethylocta-2,6-dien-1-ol;(2e)-3,7-dimethylocta-2,6-dien-1-ol Chemical compound CC(C)=CCC\C(C)=C/CO.CC(C)=CCC\C(C)=C\CO VIINAUVGZZLXGK-WPZRUTIUSA-N 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N (E)-Geraniol Chemical compound CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- RLRINNKRRPQIGW-UHFFFAOYSA-N 1-ethenyl-2-[4-(2-ethenylphenyl)butyl]benzene Chemical compound C=CC1=CC=CC=C1CCCCC1=CC=CC=C1C=C RLRINNKRRPQIGW-UHFFFAOYSA-N 0.000 description 1
- UJIUKTDUCYLQBN-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)methoxymethyl]benzene Chemical compound C1=CC(C)=CC=C1COCC1=CC=C(C)C=C1 UJIUKTDUCYLQBN-UHFFFAOYSA-N 0.000 description 1
- OFHHDSQXFXLTKC-UHFFFAOYSA-N 10-undecenal Chemical compound C=CCCCCCCCCC=O OFHHDSQXFXLTKC-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- MJTPMXWJHPOWGH-UHFFFAOYSA-N 2-Phenoxyethyl isobutyrate Chemical compound CC(C)C(=O)OCCOC1=CC=CC=C1 MJTPMXWJHPOWGH-UHFFFAOYSA-N 0.000 description 1
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- KTCAZEVYBWMPOY-UHFFFAOYSA-N 2-benzylideneoctan-1-ol Chemical compound CCCCCCC(CO)=CC1=CC=CC=C1 KTCAZEVYBWMPOY-UHFFFAOYSA-N 0.000 description 1
- HGECJFVPNUYRJZ-UHFFFAOYSA-N 2-methyl-2-(4-propan-2-ylphenyl)propanal Chemical compound CC(C)C1=CC=C(C(C)(C)C=O)C=C1 HGECJFVPNUYRJZ-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- KEVYVLWNCKMXJX-UHFFFAOYSA-N 3,7,11,15-tetramethylhexadec-1-en-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)C=C KEVYVLWNCKMXJX-UHFFFAOYSA-N 0.000 description 1
- AJBZENLMTKDAEK-UHFFFAOYSA-N 3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-1,2,3,4,5,6,7,7a,9,10,11,11b,12,13,13a,13b-hexadecahydrocyclopenta[a]chrysene-4,9-diol Chemical compound CC12CCC(O)C(C)(C)C1CCC(C1(C)CC3O)(C)C2CCC1C1C3(C)CCC1C(=C)C AJBZENLMTKDAEK-UHFFFAOYSA-N 0.000 description 1
- MBZRJSQZCBXRGK-UHFFFAOYSA-N 4-tert-Butylcyclohexyl acetate Chemical compound CC(=O)OC1CCC(C(C)(C)C)CC1 MBZRJSQZCBXRGK-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 244000144927 Aloe barbadensis Species 0.000 description 1
- 235000002961 Aloe barbadensis Nutrition 0.000 description 1
- 235000009051 Ambrosia paniculata var. peruviana Nutrition 0.000 description 1
- 241000086254 Arnica montana Species 0.000 description 1
- 235000003097 Artemisia absinthium Nutrition 0.000 description 1
- 240000001851 Artemisia dracunculus Species 0.000 description 1
- 235000017731 Artemisia dracunculus ssp. dracunculus Nutrition 0.000 description 1
- 235000003261 Artemisia vulgaris Nutrition 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 235000003880 Calendula Nutrition 0.000 description 1
- 240000001432 Calendula officinalis Species 0.000 description 1
- 240000007436 Cananga odorata Species 0.000 description 1
- 244000037364 Cinnamomum aromaticum Species 0.000 description 1
- 235000014489 Cinnamomum aromaticum Nutrition 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 208000001840 Dandruff Diseases 0.000 description 1
- 244000133098 Echinacea angustifolia Species 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 1
- 239000001653 FEMA 3120 Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 229930186217 Glycolipid Natural products 0.000 description 1
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 240000004371 Panax ginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 235000004347 Perilla Nutrition 0.000 description 1
- 244000124853 Perilla frutescens Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 244000126014 Valeriana officinalis Species 0.000 description 1
- 235000013832 Valeriana officinalis Nutrition 0.000 description 1
- 235000004552 Yucca aloifolia Nutrition 0.000 description 1
- 235000012044 Yucca brevifolia Nutrition 0.000 description 1
- 235000017049 Yucca glauca Nutrition 0.000 description 1
- 240000005780 Yucca gloriosa Species 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 235000011399 aloe vera Nutrition 0.000 description 1
- GUUHFMWKWLOQMM-NTCAYCPXSA-N alpha-hexylcinnamaldehyde Chemical compound CCCCCC\C(C=O)=C/C1=CC=CC=C1 GUUHFMWKWLOQMM-NTCAYCPXSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010478 argan oil Substances 0.000 description 1
- 239000001138 artemisia absinthium Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PCWZHTGDXLRULT-UHFFFAOYSA-N buta-1,3-dienylbenzene styrene Chemical compound C(=C)C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 PCWZHTGDXLRULT-UHFFFAOYSA-N 0.000 description 1
- 239000007963 capsule composition Substances 0.000 description 1
- 229940106189 ceramide Drugs 0.000 description 1
- 150000001783 ceramides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GUDMZGLFZNLYEY-UHFFFAOYSA-N cyclopropylmethanol Chemical compound OCC1CC1 GUDMZGLFZNLYEY-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000014134 echinacea Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010642 eucalyptus oil Substances 0.000 description 1
- 229940044949 eucalyptus oil Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid group Chemical group C(CCCCCC)(=O)O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 239000010656 jasmine oil Substances 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HIGQPQRQIQDZMP-FLIBITNWSA-N neryl acetate Chemical compound CC(C)=CCC\C(C)=C/COC(C)=O HIGQPQRQIQDZMP-FLIBITNWSA-N 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000010668 rosemary oil Substances 0.000 description 1
- 229940058206 rosemary oil Drugs 0.000 description 1
- 239000010671 sandalwood oil Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003408 sphingolipids Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010677 tea tree oil Substances 0.000 description 1
- 229940111630 tea tree oil Drugs 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010678 thyme oil Substances 0.000 description 1
- 150000003648 triterpenes Chemical class 0.000 description 1
- 235000016788 valerian Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The application provides a composite core wall microcapsule, a preparation method and application thereof. The composite core wall microcapsule comprises an oily core material and a polymer wall material coated on the outer layer of the oily core material; the polymeric wall material includes polymeric emulsifiers, polyurethanes, and polyureas. The application provides a novel microcapsule wall material for essence/cosmetics encapsulation, which can encapsulate oily core materials containing various aldehyde compounds, and the related core-wall microcapsule is compounded with various wall materials, and polymer emulsifying agents in the wall materials are tightly connected through covalent bonds, so that the microcapsule wall material has higher stability in a detergent compared with other polyurethane/polyurea essence microcapsules.
Description
Technical Field
The application relates to the technical field of daily chemical products, in particular to a composite core wall microcapsule, a preparation method and application thereof.
Background
In order to maintain the stability and functional properties of the functional material in consumer products, especially solve the problem of stable storage in daily chemical products such as detergents, body washes and the like, microcapsule packaging technology is often adopted, functional material essence/cosmetic raw materials are embedded in wall materials, so that the functional material essence/cosmetic raw materials are isolated from the surrounding environment, chemical and physical reactions are avoided, and the stability of the functional material essence/cosmetic raw materials is prolonged; the release of the functional material is achieved by friction or the like after the microcapsules are deposited on a substrate such as fabric, hair, skin or the like.
In addition, the amount of functionality added to these consumer products can be greatly reduced, as the encapsulation of the microcapsules slows down the volatilization of the functional material and makes the use of the functional material more efficient by the directional release of the microcapsules. In addition, the excellent experience of post-consumer harvesting with this type of consumer product can reduce the number of consumer washing or cosmetic uses, thereby playing a natural resource saving role.
At present, the microcapsule shell wall material of the microcapsule which is most widely applied in detergents on the market is an aminoplast resin wall material, and the microcapsule has excellent wrapping property and friction aroma release effect on essence, but the wall material has poor wrapping property on essence with higher aldehyde compound content.
WO2020/233887 discloses a perfume core-wall microcapsule using polymer ZeMac 400 as polymer stabilizer. The microcapsule has fragrance releasing property equivalent to that of an aminoplast type resin wall material, but the problem of stability in washing products is not solved.
CN105722495a discloses a polyurea or polyurethane capsule composition. These compositions contain a plurality of capsules and a capsule forming aid, wherein each capsule contains a polyurea or polyurethane wall and an oil core; the polyurea or polyurethane wall is formed from the reaction product of a polyisocyanate and a crosslinker in the presence of a capsule forming aid; and the oil core contains an active substance, but its stability in detergents is poor.
CN113557082a discloses a microcapsule having: an oil-based core comprising a hydrophobic material, the first material being a coacervate comprising a first polyelectrolyte and a second polyelectrolyte, wherein the first polyelectrolyte is selected from the group consisting of proteins, polypeptides, polysaccharides, or mixtures thereof, and wherein the second polyelectrolyte is selected from the group consisting of acacia, xanthan, and the like; the second material is a polymeric material. Wherein the second material is selected from the group consisting of: polyureas, polyesters, polyurethanes, polyamides, but the problem of their stability in washing products is not solved.
In view of this, the present application has been made.
Disclosure of Invention
One of the purposes of the application is to provide a composite core wall microcapsule, which comprises an oily core material and a polymer wall material coated on the outer layer of the oily core material; the polymeric wall material includes polymeric emulsifiers, polyurethanes, and polyureas. According to the application, the polymer emulsifier, polyurethane and polyurea are tightly bonded, so that the coating property of the polymer wall material is greatly improved, and the stability of the polymer wall material in a washing product is greatly improved.
The second object of the present application is to provide a method for preparing the composite core wall microcapsule, which comprises the following steps: respectively preparing an oil phase containing the oil core material and a water phase containing the polymer emulsifier, emulsifying, and then performing polycondensation to form a polyurethane and polyurea mixed layer, thereby obtaining the composite core wall microcapsule.
The application also aims at the application of the composite core wall microcapsule in preparing a detergent.
In order to achieve the above object of the present application, the following technical solutions are specifically adopted:
in a first aspect, the present application provides a composite core wall microcapsule, the composite core wall microcapsule includes an oily core material and a polymer wall material coated on an outer layer of the oily core material;
the polymeric wall material includes polymeric emulsifiers, polyurethanes, and polyureas.
In the application, the polymer emulsifier, polyurethane and polyurea are tightly bonded, so that the coating property of the polymer wall material is greatly improved, and the stability of the polymer wall material in a washing product is greatly improved. Core wall microcapsules are obtained by forming an encapsulating wall around the oil droplets dispersed in the aqueous phase in the form of an oil-in-water emulsion. The size of the microcapsules affects the deposition and release properties of the microcapsules on substrates such as textiles, hair, skin, etc.
Preferably, the polymer wall material comprises a polymer emulsion layer, a polyurethane and polyurea mixed layer from inside to outside.
Preferably, the polymer emulsifier comprises polyvinyl alcohol and polysiloxane, wherein the polysiloxane and the polyvinyl alcohol are connected through epoxy groups and hydroxyl groups.
Preferably, the polysiloxane is formed by polycondensation of epoxysiloxanes.
Preferably, the polyurethane is formed by polycondensation of polyvinyl alcohol and a polyisocyanate-based compound.
Preferably, the polyurea is formed by polycondensation of a polyisocyanate-based compound and an amine-based compound, or the polyurea is formed by polycondensation of a polyisocyanate-based compound, an amine-based compound and an alcohol-based compound.
Preferably, the polymer wall material comprises a polysiloxane layer, a polyvinyl alcohol layer, a polyurethane and polyurea mixed layer from inside to outside.
In the application, the polymer emulsifier is formed by combining polyvinyl alcohol and epoxy siloxane, the polysiloxane layer and the polyvinyl alcohol layer can be tightly connected through the reaction between epoxy groups and hydroxyl groups, meanwhile, the polyvinyl alcohol and polyisocyanate-based compound are polymerized to form polyurethane, the polyisocyanate-based compound is condensed with amine-based compound to form polyurea, each layer is tightly connected through chemical bonds, and a microcapsule structure of coating oily core materials by three layers of polymer wall materials is formed, so that the strength of the polymer wall materials is further improved, the core materials are tightly packed, the produced microcapsule can be well stabilized, and leakage is not easy to occur.
Preferably, the alcoholysis degree of the polyvinyl alcohol is 73 to 99%, for example, 73%, 75%, 80%, 85%, 90%, 95%, 99%, etc., and the molecular weight of the polyvinyl alcohol is 10000 to 250000, for example, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 120000, 130000, 140000, 150000, 160000, 170000, 180000, 190000, 200000, 210000, 220000, 230000, 240000, 250000, etc.
In the present application, polyvinyl alcohol is obtained by alcoholysis of polyvinyl acetate, and the alcoholysis degree refers to the percentage of the number of vinyl alcohol units in a molecular chain to the total number of molecular structural units.
Among them, the alcoholysis degree of polyvinyl alcohol is more preferably in the range of 73% to 88%, and the alcoholysis degree is more preferably 88%.
Among them, the polyvinyl alcohol has a more preferable molecular weight range of 14000 to 205000, and a more preferable molecular weight range of 30000 to 205000.
Preferably, the epoxysiloxane has the structure shown in formula I below:
CH 2 OCHR 1 XR 2 Si(OR 3 ) 3-n (R 4 ) n i is a kind of
Wherein R is 1 Selected from linear or branched alkyl groups having 1 to 6 carbon atoms, R 2 Selected from linear or branched alkyl groups of 1 to 6 carbon atoms, R 3 Selected from H or straight-chain or branched alkyl having 1 to 4 carbon atoms, R 4 Selected from linear or branched alkyl groups having 1 to 4 carbon atoms, X is selected from O, S, CH 2 Or c=o, n is 0, 1 or 2.
Preferably, the epoxysiloxane is selected from any one or a combination of at least two of (3-glycidoxy) trimethoxysilane, epoxybutyltrimethoxysilane or 5, 6-epoxyhexyltriethoxysilane.
Preferably, the amine compound is selected from polyamine polymers and/or small molecule polyamines.
Preferably, the polyamine polymer is selected from the group consisting of polyacetylimines.
Preferably, the molecular weight of the polyacetylimide is 300-250000, and for example, 300, 1000, 2000, 5000, 8000, 10000, 20000, 30000, 40000, 50000, 60000, 80000, 100000, 120000, 150000, 200000, 250000, and the like can be used.
Preferably, the small molecule polyamine is a small molecule compound containing more than two amine groups, preferably diethylenetriamine and/or triethylenetetramine.
Preferably, the alcohol compound is a small molecule polyol.
Preferably, the small molecule polyol is a small molecule compound containing more than two alcohol groups, preferably diethanolamine and/or triethanolamine.
Preferably, the polyisocyanate-based compound is a compound containing two or more isocyanate groups, preferably anionically modified Hexamethylene Diisocyanate (HDI) - ) Any one or a combination of at least two of dicyclohexylmethane-4, 4' -diisocyanate (HMDI) or isophorone diisocyanate (IPDI).
Preferably, the mass ratio of the polymer wall material of the outer layer of the oily core material is (2.05-5.05): 1, for example, 2.05:1, 2.55:1, 3.05:1, 3.55:1, 4.05:1, 4.55:1, 5.05:1, etc.
Preferably, the polymer wall material is prepared from the following raw materials in percentage by mass:
the polyvinyl alcohol content is 5 to 25%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., preferably 8.6 to 20.2%, based on 100% by mass of the total raw material for preparing the polymer wall material.
The epoxysiloxane content is 0.1 to 15%, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., preferably 0.1 to 12.1%, based on 100% by mass of the total raw material for producing the polymer wall material.
The content of the polyisocyanate-based compound is 40 to 70%, for example, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, etc., preferably 49 to 69%, based on 100% by mass of the total raw material for producing the polymer wall material.
The amine compound may be contained in an amount of 5 to 25%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., preferably 5.2 to 21.2% based on 100% by mass of the total raw material for producing the polymer wall material.
Preferably, the preparation raw material of the polymer wall material further comprises an amphoteric polymer.
Preferably, the amphoteric polymer is an amphoteric polymer whose cation is a quaternary ammonium group, preferably a dimethyl-dipropyleneammonium chloride-acrylic acid copolymer.
Preferably, the amphoteric polymer is added in an amount of 0-25% by weight of the total mass of the preparation raw materials of the polymer wall material, for example, 0.1%, 0.5%, 1%, 2%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% and the like.
Preferably, the oily core material at least comprises one essence or/and one cosmetic ingredient.
Preferably, the method comprises the steps of, the essence is selected from benzyl benzoate, benzyl acetate, methyl 3-oxo-2-pentylcyclovalerate, 4-tert-butylcyclohexyl acetate, 2-methyl-propionic acid-2-phenoxyethyl ester, heptanoic acid-2-propylene ester, (3-methylbutoxy) -acetic acid-2-propenol ester, linalyl acetate, 2- (benzylidene) octanol, 2, 6-dimethyl-7-octen-2-ol, 3, 7-dimethyl-3-octanol, terpineol, 3, 7-dimethyl-6-octen-1-ol, phenethyl alcohol, (E) -3, 7-dimethyl-2, 6-octadien-1-ol (Z) -3, 7-dimethyl-2, 6-octadien-1-ol, 4- (1, 1-dimethylethyl) -alpha-methyl-phenylpropionaldehyde, dodecanal, beta- (3, 4-methylenedioxy) phenyl-alpha-methylpropanal, 10-undecenal, alpha-methyl-4- (1-methylethyl) phenylpropionaldehyde, 1- (1, 2,3,4,5,6,7,8 a-octahydro-2, 3, 8-tetramethyl-2-naphthyl) ethanone, (R-) 1-methyl-4- (1-methylethenyl) cyclohexene, diphenyl ether, (E) -3, 7-dimethyl-2, 6-octadien-1-ol acetate, benzyl benzoate, neryl acetate, 2, 6-dimethyl-7-octen-2-ol, (E) -3, 7-dimethyl-2, 6-octadien-1-ol, 3,7,11, 15-tetramethyl-1-hexadecen-3-ol, 1-methyl-2- [ (1, 2-trimethylbicyclo [3,1,0] hex-3-yl) methyl ] cyclopropylmethanol, beta- (3, 4-methylenedioxy) phenyl-alpha-methylpropal, alpha-methyl-4- (1-methylethyl) phenylpropionalal, 6-pentyl-2H-tetrahydropyran-2-one, 1- [4- (1, 1-dimethylethyl) -2, 6-dimethyl-3, 5-dinitrophenyl ] ethanone, 4-methylbenzyl ether, 6-dimethyl-2-bicyclo [3.1.1] -heptane, 1-methyl-4- (1-methylethyl) -1, 4-cyclohexadiene, alpha-pinene, 3a, 6,7 a-hexahydro-2-one, 6-hydroxyphenylethyl propionate, 1-hydroxy-7-2-ethyl-7-phenylpropionate, 1-hydroxy-2-methyl-7-ethyl-7-phenylpropionate, 6-hydroxy-1-ethyl-7-phenylpropionate, 1-hydroxy-4-methyl-7-2-oxonate, 6-hydroxy-ethyl-7-phenylpropionate, 1-hydroxy-ethyl-2-propionate, methyl 2, 4-dihydroxy-3, 6-dimethylbenzoate, 2-propenyl hexanoate, 3, 7-dimethyl-1, 6-octadien-3-ol, terpineol, 3, 7-dimethyl-3-octanol, 3-phenyl-2-propen-1-ol, phenethyl alcohol, 4- (1, 1-dimethylethyl) -alpha-methyl-phenylpropionaldehyde, 3-phenyl-2-propenal, 10-undecylaldehyde, 1, 3-benzodioxole-5-carbaldehyde, undecylaldehyde, dodecanal, 2- (phenylmethylene) octanal, 2H-1-benzopyran-2-one, 1- [4- (1, 1-dimethylethyl) -2, 6-dimethyl-3, 5-dinitrophenyl ] ethanone, 1,3,4,6,7,8-hexahydro-4, 6,7, 8-hexamethylcyclopenta [ g ] -2-benzopyran or 1, 3-trimethyl-2-oxabicyclo [2.2.2] octane.
Preferably, the cosmetic ingredient has a calculated octanol/water partition coefficient (ClogP) of 1.5 or more (for example, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5,6,7, 9, etc.), more preferably 3 or more, still more preferably 2 to 7.
Preferably, the cosmetic ingredient may be selected from any one or a combination of at least two of an emollient, a smoothing active, a hydrating active, a smoothing and soothing active, a decorative active, an anti-aging active, a drainage active, a reshaping active, a skin leveling active, a preservative, an antioxidant active, an antibacterial or bacteriostatic active, a cleansing active, a lubricating active, a structuring active, a hair conditioning active, a whitening active, a texturing active, a softening active, an anti-dandruff active, or an exfoliating active.
Preferably, the cosmetic ingredients include, but are not limited to, hydrophobic polymers such as alkyl dimethicones, polymethylsilsesquioxanes, polyethylenes, polyisobutylenes, styrene vinyl styrene and styrene butylene styrene block copolymers, mineral oils such as hydrogenated isoparaffins, silicones, vegetable oils such as argan oil, jojoba oil, aloe vera oil, fatty acids and fatty alcohols and esters thereof, glycolipids, phospholipids, sphingolipids such as ceramides, sterols, terpenes, sesquiterpenes, triterpenes and derivatives thereof, essential oils such as arnica oil, artefact oil, tree bark oil, birch leaf oil, calendula oil, cassia oil, echinacea oil, eucalyptus oil, ginseng oil, jujube oil, sunflower oil, jasmine oil, lavender oil, lotus seed oil, perilla oil, rosemary oil, sandalwood oil, tea tree oil, thyme oil, valerian oil, wormwood oil, ylang-ylang oil or yucca oil, or a combination of at least two of any of the foregoing.
In a second aspect, the present application provides a method for preparing a composite core wall microcapsule according to the first aspect, the method comprising:
respectively preparing an oil phase containing the oil core material and a water phase containing the polymer emulsifier, emulsifying, and then performing polycondensation to form a polyurethane and polyurea mixed layer, thereby obtaining the composite core wall microcapsule.
Preferably, the preparation method specifically comprises the following steps:
configuration of oil phase: mixing epoxy siloxane and an oily core material to obtain an oil phase O;
configuration of aqueous phase: mixing polyvinyl alcohol and water to obtain a water phase W;
emulsification: mixing the oil phase O and the water phase W, and emulsifying to obtain an emulsion;
polycondensation: firstly, carrying out polycondensation reaction on the emulsion and a polyisocyanate-based compound, and then carrying out polycondensation reaction on the emulsion and an amine-based compound to form a polyurethane and polyurea mixed layer, thereby obtaining the composite core wall microcapsule.
Preferably, the mass ratio of polyvinyl alcohol to water is 1 (10-35), which may be, for example, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:32, 1:35, etc.
The mixing temperature of the oil phase is preferably 10 to 30 ℃, and may be, for example, 10 ℃, 12 ℃, 14 ℃, 16 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, or the like.
The temperature of the aqueous phase is preferably 75 to 85 ℃, and may be, for example, 75 ℃, 76 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, or the like.
Preferably, the temperature of the mixture in the emulsification is 60 to 70 ℃, and for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃ and the like can be used.
Preferably, the emulsification is carried out by stirring at a speed of 300-400rpm, for example, 300rpm, 320rpm, 340rpm, 360rpm, 380rpm, 400rpm, etc.
Preferably, water and/or lye is added to the emulsion obtained by emulsification.
Preferably, the lye is an aqueous sodium hydroxide solution having a solids content of 0.5-2%, for example, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, etc.
Preferably, the mass ratio of the emulsion to the water to the alkali liquor is (50-55): 10-30): 0.1-1;
wherein, "50-55" may be, for example, 50, 51, 52, 53, 54, 55, etc.;
wherein, "10-30" may be, for example, 10, 15, 20, 25, 30, etc.;
the term "0.1 to 1" may be, for example, 0.1, 0.2, 0.4, 0.6, 0.8, 1, etc.
Preferably, the specific process of polycondensation is as follows: dropping a polyisocyanate-based compound into the emulsion and stirring at 20 to 30 ℃ (for example, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃ and the like) at a rotation speed of 200 to 300rpm (for example, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm and the like) for 1 to 3 hours (for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours and the like); then, the amine compound is added dropwise at 20 to 30℃such as 20℃at 22℃at 24℃at 26℃at 28℃at 30℃and the like, followed by heating to 65 to 75℃such as 65℃at 66℃at 68℃at 70℃at 72℃at 75℃and stirring at 200 to 300rpm such as 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm and the like for 1 to 3 hours such as 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours and the like.
Preferably, the polycondensation further comprises: the reaction mixture obtained by polycondensation and the amphoteric polymer are mixed and stirred at 65 to 75℃such as 65℃and 66℃and 68℃and 70℃and 72℃and 75℃for 1 to 3 hours (for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, etc.) at 200 to 300rpm (for example, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, etc.).
In a third aspect, the present application provides the use of a composite core wall microcapsule according to the first aspect of the claims for the preparation of a detergent.
In the present application, the composite core wall microcapsules can be added to consumer products, wherein the consumer products include fabric care detergents and conditioners, hair care conditioners, shampoos, heavy duty liquid detergents, hard surface cleaners, laundry powders, soaps, body washes and skin care products.
[ PREPARATION ] A method for producing a polypeptide
In the context of the present application, the term "polymeric emulsifier" refers to a polymer which, when dissolved in one or both of the oil and water phases, is capable of reducing the interfacial tension between the oil and water phases.
In the context of the present application, the term "emulsion" refers to the phenomenon of liquid-liquid interface in which one liquid can be dispersed into another, immiscible liquid under the action of a surfactant.
In the context of the present application, the term "emulsion" refers to a stable, homogeneous mixture of two or more immiscible liquids formed after emulsification, in which the dispersed phase is present in the continuous phase in the form of droplets. If the two phases are mixed and stirred to form a uniform mixture in the presence of the polymer emulsifier, the uniform mixture during stirring cannot be called an emulsion and is considered to be emulsion failure once the two phases are obviously layered after stirring is stopped.
In the present application, the product of the core-wall microcapsules is in an emulsion state. After the polymer emulsifier is added, emulsion is formed, if small liquid drops originally dispersed in the emulsion are mutually attracted to form large particles in the subsequent feeding or reaction process, the flowable emulsion becomes a non-flowable solid at the moment, and the phenomenon of agglomeration solidification is considered to appear, and the core-wall microcapsule synthesis is considered to be failed.
In the context of the present application, the term "alkyl" is meant to include both branched and straight chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. For example, a group having 1,2,3,4,5, or 6 carbon atoms in a straight or branched chain structure is defined to include "straight or branched chain alkyl group having 1 to 6 carbon atoms". For example, in the present application, the straight-chain or branched alkyl groups having 1 to 6 carbon atoms are each independently methyl, ethyl, propyl, butyl, pentyl or hexyl; wherein propyl is C3 alkyl (including isomers such as n-propyl or isopropyl); butyl is C4 alkyl (including isomers such as n-butyl, sec-butyl, isobutyl, or tert-butyl); pentyl is C5 alkyl (including isomers such as n-pentyl, 1-methyl-butyl, 1-ethyl-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, isopentyl, t-pentyl or neopentyl); hexyl is C6 alkyl (including isomers such as n-hexyl or isohexyl).
In the context of the present application, the term "epoxysiloxane" means a polymer comprising at least one epoxy group and at least one alkoxy silicon group.
In the context of the present application, the term "bound by … …" means that interactions between the polymeric emulsifier and the epoxysiloxane, such as electrostatic forces, hydrogen bonds, covalent bonds, act to jointly reduce the surface tension between the oil and water phases.
In the present application, the polymeric emulsifier is a combination of hydroxyl groups of polyvinyl alcohol and epoxy groups of an epoxysilane in the manner mentioned above, which interact with each other to form covalent bonds.
Compared with the prior art, the application has the following beneficial effects:
(1) The application provides a novel microcapsule wall material for essence/cosmetic wrapping, which can wrap an oily core material containing various aldehyde compounds;
(2) The core-wall microcapsule is compounded with a plurality of wall materials, and polymer emulsifying agents in the wall materials are tightly connected through covalent bonds, so that the core-wall microcapsule has higher stability in a detergent compared with other polyurethane/polyurea essence microcapsules.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a composite core wall microcapsule structure provided by the application;
wherein 1 is an oily core material, 2 is a polysiloxane layer, 3 is a polyvinyl alcohol layer, and 4 is a polyurethane and polyurea mixed layer.
FIG. 2 is a graph of IR spectrum contrast of polyvinyl alcohol, (3-glycidoxy) trimethoxysilane and polymer emulsifier.
Detailed Description
Unless defined otherwise herein, scientific and technical terms used in connection with the present application shall have the meanings commonly understood by one of ordinary skill in the art. The meaning and scope of terms should be clear, however, in the event of any potential ambiguity, the definitions provided herein take precedence over any dictionary or extraneous definition. In the present application, the use of "or" means "and/or" unless stated otherwise. Furthermore, the use of the term "include" and other forms is not limiting.
Generally, the nomenclature used in connection with the cell and tissue culture, molecular biology, immunology, microbiology, genetics, and protein and nucleic acid chemistry and hybridization described herein and the techniques thereof are those well known and commonly employed in the art. Unless otherwise indicated, the methods and techniques of the present application are generally well known in the art and are performed according to conventional methods as described in various general and more specific references cited and discussed throughout the present specification. Enzymatic reactions and purification techniques are performed according to manufacturer's instructions, as commonly accomplished in the art, or as described herein. Nomenclature used in connection with the analytical chemistry, synthetic organic chemistry, and medical and pharmaceutical chemistry described herein, and the laboratory procedures and techniques therefor, are those well known and commonly employed in the art.
The technical solutions of the present application will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
The raw material names and terms in the following examples are shown below in comparison with the following examples
Abbreviation of Compounds terminology
PVA polyvinyl alcohol
GPTS (3-glycidoxy) trimethoxysilane
HMDI 4,4' -dicyclohexylmethane diisocyanate
HDI - Anionically modified diisocyanate compounds
IPDI isophorone diisocyanate
PEI polyethylenimine
FIG. 1 is a schematic diagram of a composite core wall microcapsule structure provided by the application; as shown in fig. 1, the composite core wall microcapsule comprises an oily core material and a polymer wall material coated on the outer layer of the oily core material 1; the polymer wall material sequentially comprises a polysiloxane layer 2, a polyvinyl alcohol layer 3 and a polyurethane and polyurea mixed layer 4 from inside to outside.
FIG. 2 is a graph of IR spectrum contrast of polyvinyl alcohol, (3-glycidoxy) trimethoxysilane and polymer emulsifier. As shown in fig. 2, the polymeric emulsifier is formed by bonding between the hydroxyl groups of the polyvinyl alcohol and the epoxy groups of the epoxysilane in the manner mentioned above, which interact with each other to form covalent bonds. The results of the IR spectrum show that, in the polymer emulsifier, the raw material (3-glycidoxy) trimethoxysilane is present at 819cm -1 780cm -1 The peak of the stretching vibration and bending vibration of the ethylene oxide ternary ring disappears, while the peak of the polyvinyl alcohol remains unchanged, which means that the epoxy group is subjected to ring-opening reaction and modified into the polyvinyl alcohol. In the present application, after the polymeric emulsifier is formed, the siloxane groups in the polymeric emulsifier undergo polycondensation to form a polysiloxane. The infrared spectrum results show that the polymer emulsifier is 1093cm -1 、1020cm -1 There appears a distinct polysiloxane telescopic vibration absorption peak confirming the polycondensation reaction of the siloxanes.
Examples 1 to 8
Examples 1-8 provide composite core wall microcapsules prepared from different materials, the specific material usage details are shown in Table 1 below (average molecular weight 74800G/mol for PVA1788 in the examples below, degree of alcoholysis 88%, average molecular weight for PEI is 2000G/mol, fragrances are available from Qi Hua Du fragrance and flavor company under the trade designation Pure Life 2G):
TABLE 1
Examples 1-8 above were each prepared as follows:
(1) Dissolving epoxy siloxane in essence and/or cosmetics according to the formula amount of Table 1, slowly stirring with a glass rod until the solution is uniform, and obtaining oil phase O;
(2) Adding polyvinyl alcohol into 25g of hot water at 80 ℃, slowly stirring with a glass rod until the solution becomes a uniform, colorless and transparent solution, and obtaining a water phase W;
(3) Cooling the water phase W to 65 ℃, mixing the oil phase O and the water phase W, stirring with a stirring rod at a rotating speed of 350rpm until a uniform milky opaque flowable liquid system called emulsion is formed, and adding 15mL of water and 0.5g of 1% NaOH aqueous solution after the emulsion is considered to be successful;
(4) Cooling to room temperature, adding the polyisocyanate-based compound, stirring at a rotation speed of 250rpm, and maintaining for 2 hours;
(5) Polyamine polymer (24% Polyethylenimine (PEI) in water) and/or polyamine small molecules (diethylenetriamine) were added dropwise at room temperature, followed by heating to 70 ℃ and holding for 2h;
(6) 0.6g of dimethyl-dipropyleneammonium chloride/acrylic acid copolymer was added at 70℃and kept for 2 hours, and after cooling to room temperature, the mixture was discharged.
Examples 9 to 14
Examples 9 to 14 differ from example 3 only in the degree of alcoholysis and the molecular weight of the polyvinyl alcohol, and the specific raw material amounts are shown in Table 2 below:
TABLE 2
Example 15
This example provides a composite core wall microcapsule differing from example 3 only in that the small molecule polyamine compound was replaced with 0.6g of diethanolamine of equivalent mass, and the other steps were exactly the same as in example 3.
Example 16
This example provides a composite core wall microcapsule differing from example 3 only in that the small molecule polyamine compound was replaced with 0.6g of triethanolamine of equivalent mass, and the other steps were exactly the same as in example 3.
Comparative examples 1 to 4
Comparative examples 1-4 provide composite core wall microcapsules prepared from different materials, and detailed information about the amount of the materials is shown in table 3 below:
TABLE 3 Table 3
Comparative examples 1-4 were prepared in the same manner as described above for examples 1-8.
Comparative examples 5 to 6
Comparative examples 5 to 6 differ from example 3 only in the degree of alcoholysis and the molecular weight of polyvinyl alcohol, and detailed information on the amounts of raw materials used are shown in Table 4 below:
TABLE 4 Table 4
Comparative example 7
This comparative example provides a process for preparing a composite core wall microcapsule from polyvinylpyrrolidone, the process comprising the steps of:
(1) 2.0g polyvinylpyrrolidone PVP was dissolved in 50g deionized water to form aqueous phase W;
(2) Dissolving 0.5g of (3-glycidoxy) trimethoxy silane in 25g of essence, slowly stirring with a glass rod until the solution is uniform, and obtaining an oil phase O;
(3) Mixing the oil phase O and the water phase W, stirring by a stirring rod at a rotating speed of 350rpm and stirring at 350rpm, and cooling to room temperature after 1.5 h;
(4) 2.5g of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 0.8g of an anionically modified diisocyanate compound (HDI-), and stirring for 1h;
(5) 2.0g of 25% aqueous Polyethylenimine (PEI) was added dropwise at room temperature, warmed to 70℃and stirred for 2h;
(6) 0.6g of dimethyl dipropyleneammonium chloride/acrylic acid copolymer is added at 70 ℃, stirring is continued for 2 hours, cooling to room temperature is carried out, and discharging is carried out.
Since there was no chemical bond connection between polyvinylpyrrolidone and the (3-glycidoxy) trimethoxysilane mixture, the agglomeration of the microcapsules finally obtained in comparative example 7 was serious, and solid particles were produced which could be observed with naked eyes.
Test example 1
Determination of microcapsule size
Test sample: the composite core wall microcapsules provided in examples 1 to 16, the composite core wall microcapsules provided in comparative examples 1 to 4, 7;
the testing method comprises the following steps:
(1) Preparation of laundry detergent samples: diluting the microcapsule samples by deionized water for one tenth, respectively adding 1.5g of diluent into 98g of essence-free laundry detergent base material containing suspending agent, respectively adding 0.5g of wrapped essence, and stirring and mixing until the laundry detergent is observed to be in a uniform color and no agglomeration state by naked eyes to obtain a series of laundry detergent samples containing core-wall microcapsules;
(2) Determining the size and size distribution of the microcapsules:
one specific method of measuring microcapsule size is light scattering. Light scattering measurements can be made using Malvern Mastersizer2000S instruments and mie scattering theory. By experiment, a few drops of slurry were added to a degassed circulating water stream connected to a scattering cell. Under this dilution condition, the angular distribution of scattering intensity was measured and analyzed by Malvern copyrighted software attached to the apparatus to provide the average size and size distribution of the droplets present in the sample. In the case of unimodal (monodisperse) droplet distributions, the percentiles Dv (10), dv (50) and Dv (90) are used as a representation of the droplet size distribution, whereas Dv (50) corresponds to the median value of the distribution and is taken as a measure of the volume average size of the microcapsules. In the present application, the microcapsule size is considered to be too large when Dv (50) >30 μm and too small when Dv (50) <2 μm, according to the experience of those skilled in the art.
The specific test results are shown in table 5 below:
TABLE 5
As can be seen from the test data in Table 5, the microcapsule D50 prepared in the present application is 5-30. Mu.m, and the microcapsule size is too large for the comparative example 3 sample because the amount of the polyvinyl alcohol added is too small. For the sample of comparative example 4, the microcapsule size was too small due to the excessive amount of polyvinyl alcohol added. For the sample of comparative example 7, the microcapsule size was too large because the product had agglomerated.
Test example 2
Release Performance test of microcapsules
Test sample: the composite core wall microcapsules provided in examples 1 to 16, the composite core wall microcapsules provided in comparative examples 1 to 4, 7;
the test principle is as follows: when the core material of the core-wall microcapsule is essence, the release performance of the microcapsule can be determined by testing the friction release performance of the core-wall microcapsule. The friction release properties of the core-wall microcapsules were evaluated by comparing the degree of fragrance before and after rubbing of the samples after consumer product use.
Fragrance intensity was assessed by a panel of 4 experts, ranging from 1 to 10. A difference between the fragrance levels before and after rubbing of 4 or more is considered to be excellent in the friction releasing property, corresponding to the high releasing property of the microcapsules. A fragrance level after rubbing of less than 4 is considered to be poor in the friction release properties, corresponding to the low release properties of microcapsules.
The fragrance evaluation criteria are shown in Table 5 below:
TABLE 5
The stability of the core-wall microcapsule refers to the change condition of the appearance of the consumer product and the retention condition of the release performance of the microcapsule after the microcapsule is stored in the consumer product, such as bath lotion and laundry detergent, and the stability of the core-wall microcapsule is high if the appearance of the consumer product is unchanged, namely the color of the consumer product is unchanged, no precipitate is separated out from the consumer product, and the release performance of the microcapsule in the consumer product still keeps good friction and fragrance release performance.
The testing method comprises the following steps: dissolving 10g of liquid laundry detergent with 2L of water, adding the towel into the liquid laundry detergent, soaking for 15min, rubbing and washing for 10 times, wringing, rinsing twice with 2L of water, naturally airing (4 h), and evaluating the fragrance of the towel before and after friction.
The specific test results are shown in table 6 below:
TABLE 6
As shown in the test results of Table 6, the composite core wall microcapsule prepared by the application has excellent release performance, and the fragrance score of the towel after being washed by the application is more than 4, and the preferable technical scheme reaches the above. Whereas the samples of comparative examples 3,4 and 7 all had too large or too small microcapsule sizes, resulting in poor release properties of the microcapsules.
Test example 3
Stability test
Test sample: the composite core wall microcapsules provided in examples 1 to 16, the composite core wall microcapsules provided in comparative examples 1 to 4, 7;
the test principle is as follows: the same as in test example 2;
the testing method comprises the following steps: the laundry detergent samples of the microcapsule samples were placed at room temperature, 40 ℃ and 45 ℃ for 14 days, respectively. The appearance of all the liquid laundry detergent containing the microcapsules is not obviously changed after the liquid laundry detergent is taken out. Microcapsule release performance test was performed: dissolving 10g of liquid laundry detergent with 2L of water, adding the towel into the liquid laundry detergent, soaking for 15min, rubbing and washing for 10 times, wringing, rinsing twice with 2L of water, naturally airing (4 h), and evaluating the fragrance intensity of the towel before and after friction.
The specific test results are shown in table 7 below:
TABLE 7
As shown in the test results of Table 7, the core-wall microcapsules of the present application have a plurality of wall materials, and the polymer emulsifiers in the wall materials are tightly connected through covalent bonds, so that the core-wall microcapsules have higher stability in detergents than other polyurethane/polyurea type essence microcapsules.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (10)
1. The composite core wall microcapsule is characterized by comprising an oily core material and a polymer wall material coated on the outer layer of the oily core material;
the polymeric wall material includes polymeric emulsifiers, polyurethanes, and polyureas.
2. The composite core wall microcapsule according to claim 1, wherein the polymeric wall material comprises, in order from inside to outside, a polymeric emulsifier layer, a polyurethane and polyurea blend layer;
preferably, the polymer emulsifier comprises polyvinyl alcohol and polysiloxane, wherein the polysiloxane and the polyvinyl alcohol are connected through epoxy groups and hydroxyl groups;
preferably, the polysiloxane is formed by polycondensation of epoxysiloxane;
preferably, the polyurethane is formed by polycondensation of polyvinyl alcohol and a polyisocyanate-based compound;
preferably, the polyurea is formed by polycondensation of a polyisocyanate-based compound and an amine-based compound, or the polyurea is formed by polycondensation of a polyisocyanate-based compound, an amine-based compound and an alcohol-based compound;
preferably, the polymer wall material comprises a polysiloxane layer, a polyvinyl alcohol layer, a polyurethane and polyurea mixed layer from inside to outside.
3. The composite core wall microcapsule according to claim 2, wherein the degree of alcoholysis of the polyvinyl alcohol is 73-88%, and the molecular weight of the polyvinyl alcohol is 14000-205000;
preferably, the epoxysiloxane has the structure shown in formula I below:
CH 2 OCHR 1 XR 2 Si(OR 3 ) 3-n (R 4 ) n i is a kind of
Wherein R is 1 Selected from linear or branched alkyl groups having 1 to 6 carbon atoms, R 2 Selected from linear or branched alkyl groups of 1 to 6 carbon atoms, R 3 Selected from H or straight-chain or branched alkyl having 1 to 4 carbon atoms, R 4 Selected from linear or branched alkyl groups having 1 to 4 carbon atoms, X is selected from O, S, CH 2 Or c=o, n is 0, 1 or 2;
preferably, the epoxysiloxane is selected from any one or a combination of at least two of (3-glycidoxy) trimethoxysilane, epoxybutyltrimethoxysilane or 5, 6-epoxyhexyltriethoxysilane.
4. The composite core wall microcapsule according to claim 2, wherein the amine compound is selected from polyamine polymers and/or small molecule polyamines;
preferably, the polyamine polymer is selected from the group consisting of polyacetylimines;
preferably, the molecular weight of the polyacetylimine is 300-250000;
preferably, the small molecule polyamine is a small molecule compound containing more than two amine groups, preferably diethylenetriamine and/or triethylenetetramine;
preferably, the alcohol compound is a small molecule polyol;
preferably, the small molecule polyol is a small molecule compound containing more than two alcohol groups, preferably diethanolamine and/or triethanolamine;
preferably, the polyisocyanate-based compound is a compound having two or more isocyanate groups, preferably any one or a combination of at least two of anionically modified hexamethylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate or isophorone diisocyanate.
5. The composite core wall microcapsule according to any one of claims 1-4, wherein the mass ratio of the polymer wall material of the outer layer of the oily core material is (2.05-5.05): 1;
preferably, the polymer wall material is prepared from the following raw materials in percentage by mass:
6. the composite core wall microcapsule according to any one of claims 1-5, wherein the polymeric wall material is prepared from a starting material further comprising an amphoteric polymer;
preferably, the amphoteric polymer is an amphoteric polymer whose cation is a quaternary ammonium group, preferably a dimethyl-dipropyleneammonium chloride-acrylic acid copolymer;
preferably, the addition amount of the amphoteric polymer accounts for 0-25% of the total mass of the preparation raw materials of the polymer wall material;
preferably, the oily core material at least comprises one essence or/and one cosmetic ingredient.
7. A method of preparing a composite core wall microcapsule according to any one of claims 1-6, comprising:
respectively preparing an oil phase containing the oil core material and a water phase containing the polymer emulsifier, emulsifying, and then performing polycondensation to form a polyurethane and polyurea mixed layer, thereby obtaining the composite core wall microcapsule.
8. The method for preparing the composite core wall microcapsule according to claim 7, characterized in that the method specifically comprises the following steps:
configuration of oil phase: mixing epoxy siloxane and an oily core material to obtain an oil phase O;
configuration of aqueous phase: mixing polyvinyl alcohol and water to obtain a water phase W;
emulsification: mixing the oil phase O and the water phase W, and emulsifying to obtain an emulsion;
polycondensation: firstly, carrying out polycondensation reaction on the emulsion and a polyisocyanate-based compound, and then carrying out polycondensation reaction on the emulsion and an amine-based compound to form a polyurethane and polyurea mixed layer, thereby obtaining the composite core wall microcapsule.
9. The method for preparing the composite core wall microcapsule according to claim 8, wherein the mass ratio of the polyvinyl alcohol to the water is 1 (10-35);
preferably, the mixing temperature of the configuration of the oil phase is 10-30 ℃;
preferably, the aqueous phase is configured at a temperature of 75-85 ℃;
preferably, the temperature of mixing in the emulsification is 60-70 ℃;
preferably, the emulsification is performed by stirring at a speed of 300-400rpm;
preferably, water and/or alkali liquor is/are added into the emulsion obtained by emulsification;
preferably, the alkali liquor is sodium hydroxide aqueous solution, and the solid content of the sodium hydroxide aqueous solution is 0.5-2%;
preferably, the mass ratio of the emulsion to the water to the alkali liquor is (50-55): 10-30): 0.1-1;
preferably, the specific process of polycondensation is as follows: dropping polyisocyanate-based compound into the emulsion, and stirring at 20-30deg.C and 200-300rpm for 1-3 hr; then dropwise adding amine compounds at 20-30 ℃, then heating to 65-75 ℃, and stirring for 1-3h at a rotating speed of 200-300 rpm;
preferably, the polycondensation further comprises: mixing the reaction liquid obtained by polycondensation with amphoteric polymer, and stirring at 65-75deg.C and 200-300rpm for 1-3 hr.
10. Use of a composite core wall microcapsule according to any one of claims 1-6 in the preparation of a detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310745017.9A CN116786044A (en) | 2023-06-21 | 2023-06-21 | Composite core wall microcapsule and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310745017.9A CN116786044A (en) | 2023-06-21 | 2023-06-21 | Composite core wall microcapsule and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116786044A true CN116786044A (en) | 2023-09-22 |
Family
ID=88039248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310745017.9A Pending CN116786044A (en) | 2023-06-21 | 2023-06-21 | Composite core wall microcapsule and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116786044A (en) |
-
2023
- 2023-06-21 CN CN202310745017.9A patent/CN116786044A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11382845B2 (en) | Organic compounds | |
| CN102256588B (en) | Microcapsules and uses thereof | |
| US20220202665A1 (en) | Core-shell encapsulate composition comprising a benefit agent | |
| EP2349551A1 (en) | Benefit agent containing delivery particle | |
| BR112020012385A2 (en) | encapsulated perfume composition and methods for preparing them | |
| US20230166230A1 (en) | Encapsulated composition comprising core-shell microcapsules and process for its preparation | |
| JP7496777B2 (en) | Improvements in or relating to organic compounds | |
| EP3497191A1 (en) | Improvements in or relating to organic compounds | |
| KR20240048014A (en) | Improvements in and related to organic compounds | |
| CN112739454A (en) | Improvements in or relating to organic compounds | |
| JP5364305B2 (en) | Aroma-sustaining microcapsule | |
| WO2022109123A1 (en) | Biodegradable delivery particles | |
| JP2022526623A (en) | Encapsulated composition | |
| CN116786044A (en) | Composite core wall microcapsule and preparation method and application thereof | |
| EP4213979A1 (en) | Multifunctional (meth)acrylate polysaccharide microcapsules | |
| RU2810713C2 (en) | Encapsulated core-shell type composition containing beneficial agent | |
| WO2024132966A1 (en) | Microcapsules | |
| CN114340775A (en) | Improvements in or relating to organic compounds | |
| CN118251271A (en) | Improvements in or relating to organic compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |