CN106221377A - A kind of photochromic gravure water color ink and preparation method thereof - Google Patents
A kind of photochromic gravure water color ink and preparation method thereof Download PDFInfo
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- CN106221377A CN106221377A CN201610748862.1A CN201610748862A CN106221377A CN 106221377 A CN106221377 A CN 106221377A CN 201610748862 A CN201610748862 A CN 201610748862A CN 106221377 A CN106221377 A CN 106221377A
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- diatomite
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 74
- 238000001035 drying Methods 0.000 claims abstract description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 239000012860 organic pigment Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 206
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 120
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 105
- 229910052709 silver Inorganic materials 0.000 claims description 95
- 239000004332 silver Substances 0.000 claims description 95
- 229910021389 graphene Inorganic materials 0.000 claims description 94
- 239000000243 solution Substances 0.000 claims description 64
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 60
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 56
- 239000000843 powder Substances 0.000 claims description 55
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000002096 quantum dot Substances 0.000 claims description 48
- 239000000725 suspension Substances 0.000 claims description 48
- 238000004140 cleaning Methods 0.000 claims description 46
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 44
- 238000005303 weighing Methods 0.000 claims description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- 239000006185 dispersion Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 28
- 239000004408 titanium dioxide Substances 0.000 claims description 28
- 229910052681 coesite Inorganic materials 0.000 claims description 26
- 229910052906 cristobalite Inorganic materials 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 229910052682 stishovite Inorganic materials 0.000 claims description 26
- 229910052905 tridymite Inorganic materials 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 23
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 23
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 20
- 238000004381 surface treatment Methods 0.000 claims description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 229920000767 polyaniline Polymers 0.000 claims description 16
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 229910001923 silver oxide Inorganic materials 0.000 claims description 15
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 239000002274 desiccant Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013530 defoamer Substances 0.000 abstract 1
- 238000004332 deodorization Methods 0.000 abstract 1
- 239000005457 ice water Substances 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 16
- 239000012286 potassium permanganate Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 8
- 238000000502 dialysis Methods 0.000 description 8
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
- C09D11/105—Alkyd resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of photochromic gravure water color ink and preparation method thereof, described photochromic gravure water color ink is prepared by following components: water-soluble resin 70～75%, deionized water 10～15%, aqueous organic pigment 5～10%, ethanol 3～6%, kieselguhr/antibiotic complex 0.5～1%, dispersant 1～2%, drying retardant 0～1%, aqueous levelling agent 0.5～1%, water-borne wax emulsion 0.5～1%, kieselguhr/inorganic oxide 0.5 ~ 1%, organic amine 0.5～1%, defoamer 0.5～1% and photochromic complex 0.1 ~ 2%.Ink has excellent antibacterial and anti-formaldehyde and deodorization properties, has photochromic characteristic simultaneously, meets multi-functional demand, widens the application of ink further.
Description
Technical Field
The invention relates to the technical field of ink, in particular to photochromic gravure water-based ink and a preparation method thereof.
Background
The printing ink is an important material for printing packaging materials, and is used for expressing patterns and characters on printing materials by printing, and comprises main components and auxiliary components which are uniformly mixed and repeatedly rolled to form a viscous colloidal fluid; it is composed of pigment, binder and auxiliary agent; it is used for printing books, periodicals, package decoration, building decoration, etc. As social demands increase, ink varieties and yields also expand and grow accordingly. The gravure water-based ink is a novel ink which is low in toxicity, free of pungent odor, non-combustible, energy-saving and environment-friendly, but common water-based ink does not have antibacterial performance, and in order to meet the increasing health requirements of people, the gravure water-based ink with high-efficiency antibacterial performance is provided, printed matters printed by using the antibacterial water-based ink can be endowed with high-efficiency antibacterial performance, people can be prevented from being infected by germs on the printed matters when contacting the printed matters, the propagation path of the germs is effectively cut off, and the health of people is guaranteed. Meanwhile, the traditional ink has single function and can not meet the diversified requirements of people.
Disclosure of Invention
The invention aims to solve the technical problem of providing photochromic gravure water-based ink and a preparation method thereof.
The technical problem to be solved by the invention is realized by the following technical scheme:
a preparation method of photochromic gravure water-based ink comprises the following steps:
(1) putting the water-soluble resin and the diatomite/antibacterial compound into a reaction kettle, and keeping the temperature at 55-65 ℃ and the rotating speed at 800-1000 r/min;
(2) under the condition of the step (1), sequentially adding deionized water, ethanol and a dispersing agent, and mixing and stirring for 30-60 min;
(3) adding an organic pigment, adjusting the stirring speed to 1200-1500 r/min, adding the organic pigment while stirring, stirring for 30-60 min, and adding a defoaming agent and a photochromic compound; continuously stirring for 60-90 min, and grinding into standby color paste with the fineness of 20-30 mu m by a three-roll grinder;
(4) sequentially adding deionized water, ethanol, aqueous wax emulsion, diatomite/inorganic oxide, an aqueous flatting agent and a slow-drying agent into the standby color paste, stirring uniformly at the rotating speed of 1200-1500 r/min, slowly adding organic amine to adjust the pH value to 8.0-9.5, and grinding and dispersing by a three-roll grinder to achieve the fineness of 10-20 mu m;
(5) filtering and packaging the mixture prepared in the step (4) to finish the preparation; wherein,
the preparation method of the diatomite/antibacterial compound comprises the following steps: dispersing diatomite in an aqueous solution, and dropwise adding an antibacterial compound aqueous dispersion while ultrasonically stirring; standing, performing suction filtration and cleaning for multiple times, and drying to obtain a diatomite/antibacterial compound; the weight ratio of the diatomite to the antibacterial compound is 1-3: 4-6.
The preparation method of the diatomite/inorganic oxide comprises the following steps: mixing the following raw materials in percentage by weight: ZrO 25%, TiO28%, SiO 216%, V2O 54%, K2O 2%, SnO 23%, Cr2O 33%, Al2O 313%, Fe2O 311%, MgO 20%, Na2O8%, MnO 27%, and grinding in a large-flow circulating horizontal sand mill developed by PUHLER company, wherein the particle size is controlled to be 10-300 nm; dispersing diatomite in 120ml of aqueous solution, adding inorganic oxide, stirring for 2 hours at 100-200W ultrasonic speed of 100-300 rpm to allow the nano material to fully enter the diatomite pores, performing suction filtration and cleaning for many times, and drying to obtain diatomite/inorganic oxide; wherein the weight ratio of the diatomite to the inorganic oxide is 1-2: 5.
The gravure water-based ink is prepared from the following components in percentage by weight: 70-75% of water-soluble resin, 10-15% of deionized water, 5-10% of water-based organic pigment, 3-6% of ethanol, 0.5-1% of diatomite/antibacterial compound, 1-2% of dispersing agent, 0-1% of slow drying agent, 0.5-1% of water-based flatting agent, 0.5-1% of water-based wax emulsion, 0.5-1% of diatomite/inorganic oxide, 0.5-1% of organic amine, 0.5-1% of defoaming agent and 0.1-2% of photochromic compound.
The water-soluble resin is any one or combination of a plurality of water-soluble acrylic resin, water-soluble epoxy resin, water-soluble alkyd resin and the like; the water-based organic pigment is any one of benzidine yellow, transparent yellow, phthalocyanine blue, mauve F2R and the like; the organic amine is any one of N-octadecyl propylene diamine and N-cyclohexane propylene diamine, the pH value of the ink is kept between 8.0 and 9.5, the oxidative polymerization of the water-based ink and the formation of a volatile firm ink film can be delayed if the pH value is too low, and the adhesion is influenced by the fact that the ink is wet inside and dry outside if the pH value is too high; the defoaming agent is any one of tributyl phosphate, dibutyl phosphate and silicone oil and is used for eliminating bubbles. The water-based leveling agent is a water-based leveling agent HP-855; the aqueous wax emulsion is E-340FM, and the slow-drying agent is propylene glycol methyl ether. The dispersing agent is sodium hexametaphosphate, and can prevent the ink from coalescing in storage and transportation.
In the present invention, the photochromic compound is prepared as follows: under the nitrogen environment, mixing 0.05-0.5 mol/L protonic acid solution and 0.05-0.5 mol/L dodecylbenzene sulfonic acid in a volume ratio of 3: 1-3, adding photochromic powder, magnetically stirring for 60-120 min, and adding aniline, wherein the mass ratio of the photochromic powder to the aniline is 1: 5-10; continuously stirring for 60-90 min, and dropwise adding ammonium persulfate with the molar ratio of aniline to ammonium persulfate being 1: 1; reacting for 12-36 h at 20-30 ℃; washing with acetone and deionized water for several times, vacuum drying, and grinding to obtain nanometer polyaniline/photochromic powder compound; ultrasonically stirring and dispersing 1-10 g of nano polyaniline/photochromic powder composite in an aqueous solution; then adding water and ammonia water in a volume ratio of 4:1, uniformly stirring, adding ethyl orthosilicate, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, and reacting for 60-90 min; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; drying the precipitate at 90 deg.C for 3h to obtain nanometer polyaniline/photochromic powder composite/SiO2(ii) a Nano polyaniline/photochromic powder compound/SiO2Placing the mixture in an argon atmosphere for heat treatment at 800-1000 ℃ for 1-2 h to remove polyaniline and photochromic powder/porous SiO2I.e. a photochromic complex. The photochromic powder is rare earth oxide which is Nd2O3、Er2O3、Pr2O3、CeO2、Sm2O3、La2O3、Y2O3、Yb2O3At least one of them.
The antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.5-0.8 g C60 powder, weighing 50-100 ml of 98 mass percent concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 300-500 rpm to obtain a mixed solution; weighing 0.5-3 g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5-8 h; quickly adding 100-200 ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30-60 min, wherein the laser irradiation power is 1-2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (300-500W ultrasonic power, stirring speed of 200-300 rpm) 50-60 ml of graphene quantum dot suspension, dropwise adding 0.001-0.005 mol/L silver nitrate solution, controlling the reaction temperature to be 45-60 ℃, dropwise adding 0.01-0.08 mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3-4: 2-3: 1-2.
(3) Dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (500-1000W of ultrasonic power and stirring speed of 300-500 rpm); then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1-2: 1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1-3 hours, centrifuging, sequentially washing with acetone and deionized water to obtain a precipitate, and placing the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: adding 0.005-0.01 g of graphite oxide into 5Adding 0.1-0.3 g of silver-loaded graphene quantum dots into 10-10 mL of a dispersing agent (DMSO) by ultrasonic stirring (300-500W of ultrasonic power and 200-300 rpm of stirring speed), continuing to stir ultrasonically for 10-30 min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer with the microwave power of 200-400W, and reacting at 200-240 ℃ for 60-90 min; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 10-30 min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 15-30 min at 80-120 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.5-0.8 g C60 powder, weighing 50-100 ml of 98 mass percent concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 300-500 rpm to obtain a mixed solution; weighing 0.5-3 g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5-8 h; quickly adding 100-200 ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30-60 min, wherein the laser irradiation power is 1-2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (300-500W ultrasonic power, stirring speed of 200-300 rpm) 50-60 ml of graphene quantum dot suspension, dropwise adding 0.001-0.005 mol/L silver nitrate solution, controlling the reaction temperature to be 45-60 ℃, dropwise adding 0.01-0.08 mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3-4: 2-3: 1-2.
(3) Dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (500-1000W of ultrasonic power and stirring speed of 300-500 rpm); then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1-2: 1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1-3 hours, centrifuging, sequentially washing with acetone and deionized water to obtain a precipitate, and placing the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(4) Adding 0.1-0.3 mol/L titanium source (the titanium source is potassium fluotitanate, ammonium fluotitanate, isopropyl titanate or titanium tetrachloride) into 1mol/L sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (3)2Coating the silver-loaded graphene quantum dots, heating to 100-110 ℃, reacting for 2-4 h, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6h, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(5) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent (DMSO), carrying out ultrasonic stirring (300-500W of ultrasonic power and stirring speed of 200-300 rpm) and adding 0.1-0.3 g of silver-loaded/titanium dioxide graphene quantum dots, continuing to carry out ultrasonic stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, carrying out reaction for 60-90 min at 200-240 ℃ and with the microwave power of 200-400W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(6) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of graphene dispersion solution, adding the silver-loaded/titanium dioxide graphene quantum dots prepared in the step (5), ultrasonically stirring for 10-30 min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 15-30 min at 80-120 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.5-0.8 g C60 powder, weighing 50-100 ml of 98 mass percent concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 300-500 rpm to obtain a mixed solution; weighing 0.5-3 g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5-8 h; quickly adding 100-200 ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30-60 min, wherein the laser irradiation power is 1-2W.
(2) Weighing zinc oxide quantum dots (with the particle size of about 2-5 nm) to prepare a dispersion liquid with the concentration of 0.5-1 mg/ml, wherein the solvent is water; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of zinc oxide dispersion liquid, dropwise adding half of the graphene quantum dot suspension liquid prepared in the step (1), and continuously ultrasonically stirring for 30-60 min; centrifuging, cleaning and drying to obtain the graphene quantum dots loaded with zinc oxide.
(3) Surface treatment of graphene quantum dots loaded with zinc oxide: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent (DMSO), carrying out ultrasonic stirring (300-500W of ultrasonic power and stirring speed of 200-300 rpm) and adding 0.1-0.3 g of graphene quantum dots loaded with zinc oxide, continuing to carry out ultrasonic stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, carrying out reaction for 60-90 min at 200-240 ℃ and with the microwave power of 200-400W; and cooling, filtering and drying to obtain the surface-treated graphene quantum dots loaded with zinc oxide.
(4) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (300-500W ultrasonic power, stirring speed of 200-300 rpm) the other half of the graphene quantum dot suspension, dropwise adding a silver nitrate solution with the concentration of 0.001-0.005 mol/L, controlling the reaction temperature to be 45-60 ℃, dropwise adding trisodium citrate dihydrate with the concentration of 0.01-0.08 mol/L, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3-4: 2-3: 1-2.
(5) Dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (500-1000W of ultrasonic power and stirring speed of 300-500 rpm); then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1-2: 1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1-3 hours, centrifuging, sequentially washing with acetone and deionized water to obtain a precipitate, and placing the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(6) Adding 0.1-0.3 mol/L titanium source (the titanium source is potassium fluotitanate, ammonium fluotitanate, isopropyl titanate or titanium tetrachloride) into 1M sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (5)2Coating the silver-loaded graphene quantum dots, heating to 100-110 ℃, reacting for 2-4 h, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6h, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(7) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent (DMSO), carrying out ultrasonic stirring (300-500W of ultrasonic power and stirring speed of 200-300 rpm) and adding 0.1-0.3 g of silver-loaded/titanium dioxide graphene quantum dots, continuing to carry out ultrasonic stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, carrying out reaction for 60-90 min at 200-240 ℃ and with the microwave power of 200-400W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(8) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of graphene dispersion solution, adding the zinc oxide-loaded graphene quantum dots prepared in the step (3) and the silver/titanium dioxide-loaded graphene quantum dots prepared in the step (7) (the mass ratio of the two is 2: 1-3) and ultrasonically stirring for 10-30 min, then moving the mixture into a polytetrafluoroethylene reaction kettle, and keeping the temperature at 80-120 ℃ for 15-30 min; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The invention has the following beneficial effects:
according to the antibacterial compound method, the graphene quantum dots subjected to laser irradiation are used as carriers of the antibacterial agent, the surface treatment is carried out, and the graphene quantum dots are finally attached to the porous graphene, so that the antibacterial agents such as silver nanoparticles can be better loaded and fixed, the aggregation of the antibacterial agents is prevented, the stability of the antibacterial agent is remarkably improved, and the antibacterial agent has longer-acting antibacterial activity;
the main components of the inorganic oxide adopted by the invention comprise more than 10 trace elements such as magnesium, aluminum, iron and the like which are beneficial to human bodies, and the inorganic oxide is a polar crystal with a special structure, can generate electric ions for a long time and permanently release air negative ions, thereby achieving the effects of deodorizing and purifying air. The inorganic oxide is ground and then is immersed into the diatomite, so that the stability of the diatomite can be effectively improved, meanwhile, the diatomite can also adsorb harmful gases in the air, particularly formaldehyde, and the air purification effect is further improved;
the photochromic compound adopted by the invention has photochromic effect, so that the product is more colorful, and various colors which can be changed along with the difference of the intensity of the illuminating light are colorful, and the product is magnificent and colorful, and adds sentiment and artistic effect;
by reasonably matching the photochromic compound, the diatomite/antibacterial composite material, the diatomite/inorganic oxide and the functional additive, the printing ink has excellent antibacterial, anti-formaldehyde and deodorizing properties, and also has photochromic properties, so that the multifunctional requirements are met, and the application of the printing ink is further widened.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Example 1
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.5g C60 powder, weighing 50ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 0.5g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, replacing the ice water bath with a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 8 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30min, wherein the laser irradiation power is 1W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 60ml of graphene quantum dot suspension, dropwise adding 0.005mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.08mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:2: 2.
(3) Dispersing 0.5g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (1000W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 5:1, uniformly stirring, adding ethyl orthosilicate in a mass ratio of 2:1 to the silver-loaded graphene quantum dots, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃ for 3 hours; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: adding 0.005g of graphite oxide into 5mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.3g of silver-loaded graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer with microwave power of 400W, and reacting at 240 ℃ for 90 min; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.2mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 30min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Example 2
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.6g C60 powder, weighing 80ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 1g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice-water bath, changing the ice-water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 6 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 40min, wherein the laser irradiation power is 1.3W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 50ml of graphene quantum dot suspension, dropwise adding 0.003mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.05mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:3: 2.
(3) Dispersing 0.3g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (800W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 4:1, stirring uniformly, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 2:1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1.2 hours, centrifuging, sequentially cleaning with acetone and deionized water to obtain a precipitate, and putting the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: 0.008g of graphite oxide is added into 8mL of Dispersant (DMSO), ultrasonically stirred (500W ultrasonic power, stirring speed of 300 rpm) and 0.2g of silver-loaded graphene quantum dots are addedContinuing to ultrasonically stir for 30min, moving the mixture into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing the mixture, and placing the mixture into a microwave-assisted hydrothermal synthesizer, wherein the microwave power is 300W, and reacting the mixture for 60min at 220 ℃; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.5mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 30min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Example 3
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.8g C60 powder, weighing 100ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 3g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice-water bath, changing the ice-water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5 hours; quickly adding 100ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30min, wherein the laser irradiation power is 2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 60ml of graphene quantum dot suspension, dropwise adding 0.001mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.01mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 4:3: 2.
(3) Dispersing 0.5g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (500W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 3:1, stirring uniformly, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1:1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1 hour, centrifuging, sequentially cleaning with acetone and deionized water to obtain a precipitate, and putting the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: adding 0.01g of graphite oxide into 10mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.1g of silver-loaded graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer, reacting at 200 ℃ for 90min under the microwave power of 200W; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.8mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 30min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Comparative example 1
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps: weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.8mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, dropwise adding 0.001mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.01mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; and aging, cleaning and drying to obtain the antibacterial composite material.
Comparative example 2
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a silver nitrate solution with the concentration of 0.001mol/L, controlling the reaction temperature to be 50 ℃, dropwise adding trisodium citrate dihydrate with the concentration of 0.01mol/L, and ultrasonically stirring for 90min, wherein the volume ratio of the silver nitrate solution to the trisodium citrate dihydrate is 3: 2; then adding water and ammonia water in a volume ratio of 3:1, stirring uniformly, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1:1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1 hour, centrifuging, sequentially cleaning with acetone and deionized water to obtain a precipitate, and putting the precipitate at 90 DEG CoDrying for 3h to obtain Ag/SiO2。
(2) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.8mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the Ag/SiO prepared in the step (2)2Ultrasonically stirring for 30min, then moving into a polytetrafluoroethylene reaction kettle, and preserving the temperature for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The specific process and steps of the antibacterial activity evaluation of the antibacterial composite material prepared by the invention are as follows:
details of the testThe bacteria are respectively staphylococcus aureus and escherichia coli; referring to the test method for Minimum Inhibitory Concentration (MIC) (Xiaoaininghibitory concentration, MIC) (Xiaoang Cai, Shaozao Tan, Aili Yu, Jinglin Zhang, Jianao Liu, Wenjie Mai, Zhenyou Jiang, Source 1-naphthalene sulfonate-functional reduced graphene oxide stabilize the silver nanoparticles with low toxicity and long-term antibacterial activity chemistry-An antibiotic journal 2012, 7(7):1664-6pieces/mL, followed by shaking culture at 37 ℃ for 24 hours, the results were observed as shown in Table 1. The test tube without the antibacterial sample is used as a control tube, the liquid of the test tube with aseptic growth is transparent, and the antibacterial agent of the test tube without the antibacterial sample is measured as the Minimum Inhibitory Concentration (MIC) of the antibacterial agent.
Table 1: antibacterial performance of antibacterial composite materials of examples 1-3 and comparative examples 1 and 2
And (3) long-acting performance test: an erlenmeyer flask was placed in a constant temperature water bath at 40 ℃, 1g of the antibacterial composite material sample prepared in each example and comparative example and 200mL of saline (0.9 mass%) were added to the erlenmeyer flask, and samples were taken after soaking in water for 6, 24, and 72 hours, respectively, to determine the minimum inhibitory concentration, as shown in table 2.
Table 2: long-acting antibacterial activity of antibacterial composite materials of examples 1-3 and comparative examples 1 and 2
Example 4
A preparation method of gravure water-based ink comprises the following steps:
(1) putting 70% of water-soluble resin and 0.8% of diatomite/antibacterial compound into a reaction kettle, and keeping the temperature at 60 ℃ and the rotating speed at 900 r/min;
(2) under the condition of the step (1), sequentially adding 6% of deionized water, 2% of ethanol and 1% of dispersing agent, mixing and stirring for 30-60 min;
(3) adding 8% of organic pigment, adjusting the stirring speed to 1200-1500 r/min, adding the organic pigment while stirring, stirring for 30-60 min, and then adding 0.5% of defoaming agent and 1% of photochromic compound; continuously stirring for 60-90 min, and grinding into standby color paste with the fineness of 20-30 mu m by a three-roll grinder;
(4) sequentially adding 6% of deionized water, 2% of ethanol, 0.5% of water-based wax emulsion, 0.5% of water-based flatting agent, 0.8% of diatomite/inorganic oxide and 0.1% of slow-drying agent into the standby color paste, stirring uniformly at the rotating speed of 1200-1500 r/min, slowly adding 0.8% of organic amine to adjust the PH, and grinding and dispersing by a three-roll grinder to achieve the fineness of 10-20 mu m;
(5) filtering and packaging the mixture prepared in the step (4) to finish the preparation; wherein,
the preparation method of the diatomite/antibacterial compound comprises the following steps: dispersing diatomite into the aqueous solution, and dropwise adding the aqueous dispersion of the antibacterial compound in the example 2 while ultrasonically stirring; standing, performing suction filtration and cleaning for multiple times, and drying to obtain a diatomite/antibacterial compound; the weight ratio of the diatomite to the antibacterial compound is 2: 5;
the preparation method of the diatomite/inorganic oxide comprises the following steps: mixing the following raw materials in percentage by weight: ZrO 25%, TiO28%, SiO 216%, V2O 54%, K2O 2%, SnO 23%, Cr2O 33%, Al2O 313%, Fe2O 311%, MgO 20%, Na2O8%, MnO 27%, and grinding in a large-flow circulating horizontal sand mill developed by PUHLER company, wherein the particle size is controlled to be 10-300 nm; dispersing diatomite in 120ml of aqueous solution, adding inorganic oxide, stirring for 2 hours at 200W ultrasonic speed of 300rpm to allow the nano material to fully enter pores of the diatomite, performing suction filtration and cleaning for multiple times, and drying to obtain diatomite/inorganic oxide; wherein the weight ratio of the diatomite to the inorganic oxide is 2: 5;
the photochromic compound is prepared by the following method: under the nitrogen atmosphere, 0.4mol/L protonic acid solution and 0.3mol/L dodecylbenzene sulfonic acid are mixed in a volume ratio of 3:2, and photochromic powder (Nd) is added at the same time2O3、Pr2O3、La2O3And Yb2O3Mixing according to the weight ratio of 1:2:1: 3), magnetically stirring for 90min, and adding aniline, wherein the mass ratio of the photo-discoloration powder to the aniline is 1: 8; continuously stirring for 90min, and dropwise adding ammonium persulfate with the molar ratio of aniline to ammonium persulfate being 1: 1; reacting for 20 hours at the temperature of 20-30 ℃; washing with acetone and deionized water for several times, vacuum drying, and grinding to obtain nanometer polyaniline/photochromic powder compound; ultrasonically stirring and dispersing 6g of nano polyaniline/photochromic powder composite in an aqueous solution; then adding water and ammonia water in a volume ratio of 4:1, uniformly stirring, adding tetraethoxysilane (the mass ratio of tetraethoxysilane to the nano polyaniline/photochromic powder compound is 5: 3), adjusting the pH value to 9-10, and reacting at the temperature of 20-25 ℃ for 60 min; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; drying the precipitate at 90 deg.C for 3h to obtain nanometer polyaniline/photochromic powder composite/SiO2(ii) a Nano polyaniline/photochromic powder compound/SiO2Heat treating at 800 deg.C for 1 hr in argon atmosphere to remove polyaniline and obtain photochromic powder/porous SiO2I.e. a photochromic complex.
Example 5
The preparation process is based on example 4, with the difference that: the preparation method of the antibacterial compound comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.6g C60 powder, weighing 50-100 ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 1g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 7 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 45min, wherein the laser irradiation power is 1.2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 60ml of graphene quantum dot suspension, dropwise adding 0.003mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.05mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:3: 2.
(3) Dispersing 0.3g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (1000W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 4:1, uniformly stirring, adding ethyl orthosilicate in a mass ratio of 2:1 to the silver-loaded graphene quantum dots, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃ for 1 hour; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(4) Adding 0.2mol/L titanium source (the titanium source is ammonium fluotitanate) into 1mol/L sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (3)2Coating the silver-loaded graphene quantum dots, heating to 100 ℃, reacting for 3 hours, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6 hours, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(5) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.008g of graphite oxide into 8mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.2g of silver-loaded/titanium dioxide graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer, reacting at 220 ℃ for 60min and with the microwave power of 300W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(6) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.5mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, adding the silver/titanium dioxide graphene quantum dots prepared in the step (5), ultrasonically stirring for 30min, then moving into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Example 6
The preparation process is based on example 4, with the difference that: the preparation method of the antibacterial compound comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.7g C60 powder, weighing 80ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 2g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice-water bath, changing the ice-water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 6 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 45min, wherein the laser irradiation power is 1.5W.
(2) Weighing zinc oxide quantum dots (with the particle size of about 2-5 nm) to prepare a dispersion liquid with the concentration of 0.8mg/ml, wherein the solvent is water; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 100ml of zinc oxide dispersion liquid, dropwise adding half of the graphene quantum dot suspension liquid prepared in the step (1), and continuously ultrasonically stirring for 60 min; centrifuging, cleaning and drying to obtain the graphene quantum dots loaded with zinc oxide.
(3) Surface treatment of graphene quantum dots loaded with zinc oxide: adding 0.008g of graphite oxide into 10mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.1g of graphene quantum dots loaded with zinc oxide, continuously ultrasonically stirring for 20min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer with microwave power of 300W, and reacting at 220 ℃ for 60 min; and cooling, filtering and drying to obtain the surface-treated graphene quantum dots loaded with zinc oxide.
(4) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) the other half of the graphene quantum dot suspension, dropwise adding a silver nitrate solution with the concentration of 0.003mol/L, controlling the reaction temperature to be 50 ℃, dropwise adding trisodium citrate dihydrate with the concentration of 0.05mol/L, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:3: 2.
(5) Dispersing 0.3g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (1000W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 4:1, uniformly stirring, adding ethyl orthosilicate in a mass ratio of 2:1 to the silver-loaded graphene quantum dots, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃ for 1 hour; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(6) Adding 0.2mol/L titanium source (the titanium source is ammonium fluotitanate) into 1mol/L sulfuric acid solution, and uniformly mixing(ii) a Adding the SiO prepared in the step (5)2Coating the silver-loaded graphene quantum dots, heating to 100 ℃, reacting for 3 hours, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6 hours, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(7) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.008g of graphite oxide into 8mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.2g of silver-loaded/titanium dioxide graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer, reacting at 220 ℃ for 60min and with the microwave power of 300W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(8) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm, and the layer size is about 100-500 nm) to prepare a graphene dispersion solution with the concentration of 0.5mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, adding the zinc oxide-loaded graphene quantum dots prepared in the step (3) and the silver/titanium dioxide-loaded graphene quantum dots prepared in the step (7) (the mass ratio of the two is 2: 3), ultrasonically stirring for 30min, then moving to a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Comparative example 3
The preparation process is based on example 4, with the difference that: no diatomaceous earth was added.
Comparative example 4
The preparation process is based on example 4, with the difference that: the diatomite/antibacterial compound is replaced by the following components in parts by weight: 10 percent of nano ZnO and 90 percent of nano CaCO 3.
Comparative example 5
Based on example 4The preparation method is different in that: no diatomaceous earth/inorganic oxide addition; the photochromic compound is Nd2O3、Pr2O3、La2O3And Yb2O3Mixing according to the weight ratio of 1:2:1: 3.
The main technical indexes of the examples 4-6 and the comparative examples 3 and 4 are as follows:
evaluation of antibacterial uniformity: ink was sprayed onto glass or ceramic plates, 100 areas were selected for sterilization testing, and the measured data were analyzed for uniformity by uniformity =100 (1-standard deviation/mean). When the uniformity is more than 97%, marking as a tangle-solidup; when the uniformity is greater than 90% and less than 97%, it is marked as four; when the uniformity is below 90%, the mark is gamma.
The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should fall within the protection scope of the present invention.
Claims (5)
1. A preparation method of photochromic gravure water-based ink comprises the following steps:
(1) putting the water-soluble resin and the diatomite/antibacterial compound into a reaction kettle, and keeping the temperature at 55-65 ℃ and the rotating speed at 800-1000 r/min;
(2) under the condition of the step (1), sequentially adding deionized water, ethanol and a dispersing agent, and mixing and stirring for 30-60 min;
(3) adding an organic pigment, adjusting the stirring speed to 1200-1500 r/min, adding the organic pigment while stirring, stirring for 30-60 min, and adding a defoaming agent and a photochromic compound; continuously stirring for 60-90 min, and grinding into standby color paste with the fineness of 20-30 mu m by a three-roll grinder;
(4) sequentially adding deionized water, ethanol, aqueous wax emulsion, diatomite/inorganic oxide, an aqueous flatting agent and a slow-drying agent into the standby color paste, stirring uniformly at the rotating speed of 1200-1500 r/min, slowly adding organic amine to adjust the pH value to 8.0-9.5, and grinding and dispersing by a three-roll grinder to achieve the fineness of 10-20 mu m;
(5) filtering and packaging the mixture prepared in the step (4) to finish the preparation; wherein,
the preparation method of the diatomite/antibacterial compound comprises the following steps: dispersing diatomite in an aqueous solution, and dropwise adding an antibacterial compound aqueous dispersion while ultrasonically stirring; standing, performing suction filtration and cleaning for multiple times, and drying to obtain a diatomite/antibacterial compound; the weight ratio of the diatomite to the antibacterial compound is 1-3: 4-6;
the preparation method of the diatomite/inorganic oxide comprises the following steps: mixing the following raw materials in percentage by weight: ZrO 25%, TiO28%, SiO 216%, V2O 54%, K2O 2%, SnO 23%, Cr2O 33%, Al2O 313%, Fe2O 311%, MgO 20%, Na2O8%, MnO 27%, and grinding in a large-flow circulating horizontal sand mill developed by PUHLER company, wherein the particle size is controlled to be 10-300 nm; dispersing diatomite in 120ml of aqueous solution, adding inorganic oxide, stirring for 2 hours at 100-200W ultrasonic speed of 100-300 rpm to allow the nano material to fully enter the diatomite pores, performing suction filtration and cleaning for many times, and drying to obtain diatomite/inorganic oxide; wherein the weight ratio of the diatomite to the inorganic oxide is 1-2: 5;
the preparation method of the antibacterial compound comprises the following steps:
(1) preparing silver-loaded graphene quantum dots: ultrasonically stirring 50-60 ml of graphene quantum dot suspension, dropwise adding a silver nitrate solution, controlling the reaction temperature to be 45-60 ℃, dropwise adding trisodium citrate dihydrate, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots;
(2) ultrasonically stirring and dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol; then adding water and ammonia water in a volume ratio of 3-5: 1, and stirringAfter uniformly stirring, adding tetraethoxysilane, adjusting the pH value to 9-10, and reacting at the temperature of 20-25 ℃ for 1-3 hours; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots;
（3）SiO2surface treatment of coating silver-loaded graphene quantum dots;
(4) weighing porous graphene to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring 80-100 ml of graphene dispersion solution, and adding the SiO prepared in the step (3)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 10-30 min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 15-30 min at 80-120 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
2. A preparation method of photochromic gravure water-based ink comprises the following steps:
(1) putting the water-soluble resin and the diatomite/antibacterial compound into a reaction kettle, and keeping the temperature at 55-65 ℃ and the rotating speed at 800-1000 r/min;
(2) under the condition of the step (1), sequentially adding deionized water, ethanol and a dispersing agent, and mixing and stirring for 30-60 min;
(3) adding an organic pigment, adjusting the stirring speed to 1200-1500 r/min, adding the organic pigment while stirring, stirring for 30-60 min, and adding a defoaming agent and a photochromic compound; continuously stirring for 60-90 min, and grinding into standby color paste with the fineness of 20-30 mu m by a three-roll grinder;
(4) sequentially adding deionized water, ethanol, aqueous wax emulsion, diatomite/inorganic oxide, aqueous flatting agent and slow drying agent into the standby color paste, stirring uniformly at the rotating speed of 1200-1500 r/min, slowly adding organic amine to adjust the pH value to 8.0-9.5, and grinding by a three-roll grinder
Grinding and dispersing to obtain a fineness of 10-20 μm;
(5) filtering and packaging the mixture prepared in the step (4) to finish the preparation; wherein,
the preparation method of the diatomite/antibacterial compound comprises the following steps: dispersing diatomite in an aqueous solution, and dropwise adding an antibacterial compound aqueous dispersion while ultrasonically stirring; standing, performing suction filtration and cleaning for multiple times, and drying to obtain a diatomite/antibacterial compound; the weight ratio of the diatomite to the antibacterial compound is 1-3: 4-6;
the preparation method of the diatomite/inorganic oxide comprises the following steps: mixing the following raw materials in percentage by weight: ZrO 25%, TiO28%, SiO 216%, V2O 54%, K2O 2%, SnO 23%, Cr2O 33%, Al2O 313%, Fe2O 311%, MgO 20%, Na2O8%, MnO 27%, and grinding in a large-flow circulating horizontal sand mill developed by PUHLER company, wherein the particle size is controlled to be 10-300 nm; dispersing diatomite in 120ml of aqueous solution, adding inorganic oxide, stirring for 2 hours at 100-200W ultrasonic speed of 100-300 rpm to allow the nano material to fully enter the diatomite pores, performing suction filtration and cleaning for many times, and drying to obtain diatomite/inorganic oxide; wherein the weight ratio of the diatomite to the inorganic oxide is 1-2: 5;
the preparation method of the antibacterial compound comprises the following steps:
(1) preparing silver-loaded graphene quantum dots: ultrasonically stirring 50-60 ml of graphene quantum dot suspension, dropwise adding a silver nitrate solution, controlling the reaction temperature to be 45-60 ℃, dropwise adding, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots;
(2) ultrasonically stirring and dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol; then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, and reacting for 1-3 hours; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; drying to obtain SiO2Coated silver-loaded graphene quantum dots;
(3) adding 0.1-0.3 mol/L of titanium source into 1mol/L of sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (2)2Coating the silver-loaded graphene quantum dots, heating to 100-110 ℃, reacting for 2-4 h, adjusting the pH value to 7 by using concentrated ammonia water solution, aging, cleaning and drying to obtain silver-loaded/titanium dioxide graphene quantum dots;
(4) carrying out surface treatment on the silver/titanium dioxide graphene quantum dots;
(5) weighing porous graphene to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring 80-100 ml of graphene dispersion solution, adding the silver-loaded/titanium dioxide graphene quantum dots prepared in the step (4), ultrasonically stirring for 10-30 min, then transferring to a polytetrafluoroethylene reaction kettle, and preserving heat for 15-30 min at 80-120 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
3. A preparation method of photochromic gravure water-based ink comprises the following steps:
(1) putting the water-soluble resin and the diatomite/antibacterial compound into a reaction kettle, and keeping the temperature at 55-65 ℃ and the rotating speed at 800-1000 r/min;
(2) under the condition of the step (1), sequentially adding deionized water, ethanol and a dispersing agent, and mixing and stirring for 30-60 min;
(3) adding an organic pigment, adjusting the stirring speed to 1200-1500 r/min, adding the organic pigment while stirring, stirring for 30-60 min, and adding a defoaming agent and a photochromic compound; continuously stirring for 60-90 min, and grinding into standby color paste with the fineness of 20-30 mu m by a three-roll grinder;
(4) sequentially adding deionized water, ethanol, aqueous wax emulsion, diatomite/inorganic oxide, aqueous flatting agent and slow drying agent into the standby color paste, stirring uniformly at the rotating speed of 1200-1500 r/min, slowly adding organic amine to adjust the pH value to 8.0-9.5, and grinding by a three-roll grinder
Grinding and dispersing to obtain a fineness of 10-20 μm;
(5) filtering and packaging the mixture prepared in the step (4) to finish the preparation; wherein,
the preparation method of the diatomite/antibacterial compound comprises the following steps: dispersing diatomite in an aqueous solution, and dropwise adding an antibacterial compound aqueous dispersion while ultrasonically stirring; standing, performing suction filtration and cleaning for multiple times, and drying to obtain a diatomite/antibacterial compound; the weight ratio of the diatomite to the antibacterial compound is 1-3: 4-6;
the preparation method of the diatomite/inorganic oxide comprises the following steps: mixing the following raw materials in percentage by weight: ZrO 25%, TiO28%, SiO 216%, V2O 54%, K2O 2%, SnO 23%, Cr2O 33%, Al2O 313%, Fe2O 311%, MgO 20%, Na2O8%, MnO 27%, and grinding in a large-flow circulating horizontal sand mill developed by PUHLER company, wherein the particle size is controlled to be 10-300 nm; dispersing diatomite in 120ml of aqueous solution, adding inorganic oxide, stirring for 2 hours at 100-200W ultrasonic speed of 100-300 rpm to allow the nano material to fully enter the diatomite pores, performing suction filtration and cleaning for many times, and drying to obtain diatomite/inorganic oxide; wherein the weight ratio of the diatomite to the inorganic oxide is 1-2: 5;
the preparation method of the antibacterial compound comprises the following steps:
(1) preparing a graphene quantum dot suspension: stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30-60 min, wherein the laser irradiation power is 1-2W;
(2) weighing zinc oxide quantum dots to prepare a dispersion liquid with the concentration of 0.5-1 mg/ml, wherein the solvent is water; ultrasonically stirring 80-100 ml of zinc oxide dispersion liquid, dropwise adding the half graphene quantum dot suspension liquid prepared in the step (1), and continuously ultrasonically stirring for 30-60 min; centrifuging, cleaning and drying to obtain the graphene quantum dots loaded with zinc oxide;
(3) carrying out surface treatment on the graphene quantum dots loaded with zinc oxide;
(4) preparing silver-loaded graphene quantum dots: ultrasonically stirring the other half of the graphene quantum dot suspension, dropwise adding a silver nitrate solution, controlling the reaction temperature to be 45-60 ℃, dropwise adding trisodium citrate dihydrate, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots;
(5) ultrasonically stirring and dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol; then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, and reacting for 1-3 hours; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; drying to obtain SiO2Coated silver-loaded graphene quantum dots;
(6) adding 0.1-0.3 mol/L of titanium sourceAdding the mixture into 1mol/L sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (5)2Coating the silver-loaded graphene quantum dots, heating to 100-110 ℃, reacting for 2-4 h, adjusting the pH value to 7 by using concentrated ammonia water solution, aging, cleaning and drying to obtain silver-loaded/titanium dioxide graphene quantum dots;
(7) carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent, ultrasonically stirring, adding 0.1-0.3 g of silver-loaded/titanium dioxide graphene quantum dots, continuously ultrasonically stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, and reacting at 200-240 ℃ for 60-90 min, wherein the microwave power is 200-400W; cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated;
(8) weighing porous graphene to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml; ultrasonically stirring 80-100 ml of graphene dispersion solution, adding the zinc oxide-loaded graphene quantum dots prepared in the step (3) and the silver/titanium dioxide-loaded graphene quantum dots prepared in the step (7), ultrasonically stirring for 10-30 min, then transferring to a polytetrafluoroethylene reaction kettle, and preserving heat at 80-120 ℃ for 15-30 min; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
4. The method for preparing the photochromic gravure aqueous ink as set forth in any one of claims 1 to 3, wherein the photochromic complex is prepared by: under the nitrogen environment, mixing 0.05-0.5 mol/L protonic acid solution and 0.05-0.5 mol/L dodecylbenzene sulfonic acid in a volume ratio of 3: 1-3, adding photochromic powder, magnetically stirring for 60-120 min, and adding aniline, wherein the mass ratio of the photochromic powder to the aniline is 1: 5-10; continuously stirring for 60-90 min, and dropwise adding ammonium persulfate with the molar ratio of aniline to ammonium persulfate being 1: 1; reacting for 12-36 h at 20-30 ℃; washing with acetone and deionized water for several times, vacuum drying, and grinding to obtain nanometer polyaniline/photochromic powder compound; ultrasonically stirring and dispersing 1-10 g of nano polyaniline/photochromic powder composite in an aqueous solution; then addAdding water and ammonia water in a volume ratio of 4:1, uniformly stirring, adding ethyl orthosilicate, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃ for 60-90 min; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; drying the precipitate at 90 deg.C for 3h to obtain nanometer polyaniline/photochromic powder composite/SiO2(ii) a Nano polyaniline/photochromic powder compound/SiO2Placing the mixture in an argon atmosphere for heat treatment at 800-1000 ℃ for 1-2 h to remove polyaniline and photochromic powder/porous SiO2I.e. a photochromic complex.
5. The photochromic gravure water-based ink is characterized by being prepared from the following components in percentage by weight: 70-75% of water-soluble resin, 10-15% of deionized water, 5-10% of water-based organic pigment, 3-6% of ethanol, 0.5-1% of diatomite/antibacterial compound, 1-2% of dispersing agent, 0-1% of slow drying agent, 0.5-1% of water-based flatting agent, 0.5-1% of water-based wax emulsion, 0.5-1% of diatomite/inorganic oxide, 0.5-1% of organic amine, 0.5-1% of defoaming agent and 0.1-2% of photochromic compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| WO2021229198A1 (en) * | 2020-05-14 | 2021-11-18 | Graphene Composites Limited | Viral active and/or anti-microbial inks and coatings |
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