CN104725956A - Preparation method of antibacterial water-soluble varnish used for package printing - Google Patents
Preparation method of antibacterial water-soluble varnish used for package printing Download PDFInfo
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- CN104725956A CN104725956A CN201510069468.0A CN201510069468A CN104725956A CN 104725956 A CN104725956 A CN 104725956A CN 201510069468 A CN201510069468 A CN 201510069468A CN 104725956 A CN104725956 A CN 104725956A
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- water
- halloysite nanotubes
- resin liquid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 39
- 238000007639 printing Methods 0.000 title claims abstract description 29
- 239000002966 varnish Substances 0.000 title abstract description 7
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical class O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002071 nanotube Substances 0.000 claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 89
- 239000007788 liquid Substances 0.000 claims abstract description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229920001661 Chitosan Polymers 0.000 claims abstract description 41
- 239000008367 deionised water Substances 0.000 claims abstract description 39
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 229930182490 saponin Natural products 0.000 claims abstract description 22
- 150000007949 saponins Chemical class 0.000 claims abstract description 22
- 241001122767 Theaceae Species 0.000 claims abstract description 21
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 27
- 239000004925 Acrylic resin Substances 0.000 claims description 26
- 229920000178 Acrylic resin Polymers 0.000 claims description 26
- 238000007725 thermal activation Methods 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 229920002101 Chitin Polymers 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000005119 centrifugation Methods 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- 239000013530 defoamer Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001994 activation Methods 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000003643 water by type Substances 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 229920003180 amino resin Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229920005749 polyurethane resin Polymers 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 235000017709 saponins Nutrition 0.000 description 18
- 239000002585 base Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000000845 anti-microbial effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000007799 cork Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- IAFBRPFISOTXSO-UHFFFAOYSA-N 2-[[2-chloro-4-[3-chloro-4-[[1-(2,4-dimethylanilino)-1,3-dioxobutan-2-yl]diazenyl]phenyl]phenyl]diazenyl]-n-(2,4-dimethylphenyl)-3-oxobutanamide Chemical compound C=1C=C(C)C=C(C)C=1NC(=O)C(C(=O)C)N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(C)=O)C(=O)NC1=CC=C(C)C=C1C IAFBRPFISOTXSO-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 208000009146 rhinoscleroma Diseases 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000000080 wetting agent 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to the technical field of water-soluble varnish and discloses a preparation method of antibacterial water-soluble varnish used for package printing. The preparation method comprises the following steps: (1) preparing a chitosan modified halloysite nanotube; (2) preparing an Ag-carrying halloysite nanotube; (3) compounding the Ag-carrying halloysite nanotube with a water-soluble resin liquid A and a water-soluble resin liquid B and then compounding a mixed resin liquid with water-soluble wax emulsion, deionized water, ethanol, tea saponin, a defoaming agent, a levelling agent and a buffer agent, thus preparing the antibacterial water-soluble varnish used for package printing. The preparation method has the beneficial effects that containing various antibacterial components, such as nano-silver, chitosan, titanium dioxide and tea saponin, the water-soluble varnish prepared by the preparation method has strong bactericidal broad-spectrum property; the bactericidal components have synergistic effects, so that the bactericidal effects are greatly enhanced; the dispersibility of the bactericidal components in the water-soluble varnish is quite outstanding.
Description
Technical field
The present invention relates to technical field of water-base varnish, particularly relate to the preparation method of a kind of packages printing with antibacterial aqueous gloss oil.
Background technology
Water-based gloss oil is as a kind of emerging environmental protection printing material, be widely used in the printings such as food product pack, medical packaging, tobacco bale, books and periodicals, wall calendar, water-based gloss oil has outstanding surface gloss, because its solvent is mainly water, the volatile gases that can not be harmful to airborne release, relatively environmental protection, meets the current theory advocating environment protection health.Therefore water-based gloss oil is having wide development space from now on.
For the water-based gloss oil for higher fields of hygienic requirements such as tobacco bale, medical packaging, food product pack printings, require that water-based gloss oil self is nontoxic.Although but water-based gloss oil self has done harm to human non-toxic, tobacco bale, medical packaging and food pack easily grow germ, if water-based gloss oil has antibacterial, can effectively address this problem.
Wang Can just waits in " the Tipping Paper Antibacterial Water-based Ink research " delivered at " Packaging Engineering " and discloses a kind of antibacterial aqueous ink, and its formula is: diarylide yellow 5%, titanium dioxide 25%, water-borne acrylic resin liquid 45%, ethanol 15% and deionized water 10%.This water color ink has good printability on cork paper, and has good antibacterial effect.
Chinese invention patent CN 102477238B discloses a kind of water-based gloss oil, its formula comprises water, acrylate copolymer, titanium dioxide, a huge sum of money stone flour, water-ground limestone, kaolin, Yu Mufen, wetting dispersing agent, defoamer, flow agent, thickening material, multifunctional assistant, film coalescence aid and biocide mildewcide, this water-based gloss oil environment-protecting asepsis, alkali resistant mildew-resistant, protection against the tide.
Above two kinds of products but weak point be: antimicrobial component and other compositions are only physical mixed, although serve anti-microbial effect, dispersed and effect is all general.
Chinese invention patent CN 102952431A discloses a kind of cigarette cork paper water color ink and preparation method thereof, comprises one or more 0.5-1 parts in aqueous emulsifying sylvic oil 50-60 part+iron oxide pigment 10-20 part+deionized water 10-20 part+defoamer, anti-sedimentation agent, flow agent, wetting agent, antiseptic-germicide, wetting dispersing agent, surface tension agent aid.It is little that the cigarette cork paper water color ink of this invention has fineness, and rate of drying is fast, and denseness is high, viscosity is low, dispersion stabilization is good, without scleroma property precipitation, without cohesion, the advantages such as noresidue peculiar smell, but sterilant is directly allocated in water color ink by this invention, although this sterilant can play germicidal action, bactericidal range is single, may also can be harmful, cause side effect.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides the preparation method of a kind of packages printing with antibacterial aqueous gloss oil, water-based gloss oil sterilant dispersion effect prepared by the method is good, broad-spectrum is strong, antibacterial effect is strong.
Concrete technical scheme of the present invention is: a kind of packages printing preparation method of antibacterial aqueous gloss oil, carries out as follows, and wherein following material number is parts by weight,
(1) preparation of chitin modified halloysite nanotubes:
Getting chitosan, to be made an addition to concentration be stir in the acetic acid aqueous solution of 1-5wt%, treats that chitosan dissolves in backward solution completely and add Succinic anhydried and ethanol, obtain modified chitosan mixed solution after being uniformly mixed liquid 8h; By halloysite nanotubes at 300-500 DEG C of roasting temperature 3-4 hour, removed the thermal activation halloysite nanotubes of crystal water; Get the thermal activation halloysite nanotubes 10 parts of above-mentioned gained, to be made an addition in 10-15 part modified chitosan mixed solution and be stirred to thermal activation halloysite nanotubes and be uniformly dispersed, adding acid solution is afterwards adjusted to 2.5-3 by mixed solution pH value, after being uniformly mixed liquid 3h first after through centrifugation, get washing of precipitate, vacuum-drying obtains chitin modified halloysite nanotubes.
Halloysite nanotubes has nano level hollow tubular structure, and having very high specific surface area, very strong adsorptive power and good thermostability, dispersiveness, is desirable support materials, and with a large amount of hydroxyls on tube wall, is conducive to organically-modified.Thermal activation is carried out to halloysite nanotubes, makes it have stronger adsorptive power; Chitosan has the ability of stronger complex silver ion, first modification is carried out to chitosan, graft modification can be carried out to halloysite nanotubes, by modified chitosan, modification be carried out to halloysite nanotubes, make halloysite nanotubes have the ability of silver ions being carried out to complexing.
(2) preparation of silver-colored halloysite nanotubes is carried:
Getting 10 parts of Silver Nitrates is dissolved in deionized water, the chitin modified halloysite nanotubes of 10 parts of above-mentioned gained is added again in silver nitrate solution, 12h is stirred at 50-70 DEG C of temperature, suspension is carried out centrifugal after get solid matter, after washing, vacuum-drying, get 10 parts of above-mentioned solid matters and 0.5 part of sodium borohydride joins in the aqueous sodium hydroxide solution of 0.01mol/L, add deionized water and regulate pH to 7.5-8, get solid finally by stirring, centrifugation, washing, drying obtain carrying a silver-colored halloysite nanotubes.
After modified halloysite nanotubes carries out complexing to silver ions, then silver ion reduction is become more stable nano-Ag particles, nanometer silver has very strong sterilizing ability, and broad-spectrum is strong.In addition chitosan self also has certain anti-microbial property.
(3) preparation of water-based gloss oil:
The silver-colored halloysite nanotubes that carries of above-mentioned gained to be added in the mixed resin liquid of water-base resin liquid A and water-base resin liquid B and stirs, in mixed resin liquid, add water wax emulsion, ionized water, ethanol, tea saponin, defoamer, flow agent and buffer reagent again, obtain the antibacterial aqueous gloss oil of packages printing finally by grinding distribution.
In wherein said water-based gloss oil, each component concentration is as follows:
45-55wt% water-base resin liquid A;
15-25 wt% water-base resin liquid B;
3-5%wt% carries silver-colored halloysite nanotubes;
3-7wt% water-borne wax emulsion;
1-2wt% tea saponin;
5-10 wt% deionized water;
5-10 wt% ethanol;
1-2wt% defoamer;
1-2 wt% flow agent;
1-2 wt% buffer reagent.
Described water-base resin liquid A is water-borne acrylic resin liquid,
Described water-base resin liquid B is selected from the one in water-compatible amino resin liquid, maleic acid resin liquid, waterborne polyurethane resin liquid.
As preferably, the chitosan in described step (1) is Nano chitosan.
As preferably, the purity of halloysite nanotubes before thermal activation in described step (1) is not less than 85%, and halloysite nanotubes before thermal activation through acid activation, acid activation method is as follows:
Be that 2-4wt% hydrochloric acid soln successively joins in 200 parts of deionized waters by 20 parts of halloysite nanotubes, 200 parts of concentration, stir at 50 DEG C of temperature after 4 hours filter, dry, obtain acid activation halloysite nanotubes.
As preferably, the halloysite nanotubes in described step (1) crosses 500 mesh sieve before the reaction.
As preferably, the water-borne acrylic resin liquid in described step (3) is nano-titanium dioxide modified water-borne acrylic resin liquid, and method of modifying is as follows:
A, nano titanium oxide, ethanol, deionized water and silane coupling agent are mixed after at 60 DEG C of water-bath back flow reaction 8-16h, then room temperature is down to, product is through centrifugation and washing, obtain silane coupler modified inorganic nano-particle, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupling agent is than being 1:30-50:5-15:1-3;
B, 30-60 part deionized water and 1-3 part emulsifying agent are put into reactor and is heated to 80 DEG C, again by 20-40 part acrylic monomer, the silane coupler modified inorganic nano-particle of 15-25 part step a gained, stir after 3-5 part polyoxyethylene glycol and 0.25-0.5 part water soluble starter put into reactor, be incubated after 0.5-1 hour, 0.25-0.5 part water soluble starter is at the uniform velocity added in 2 hours, and then be incubated 4-8 hour, stir while add ammoniacal liquor and neutralize afterwards, pH value of solution is made to maintain between 7.5-8.5, vacuumize again and remove free ammoniacal liquor, finally filter and obtain nano-titanium dioxide modified water-borne acrylic resin liquid, above material number is parts by weight.
Silane coupling agent is adopted to carry out modification to nano titanium oxide, can with acrylic monomer copolymerization, nano titanium oxide and hydroxyalkyl are incorporated on water-borne acrylic resin, nano titanium oxide after modified participates in polymerization directly, being evenly distributed in resin, better to the modified effect of water-borne acrylic resin.Nano titanium oxide has outstanding light aging resisting property and antibacterial and mouldproof performance.
As preferably, the particle diameter of described nano titanium oxide is at 10-20nm.
As preferably, described acrylic monomer is selected from least two kinds in methyl methacrylate, methyl acrylate, vinylbenzene, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methylacrylate, acrylamide.
The invention has the beneficial effects as follows: the present invention carries out graft modification by the chitosan of modification to halloysite nanotubes, halloysite nanotubes is made to have the ability of silver ions being carried out to complexing, again silver ion reduction is become more stable nano-Ag particles, after silver-colored halloysite nanotubes and water-base resin compound will be carried, the load fastness of nanometer silver on halloysite is good, nanometer silver can play its outstanding bacteriostasis, and chitosan is also a kind of natural antibacterial, makes water-based gloss oil have anti-microbial property.
Water-borne acrylic resin liquid and water-compatible amino resin liquid, maleic acid resin liquid or waterborne polyurethane resin liquid are carried out composite, has merged the advantage of various resin, compensate for the shortcoming of each genus resin.
Tea saponin is with the addition of in the formula of water-based gloss oil, tea saponin has outstanding emulsification, wetting, dispersing property, the effect of dispersion agent can be played in water-based gloss oil, moreover, tea saponin also has certain sterilizing function, to streptococcus aureus, intestinal bacteria etc., there is good rejection ability, tea saponin solvability in alcohol solution is good, as the dispersion agent of water-based gloss oil and antiseptic-germicide, there are bright prospects, although tea saponin has the problem of bubbling under oscillatory condition, just can be solved by defoamer.
Containing antimicrobial components such as nanometer silver, chitosan, titanium dioxide and tea saponins in the present invention, water-based gloss oil is made to have very strong broad-spectrum, various sterilization component synergy, sterilization effect is also strengthened greatly, and the dispersiveness of each sterilization component in water-based gloss oil is very outstanding.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
A packages printing preparation method for antibacterial aqueous gloss oil, carries out as follows, and wherein following material number is parts by weight,
(1) preparation of chitin modified halloysite nanotubes:
Getting Nano chitosan, to be made an addition to concentration be stir in the acetic acid aqueous solution of 3wt%, treats that chitosan dissolves in backward solution completely and add Succinic anhydried and ethanol, obtain modified chitosan mixed solution after being uniformly mixed liquid 8h.
By cross the purity of 500 mesh sieve be the halloysite nanotubes of 85% 400 DEG C of roasting temperatures 3.5 hours, removed the thermal activation halloysite nanotubes of crystal water; Get the thermal activation halloysite nanotubes 10 parts of above-mentioned gained, to be made an addition in 13 portions of modified chitosan mixed solutions and be stirred to thermal activation halloysite nanotubes and be uniformly dispersed, adding acid solution is afterwards adjusted to 2.5-3 by mixed solution pH value, after being uniformly mixed liquid 3h first after through centrifugation, get washing of precipitate, vacuum-drying obtains chitin modified halloysite nanotubes.
(2) preparation of silver-colored halloysite nanotubes is carried:
Getting 10 parts of Silver Nitrates is dissolved in deionized water, the chitin modified halloysite nanotubes of 10 parts of above-mentioned gained is added again in silver nitrate solution, 12h is stirred at 60 DEG C of temperature, suspension is carried out centrifugal after get solid matter, after washing, vacuum-drying, get 10 parts of above-mentioned solid matters and 0.5 part of sodium borohydride joins in the aqueous sodium hydroxide solution of 0.1mol/L, add deionized water and regulate pH to 7.5-8, get solid finally by stirring, centrifugation, washing, drying obtain carrying a silver-colored halloysite nanotubes.
(3) preparation of water-based gloss oil:
The silver-colored halloysite nanotubes that carries of above-mentioned gained to be added in the mixed resin liquid of water-borne acrylic resin liquid and water-compatible amino resin liquid and stirs, in mixed resin liquid, add water-borne wax emulsion, deionized water, ethanol, tea saponin, defoamer, flow agent and buffer reagent again, obtain the antibacterial aqueous gloss oil of packages printing finally by grinding distribution.
In wherein said water-based gloss oil, each component concentration is as follows:
50wt% water-borne acrylic resin liquid;
20wt% water-compatible amino resin liquid;
4%wt% carries silver-colored halloysite nanotubes;
5wt% water-borne wax emulsion;
1.5wt% tea saponin;
7.5 wt% deionized waters;
7.5 wt% ethanol;
1.5wt% defoamer;
1.5wt% flow agent;
1.5 wt% buffer reagents.
Embodiment 2
A packages printing preparation method for antibacterial aqueous gloss oil, carries out as follows, and wherein following material number is parts by weight,
(1) preparation of chitin modified halloysite nanotubes:
Getting Nano chitosan, to be made an addition to concentration be stir in the acetic acid aqueous solution of 1wt%, treats that chitosan dissolves in backward solution completely and add Succinic anhydried and ethanol, obtain modified chitosan mixed solution after being uniformly mixed liquid 8h.
By purity be 85% halloysite nanotubes cross 500 mesh sieve, get 20 parts of halloysite nanotubes, 200 parts of concentration are that 3wt% hydrochloric acid soln successively joins in 200 parts of deionized waters, at 50 DEG C of temperature, stir filtration after 4 hours, drying, obtain acid activation halloysite nanotubes.By gained acid activation halloysite nanotubes 400 DEG C of roasting temperatures 3.5 hours, removed the thermal activation halloysite nanotubes of crystal water; Get the thermal activation halloysite nanotubes 10 parts of above-mentioned gained, to be made an addition in 13 portions of modified chitosan mixed solutions and be stirred to thermal activation halloysite nanotubes and be uniformly dispersed, adding acid solution is afterwards adjusted to 2.5-3 by mixed solution pH value, after being uniformly mixed liquid 3h first after through centrifugation, get washing of precipitate, vacuum-drying obtains chitin modified halloysite nanotubes.
(2) preparation of silver-colored halloysite nanotubes is carried:
Getting 10 parts of Silver Nitrates is dissolved in deionized water, the chitin modified halloysite nanotubes of 10 parts of above-mentioned gained is added again in silver nitrate solution, 12h is stirred at 60 DEG C of temperature, suspension is carried out centrifugal after get solid matter, after washing, vacuum-drying, get 10 parts of above-mentioned solid matters and 0.5 part of sodium borohydride joins in the aqueous sodium hydroxide solution of 0.1mol/L, add deionized water and regulate pH to 7.5-8, get solid finally by stirring, centrifugation, washing, drying obtain carrying a silver-colored halloysite nanotubes.
(3) preparation of water-based gloss oil:
Be at 60 DEG C of water-bath back flow reaction 12h by particle diameter after the nano titanium oxide of 15nm, ethanol, deionized water and silane coupling agent mix, then room temperature is down to, product is through centrifugation and washing, obtain silane coupler modified inorganic nano-particle, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupling agent is than being 1:40:10:2.
B, 45 parts of deionized waters and 2 parts of emulsifying agents are put into reactor and is heated to 80 DEG C, again by 15 parts of methyl methacrylates, 15 parts of hydroxyethyl methylacrylates, the silane coupler modified inorganic nano-particle of 20 parts of step a gained, stir after 4 parts of polyoxyethylene glycol and 0.4 part of water soluble starter put into reactor, be incubated after 0.75 hour, 0.4 part of water soluble starter is at the uniform velocity added in 2 hours, and then be incubated 6 hours, stir while add ammoniacal liquor and neutralize afterwards, pH value of solution is made to maintain between 7.5-8.5, vacuumize again and remove free ammoniacal liquor, finally filter and obtain nano-titanium dioxide modified water-borne acrylic resin liquid, above material number is parts by weight.
C, the silver-colored halloysite nanotubes that carries of above-mentioned gained to be added in the mixed resin liquid of nano-titanium dioxide modified water-borne acrylic resin liquid and water-compatible amino resin liquid and stirs, interpolation, water-borne wax emulsion, deionized water, ethanol, tea saponin, defoamer, flow agent and buffer reagent in mixed resin liquid, obtain the antibacterial aqueous gloss oil of packages printing finally by grinding distribution again.
In wherein said water-based gloss oil, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 45wt%;
20 wt% water-compatible amino resin liquid;
4%wt% carries silver-colored halloysite nanotubes;
5wt% water-borne wax emulsion;
1.5wt% tea saponin;
10 wt% deionized waters;
10 wt% ethanol;
1.5wt% defoamer;
1.5wt% flow agent;
1.5 wt% buffer reagents.
Embodiment 3
A packages printing preparation method for antibacterial aqueous gloss oil, carries out as follows, and wherein following material number is parts by weight,
(1) preparation of chitin modified halloysite nanotubes:
Getting Nano chitosan, to be made an addition to concentration be stir in the acetic acid aqueous solution of 5wt%, treats that chitosan dissolves in backward solution completely and add Succinic anhydried and ethanol, obtain modified chitosan mixed solution after being uniformly mixed liquid 8h.
By purity be 90% halloysite nanotubes cross 500 mesh sieve, get 20 parts of halloysite nanotubes, 200 parts of concentration are that 2wt% hydrochloric acid soln successively joins in 200 parts of deionized waters, at 50 DEG C of temperature, stir filtration after 4 hours, drying, obtain acid activation halloysite nanotubes.By gained acid activation halloysite nanotubes 300 DEG C of roasting temperatures 4 hours, removed the thermal activation halloysite nanotubes of crystal water; Get the thermal activation halloysite nanotubes 10 parts of above-mentioned gained, to be made an addition in 10 portions of modified chitosan mixed solutions and be stirred to thermal activation halloysite nanotubes and be uniformly dispersed, adding acid solution is afterwards adjusted to 2.5-3 by mixed solution pH value, after being uniformly mixed liquid 3h first after through centrifugation, get washing of precipitate, vacuum-drying obtains chitin modified halloysite nanotubes.
(2) preparation of silver-colored halloysite nanotubes is carried:
Getting 10 parts of Silver Nitrates is dissolved in deionized water, the chitin modified halloysite nanotubes of 10 parts of above-mentioned gained is added again in silver nitrate solution, 12h is stirred at 50 DEG C of temperature, suspension is carried out centrifugal after get solid matter, after washing, vacuum-drying, get 10 parts of above-mentioned solid matters and 0.5 part of sodium borohydride joins in the aqueous sodium hydroxide solution of 0.1mol/L, add deionized water and regulate pH to 7.5-8, get solid finally by stirring, centrifugation, washing, drying obtain carrying a silver-colored halloysite nanotubes.
(3) preparation of water-based gloss oil:
Be at 60 DEG C of water-bath back flow reaction 8h by particle diameter after the nano titanium oxide of 10nm, ethanol, deionized water and silane coupling agent mix, then room temperature is down to, product is through centrifugation and washing, obtain silane coupler modified inorganic nano-particle, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupling agent is than being 1:30:5:1.
B, 30 parts of deionized waters and 1 part of emulsifying agent are put into reactor and is heated to 80 DEG C, again by 10 parts of acrylic acid amides, 5 parts of methyl acrylates, 5 parts of vinylbenzene, the silane coupler modified inorganic nano-particle of 15 parts of step a gained, stir after 3 parts of polyoxyethylene glycol and 0.25 part of water soluble starter put into reactor, after being incubated 0. 5 hours, 0.25 part of water soluble starter is at the uniform velocity added in 2 hours, and then be incubated 4 hours, stir while add ammoniacal liquor and neutralize afterwards, pH value of solution is made to maintain between 7.5-8.5, vacuumize again and remove free ammoniacal liquor, finally filter and obtain nano-titanium dioxide modified water-borne acrylic resin liquid, above material number is parts by weight.
C, the silver-colored halloysite nanotubes that carries of above-mentioned gained to be added in the mixed resin liquid of nano-titanium dioxide modified water-borne acrylic resin liquid and waterborne polyurethane resin liquid and stirs, interpolation, water-borne wax emulsion, deionized water, ethanol, tea saponin, defoamer, flow agent and buffer reagent in mixed resin liquid, obtain the antibacterial aqueous gloss oil of packages printing finally by grinding distribution again.
In wherein said water-based gloss oil, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 45wt%;
25 wt% waterborne polyurethane resin liquid;
3%wt% carries silver-colored halloysite nanotubes;
3wt% water-borne wax emulsion;
1wt% tea saponin;
10 wt% deionized waters;
10wt% ethanol;
1wt% defoamer;
1wt% flow agent;
1 wt% buffer reagent.
Embodiment 4
A packages printing preparation method for antibacterial aqueous gloss oil, carries out as follows, and wherein following material number is parts by weight,
(1) preparation of chitin modified halloysite nanotubes:
Getting Nano chitosan, to be made an addition to concentration be stir in the acetic acid aqueous solution of 4wt%, treats that chitosan dissolves in backward solution completely and add Succinic anhydried and ethanol, obtain modified chitosan mixed solution after being uniformly mixed liquid 8h.
By purity be 90% halloysite nanotubes cross 500 mesh sieve, get 20 parts of halloysite nanotubes, 200 parts of concentration are that 4wt% hydrochloric acid soln successively joins in 200 parts of deionized waters, at 50 DEG C of temperature, stir filtration after 4 hours, drying, obtain acid activation halloysite nanotubes.By gained acid activation halloysite nanotubes 500 DEG C of roasting temperatures 3 hours, removed the thermal activation halloysite nanotubes of crystal water; Get the thermal activation halloysite nanotubes 10 parts of above-mentioned gained, to be made an addition in 15 portions of modified chitosan mixed solutions and be stirred to thermal activation halloysite nanotubes and be uniformly dispersed, adding acid solution is afterwards adjusted to 2.5-3 by mixed solution pH value, after being uniformly mixed liquid 3h first after through centrifugation, get washing of precipitate, vacuum-drying obtains chitin modified halloysite nanotubes.
(2) preparation of silver-colored halloysite nanotubes is carried:
Getting 10 parts of Silver Nitrates is dissolved in deionized water, the chitin modified halloysite nanotubes of 10 parts of above-mentioned gained is added again in silver nitrate solution, 12h is stirred at 70 DEG C of temperature, suspension is carried out centrifugal after get solid matter, after washing, vacuum-drying, get 10 parts of above-mentioned solid matters and 0.5 part of sodium borohydride joins in the aqueous sodium hydroxide solution of 0.1mol/L, add deionized water and regulate pH to 7.5-8, get solid finally by stirring, centrifugation, washing, drying obtain carrying a silver-colored halloysite nanotubes.
(3) preparation of water-based gloss oil:
Be at 60 DEG C of water-bath back flow reaction 16h by particle diameter after the nano titanium oxide of 20nm, ethanol, deionized water and silane coupling agent mix, then room temperature is down to, product is through centrifugation and washing, obtain silane coupler modified inorganic nano-particle, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupling agent is than being 1:50:15:3.
B, 60 parts of deionized waters and 3 parts of emulsifying agents are put into reactor and is heated to 80 DEG C, again by 20 parts of β-dimethyl-aminoethylmethacrylates, 10 parts of hydroxyethyl methylacrylates, 10 parts of vinylbenzene, the silane coupler modified inorganic nano-particle of 25 parts of step a gained, stir after 5 parts of polyoxyethylene glycol and 0.5 part of water soluble starter put into reactor, be incubated after 1 hour, 0.5 part of water soluble starter is at the uniform velocity added in 2 hours, and then be incubated 8 hours, stir while add ammoniacal liquor and neutralize afterwards, pH value of solution is made to maintain between 7.5-8.5, vacuumize again and remove free ammoniacal liquor, finally filter and obtain nano-titanium dioxide modified water-borne acrylic resin liquid, above material number is parts by weight.
C, the silver-colored halloysite nanotubes that carries of above-mentioned gained to be added in the mixed resin liquid of nano-titanium dioxide modified water-borne acrylic resin liquid and water-compatible amino resin liquid and stirs, interpolation, water-borne wax emulsion, deionized water, ethanol, tea saponin, defoamer, flow agent and buffer reagent in mixed resin liquid, obtain the antibacterial aqueous gloss oil of packages printing finally by grinding distribution again.
In wherein said water-based gloss oil, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 45wt%;
15 wt% maleic acid resin liquid;
5%wt% carries silver-colored halloysite nanotubes;
7wt% water-borne wax emulsion;
2wt% tea saponin;
10wt% deionized water;
10 wt% ethanol;
2wt% defoamer;
2wt% flow agent;
2 wt% buffer reagents.
Embodiment 5
A packages printing preparation method for antibacterial aqueous gloss oil, carries out as follows, and wherein following material number is parts by weight,
(1) preparation of chitin modified halloysite nanotubes:
Getting Nano chitosan, to be made an addition to concentration be stir in the acetic acid aqueous solution of 3wt%, treats that chitosan dissolves in backward solution completely and add Succinic anhydried and ethanol, obtain modified chitosan mixed solution after being uniformly mixed liquid 8h.
By purity be 90% halloysite nanotubes cross 500 mesh sieve, get 20 parts of halloysite nanotubes, 200 parts of concentration are that 3wt% hydrochloric acid soln successively joins in 200 parts of deionized waters, at 50 DEG C of temperature, stir filtration after 4 hours, drying, obtain acid activation halloysite nanotubes.By gained acid activation halloysite nanotubes 400 DEG C of roasting temperatures 4 hours, removed the thermal activation halloysite nanotubes of crystal water; Get the thermal activation halloysite nanotubes 10 parts of above-mentioned gained, to be made an addition in 12 portions of modified chitosan mixed solutions and be stirred to thermal activation halloysite nanotubes and be uniformly dispersed, adding acid solution is afterwards adjusted to 2.5-3 by mixed solution pH value, after being uniformly mixed liquid 3h first after through centrifugation, get washing of precipitate, vacuum-drying obtains chitin modified halloysite nanotubes.
(2) preparation of silver-colored halloysite nanotubes is carried:
Getting 10 parts of Silver Nitrates is dissolved in deionized water, the chitin modified halloysite nanotubes of 10 parts of above-mentioned gained is added again in silver nitrate solution, 12h is stirred at 55 DEG C of temperature, suspension is carried out centrifugal after get solid matter, after washing, vacuum-drying, get 10 parts of above-mentioned solid matters and 0.5 part of sodium borohydride joins in the aqueous sodium hydroxide solution of 0.1mol/L, add deionized water and regulate pH to 7.5-8, get solid finally by stirring, centrifugation, washing, drying obtain carrying a silver-colored halloysite nanotubes.
(3) preparation of water-based gloss oil:
Be at 60 DEG C of water-bath back flow reaction 11h by particle diameter after the nano titanium oxide of 10nm, ethanol, deionized water and silane coupling agent mix, then room temperature is down to, product is through centrifugation and washing, obtain silane coupler modified inorganic nano-particle, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupling agent is than being 1:35:8:2.
B, 50 parts of deionized waters and 2 parts of emulsifying agents are put into reactor and is heated to 80 DEG C, again by 14 parts of β-dimethyl-aminoethylmethacrylates, 14 parts of acrylamides, the silane coupler modified inorganic nano-particle of 18 parts of step a gained, stir after 3 parts of polyoxyethylene glycol and 0.4 part of water soluble starter put into reactor, after being incubated 0. 5 hours, 0.4 part of water soluble starter is at the uniform velocity added in 2 hours, and then be incubated 5 hours, stir while add ammoniacal liquor and neutralize afterwards, pH value of solution is made to maintain between 7.5-8.5, vacuumize again and remove free ammoniacal liquor, finally filter and obtain nano-titanium dioxide modified water-borne acrylic resin liquid, above material number is parts by weight.
C, the silver-colored halloysite nanotubes that carries of above-mentioned gained to be added in the mixed resin liquid of nano-titanium dioxide modified water-borne acrylic resin liquid and waterborne polyurethane resin liquid and stirs, in mixed resin liquid, add water-borne wax emulsion, deionized water, ethanol, tea saponin, defoamer, flow agent and buffer reagent again, obtain the antibacterial aqueous gloss oil of packages printing finally by grinding distribution.
In wherein said water-based gloss oil, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 51wt%;
20wt% waterborne polyurethane resin liquid;
3%wt% carries silver-colored halloysite nanotubes;
3wt% water-borne wax emulsion;
1wt% tea saponin;
8 wt% deionized waters;
10wt% ethanol;
1wt% defoamer;
1wt% flow agent;
1 wt% buffer reagent.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent transformation, all still belong to the protection domain of technical solution of the present invention.
Claims (7)
1. a packages printing preparation method for antibacterial aqueous gloss oil, it is characterized in that carrying out as follows, wherein following material number is parts by weight,
(1) preparation of chitin modified halloysite nanotubes:
Getting chitosan, to be made an addition to concentration be stir in the acetic acid aqueous solution of 1-5wt%, treats that chitosan dissolves in backward solution completely and add Succinic anhydried and ethanol, obtain modified chitosan mixed solution after being uniformly mixed liquid 8h; By halloysite nanotubes at 300-500 DEG C of roasting temperature 3-4 hour, removed the thermal activation halloysite nanotubes of crystal water; Get the thermal activation halloysite nanotubes 10 parts of above-mentioned gained, to be made an addition in 10-15 part modified chitosan mixed solution and be stirred to thermal activation halloysite nanotubes and be uniformly dispersed, adding acid solution is afterwards adjusted to 2.5-3 by mixed solution pH value, after being uniformly mixed liquid 3h first after through centrifugation, get washing of precipitate, vacuum-drying obtains chitin modified halloysite nanotubes;
(2) preparation of silver-colored halloysite nanotubes is carried:
Getting 10 parts of Silver Nitrates is dissolved in deionized water, the chitin modified halloysite nanotubes of 10 parts of above-mentioned gained is added again in silver nitrate solution, 12h is stirred at 50-70 DEG C of temperature, suspension is carried out centrifugal after get solid matter, after washing, vacuum-drying, get 10 parts of above-mentioned solid matters and 0.5 part of sodium borohydride joins in the aqueous sodium hydroxide solution of 0.01mol/L, add deionized water and regulate pH to 7.5-8, get solid finally by stirring, centrifugation, washing, drying obtain carrying a silver-colored halloysite nanotubes;
(3) preparation of water-based gloss oil:
The silver-colored halloysite nanotubes that carries of above-mentioned gained to be added in the mixed resin liquid of water-base resin liquid A and water-base resin liquid B and stirs, in mixed resin liquid, add water wax emulsion, ionized water, ethanol, tea saponin, defoamer, flow agent and buffer reagent again, obtain the antibacterial aqueous gloss oil of packages printing finally by grinding distribution;
In wherein said water-based gloss oil, each component concentration is as follows:
45-55wt% water-base resin liquid A;
15-25 wt% water-base resin liquid B;
3-5%wt% carries silver-colored halloysite nanotubes;
3-7wt% water-borne wax emulsion;
1-2wt% tea saponin;
5-10 wt% deionized water;
5-10 wt% ethanol;
1-2wt% defoamer;
1-2 wt% flow agent;
1-2 wt% buffer reagent;
Described water-base resin liquid A is water-borne acrylic resin liquid,
Described water-base resin liquid B is selected from the one in water-compatible amino resin liquid, maleic acid resin liquid, waterborne polyurethane resin liquid.
2. the packages printing preparation method of antibacterial aqueous gloss oil as claimed in claim 1, it is characterized in that, the chitosan in described step (1) is Nano chitosan.
3. the packages printing as claimed in claim 1 preparation method of antibacterial aqueous gloss oil, it is characterized in that, the purity of halloysite nanotubes before thermal activation in described step (1) is not less than 85%, and halloysite nanotubes before thermal activation through acid activation, acid activation method is as follows:
Be that 2-4wt% hydrochloric acid soln successively joins in 200 parts of deionized waters by 20 parts of halloysite nanotubes, 200 parts of concentration, stir at 50 DEG C of temperature after 4 hours filter, dry, obtain acid activation halloysite nanotubes.
4. the preparation method of antibacterial aqueous gloss oil of the packages printing as described in claim 1 or 3, is characterized in that, the halloysite nanotubes in described step (1) crosses 500 mesh sieve before the reaction.
5. the packages printing preparation method of antibacterial aqueous gloss oil as claimed in claim 1, it is characterized in that, the water-borne acrylic resin liquid in described step (3) is nano-titanium dioxide modified water-borne acrylic resin liquid, and method of modifying is as follows:
A, nano titanium oxide, ethanol, deionized water and silane coupling agent are mixed after at 60 DEG C of water-bath back flow reaction 8-16h, then room temperature is down to, product is through centrifugation and washing, obtain silane coupler modified inorganic nano-particle, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupling agent is than being 1:30-50:5-15:1-3;
B, 30-60 part deionized water and 1-3 part emulsifying agent are put into reactor and is heated to 80 DEG C, again by 20-40 part acrylic monomer, the silane coupler modified inorganic nano-particle of 15-25 part step a gained, stir after 3-5 part polyoxyethylene glycol and 0.25-0.5 part water soluble starter put into reactor, be incubated after 0.5-1 hour, 0.25-0.5 part water soluble starter is at the uniform velocity added in 2 hours, and then be incubated 4-8 hour, stir while add ammoniacal liquor and neutralize afterwards, pH value of solution is made to maintain between 7.5-8.5, vacuumize again and remove free ammoniacal liquor, finally filter and obtain nano-titanium dioxide modified water-borne acrylic resin liquid, above material number is parts by weight.
6. the packages printing preparation method of antibacterial aqueous gloss oil as claimed in claim 5, it is characterized in that, the particle diameter of described nano titanium oxide is at 10-20nm.
7. the packages printing as claimed in claim 5 preparation method of antibacterial aqueous gloss oil, it is characterized in that, described acrylic monomer is selected from least two kinds in methyl methacrylate, methyl acrylate, vinylbenzene, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methylacrylate, acrylamide.
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| CN106189496A (en) * | 2016-08-17 | 2016-12-07 | 郑文忠 | A kind of preparation method of antibacterial composite joint material water color ink |
| CN106221362A (en) * | 2016-08-17 | 2016-12-14 | 陈年康 | A kind of low murder by poisoning UV cured printing ink composition |
| CN106221371A (en) * | 2016-08-17 | 2016-12-14 | 郑文忠 | A kind of antibacterial composite joint material water color ink |
| CN106280703A (en) * | 2016-08-17 | 2017-01-04 | 陈年康 | A kind of preparation method of ink based on natural modified binder |
| CN106318035A (en) * | 2016-08-17 | 2017-01-11 | 陈年康 | Ink based on naturally-modified binding material |
| CN106318020A (en) * | 2016-08-17 | 2017-01-11 | 郑文忠 | Wear-proof UV solidification ink composition |
| CN106349804A (en) * | 2016-08-17 | 2017-01-25 | 陈年康 | Preparation method of low-poison UV (ultraviolet)-curing ink composition |
| CN106883707A (en) * | 2017-03-21 | 2017-06-23 | 广州润沃材料科技有限公司 | A kind of galapectite antibiotic water paint and preparation method and application |
| CN107604764A (en) * | 2017-10-13 | 2018-01-19 | 惠州市惠强塑料包装有限公司 | A kind of preparation method of antibacterial wrapping paper |
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