CN104725933A - Preparation method of water-based ink, containing Ag-carrying chitosan composite antibacterial material, for tipping paper - Google Patents
Preparation method of water-based ink, containing Ag-carrying chitosan composite antibacterial material, for tipping paper Download PDFInfo
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- CN104725933A CN104725933A CN201510069503.9A CN201510069503A CN104725933A CN 104725933 A CN104725933 A CN 104725933A CN 201510069503 A CN201510069503 A CN 201510069503A CN 104725933 A CN104725933 A CN 104725933A
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- water
- resin liquid
- silver
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- chitosan
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000008367 deionised water Substances 0.000 claims abstract description 41
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 41
- 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
- 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
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims description 47
- 239000007799 cork Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 239000004925 Acrylic resin Substances 0.000 claims description 26
- 229920000178 Acrylic resin Polymers 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000005119 centrifugation Methods 0.000 claims description 20
- 238000005406 washing 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 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000003115 biocidal effect Effects 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 239000000049 pigment 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- -1 hydroxyalkyl acrylates Chemical class 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
- 239000000975 dye Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 229920003180 amino resin Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229920005749 polyurethane resin Polymers 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 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
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- 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 group 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 6
- 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
- 239000012860 organic pigment Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 235000017709 saponins Nutrition 0.000 description 18
- 239000003643 water by type Substances 0.000 description 8
- 235000019504 cigarettes Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009736 wetting Methods 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002070 germicidal effect Effects 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
- 230000003534 oscillatory effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 208000009146 rhinoscleroma Diseases 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- 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
-
- 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
- C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde 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
- C09D11/14—Printing inks based on carbohydrates
Abstract
The invention relates to the technical field of water-based ink and discloses a preparation method of water-based ink, containing an Ag-carrying chitosan composite antibacterial material, for tipping paper. The preparation method comprises the following steps: (1) preparing Ag-carrying chitosan; (2) compounding Ag-carrying chitosan with a water-based resin liquid A and a water-based resin liquid B and then compounding a mixed resin liquid with deionized water, ethanol, tea saponin, an organic pigment, a defoaming agent, a levelling agent and a buffer agent, thus preparing the water-based ink, containing the Ag-carrying chitosan composite antibacterial material, for tipping paper. The preparation method has the beneficial effects that containing various antibacterial components, such as nano-silver, chitosan, titanium dioxide and tea saponin, the water-based ink 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-based ink is quite outstanding.
Description
Technical field
The present invention relates to water color ink technical field, particularly relate to a kind of preparation method of the cork paper water color ink containing year silver-colored chitosan composite antibiotic material.
Background technology
Cork paper, has another name called " tipping paper ", is one of important materials of producing cigarette.It take tipping base paper as base material, by operations such as design before printing, printing processing and print aftertreatments, and a kind of Special industrial paper that filter tip and Cigarette cigarette are got up.Because cork paper directly contacts with lip in use, therefore, the paper of cork paper and the ink be printed on cork paper must be harmless to human non-toxic.Because solvent type ink contains a large amount of organic volatile solvents, not only harmful, be also unfavorable for environmental protection, because water color ink more and more obtains attention gradually.But for the development of water color ink, especially for the water color ink of cork paper, can not only rest in self nontoxic research, because cigarette holder contacts with mouth continually, the hygienic requirements of cigarette holder is very high, germyly can not exist, if cork paper use ink 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.But weak point is titanium dioxide and other compositions is only physical mixed, although serve anti-microbial effect, dispersed 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, and dispersion stabilization is good, without scleroma property precipitation, without cohesion, the advantages such as noresidue peculiar smell, sterilant is directly allocated in water color ink by this invention, although this sterilant can play germicidal action, but the broad-spectrum of single sterilant is little, sterilization effect is limited, in addition may also can be harmful, causes side effect.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of the cork paper water color ink containing year silver-colored chitosan composite antibiotic material, water color ink 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 preparation method of the cork paper water color ink containing year silver-colored chitosan composite antibiotic material, and carry out as follows, wherein following material number is parts by weight,
(1) preparation of silver-colored chitosan is carried:
Get 10 parts of chitosans and made an addition to 100 parts of deionized water for stirring to dissolving, 10 parts of Silver Nitrates are added again in chitosan solution, diluted nitric acid aqueous solution is dripped until pH value of solution is 3-4 after stirring, then 60 DEG C of stirring heating 3h are bathed at lucifuge Water Under, again by suspension first after through centrifugation, get solid matter washing, after 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, finally by stirring, solid is got in centrifugation, washing, drying obtains carrying silver-colored chitosan.
Nanometer silver has very strong sterilizing ability, and broad-spectrum is strong.Chitosan has the ability of stronger complex silver ion, after chitosan carries out complexing to silver ions, then silver ion reduction is become more stable nano-Ag particles, and thus on nano-silver loaded and chitosan basal body, chitosan self also has certain anti-microbial property in addition.
(2) preparation of water color ink:
The silver-colored chitosan 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 deionized water, ethanol, pigment dyestuff, tea saponin, defoamer, flow agent and buffer reagent again, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution;
In wherein said water color ink, each component concentration is as follows:
30-40wt% water-base resin liquid A;
10-20 wt% water-base resin liquid B;
3-5%wt% carries silver-colored chitosan;
0.5-1.5wt% tea saponin;
5-15 wt% deionized water;
10-20 wt% ethanol;
10-25 wt% pigment dyestuff;
0.5-1.5wt% 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 water-borne acrylic resin liquid in described step (2) 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 10-20 part alkyl acrylate monomer, 10-20 part hydroxyalkyl acrylates 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.
As preferably, the particle diameter of described nano titanium oxide is at 10-20nm.
As preferably, described alkyl acrylate monomer is methyl methacrylate, β-dimethyl-aminoethylmethacrylate or butyl acrylate; Described hydroxyalkyl acrylates monomer is hydroxyethyl methylacrylate or Rocryl 410.
Silane coupling agent is adopted to carry out modification to nano titanium oxide, can with acrylate 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.
The invention has the beneficial effects as follows: the present invention carries out complexing by chitosan to silver ions, again silver ion reduction is become more stable nano-Ag particles, make nano-silver loaded on chitosan, after silver-colored chitosan and water-base resin compound will be carried, nanometer silver can play its outstanding bacteriostasis, meanwhile, chitosan is also a kind of natural antibacterial, makes water color ink 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 color ink, tea saponin has outstanding emulsification, wetting, dispersing property, the effect of dispersion agent can be played in water color ink, 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 color ink 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 color ink 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 color ink is very outstanding.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
A preparation method for cork paper water color ink containing year silver-colored chitosan composite antibiotic material, carry out as follows, wherein following material number is parts by weight,
(1) preparation of silver-colored chitosan is carried:
Get 10 parts of Nano chitosans and made an addition to 100 parts of deionized water for stirring to dissolving, 10 parts of Silver Nitrates are added again in chitosan solution, diluted nitric acid aqueous solution is dripped until pH value of solution is 3-4 after stirring, then 60 DEG C of stirring heating 3h are bathed at lucifuge Water Under, again by suspension first after through centrifugation, get solid matter washing, after 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, finally by stirring, solid is got in centrifugation, washing, drying obtains carrying silver-colored chitosan.
(2) preparation of water color ink:
The silver-colored chitosan 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 deionized water, ethanol, pigment dyestuff, tea saponin, defoamer, flow agent and buffer reagent again, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution.
In wherein said water color ink, each component concentration is as follows:
35wt% water-borne acrylic resin liquid;
15 wt% water-compatible amino resin liquid;
4%wt% carries silver-colored chitosan;
1wt% tea saponin;
10 wt% deionized waters;
15 wt% ethanol;
16 wt% pigment dyestuffs;
1wt% defoamer;
1.5wt% flow agent;
1.5 wt% buffer reagents.
Embodiment 2
A preparation method for cork paper water color ink containing year silver-colored chitosan composite antibiotic material, carry out as follows, wherein following material number is parts by weight,
(1) preparation of silver-colored chitosan is carried:
Get 10 parts of Nano chitosans and made an addition to 100 parts of deionized water for stirring to dissolving, 10 parts of Silver Nitrates are added again in chitosan solution, diluted nitric acid aqueous solution is dripped until pH value of solution is 3-4 after stirring, then 60 DEG C of stirring heating 3h are bathed at lucifuge Water Under, again by suspension first after through centrifugation, get solid matter washing, after 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, finally by stirring, solid is got in centrifugation, washing, drying obtains carrying silver-colored chitosan.
(2) preparation of water color ink:
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 chitosan 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, in mixed resin liquid, add deionized water, ethanol, pigment dyestuff, tea saponin, defoamer, flow agent and buffer reagent again, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution.
In wherein said water color ink, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 35wt%;
15 wt% water-compatible amino resin liquid;
4%wt% carries silver-colored chitosan;
1wt% tea saponin;
10 wt% deionized waters;
15 wt% ethanol;
16 wt% pigment dyestuffs;
1wt% defoamer;
1.5wt% flow agent;
1.5 wt% buffer reagents.
Embodiment 3
A preparation method for cork paper water color ink containing year silver-colored chitosan composite antibiotic material, carry out as follows, wherein following material number is parts by weight,
(1) preparation of silver-colored chitosan is carried:
Get 10 parts of Nano chitosans and made an addition to 100 parts of deionized water for stirring to dissolving, 10 parts of Silver Nitrates are added again in chitosan solution, diluted nitric acid aqueous solution is dripped until pH value of solution is 3-4 after stirring, then 60 DEG C of stirring heating 3h are bathed at lucifuge Water Under, again by suspension first after through centrifugation, get solid matter washing, after 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, finally by stirring, solid is got in centrifugation, washing, drying obtains carrying silver-colored chitosan.
(2) preparation of water color ink:
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 butyl acrylates, 10 parts of Rocryl 410s, 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 chitosan 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 deionized water, ethanol, pigment dyestuff, tea saponin, defoamer, flow agent and buffer reagent again, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution.
In wherein said water color ink, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 30wt%;
15 wt% waterborne polyurethane resin liquid;
3%wt% carries silver-colored chitosan;
0.5wt% tea saponin;
15 wt% deionized waters;
20wt% ethanol;
14 wt% pigment dyestuffs;
0.5wt% defoamer;
1wt% flow agent;
1 wt% buffer reagent.
Embodiment 4
A preparation method for cork paper water color ink containing year silver-colored chitosan composite antibiotic material, carry out as follows, wherein following material number is parts by weight,
(1) preparation of silver-colored chitosan is carried:
Get 10 parts of Nano chitosans and made an addition to 100 parts of deionized water for stirring to dissolving, 10 parts of Silver Nitrates are added again in chitosan solution, diluted nitric acid aqueous solution is dripped until pH value of solution is 3-4 after stirring, then 60 DEG C of stirring heating 3h are bathed at lucifuge Water Under, again by suspension first after through centrifugation, get solid matter washing, after 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, finally by stirring, solid is got in centrifugation, washing, drying obtains carrying silver-colored chitosan.
(2) preparation of water color ink:
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 methyl methacrylates, 20 parts of hydroxyethyl methylacrylates, 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 chitosan 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, in mixed resin liquid, add deionized water, ethanol, pigment dyestuff, tea saponin, defoamer, flow agent and buffer reagent again, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution.
In wherein said water color ink, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 40wt%;
10 wt% maleic acid resin liquid;
5%wt% carries silver-colored chitosan;
1.5wt% tea saponin;
10wt% deionized water;
10 wt% ethanol;
21 wt% pigment dyestuffs;
0.5wt% defoamer;
1wt% flow agent;
1 wt% buffer reagent.
Embodiment 5
A preparation method for cork paper water color ink containing year silver-colored chitosan composite antibiotic material, carry out as follows, wherein following material number is parts by weight,
(1) preparation of silver-colored chitosan is carried:
Get 10 parts of Nano chitosans and made an addition to 100 parts of deionized water for stirring to dissolving, 10 parts of Silver Nitrates are added again in chitosan solution, diluted nitric acid aqueous solution is dripped until pH value of solution is 3-4 after stirring, then 60 DEG C of stirring heating 3h are bathed at lucifuge Water Under, again by suspension first after through centrifugation, get solid matter washing, after 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, finally by stirring, solid is got in centrifugation, washing, drying obtains carrying silver-colored chitosan.
(2) preparation of water color ink:
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 Rocryl 410s, 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 chitosan 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 deionized water, ethanol, pigment dyestuff, tea saponin, defoamer, flow agent and buffer reagent again, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution.
In wherein said water color ink, each component concentration is as follows:
The nano-titanium dioxide modified water-borne acrylic resin liquid of 31wt%;
13wt% waterborne polyurethane resin liquid;
3%wt% carries silver-colored chitosan;
1wt% tea saponin;
11 wt% deionized waters;
13wt% ethanol;
25wt% pigment dyestuff;
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 (5)
1. a preparation method for the cork paper water color ink containing year silver-colored chitosan composite antibiotic material, it is characterized in that carrying out as follows, wherein following material number is parts by weight,
(1) preparation of silver-colored chitosan is carried:
Get 10 parts of chitosans and made an addition to 100 parts of deionized water for stirring to dissolving, 10 parts of Silver Nitrates are added again in chitosan solution, diluted nitric acid aqueous solution is dripped until pH value of solution is 3-4 after stirring, then 60 DEG C of stirring heating 3h are bathed at lucifuge Water Under, again by suspension first after through centrifugation, get solid matter washing, after 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, finally by stirring, solid is got in centrifugation, washing, drying obtains carrying silver-colored chitosan,
(2) preparation of water color ink:
The silver-colored chitosan 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 deionized water, ethanol, pigment dyestuff, tea saponin, defoamer, flow agent and buffer reagent again, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution;
In wherein said water color ink, each component concentration is as follows:
30-40wt% water-base resin liquid A;
10-20 wt% water-base resin liquid B;
3-5%wt% carries silver-colored chitosan;
0.5-1.5wt% tea saponin;
5-15 wt% deionized water;
10-20 wt% ethanol;
10-25 wt% pigment dyestuff;
0.5-1.5wt% 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 preparation method of the cork paper water color ink containing year silver-colored chitosan composite antibiotic material as claimed in claim 1, it is characterized in that, the chitosan in described step (1) is Nano chitosan.
3. the preparation method of the cork paper water color ink containing year silver-colored chitosan composite antibiotic material as claimed in claim 1, it is characterized in that, water-borne acrylic resin liquid in described step (2) 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 10-20 part alkyl acrylate monomer, 10-20 part hydroxyalkyl acrylates 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.
4. the preparation method of the cork paper water color ink containing year silver-colored chitosan composite antibiotic material as claimed in claim 3, it is characterized in that, the particle diameter of described nano titanium oxide is at 10-20nm.
5. the preparation method of the cork paper water color ink containing year silver-colored chitosan composite antibiotic material as claimed in claim 3, it is characterized in that, described alkyl acrylate monomer is methyl methacrylate, β-dimethyl-aminoethylmethacrylate or butyl acrylate; Described hydroxyalkyl acrylates monomer is hydroxyethyl methylacrylate or Rocryl 410.
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| CN109911837A (en) * | 2019-04-08 | 2019-06-21 | 宁波博洋家纺集团有限公司 | One kind keeps warm fluffy eiderdown quilt and its preparation process |
| CN113389043A (en) * | 2021-05-28 | 2021-09-14 | 朱德内 | Crease-resistant antifouling suit fabric and preparation method thereof |
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Cited By (5)
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| CN105542561A (en) * | 2016-03-01 | 2016-05-04 | 蒋彩云 | Antibacterial water-based ink and preparation method thereof |
| CN108939708A (en) * | 2018-06-26 | 2018-12-07 | 江苏新亿源环保科技有限公司 | A kind of preparation method of air disinfection filter membrane |
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| CN113389043A (en) * | 2021-05-28 | 2021-09-14 | 朱德内 | Crease-resistant antifouling suit fabric and preparation method thereof |
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Denomination of invention: A preparation method of tipping paper water-based ink containing silver loaded chitosan composite antibacterial material Effective date of registration: 20220708 Granted publication date: 20170118 Pledgee: Changxin Zhejiang rural commercial bank Limited by Share Ltd. Pledgor: CHANGXING AIFEITE PLASTIC TECHNOLOGY CO.,LTD. Registration number: Y2022330001299 |