CN104725933B - 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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- CN104725933B CN104725933B CN201510069503.9A CN201510069503A CN104725933B CN 104725933 B CN104725933 B CN 104725933B CN 201510069503 A CN201510069503 A CN 201510069503A CN 104725933 B CN104725933 B CN 104725933B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 39
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001397 quillaja saponaria molina bark 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
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000000872 buffer Substances 0.000 claims abstract description 14
- 239000012860 organic pigment Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 35
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- 229910000077 silane Inorganic materials 0.000 claims description 25
- 239000004925 Acrylic resin Substances 0.000 claims description 24
- 239000007799 cork Substances 0.000 claims description 24
- 229920000178 Acrylic resin Polymers 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 21
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 239000013530 defoamer Substances 0.000 claims description 15
- 239000003643 water by type Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000003115 biocidal effect Effects 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- -1 hydroxyalkyl acrylates Chemical class 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000000470 constituent 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
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 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
- 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
- 238000000034 method Methods 0.000 claims description 4
- 235000009566 rice Nutrition 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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 230000003139 buffering effect Effects 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 241001122767 Theaceae Species 0.000 abstract 2
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 235000019504 cigarettes Nutrition 0.000 description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000003899 bactericide agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000049 pigment Substances 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
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 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
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012805 post-processing 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
- 238000007665 sagging Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
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, more particularly, to a kind of water containing the silver-colored chitosan composite antibiotic material of load
The preparation method of loose paper water color ink.
Background technology
Cork paper, also known as " tipping paper ", are to produce one of important materials of cigarette.It is passed through with tipping base paper as base material
The operations such as design before printing, printing processing and print post processing, a kind of Special industrial paper that filter tip and Cigarette cigarette are got up.By
It is and lip directly contact that therefore, the paper of cork paper and the ink being printed on cork paper must in cork paper when using
Must be nontoxic to human body.Because solvent type ink contains substantial amounts of organic volatile solvent, it is not only harmful to human body, also not
Beneficial to environmental protection, because water color ink is gradually increasingly paid attention to.But the development for water color ink, especially for water
The water color ink of loose paper it is impossible to only reside within itself nontoxic research, because cigarette holder is continually contacted with mouth, cigarette holder
Hygienic requirements very high it is impossible to germy presence, if cork paper water color ink has antibacterial functions, can effectively solving
This problem.
Wang Can just waits and discloses a kind of antibacterial water in " the Tipping Paper Antibacterial Water-based Ink research " that " Packaging Engineering " is delivered
Property ink, it is filled a prescription and is: benzidine yellow 5%, titanium dioxide 25%, water-borne acrylic resin liquid 45%, ethanol 15% and deionization
Water 10%.This water color ink has good printability on cork paper, and has good antibacterial effect.But deficiency
Place be titanium dioxide with other compositions be only physical mixed although serving antibacterial action, but dispersiveness is general.
Chinese invention patent cn 102952431a discloses a kind of cigarette cork paper water color ink and preparation method thereof, bag
Include aqueous emulsifying resinon 50-60 part+iron oxide pigment 10-20 part+deionized water 10-20 part+defoamer, sagging inhibitor, stream
One of flat agent, wetting agent, antiseptic, wetting dispersing agent, surface tension agent aid or more than one 0.5-1 parts.This invention
Cigarette cork paper water color ink to have a fineness little, rate of drying is fast, and denseness is high, and viscosity is low, and dispersion stabilization is good, no scleroma property
Precipitation, no condenses, and the advantages of noresidue peculiar smell, bactericide is directly allocated in water color ink by this invention, though this bactericide
Bactericidal action so can be played, but the broad-spectrum of single bactericide is little, bactericidal effect is limited, additionally may also can be right
Human body is harmful to, and causes side effect.
Content of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of yew containing the silver-colored chitosan composite antibiotic material of load
The preparation method of paper water color ink, the water color ink bactericide dispersion effect of the method preparation is good, broad-spectrum is strong, antibacterial effect
Fruit is strong.
The concrete technical scheme of the present invention is: a kind of cork paper water color ink containing the silver-colored chitosan composite antibiotic material of load
Preparation method, carry out as follows, wherein following material number is parts by weight,
(1) preparation of the silver-colored shitosan of load:
Take 10 parts of shitosans being made an addition in 100 parts of deionized waters to stir to dissolving, then add in chitosan solution
Plus 10 parts of silver nitrates, after stirring, dropping diluted nitric acid aqueous solution is 3-4 up to solution ph, then water-bath 60 under the conditions of lucifuge
DEG C agitating heating 3h, then suspension priority is centrifuged, takes solid matter washing, after vacuum drying, take 10 parts above-mentioned solid
Body material and 0.5 part of sodium borohydride are added in the sodium hydrate aqueous solution of 0.01mol/l, plus deionized water adjusts ph to 7.5-
8, finally agitated, centrifugation takes solid, washs, is dried to obtain the silver-colored shitosan of load.
Nano Silver has very strong sterilizing ability, and broad-spectrum is strong.Shitosan has stronger complexing silver ion
Ability, after shitosan is complexed to silver ion, then silver ion reduction is become more stable nano-Ag particles, is born by this Nano Silver
In load and chitosan basal body, shitosan itself also has certain anti-microbial property in addition.
(2) preparation of water color ink:
The silver-colored shitosan that carries of above-mentioned gained is added in the mixed resin liquid of water-base resin liquid a and water-base resin liquid b simultaneously
And stir, then in mixed resin liquid add deionized water, ethanol, organic pigment, Tea Saponin, defoamer, levelling agent and
Buffer, obtains the cork paper water color ink containing composite antibacterial material finally by grinding distribution；
In wherein said water color ink, each constituent content is as follows:
30-40wt% water-base resin liquid a；
10-20 wt% water-base resin liquid b；
3-5%wt% carries silver-colored shitosan；
0.5-1.5wt% Tea Saponin；
5-15 wt% deionized water；
10-20 wt% ethanol；
10-25 wt% organic pigment；
0.5-1.5wt% defoamer；
1-2 wt% levelling agent；
1-2 wt% buffer;
Described water-base resin liquid a is water-borne acrylic resin liquid,
Described water-base resin liquid b be selected from water-compatible amino resin liquid, maleic acid resin liquid, in waterborne polyurethane resin liquid one
Kind.
Preferably, the shitosan in described step (1) is Nano chitosan.
Preferably, the water-borne acrylic resin liquid in described step (2) is nano-titanium dioxide modified water soluble acrylic acid
Resin liquid, method of modifying is as follows:
A, nano titanium oxide, ethanol, deionized water and silane coupler are mixed after anti-in 60 DEG C of water-baths backflow
Answer 8-16h, be then down to room temperature, product, through centrifugation and washing, obtains silane coupler modified inorganic nano-particle, institute
State the weight consumption of nano titanium oxide, ethanol, deionized water and silane coupler than for 1:30-50:5-15:1-3；
B, 30-60 part deionized water and 1-3 part emulsifying agent are put into reactor it is heated to 80 DEG C, then by 10-20 part alkane
Base acrylate monomer, 10-20 part hydroxyalkyl acrylates monomer, 15-25 part step a gained silane coupler modified inorganic
Nano-particle, 3-5 part polyethylene glycol and 0.25-0.5 part water soluble starter stir after putting into reactor, are incubated 0.5-1
After hour, at the uniform velocity add 0.25-0.5 part water soluble starter in 2 hours, be then incubated 4-8 hour again, stir afterwards
While adding ammoniacal liquor to be neutralized, so that solution ph is maintained between 7.5-8.5, then vacuumize the free ammoniacal liquor of removal, finally mistake
Filter obtains nano-titanium dioxide modified water-borne acrylic resin liquid, and above material number is parts by weight.
Preferably, the particle diameter of described nano titanium oxide is in 10-20nm.
Preferably, described alkyl acrylate monomer is methyl methacrylate, EMA or third
Olefin(e) acid butyl ester；Described hydroxyalkyl acrylates monomer is hydroxyethyl methacrylate or hydroxy propyl methacrylate.
Using silane coupler, nano titanium oxide is modified so as to can be with acrylate monomer copolymerization, by nanometer
Titanium dioxide and hydroxyalkyl are incorporated on water-borne acrylic resin, modified after nano titanium oxide directly participate in be polymerized,
Being evenly distributed in resin, to the modified effect of water-borne acrylic resin more preferably.Nano titanium oxide has outstanding fast light old
Change performance and antibacterial and mouldproof performance.
The invention has the beneficial effects as follows: the present invention is complexed to silver ion by shitosan, then silver ion reduction is become
More stable nano-Ag particles, so that nano-silver loaded is on shitosan, will carry after silver-colored shitosan is combined with water-base resin, nanometer
Silver can play its outstanding bacteriostasis, and meanwhile, shitosan is also a kind of natural antibacterial, makes water color ink have antibiotic property
Energy.
Water-borne acrylic resin liquid is carried out with water-compatible amino resin liquid, maleic acid resin liquid or waterborne polyurethane resin liquid
Compounding, the advantage having merged various resins, compensate for each shortcoming belonging to resin.
With the addition of Tea Saponin in the formula of water color ink, Tea Saponin has outstanding emulsification, wetting, dispersive property,
The effect of dispersant can be played, moreover, Tea Saponin also has certain sterilizing function, to golden yellow Portugal in water color ink
Grape coccus, Escherichia coli etc. have good rejection ability, and Tea Saponin dissolubility in alcohol solution is good, as water color ink
Dispersant and antiseptic have bright prospects although Tea Saponin has the problem bubbled under oscillatory condition, but passes through froth breaking
Agent just can solve.
Contain the antimicrobial components such as Nano Silver, shitosan, titanium dioxide and Tea Saponin in the present invention, so that water color ink is had
Very strong broad-spectrum, various sterilization component synergies, bactericidal effect also greatly reinforces, and each sterilization component is in aqueous oil
Dispersiveness in ink is very outstanding.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material, enters as follows
OK, wherein following material number is parts by weight,
(1) preparation of the silver-colored shitosan of load:
10 parts of Nano chitosans being made an addition in 100 parts of deionized waters are taken to stir to dissolving, then to chitosan solution
10 parts of silver nitrates of middle interpolation, after stirring, dropping diluted nitric acid aqueous solution is 3-4 up to solution ph, then water under the conditions of lucifuge
Bath 60 DEG C of agitating heating 3h, then suspension priority is centrifuged, take solid matter washing, vacuum drying after, take on 10 parts
State solid matter and 0.5 part of sodium borohydride be added in the sodium hydrate aqueous solution of 0.01mol/l, plus deionized water adjust ph to
7.5-8, finally agitated, centrifugation takes solid, washs, is dried to obtain the silver-colored shitosan of load.
(2) preparation of water color ink:
Silver-colored for the load of above-mentioned gained shitosan is added to the compound tree of water-borne acrylic resin liquid and water-compatible amino resin liquid
In fat liquid and stir, then add in mixed resin liquid deionized water, ethanol, organic pigment, Tea Saponin, defoamer,
Levelling agent and buffer, obtain the cork paper water color ink containing composite antibacterial material finally by grinding distribution.
In wherein said water color ink, each constituent content is as follows:
35wt% water-borne acrylic resin liquid；
15 wt% water-compatible amino resin liquid；
4%wt% carries silver-colored shitosan；
1wt% Tea Saponin；
10 wt% deionized waters；
15 wt% ethanol；
16 wt% organic pigments；
1wt% defoamer；
1.5wt% levelling agent；
1.5 wt% buffers.
Embodiment 2
A kind of preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material, enters as follows
OK, wherein following material number is parts by weight,
(1) preparation of the silver-colored shitosan of load:
10 parts of Nano chitosans being made an addition in 100 parts of deionized waters are taken to stir to dissolving, then to chitosan solution
10 parts of silver nitrates of middle interpolation, after stirring, dropping diluted nitric acid aqueous solution is 3-4 up to solution ph, then water under the conditions of lucifuge
Bath 60 DEG C of agitating heating 3h, then suspension priority is centrifuged, take solid matter washing, vacuum drying after, take on 10 parts
State solid matter and 0.5 part of sodium borohydride be added in the sodium hydrate aqueous solution of 0.01mol/l, plus deionized water adjust ph to
7.5-8, finally agitated, centrifugation takes solid, washs, is dried to obtain the silver-colored shitosan of load.
(2) preparation of water color ink:
At 60 DEG C after the nano titanium oxide for 15nm for the particle diameter, ethanol, deionized water and silane coupler are mixed
Water-bath back flow reaction 12h, is then down to room temperature, and product, through centrifugation and washing, obtains silane coupler modified inorganic receive
Rice corpuscles, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupler is than for 1:40:10:2.
B, 45 parts of deionized waters and 2 parts of emulsifying agents are put into reactor and are heated to 80 DEG C, then by 15 parts of methyl methacrylates
Ester, 15 parts of hydroxyethyl methacrylates, the silane coupler modified inorganic nano-particle of 20 parts of step a gained, 4 parts of polyethylene glycol
Put into 0.4 part of water soluble starter and stir after reactor, after being incubated 0.75 hour, at the uniform velocity add 0.4 part in 2 hours
Water soluble starter, is then incubated 6 hours again, stirs afterwards and add ammoniacal liquor to be neutralized, and so that solution ph is maintained
Between 7.5-8.5, then vacuumize the free ammoniacal liquor of removal, be finally filtrated to get nano-titanium dioxide modified water-borne acrylic resin
Liquid, above material number is parts by weight.
C, the load of above-mentioned gained silver shitosan is added to nano-titanium dioxide modified water-borne acrylic resin liquid with aqueous
In the mixed resin liquid of amine resin solution and stir, then add deionized water, ethanol, You Jiyan in mixed resin liquid
Material, Tea Saponin, defoamer, levelling agent and buffer, obtain the cork paper containing composite antibacterial material finally by grinding distribution
Water color ink.
In wherein said water color ink, each constituent content is as follows:
35wt% nano-titanium dioxide modified water-borne acrylic resin liquid；
15 wt% water-compatible amino resin liquid；
4%wt% carries silver-colored shitosan；
1wt% Tea Saponin；
10 wt% deionized waters；
15 wt% ethanol；
16 wt% organic pigments；
1wt% defoamer；
1.5wt% levelling agent；
1.5 wt% buffers.
Embodiment 3
A kind of preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material, enters as follows
OK, wherein following material number is parts by weight,
(1) preparation of the silver-colored shitosan of load:
10 parts of Nano chitosans being made an addition in 100 parts of deionized waters are taken to stir to dissolving, then to chitosan solution
10 parts of silver nitrates of middle interpolation, after stirring, dropping diluted nitric acid aqueous solution is 3-4 up to solution ph, then water under the conditions of lucifuge
Bath 60 DEG C of agitating heating 3h, then suspension priority is centrifuged, take solid matter washing, vacuum drying after, take on 10 parts
State solid matter and 0.5 part of sodium borohydride be added in the sodium hydrate aqueous solution of 0.01mol/l, plus deionized water adjust ph to
7.5-8, finally agitated, centrifugation takes solid, washs, is dried to obtain the silver-colored shitosan of load.
(2) preparation of water color ink:
At 60 DEG C after the nano titanium oxide for 10nm for the particle diameter, ethanol, deionized water and silane coupler are mixed
Water-bath back flow reaction 8h, is then down to room temperature, and product, through centrifugation and washing, obtains silane coupler modified inorganic nano
Particle, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupler is than for 1:30:5:1.
B, 30 parts of deionized waters and 1 part of emulsifying agent are put into reactor and are heated to 80 DEG C, then by 10 parts of butyl acrylates, 10
Part hydroxy propyl methacrylate, the silane coupler modified inorganic nano-particle of 15 parts of step a gained, 3 parts of polyethylene glycol and
0.25 part of water soluble starter stirs after putting into reactor, after being incubated 0. 5 hours, at the uniform velocity adds 0.25 part in 2 hours
Water soluble starter, is then incubated 4 hours again, stirs afterwards and add ammoniacal liquor to be neutralized, and so that solution ph is maintained
Between 7.5-8.5, then vacuumize the free ammoniacal liquor of removal, be finally filtrated to get nano-titanium dioxide modified water-borne acrylic resin
Liquid, above material number is parts by weight.
C, the load of above-mentioned gained silver shitosan is added to nano-titanium dioxide modified water-borne acrylic resin liquid with aqueous
In the mixed resin liquid of polyurethane resin liquid and stir, then add deionized water, ethanol, organic in mixed resin liquid
Pigment, Tea Saponin, defoamer, levelling agent and buffer, obtain the yew containing composite antibacterial material finally by grinding distribution
Paper water color ink.
In wherein said water color ink, each constituent content is as follows:
30wt% nano-titanium dioxide modified water-borne acrylic resin liquid；
15 wt% waterborne polyurethane resin liquid；
3%wt% carries silver-colored shitosan；
0.5wt% Tea Saponin；
15 wt% deionized waters；
20wt% ethanol；
14 wt% organic pigments；
0.5wt% defoamer；
1wt% levelling agent；
1 wt% buffer.
Embodiment 4
A kind of preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material, enters as follows
OK, wherein following material number is parts by weight,
(1) preparation of the silver-colored shitosan of load:
10 parts of Nano chitosans being made an addition in 100 parts of deionized waters are taken to stir to dissolving, then to chitosan solution
10 parts of silver nitrates of middle interpolation, after stirring, dropping diluted nitric acid aqueous solution is 3-4 up to solution ph, then water under the conditions of lucifuge
Bath 60 DEG C of agitating heating 3h, then suspension priority is centrifuged, take solid matter washing, vacuum drying after, take on 10 parts
State solid matter and 0.5 part of sodium borohydride be added in the sodium hydrate aqueous solution of 0.01mol/l, plus deionized water adjust ph to
7.5-8, finally agitated, centrifugation takes solid, washs, is dried to obtain the silver-colored shitosan of load.
(2) preparation of water color ink:
At 60 DEG C after the nano titanium oxide for 20nm for the particle diameter, ethanol, deionized water and silane coupler are mixed
Water-bath back flow reaction 16h, is then down to room temperature, and product, through centrifugation and washing, obtains silane coupler modified inorganic receive
Rice corpuscles, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupler is than for 1:50:15:3.
B, 60 parts of deionized waters and 3 parts of emulsifying agents are put into reactor and are heated to 80 DEG C, then by 20 parts of methyl methacrylates
Ester, 20 parts of hydroxyethyl methacrylates, the silane coupler modified inorganic nano-particle of 25 parts of step a gained, 5 parts of polyethylene glycol
Put into 0.5 part of water soluble starter and stir after reactor, after being incubated 1 hour, at the uniform velocity add 0.5 part of water in 2 hours
Soluble initiator, is then incubated 8 hours again, stirs afterwards and add ammoniacal liquor to be neutralized, and so that solution ph is maintained
Between 7.5-8.5, then vacuumize the free ammoniacal liquor of removal, be finally filtrated to get nano-titanium dioxide modified water-borne acrylic resin
Liquid, above material number is parts by weight.
C, the load of above-mentioned gained silver shitosan is added to nano-titanium dioxide modified water-borne acrylic resin liquid with aqueous
In the mixed resin liquid of amine resin solution and stir, then add deionized water, ethanol, You Jiyan in mixed resin liquid
Material, Tea Saponin, defoamer, levelling agent and buffer, obtain the cork paper containing composite antibacterial material finally by grinding distribution
Water color ink.
In wherein said water color ink, each constituent content is as follows:
40wt% nano-titanium dioxide modified water-borne acrylic resin liquid；
10 wt% maleic acid resin liquid；
5%wt% carries silver-colored shitosan；
1.5wt% Tea Saponin；
10wt% deionized water；
10 wt% ethanol；
21 wt% organic pigments；
0.5wt% defoamer；
1wt% levelling agent；
1 wt% buffer.
Embodiment 5
A kind of preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material, enters as follows
OK, wherein following material number is parts by weight,
(1) preparation of the silver-colored shitosan of load:
10 parts of Nano chitosans being made an addition in 100 parts of deionized waters are taken to stir to dissolving, then to chitosan solution
10 parts of silver nitrates of middle interpolation, after stirring, dropping diluted nitric acid aqueous solution is 3-4 up to solution ph, then water under the conditions of lucifuge
Bath 60 DEG C of agitating heating 3h, then suspension priority is centrifuged, take solid matter washing, vacuum drying after, take on 10 parts
State solid matter and 0.5 part of sodium borohydride be added in the sodium hydrate aqueous solution of 0.01mol/l, plus deionized water adjust ph to
7.5-8, finally agitated, centrifugation takes solid, washs, is dried to obtain the silver-colored shitosan of load.
(2) preparation of water color ink:
At 60 DEG C after the nano titanium oxide for 10nm for the particle diameter, ethanol, deionized water and silane coupler are mixed
Water-bath back flow reaction 11h, is then down to room temperature, and product, through centrifugation and washing, obtains silane coupler modified inorganic receive
Rice corpuscles, the weight consumption of described nano titanium oxide, ethanol, deionized water and silane coupler is than for 1:35:8:2.
B, 50 parts of deionized waters and 2 parts of emulsifying agents are put into reactor and are heated to 80 DEG C, then by 14 parts of methacrylic acid second
Ester, 14 parts of hydroxy propyl methacrylates, the silane coupler modified inorganic nano-particle of 18 parts of step a gained, 3 parts of polyethylene glycol
Put into 0.4 part of water soluble starter and stir after reactor, after being incubated 0. 5 hours, at the uniform velocity add 0.4 part in 2 hours
Water soluble starter, is then incubated 5 hours again, stirs afterwards and add ammoniacal liquor to be neutralized, and so that solution ph is maintained
Between 7.5-8.5, then vacuumize the free ammoniacal liquor of removal, be finally filtrated to get nano-titanium dioxide modified water-borne acrylic resin
Liquid, above material number is parts by weight.
C, the load of above-mentioned gained silver shitosan is added to nano-titanium dioxide modified water-borne acrylic resin liquid with aqueous
In the mixed resin liquid of polyurethane resin liquid and stir, then add deionized water, ethanol, organic in mixed resin liquid
Pigment, Tea Saponin, defoamer, levelling agent and buffer, obtain the yew containing composite antibacterial material finally by grinding distribution
Paper water color ink.
In wherein said water color ink, each constituent content is as follows:
31wt% nano-titanium dioxide modified water-borne acrylic resin liquid；
13wt% waterborne polyurethane resin liquid；
3%wt% carries silver-colored shitosan；
1wt% Tea Saponin；
11 wt% deionized waters；
13wt% ethanol；
25wt% organic pigment；
1wt% defoamer；
1wt% levelling agent；
1 wt% buffer.
The above, be only presently preferred embodiments of the present invention, not the present invention imposed any restrictions, every according to the present invention
Any simple modification, change and equivalent transformation that technical spirit is made to above example, all still fall within the technology of the present invention side
The protection domain of case.
Claims (4)
1. a kind of preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material is it is characterised in that press such as
Lower step is carried out, and wherein following material number is parts by weight,
(1) preparation of the silver-colored shitosan of load:
Take 10 parts of shitosans being made an addition in 100 parts of deionized waters to stir to dissolving, then add 10 in chitosan solution
Part silver nitrate, dropping diluted nitric acid aqueous solution after stirring until solution ph is 3-4, then under the conditions of lucifuge, stir by 60 DEG C of water-bath
Mix heating 3h, then suspension priority is centrifuged, take solid matter washing, vacuum drying after, take 10 parts of above-mentioned solids
Matter and 0.5 part of sodium borohydride are added in the sodium hydrate aqueous solution of 0.01mol/l, plus deionized water adjusts ph to 7.5-8,
Take solid, wash, be dried to obtain the silver-colored shitosan of load by stirring, centrifugation；
(2) preparation of water color ink:
The silver-colored shitosan that carries of above-mentioned gained is added in water-base resin liquid a and the mixed resin liquid of water-base resin liquid b and stirs
Mix uniformly, then add deionized water, ethanol, organic pigment, Tea Saponin, defoamer, levelling agent and buffering in mixed resin liquid
Agent, obtains the cork paper water color ink containing composite antibacterial material finally by grinding distribution；
In wherein said water color ink, each constituent content is as follows:
30-40wt% water-base resin liquid a；
10-20 wt% water-base resin liquid b；
3-5%wt% carries silver-colored shitosan；
0.5-1.5wt% Tea Saponin；
5-15 wt% deionized water；
10-20 wt% ethanol；
10-25 wt% organic pigment；
0.5-1.5wt% defoamer；
1-2 wt% levelling agent；
1-2 wt% buffer;
Described water-base resin liquid b is selected from one of water-compatible amino resin liquid, maleic acid resin liquid, waterborne polyurethane resin liquid；
Described water-base resin liquid a 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 coupler are mixed after in 60 DEG C of water-bath back flow reaction 8-
16h, is then down to room temperature, and product, through centrifugation and washing, obtains silane coupler modified inorganic nano-particle, described receives
Rice titanium dioxide, the weight consumption ratio of ethanol, deionized water and silane coupler are for 1:30-50:5-15:1-3；
B, 30-60 part deionized water and 1-3 part emulsifying agent are put into reactor it is heated to 80 DEG C, then by 10-20 part alkyl third
Olefin(e) acid ester monomer, 10-20 part hydroxyalkyl acrylates monomer, the silane coupler modified inorganic nano of 15-25 part step a gained
Particle, 3-5 part polyethylene glycol and 0.25-0.5 part water soluble starter stir after putting into reactor, are incubated 0.5-1 hour
Afterwards, at the uniform velocity add 0.25-0.5 part water soluble starter in 2 hours, be then incubated 4-8 hour again, stir afterwards
Add ammoniacal liquor to be neutralized, so that solution ph is maintained between 7.5-8.5, then vacuumize the free ammoniacal liquor of removal, finally filter
To nano-titanium dioxide modified water-borne acrylic resin liquid, above material number is parts by weight.
2. the preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material as claimed in claim 1,
It is characterized in that, the shitosan in described step (1) is Nano chitosan.
3. the preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material as claimed in claim 1,
It is characterized in that, the particle diameter of described nano titanium oxide is in 10-20nm.
4. the preparation method containing the cork paper water color ink carrying silver-colored chitosan composite antibiotic material as claimed in claim 1,
It is characterized in that, described alkyl acrylate monomer is methyl methacrylate, EMA or acrylic acid fourth
Ester；Described hydroxyalkyl acrylates monomer is hydroxyethyl methacrylate or hydroxy propyl methacrylate.
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| CN201510069503.9A CN104725933B (en) | 2015-02-11 | 2015-02-11 | Preparation method of water-based ink, containing Ag-carrying chitosan composite antibacterial material, for tipping paper |
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| CN108939708B (en) * | 2018-06-26 | 2021-03-12 | 北京芮赛环保科技有限公司 | Preparation method of air sterilization filtering membrane |
| CN109911837B (en) * | 2019-04-08 | 2021-02-26 | 宁波博洋家纺集团有限公司 | Warm-keeping fluffy down quilt and preparation process thereof |
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Address after: Chen Industrial Park 313106 Zhejiang city of Huzhou province Changxing County Hong Qiao Zhen Applicant after: CHANGXING AIFEITE PLASTIC TECHNOLOGY CO.,LTD. Address before: Chen Industrial Park 313106 Zhejiang city of Huzhou province Changxing County Hong Qiao Zhen Applicant before: CHANGXING AIFEITE PLASTIC TECHNOLOGY CO.,LTD. |
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Denomination of invention: Preparation method of water-based ink for tipping paper containing silver loaded chitosan composite antibacterial material Effective date of registration: 20210630 Granted publication date: 20170118 Pledgee: Changxin Zhejiang rural commercial bank Limited by Share Ltd. Pledgor: CHANGXING AIFEITE PLASTIC TECHNOLOGY Co.,Ltd. Registration number: Y2021330000728 |
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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 |