CN117820896A - Sericin micro-nano particle neutral ink, preparation method and application thereof - Google Patents
Sericin micro-nano particle neutral ink, preparation method and application thereof Download PDFInfo
- Publication number
- CN117820896A CN117820896A CN202311818833.4A CN202311818833A CN117820896A CN 117820896 A CN117820896 A CN 117820896A CN 202311818833 A CN202311818833 A CN 202311818833A CN 117820896 A CN117820896 A CN 117820896A
- Authority
- CN
- China
- Prior art keywords
- sericin
- micro
- pigment
- nano particle
- neutral ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 108010013296 Sericins Proteins 0.000 title claims abstract description 153
- 230000007935 neutral effect Effects 0.000 title claims abstract description 97
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000049 pigment Substances 0.000 claims abstract description 43
- 108010010779 glutamine-pyruvate aminotransferase Proteins 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- KINGXFAMZNIVNL-SXQDSXCISA-N safflor yellow A Natural products OC[C@@H]1O[C@H]2[C@H](OC3=C2C(=O)C(=C(O)C=Cc4ccc(O)cc4)C(=O)[C@]3(O)[C@@H]5O[C@H](CO)[C@@H](O)[C@H](O)[C@H]5O)[C@@H](O)[C@H]1O KINGXFAMZNIVNL-SXQDSXCISA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 108010053210 Phycocyanin Proteins 0.000 claims description 7
- 229920001353 Dextrin Polymers 0.000 claims description 6
- 239000004375 Dextrin Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 235000019425 dextrin Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002101 Chitin Polymers 0.000 claims description 4
- 229930002875 chlorophyll Natural products 0.000 claims description 4
- 235000019804 chlorophyll Nutrition 0.000 claims description 4
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 4
- 239000001054 red pigment Substances 0.000 claims description 4
- 108010035532 Collagen Proteins 0.000 claims description 3
- 102000008186 Collagen Human genes 0.000 claims description 3
- 229920001436 collagen Polymers 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- -1 pentosan Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940034586 silk sericin Drugs 0.000 claims description 3
- 241000710149 Beet yellows virus Species 0.000 claims description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 claims description 2
- 241000335053 Beta vulgaris Species 0.000 claims description 2
- 244000017106 Bixa orellana Species 0.000 claims description 2
- 244000020518 Carthamus tinctorius Species 0.000 claims description 2
- 235000003255 Carthamus tinctorius Nutrition 0.000 claims description 2
- 108010076119 Caseins Proteins 0.000 claims description 2
- 206010015150 Erythema Diseases 0.000 claims description 2
- 241000228347 Monascus <ascomycete fungus> Species 0.000 claims description 2
- 108010058846 Ovalbumin Proteins 0.000 claims description 2
- 240000006394 Sorghum bicolor Species 0.000 claims description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- 108010073771 Soybean Proteins Proteins 0.000 claims description 2
- 244000299461 Theobroma cacao Species 0.000 claims description 2
- 235000009470 Theobroma cacao Nutrition 0.000 claims description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 2
- 240000006365 Vitis vinifera Species 0.000 claims description 2
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 2
- 102000007544 Whey Proteins Human genes 0.000 claims description 2
- 108010046377 Whey Proteins Proteins 0.000 claims description 2
- 235000012665 annatto Nutrition 0.000 claims description 2
- 239000010362 annatto Substances 0.000 claims description 2
- 239000004106 carminic acid Substances 0.000 claims description 2
- 235000012730 carminic acid Nutrition 0.000 claims description 2
- 235000021466 carotenoid Nutrition 0.000 claims description 2
- 150000001747 carotenoids Chemical class 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 229940080423 cochineal Drugs 0.000 claims description 2
- 150000002402 hexoses Chemical class 0.000 claims description 2
- 229940092253 ovalbumin Drugs 0.000 claims description 2
- 229920001277 pectin Polymers 0.000 claims description 2
- 235000010987 pectin Nutrition 0.000 claims description 2
- 239000001814 pectin Substances 0.000 claims description 2
- 235000018102 proteins Nutrition 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 235000019710 soybean protein Nutrition 0.000 claims description 2
- 235000021119 whey protein Nutrition 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 claims 1
- 239000001052 yellow pigment Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 100
- 230000014759 maintenance of location Effects 0.000 description 10
- 241000255789 Bombyx mori Species 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000009471 action Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 4
- 238000003302 UV-light treatment Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000004472 Lysine Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 101100462438 Mus musculus Otulin gene Proteins 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical class O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000404 glutamine group Chemical group N[C@@H](CCC(N)=O)C(=O)* 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the technical field of neutral ink, in particular to sericin micro-nano particle neutral ink, a preparation method and application thereof, wherein the sericin micro-nano particle is 0.05% -20%, pigment is 0.05% -40%, auxiliary agent is 0.05% -1.0%, antibacterial agent is 0.05% -1.0%, and the balance is water; the sericin micro-nano particles are prepared by crosslinking sericin through glutamine transaminase. According to the invention, the sericin micro-nano particles are formed by adopting glutamine transaminase to crosslink sericin as a film forming agent and a load stable base material, and are added into neutral ink, so that the neutral ink has a relatively high specific surface area, a relatively large number of hydrophobic groups and hydrophilic groups, and can be loaded and dispersed with biodegradable natural pigment through interfacial interaction, so that the neutral ink is functionalized, has relatively high pigment loading property, and meanwhile, the sericin micro-nano particles have excellent oxidation resistance, can effectively protect the biodegradable pigment, and improve the photo-thermal stability of the biodegradable pigment.
Description
Technical Field
The invention relates to the technical field of neutral ink, in particular to sericin micro-nano particle neutral ink, a preparation method and application thereof.
Background
At present, the traditional ink is commonly used in the markets at home and abroad, however, some traditional ink contains partial harmful substances (such as heavy metals, sulfuric acid, volatile organic compounds and the like) in the composition of raw materials, and the substances can form a certain threat to the health of ink production workers in the process of preparing the ink, and also can have a certain influence on consumers, especially the low-age student population, and the potential safety hazard can be caused by misuse caused by strong curiosity; after the ink material wastes flow into the environment, certain environmental pollution can be possibly caused, and the related disputes of environmental protection, degradation and the like are initiated; meanwhile, the existing neutral ink has fewer colors, limits the application scene of the ink, and restricts the potential of expanding the market share of the ink. The green, environment-friendly, safe and harmless development of the ink is based on the global green development and the general trend of national policy, and the degradable neutral ink is novel, green and environment-friendly ink, and the components of the ink adopt biodegradable raw materials, so that the safety, compatibility and sanitation are met. At present, the degradable neutral ink is relatively rare in research, and the technology is not mature. The natural pigment has the advantages of excellent color development, degradability, wide sources and the like, can be used as a pigment for preparing green degradable ink, but is easy to degrade and fade under the conditions of illumination and the like, so that the stability of the ink needs to be improved; and meanwhile, the writing adhesiveness and firmness of the neutral ink are required to be improved so as to improve the writing property and the application property of the neutral pen core.
Disclosure of Invention
The invention aims to provide the sericin micro-nano particle neutral ink which has the advantages of high stability, good adhesiveness, environment friendliness and safety.
The second purpose of the invention is to provide a preparation method of the sericin micro-nano particle neutral ink, which is simple and feasible in operation and low in process cost.
The invention further aims to provide an application of the sericin micro-nano particle neutral ink.
The scheme adopted by the invention for achieving one of the purposes is as follows: the sericin micro-nano particle neutral ink comprises the following components in percentage by mass: 0.05 to 20 percent of sericin micro-nano particles, 0.05 to 40 percent of pigment, 0.05 to 1.0 percent of auxiliary agent, 0.05 to 1.0 percent of antibacterial agent and the balance of water; the sericin micro-nano particles are prepared by crosslinking sericin through glutamine transaminase.
Preferably, the preparation method of the sericin micro-nano particles comprises the following steps:
a1, adding silk sericin into deionized water, and dissolving to obtain sericin solution;
a2, regulating the sericin solution to be weak acid;
a3, adding a glutamine transaminase solution into the weak acid sericin solution obtained in the step A2, reacting at a certain temperature, and heating to inactivate the glutamine transaminase after the reaction is finished;
and A4, regulating the pH value of the reaction solution to be neutral to obtain the sericin micro-nano particles.
Preferably, in the step A1, the dissolution temperature is 25-40 ℃; in the step A2, the final concentration of the sericin is 0.05wt.% to 26wt.%.
Preferably, in the step A3, the concentration of the glutamine transaminase solution is 1-20 mg/mL, and the mass ratio of sericin to glutamine transaminase is 0.025-260:1; the reaction temperature is 40-45 ℃ and the reaction time is 1-24 h.
The enzyme deactivation temperature is 80 ℃ or higher.
Preferably, the pigment is a biodegradable pigment comprising at least one of beet yellow, phycocyanin, beet red, phycocyanin, safflower yellow, safflower red, sorghum red pigment, carotenoid, lac pigment, chlorophyll, annatto pigment, cochineal pigment, grape skin red pigment, cocoa shell pigment, monascus pigment.
Preferably, the auxiliary agent is a degradable auxiliary agent, comprising at least one of polyethylene glycol, pentose gum, pectin, dextrin, hexose gum, casein, collagen, ovalbumin, soybean protein, whey protein and myofibrillar protein.
Preferably, the antibacterial agent is an edible antibacterial agent, and comprises at least one of amino chitosan oligosaccharide, amino chitin and amino chitosan.
The scheme adopted by the invention for achieving the second purpose is as follows: the preparation method of the sericin micro-nano particle neutral ink comprises the following steps:
b1, dispersing sericin micro-nano particles in water to obtain a sericin micro-nano particle aqueous solution;
b2, adding the pigment into the aqueous solution of the sericin micro-nano particles obtained in the step B1, and uniformly mixing to obtain a sericin micro-nano particle-pigment mixture;
b3, adding an auxiliary agent into the sericin micro-nano particle-pigment mixture obtained in the step B2, and uniformly mixing;
b4, adding an antibacterial agent into the mixture obtained in the step B3, and uniformly mixing;
and B5, ball milling the mixed system obtained in the step B4 to obtain the uniformly dispersed sericin micro-nano particle neutral ink.
Preferably, in the step B1, the mass fraction of the aqueous solution of the sericin micro-nano particles is 0.05% -15%; in the steps (B1) - (B2), stirring and mixing are uniform, the stirring speed is 100r/min-1500r/min, and in the steps (B3) - (B4), stirring and mixing are uniform, and the stirring speed is 100r/min-2000r/min; in the step (B5), the ball milling speed is 100-1000r/min.
The preparation of steps B1 to B5 is carried out at room temperature.
The scheme adopted by the invention for achieving the third purpose is as follows: the application of the sericin micro-nano particle neutral ink applies the sericin micro-nano particle neutral ink to a neutral pen refill.
Sericin is a part of peripheral silk collagen, and has binding effect in silk cocoons, and has many amino acids with longer side chains, such as lysine, tryptophan, tyrosine, etc., and many polar hydrophilic groups (such as-OH, -COOH, -NH) 2 -NH, etc.)On the surface of the polypeptide chain, the structural characteristics endow the sericin with excellent loading, humidity adjusting, moisturizing and compatibility effects, and simultaneously have excellent film forming property, mechanical property, good appearance and color and luster and other excellent properties. The sericin is crosslinked by glutamine transaminase, the crosslinking reaction is mainly amide group transfer reaction between gamma-amido of glutamine residue and lysine epsilon-amino in the sericin, the reaction can be carried out in molecules or among molecules, and then the profiled peptide bond of epsilon- (gamma-glutamine) -lysine is formed, so that the sericin micro-nano particles can be obtained, have higher specific surface area, more hydrophobic groups and hydrophilic groups, can be used for loading and dispersing biodegradable pigment through interfacial interaction, and meanwhile, the sericin micro-nano particles have excellent oxidation resistance, can effectively protect biodegradable natural pigment and improve the photo-thermal stability; under the action of an auxiliary agent, the molecular chains are interpenetrated and intertwined to form a stable shell-core structure (the pigment is stably fixed between the shells and the cores); the gel micro-nano particles prepared by the method have the advantages of simple preparation process, environment friendliness, no pollution, good color development effect, smooth writing, stable and bright color, clear and bright writing and full and rich color on paper, and can reduce the worry of people on the preparation and use safety of the ink, especially ink production workers and low-age use consumers, so that the research of the gel has important significance. The sericin is derived from the cocoons, and is also beneficial to the high-value utilization of the cocoons.
The invention has the following advantages and beneficial effects:
according to the invention, the glutamine transaminase crosslinked sericin is adopted to form the sericin micro-nano particles as a film forming agent and a loading base material, and the sericin micro-nano particles are added into neutral ink, so that the neutral ink has higher specific surface area, more hydrophobic groups and hydrophilic groups, and can be loaded and dispersed with biodegradable pigment through interfacial interaction, so that the neutral ink is functionalized, has higher pigment loading property, and meanwhile, the sericin micro-nano particles have excellent oxidation resistance, can effectively protect the biodegradable pigment and improve the photo-thermal stability of the biodegradable pigment; under the action of an auxiliary agent, the molecular chains are interpenetrated and intertwined to form a stable shell-core structure (the pigment is stably fixed between the shells and the cores); the integral net structure is formed under the action of the subsequent antibacterial agent, so that the system stability is further promoted, and the preparation and the use of the neutral ink can be further promoted.
The production equipment adopted in the invention is common and easily available mechanical equipment, has controllable cost and simple operation, and is beneficial to realizing the large-scale industrial production of the neutral ink and the actual filling application of the neutral pen core.
All components in the formula of the neutral ink have biodegradability (biodegradable film forming agent, biodegradable natural pigment, biodegradable auxiliary agent and biodegradable antibacterial agent), and the neutral ink has the characteristics of green, low carbon, degradability, environmental protection, safety, sustainability and environmental friendliness, so that the potential threat of the traditional ink to human bodies (such as ink producers and ink consumers) is avoided.
The biodegradable neutral ink can be used for writing after filling the neutral pen core, has good color effect, strong adhesive force and stable color, and has good market application prospect.
Drawings
FIG. 1 shows the dispersion mechanism and writing effect of the glutamine transaminase crosslinking-induced sericin micro-nano particle neutral ink (a) and the uncrosslinked sericin neutral ink (b) of the present invention;
FIG. 2 is a liquid dispersion microscopy image of a glutamine transaminase cross-linked induced-sericin micro-nano particle neutral ink (a) and an uncrosslinked sericin neutral ink (b) of the present invention;
FIG. 3 is a graph of UV light stability performance of neutral inks of the glutamine transaminase crosslinking-induced sericin micro-nano particles of the present invention and uncrosslinked sericin neutral inks;
FIG. 4 is a graph of the thermal stability properties of neutral inks of the glutamine transaminase crosslinked induced sericin micro-nano particles of the present invention and uncrosslinked sericin neutral inks;
FIG. 5 is a physical diagram of the neutral ink (left) of the glutamine transaminase crosslinking-induced sericin micro-nano particle and the uncrosslinked sericin neutral ink (right) of the present invention after being heated at 100 ℃ for 5 hours;
FIG. 6 is a graph showing the stability performance of the neutral ink of the glutamine transaminase-crosslinked induced-sericin micro-nano particle of the present invention and the uncrosslinked sericin neutral ink after one year of storage;
FIG. 7 is a graph of abrasion resistance and fastness properties of the neutral ink of the glutamine transaminase-crosslinked induced sericin micro-nano particle of the present invention and the uncrosslinked sericin neutral ink after writing.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrative of the present invention, but the contents of the present invention are not limited to the following examples only.
The sericin is sericin obtained by silkworm cocoon treatment. And (3) performing microwave-alkali process treatment on the obtained sericin to obtain the sericin with the steady-state molecular weight distribution of 10kDa-65kDa.
The preparation of sericin comprises the following steps:
(1) The silkworm cocoons are processed into small blocks and then washed, then the silkworm cocoons are processed under the action of microwaves, and the silkworm cocoons are slightly kneaded at regular intervals in the processing process so as to ensure that samples are uniformly processed in the microwave process;
(2) Adding 0.5% Na into the sample after microwave treatment 2 CO 3 (w/v) solution, heating and boiling for a certain time;
(3) Filtering to remove insoluble substances, centrifuging and collecting supernatant;
(4) Dialyzing the collected supernatant to obtain sericin with molecular weight distribution range of 10kDa-65kDa.
Specifically, the preparation of sericin comprises the following steps:
(1) Weighing silkworm cocoons, cutting the silkworm cocoons into small blocks, cleaning the silkworm cocoons with ultrapure water for four times, placing the silkworm cocoons into a steaming bag, and then carrying out microwave treatment for 15-420 min under the condition of 350W, and slightly kneading the steaming bag every 30min in the treatment process so as to ensure that samples are uniformly treated in the microwave process;
(2) Adding 0.5% Na 2 CO 3 (w/v) solution, heating and boiling for 1h;
(3) Filtering to remove insoluble substances, centrifuging at 5000rpm for 10min, and collecting supernatant;
(4) Transferring the collected supernatant into a dialysis bag (1500 Da), dialyzing at room temperature for 36h, and changing ultrapure water every 6 h; the molecular weight distribution ranges from 10kDa to 65kDa.
And freeze-drying the sericin solution for 24 hours, and storing for later use.
The preparation method of the sericin micro-nano particles comprises the following steps:
a1, adding silk sericin into deionized water, and dissolving to obtain sericin solution;
a2, regulating the sericin solution to be weak acid;
a3, adding a glutamine transaminase solution into the weak acid sericin solution obtained in the step A2, reacting at a certain temperature, and heating to inactivate the glutamine transaminase after the reaction is finished;
and A4, regulating the pH value of the reaction solution to be neutral to obtain the sericin micro-nano particles.
In the step A1, the dissolution temperature is 25-40 ℃.
In the step A2, the final concentration of the sericin is 0.05wt.% to 26wt.%.
In the step A3, the concentration of the glutamine transaminase solution is 1-20 mg/mL, and the mass ratio of sericin to glutamine transaminase is 0.025-260:1; the reaction temperature is 40-45 ℃, the reaction time is 1-24 h, and the deactivation temperature is more than 80 ℃.
Example 1
A preparation method of a glutamine transaminase crosslinking induced sericin micro-nano particle neutral ink comprises the following steps: dispersing the sericin micro-nano particle system in water, regulating the concentration by using distilled water, and stirring at 45 ℃ for 500r/min for 0.5h; adding biodegradable phycocyanin to obtain a sericin micro-nano particle-phycocyanin mixture, and stirring at 45 ℃ for 1000r/min for 1h; adding biodegradable auxiliary dextrin into the mixture of sericin micro-nano particles and phycocyanin, and stirring at 45 ℃ for 1500r/min for 1h; adding an antibacterial agent amino chitin into a mixture of sericin micro-nano particles and phycocyanin, and stirring at 45 ℃ for 1000r/min and 1h; ball milling (500 r/min, 4 h) is carried out on the mixed system to obtain the uniformly dispersed sericin micro-nano particle neutral ink. The mass percentage of the sericin micro-nano particles, the phycocyanin, the dextrin and the aminated chitin respectively accounts for 1.0%, 10.0%, 0.3% of the mass percentage of the neutral ink, and the balance is water, so that the glutamine transaminase crosslinking induced sericin micro-nano particle neutral ink is obtained.
Example 2
A preparation method of a glutamine transaminase crosslinking induced sericin micro-nano particle neutral ink comprises the following steps: dispersing the sericin micro-nano particle system in water, regulating the concentration by using distilled water, and stirring at 45 ℃ for 1000r/min for 0.5h; adding biodegradable safflower yellow to obtain a sericin micro-nano particle-safflower yellow mixture, and stirring at 45 ℃ for 1500r/min for 1h; adding biodegradable auxiliary agent polyethylene glycol into the mixture of sericin micro-nano particles and safflower yellow, and stirring at 45 ℃ for 1400r/min for 1h; adding an antibacterial agent amino chitosan into a mixture of sericin micro-nano particles and safflower yellow, and stirring at 45 ℃ for 1000r/min and 1h; ball milling (1000 r/min, 2 h) is carried out on the mixed system to obtain the uniformly dispersed sericin micro-nano particle neutral ink. The mass percentages of the sericin micro-nano particles, the safflower yellow, the polyethylene glycol and the aminated chitosan respectively account for 20 percent, 10.0 percent, 0.05 percent and 0.05 percent of the mass percentage of the neutral ink, and the balance is water, so that the glutamine transaminase crosslinking induced sericin micro-nano particle neutral ink is obtained.
Example 3
A preparation method of a glutamine transaminase crosslinking induced sericin micro-nano particle neutral ink comprises the following steps: dispersing the sericin micro-nano particle system in water, regulating the concentration by using distilled water, and stirring at 45 ℃ for 100r/min for 0.5h; adding biodegradable safflower yellow to obtain sericin micro-nano particle-chlorophyll mixture, stirring at 45deg.C for 1500r/min for 1 hr; adding biodegradable auxiliary agent polyethylene glycol into the sericin micro-nano particle-chlorophyll mixture, and stirring at 45 ℃ for 2000r/min for 1h; adding an antibacterial agent amino chitosan into a mixture of sericin micro-nano particles and chlorophyll, and stirring at 45 ℃ for 2000r/min and 1h; ball milling (100 r/min, 8 h) the mixed system to obtain the uniformly dispersed sericin micro-nano particle neutral ink. The mass percentages of the sericin micro-nano particles, chlorophyll, polyethylene glycol and aminated chitosan oligosaccharide are respectively 0.05%, 40%, 1.0% and 1.0% of the mass percentages of the neutral ink, and the balance is water, so that the glutamine transaminase crosslinking induced sericin micro-nano particle neutral ink is obtained.
Comparative example 1
A preparation method of sericin neutral ink comprises the following steps: dispersing the uncrosslinked silk colloid system obtained by extraction in water, regulating the concentration by using distilled water, and stirring at 45 ℃ for 500r/min for 0.5h; adding biodegradable safflower yellow to obtain a mixture of sericin and safflower yellow, and stirring at 45deg.C for 1200r/min and 1 hr; adding biodegradable auxiliary dextrin into the mixture of sericin and safflower yellow, and stirring at 45 ℃ for 1400r/min and 1h; adding an antibacterial agent amino chitosan into a mixture of sericin and safflower yellow amino chitosan, and stirring at 45 ℃ for 1000r/min and 1h; ball milling (500 r/min, 4 h) the mixed system to obtain the uniformly dispersed sericin neutral ink. The mass percentage of the sericin, the safflower yellow, the dextrin and the amino chitosan respectively accounts for 1.4 percent, 8.0 percent, 0.2 percent and 0.5 percent of the mass percentage of the neutral ink, and the balance is water, so that the non-sericin neutral ink is obtained.
Comparison of fig. 1a (glutamine transaminase cross-linking induced sericin micro-nano particle neutral ink, example 2) and fig. 1b (uncrosslinked sericin neutral ink). It can be seen that the former crosslinked sericin neutral ink is still dispersed uniformly and stably after being stored for 1 month; after the gel ink is filled, the ink is written smoothly, has good adhesiveness and good color development effect. However, the latter uncrosslinked neutral ink has the phenomena of sedimentation, delamination, flocculation and the like after being stored for 1 month; after filling by a gel ink pen, the ink is easy to break, has poor adhesiveness and is discontinuous in color in the ink writing process.
Comparing fig. 2a (glutamine transaminase cross-linking induced-sericin micro-nano particle neutral ink, example 2) with fig. 2b (uncrosslinked sericin neutral ink), the cross-linked ink has a micro-nano structure and is uniformly dispersed; the microstructure of the uncrosslinked sericin ink has larger aggregated particles and different dispersion sizes.
In contrast to the stability of the glutamine transaminase-crosslinked induced-sericin micro-nanoparticle neutral ink and the uncrosslinked sericin ink of fig. 3 (example 2), the color retention of the crosslinked sericin neutral ink was nearly 100% after UV light treatment for 48 hours and 96 hours, the color retention was not affected, the color retention of the uncrosslinked sericin neutral ink was low after UV light treatment, and the color retention continued to decrease as the irradiation time was prolonged, the color retention after UV light treatment for 48 hours was only about 65%, and the color retention after UV light treatment for 96 hours was only about 55%.
As can be seen from fig. 4, after the heat treatment at 100 ℃ for 1 hour (example 2), the color retention of the crosslinked sericin neutral ink was still high (up to 99%), while the color retention of the uncrosslinked sericin neutral ink was only about 65%, after 5 hours, the color retention of the crosslinked sericin neutral ink was still high (fig. 4), and the yellow color remained good (fig. 5), while the color retention of the uncrosslinked ink was greatly reduced (fig. 4), and the yellow color was significantly lighter (fig. 5). The recovery of the rheological viscosity of the crosslinked sericin neutral ink was higher within one year of storage (fig. 6), while the recovery of the rheological viscosity of the uncrosslinked sericin neutral ink was rapidly decreased with the storage time. On the one hand, in the uncrosslinked sericin ink, sericin can be used as a film coating agent, other auxiliary agents and antibacterial agents can assist the sericin to load pigment, but the network structure is weaker, and instability phenomena such as flocculation, precipitation and the like occur in the system along with the extension of the storage time, and meanwhile, under the conditions of UV illumination and high temperature treatment at 100 ℃, the system cannot effectively protect safflower yellow, and the structure of the safflower yellow is subjected to photo-thermal degradation, so that the color of the ink system is influenced. On the other hand, the glutamine transaminase crosslinked Ming sericin micro-nano particles are used as a film forming agent and a loading base material to be added into a neutral ink system, the crosslinked sericin particles have higher specific surface area, more hydrophobic groups and hydrophilic groups, so that biodegradable safflower yellow can be loaded and dispersed through interfacial interaction, the neutral ink is functionalized, the high pigment loading performance is achieved, and meanwhile, the sericin micro-nano particles can effectively protect biodegradable pigments and improve the photo-thermal stability of the biodegradable pigments; under the action of an auxiliary agent, the molecular chains are interpenetrated and intertwined to form a stable shell-core structure (the pigment is stably fixed between the shells and the cores); the integral reticular structure is formed under the action of the subsequent antibacterial agent, so that the UV illumination, heat and storage stability of the system are further promoted, and the practical application of the crosslinked sericin neutral ink can be further promoted. Thus, after writing, the crosslinked sericin ink has higher firmness than the uncrosslinked sericin ink even if stored for one year (FIG. 7)
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (10)
1. A sericin micro-nano particle neutral ink is characterized in that: comprises the following components in percentage by mass: 0.05 to 20 percent of sericin micro-nano particles, 0.05 to 40 percent of pigment, 0.05 to 1.0 percent of auxiliary agent, 0.05 to 1.0 percent of antibacterial agent and the balance of water; the sericin micro-nano particles are prepared by crosslinking sericin through glutamine transaminase.
2. The sericin micro-nano particle neutral ink according to claim 1, wherein: the preparation method of the sericin micro-nano particles comprises the following steps:
a1, adding silk sericin into deionized water, and dissolving to obtain sericin solution;
a2, regulating the sericin solution to be weak acid;
a3, adding a glutamine transaminase solution into the weak acid sericin solution obtained in the step A2, reacting at a certain temperature, and heating to inactivate the glutamine transaminase after the reaction is finished;
and A4, regulating the pH value of the reaction solution to be neutral to obtain the sericin micro-nano particles.
3. The sericin micro-nano particle neutral ink according to claim 2, wherein: in the step A1, the dissolution temperature is 25-40 ℃; in the step A2, the final concentration of the sericin is 0.05wt.% to 26wt.%.
4. The sericin micro-nano particle neutral ink according to claim 2, wherein: in the step A3, the concentration of the glutamine transaminase solution is 1-20 mg/mL, and the mass ratio of sericin to glutamine transaminase is 0.025-260:1; the reaction temperature is 40-45 ℃ and the reaction time is 1-24 h.
5. The sericin micro-nano particle neutral ink according to claim 1, wherein: the pigment is biodegradable pigment, including at least one of beet yellow, phycocyanin, beet red, algae pigment, safflower yellow, safflower red, sorghum red pigment, carotenoid, lac pigment, chlorophyll, annatto pigment, cochineal pigment, grape skin red pigment, cocoa shell pigment, and monascus yellow pigment.
6. The sericin micro-nano particle neutral ink according to claim 1, wherein: the auxiliary agent is a degradable auxiliary agent and comprises at least one of polyethylene glycol, pentosan, pectin, dextrin, hexose, casein, collagen, ovalbumin, soybean protein, whey protein and myofibrillar protein.
7. The sericin micro-nano particle neutral ink according to claim 1, wherein: the antibacterial agent is edible antibacterial agent and comprises at least one of amino chitosan oligosaccharide, amino chitin and amino chitosan.
8. A method for preparing the sericin micro-nano particle neutral ink according to any one of claims 1 to 7, which comprises the following steps:
b1, dispersing sericin micro-nano particles in water to obtain a sericin micro-nano particle aqueous solution;
b2, adding the pigment into the aqueous solution of the sericin micro-nano particles obtained in the step B1, and uniformly mixing to obtain a sericin micro-nano particle-pigment mixture;
b3, adding an auxiliary agent into the sericin micro-nano particle-pigment mixture obtained in the step B2, and uniformly mixing;
b4, adding an antibacterial agent into the mixture obtained in the step B3, and uniformly mixing;
and B5, ball milling the mixed system obtained in the step B4 to obtain the uniformly dispersed sericin micro-nano particle neutral ink.
9. The method for preparing the sericin micro-nano particle neutral ink according to claim 8, wherein the method comprises the following steps: in the step B1, the mass fraction of the sericin micro-nano particle aqueous solution is 0.05% -15%; in the steps (B1) - (B2), stirring and mixing are uniform, the stirring speed is 100r/min-1500r/min, and in the steps (B3) - (B4), stirring and mixing are uniform, and the stirring speed is 100r/min-2000r/min; in the step (B5), the ball milling speed is 100-1000r/min.
10. Use of a sericin micro-nano particle neutral ink according to any one of claims 1 to 7 or a neutral ink prepared by the preparation method according to claim 8 or 9, characterized in that: and applying the sericin micro-nano particle neutral ink to a neutral pen refill.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311818833.4A CN117820896A (en) | 2023-12-26 | 2023-12-26 | Sericin micro-nano particle neutral ink, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311818833.4A CN117820896A (en) | 2023-12-26 | 2023-12-26 | Sericin micro-nano particle neutral ink, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117820896A true CN117820896A (en) | 2024-04-05 |
Family
ID=90516686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311818833.4A Pending CN117820896A (en) | 2023-12-26 | 2023-12-26 | Sericin micro-nano particle neutral ink, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117820896A (en) |
-
2023
- 2023-12-26 CN CN202311818833.4A patent/CN117820896A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2633259A1 (en) | PROCESS FOR THE PRODUCTION OF IMMOBILIZED ENZYMES | |
| CN109749097B (en) | Preparation method of environment-friendly rapid self-repairing hydrogel | |
| CN113575951B (en) | Starch-based dual-load functional nanoparticle, and preparation method and application thereof | |
| CN105125580B (en) | Fullerene-macromolecule composite and preparation method thereof | |
| CN103540068A (en) | Production process of PVA (polyvinyl alcohol)-based composite packaging material | |
| CN113413885B (en) | Magnetic microsphere adsorbent with core-shell structure and preparation method and application thereof | |
| CN117820896A (en) | Sericin micro-nano particle neutral ink, preparation method and application thereof | |
| DE2727143A1 (en) | PROCESS FOR THE MANUFACTURING OF POROESE FABRICS | |
| JP3840280B2 (en) | Multi-pattern coating composition | |
| CN110437527A (en) | Long afterglow PE master batch, preparation method, PE plastic part and preparation method thereof | |
| CN114292523A (en) | Tea polyphenol cross-linked nano cerium oxide-embedded protein/polysaccharide composite membrane material and preparation method thereof | |
| Lakshmi et al. | Maiden exploration of ulvan, a sulfated green seaweed polysaccharide as morphology-controlled porogen | |
| CN1297957A (en) | Preparation and use of intermingled film or fiber of carboxymethyl chitosan and alginic acid | |
| CN113426389A (en) | Preparation method of alcohol soluble protein microcapsule and product | |
| CN113304732B (en) | Porous composite material, preparation method and application thereof | |
| CN113150612B (en) | Edible gelatin protein nano ink, preparation method and application thereof | |
| KR0159976B1 (en) | Process for preparing biodegradable chitosan cellulose film | |
| CN114224769B (en) | Preparation method of color-changeable natural pigment water-based nail beautifying agent | |
| CN112940513B (en) | Anti-ultraviolet color master batch not prone to color change and preparation method thereof | |
| CN112569810B (en) | PMIA modified ultrafiltration membrane for white spirit catalytic filtration and preparation and application thereof | |
| CN113712935B (en) | Modified vegetable gum soft capsule shell and preparation method thereof | |
| CN108498370B (en) | Rutin-containing multifunctional facial mask and preparation method thereof | |
| WO2023080319A1 (en) | Method for preparing natural ink for digital textile printing, and ink | |
| Kubheka et al. | Fabrication of Zein/PVA Fibre Blends: Optimizing Concentration and Applied Voltage | |
| CN115262023A (en) | Antibacterial negative ion coffee bean polyester fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |