CN114672197A - Rapid color development ink and application thereof in color development paper - Google Patents
Rapid color development ink and application thereof in color development paper Download PDFInfo
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- CN114672197A CN114672197A CN202210437309.1A CN202210437309A CN114672197A CN 114672197 A CN114672197 A CN 114672197A CN 202210437309 A CN202210437309 A CN 202210437309A CN 114672197 A CN114672197 A CN 114672197A
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- 238000011161 development Methods 0.000 title claims abstract description 22
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 32
- -1 rhodamine hydrazine Schiff base Chemical class 0.000 claims abstract description 30
- 239000002262 Schiff base Substances 0.000 claims abstract description 22
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000002161 passivation Methods 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 239000000123 paper Substances 0.000 claims description 28
- 239000004744 fabric Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 3
- 239000011087 paperboard Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 7
- 230000005284 excitation Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 15
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 10
- 229940125904 compound 1 Drugs 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- QYOUEYXPOYMCDV-UHFFFAOYSA-N C(C)O[AlH]OCC.[Li] Chemical compound C(C)O[AlH]OCC.[Li] QYOUEYXPOYMCDV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/004—Dyeing with phototropic dyes; Obtaining camouflage effects
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Textile Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paper (AREA)
Abstract
The invention relates to a quick color development ink and application thereof in color development paper. The preparation method of the quick color development ink comprises the following steps: weighing the following components in parts by weight: 3-5 parts of rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J), 10-20 parts of resin material, 20-40 parts of deionized water and 60-90 parts of ethanol or methanol; mixing RhB-J with ethanol, and mixing the resin material with deionized water; and uniformly mixing the mixture to obtain the rapid chromogenic ink containing RhB-J. The color developing paper with fast color developing ink as color developing layer includes base material, PEG passivation layer and color developing layer. The quick color development ink can quickly develop color under the irradiation of sunlight or ultraviolet light, and the fluorescence intensity is continuously increased along with the extension of the illumination time; the color paper can change from colorless to red or purple under the excitation of ultraviolet rays, and the color development time is long. The color developing printing ink and the color developing paper can be used for manufacturing various luminous and color developing packaging products.
Description
Technical Field
The invention belongs to the technical field of color-changing materials, and particularly relates to quick color-developing ink and application thereof in color-developing paper.
Background
With the close combination of the anti-counterfeiting technology and the printing technology, the method has great significance for fighting against counterfeit and shoddy products and standardizing the market order. The printing ink technology has good development situation, increasingly wide application range and better benefit, and is combined with a plurality of subject fields (such as optics, chemistry, electromagnetism, spectral technology and the like) to develop a comprehensive ink anti-counterfeiting technology. The photochromic and color-changing material has potential application in developing molecular switches, molecular logic gates, optical data storage, photoelectric devices, advanced anti-counterfeiting, optically-controllable drug or ion transfer, biological imaging and molecular machines. In 1950, Dame and Company Ltd used fluorescent pigments for the first time in inks to form practical products. In recent years, organic fluorescent dyes have been studied more and more, and examples thereof include coumarins, naphthalimide derivatives, phthalocyanines, xanthenes, ketones, and thioxanthones. Common organic photochromic molecules, including azobenzene, spiropyran, dithienylethylene, spirooxazine, fulgide, and the like, can undergo color change under light irradiation, and show good performance in chemical, biological, physical and nanotechnology applications. Spiropyrans have an increased dipole moment and a large change in spectral absorption under UV irradiation, and also have moderate fatigue resistance, especially under strong radiation. The above-mentioned photochromism dyes have weak or no fluorescence in spite of their good photochromism properties.
Rhodamine (Rhodamine) is a basic xanthene dye taking xanthene as a parent, has a spiro-ring and ring-opening interconversion molecular structure, is a dye with strong fluorescence and high laser output power, an oxygen bridge between two benzene rings in a chromophore of the dye is connected, a carbon atom and an oxygen atom are in para position to form a six-membered ring, a very long conjugated system is arranged in the molecule, and the molecule has a rigid planar structure, so that the stability of the molecule is enhanced, the light is easily absorbed to emit wavelength, thereby forming fluorescence, the thermal motion in the molecule can be reduced, the energy loss of an excited state is reduced, and the fluorescence emission efficiency is improved.
Rhodamine dyes have become an important branch of fluorescent probe research in recent years due to their unique structures and corresponding fluorescent properties. Many reports on the aspects of synthesis, optical characteristics, ionized structure, analysis and the like of rhodamine fluorescent dye are available. Compared with other fluorescent dyes, the rhodamine fluorescent dye has the advantages of longer wavelength range, good light stability, insensitivity to pH, higher fluorescence quantum yield and the like, has wide application in the fields of molecular biology, cytobiology, pharmacology, molecular genetics, environmental chemistry, information science, single molecule detection, fluorescent labeling, laser dyes and the like, and is one of the most commonly used fluorescent dyes in the fields of analytical chemistry, biological medicine science and the like. The rhodamine B is a common fluorescent probe matrix due to the advantages of no toxicity, good water solubility, higher extinction coefficient, higher fluorescence quantum yield, easiness in preparation and the like.
However, to date, no reports have been made concerning rhodamine derivatives as long-lived photochromics. Therefore, the synthesized good photochromic fluorescent dye is used as an anti-counterfeiting identification material for tickets, securities, trademarks or packages and the like, prevents counterfeit and shoddy products, protects the intellectual property rights of famous brands, high-quality, special and novel products, maintains the legal rights and interests of manufacturers and consumers, and has important practical significance for the benign development of national economy.
Disclosure of Invention
In order to solve the problems of the existing quick color developing ink and color developing paper, the invention provides quick color developing ink containing a rhodamine hydrazine schiff base derivative photochromic fluorescent dye (RhB-J) component and application thereof in color developing paper.
The technical scheme adopted by the invention is as follows:
the quick color development ink comprises the following components in parts by weight:
further, in the above fast color developing ink, the resin material is polyethylene glycol 20000(PEG), PMMA, PVA, PET or PVC.
Further, the rhodamine hydrazine schiff base derivative photochromic fluorescent dye has a structural general formula shown in (I):
wherein,
R1＝R2＝R3＝R4＝H；
or R1＝R4＝H，R2＝-CH2CH3，R3＝-CH3；
Or R1＝R2＝-CH3，R3＝R4＝H；
Or R1＝R2＝-CH2CH3，R3＝R4＝H；
Or R1And R4Together form- (CH)2)3-，R2And R3Together form- (CH)2)3-。
Furthermore, the preparation method of the rhodamine hydrazine schiff base derivative photochromic fluorescent dye comprises the following steps:
1) mixing rhodamine B, a reducing agent and tetrahydrofuran according to a molar ratio, reacting for 48 hours under the condition of filling nitrogen, adding a proper amount of anhydrous magnesium sulfate, performing suction filtration, and performing spin drying to obtain a solid compound 1, wherein the ratio of rhodamine B to the reducing agent to tetrahydrofuran is 1:1: 1;
2) mixing the obtained solid compound 1 with dichloromethane, adding pyridinium chlorochromate (PCC) according to a molar ratio, stirring and reacting the solid compound 1: PCC 1:1 at room temperature for 0.5h, extracting, filtering, and spin-drying to obtain a solid compound 2;
3) taking a solid compound 2, hydrazine hydrate and a proper amount of absolute ethyl alcohol, reacting at 78 ℃ for 6-7 h according to a molar ratio, observing the color change of a reactant, observing a spot plate until the reaction is not carried out any more, cooling to room temperature, spin-drying a solvent, and purifying the obtained product through silica gel column chromatography to obtain the rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J).
Preferably, in the above method for preparing rhodamine hydrazine schiff base derivative photochromic fluorescent dye, the reducing agent is lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium triethoxyaluminum hydride, lithium diethoxyaluminum hydride or borane.
Preferably, in the preparation method of the rhodamine hydrazine schiff base derivative photochromic fluorescent dye, the solid compound 1 is an alcohol rhodamine compound, and the solid compound 2 is an aldehyde rhodamine compound.
Furthermore, the preparation method of the rapid color development ink comprises the following steps: weighing the components in parts by weight; fully mixing rhodamine hydrazine Schiff base derivative photochromic fluorescent dye with ethanol or methanol to obtain a mixture A; fully mixing the resin material with deionized water to obtain a mixture B; and uniformly mixing the mixture A and the mixture B to obtain the quick color development ink.
A color developing paper comprising a three-layer structure:
layer 1: a base material;
layer 2: a PEG passivation layer in direct contact with the base material;
layer 3: a color developing layer made of the rapid color developing ink according to claim 1.
Further, in the color paper, the substrate material of the layer 1 is common paper, filter paper, glass, cotton-linen fabric or chemical fiber fabric.
Further, in the color paper, the PEG content in the PEG passivation layer is 10% -15%.
The quick color developing ink is used for being added into paint, glaze and printing paste.
The quick color-developing ink is used for developing and printing characters or patterns on paper, cotton and linen fabrics, paperboards or plastics.
The invention has the beneficial effects that:
1. the rhodamine hydrazine Schiff base derivative photochromic fluorescent dye prepared by the invention has the characteristics of stable property, good glossiness, fatigue resistance, long open loop life, high fluorescence quantum efficiency, no obvious fading, no toxicity, no harm and environmental friendliness. Firstly, the six-membered ring structure has higher stability, so that the structure of Schiff base is more stable, a probe of the structure is placed at room temperature for 60 days, and the structure is not changed by monitoring through a thin-layer plate; secondly, the probe with the rhodamine hydrazine Schiff base six-membered ring structure develops color after illumination, the generated strong fluorescent bright red rhodamine, the solution is changed into macroscopic bright red and strong fluorescence from colorless and non-fluorescence, the higher the content of the photochromic fluorescent dye is, the better the color development effect is, the photochromic fluorescent dye can be used for printing patterns and figures, including but not limited to characters, two-dimensional codes and the like, and is suitable for various articles and printing ink and the like which need sensitive color development.
2. The rapid color development ink containing RhB-J prepared by the invention can rapidly develop color under the irradiation of sunlight or ultraviolet light, and the color is red or purple red; the fluorescence intensity is continuously increased along with the extension of the illumination time; the color changing efficiency can be different by changing different resin materials, such as PEG, PMMA, PVA, PET, PVC and the like. The fast color developing ink can be used in paint, glaze and printing paste, can be used for developing and printing characters or patterns on paper, cotton and linen fabrics, paperboards or plastics, can be used for manufacturing various luminous and color developing packaging products, can be used for designing color sequences according to user requirements, and can be used for modulating and printing luminous waves, patterns, figures, characters, two-dimensional codes and the like on the nanometer order of magnitude.
3. The color developing paper prepared by the invention can be changed into red or purple from colorless under the excitation of ultraviolet rays, and the color developing time is long.
Drawings
FIG. 1 is a photo-chromogenic analytical diagram of rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J).
FIG. 2 shows the selectivity of ultraviolet-visible absorption spectrum of rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J) under illumination.
FIG. 3 shows the selectivity of the fluorescence spectrum of rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J) under illumination.
In fig. 2 and 3, 1 visible light is 0min, 2 visible light is 5min, 3 visible light is 10min, 4 visible light is 15min, 5 visible light is 20min, 6 visible light is 25min, and 7 visible light is 30 min.
FIG. 4 is a comparison graph of color changes of rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J) solution before and after light irradiation.
FIG. 5 is a contrast chart of color change before and after UV irradiation for printing characters and patterns with fast developing ink.
FIG. 6 is a comparison of the color change before and after UV exposure of a printed text using a fast developing ink.
FIG. 7 is a schematic view of the structure of the color paper.
Detailed Description
EXAMPLE 1 preparation of rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J)
The method comprises the following steps:
1) mixing rhodamine B, lithium aluminum hydride and tetrahydrofuran according to a molar ratio, reacting for 48 hours under the condition of filling nitrogen, then adding a proper amount of anhydrous magnesium sulfate, filtering, and spin-drying to obtain a solid compound 1;
2) mixing the obtained solid compound 1 with dichloromethane, adding pyridinium chlorochromate (PCC) according to a molar ratio, stirring and reacting the solid compound 1: PCC 1:1 at room temperature for 0.5h, extracting, filtering, and spin-drying to obtain a solid compound 2;
3) taking a solid compound 2, hydrazine hydrate and a proper amount of absolute ethyl alcohol according to a molar ratio, reacting the solid compound 2 and the hydrazine hydrate for 6-7 h at 78 ℃, observing the color change of a reactant, observing a spot plate until the reaction is not carried out any more, cooling to room temperature, spin-drying a solvent, and purifying the obtained product through silica gel column chromatography to obtain the rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J).
The solid compound 1 is an alcohol rhodamine compound, and the solid compound 2 is an aldehyde rhodamine compound.
The reaction general formula of the rhodamine hydrazine Schiff base derivative photochromic fluorescent dye is as follows:
wherein,
R1＝R2＝R3＝R4＝H；
or R1＝R4＝H，R2＝-CH2CH3，R3＝-CH3；
Or R1＝R2＝-CH3，R3＝R4＝H；
Or R1＝R2＝-CH2CH3，R3＝R4＝H；
Or R1And R4Together form- (CH)2)3-，R2And R3Together form- (CH)2)3-。
Example 2 preparation of a Rapid color development ink
The method comprises the following steps:
1) weighing the following components in parts by weight: 3 parts of RhB-J prepared in example 1, 15 parts of PEG, 22 parts of deionized water and 70 parts of ethanol;
2) fully mixing RhB-J with ethanol to obtain a mixture A;
3) fully mixing PEG and deionized water to obtain a mixture B;
4) and uniformly mixing the mixture A and the mixture B to obtain the rapid chromogenic ink containing RhB-J.
EXAMPLE 3 preparation of a color developing paper
The method comprises the following steps:
1) layer 1: selecting filter paper as a substrate material;
2) layer 2: directly coating a 15% PEG passivation layer on the surface of a substrate material;
3) layer 3: the fast developing ink containing RhB-J prepared in example 2 was coated on the surface of the layer 2 as a developing layer.
As can be seen from figure 1, the rhodamine hydrazine Schiff base derivative photochromic fluorescent dye (RhB-J) is a six-membered ring structure, has stable property, good glossiness, fatigue resistance, long open-loop service life, high fluorescence quantum efficiency and no obvious fading, and the sensitivity of the photoswitch can be seen, the probe of the structure is placed at room temperature for 60 days, and the structure is not changed by monitoring through a thin-layer plate. Through the structure, the material with the hydrazine structure can be researched in the future, more stable fluorescent color-changing dyes can be prepared, and the fluorescent color-changing dyes can be applied to various fields such as color-developing paper, color-developing ink and the like.
As shown in fig. 2 and 3, by analyzing the selectivity of the ultraviolet-visible absorption spectrum and the fluorescence spectrum, the substance is qualitatively, quantitatively and structurally analyzed by using the absorption of molecules or ions of the substance to light in a certain wavelength range, and the precision and accuracy are high. Meanwhile, through the analysis and data determination of the illumination time, the utilization efficiency of the dye at which moment is higher can be obtained more accurately, so that the time cost and loss of dye application are reduced, and the product is applied accurately.
The color change of the rhodamine hydrazine schiff base derivative photochromic fluorescent dye (RhB-J) solution before and after light irradiation can be visually seen through a graph 4, the solution is changed from colorless and non-fluorescence into bright red and strong fluorescence which can be seen by naked eyes, the higher the content of the photochromic fluorescent dye is, the better the color development effect is, so that the concentration content of the solution can be properly increased according to the requirement in the practical application, thereby achieving the ideal effect and bringing better beneficial effect for self experiments.
Through the effects shown in fig. 5 and fig. 6, the quick color development ink containing RhB-J can be applied to different industrial fields, and under the irradiation of sunlight or ultraviolet light, the ink can quickly develop the color, wherein the color is red or purple red; the fluorescence intensity is continuously increased along with the extension of the illumination time; the color changing efficiency can be different by changing different resin materials, such as PEG, PMMA, PVA, PET, PVC and the like. Meanwhile, the quick color developing ink can be used for coating, paper, cotton and linen fabrics, plastic plates and the like according to the technical requirements for printing characters or patterns; the color developing paper can also be used in different fields, printing and the like, and different requirements of users are met.
Fig. 7 is a schematic structural view of the color paper, and the specific internal structure of the color paper can be seen more clearly. Meanwhile, according to the remarkable characteristics that the color-developing paper can be changed from colorless to red or purple under the excitation of ultraviolet rays and the color-developing time is long, technical personnel needing to be applied can make the color-developing paper more convenient and fast, and higher benefits are brought to the application field.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative and not restrictive of the scope of the invention, and that various changes or modifications may be made to the embodiments and equivalents using the principles and spirit of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The quick color development ink is characterized by comprising the following components in parts by weight:
2. the fast color developing ink as claimed in claim 1, wherein the rhodamine hydrazine schiff base derivative photochromic fluorescent dye has a structural general formula (I):
wherein,
R1＝R2＝R3＝R4＝H；
or R1＝R4＝H，R2＝-CH2CH3，R3＝-CH3；
Or R1＝R2＝-CH3，R3＝R4＝H；
Or R1＝R2＝-CH2CH3，R3＝R4＝H；
Or R1And R4Together form- (CH)2)3-，R2And R3Together form- (CH)2)3-。
3. The fast developing ink according to claim 1, wherein the resin material is PEG, PMMA, PVA, PET or PVC.
4. The fast developing ink according to claim 1, characterized in that the preparation method is as follows: weighing the components in parts by weight; fully mixing the rhodamine hydrazine Schiff base derivative photochromic fluorescent dye with ethanol or methanol to obtain a mixture A; fully mixing the resin material with deionized water to obtain a mixture B; and uniformly mixing the mixture A and the mixture B to obtain the quick color development ink.
5. The color developing paper is characterized by comprising a three-layer structure:
layer 1: a base material;
layer 2: a PEG passivation layer in direct contact with the base material;
layer 3: a color developing layer made of the rapid color developing ink according to claim 1.
6. The color developing paper according to claim 5, wherein the substrate material of the layer 1 is plain paper, filter paper, glass, cotton-linen fabric or chemical fiber fabric.
7. The color developing paper as claimed in claim 5, wherein the PEG content in the PEG passivation layer is 10% -15%.
8. A fast developing ink as claimed in claim 1 for use as an additive in paints, glazes, printing pastes.
9. The fast color developing ink as claimed in claim 1 is used for color printing of characters or patterns on paper, cotton and linen fabric, paperboard or plastic.
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