CN109135728A - A kind of fluorescent material and its preparation method and application - Google Patents
A kind of fluorescent material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of fluorescent materials, the fluorescent material is that can be obtained by the proportion of the modified more carbohydrates and their derivatives of control three primary colours fluorescence with rgb value is adjustable and/or Color tunable, the even fluorescent material of the full-color photoluminescent property of polysaccharide-based dynamic, under ultraviolet excitation the gradual change of color can occur with the extension of ultraviolet excitation time for the fluorescent material.Due in the fluorescent material, the degree of substitution of fluorophor is smaller, the fluorescent material remains to remain the excellent properties of polysaccharide and polysaccharide derivates, such as mechanical property, solubility property, processing performance, different types of fluorescent material, such as fluoresent coating, fluorescence electrospinning film, fluorescent fiber, fluorescence micella, fluorescent ink can be extremely easily processed into.The fluorescent ink has good film forming, can be printed in different substrates such as paper, plastics, metal surface.Thus there is highly important practical value in fields such as security printing, certificate false proofs.
Description
Technical field
The present invention relates to a kind of fluorescent materials and its preparation method and application, belong to organic fluorescence materials field.
Background technique
Off-color material is a kind of color or the special material that absorption spectrum can change with environmental stimulus.According to ring
The type of border stimulation or the principle of discoloration are different, and common off-color material can be divided into photochromic, electrochromism, solvation is shown
Color, thermochromism, changing color resulting from acid, power mutagens color, friction discoloration, ionization discoloration etc..In numerous off-color materials, light-induced variable
Color material is most commonly seen, and this kind of material, which passes through control illumination condition, can realize the transformation of color, has simple, sound
Many advantages, such as speed is fast, color change comparison is obvious is answered, thus is widely used in coating, cosmetics, textile printing and dyeing, prevents
In the even intelligent door and window design of pseudo- printing, photoswitch, optical storage.
In recent years, in photochromic material, photoluminescence off-color material color not only under visible light or absorption spectrum
It can change with illumination condition, fluorescence color or fluorescence spectrum can also change under ultraviolet lighting.This material
There is highly important application value in the fields such as bio-imaging, multiple analysis diagnosis, chemical sensitisation, anti-counterfeit printing, thus
It is the hot spot of current research.Currently, reported photoluminescence off-color material is mainly based upon the photochromic molecules of conjugation
Fluorescence spectrum variation before and after photoisomerization reaction process, color change is relatively single, so that having spy in some pairs of colors
It is difficult to preferably utilize in the field of different demand.
Fluorescence resonance energy transfer (FRET) refers to, when the fluorescence emission spectrum and acceptor fluorescence molecule of donor fluorescent molecule
Excitation or absorption spectrum when overlapping, the energy of donor fluorescent molecule excitation state can pass to acceptor fluorescence molecule and promote by
Body fluorescent molecule shines, while the fluorescence-intensity decay of donor fluorescent molecule itself, or even is quenched completely.The RGB principle of three primary colours
Refer to, most colors in nature, can be mixed in a certain ratio to obtain by three kinds of primary colours of red, green, blue;Conversely,
Any one colour can be broken down into three kinds of primary colours, corresponding tristimulus value.
Summary of the invention
Inventor by a large amount of experimental studies have found that, designed by reasonable donor and receptor, by fluorescence resonance energy
Transfer (FRET) is introduced into three primary colours (red, green and blue) fluorescence system, and guarantees at least one of three components component
Receptor is served as, at least one component serves as donor, by the efficiency of fluorescence resonance energy transfer between three components of control, can get
Rgb value is adjustable and/or the fluorescent material of Color tunable, or even can get the adjustable full-color fluorescent material of dynamic.Small molecule fluorescent
The mechanical property or processing performance of material generally will be poorer than high molecular fluorescent material;Other than photoluminescent property, fluorescent functional is high
Molecular physics performance is often depending on the performance of its macromolecule matrix.The polysaccharides natural polymer such as cellulose, starch, chitosan
Son is easy to chemical modification, biodegradable, good biocompatibility, in addition, these polysaccharide polymer materials are in nature reserves ten
Divide and enrich, thus be ideal functional polymer basis material, the fluorescent functional macromolecule synthesized based on this can obtain
While obtaining excellent fluorescence property, retain original good mechanical property, solubility property and processing performance, thus possesses larger
Application potential.
The present invention is led to using the hydroxyl or amino isoreactivity group of aligned transfer in semirigid polysaccharide polymer structure
It crosses chemical bond different fluorescent molecules is linked on polysaccharide polymer chain, by purposefully selecting suitable fluorophor,
The fluorescent material with red, green, blue three primary colours fluorescent emission can be obtained respectively.Simultaneously in above-mentioned material, from spectral property
It is upper to guarantee at least have two components --- receptor components and the donor component of fluorescence resonance energy transfer, and donor component or by
In body component, at least one group point has photochromic or photoluminescence discoloration property, i.e. its absorption spectrum or fluorescence spectrum meeting
It changes with the change of illumination condition (wavelength, intensity, time).On this basis, it is blended using simple physical, passes through tune
The ratio of whole three base fluorescent material of red, green, blue can obtain the full-color fluorescent material of polysaccharide-based dynamic.
Since the main body of above-mentioned fluorescent material is still polysaccharide polymer structure, the fluorophor introduced on a small quantity will not be to polysaccharide
The fundamental property of derivative impacts, and therefore, above-mentioned fluorescent material can still keep original excellent properties, such as mechanical property
And processing performance.Can be according to different purposes, and then various forms of materials are processed into, such as fluorescent film, fluorescent fiber, fluorescence
Nano particle etc..In particular, it can be prepared into full-color fluoroleum using above-mentioned fluorescent material good dissolubility and film forming
Black (a kind of more optimizedly full-color fluorescent ink of dynamic), can be realized three primary colours FRET system using general commercial ink-jet printer
It is accurate mixing and regulation, finally on the different substrate materials such as paper, plastics complete fluorescence falsification preventing icon printing, thus have very
Important application value.
In the present invention, the modified more carbohydrates and their derivatives of the three primary colours fluorescence refer to the modified polysaccharide of red fluorescence and
More carbohydrates and their derivatives that the modified more carbohydrates and their derivatives of its derivative, green fluorescence and blue-fluorescence are modified.
To achieve the above object, the invention provides the following technical scheme:
A kind of fluorescent material, the fluorescent material include that the modified more carbohydrates and their derivatives of red fluorescence, green fluorescence change
Property the modified more carbohydrates and their derivatives of more carbohydrates and their derivatives and blue-fluorescence at least two, at least two fluorescence
Modified more carbohydrates and their derivatives can form fluorescence resonance energy transfer system.
According to the present invention, the fluorescent material is that rgb value is adjustable and/or the polysaccharide-based fluorescent material of Color tunable.
According to the present invention, the fluorescent material is a kind of full-color fluorescent material of polysaccharide-based dynamic.
According to the present invention, the polysaccharide and its spread out that the modified more carbohydrates and their derivatives of the red fluorescence, green fluorescence are modified
At least one of more carbohydrates and their derivatives that biology and blue-fluorescence are modified is in the fluorescence resonance energy transfer systems
Donor component, the modified more carbohydrates and their derivatives of the red fluorescence, green fluorescence modified more carbohydrates and their derivatives and blue
At least another receptor components in the fluorescence resonance energy transfer system in the modified more carbohydrates and their derivatives of fluorescence,
And the fluorescence emission spectrum of donor component and the absorption spectrum of receptor components or excitation spectrum can be completely overlapped or partly overlap, and give
At least one group point has photochromic or photoluminescence discoloration property, i.e. absorption spectrum or fluorescence in body component and receptor components
Spectrum can shine with exterior light and be changed.
For example, the fluorescent material as downconversion fluorescent material in use, receptor components can be it is longer wavelengths of red
The modified more carbohydrates and their derivatives of color fluorescence, donor component can be the modified polysaccharide and its derivative of the shorter blue-fluorescence of wavelength
More carbohydrates and their derivatives that object or green fluorescence are modified;The fluorescent material is as upconverting fluorescent material in use, receptor group
Divide and can be the modified more carbohydrates and their derivatives of the shorter blue-fluorescence of wavelength modified more carbohydrates and their derivatives or green fluorescence,
Donor component can be the modified more carbohydrates and their derivatives of longer wavelengths of red fluorescence.
According to the present invention, the fluorescent material for example may include the modified more carbohydrates and their derivatives of red fluorescence and blue
The modified polysaccharide of the modified more carbohydrates and their derivatives of fluorescence, red fluorescence modified more carbohydrates and their derivatives and green fluorescence and its
More carbohydrates and their derivatives that the modified more carbohydrates and their derivatives of derivative, blue-fluorescence and green fluorescence are modified, or including red
The modified polysaccharide of the modified more carbohydrates and their derivatives of color fluorescence, blue-fluorescence modified more carbohydrates and their derivatives and green fluorescence and
Its derivative.
According to the present invention, the modified more carbohydrates and their derivatives of the fluorescence have structural formula shown in formula (I):
Wherein, R is identical or different, is independently from each other H-, CH3CO-, fluorophor, and fluorescence modification is more
The degree of substitution of fluorophor is 0.0001-2.0 in carbohydrates and their derivative.
Preferably, the degree of substitution of fluorophor is 0.001-1.0 in the modified more carbohydrates and their derivatives of the fluorescence, more excellent
It is selected as 0.005-0.1.
Preferably, the fluorophor, which is selected from, contains spiro-pyrans, spirooxazine, porphyrin, BODIPY, cyanine, rhodamine, fluorescence
The isostructural group of element, anthracene, pyrene, carbazole;The fluorophor is also possible to substituted above-mentioned fluorophor, the substituent group
It can be-COOH ,-X (- Cl ,-Br ,-I) ,-CN ,-NO2、-NH2、-CH3、-CH2CH3,-C (CH3)3Deng.
As illustratively, the fluorophor is selected from least one of the group with following structures:
Preferably, the modified more carbohydrates and their derivatives of the red fluorescence be selected from containing spiro-pyrans, porphyrin, BODIPY, cyanine,
The isostructural more carbohydrates and their derivatives of rhodamine.It is highly preferred that more carbohydrates and their derivatives that the red fluorescence is modified are selected from and contain
The isostructural more carbohydrates and their derivatives of spiro-pyrans, porphyrin, BODIPY.
Preferably, the modified more carbohydrates and their derivatives of the green fluorescence are selected from isostructural containing fluorescein, anthracene, BODIPY
More carbohydrates and their derivatives.
Preferably, the modified more carbohydrates and their derivatives of the blue-fluorescence are selected from isostructural more containing pyrene, spirooxazine, carbazole
Carbohydrates and their derivative.
According to the present invention, more carbohydrates and their derivatives are selected from starch, glucan, chitosan, chitin, alginic acid, fibre
One of dimension element and cellulose derivative are a variety of.
Preferably, the starch does not limit specifically, skilled person will appreciate that be suitable for it is of the present invention
System;Such as the starch is selected from least one of amylopectin, amylose, high amylose starches, converted starch;Or
Person, the starch are selected from soluble starch;Alternatively, the starch is selected from potato starch, cornstarch, tapioca, wheat
At least one of starch, starch from sweet potato, pea starch, Chinese Water Chestnut Starch, soybean starch.
Preferably, the cellulose is selected from microcrystalline cellulose, Cotton Pulp, wood pulps, bamboo pulp, straw pulp, absorbent cotton, sweet
Bagasse, timber and at least one of cellulose obtained from straw.
Preferably, the cellulose derivative in cellulose ether and cellulose esters containing substituent group at least one
Kind.
Preferably, the cellulose esters is selected from cellulose acetate, cellulose acetate-butyrate, cellulose propionate, butyric acid fiber
At least one of element, cellulose nitrate, cellulose benzoate, cellulose cinnamate.
Preferably, the cellulose ether is selected from methylcellulose, ethyl cellulose, carboxymethyl cellulose, hydroxy ethyl fiber
At least one of element.
In the present invention, the rgb value is adjustable and/or the polysaccharide-based fluorescent material of Color tunable refers to by the way that difference is added
The dosage of component and/or control illumination condition (such as intensity of illumination and light application time), available rgb value and/or color can be with
The fluorescent material of adjusting.
In the present invention, the full-color fluorescent material of polysaccharide-based dynamic refers to that color covers entire visible light colors range
(from blue to red), moreover, fluorescence color obtained can also change with illumination " time " or gradual change, i.e.,
Dynamically full-color fluorescence.
The present invention also provides the preparation methods of above-mentioned fluorescent material, which comprises
It is glimmering to prepare the modified more carbohydrates and their derivatives of red fluorescence, green fluorescence modified more carbohydrates and their derivatives and blue
At least two in the modified more carbohydrates and their derivatives of light, the modified more carbohydrates and their derivatives of at least two fluorescence can form
Fluorescence resonance energy transfer system;
It is realized using polishing, solwution method or ink-jet printing to the modified more carbohydrates and their derivatives of red fluorescence, green
At least two mixing in more carbohydrates and their derivatives that the modified more carbohydrates and their derivatives of fluorescence and blue-fluorescence are modified, preparation
Obtain the fluorescent material.
Preferably, the polishing specifically comprises the following steps:
It weighs the modified more carbohydrates and their derivatives of the red fluorescence of different quality ratio, the modified polysaccharide of green fluorescence and its spreads out
The fluorescent material is prepared at least two in more carbohydrates and their derivatives that biology and blue-fluorescence are modified, grinding.
Preferably, the grinding is selected from modes such as mortar grinder, freeze grinding, ball millings.
Preferably, the solwution method specifically comprises the following steps:
The modified more carbohydrates and their derivatives of red fluorescence, green fluorescence modified more carbohydrates and their derivatives and indigo plant are prepared respectively
At least two solution in the modified more carbohydrates and their derivatives of color fluorescence, measure different volumes ratio described at least two are molten
The fluorescent material is prepared in liquid, mixing, reprecipitation.
Preferably, the ink-jet printing specifically comprises the following steps:
By the modified more carbohydrates and their derivatives of red fluorescence, green fluorescence modified more carbohydrates and their derivatives and blue-fluorescence
At least two in modified more carbohydrates and their derivatives are configured to fluorescent ink, glimmering using inkjet printing control described at least two
The mixed proportion of light ink volatilizees to solvent, the fluorescent material is prepared.
The present invention also provides a kind of fluorescent ink, the fluorescent ink includes above-mentioned fluorescent material.
According to the present invention, the fluorescent ink is that rgb value is adjustable and/or the fluorescent ink of Color tunable.
According to the present invention, the fluorescent ink is the full-color fluorescent ink of polysaccharide-based dynamic.
According to the present invention, fluorescent material mass ratio shared in fluorescent ink is 0.5-15%, preferably 3-
8%.
According to the present invention, the fluorescent ink further includes solvent and additive.
Preferably, the solvent is selected from dimethyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF), N, N- dimethyl
Acetamide (DMAc), tetrahydrofuran (THF), ethyl alcohol, n-butanol, ethyl acetate, acetone, butanone, chloroform, pyridine, N- methyl pyrrole
At least one of pyrrolidone.
Preferably, the additive in fatty acid sorbitan, polysorbate, neopelex at least one
Kind and at least one of 2,6 di tert butyl 4 methyl phenol, ascorbic acid.
According to the present invention, additive mass ratio shared in fluorescent ink is 0.1-15%, preferably 1-5%.
The present invention also provides a kind of anti-counterfeiting marks, are made by above-mentioned fluorescent ink printing.
The present invention also provides a kind of anti-adulterants comprising above-mentioned anti-counterfeiting mark.
According to the present invention, the anti-adulterant can be bill, marketable securities, printed matter, package packing supplies etc..
The present invention also provides a kind of fluorescent articles comprising above-mentioned fluorescent material.
According to the present invention, the fluorescent article is one of fluorescent film, fluorescent fiber or fluorescent nano particle.
The beneficial effects of the present invention are:
The present invention provides a kind of fluorescent material, the fluorescent material be by the modified polysaccharide of control three primary colours fluorescence and
The proportion of its derivative can be obtained with rgb value is adjustable and/or Color tunable, even the full-color photoluminescent property of polysaccharide-based dynamic
Fluorescent material, it is often more important that, the fluorescent material, can be extended with the ultraviolet excitation time under ultraviolet excitation
The gradual change of color occurs.Further, since the degree of substitution of fluorophor is smaller in the fluorescent material, to polysaccharide polymer main body
Material property influences less, thus the fluorescent material remains to remain the excellent properties of polysaccharide and polysaccharide derivates, such as mechanics
Performance, solubility property, processing performance etc. can extremely be easily processed into different types of fluorescent material, such as fluoresent coating, glimmering
Photoelectricity spins film, fluorescent fiber, fluorescence micella, fluorescent ink etc..Especially fluorescent ink, since it is with good film forming,
It can be printed in different substrates such as paper, plastics, metal surface.Thus have in fields such as security printing, certificate false proofs
Highly important practical value.
Detailed description of the invention
Fig. 1 is modified more carbohydrates and their derivative CA-SP, CA-FITC, the CA- of the three primary colours fluorescence of preparation example 1,3 and 4
The fluorescence emission spectrum of Pyrene.
Fig. 2 is the fluorescence of donor CA-FITC, CA-Pyrene in the fluorescence resonance energy transfer system of preparation example 1,3 and 4
Overlapping cases between emission spectrum and the excitation spectrum or excitation spectrum of receptor CA-SP.
Fig. 3 is more carbohydrates and their derivative CA-SP, CA-FITC, CA-s modified using three primary colours fluorescence of embodiment 1
The full-color fluorescent powder of polysaccharide-based of the obtained color gradient type of Pyrene grinding and mixing.
Fig. 4 is more carbohydrates and their derivative CA-SP, CA-FITC, CA-s modified using three primary colours fluorescence of embodiment 2
In kind photo of the full-color fluoresent coating sample before and after ultraviolet lighting prepared by Pyrene solution blending.
Fig. 5 is more carbohydrates and their derivative CA-SP, CA-FITC, CA-s modified using three primary colours fluorescence of embodiment 3
The full-color fluorescent ink that Pyrene is prepared.
Fig. 6 is that the full-color bar code using polysaccharide-based full-color fluorescent ink printing of embodiment 4 changes with time figure.
Fig. 7 by embodiment 4 the fluorescent samples printed using the full-color ink of polysaccharide-based color-gamut (CIE1931).
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read documented content of the invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
The method is conventional method unless otherwise instructed.The raw material unless otherwise instructed can be from open business
Approach and obtain.
Wherein, the Chinese of the SPCOOH is 3- (3', 3'- dimethyl -6- nitro spiral shell [chromene -2,2'- Yin
Diindyl quinoline] -1'-yl) propionic acid or be N- propionyloxy -3,3- dimethyl -6- nitroindoline quinoline spiro-pyrans;Its English name are as follows: 3-
(3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indolin]-1'-yl)propanoic acid.Preparation
Example 1
The preparation of the modified more carbohydrates and their derivative CA-SP of red fluorescence
By 2.70g cellulose acetate (CA2.55) and 0.19g SPCOOH it is molten with 80mL N,N-dimethylformamide (DMF)
Solution is stated 2.06g dicyclohexylcarbodiimide (DCC) and 1.21g 4-dimethylaminopyridine (DMAP) are added in solution then up
As catalyst.Mixed solution stops after back flow reaction reflux 3h at 155 DEG C, and mixed solution is then poured into deionized water
Middle precipitating is dissolved with DMF after dry, is then precipitated again with deionized water, is so repeated 2-3 times, last filter cake is chilled
It is dried to obtain the CA-SP of the powder 2.9g of kermesinus, yield 88%.
The CA-SP is that cellulose acetate connects the modified ester of spiro-pyrans, and spiro-pyrans degree of substitution is 0.07.
Preparation example 2
The preparation of the modified more carbohydrates and their derivative CA-SP ' of red fluorescence
By 2.70g cellulose acetate (CA2.55) and 0.048g SPCOOH it is molten with 80mL N,N-dimethylformamide (DMF)
Solution is stated 2.06g dicyclohexylcarbodiimide (DCC) and 1.21g 4-dimethylaminopyridine (DMAP) are added in solution then up
As catalyst.Mixed solution stops after back flow reaction reflux 3h at 155 DEG C, and mixed solution is then poured into deionized water
Middle precipitating is dissolved with DMF after dry, is then precipitated again with deionized water, is so repeated 2-3 times, last filter cake is chilled
It is dried to obtain the CA-SP ' of the powder 2.9g of kermesinus, yield 88%.
The CA-SP ' is that cellulose acetate connects the modified ester of spiro-pyrans, and spiro-pyrans degree of substitution is 0.02.
Preparation example 3
The preparation of the modified more carbohydrates and their derivative CA-FITC of green fluorescence
By 3.0g cellulose acetate (CA2.55) be added in 250mL round bottom Schlenk reaction flask, anhydrous and oxygen-free operation (is taken out
Inflated with nitrogen after vacuum) three times, pipette 60mL anhydrous DMF (Molecule saves) dissolution.By 0.1298g fluorescein isothiocynate
(FITC) it is added to water oxygen free operation in 100mL Schlenk pipe and three times, then pipettes the dissolution of 20mL anhydrous DMF.It will dissolve
FITC solution be transferred in CA solution, 50 μ L dibutyl tin dilaurates (DBTDL) are added, mixed solution is anti-at 100 DEG C
4h is answered to stop reaction.Reactant is poured directly into methanol and is precipitated, a small amount of washed with ether of filter cake uses DMF after dry again
It after dissolution, is poured into deionized water and precipitates, filter, freeze-drying obtains the CA-FITC of pale yellow powder 2.80g, and yield is about
90%.
The CA-FITC is that cellulose acetate connects the modified ester of fluorescein, and fluorescein degree of substitution is 0.05.
Preparation example 4
The preparation of the modified more carbohydrates and their derivative CA-Pyrene (referred to as CA-Pyr) of blue-fluorescence
By 3.10g cellulose acetate (CA2.55) and 0.09g 1- pyrene formic acid be dissolved into 80mL DMF solution, be then added
2.06g DCC and 1.21g DMAP are as catalyst.Mixed solution back flow reaction 2h at 155 DEG C, then pours into solution about
Direct precipitation in 400mL water is dissolved with DMF after dry, is then precipitated again with deionized water, is so repeated 2-3 times, final filtration
The CA-Pyrene of pale powder 2.7g, yield 87% are obtained after obtained filter cake is freeze-dried.
CA-Pyrene cellulose acetate connects the modified ester of pyrene, and pyrene degree of substitution is 0.04.
Fig. 1 is modified more carbohydrates and their derivative CA-SP, CA-FITC, the CA- of the three primary colours fluorescence of preparation example 1,3 and 4
The fluorescence emission spectrum of Pyrene.It can be seen from the figure that the maximum emission peak of CA-SP is located at 633nm, half-peak breadth (FWHM) is
72nm;The maximum emission peak of CA-FITC is in 525nm, half-peak breadth 65nm;The maximum emission peak of CA-Pyrene is located at 387nm
(emission peak at 403nm, the fluorescent emission of corresponding aggregation), half-peak breadth is about 40nm.Just respectively locate at the generation peak of three
In in three primary colours wave-length coverage.
Fig. 2 is the fluorescence of donor CA-FITC, CA-Pyrene in the fluorescence resonance energy transfer system of preparation example 1,3 and 4
Overlapping cases between emission spectrum and the absorption spectrum or excitation spectrum of receptor CA-SP.It can be seen from the figure that CA-SP
Absorption spectrum can be divided into two parts: the absorption band of 500-700nm and the absorption band less than 500nm;Wherein, the suction of 500-700nm
Take-up (maximum absorption band 568nm) corresponds to the absorption that spiro-pyrans opens ring body structurc (merocyanine), and is less than the absorption band of 500nm
Then correspond to light absorption (excitation spectrum of CA-SP, the substantially absorption with spiro-pyrans open loop body of spiro-pyrans closed loop body (spiro-pyrans)
Band is overlapped).It can be found that two absorption bands of CA-SP are effectively be overlapped with the emission peak of CA-FITC, CA-Pyrene respectively.This
Outside, with the extension of ultraviolet lighting time, the intensity of CA-SP emission spectrum is gradually increased.
Embodiment 1
Ground and mixed method prepares the polysaccharide-based fluorescent powder of color gradient type
0.04) and 0.1g CA-SP weighing 0.2g CA-Pyrene, (cellulose acetate connects the modified ester of pyrene, and pyrene degree of substitution is
(cellulose acetate connects the modified ester of spiro-pyrans, 0.07) spiro-pyrans degree of substitution is that ground and mixed can be obtained from blue to pink
The fluorescent powder of color gradient.
0.05) and 0.1g weighing 0.3g CA-FITC, (cellulose acetate connects the modified ester of fluorescein, and fluorescein degree of substitution is
(cellulose acetate connects the modified ester of spiro-pyrans to CA-SP ', and spiro-pyrans degree of substitution is that 0.02), by ground and mixed, can be obtained from green
Fluorescent powder of the color to yellow-orange color gradual change.
Similarly, by changing the ratio of different component, it can be obtained the fluorescent powder of the color gradient in gamut, such as
Shown in Figure of description 3, Fig. 3 is more carbohydrates and their derivative CA-SP, CA-s modified using three primary colours fluorescence of embodiment 1
The full-color fluorescent powder of polysaccharide-based of the obtained color gradient of FITC, CA-Pyrene grinding and mixing.From figure 3, it can be seen that with
The extension of ultraviolet lighting time, the red fluorescence of first row CA-SP solid powder from scratch, change from weak to strong.Second row is
CA-Pyrene/CA-SP (mass ratio 2:1) mixes sample, and fluorescence color extends with time of ultraviolet irradiation, gradually becomes from blue
For pink.Third row be CA-FITC/CA-SP ' (mass ratio 3:1), with the ultraviolet lighting time extend, fluorescence color by
Gradually from green to orange-yellow.4th row is CA-SP/CA-FITC/CA-Pyrene (mass ratio 1:2:2), with ultraviolet light
Extend according to the time, fluorescence color is gradually transitions pink from Indigo.
Embodiment 2
Solution mixing method prepares the polysaccharide-based fluoresent coating of color gradient type
Firstly, selecting DMF is solvent, by CA-Pyrene, CA-SP, CA-FITC and CA-SP of preparation example 1-4 ' match respectively
Concentration processed is the solution of 0.05g/mL.
Then according to different volumes ratio (volume ratio variation range is 200:1 to 1:200), different volumes are pipetted respectively
It is molten to be mixed to get a series of mixing with different component and proportion for CA-Pyrene, CA-SP, CA-FITC and CA-SP ' solution
Liquid.
Above-mentioned solution is finally coated in the surface of different substrate materials (paper, plastics, metal etc.), or substrate is directly soaked
Taking-up after steeping in above-mentioned solution.It volatilizees to solvent, thoroughly the dry fluorescence that can be obtained with different colours gradual change applies sample
Layer.Fig. 4 is that more carbohydrates and their derivative CA-SP, CA-FITC, CA-Pyrenes modified using three primary colours fluorescence of embodiment 2 are molten
In kind photo of the prepared full-color fluoresent coating sample before and after ultraviolet lighting is blended in liquid.As shown in Figure of description 4, use
Filter paper does substrate, by the solution with different component coated on filter paper, can obtain a series of face in gamuts after dry
The fluoresent coating sample of color gradual change.
Figure 4, it is seen that by CA-SP, CA-SP ', CA-FITC and CA-Pyrene solution (0.06g/mL) presses respectively
According to certain mass ratio, (after evenly mixing, the filter paper fluorescent samples of infiltration coating preparation are arranged in 10:1 to 1:10) in sequence
" 2016 " printed words, it is (partially red glimmering when beginning as the phosphor pattern of dominant hue using blue-green with the extension of ultraviolet lighting time
The fluorescence intensity of light sample is weaker) gradually become " 2016 " phosphor pattern of full color.
Embodiment 3
Three primary colours fluorescent ink is prepared
Firstly, selecting DMF is solvent, by CA-Pyrene, CA-SP, CA-FITC and CA-SP of preparation example 1-4 ' match respectively
Concentration processed is the solution of 0.06g/mL, waits mass mixings, obtains mixed solution.
Then 7wt% fatty acid sorbitan and 1wt% ascorbic acid are added into above-mentioned mixed solution, uses ultrasonic wave added
Dissolution is uniformly mixed.
Finally filter above-mentioned solution respectively using 0.2 μm of syringe filters, thus obtain it is uniform, can be used for printing
Fluorescent ink, ink sample is as shown in Figure of description 5.Fig. 5 be embodiment 3 the polysaccharide modified using three primary colours fluorescence and its
The full-color fluorescent ink that derivative CA-SP, CA-FITC, CA-Pyrene are prepared.
From figure 5 it can be seen that from left to right, being followed successively by CA-FITC, CA-Pyrene, CA-SP ' and CA-SP fluoroleum
The photo in kind of ink, above-mentioned ink is all homogeneous phase solution, and color is successively deepened.
Embodiment 4
Full-color inkjet printing
Using the three primary colours fluorescent ink in embodiment 3, by CA-Pyrene, CA-SP, CA-FITC, CA-SP ' it fills respectively
Enter in tetra- print cartridges of CMYK of conventional commercial desktop inkjet printers, the CMYK of image is then controlled by image processing software
Value, and then the color of print image is controlled, it prints and different substrate materials, such as filter paper, Kang Songzhi, polycarbonate film can be selected, beat
Obtained pattern is printed, color gradient can occur under ultraviolet light, as shown in Figure of description 6 and Fig. 7, using above-mentioned glimmering
The bar code of light ink printing, under ultraviolet lighting, with time of ultraviolet irradiation gradual change, i.e. bar code information can occur for barcoded color
It can change at any time, thus can be used as a kind of dynamic anti-fake materials'use.Fig. 6 is the complete using polysaccharide-based of embodiment 4
The full-color bar code of color fluorescent ink printing changes with time figure.From fig. 6 it can be seen that the fluorescence bar code (Bar of printing
Code), under dark condition, in the channel 365nm, with the extension of ultraviolet (365nm) irradiation time, blue-green combine bar code by
Gradually it is changed into full color combination bar code.In visible channel or under natural light, white print area is gradually shown on filter paper
Another combining form aubergine bar code is gone out.By the phosphor pattern in the channel 365nm decompose R, G, B tri- it is different logical
In road, three kinds of different bar code combining forms can be obtained respectively, wherein G, channel B bar code change over time small, the channel R
Bar code variation is bigger, and the variation of progressive formation and visible channel code coincide substantially, the dynamic of corresponding full-color fluorescence
Component.
Fig. 7 by embodiment 4 the fluorescent samples printed using the full-color ink of polysaccharide-based color-gamut (CIE1931).
It can be seen from figure 7 that it is corresponding in CIE coordinate system delta-shaped region [(0.17,0.07), (0.29,0.51), (0.55,
0.30)] it is entire color gamut space that the fluorescent material is able to achieve, belongs to full-color fluorescent material.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of fluorescent material, which is characterized in that the fluorescent material includes the modified more carbohydrates and their derivatives of red fluorescence, green
At least two in the modified more carbohydrates and their derivatives of color fluorescence and the modified more carbohydrates and their derivatives of blue-fluorescence, it is described at least
The modified more carbohydrates and their derivatives of two kinds of fluorescence can form fluorescence resonance energy transfer system.
2. fluorescent material according to claim 1, which is characterized in that the fluorescent material is that rgb value is adjustable and/or color
Adjustable polysaccharide-based fluorescent material;Alternatively, the fluorescent material is a kind of full-color fluorescent material of polysaccharide-based dynamic.
Preferably, the modified more carbohydrates and their derivatives of the red fluorescence, green fluorescence modified more carbohydrates and their derivatives and indigo plant
At least one of modified more carbohydrates and their derivatives of color fluorescence are the donor component in the fluorescence resonance energy transfer system,
What the modified more carbohydrates and their derivatives of the red fluorescence, green fluorescence modified more carbohydrates and their derivatives and blue-fluorescence were modified
At least another receptor components in the fluorescence resonance energy transfer system in more carbohydrates and their derivatives, and donor component
Fluorescence emission spectrum and the absorption spectrum or excitation spectrum of receptor components can be completely overlapped or partly overlap, donor component and by
At least one group point has photochromic or photoluminescence discoloration property in body component, i.e. absorption spectrum or fluorescence spectrum can be with outer
Portion's illumination and change.
Preferably, the fluorescent material may include the modified more carbohydrates and their derivatives of red fluorescence and modified more of blue-fluorescence
The modified more carbohydrates and their derivatives of the more carbohydrates and their derivatives and green fluorescence that carbohydrates and their derivative, red fluorescence are modified, blue
More carbohydrates and their derivatives that the modified more carbohydrates and their derivatives of fluorescence and green fluorescence are modified, or modified including red fluorescence
More carbohydrates and their derivatives that the modified more carbohydrates and their derivatives of more carbohydrates and their derivatives, blue-fluorescence and green fluorescence are modified.
3. fluorescent material according to claim 1 or 2, which is characterized in that the modified more carbohydrates and their derivatives of the fluorescence
With structural formula shown in formula (I):
Wherein, R is identical or different, is independently from each other H, CH3CO-, fluorophor, and the modified polysaccharide of the fluorescence and its
The degree of substitution of fluorophor is 0.0001-2.0 in derivative.
Preferably, the degree of substitution of fluorophor is 0.001-1.0 in the modified more carbohydrates and their derivatives of the fluorescence, more preferably
0.005-0.1。
Preferably, the fluorophor be selected from containing spiro-pyrans, spirooxazine, porphyrin, BODIPY, cyanine, rhodamine, fluorescein,
Anthracene, pyrene, carbazole structure group;The fluorophor is also possible to substituted above-mentioned fluorophor, and the substituent group can be with
It is-COOH ,-X (- Cl ,-Br ,-I) ,-CN ,-NO2、-NH2、-CH3、-CH2CH3、-C(CH3)3。
Preferably, the modified more carbohydrates and their derivatives of the red fluorescence, which are selected from, contains spiro-pyrans, porphyrin, BODIPY, cyanine, Luo Dan
Bright isostructural more carbohydrates and their derivatives.It is highly preferred that more carbohydrates and their derivatives that the red fluorescence is modified are selected from pyrrole containing spiral shell
It mutters, porphyrin, the isostructural more carbohydrates and their derivatives of BODIPY.
Preferably, the modified more carbohydrates and their derivatives of the green fluorescence, which are selected from, contains fluorescein, anthracene, the isostructural polysaccharide of BODIPY
And its derivative.
Preferably, the modified more carbohydrates and their derivatives of the blue-fluorescence be selected from containing pyrene, spirooxazine, the isostructural polysaccharide of carbazole and
Its derivative.
4. fluorescent material according to any one of claim 1-3, which is characterized in that more carbohydrates and their derivatives are selected from
One of starch, glucan, chitosan, chitin, alginic acid, cellulose and cellulose derivative are a variety of.
Preferably, the starch is selected from least one of amylopectin, amylose, high amylose starches, converted starch;Or
Person, the starch are selected from soluble starch;
Alternatively, the starch be selected from potato starch, cornstarch, tapioca, wheaten starch, starch from sweet potato, pea starch,
At least one of Chinese Water Chestnut Starch, soybean starch.
Preferably, the cellulose is selected from microcrystalline cellulose, Cotton Pulp, wood pulps, bamboo pulp, straw pulp, absorbent cotton, sugarcane
Slag, timber and at least one of cellulose obtained from straw.
Preferably, the cellulose derivative is selected from least one of the cellulose ether containing substituent group and cellulose esters.
Preferably, the cellulose esters is selected from cellulose acetate, cellulose acetate-butyrate, cellulose propionate, cellulose butyrate, fibre
Tie up at least one of plain nitrate, cellulose benzoate, cellulose cinnamate.
Preferably, the cellulose ether is in methylcellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose
At least one.
5. the preparation method of the described in any item fluorescent materials of claim 1-4 characterized by comprising
Prepare the modified more carbohydrates and their derivatives of red fluorescence, green fluorescence modified more carbohydrates and their derivatives and blue-fluorescence to change
Property more carbohydrates and their derivatives at least two, the modified more carbohydrates and their derivatives of at least two fluorescence can form fluorescence
Resonance energy transfer system;
It is realized using polishing, solwution method or ink-jet printing to the modified more carbohydrates and their derivatives of red fluorescence, green fluorescence
At least two mixing in more carbohydrates and their derivatives that modified more carbohydrates and their derivatives and blue-fluorescence are modified, is prepared
The fluorescent material.
6. preparation method according to claim 5, which is characterized in that the polishing specifically comprises the following steps:
Weigh the modified more carbohydrates and their derivatives of the modified more carbohydrates and their derivatives of the red fluorescence of different quality ratio, green fluorescence
The fluorescent material is prepared at least two in more carbohydrates and their derivatives being modified with blue-fluorescence, grinding.
Preferably, the grinding is selected from modes such as mortar grinder, freeze grinding, ball millings.
Preferably, the solwution method specifically comprises the following steps:
It is glimmering that the modified more carbohydrates and their derivatives of red fluorescence, green fluorescence modified more carbohydrates and their derivatives and blue are prepared respectively
At least two solution in the modified more carbohydrates and their derivatives of light, measures at least two solution of different volumes ratio, mixes
It closes, the fluorescent material is prepared in reprecipitation.
Preferably, the ink-jet printing specifically comprises the following steps:
The modified more carbohydrates and their derivatives of red fluorescence, green fluorescence modified more carbohydrates and their derivatives and blue-fluorescence are modified
More carbohydrates and their derivatives at least two be configured to fluorescent ink, at least two fluoroleum is controlled using inkjet printing
The mixed proportion of ink volatilizees to solvent, the fluorescent material is prepared.
7. a kind of fluorescent ink, which is characterized in that the fluorescent ink includes the described in any item phosphors of claim 1-4
Material.
Preferably, the fluorescent ink is that rgb value is adjustable and/or the fluorescent ink of Color tunable.
Preferably, the fluorescent ink is the full-color fluorescent ink of polysaccharide-based dynamic.
Preferably, fluorescent material mass ratio shared in fluorescent ink is 0.5-15%, preferably 3-8%.
Preferably, the fluorescent ink further includes solvent and additive.
Preferably, the solvent is selected from dimethyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF), N, N- dimethylacetamide
Amine (DMAc), tetrahydrofuran (THF), ethyl alcohol, n-butanol, ethyl acetate, acetone, butanone, chloroform, pyridine, N- crassitude
At least one of ketone.
Preferably, the additive be selected from least one of fatty acid sorbitan, polysorbate, neopelex and
At least one of 2,6 di tert butyl 4 methyl phenol, ascorbic acid.
Preferably, additive mass ratio shared in fluorescent ink is 0.1-15%, preferably 1-5%.
8. a kind of anti-counterfeiting mark is made by fluorescent ink as claimed in claim 7 printing.
9. a kind of anti-adulterant comprising anti-counterfeiting mark according to any one of claims 8.
Preferably, the anti-adulterant can be bill, marketable securities, printed matter, package packing supplies etc..
10. a kind of fluorescent article comprising the described in any item fluorescent materials of claim 1-4.
Preferably, the fluorescent article is one of fluorescent film, fluorescent fiber or fluorescent nano particle.
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CN104031477A (en) * | 2014-06-25 | 2014-09-10 | 吉林大学 | Panchromatic fluorescent anti-counterfeiting ink based on conjugated polymer nano-particles |
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