CN103666457A - Environmental protection type organic coumarin-base photoluminescence anti-counterfeiting pigment, environmental protection type organic coumarin-base photoluminescence anti-counterfeiting ink,and preparation methods thereof - Google Patents
Environmental protection type organic coumarin-base photoluminescence anti-counterfeiting pigment, environmental protection type organic coumarin-base photoluminescence anti-counterfeiting ink,and preparation methods thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 238000005424 photoluminescence Methods 0.000 title claims abstract description 38
- 230000007613 environmental effect Effects 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 57
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 23
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001043 yellow dye Substances 0.000 claims abstract description 9
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- 239000000976 ink Substances 0.000 claims description 138
- 238000002844 melting Methods 0.000 claims description 65
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
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Abstract
The present invention relates to an environmental protection type organic coumarin-base photoluminescence anti-counterfeiting pigment, an environmental protection type organic coumarin-base photoluminescence anti-counterfeiting ink, and preparation methods of the environmental protection type organic coumarin-base photoluminescence anti-counterfeiting pigment and the environmental protection type organic coumarin-base photoluminescence anti-counterfeiting ink. The photoluminescence anti-counterfeiting pigment contains 60-70 parts by weight of a cross-linked melamine-formaldehyde resin, and 1.0-2.0 parts by weight of a yellow dye. The method for preparing the photoluminescence anti-counterfeiting pigment and the photoluminescence anti-counterfeiting ink comprises: adding a formaldehyde solution and triethanolamine to a reactor, and adjusting the pH value to 8-9; adding melamine to the obtained mixture, adjusting the temperature to 75-85 DEG C, and adding an alcohol solvent to obtain a colorless and transparent melamine-formaldehyde resin solution; adding a coumarin-base dye and acetic anhydride, adjusting the pH value of the reaction system to 4.0-6.0, and carrying out cross-linking curing to obtain a cross-linked and cured colored resin dye mixture; drying, crushing, and screening to obtain the organic luminescence pigment; and adding the pigment to an aqueous binder resin to obtain the luminescence anti-counterfeiting ink. The anti-counterfeiting ink has characteristics of no polluting, fire retardation, no toxicity, no odor and the like, wherein destruction of the printing industry on the ecological environment can be reduced.
Description
Technical field
The invention belongs to environment-friendly type anti-forgery ink technical field, relate to the organic tonka bean camphor base of a kind of environment-friendly type photoluminescence security pigment, ink and their preparation method.
Background technology
Along with socioeconomic development, on market, be flooded with diversiform counterfeit and shoddy goods, especially serious with famous brand tobacco and wine.China tobacco reaches tens yuans because of the loss that personation, forgery, smuggling etc. cause every year, and market surpervision difficulty is large.At present, the personation goods of packages printing are every year with 20% speed increment in the world, and anti-fake product only has the growth of 8% left and right every year, and anti-counterfeiting technology with high content of technology is less again, the current situation facing is still very severe, therefore except strengthening supervision, for the false proof of tobacco bale self, seem quite important.Developing a kind of false proof means of tobacco bale with low cost, that be easy to identify, anti-counterfeiting power is high is the task of top priority.
The scientific domain that anti-counterfeiting technology relates to is a lot, wherein chemical anti-fake material and technology are one of false proof basic technologies, comprise and utilize various chemical materials and technology to realize antiforge function, wherein anti-forgery ink technology occupies considerable position, and the antiforge function that anti-forgery ink possesses in product application has irreplaceable effect.Luminous printing ink is a kind of application anti-forgery ink very widely, and the pigment/dye that luminous printing ink comprises can absorb ultraviolet band or visible light energy, and converts the energy into the longer visible ray of wavelength and discharge.Therefore, luminous anti-forgery ink not only can reflect self color as common ink, and can absorb other colors and convert thereof into self look and launch, thereby forms illumination effect.Luminous pigment/dyestuff is as the core functionality integral part of anti-forgery ink, ubiquitous luminous anti-fake material forms by inorganic rare earth preparation of metals at present, be called again inorganic light-emitting pigment/dye, it is also referred to as ultraviolet photoluminescence pigment/dye, by metal (zinc, chromium) sulfide or rare earth oxide form, colourless or shallow white, just under UV-irradiation, present versicolor spectrum, such luminescent material also need could be identified by extra UV-light equipment, although luminous anti-forgery ink prepared by inorganic rare earth metal species material possesses excellent luminous antiforge function, but such material belongs to national strategy scarce resource, scarcity day by day along with such resource, the importance of the luminous anti-fake material of the environment-friendly type Sustainable development of development of new is self-evident.At present every profession and trade all at the various functional organic materials of active development to replace inorganic materials application aborning, the development of luminous anti-forgery ink is like this too.Organic light emission pigment claims again daylight type luminous pigment, by luminescent dye, be well-dispersed in water white transparency, insoluble resin and make, conventional carrier has urea-formaldehyde resin, para toluene sulfonamide-formaldehyde-melamine resin, para toluene sulfonamide-formaldehyde-benzoguanamine resin, acrylic resin, vibrin, polyamide resin, urethane resin etc., and color is determined by luminous pigment/dye molecule.When sun exposure, launch a kind of high intensity visible except general color, for false proof, be simply easy to identification and when identification need to be by additional means.But, organic light emission anti-forgery ink is on stream because organic solvent and relevant organic additive exist, possess not environmental protection, the serious problems such as harmful, a kind of therefore develop safer environmental protection method prepares organic luminous pigment and anti-forgery ink is very necessary.
Summary of the invention
The technical problem that the present invention solves be in the past organic light emission anti-forgery ink because exist organic solvent and organic additive to cause not environmental protection, harmful problem in preparation process, in order to solve this technical problem, the invention provides a kind of environment-friendly type pigment dyestuff that possesses daylight photoluminescence, and this pigment and homemade water-based low-melting ink vehicle are carried out compositely preparing environment-friendly type photoluminescence anti-forgery ink, and the preparation method of this environment-friendly type photoluminescence anti-forgery ink is provided.
Specifically, technical scheme of the present invention is as follows:
A first aspect of the present invention, provides a kind of organic tonka bean camphor base photo-luminescent pigment, and it contains crosslinked melamine formaldehyde resin 60-70 weight part and tonka bean camphor radical dye 1.0-2.0 weight part.
Preferably, above-mentioned organic electroluminescent light pigment, it adopts the raw material that contains following component to make: crosslinked melamine formaldehyde resin 60-70 weight part, alcohol, tonka bean camphor base yellow dyes 1.0-2.0 weight part and carboxylic acid.
Preferably, above-mentioned photo-luminescent pigment, it adopts the raw material that contains following component to make: trimeric cyanamide 20-30 weight part, formaldehyde 33-45 weight part, tonka bean camphor base yellow dyes 1.0-2.0 weight part, organic amine, alcohol and carboxylic acid.
Preferably, above-mentioned photo-luminescent pigment, it adopts the raw material that contains following component to make: trimeric cyanamide 20-30 weight part, 37% formalin 90-120 weight part, trolamine 0.01-0.03 weight part, methyl alcohol, yellow 82 dyestuff 1.0-2.0 weight part and anhydrous acetic acids.
Preferably, above-mentioned photo-luminescent pigment, it adopts the raw material that contains following component to make: trimeric cyanamide 20-30 weight part, 37% formalin 90-120 weight part, trolamine 0.01-0.03 weight part, methyl alcohol 25-35 weight part, yellow 82 dyestuff 1.0 weight part-2.0 weight parts and anhydrous acetic acid 20-28 weight parts.
Preferably, above-mentioned photo-luminescent pigment, it adopts the raw material that contains following component to make: trimeric cyanamide 25 weight parts, 37% formalin 108 weight parts, trolamine 0.02 weight part, methyl alcohol 29.3 weight parts, yellow 82 dyestuff 1.6 weight parts and anhydrous acetic acid 23 weight parts.
Preferably, above-mentioned photo-luminescent pigment, it obtains by the preparation method who comprises the steps:
1) in reactor, add formaldehyde solution and trolamine, regulate pH value to 8-9;
2) in the mixture of step 1), add trimeric cyanamide, temperature is adjusted to after 75-85 ℃ (preferably 80 ℃), adds alcoholic solvent (particular methanol) reaction to obtain water white transparency melamine-formaldehyde resin solution;
3) in step 2) add tonka bean camphor radical dye in the melamine-formaldehyde resin solution that obtains, anhydrous acetic acid, is adjusted to 4.0-6.0 by pH value of reaction system, carries out crosslinking curing, obtains the colouring resin dye mixture of crosslinking curing;
4) product of step 3) is dried, pulverized and obtain luminous pigment.
A second aspect of the present invention, provides a kind of preparation method of organic tonka bean camphor base photo-luminescent pigment, and it comprises the steps:
1) in reactor, add formaldehyde solution and trolamine, regulate pH value to 8-9;
2) in the mixture of step 1), add trimeric cyanamide, temperature is adjusted to after 75-85 ℃ (preferably 80 ℃), adds alcoholic solvent (particular methanol) reaction to obtain water white transparency melamine-formaldehyde resin solution;
3) in step 2) add tonka bean camphor radical dye in the melamine-formaldehyde resin solution that obtains, anhydrous acetic acid, is adjusted to 4.0-6.0 by pH value of reaction system, carries out crosslinking curing, obtains the colouring resin dye mixture of crosslinking curing;
4) product of step 3) is dried, pulverized and obtain luminous pigment.
A third aspect of the present invention, a kind of organic tonka bean camphor base photoluminescence anti-forgery ink is provided, and it prepares by the raw material that contains following component: the organic tonka bean camphor base photo-luminescent pigment 8-15 weight part described in claim 1-7 any one, preferably 10 weight parts and water-based low-melting ink vehicle resin 45-55 weight part, preferred 50 weight parts.
Preferably, above-mentioned anti-forgery ink, wherein, described water-based low-melting ink vehicle resin is aqueous polyurethane low-melting ink vehicle resin, preferably Acrylate Modified Aqueous Polyurethane low-melting ink vehicle resin.
Preferably, above-mentioned anti-forgery ink, it prepares by the raw material that contains following component: the organic tonka bean camphor base photo-luminescent pigment 8-15 weight part described in claim 1-7 any one, preferably 10 weight parts, water-based low-melting ink vehicle resin 45-55 weight part, preferably 50 weight parts, and quadrol 2-6 weight part, preferably 4 weight parts and dibutyl phthalate 8-15 weight part, preferred 10 weight parts.
A fourth aspect of the present invention, provides a kind of preparation method of described organic tonka bean camphor base photoluminescence anti-forgery ink, and it comprises the steps:
1) in reactor, add formaldehyde solution and trolamine, regulate pH value to 8-9;
2) in the mixture of step 1), add trimeric cyanamide, temperature is adjusted to after 75-85 ℃ (preferably 80 ℃), adds alcoholic solvent (particular methanol) reaction to obtain water white transparency melamine-formaldehyde resin solution;
3) in step 2) add the preferred yellow dyes of tonka bean camphor radical dye in the melamine-formaldehyde resin solution that obtains, anhydrous acetic acid, is adjusted to 4.0-6.0 by pH value of reaction system, carries out crosslinking curing, obtains the colouring resin dye mixture of crosslinking curing;
4) product of step 3) is dried, pulverizes, sieved and obtain luminous pigment;
5) luminous pigment step 4) being obtained adds water-based low-melting ink vehicle resin to obtain organic light emission ink.
Preferably, the preparation method of above-mentioned anti-forgery ink, in step 5), the part by weight of described organic tonka bean camphor base photo-luminescent pigment and water-based low-melting ink vehicle resin is: organic tonka bean camphor base photo-luminescent pigment 8-15 weight part, preferably 10 weight parts and water-based low-melting ink vehicle resin 45-55 weight part, preferred 50 weight parts.
Preferably, the preparation method of above-mentioned anti-forgery ink, in step 5), described water-based low-melting ink vehicle resin is aqueous polyurethane low-melting ink vehicle resin, preferably Acrylate Modified Aqueous Polyurethane low-melting ink vehicle resin.
Preferably, the preparation method of above-mentioned anti-forgery ink, in step 5), the luminous pigment that step 4) is obtained also adds following substances to obtain anti-forgery ink: quadrol: 2-6 weight part, preferably 4 weight parts and dibutyl phthalate: 8-15 weight part, preferred 10 weight parts.
The present invention adopts block resin comminuting method to carry out the preparation of environment-friendly type organic electroluminescent light pigment, first production of melamine formaldehyde resin as the resin matrix of preparing pigment, in the preparation process of matrix resin, adding yellow 82 dyestuffs is luminous component, luminescent dye, by organic solvent and the abundant dispersing and mixing after fixing of matrix resin, is obtained to frangible luminous resin.After mechanical disintegration, prepare photoluminescence powder, and take it as pigment and the composite photoluminescence anti-forgery ink of finally developing safety and environmental protection of homemade water-based low-melting ink vehicle resin.
Resin matrix-the terpolycyantoamino-formaldehyde resin of pigment dyestuff of the present invention, is the resulting polymkeric substance of trimeric cyanamide and formaldehyde reaction, and crosslinking reaction occurs during machine-shaping, and goods are insoluble not molten thermosetting resin.Terpolycyantoamino-formaldehyde resin water white transparency after solidifying, stable in boiling water, even can be 150 ℃ of uses, and there is self-extinguishing, arc resistance and good mechanical property.The terpolycyantoamino-formaldehyde resin making, by mixing with dyestuff, can make the block colored translucent resin of the thermoset comminuted, luminescent properties is excellent, by making safe color luminous pigment after mechanical disintegration.And the formaldehyde in the pigment of preparing and trimeric cyanamide are cross-linked with each other, can reduce the volatilization of objectionable impurities, thereby reduce the injury of formaldehyde to human body and environment, this kind of pigment dyestuff is by having the features such as pollution-free, non-combustible, nontoxicity, free from extraneous odour with the composite luminous anti-forgery ink making of water-based low-melting ink vehicle, reduced the destruction of Printing industry to ecotope, accelerated " green engineering " paces of packages printing industry, and " environmental protection " and industry have been organically combined.
Accompanying drawing explanation
The luminescence exitation spectrum of the pigment dyestuff light of Fig. 1: embodiment 1 preparation.
The luminescent emission spectrum of the pigment dyestuff light of Fig. 2: embodiment 1 preparation.
Embodiment
As mentioned above, the present invention first production of melamine formaldehyde resin as the resin matrix of preparing pigment, in the preparation process of matrix resin, adding organic tonka bean camphor radical dye is luminous component, by luminescent dye (in the present invention by dyestuff is mixed with resin-phase, by crosslinking curing to obtain insoluble pigment dyestuff) by organic solvent and the abundant dispersing and mixing after fixing of matrix resin, obtain frangible luminous resin.After mechanical disintegration, prepare photoluminescence powder, and take the composite photoluminescence anti-forgery ink of finally developing safety and environmental protection of its water-based low-melting ink vehicle resin that is pigment and preparation.
In the present invention, described tonka bean camphor based compound is to well known to a person skilled in the art the yellow or red fluorescent chemicals that is that can commercially obtain, specifically, refer to precursor structure following be yellow or red fluorescent chemicals:
At room temperature, this Compound I is colorless substance conventionally, 3, introduce electron-withdrawing group for 4, at 7, introduce electron-donating groups, can make whole molecule form the conjugation pattern of the electronics " D-A " of a standard, it is yellow or red and with the functional dye of intense fluorescence that compound has also become.
In the preferred embodiment of the present invention, described tonka bean camphor radical dye is preferably yellow 82 dyestuffs, and in embodiments of the invention, it is purchased from Shanghai Peng Teng Fine Chemical Co., Ltd product.Yellow 82 dyestuffs (C.I.551200) are tonka bean camphor heterocyclic dye, and it presents with the green glow of fluorescence yellow, and also referred to as DISPERSE YELLOW 8GFF, disperse light yellow 8GFF, scattered fluorescent yellow 8GFF, scattered fluorescent yellow H8GFF, this dye structure is as follows:
Water-based low-melting ink vehicle resin used (i.e. " the water-based low-melting ink vehicle resin of preparation " mentioned above) is that another application for a patent for invention number by invention disclosed people is 201210302618.4(publication number CN102786651A in the present invention) in the method recorded prepare; Or another application for a patent for invention number by contriver is prepared by the method for recording in 201210303614.8 (publication number is 102786654A).The content of above-mentioned patent application being recorded at this is all introduced in this patent application, for your guidance.
Wherein, number of patent application is 201210302618.4(publication number CN102786651A) in the method recorded as follows:
First prepare aqueous polyurethane low-melting ink vehicle raw material, specifically comprise the steps:
A, by vulcabond, (it is isophorone diisocyanate, tolylene diisocyanate, 1, the mixture of one or more in 6-hexamethylene diisocyanate, cyclohexyl diisocyanate and diphenylmethanediisocyanate) 5～10 weight parts and polypropylene glycol (PPG-2000) 30～40 weight parts are warming up to 80～90 ℃ and stir 2～3 hours, add catalyzer dibutyl tin dilaurate (account for prepare aqueous polyurethane low-melting ink vehicle raw material gross weight 0.1 ‰) to continue to stir reaction in 1～2 hour;
B, then the reaction soln temperature of step a is reduced to 60～65 ℃, to be well-dispersed in hydrophilic chain extender 2～7 weight parts in a small amount of N-Methyl pyrrolidone for example DMPA (trishydroxymethyl propionic acid) or DMBA(dimethylolpropionic acid again) add in the reaction soln of step a, be warming up to 80～90 ℃ of reactions and within 2～3 hours, obtain Waterborne Polyurethane Prepolymer;
C, then the Waterborne Polyurethane Prepolymer temperature of step b is down to 35～40 ℃, after quadrol 0.5～3 weight part is dissolved in to residue N-Methyl pyrrolidone (total consumption 5～10 weight parts in this preparation), add in Waterborne Polyurethane Prepolymer, high-speed stirring is sheared 30min～2 hour;
D, by tertiary amine for example triethylamine 1～4 weight part be dissolved in deionized water (in this preparation total consumption 40～80 weight parts), under high-speed stirring, add step c to stir in the reaction soln after shearing and react 5～15 minutes;
E, reacted after, the reaction soln of steps d is filtered and obtains aqueous polyurethane low-melting ink vehicle raw material.
Then, with the aqueous polyurethane low-melting ink vehicle raw material of above-mentioned preparation, prepare the compound low-melting ink vehicle of aqueous polyurethane, as water-based low-melting ink vehicle resin of the present invention, specifically by the method that comprises following step, prepare:
A, by described aqueous polyurethane low-melting ink vehicle 10～40 weight part water-bath preheating 10～20 minutes;
B, emulsifying agent (mixture of sodium lauryl sulphate and alkylphenol polyoxyethylene) and initiator (mixture of Diisopropyl azodicarboxylate and Potassium Persulphate) are all divided into respectively to two parts (wherein, two parts of total weight parts of emulsifying agent are 3～9 parts, two parts of total weight parts of initiator are 0.1～0.8 part), first a copy of it emulsifying agent is mixed to the aqueous solution that obtains emulsifying agent with the deionized water of 10～15 parts, join in aqueous polyurethane low-melting ink vehicle raw material, again by another part of emulsifying agent and a initiator and acrylic ester monomer mixture (methyl methacrylate, butyl acrylate, in butyl methacrylate any two kinds according to the mixture of weight ratio 2:1, in this preparation, the total consumption of mixture is 15～35 weight parts) carry out emulsion dispersion with remaining deionized water (in this preparation, the total consumption of water is 40～80 weight parts) stirring and obtain acrylic ester monomer emulsifying mixture liquid, in hydrotropisms's urethane low-melting ink vehicle raw material, drip this acrylic ester monomer emulsifying mixture liquid, drip 1.5～2.5 hours, drop to residue 10%～15%(weight percent) during acrylic ester monomer emulsifying mixture liquid, another part of initiator joined in this acrylic ester monomer emulsifying mixture liquid and evenly mixed, continue to drip, in 1～2 hour, dropwise, finally use alkaline solution to regulate pH value to 7.5-9, filter and obtain the compound low-melting ink vehicle of Acrylate Modified Aqueous Polyurethane.
Wherein, number of patent application is the method for recording in 201210303614.8 (publication number is 102786654A), specifically comprises the method for being prepared as follows:
A, isophorone diisocyanate 7～15 weight parts and polypropylene glycol (PPG-2000) 20～30 weight parts are warming up to 80～90 ℃ stir 2～3 hours, add 0.1 ‰ of total raw material gross weight～1 ‰ catalyzer dibutyl tin dilaurate to continue to stir 20min～50min reaction; In reaction process, detect the residual content of isocyanate group, detect when residual content reaches theoretical value and start reaction soln to lower the temperature;
When the reaction soln temperature of b, step a is reduced to 50～60 ℃, again hydrophilic chain extender 0.5～5 weight part (dimethylol propionic acid) being well-dispersed in N-Methyl pyrrolidone (1～7 weight part) is added in reaction soln, intensification was reacted between 60-65 ℃ after 10～20 minutes, add acetone adjusting viscosity, add the amount of acetone to meet: the viscosity of reaction soln remains on the phenomenon that does not occur climbing wall of container and pole-climbing while stirring, be then warming up to again 80～90 ℃ of reactions and within 2～3 hours, obtain Waterborne Polyurethane Prepolymer;
C, then the Waterborne Polyurethane Prepolymer temperature of step b is down to 25～30 ℃, by 1,4-butyleneglycol (0.1～5 weight part) slowly adds in Waterborne Polyurethane Prepolymer after being dissolved in the acetone of equivalent, high-speed stirring is sheared 30min～2 hour, wherein in whipping process, add remaining acetone (acetone total consumption in whole preparation process is 15～35 weight parts) adjusting viscosity, to guarantee that reaction soln there will not be the phenomenon of climbing wall and pole-climbing in batches;
D, triethylamine 1～5 weight part is dissolved in the deionized water of 5-10 weight part, under high-speed stirring, being added drop-wise to step c stirs in the reaction soln after shearing, after being added dropwise to complete, add deionized water (in whole preparation process, the total consumption of water is 50-70 weight part) in high-speed stirring, after 5～10 minutes, add alkaline solution to regulate the pH value of reaction soln to 7.5-9;
E, the reaction soln of steps d is carried out to underpressure distillation after having reacted, steam acetone, obtain nano aqueous ink vehicle.
In one embodiment of the invention, the invention provides a kind of photo-luminescent pigment, it contains crosslinked melamine formaldehyde resin 60-70 weight part and tonka bean camphor radical dye 1.0-2.0 weight part.
In one embodiment of the invention, photo-luminescent pigment of the present invention, it adopts the raw material that contains following component to make: crosslinked melamine formaldehyde resin 60-70 weight part, alcohol, coumarins yellow dyes 1.0-2.0 weight part and carboxylic acid.
In one embodiment of the invention, organic electroluminescent light anti-forgery ink of the present invention, it prepares by the raw material that contains following component: the organic electroluminescent light pigment 8-15 weight part (preferably 10 weight parts) of the invention described above and water-based low-melting ink vehicle resin 45-55 weight part (preferably 50 weight parts).
In one embodiment of the invention, the preparation method of anti-forgery ink of the present invention, it comprises the steps:
1) in reactor, add formaldehyde solution and trolamine, regulate pH value to 8-9;
2) in the mixture of step 1), add trimeric cyanamide, temperature is adjusted to after 75-85 ℃ (preferably 80 ℃), adds alcoholic solvent (particular methanol) reaction to obtain water white transparency melamine-formaldehyde resin solution;
3) in step 2) add tonka bean camphor radical dye (preferably yellow dyes) in the melamine-formaldehyde resin solution that obtains, anhydrous acetic acid, is adjusted to 4.0-6.0 by pH value of reaction system, carries out crosslinking curing, obtains the colouring resin dye mixture of crosslinking curing;
4) product of step 3) is dried, pulverizes, sieved and obtain organic light emission pigment of the present invention;
Then, 5) organic electroluminescent light pigment step 4) being obtained adds water-based low-melting ink vehicle resin to obtain organic light emission ink of the present invention.
In the preferred embodiment of the present invention, as photoluminescence anti-forgery ink of the present invention, adopt the component contain following raw material to make according to following proportioning (according to parts by weight): trimeric cyanamide 25 weight parts, 37% formalin 108 weight parts, trolamine 0.02 weight part, methyl alcohol 29.3 weight parts, yellow 82 dyestuff 1.6 weight parts, anhydrous acetic acid 23 weight parts.
For clearer explanation the present invention, below by specific embodiment, photo-luminescent pigment of the present invention is described and preparation and the performance of the photoluminescence anti-forgery ink made thus.
Embodiment
Each reagent specification of using in embodiment is below as follows:
Trimeric cyanamide, analytical pure, Tianjin BASF Chemical Co., Ltd.; 37% formalin, analytical pure, Kingsoft, Chengdu chemical reagent company limited; Trolamine, methyl alcohol, analytical pure, Tianjin Jin Yu Fine Chemical Co., Ltd; Yellow 82 dyestuffs, industrial goods, Shanghai Peng Teng Fine Chemical Co., Ltd product; Anhydrous acetic acid, analytical pure, Shanghai Qing Xi Chemical Industry Science Co., Ltd.Quadrol, dibutyl phthalate, analytical pure, Tianjin good fortune chemical reagent factory in morning.
Embodiment 1
the preparation of photo-luminescent pigment
1) 108g37% formalin is added in the clean four-hole reactor that is equipped with reflux exchanger, thermometer and whipping appts, and add trolamine 0.02g in four-hole reactor, the pH value of regulator solution, making it is 8.5, uses whipping appts to open and keep mechanical stirring state in this process;
2) then, in four-hole reactor, add trimeric cyanamide 25g, stir 10 minutes, after trimeric cyanamide is uniformly dispersed in formalin, reactor is put into the thermostat water bath having heated, make temperature in reactor be 80 ℃ and be uniformly mixed reaction, after solution bleach, add 29.3g methyl alcohol, react and within 30 minutes, obtain colourless transparent liquid;
3) yellow 82 dyestuffs of 1.6g are joined in colourless transparent liquid system obtained above, after being fully uniformly mixed, use drop-burette to drip 23g anhydrous acetic acid, making pH value of reaction system is 5.5, thereby make the crosslinking curing of terpolycyantoamino-formaldehyde resin generation, obtain the colouring resin dye mixture of crosslinking curing;
4) by 3) in product be put in constant temperature oven, at 105 ℃, be incubated 8 hours and obtain block brittle resin, it is fully pulverized, after pulverizing, powder is put into 105 ℃ of baking ovens dry 2 hours, taking-up is pulverized for the second time, after pulverizing for the second time, puts into 105 ℃ of baking ovens dry 4 hours again.Then use the standard inspection sieve of 300 orders (Tyler mesh) that the resin after pulverizing is sieved and got, get the powder under sieve, obtain organic light emission pigment.
Adopt the U.S. Perkin Elmer LS-55 of company type fluorescent/phosphorescent/luminescence spectrophotometer to detect, instrument testing conditions is sweep velocity: 10-1500nm/min, and adjusting step pitch is 1nm; Transmitting spectral filter: 290,350,390,430,515nm, totally 5; Separately there is 1% attenuator, by software, select.The excitation spectrum of organic light emission pigment obtained above and emmission spectrum, it as depicted in figs. 1 and 2.
As Fig. 1 and Fig. 2 can find out, prepared organic light emission pigment maximum excitation wavelength has 2, be respectively 320nm and 450nm, maximum excitation optical wavelength place lays respectively at ultraviolet light wave long-wave band (190-400nm) and visible wavelength wave band (380-780nm), and the maximum emission wavelength of the sample of this experiment preparation is 525nm, be in yellow-green light wavelength range (490-590nm, yellow and green), in this experiment, the organic light emission pigment outward appearance of preparation presents slightly light green of yellow, as can be seen here, organic light emission pigment of the present invention has excited by visible light luminescent properties.
the preparation of photoluminescence ink
(1) preparation of water-based low-melting ink vehicle resin:
First according to the method for disclosed embodiment 2 in disclosed Chinese patent application CN102786651A, prepare water-based low-melting ink vehicle resin,, the present invention's water-based low-melting ink vehicle resin used is the compound low-melting ink vehicle of aqueous polyurethane, specifically prepares by the following method water-based low-melting ink vehicle resin:
1) preparation of aqueous polyurethane low-melting ink vehicle raw material, its (being called for short WPU) made by following parts by weight raw material:
Wherein, above-mentioned each raw material sources are as follows:
Tolylene diisocyanate (TDI), industrial goods, Aladdin reagent;
Polypropylene glycol-2000(PPG-2000), industrial goods, Aladdin reagent;
Dimethylolpropionic acid (DMBA), industrial goods, Shanghai Peng Teng Fine Chemical Co., Ltd product;
N-Methyl pyrrolidone (NMP), analytical pure, Tianjin recovery fine chemistry industry institute;
Quadrol (EDA), analytical pure, Tianjin good fortune chemical reagent factory in morning;
Triethylamine (TEA), analytical pure, Tianjin Jin Yu Fine Chemical Co., Ltd;
Alkaline solution potassium hydroxide solution (KOH, 2mol/L), analytical pure, Tianjin Chemical Co., Ltd.'s all generations;
Catalyzer: dibutyl tin dilaurate (DBTDL), chemical pure, Shanghai Qing Xi Chemical Industry Science Co., Ltd;
The method of preparing aqueous polyurethane low-melting ink vehicle raw material: specifically comprise the steps:
A, the PPG-2000 that will measure according to upper table are put in 120 ℃ of vacuum drying ovens and are dried 2 hours, take out and mix with TDI, TDI and PPG-2000 add in the clean four-hole boiling flask with reflux exchanger, thermometer and whipping appts, be warming up to 80 ℃, in 80 ℃ of thermostat water baths, stirring reaction is 3 hours, add DBTDL as catalyzer, react 2 hours, make sufficient reacting between TDI and PPG-2000;
B, then the reaction soln temperature of step a is reduced to 60 ℃, pulverous DMPA is well-dispersed in a small amount of NMP, add in reaction soln, thereby make DMPA under the effect of NMP with the abundant contact reacts of reaction soln, better complete linking of hydrophilic radical and main chain, from 60 ℃, continue to be warming up to 88 ℃ of reactions and within 2.5 hours, obtain Waterborne Polyurethane Prepolymer;
C, then Waterborne Polyurethane Prepolymer is down to 35 ℃, EDA is dissolved in the NMP of equivalent, add in Waterborne Polyurethane Prepolymer, promote rotating speed simultaneously, high-speed stirring is sheared 2 hours;
D, triethylamine is dissolved in deionized water, under high-speed stirring, adds step c to stir in the reaction soln after shearing, high-speed stirring reaction 10 minutes.
E, the aqueous polyurethane low-melting ink vehicle raw material (being called for short WPU) that the reaction soln of steps d is used 200 orders (Tyler standard sieve) mesh screen sieve to get to obtain milky white blue light after having reacted.
2) water-based low-melting ink vehicle resin used in the present invention is the preparation of the compound low-melting ink vehicle of aqueous polyurethane, and its raw material by following parts by weight is made:
The weight ratio of methyl methacrylate, butyl acrylate is 2:1.
In initiator, the weight percentage of Diisopropyl azodicarboxylate in mixture is 40%, and all the other are Potassium Persulphate.
Emulsifying agent is the mixture of sodium lauryl sulphate and alkylphenol polyoxyethylene, and wherein the weight percentage of sodium lauryl sulphate in mixture is 60%, and all the other are alkylphenol polyoxyethylene.
Wherein, in concrete preparation, each raw material sources used are as follows:
Methyl methacrylate, analytical pure, Tianjin benchmark chemical reagent company limited;
Butyl acrylate, analytical pure, Tianjin good fortune chemical reagent factory in morning;
Potassium Persulphate, analytical pure, Tianjin good fortune chemical reagent factory in morning;
Diisopropyl azodicarboxylate, analytical pure, Chengdu Ke Long chemical reagent factory;
Sodium lauryl sulphate, analytical pure, Tianjin Deng Feng chemical reagent factory;
Alkaline solution potassium hydroxide solution (KOH, 2mol/L), analytical pure, Tianjin Chemical Co., Ltd.'s all generations;
Alkylphenol polyoxyethylene (emulsifier op-10), chemical pure, Tianjin Yong Sheng Fine Chemical Co., Ltd; Deionized water.
Prepare the compound low-melting ink vehicle of aqueous polyurethane, be specially following steps:
A, the above-mentioned aqueous polyurethane low-melting ink vehicle raw material making is placed in to the four-hole boiling flask that stirrer, condenser and thermometer are installed, in water-bath, preheating is 15 minutes;
B, two kinds of emulsifying agents and two kinds of initiators are all equally divided into respectively to two parts, distribution can be to divide equally also not divide equally, first part of emulsifying agent mixed to the aqueous solution that obtains emulsifying agent with the deionized water of approximately 5 weight parts, add in the aqueous polyurethane low-melting ink vehicle in four-hole boiling flask, stir, second part of emulsifying agent mixed with remaining deionized water with acrylic ester monomer mixture with first part of initiator, fully stir and it is mixed and monomer is carried out to emulsification, obtain acrylic ester monomer emulsifying mixture liquid, in the reaction soln in four-hole boiling flask, drip acrylic ester monomer emulsifying mixture liquid, drip after approximately 2.5 hours, drop to residue 12%(weight percent) during acrylic ester monomer emulsifying mixture liquid, second part of initiator evenly mixed with remaining acrylic ester monomer emulsifying mixture liquid, continue to drip and react for approximately 2 hours, after being added dropwise to complete, use the KOH solution of 2mol/L to regulate pH value to 7.5, after discharging, with 200 eye mesh screens, filter and obtain the Acrylate Modified Aqueous Polyurethane low-melting ink vehicle that blueing light is milky white.
Through solid content, detect: the solid content of aqueous polyurethane low-melting ink vehicle is 27.9%, and the compound low-melting ink vehicle solid content of aqueous polyurethane is 24.6%; Through infrared detection, in the compound low-melting ink vehicle of aqueous polyurethane, successfully acrylate monomer is linked on the segment of aqueous polyurethane low-melting ink vehicle.
(2) preparation of photoluminescence ink
According to following step, prepare photoluminescence anti-forgery ink of the present invention:
By load weighted as above preparation 10g organic electroluminescent light colo(u)rant dispersion in as above preparation 50g water-based low-melting ink vehicle resin in, (frequency is 50HZ to the ultrasonic field that use whipping appts provides at KH-600KDB type ultrasonic instrument, power is 600W) in ultrasonic agitation disperse 4 hours, make mill base; After load weighted 4g quadrol is mixed with 10g dibutyl phthalate, add in mill base, obtain water-based organic electroluminescent light anti-forgery ink.
the performance test of photoluminescence ink
Use U.S. X-Rite Spectrodensiotometer to detect the color of the luminous printing ink of preparing above, light source adopts D65, and visual field selects 2.Survey its L, a, b value, Lab pattern is according to Commission Internationale Eclairage(CIE) a kind of international standard of measuring color of formulating in 1931 of international lighting association sets up, in 1976, be modified, and a kind of color mode of name.Lab colour model is a by illumination (L) and relevant color, and tri-key elements of b form.L represents illumination (Luminosity), is equivalent to brightness, and a represents that, from redness to green scope, b represents from blueness to yellow scope.The codomain of L by 0 to 100, L=50 time, be just equivalent to 50% black; The codomain of a and b is all by+120 to-120, and wherein+120a is exactly red, just becomes green in the time of be gradually transitioned into-120a; Same principle ,+120b is yellow ,-120b is blue.All color relations are formed with the mutual variation of these three values.Sample is got to different 10 somes measurements averages.
By the uniform ink mill base of aforementioned preparation, with ordinary method, use scraping blade blade coating on wood-free writing paper, rear detection to be filmed, detects color data as shown in table 1, by the known pigment color of experimental result, is glassy yellow, and L value is higher, and brightness is higher.And use to be coated with the viscosity that 4 glasss (press GB/T1723-93 design) detect ink, its viscosity number is 30s, is applicable to silk screen printing demand, and uses IGT Company(Holland) the printability of G1 type intaglio printing adaptive instrument detection luminous printing ink.On white board, printing effect is good, and printing figure message, after white light, can send yellow-green light.Therefore, organic electroluminescent light pigment prepared by the present invention and photoluminescence anti-forgery ink can simply be easy to identification for false proof, and not containing harmful organic solvent and auxiliary agent.
Table 1 color L, a, b value
Embodiment 2
the preparation of photo-luminescent pigment
1) 90g37% formalin is added in the clean four-hole reactor that is equipped with reflux exchanger, thermometer and whipping appts, and add trolamine 0.01g in four-hole reactor, the pH value of regulator solution, making it is 8, uses whipping appts to open and keep mechanical stirring state in this process;
2) then, in four-hole reactor, add trimeric cyanamide 20g, stir 15 minutes, after trimeric cyanamide is uniformly dispersed in formalin, reactor is put into the thermostat water bath having heated, make temperature in reactor be 75 ℃ and be uniformly mixed reaction, after solution bleach, add 25g methyl alcohol, react and within 30 minutes, obtain colourless transparent liquid;
3) yellow 82 dyestuffs of 1.0g are joined in colourless transparent liquid system obtained above, after being fully uniformly mixed, use drop-burette to drip 20g anhydrous acetic acid, making pH value of reaction system is 6.0, thereby make the crosslinking curing of terpolycyantoamino-formaldehyde resin generation, obtain the colouring resin dye mixture of crosslinking curing;
4) by 3) in product be put in constant temperature oven, at 105 ℃, be incubated 8 hours and obtain block brittle resin, it is fully pulverized, after pulverizing, powder is put into 105 ℃ of baking ovens dry 2 hours, taking-up is pulverized for the second time, after pulverizing for the second time, puts into 105 ℃ of baking ovens dry 4 hours again.Then use the standard inspection sieve of 300 orders (Tyler mesh) that the resin after pulverizing is sieved and got, get the powder under sieve, obtain organic light emission pigment.
Adopt instrument and the condition identical with embodiment 1, measure excitation spectrum and the emmission spectrum of this organic light emission pigment obtained above.
By excitation spectrum and emmission spectrum, can be found out, prepared organic light emission pigment maximum excitation wavelength has 2, be respectively 320nm and 450nm, maximum excitation optical wavelength place lays respectively at ultraviolet light wave long-wave band (190-400nm) and visible wavelength wave band (380-780nm), and the maximum emission wavelength of the sample of this experiment preparation is 510nm, be in yellow-green light wavelength range (490-590nm, yellow and green), in this experiment, the organic light emission pigment outward appearance of preparation presents slightly light green of yellow, as can be seen here, organic light emission pigment of the present invention has excited by visible light luminescent properties.
the preparation of photoluminescence ink
First according to the method for embodiment 1 above, prepare Acrylate Modified Aqueous Polyurethane low-melting ink vehicle, as the water-based low-melting ink vehicle resin of the present embodiment.
Then, according to following step, prepare photoluminescence anti-forgery ink of the present invention:
By load weighted as above preparation 8g organic electroluminescent light colo(u)rant dispersion in as above preparation 45g water-based low-melting ink vehicle resin in, (frequency is 50HZ to the ultrasonic field that use whipping appts provides at KH-600KDB type ultrasonic instrument, power is 600W) in ultrasonic agitation disperse 4 hours, make mill base; After load weighted 2g quadrol is mixed with 8g dibutyl phthalate, add in mill base, obtain water-based organic electroluminescent light anti-forgery ink.
the performance test of photoluminescence ink
Adopt instrument, method and the same light source identical with embodiment 1 and visual field to measure the color of the luminous printing ink of preparing above, same method, measures its L, a and b value by the above-mentioned ink making, and its result is as shown in table 2.By the known pigment color of experimental result, be glassy yellow, L value is higher, and brightness is higher.And use to be coated with 4 glasss of viscosity that detect ink, its viscosity number is 35s, is applicable to silk screen printing demand, and uses IGT Company(Holland) G1 type intaglio printing adaptive instrument detect the printability of luminous printing ink.On white board, printing effect is good, and printing figure message, after white light, can send yellow-green light.Therefore, organic electroluminescent light pigment prepared by the present invention and photoluminescence anti-forgery ink can simply be easy to identification for false proof, and not containing harmful organic solvent and auxiliary agent.
Table 2 color L, a, b value
embodiment 3
the preparation of photo-luminescent pigment
1) 120kg37% formalin is added in the clean four-hole reactor that is equipped with reflux exchanger, thermometer and whipping appts, and add trolamine 0.03kg in four-hole reactor, the pH value of regulator solution, making it is 9, uses whipping appts to open and keep mechanical stirring state in this process;
2) then, in four-hole reactor, add trimeric cyanamide 30kg, stir 15 minutes, after trimeric cyanamide is uniformly dispersed in formalin, reactor is put into the thermostat water bath having heated, make temperature in reactor be 85 ℃ and be uniformly mixed reaction, after solution bleach, add 35kg methyl alcohol, react and within 30 minutes, obtain colourless transparent liquid;
3) yellow 82 dyestuffs of 2.0kg are joined in colourless transparent liquid system obtained above, after being fully uniformly mixed, use drop-burette to drip 28kg anhydrous acetic acid, making pH value of reaction system is 4.0, thereby make the crosslinking curing of terpolycyantoamino-formaldehyde resin generation, obtain the colouring resin dye mixture of crosslinking curing;
4) by 3) in product be put in constant temperature oven, at 105 ℃, be incubated 8 hours and obtain block brittle resin, it is fully pulverized, after pulverizing, powder is put into 105 ℃ of baking ovens dry 2 hours, taking-up is pulverized for the second time, after pulverizing for the second time, puts into 105 ℃ of baking ovens dry 4 hours again.Then use the standard inspection sieve of 300 orders (Tyler mesh) that the resin after pulverizing is sieved and got, get the powder under sieve, obtain organic light emission pigment.
Adopt instrument and the condition identical with embodiment 1, measure excitation spectrum and the emmission spectrum of this organic light emission pigment obtained above.
By excitation spectrum and emmission spectrum, can be found out, by excitation spectrum and emmission spectrum, can be found out, prepared organic light emission pigment maximum excitation wavelength has 2, be respectively 320nm and 450nm, maximum excitation optical wavelength place lays respectively at ultraviolet light wave long-wave band (190-400nm) and visible wavelength wave band (380-780nm), and the maximum emission wavelength of the sample of this experiment preparation is 495nm, be in yellow-green light wavelength range (490-590nm, yellow and green), in this experiment, the organic light emission pigment outward appearance of preparation presents slightly light green of yellow, as can be seen here, organic light emission pigment of the present invention has excited by visible light luminescent properties.
the preparation of photoluminescence ink
First according to the method for embodiment 1 above, prepare Acrylate Modified Aqueous Polyurethane low-melting ink vehicle, as the water-based low-melting ink vehicle resin of the present embodiment.
Then, according to following step, prepare photoluminescence anti-forgery ink of the present invention:
By load weighted as above preparation 15g organic electroluminescent light colo(u)rant dispersion in as above preparation 55g water-based low-melting ink vehicle resin in, (frequency is 50HZ to the ultrasonic field that use whipping appts provides at KH-600KDB type ultrasonic instrument, power is 600W) in ultrasonic agitation disperse 4 hours, make mill base; After load weighted 6g quadrol is mixed with 15g dibutyl phthalate, add in mill base, obtain water-based organic electroluminescent light anti-forgery ink.
the performance test of photoluminescence ink
Adopt instrument, method and the same light source identical with embodiment 1 and visual field to measure the color of the luminous printing ink of preparing above, same method, measures its L, a and b value by the above-mentioned ink making, and its result is as shown in table 3.By the known pigment color of experimental result, be glassy yellow, L value is higher, and brightness is higher.And use to be coated with 4 glasss of viscosity that detect ink, its viscosity number is 32s, is applicable to silk screen printing demand, and uses IGT Company(Holland) G1 type intaglio printing adaptive instrument detect the printability of luminous printing ink.On white board, printing effect is good, and printing figure message, after white light, can send yellow-green light.Therefore, organic electroluminescent light pigment prepared by the present invention and photoluminescence anti-forgery ink can simply be easy to identification for false proof, and not containing harmful organic solvent and auxiliary agent.
Table 3 color L, a, b value
Claims (15)
1. an organic tonka bean camphor base photo-luminescent pigment, it contains crosslinked melamine formaldehyde resin 60-70 weight part and tonka bean camphor radical dye 1.0-2.0 weight part.
2. organic electroluminescent light pigment according to claim 1, it adopts the raw material that contains following component to make: crosslinked melamine formaldehyde resin 60-70 weight part, alcohol, tonka bean camphor base yellow dyes 1.0-2.0 weight part and carboxylic acid.
3. photo-luminescent pigment according to claim 2, it adopts the raw material that contains following component to make: trimeric cyanamide 20-30 weight part, formaldehyde 33-45 weight part, tonka bean camphor base yellow dyes 1.0-2.0 weight part, organic amine, alcohol and carboxylic acid.
4. photo-luminescent pigment according to claim 3, it adopts the raw material that contains following component to make: trimeric cyanamide 20-30 weight part, 37% formalin 90-120 weight part, trolamine 0.01-0.03 weight part, methyl alcohol, yellow 82 dyestuff 1.0-2.0 weight part and anhydrous acetic acids.
5. photo-luminescent pigment according to claim 4, it adopts the raw material that contains following component to make: trimeric cyanamide 20-30 weight part, 37% formalin 90-120 weight part, trolamine 0.01-0.03 weight part, methyl alcohol 25-35 weight part, yellow 82 dyestuff 1.0 weight part-2.0 weight parts and anhydrous acetic acid 20-28 weight parts.
6. photo-luminescent pigment according to claim 5, it adopts the raw material that contains following component to make: trimeric cyanamide 25 weight parts, 37% formalin 108 weight parts, trolamine 0.02 weight part, methyl alcohol 29.3 weight parts, yellow 82 dyestuff 1.6 weight parts and anhydrous acetic acid 23 weight parts.
7. according to the photo-luminescent pigment described in claim 1-6 any one, it obtains by the preparation method who comprises the steps:
1) in reactor, add formaldehyde solution and trolamine, regulate pH value to 8-9;
2) in the mixture of step 1), add trimeric cyanamide, temperature is adjusted to after 75-85 ℃, adds alcoholic solvent reaction to obtain water white transparency melamine-formaldehyde resin solution;
3) in step 2) add tonka bean camphor radical dye in the melamine-formaldehyde resin solution that obtains, anhydrous acetic acid, is adjusted to 4.0-6.0 by pH value of reaction system, carries out crosslinking curing, obtains the colouring resin dye mixture of crosslinking curing;
4) product of step 3) is dried, pulverized and obtain luminous pigment.
8. according to the preparation method of the organic tonka bean camphor base photo-luminescent pigment described in claim 1-6 any one, it comprises the steps:
1) in reactor, add formaldehyde solution and trolamine, regulate pH value to 8-9;
2) in the mixture of step 1), add trimeric cyanamide, temperature is adjusted to after 75-85 ℃, adds alcoholic solvent reaction to obtain water white transparency melamine-formaldehyde resin solution;
3) in step 2) add tonka bean camphor radical dye in the melamine-formaldehyde resin solution that obtains, anhydrous acetic acid, is adjusted to 4.0-6.0 by pH value of reaction system, carries out crosslinking curing, obtains the colouring resin dye mixture of crosslinking curing;
4) product of step 3) is dried, pulverized and obtain luminous pigment.
9. an organic tonka bean camphor base photoluminescence anti-forgery ink, it prepares by the raw material that contains following component: the organic tonka bean camphor base photo-luminescent pigment 8-15 weight part described in claim 1-7 any one, preferably 10 weight parts and water-based low-melting ink vehicle resin 45-55 weight part, preferred 50 weight parts.
10. anti-forgery ink claimed in claim 9, wherein, described water-based low-melting ink vehicle resin is aqueous polyurethane low-melting ink vehicle resin, preferably Acrylate Modified Aqueous Polyurethane low-melting ink vehicle resin.
11. anti-forgery inks claimed in claim 10, it prepares by the raw material that contains following component: the organic tonka bean camphor base photo-luminescent pigment 8-15 weight part described in claim 1-7 any one, preferably 10 weight parts, water-based low-melting ink vehicle resin 45-55 weight part, preferably 50 weight parts, and quadrol 2-6 weight part, preferably 4 weight parts and dibutyl phthalate 8-15 weight part, preferred 10 weight parts.
The preparation method of the organic tonka bean camphor base photoluminescence anti-forgery ink described in 12. claim 10-11 any one, it comprises the steps:
1) in reactor, add formaldehyde solution and trolamine, regulate pH value to 8-9;
2) in the mixture of step 1), add trimeric cyanamide, temperature is adjusted to after 75-85 ℃, adds alcoholic solvent reaction to obtain water white transparency melamine-formaldehyde resin solution;
3) in step 2) add the preferred yellow dyes of tonka bean camphor radical dye in the melamine-formaldehyde resin solution that obtains, anhydrous acetic acid, is adjusted to 4.0-6.0 by pH value of reaction system, carries out crosslinking curing, obtains the colouring resin dye mixture of crosslinking curing;
4) product of step 3) is dried, pulverizes, sieved and obtain luminous pigment;
5) luminous pigment step 4) being obtained adds water-based low-melting ink vehicle resin to obtain organic light emission ink.
13. according to the preparation method of anti-forgery ink described in claim 12, in step 5), the part by weight of described organic tonka bean camphor base photo-luminescent pigment and water-based low-melting ink vehicle resin is: organic tonka bean camphor base photo-luminescent pigment 8-15 weight part, preferably 10 weight parts and water-based low-melting ink vehicle resin 45-55 weight part, preferred 50 weight parts.
14. according to the preparation method of anti-forgery ink described in claim 13, and in step 5), described water-based low-melting ink vehicle resin is aqueous polyurethane low-melting ink vehicle resin, preferably Acrylate Modified Aqueous Polyurethane low-melting ink vehicle resin.
The preparation method of 15. anti-forgery inks according to claim 14, in step 5), the luminous pigment that step 4) is obtained also adds following substances to obtain anti-forgery ink: quadrol: 2-6 weight part, preferably 4 weight parts and dibutyl phthalate: 8-15 weight part, preferred 10 weight parts.
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| CN114395273A (en) * | 2021-12-09 | 2022-04-26 | 陕西中核大地实业有限公司 | Organic chlorophyll-based photoluminescent pigment and preparation method and application thereof |
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| CN115746833A (en) * | 2022-10-21 | 2023-03-07 | 华南师范大学 | Organic long-afterglow material and preparation method and application thereof |
| CN116731560A (en) * | 2023-06-07 | 2023-09-12 | 中国刑事警察学院 | Preparation method and application of stimulus-responsive invisible anti-counterfeiting ink |
| CN116731560B (en) * | 2023-06-07 | 2023-12-01 | 中国刑事警察学院 | Preparation method and application of stimulus-responsive invisible anti-counterfeiting ink |
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