CN112430462B - Fluorescent pigment, water-based fluorescent anti-counterfeiting ink and preparation and application thereof - Google Patents
Fluorescent pigment, water-based fluorescent anti-counterfeiting ink and preparation and application thereof Download PDFInfo
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- CN112430462B CN112430462B CN202011167877.1A CN202011167877A CN112430462B CN 112430462 B CN112430462 B CN 112430462B CN 202011167877 A CN202011167877 A CN 202011167877A CN 112430462 B CN112430462 B CN 112430462B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000049 pigment Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000008367 deionised water Substances 0.000 claims abstract description 36
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 36
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001723 curing Methods 0.000 claims abstract description 14
- 239000000976 ink Substances 0.000 claims description 70
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 24
- 229940043267 rhodamine b Drugs 0.000 claims description 24
- 229940057995 liquid paraffin Drugs 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000007639 printing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 phenylcarboxyl group Chemical group 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 125000003156 secondary amide group Chemical group 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a fluorescent pigment and aqueous fluorescent anti-counterfeiting ink prepared from the fluorescent pigment, and also relates to a preparation method of the pigment and the ink; and then blocking isocyanate by deionized water, and curing at a certain temperature to obtain the fluorescent pigment. And then mixing the fluorescent pigment with the water-based polyacrylate emulsion, and performing ball milling, ultrasonic treatment, curing under the conditions of constant temperature and constant humidity and the like to prepare the safe and environment-friendly water-based fluorescent anti-counterfeiting ink. The ink prepared by the method realizes water-based and organic properties, does not adopt heavy metals or rare earth metals as fluorescent parts of pigments, saves resource resources, and simultaneously avoids the problem of heavy metal pollution.
Description
Technical Field
The invention belongs to the field of preparation of environment-friendly water-based fluorescent anti-counterfeiting ink for printing and packaging, and relates to fluorescent pigment, water-based fluorescent anti-counterfeiting ink, and preparation and application thereof.
Background
The anti-counterfeiting of the functional material is realized by using paper or special printing ink, which is an effective anti-counterfeiting means of the functional material at present. Fluorescent ink usually presents white or light color under sunlight, and can emit visible light (400-800 nm) under the irradiation of light sources such as ultraviolet light (200-400 nm). The main component is fluorescent pigment (dye), which belongs to functional luminescent pigment, and is different from common pigment in that when external light (including ultraviolet light) irradiates, fluorescent substances in the system can absorb ultraviolet band or visible light energy and convert the energy into visible light with longer wavelength to release, and high-brightness fluorescent visible light with different colors from common ink is generated. The fluorescent ink has the anti-counterfeiting function realized by mainly adding a material with fluorescent property into a common ink binder, and is characterized in that: simple implementation, low cost, good concealment, bright color, convenient inspection, direct authentication, incapability of being accurately duplicated on a color copier, and the like. The dual-light-source packaging box has the advantages of playing the characteristics of the dual-light-source packaging box in two aspects of dual-light-source environment and dynamic artistic expression form, and making up the defects of the traditional packaging. Meanwhile, the packaging method has strong pertinence, and is particularly suitable for special people, environments and products which cannot be met by the traditional packaging.
Disclosure of Invention
The invention aims to solve the technical problems that the water-based fluorescent pigment and the ink have important roles in the fields of anti-counterfeiting printing, safety detection, high-performance coating and the like. The fluorescent ink products mainly existing in the current market are organic solvent type, and toxic substances remained on the surfaces of offset ink printed matters have great damage to the personal safety of producers and consumers, and the production process also has the problems of environmental pollution and the like. Along with the further development of the anti-counterfeiting technology of the printing ink and the further improvement of the anti-counterfeiting packaging performance requirement, the development of a safer and more environment-friendly method for preparing the organic luminous pigment and the anti-counterfeiting printing ink is imperative.
The inventor aims to solve the technical problems, provides a fluorescent pigment, and a water-type fluorescent anti-counterfeiting ink is obtained by compounding the fluorescent pigment and a water-based binder, and provides the fluorescent pigment, a preparation method of the water-based fluorescent anti-counterfeiting ink and application of the water-based fluorescent anti-counterfeiting ink.
Specifically, the invention provides the following technical scheme:
a fluorescent pigment prepared from reaction raw materials comprising: the coating comprises, by mass, 20-40 parts of rhodamine B, 10-25 parts of isocyanate, 2-6 parts of polyol, 10-15 parts of organic solvent and 30-40 parts of deionized water.
Preferably, the fluorescent pigment according to the above, wherein the raw materials include: 40 parts of rhodamine B, 25 parts of isocyanate, 6 parts of polyol, 15 parts of organic solvent and 40 parts of deionized water.
Preferably, the fluorescent pigment according to the above, wherein the isocyanate is selected from: one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI), preferably isophorone diisocyanate (IPDI);
preferably, the polyhydric alcohol is selected from one or more than two of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol and dipropylene glycol, preferably neopentyl glycol;
preferably, the solvent is selected from one or more than two of ethyl acetate, toluene, methyl butanone, methyl isobutyl ketone, acetonitrile and acetone; acetone is preferred.
The invention also provides a preparation method of the fluorescent pigment, which is characterized by comprising the following steps:
(1) Heating the organic solvent, adding isocyanate, stirring, adding the rhodamine B in the stirring process, and performing heating reaction;
(2) Cooling the product system obtained in the step (1), adding the polyol, and stirring for reaction;
(3) Cooling the product system obtained in the step (2), adding deionized water, and stirring for reaction;
(4) Distilling the product system obtained in the step (3) to obtain a thick product;
(5) And (3) drying and curing the thick product obtained in the step (4) to obtain the fluorescent pigment.
The preparation method according to the above, wherein step (1) comprises:
the heating temperature of the organic solvent is 72-88, preferably 80 ℃;
preferably, the rhodamine B is added during the stirring for a time controlled to 25-35 ℃ for a minute, preferably 30 minutes;
preferably, the heating reaction is carried out for a period of time of 1.5 to 2.5 hours, preferably 2 hours.
Preferably, the preparation method according to the above, wherein step (2) comprises:
cooling the product system obtained in the step (1) to 45-55 ℃, preferably 50 ℃;
preferably, the time of adding the polyol is controlled to be 20 to 40 minutes, preferably 30 minutes;
preferably, the stirring reaction time is 1.5 to 3 hours, preferably 2 hours.
Preferably, the preparation method according to the above, wherein step (3) comprises:
cooling the product system obtained in step (2) to 4-6 ℃, preferably 5 ℃, preferably by using a water bath;
preferably, the time of adding deionized water is controlled to be 0.5-1.5 hours, preferably 1 hour;
preferably, the reaction is carried out with stirring for a period of 20 to 40 minutes, preferably 30 minutes.
Preferably, according to the above preparation method, wherein the temperature at which the product system obtained in step (3) is distilled in step (4) is 50-70 ℃, preferably 60 ℃;
preferably, the temperature at which the thick product of step (4) is dried and solidified in step (5) is 110-130 ℃, preferably 120 ℃; it is further preferable to carry out the drying and curing for a period of 6 to 10 hours, preferably 8 hours.
The invention also provides a fluorescent pigment, which is prepared by the preparation method.
The invention also provides application of the fluorescent pigment in the field of preparation of water-based fluorescent anti-counterfeiting ink.
The invention also provides water-based fluorescent anti-counterfeiting ink which is characterized by comprising the fluorescent pigment, water-based polyacrylate, ethanol, deionized water and liquid paraffin;
preferably, the weight average molecular weight of the aqueous polyacrylate is 78000-82000, preferably 80000; preferably, the aqueous polyacrylate has an intrinsic viscosity of 230 to 800 mpa.s;
preferably, the viscosity of the liquid paraffin is 700-1500 mPa.S; preferably, the relative density of the liquid paraffin is 1.235-1.255.
Preferably, the aqueous fluorescent anti-counterfeiting ink comprises the following components: the fluorescent pigment according to any one of claims 1 to 3 or 9, 30 to 50 parts by mass of aqueous polyacrylate, 20 to 30 parts by mass of ethanol, 10 to 15 parts by mass of deionized water and 5 to 8 parts by mass of liquid paraffin.
The invention also provides a preparation method of the water-based fluorescent anti-counterfeiting ink, which is characterized by comprising the following steps of:
A. mixing a solid fluorescent pigment with an emulsion of an aqueous polyacrylate;
B. ball milling the mixture obtained in the step A, ethanol, deionized water and liquid paraffin,
preferably, the weight ratio of deionized water to ethanol is 1:2; preferably, the ball milling speed in the step B is 500 rpm, and the ball milling time is 1 hour.
The invention provides fluorescent anti-counterfeiting ink which is prepared by the preparation method.
The invention provides application of the aqueous fluorescent anti-counterfeiting ink in the field of anti-counterfeiting paper or anti-counterfeiting special printing ink.
The technical scheme of the invention has the beneficial effects that:
(1) The fluorescent ink prepared by the invention has good fluorescent property.
(2) The ink particles are all below micron (200 nm-2 μm), and the particle size requirement of printing on pigment is met.
(3) The pigment particles provided by the invention have good stability and are easy to process and crush. Since the modification is carried out by using isocyanate, the quantitative active ester group (the equivalent ratio of the isocyanate to the methyl is in the range of 0.02-0.3) is contained, and the subsequent structural modification of the pigment is facilitated.
(4) The fluorescent ink realizes water-based and organic properties, does not adopt heavy metal or rare earth metal as a fluorescent part of the pigment, saves resource resources and simultaneously avoids the problem of heavy metal pollution.
Drawings
FIG. 1 is a graph showing fluorescence properties of the water-based fluorescent anti-forgery inks prepared in examples 1,2,3 and 4;
FIG. 2 is a scanning electron microscope image of the aqueous fluorescent ink prepared in example 1;
FIG. 3 is a scanning electron microscope image of the aqueous fluorescent ink prepared in example 2;
FIG. 4 is a scanning electron microscope image of the aqueous fluorescent ink prepared in example 3;
FIG. 5 is a scanning electron microscope image of the aqueous fluorescent ink prepared in example 4;
FIG. 6 is an infrared spectrum of the product of rhodamine B reacted with isocyanate in example 2.
Detailed Description
Aiming at the defects of the prior art, the invention aims at providing a fluorescent pigment, and the fluorescent pigment is compounded with an aqueous binder to obtain the aqueous fluorescent anti-counterfeiting ink, and the preparation method and the application thereof.
The preparation method comprises the steps of preparing the environment-friendly organic fluorescent pigment by adopting a gradual polymerization method, namely, firstly taking fluorescent dye rhodamine B as a luminophor to perform esterification reaction with isocyanate; and then blocking isocyanate by deionized water, and curing at a certain temperature to obtain the fluorescent pigment. And then mixing the fluorescent pigment with the water-based polyacrylate emulsion, and performing ball milling, ultrasonic treatment, curing under the conditions of constant temperature and constant humidity and the like to prepare the safe and environment-friendly water-based fluorescent anti-counterfeiting ink.
In a preferred embodiment of the invention, the water-based fluorescent anti-counterfeiting ink is prepared from the following raw materials in parts by weight: 20-40 parts of rhodamine B dye, 10-25 parts of isophorone diisocyanate (IPDI), 10-15 parts of acetone, 2-6 parts of neopentyl glycol, 30-50 parts of aqueous polyacrylate emulsion, 5-8 parts of liquid paraffin, 40-55 parts of deionized water and 20-30 parts of ethanol.
In a preferred embodiment of the present invention, the aqueous fluorescent anti-forgery ink is prepared by a preparation method comprising the following steps:
and 1, adding metered acetone into a clean four-neck flask with a reflux condenser, a thermometer, a stirring device and an oil bath heating device, adding IPDI into the flask, heating the oil bath to 80 ℃ and keeping constant temperature in the process, starting the stirring device, slowly adding rhodamine B powder in the stirring process, controlling the adding time to be 30 minutes, and reacting for 2 hours at the constant temperature of 80 ℃ after the adding is finished.
In the reaction process, isocyanate is used as a reaction raw material, and the problems of removal and residue are solved, and because the invention is mainly used for preparing the water-based environment-friendly ink, the isocyanate can finally react with water to generate polyurea, thereby being beneficial to the formation of an ink film of the ink; at the same time, an excess of isocyanate is ensured in the present invention, so that the rhodamine B molecule can be completely modified.
During the above reaction, other solvents may be used: organic solvents such as ethyl acetate, toluene, methyl butanone, methyl isobutyl ketone, acetonitrile, and the like, preferably acetone, have relatively low toxicity.
And 2, maintaining the temperature of the oil bath at 50-60 ℃, slowly and continuously adding neopentyl glycol into the reaction system obtained in the step 1, controlling the adding time to be 30-60 minutes, and fully stirring and uniformly mixing, and reacting for 1 hour.
And 3, placing the reaction system obtained in the step 2 in an ice bath environment, reducing the temperature of the reaction system to 0-5 ℃, mechanically stirring, slowly dropwise adding deionized water into the cooled reaction system, controlling the dropwise adding time to be 1 hour, and continuing stirring under the ice bath condition for 30-60 minutes after the dropwise adding is completed.
And 4, placing the reaction system obtained in the step 3 in an oil bath heating device at 50-70 ℃, using a distillation flask to replace a reflux condenser, continuously heating and stirring, and evaporating and recovering excessive deionized water and acetone solvent to obtain a thick product.
And 5, placing the thick product obtained in the step 4 in a constant temperature drying oven at 120 ℃ for curing for 8 hours to obtain brittle powder, namely the fluorescent pigment.
And 6, mixing the fluorescent pigment obtained in the step 6 with the water-based polyacrylate emulsion, placing the mixture in a ball milling tank, mixing deionized water and ethanol with the fluorescent pigment, the water-based polyacrylate emulsion and liquid paraffin according to the weight ratio of 1:2, and performing ball milling for 1-3 hours at the rotating speed of 500 r/min to obtain the water-based fluorescent anti-counterfeiting ink.
The technical scheme of the invention will be further demonstrated in the following with specific embodiments.
Examples
The sources of the various materials in the present invention are:
rhodamine B, industrial, tianjin chemical reagent limited, dense european company;
isophorone diisocyanate (IPDI), chemically pure, shanghai crystal pure reagent limited;
acetone, chemically pure, tabacco market, double chemical industry limited;
neopentyl glycol, chemically pure, tianjin optical complex fine chemical institute;
aqueous polyacrylate emulsion, industrial products, basf reagent;
liquid paraffin, guangzhou city, chemical engineering, inc.;
ethanol, chemically pure, tianjin, city, jinyu fine chemical Co., ltd.
For a clearer understanding of the technical features, objects and effects of the present invention, specific embodiments of the present invention will now be described in detail with reference to examples.
Example 1
The preparation of the water-based fluorescent anti-counterfeiting ink adopts the following raw materials in parts by weight in table 1:
table 1A Water-based fluorescent anti-counterfeit ink
The preparation method comprises the following steps:
(1) 10g of acetone was added to a clean four-necked flask having a reflux condenser, a thermometer, a stirring device and an oil bath heating device, and 10g of IPDI was added to the flask, the oil bath was heated to 80℃and the stirring device was turned on to maintain a mechanically stirred state, 20g of rhodamine B powder was slowly added during stirring for 30 minutes, and after the addition was completed, the reaction was heated for 2 hours.
(2) The temperature of the oil bath heating device is set to be 50 ℃, then 2g of neopentyl glycol is slowly and continuously added into the reaction system in the step 1, the adding time is 30 minutes, and after the mixture is fully stirred and uniformly mixed, the reaction is carried out for 1 hour.
(3) And (2) placing the reaction system in the step (2) in an ice bath environment, keeping the temperature of the reaction system at 5 ℃, keeping a mechanical stirring state, slowly dropwise adding 30g of deionized water into the reaction system for 1 hour, and continuing stirring for 30 minutes after the dropwise adding is completed.
(4) And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, using a distillation flask to replace a reflux condenser, continuously heating and stirring, and evaporating and recovering excessive deionized water and acetone solvent to obtain a thick product.
(5) And (3) placing the thick product obtained in the step (4) in a constant temperature drying oven at 120 ℃ for curing for 8 hours to obtain brittle powder, namely the fluorescent pigment. Mixing fluorescent pigment with 30g of aqueous polyacrylate emulsion, placing the mixture in a ball milling tank, mixing 10g of deionized water and 20g of ethanol according to the weight ratio of 1:2 with the fluorescent pigment, the aqueous polyacrylate emulsion and 5g of liquid paraffin, and performing ball milling for 1 hour at a rotating speed of 500 rpm. After the preparation is completed, the water-based fluorescent anti-counterfeiting ink is obtained.
Example 2
The preparation of the water-based fluorescent anti-counterfeiting ink adopts the following raw materials in parts by weight in table 2:
table 2A Water-based fluorescent anti-counterfeiting ink
The preparation method comprises the following steps:
(1) 15g of acetone was added to a clean four-necked flask having a reflux condenser, a thermometer, a stirring device and an oil bath heating device, and 25g of IPDI was added to the flask, the oil bath was heated to 80℃and the stirring device was turned on to maintain a mechanically stirred state, 40g of rhodamine B powder was slowly added during stirring for 30 minutes, and after the addition was completed, the reaction was heated for 2 hours.
(2) The temperature of the oil bath heating device is set to be 50 ℃, 6g of neopentyl glycol is slowly and continuously added into the reaction system in the step 1, the adding time is 30 minutes, and the mixture is fully and uniformly stirred and then reacted for 1 hour.
(3) And (2) placing the reaction system in the step (2) in an ice bath environment, keeping the temperature of the reaction system at 5 ℃, keeping a mechanical stirring state, slowly dripping 40g of deionized water into the reaction system for 1 hour, and continuing stirring for 30 minutes after the dripping is completed.
(4) And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, using a distillation flask to replace a reflux condenser, continuously heating and stirring, and evaporating and recovering excessive deionized water and acetone solvent to obtain a thick product.
(5) And (3) placing the thick product obtained in the step (4) in a constant temperature drying oven at 120 ℃ for curing for 8 hours to obtain brittle powder, namely the fluorescent pigment. Mixing fluorescent pigment with 50g of aqueous polyacrylate emulsion, placing the mixture in a ball milling tank, mixing 15g of deionized water and 30g of ethanol according to the weight ratio of 1:2 with the fluorescent pigment, the aqueous polyacrylate emulsion and 8g of liquid paraffin, and performing ball milling for 1 hour at the rotating speed of 500 rpm. After the preparation is completed, the water-based fluorescent anti-counterfeiting ink is obtained.
Example 3
The preparation of the water-based fluorescent anti-counterfeiting ink adopts the following raw materials in parts by weight in table 3:
table 3A Water-based fluorescent anti-counterfeiting ink
The preparation method comprises the following steps:
1. 12g of acetone was added to a clean four-necked flask having a reflux condenser, a thermometer, a stirring device and an oil bath heating device, and 16g of IPDI was added to the flask, the oil bath was heated to 80℃and the stirring device was turned on to maintain a mechanically stirred state, 25g of rhodamine B powder was slowly added during stirring for 30 minutes, and after the addition was completed, the reaction was heated for 2 hours.
2. The temperature of the oil bath heating device is set to be 50 ℃, 4g of neopentyl glycol is slowly and continuously added into the reaction system in the step 1, the adding time is 30 minutes, and the reaction is carried out for 1 hour after the mixture is fully stirred and uniformly mixed.
3. And (3) placing the reaction system in the step (2) in an ice bath environment, keeping the temperature of the reaction system at 5 ℃, keeping a mechanical stirring state, slowly dropwise adding 35g of deionized water into the reaction system for 1 hour, and continuing stirring for 30 minutes after the dropwise adding is completed.
4. And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, using a distillation flask to replace a reflux condenser, continuously heating and stirring, and evaporating and recovering excessive deionized water and acetone solvent to obtain a thick product.
5. And (3) placing the thick product obtained in the step (4) in a constant temperature drying oven at 120 ℃ for curing for 8 hours to obtain brittle powder, namely the fluorescent pigment. Mixing fluorescent pigment with 40g of aqueous polyacrylate emulsion, placing the mixture in a ball milling tank, mixing 13g of deionized water and 26 ethanol according to the weight ratio of 1:2 with the fluorescent pigment, the aqueous polyacrylate emulsion and 6g of liquid paraffin, and performing ball milling for 1 hour at a rotating speed of 500 rpm. After the preparation is completed, the water-based fluorescent anti-counterfeiting ink is obtained.
Example 4
The preparation of the water-based fluorescent anti-counterfeiting ink adopts the following raw materials in parts by weight in table 4:
table 4A Water-based fluorescent anti-counterfeiting ink
The preparation method comprises the following steps:
(1) 14g of acetone was added to a clean four-necked flask having a reflux condenser, a thermometer, a stirring device and an oil bath heating device, and 20g of IPDI was added to the flask, the oil bath was heated to 80℃and the stirring device was turned on to maintain a mechanically stirred state, 32g of rhodamine B powder was slowly added during stirring for 30 minutes, and after the addition was completed, the reaction was heated for 2 hours.
(2) The temperature of the oil bath heating device is set to be 50 ℃, then 5g of neopentyl glycol is slowly and continuously added into the reaction system in the step 1, the adding time is 30 minutes, and after the mixture is fully stirred and uniformly mixed, the reaction is carried out for 1 hour.
(3) And (3) placing the reaction system in the step (2) in an ice bath environment, keeping the temperature of the reaction system at 5 ℃, keeping a mechanical stirring state, slowly dropwise adding 36g of deionized water into the reaction system for 1 hour, and continuing stirring for 30 minutes after the dropwise adding is completed.
(4) And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, using a distillation flask to replace a reflux condenser, continuously heating and stirring, and evaporating and recovering excessive deionized water and acetone solvent to obtain a thick product.
(5) And (3) placing the thick product obtained in the step (4) in a constant temperature drying oven at 120 ℃ for curing for 8 hours to obtain brittle powder, namely the fluorescent pigment. Mixing fluorescent pigment with 45g of aqueous polyacrylate emulsion, placing the mixture in a ball milling tank, mixing 14g of deionized water and 28 ethanol according to the weight ratio of 1:2 with the fluorescent pigment, the aqueous polyacrylate emulsion and 7g of liquid paraffin, and performing ball milling for 1 hour at a rotating speed of 500 rpm. After the preparation is completed, the water-based fluorescent anti-counterfeiting ink is obtained.
And (3) detecting the product performance:
(1) Fluorescence performance detection: the fluorescent performance of the aqueous fluorescent anti-counterfeiting ink obtained in the above examples and comparative examples was detected by using a FLS-920 type fluorescence spectrophotometer manufactured by Edinburgh Instruments company;
(2) Scanning electron microscope detection: manufacturer, model; a JSM-6700F type field emission scanning electron microscope of Shimadzu;
(3) Infrared spectrometer: FTIR model 8400S (CE) of Shimadzu.
Analysis of detection results:
(1) Fluorescence performance was measured as shown in fig. 1: all samples of the examples show fluorescence emission peaks at the position with the fluorescence wavelength of 615nm, which shows that the fluorescent ink prepared in the invention has good fluorescence performance. Meanwhile, the fluorescence intensities of the samples prepared in examples 1,4 and 3 to 2 were sequentially increased, and the fluorescence intensity of the sample prepared in example 2 was highest.
(2) Scanning electron microscope detection: the scanning electron microscope images of the four groups of different samples are shown in fig. 2-5, and as can be seen from fig. 2, the anti-counterfeiting ink prepared in the embodiment 1 presents a micron-sized block shape, and the particle compactness is higher. As can be seen from FIG. 3, the anti-counterfeit ink prepared in example 2 shows micro-nano particles, the particle stack shows a layered structure, the stack morphology is more regular, and the particle distribution is more uniform, thereby showing the highest fluorescence intensity. As can be seen from fig. 4, the anti-counterfeit ink prepared in example 3 presents micron-sized blocks, a large number of fine particles are distributed on the surface, and the compactness of the blocks is high. As can be seen from fig. 5, the anti-counterfeit ink prepared in example 4 presents a fluffy micron-sized block, and presents a hierarchical structure that is not tightly stacked. The ink particles of the four groups of samples are all below the micron level (200 nm-1 μm), and the particle size requirement of printing on the pigment is met.
(3) And (3) infrared spectrum detection:
the phenylcarboxyl group on rhodamine B, abbreviated as R '-COOH, reacts with isocyanate groups on isocyanate (R-NCO) to generate amide bonds, namely R-NH-CO-R', so that the existence of the amide groups in the infrared spectrum can confirm the structure of the product after the rhodamine B reacts with the isocyanate. FIG. 6 is an infrared spectrum of the product obtained after the reaction of rhodamine B with isocyanate in example 2, and it can be seen that an amide carbonyl C=O vibration peak appears at 1658cm-1, and simultaneously, an in-plane bending peak of a secondary amide N-H group in an amide group appears at 1512cm-1, and the appearance of the two characteristic peaks indicates that rhodamine B has reacted with isocyanate to generate a secondary amide group (-NH-CO-).
Claims (45)
1. A fluorescent pigment, characterized in that the fluorescent pigment is prepared from the following reaction raw materials: 20-40 parts of rhodamine B, 10-25 parts of isocyanate, 2-6 parts of polyol, 10-15 parts of organic solvent and 30-40 parts of deionized water;
the isocyanate is isophorone diisocyanate;
the polyol is neopentyl glycol;
the preparation method of the fluorescent pigment comprises the following steps:
(1) Heating the organic solvent, adding isocyanate, stirring, adding the rhodamine B in the stirring process, and performing heating reaction;
(2) Cooling the product system obtained in the step (1), and then adding the polyol for reaction;
(3) Cooling the product system obtained in the step (2), and adding deionized water for reaction;
(4) Distilling the product system obtained in the step (3) to obtain a thick product;
(5) And (3) drying and curing the thick product obtained in the step (4) to obtain the fluorescent pigment.
2. The fluorescent pigment of claim 1, wherein the raw materials include: 40 parts of rhodamine B, 25 parts of isocyanate, 6 parts of polyol, 15 parts of organic solvent and 40 parts of deionized water.
3. The fluorescent pigment according to claim 1 or 2, wherein,
the organic solvent is selected from one or more than two of ethyl acetate, toluene, methyl butanone, methyl isobutyl ketone, acetonitrile and acetone.
4. The fluorescent pigment of claim 3, wherein the organic solvent is acetone.
5. A method of preparing a fluorescent pigment according to any one of claims 1-4, further comprising the steps of:
(1) Heating the organic solvent, adding isocyanate, stirring, adding the rhodamine B in the stirring process, and performing heating reaction;
(2) Cooling the product system obtained in the step (1), and then adding the polyol for reaction;
(3) Cooling the product system obtained in the step (2), and adding deionized water for reaction;
(4) Distilling the product system obtained in the step (3) to obtain a thick product;
(5) And (3) drying and curing the thick product obtained in the step (4) to obtain the fluorescent pigment.
6. The preparation method according to claim 5, wherein step (1) comprises: the heating temperature of the organic solvent is 72-88 ℃.
7. The preparation method according to claim 6, wherein step (1) comprises: the heating temperature of the organic solvent is 80 ℃.
8. The preparation method according to claim 7, wherein step (1) comprises: the time for adding the rhodamine B in the stirring process is controlled to be 25-35 minutes.
9. The preparation method according to claim 8, wherein step (1) comprises: the time for adding the rhodamine B during stirring was controlled to be 30 minutes.
10. The preparation method according to claim 9, wherein step (1) comprises: the heating reaction time is 1.5-2.5 hours.
11. The preparation method according to claim 10, wherein step (1) comprises: the heating reaction time was 2 hours.
12. The preparation method according to claim 5, wherein step (2) comprises: and (3) cooling the product system obtained in the step (1) to 45-55 ℃.
13. The preparation method according to claim 12, wherein step (2) comprises: and (3) cooling the product system obtained in the step (1) to 50 ℃.
14. The preparation method according to claim 13, wherein step (2) comprises: the time for adding the polyol is controlled to be 20-40 minutes.
15. The method of manufacturing according to claim 14, wherein step (2) comprises: the time for adding the polyol was controlled to 30 minutes.
16. The preparation method of claim 15, wherein step (2) comprises: the stirring reaction time is 1.5-3 hours.
17. The method of manufacturing of claim 16, wherein step (2) comprises: the reaction time was 2 hours with stirring.
18. The preparation method according to claim 5, wherein step (3) comprises: cooling the product system obtained in the step (2) to 4-6 ℃.
19. The preparation method according to claim 5, wherein step (3) comprises: cooling the product system obtained in the step (2) to 5 ℃.
20. The method of manufacturing of claim 19, wherein step (3) comprises:
cooling was performed using a water bath.
21. The method of manufacturing of claim 20, wherein step (3) comprises:
the time for adding deionized water is controlled to be 0.5-1.5 hours.
22. The method of manufacturing of claim 21, wherein step (3) comprises:
the time for adding deionized water was controlled to 1 hour.
23. The method of manufacturing of claim 22, wherein step (3) comprises:
the reaction is carried out with stirring for 20-40 minutes.
24. The method of manufacturing of claim 23, wherein step (3) comprises:
the reaction was carried out with stirring for 30 minutes.
25. The process according to any one of claims 5 to 24, wherein the temperature at which the product system obtained in step (3) is distilled in step (4) is 50 to 70 ℃.
26. The process according to claim 25, wherein the temperature at which the product system obtained in step (3) is distilled in step (4) is 60 ℃.
27. The process according to claim 26, wherein the temperature at which the thick product of step (4) is dried and solidified in step (5) is 110 to 130 ℃.
28. The process according to claim 27, wherein the temperature at which the thick product of step (4) is dried and solidified in step (5) is 120 ℃.
29. The process according to claim 28, wherein the drying and curing are carried out for a period of 6 to 10 hours.
30. The method according to claim 29, wherein the drying and curing are performed for 8 hours.
31. A fluorescent pigment prepared according to the preparation method of any one of claims 5 to 30.
32. Use of the fluorescent pigment according to any one of claims 1 to 4 or 31 in the field of preparation of aqueous fluorescent security inks.
33. An aqueous fluorescent anti-forgery ink, comprising the fluorescent pigment of any one of claims 1 to 4 or the fluorescent pigment of claim 31, and aqueous polyacrylate, ethanol, deionized water and liquid paraffin.
34. The aqueous fluorescent anti-forgery ink of claim 33, wherein the weight average molecular weight of the aqueous polyacrylate is 78000-82000.
35. The aqueous fluorescent anti-forgery ink of claim 34, wherein the weight average molecular weight of the aqueous polyacrylate is 80000.
36. The aqueous fluorescent anti-forgery ink of claim 35, wherein the intrinsic viscosity of the aqueous polyacrylate is 230 to 800mpa·s.
37. The aqueous fluorescent anti-forgery ink of claim 36, wherein the viscosity of the liquid paraffin is 700-1500 mPa-S.
38. The aqueous fluorescent anti-forgery ink of claim 37, wherein the relative density of the liquid paraffin is 1.235-1.255.
39. The aqueous fluorescent anti-counterfeit ink of claim 33, comprising: 30-50 parts of the fluorescent pigment according to any one of claims 1-4 or 31, 30-50 parts of aqueous polyacrylate, 20-30 parts of ethanol, 10-15 parts of deionized water and 5-8 parts of liquid paraffin.
40. A method for preparing the aqueous fluorescent anti-counterfeit ink of claim 33, comprising the steps of:
A. mixing a solid fluorescent pigment with an emulsion of an aqueous polyacrylate;
B. and (C) ball milling the mixture obtained in the step (A) with ethanol, deionized water and liquid paraffin.
41. The method of claim 40, wherein the deionized water and ethanol are present in a weight ratio of 1:2.
42. The process of claim 41, wherein the ball milling speed in step B is 500 rpm.
43. The process of claim 42 wherein the ball milling time is 1 hour.
44. An aqueous fluorescent anti-forgery ink prepared by the preparation method of claim 40.
45. The use of the aqueous fluorescent anti-counterfeit ink of claim 33 or 44 in the field of anti-counterfeit paper or anti-counterfeit special printing ink.
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