CN112430462A - 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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- CN112430462A CN112430462A CN202011167877.1A CN202011167877A CN112430462A CN 112430462 A CN112430462 A CN 112430462A CN 202011167877 A CN202011167877 A CN 202011167877A CN 112430462 A CN112430462 A CN 112430462A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000049 pigment Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 34
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 34
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 24
- 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 abstract description 23
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 16
- 238000001723 curing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000976 ink Substances 0.000 claims description 64
- 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 44
- 238000003756 stirring Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 229940057995 liquid paraffin Drugs 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000001816 cooling Methods 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
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 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 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 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
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010419 fine particle Substances 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
- 239000008204 material by function Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000003156 secondary amide group Chemical group 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Images
Classifications
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- 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, wherein the preparation method of the environment-friendly organic fluorescent pigment is carried out by adopting a stepwise polymerization method, namely, firstly, a fluorescent dye rhodamine B is used as a luminous body and is subjected to esterification reaction with isocyanate; and then, utilizing deionized water to seal the end of the isocyanate, and curing at a certain temperature to obtain the fluorescent pigment. And then mixing the fluorescent pigment with the aqueous polyacrylate emulsion, and preparing the safe and environment-friendly aqueous fluorescent anti-counterfeiting ink by ball milling, ultrasound, curing under the conditions of constant temperature and constant humidity and the like. The ink prepared by the method realizes water-based and organic properties, does not adopt heavy metal or rare earth metal as the fluorescent part of the pigment, saves resource resources and avoids the problem of heavy metal pollution.
Description
Technical Field
The invention belongs to the field of preparation of environment-friendly aqueous fluorescent anti-counterfeiting ink for printing and packaging, and relates to a fluorescent pigment, aqueous fluorescent anti-counterfeiting ink, and preparation and application thereof.
Background
The anti-counterfeiting realization by paper or special printing ink is an effective anti-counterfeiting means of functional materials at present. The fluorescent ink is a special water-based ink which is white or light in color under sunlight and can emit visible light (400 nm-800 nm) under the irradiation of light sources such as ultraviolet light (200 nm-400 nm) and the like. The main component of the fluorescent pigment (dye) belongs to functional luminescent pigment, and is different from the common pigment in that when external light (containing ultraviolet light) is irradiated, the fluorescent substance in the system can absorb ultraviolet wave band or visible light energy, and converts the energy into visible light with longer wavelength to be released, thereby generating high-brightness fluorescent visible light different from the common ink color. The fluorescent ink anti-counterfeiting function is realized by mainly adding a material with a fluorescent property into a common ink binder, and is characterized in that: simple implementation, low cost, good concealment, bright color, convenient inspection, capability of directly identifying authenticity, incapability of being accurately copied on a color copier and the like. Its advantage lies in playing self characteristic in dual light source environment and the dynamic artistic expression two aspects, makes up the not enough of traditional packing. Meanwhile, the packaging bag 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 problem that the water-based fluorescent pigment and the water-based fluorescent ink play an important role 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, the toxic substances remained on the surface of the offset printing ink printed matter have great damage to the personal safety of producers and consumers, and the problems of environmental pollution and the like can also occur in the production process. With the further development of the ink anti-counterfeiting technology and the further improvement of the anti-counterfeiting packaging performance requirements, it is imperative to develop a safer and more environment-friendly method for preparing the organic luminescent pigment and the anti-counterfeiting ink.
In order to solve the technical problems, the inventor provides a fluorescent pigment, compounds the fluorescent pigment and an aqueous binder to obtain a water-based fluorescent anti-counterfeiting ink, and provides the fluorescent pigment, and a preparation method and application of the water-based fluorescent anti-counterfeiting ink.
Specifically, the invention provides the following technical scheme:
a fluorescent pigment is characterized by being prepared from reaction raw materials containing the following substances: 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 comprise: the paint comprises, by mass, 40 parts of rhodamine B, 25 parts of isocyanate, 6 parts of polyol, 15 parts of an 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 one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol and dipropylene glycol, and is preferably neopentyl glycol;
preferably, the solvent is one or a mixture of 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 carrying out heating reaction;
(2) cooling the product system obtained in the step (1), adding the polyhydric alcohol, 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 (5) drying and curing the thick product obtained in the step (4) to obtain the fluorescent pigment.
The production method as described above, wherein the step (1) comprises:
the heating temperature of the organic solvent is 72-88, preferably 80 ℃;
preferably, the time for adding the rhodamine B in the stirring process is controlled to be 25-35 ℃ for minutes, and preferably 30 minutes;
preferably, the heating reaction time is 1.5 to 2.5 hours, preferably 2 hours.
Preferably, according to the above production method, wherein the step (2) comprises:
cooling the product system obtained in the step (1) to 45-55 ℃, preferably 50 ℃;
preferably, the time for adding the polyol is controlled to be 20 to 40 minutes, preferably 30 minutes;
preferably, the reaction time is stirred for 1.5 to 3 hours, preferably 2 hours.
Preferably, according to the above production method, wherein the step (3) comprises:
cooling the product system obtained in the step (2) to 4-6 ℃, preferably to 5 ℃, and preferably cooling by adopting a water bath;
preferably, the time for adding the 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, the preparation method comprises the step (4) of distilling the product system obtained in the step (3) at 50-70 ℃, preferably 60 ℃;
preferably, the temperature for drying and curing the thick product obtained in the step (4) in the step (5) is 110-130 ℃, preferably 120 ℃; further preferably, the time for drying and curing is 6 to 10 hours, preferably 8 hours.
The invention also provides a fluorescent pigment which is prepared according to the preparation method.
The invention also provides application of the fluorescent pigment in the preparation field of the 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 intrinsic viscosity of the water-based polyacrylate is 230-800 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: 30-50 parts of the fluorescent pigment according to any one of claims 1-3 or claim 9, 30-50 parts of water-based polyacrylate, 20-30 parts of ethanol, 10-15 parts of deionized water and 5-8 parts of liquid paraffin in parts by mass.
The invention also provides a preparation method of the water-based fluorescent anti-counterfeiting ink, which is characterized by comprising the following steps:
A. mixing the solid fluorescent pigment with the emulsion of the water-based polyacrylate;
B. b, ball-milling the mixture obtained in the step A with ethanol, deionized water and liquid paraffin,
preferably, the weight part ratio of the deionized water to the ethanol is 1: 2; preferably, the ball milling speed in the step B is 500 r/min, 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 water-based fluorescent anti-counterfeiting ink in the field of anti-counterfeiting paper or anti-counterfeiting special printing ink.
The beneficial effects of the technical scheme of the invention comprise:
(1) the fluorescent ink prepared by the invention has good fluorescence property.
(2) The ink particles are below the micron level (200 nm-2 μm), and the requirement of printing on the particle size of the pigment is met.
(3) The pigment particles provided by the invention have good stability and are easy to process and crush. Because the modification is carried out by using isocyanate, quantitative active ester groups (equivalent ratio to methyl is in the range of 0.02-0.3) are contained, and the subsequent structural modification of the pigment is facilitated.
(4) The fluorescent ink disclosed by the invention is aqueous and organic, does not adopt heavy metal or rare earth metal as the fluorescent part of the pigment, saves resource resources and avoids the problem of heavy metal pollution.
Drawings
FIG. 1 is a graph showing the fluorescence properties of the water-type fluorescent anti-forgery inks prepared in examples 1, 2, 3 and 4;
FIG. 2 is a scanning electron micrograph of the aqueous fluorescent ink prepared in example 1;
FIG. 3 is a scanning electron micrograph of the aqueous fluorescent ink prepared in example 2;
FIG. 4 is a scanning electron micrograph of the aqueous fluorescent ink prepared in example 3;
FIG. 5 is a scanning electron micrograph of the aqueous fluorescent ink prepared in example 4;
FIG. 6 is an infrared spectrum of a product obtained by reacting rhodamine B and isocyanate in example 2.
Detailed Description
Aiming at the defects of the prior art, the invention aims to provide a fluorescent pigment, and the fluorescent pigment is compounded with a water-based binder to obtain a water-based fluorescent anti-counterfeiting ink, and a preparation method and application thereof.
Specifically, the preparation method adopts a step-by-step polymerization method to prepare the environment-friendly organic fluorescent pigment, namely, firstly, the fluorescent dye rhodamine B is used as a luminous body and is subjected to esterification reaction with isocyanate; and then, utilizing deionized water to seal the end of the isocyanate, and curing at a certain temperature to obtain the fluorescent pigment. And then mixing the fluorescent pigment with the aqueous polyacrylate emulsion, and preparing the safe and environment-friendly aqueous fluorescent anti-counterfeiting ink by ball milling, ultrasound, curing under the conditions of constant temperature and constant humidity and the like.
In a preferred embodiment of the invention, the aqueous 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 water-based 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 invention, the aqueous fluorescent anti-counterfeiting ink is prepared by a preparation method comprising the following steps:
step 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 the temperature constant, starting the stirring device, slowly adding rhodamine B powder in the stirring process, controlling the adding time to be 30 minutes, and after the adding is finished, carrying out constant-temperature reaction at 80 ℃ for 2 hours.
In the reaction process, the isocyanate is used as a reaction raw material, so that the problems of removal and residue do not exist, and the isocyanate is mainly used as the water-based environment-friendly ink, so that the isocyanate and water can finally react to generate polyurea, and the formation of an ink film is facilitated; meanwhile, the invention ensures that the isocyanate is excessive, 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, and have relatively low toxicity.
And 2, keeping the oil bath temperature 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, 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 and reacting for 30-60 minutes under the ice bath condition after the dropwise adding is finished.
And 4, placing the reaction system obtained in the step 3 in an oil bath heating device at the temperature of 50-70 ℃, continuously heating and stirring by using a distillation flask instead of a reflux condenser pipe, and evaporating and recovering redundant 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 aqueous polyacrylate emulsion, placing the mixture into a ball milling tank, mixing deionized water and ethanol with the fluorescent pigment, the aqueous polyacrylate emulsion and liquid paraffin according to the weight ratio of 1:2, and carrying out ball milling for 1-3 hours at the rotating speed of 500 revolutions per minute to obtain the aqueous fluorescent anti-counterfeiting ink.
The technical solution of the present invention will be further demonstrated with reference to specific embodiments.
Examples
The sources of the various materials in the present invention are:
rhodamine B, industrial, tianjinke miohu chemical reagents ltd;
isophorone diisocyanate (IPDI), chemically pure, shanghai crystal pure reagents ltd;
acetone, chemical pure, tabac, bisexhua chemical ltd;
neopentyl glycol, chemical purity, tianjin optometry, fine chemical research institute;
aqueous polyacrylate emulsions, industrial, basf agents;
liquid paraffin, guangzhou daodification technology ltd;
ethanol, chemical purity, Tianjin Jingyu Fine chemical Co., Ltd.
In order to clearly understand the technical features, objects and effects of the present invention, the embodiments of the present invention will be described in detail by examples.
Example 1
The preparation method of the water-based fluorescent anti-counterfeiting ink comprises the following steps of:
TABLE 1 aqueous fluorescent anti-forgery ink
The preparation method comprises the following specific steps:
(1) adding 10g of acetone into a clean four-neck flask with a reflux condenser, a thermometer, a stirring device and an oil bath heating device, adding 10g of IPDI into the flask, heating the oil bath to 80 ℃, turning on the stirring device, keeping a mechanical stirring state, slowly adding 20g of rhodamine B powder during stirring for 30 minutes, and heating for reacting for 2 hours after the addition is finished.
(2) The temperature of an oil bath heating device was set to 50 ℃, and then 2g of neopentyl glycol was slowly and continuously added to the reaction system of step 1 for 30 minutes, and after sufficiently stirring and uniformly mixing, the reaction was 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 30g of deionized water into the reaction system for 1 hour, and continuously stirring for reacting for 30 minutes after dropwise adding is completed.
(4) And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, replacing a reflux condenser tube with a distillation flask, continuously heating and stirring, and evaporating and recovering redundant deionized water and acetone solvent to obtain a thick product.
(5) And (4) 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 into a ball milling tank, mixing 10g of deionized water and 20g of ethanol with the fluorescent pigment, the aqueous polyacrylate emulsion and 5g of liquid paraffin according to the weight ratio of 1:2, and carrying out ball milling, wherein the ball milling time is 1 hour, and the rotating speed is 500 r/min. And after the preparation is finished, obtaining the water-based fluorescent anti-counterfeiting ink.
Example 2
The preparation method of the water-based fluorescent anti-counterfeiting ink comprises the following steps of:
TABLE 2 aqueous fluorescent anti-forgery ink
The preparation method comprises the following specific steps:
(1) adding 15g of acetone into a clean four-neck flask with a reflux condenser, a thermometer, a stirring device and an oil bath heating device, adding 25g of IPDI into the flask, heating the oil bath to 80 ℃, turning on the stirring device, keeping a mechanical stirring state, slowly adding 40g of rhodamine B powder during stirring for 30 minutes, and heating for reacting for 2 hours after the addition is finished.
(2) The temperature of an oil bath heating device was set to 50 ℃, and then 6g of neopentyl glycol was slowly and continuously added to the reaction system of step 1 for 30 minutes, and after sufficiently stirring and uniformly mixing, the reaction was 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 40g of deionized water into the reaction system for 1 hour, and continuously stirring for reacting for 30 minutes after dropwise adding is completed.
(4) And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, replacing a reflux condenser tube with a distillation flask, continuously heating and stirring, and evaporating and recovering redundant deionized water and acetone solvent to obtain a thick product.
(5) And (4) 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 with the fluorescent pigment, the aqueous polyacrylate emulsion and 8g of liquid paraffin according to the weight ratio of 1:2, and carrying out ball milling, wherein the ball milling time is 1 hour, and the rotating speed is 500 r/min. And after the preparation is finished, obtaining the water-based fluorescent anti-counterfeiting ink.
Example 3
The preparation method of the water-based fluorescent anti-counterfeiting ink comprises the following steps of:
TABLE 3 aqueous fluorescent anti-forgery ink
The preparation method comprises the following specific steps:
1. adding 12g of acetone into a clean four-neck flask with a reflux condenser, a thermometer, a stirring device and an oil bath heating device, adding 16g of IPDI into the flask, heating the oil bath to 80 ℃, turning on the stirring device, keeping a mechanical stirring state, slowly adding 25g of rhodamine B powder during stirring for 30 minutes, and heating for reacting for 2 hours after the addition is finished.
2. The temperature of an oil bath heating device was set to 50 ℃, and then 4g of neopentyl glycol was slowly and continuously added to the reaction system of step 1 for 30 minutes, and after sufficiently stirring and uniformly mixing, the reaction was 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 35g of deionized water into the reaction system for 1 hour, and continuously stirring for reacting for 30 minutes after dropwise adding is completed.
4. And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, replacing a reflux condenser tube with a distillation flask, continuously heating and stirring, and evaporating and recovering redundant deionized water and acetone solvent to obtain a thick product.
5. And (4) 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 a fluorescent pigment with 40g of aqueous polyacrylate emulsion, placing the mixture in a ball milling tank, mixing 13g of deionized water and 26 g of ethanol according to the weight ratio of 1:2, the fluorescent pigment, the aqueous polyacrylate emulsion and 6g of liquid paraffin, and carrying out ball milling, wherein the ball milling time is 1 hour, and the rotating speed is 500 r/min. And after the preparation is finished, obtaining the water-based fluorescent anti-counterfeiting ink.
Example 4
The preparation method of the water-based fluorescent anti-counterfeiting ink comprises the following steps of:
TABLE 4 aqueous fluorescent anti-counterfeiting ink
The preparation method comprises the following specific steps:
(1) 14g of acetone is added into a clean four-neck flask with a reflux condenser, a thermometer, a stirring device and an oil bath heating device, 20g of IPDI is added into the flask, the oil bath is heated to 80 ℃ in the process, the stirring device is started, the mechanical stirring state is kept, 32g of rhodamine B powder is slowly added in the stirring process, the adding time is 30 minutes, and after the adding is finished, the heating reaction is carried out for 2 hours.
(2) The temperature of an oil bath heating device was set to 50 ℃, and then 5g of neopentyl glycol was slowly and continuously added to the reaction system of step 1 for 30 minutes, and after sufficiently stirring and uniformly mixing, the reaction was 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 the mechanical stirring state, slowly dropwise adding 36g of deionized water into the reaction system for 1 hour, and continuously stirring for reacting for 30 minutes after dropwise adding is completed.
(4) And (3) placing the reaction system in the step (3) in an oil bath heating device at 60 ℃, replacing a reflux condenser tube with a distillation flask, continuously heating and stirring, and evaporating and recovering redundant deionized water and acetone solvent to obtain a thick product.
(5) And (4) 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 g of ethanol according to the weight ratio of 1:2, the fluorescent pigment, the aqueous polyacrylate emulsion and 7g of liquid paraffin, and carrying out ball milling, wherein the ball milling time is 1 hour, and the rotating speed is 500 r/min. And after the preparation is finished, obtaining the water-based fluorescent anti-counterfeiting ink.
And (3) product performance detection:
(1) detection of fluorescence properties: fluorescence performance detection is carried out on the aqueous fluorescent anti-counterfeiting ink obtained in the embodiment and the comparative example by using an FLS-920 type fluorescence spectrophotometer produced by Edinburgh Instruments company;
(2) and (3) detection by a scanning electron microscope: manufacturer, model; field emission scanning electron microscope of Shimadzu JSM-6700F type;
(3) an infrared spectrometer: shimadzu FTIR-8400S (CE) model Fourier Infrared Spectroscopy.
And (3) analyzing a detection result:
(1) fluorescence property detection, as shown in figure 1: all samples in the examples show fluorescence emission peaks at a fluorescence wavelength of 615nm, which indicates that the fluorescent ink prepared in the invention has good fluorescence properties. Meanwhile, the fluorescence intensities of the samples prepared in example 1, example 4, and example 3 to example 2 were sequentially increased, and the fluorescence intensity of the sample prepared in example 2 was the highest.
(2) And (3) detection by a scanning electron microscope: scanning electron micrographs of the four prepared different samples are shown in fig. 2-5, and it can be seen from fig. 2 that the anti-counterfeiting ink prepared in example 1 is in a micron-sized block shape and has high particle compactness. As can be seen from fig. 3, the anti-counterfeit ink prepared in example 2 has micro-nano particles, stacked particles are layered, the stacked morphology is regular, and the particles are distributed uniformly, so that the highest fluorescence intensity is exhibited. As can be seen from fig. 4, the anti-counterfeit ink prepared in example 3 is a micron-sized block, a large number of fine particles are distributed on the surface, and the density of the block is high. As can be seen from fig. 5, the anti-counterfeit ink prepared in example 4 is a fluffy micron-sized block and has a non-tightly stacked hierarchical structure. The ink particles of the four groups of samples are below the micron level (200 nm-1 mu m), and the requirement of printing on the particle size of the pigment is met.
(3) Infrared spectrum detection:
the benzene carboxyl group, abbreviated as R '-COOH, on the rhodamine B reacts with an isocyanate group on isocyanate (R-NCO) to generate an amido bond, namely R-NH-CO-R', so that the structure of a product generated after the rhodamine B reacts with the isocyanate can be confirmed through the existence of the amide group in infrared spectrum. FIG. 6 is an infrared spectrum of the product obtained after reacting rhodamine B with isocyanate in example 2, and it can be seen that the amide carbonyl group C ═ O oscillation peak appears at the position of 1658cm-1, and at the same time, the in-plane bending peak of the secondary amide N-H group in the amide group appears at the position of 1512cm-1, and the appearance of these two characteristic peaks indicates that rhodamine B has reacted with isocyanate to form a secondary amide group (-NH-CO-).
Claims (15)
1. A fluorescent pigment is 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.
2. The fluorescent pigment of claim 1, wherein said starting materials comprise: the paint comprises, by mass, 40 parts of rhodamine B, 25 parts of isocyanate, 6 parts of polyol, 15 parts of an organic solvent and 40 parts of deionized water.
3. The fluorescent pigment of claim 1 or 2, wherein the isocyanate is selected from the group consisting of: one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI), preferably isophorone diisocyanate (IPDI);
the polyalcohol is 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, and is preferably neopentyl glycol;
the organic solvent is one or a mixture of more than two of ethyl acetate, toluene, methyl butanone, methyl isobutyl ketone, acetonitrile and acetone; acetone is preferred.
4. A method for preparing a fluorescent pigment according to any one of claims 1 to 3, comprising the steps of:
(1) heating the organic solvent, adding isocyanate, stirring, adding the rhodamine B in the stirring process, and carrying out heating reaction;
(2) cooling the product system obtained in the step (1), and adding the polyhydric alcohol 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 (5) drying and curing the thick product obtained in the step (4) to obtain the fluorescent pigment.
5. The production method according to claim 4, wherein the step (1) includes:
the heating temperature of the organic solvent is 72-88 ℃, and preferably 80 ℃;
preferably, the time for adding the rhodamine B in the stirring process is controlled to be 25-35 ℃ for minutes, and preferably 30 minutes;
preferably, the heating reaction time is 1.5 to 2.5 hours, preferably 2 hours.
6. The production method according to claim 4 or 5, wherein the step (2) includes:
cooling the product system obtained in the step (1) to 45-55 ℃, preferably 50 ℃;
preferably, the time for adding the polyol is controlled to be 20 to 40 minutes, preferably 30 minutes;
preferably, the reaction time is stirred for 1.5 to 3 hours, preferably 2 hours.
7. The production method according to any one of claims 4 to 6, wherein the step (3) comprises:
cooling the product system obtained in the step (2) to 4-6 ℃, preferably to 5 ℃, and preferably cooling by adopting a water bath;
preferably, the time for adding the 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.
8. The preparation method according to any one of claims 4 to 7, wherein the temperature for distilling the product system obtained in step (3) in step (4) is 50-70 ℃, preferably 60 ℃;
preferably, the temperature for drying and curing the thick product obtained in the step (4) in the step (5) is 110-130 ℃, preferably 120 ℃; further preferably, the time for drying and curing is 6 to 10 hours, preferably 8 hours.
9. A fluorescent pigment produced by the production method according to any one of claims 4 to 8.
10. Use of the fluorescent pigment according to any one of claims 1 to 3 or 9 in the preparation of aqueous fluorescent security inks.
11. An aqueous fluorescent security ink, which comprises the fluorescent pigment according to any one of claims 1 to 3 or 9, and aqueous polyacrylate, ethanol, deionized water and liquid paraffin;
preferably, the weight average molecular weight of the aqueous polyacrylate is 78000-82000, preferably 80000; preferably, the intrinsic viscosity of the water-based polyacrylate is 230-800 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.
12. The aqueous fluorescent anti-counterfeiting ink according to claim 11, which comprises: 30-50 parts of the fluorescent pigment according to any one of claims 1-3 or claim 9, 30-50 parts of water-based polyacrylate, 20-30 parts of ethanol, 10-15 parts of deionized water and 5-8 parts of liquid paraffin in parts by mass.
13. A method for preparing the aqueous fluorescent anti-counterfeiting ink according to claim 11 or 12, which is characterized by comprising the following steps:
A. mixing the solid fluorescent pigment with the emulsion of the water-based polyacrylate;
B. b, ball-milling the mixture obtained in the step A with ethanol, deionized water and liquid paraffin,
preferably, the weight part ratio of the deionized water to the ethanol is 1: 2; preferably, the ball milling speed in the step B is 500 r/min, and the ball milling time is 1 hour.
14. An aqueous fluorescent anti-counterfeiting ink prepared by the preparation method of claim 13.
15. Use of the aqueous fluorescent security ink according to claim 11, 12 or 14 in the field of security paper or security specialty printing inks.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113957748A (en) * | 2021-10-28 | 2022-01-21 | 山东天和纸业有限公司 | Fiber and fluorescence anti-counterfeiting paper and preparation method thereof |
| CN114561124A (en) * | 2022-04-11 | 2022-05-31 | 辽宁大学 | Anti-counterfeiting ink with controllable color development time and anti-counterfeiting printed matter containing anti-counterfeiting ink |
| CN114672197A (en) * | 2022-04-21 | 2022-06-28 | 辽宁大学 | Rapid color development ink and application thereof in color development paper |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05239395A (en) * | 1992-02-28 | 1993-09-17 | Pentel Kk | Water-based fluorescent pigment ink |
| JP2006241298A (en) * | 2005-03-03 | 2006-09-14 | Pilot Ink Co Ltd | Aqueous ink composition for writing instruments |
| US20110027495A1 (en) * | 2009-07-28 | 2011-02-03 | Fujifilm Corporation | Pigment dispersion, ink composition, and inkjet recording method |
| WO2013099157A1 (en) * | 2011-12-27 | 2013-07-04 | 理想科学工業株式会社 | Non-aqueous pigment ink |
| CN103666457A (en) * | 2013-12-05 | 2014-03-26 | 襄阳金飞环彩色包装有限公司 | Environmental protection type organic coumarin-base photoluminescence anti-counterfeiting pigment, environmental protection type organic coumarin-base photoluminescence anti-counterfeiting ink,and preparation methods thereof |
| CN110684369A (en) * | 2018-07-05 | 2020-01-14 | 中国科学技术大学 | Water-soluble red organic fluorescent dye and preparation method thereof, and water-based invisible red fluorescent anti-counterfeiting ink and use method thereof |
| CN110862507A (en) * | 2019-10-29 | 2020-03-06 | 温州大学 | Preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane |
| CN111234601A (en) * | 2020-03-31 | 2020-06-05 | 浙江材华科技有限公司 | Water-based macromolecular fluorescent anti-counterfeiting ink and preparation method thereof |
| CN111269361A (en) * | 2020-01-20 | 2020-06-12 | 陕西科技大学 | Preparation method of fluorine-containing acrylate modified polyurethane emulsion with fluorescent property |
| CN111423765A (en) * | 2020-05-19 | 2020-07-17 | 郑梦平 | Preparation process of environment-friendly water-based ink |
-
2020
- 2020-10-27 CN CN202011167877.1A patent/CN112430462B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05239395A (en) * | 1992-02-28 | 1993-09-17 | Pentel Kk | Water-based fluorescent pigment ink |
| JP2006241298A (en) * | 2005-03-03 | 2006-09-14 | Pilot Ink Co Ltd | Aqueous ink composition for writing instruments |
| US20110027495A1 (en) * | 2009-07-28 | 2011-02-03 | Fujifilm Corporation | Pigment dispersion, ink composition, and inkjet recording method |
| WO2013099157A1 (en) * | 2011-12-27 | 2013-07-04 | 理想科学工業株式会社 | Non-aqueous pigment ink |
| CN103666457A (en) * | 2013-12-05 | 2014-03-26 | 襄阳金飞环彩色包装有限公司 | Environmental protection type organic coumarin-base photoluminescence anti-counterfeiting pigment, environmental protection type organic coumarin-base photoluminescence anti-counterfeiting ink,and preparation methods thereof |
| CN110684369A (en) * | 2018-07-05 | 2020-01-14 | 中国科学技术大学 | Water-soluble red organic fluorescent dye and preparation method thereof, and water-based invisible red fluorescent anti-counterfeiting ink and use method thereof |
| CN110862507A (en) * | 2019-10-29 | 2020-03-06 | 温州大学 | Preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane |
| CN111269361A (en) * | 2020-01-20 | 2020-06-12 | 陕西科技大学 | Preparation method of fluorine-containing acrylate modified polyurethane emulsion with fluorescent property |
| CN111234601A (en) * | 2020-03-31 | 2020-06-05 | 浙江材华科技有限公司 | Water-based macromolecular fluorescent anti-counterfeiting ink and preparation method thereof |
| CN111423765A (en) * | 2020-05-19 | 2020-07-17 | 郑梦平 | Preparation process of environment-friendly water-based ink |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113957748A (en) * | 2021-10-28 | 2022-01-21 | 山东天和纸业有限公司 | Fiber and fluorescence anti-counterfeiting paper and preparation method thereof |
| CN114561124A (en) * | 2022-04-11 | 2022-05-31 | 辽宁大学 | Anti-counterfeiting ink with controllable color development time and anti-counterfeiting printed matter containing anti-counterfeiting ink |
| CN114672197A (en) * | 2022-04-21 | 2022-06-28 | 辽宁大学 | Rapid color development ink and application thereof in color development paper |
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