CN117510785A - Water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, preparation method thereof and application thereof in anti-counterfeiting ink - Google Patents

Water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, preparation method thereof and application thereof in anti-counterfeiting ink Download PDF

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CN117510785A
CN117510785A CN202311455617.8A CN202311455617A CN117510785A CN 117510785 A CN117510785 A CN 117510785A CN 202311455617 A CN202311455617 A CN 202311455617A CN 117510785 A CN117510785 A CN 117510785A
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ultraviolet light
visible light
fluorescence
diisocyanate
group
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CN117510785B (en
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张书林
杨荣利
赵亮
魏洪涛
钱武胜
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Langfang Anding New Material Technology Co ltd
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Langfang Anding New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides visible light-induced color change and ultraviolet light-induced fluorescence waterborne polyurethane, a preparation method thereof and application thereof in anti-counterfeiting ink, and belongs to the technical field of waterborne polyurethane. The main chain of the waterborne polyurethane provided by the invention contains a bridging azo phenyl group, and the end group contains a fluorescein group. Wherein the bridged azobenzene group undergoes a cis-to-trans configuration transition under blue light irradiation and a light yellow-to-red transition in color. The fluorescein group emits yellow fluorescence under ultraviolet excitation. In the aqueous polyurethane molecular chain provided by the invention, the bridging azo phenyl group and the fluorescein group are bonded through covalent bonds, and the proportion of the two groups is adjusted, so that the color change and fluorescence emission are respectively presented under blue light and ultraviolet light, thereby realizing double anti-counterfeiting of the ink. The waterborne polyurethane provided by the invention has dual optical characteristics of visible light photochromism and ultraviolet light excited fluorescence, and has the characteristic of anti-counterfeiting compared with single photochromism or fluorescence.

Description

Water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, preparation method thereof and application thereof in anti-counterfeiting ink
Technical Field
The invention relates to the technical field of waterborne polyurethane, in particular to a visible light-induced fluorescence waterborne polyurethane, a preparation method thereof and application thereof in anti-counterfeiting ink.
Background
The anti-counterfeiting ink is widely applied to product anti-counterfeiting of paper with thinner thickness, banknote anti-counterfeiting, invoice anti-counterfeiting, book anti-counterfeiting, calligraphy and painting anti-counterfeiting and the like. According to the different anti-counterfeiting materials, the ink anti-counterfeiting mainly comprises ultraviolet excited fluorescent anti-counterfeiting ink, infrared fluorescent anti-counterfeiting ink, temperature color-changing anti-counterfeiting ink, magnetic anti-counterfeiting ink, visual angle color-changing anti-counterfeiting ink, anti-altering anti-counterfeiting ink, humidity-sensitive color-changing anti-counterfeiting ink and the like. The common practice of ink anti-counterfeiting is to disperse anti-counterfeiting chemicals such as ultraviolet excited fluorescent agent, infrared fluorescent anti-counterfeiting agent, color changing agent, magnetic powder and the like into the connecting resin to form ink, then coat the ink on the surface of an object needing anti-counterfeiting through an ink jet or transfer printing technology, and have special visual effect under special lamplight or temperature or can send anti-counterfeiting signals in a special detector, thereby playing an anti-counterfeiting role. At present, a common anti-counterfeiting ink uses an anti-counterfeiting technology, the anti-counterfeiting ink using a single anti-counterfeiting technology is easy to imitate, and multiple anti-counterfeiting ink combining two or more anti-counterfeiting technologies can effectively improve anti-counterfeiting performance. However, when different anti-counterfeiting chemicals are combined, the compatibility of the anti-counterfeiting chemicals and the connecting resin is difficult to coordinate, and one or more anti-counterfeiting chemicals can fall off from the anti-counterfeiting coating under the conditions of environmental humidity change, friction and the like, so that the anti-counterfeiting performance is influenced, and the appearance of the anti-counterfeiting product is also influenced.
The aqueous polyurethane is a green environment-friendly material widely applied to the fields of clothes, paint, ink and the like. However, the existing water-based polyurethane ink also has the defect of single anti-counterfeiting effect.
Disclosure of Invention
In view of the above, the invention aims to provide a visible light-induced fluorescence water-based polyurethane, a preparation method thereof and application thereof in anti-counterfeiting ink. The aqueous polyurethane provided by the invention can realize double anti-counterfeiting of the ink.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, which has the following characteristics of
The structure shown in formula 1:
in the formula 1, n=1 to 100; r is R 2 Is alkylene, cycloalkyl or aralkyl;
R 3 the structure of (1) is that
R 3 Wherein R is 1 Is alkylene, cycloalkyl or aralkyl, R 4 Is methyl or ethyl.
Preferably, said R 1 、R 2 Wherein the alkylene group includes an alkylene group having 1 to 6 carbon atoms, the cycloalkyl group includes a cycloalkyl group having 5 to 10 carbon atoms, and the aralkyl group includes an aralkyl group having 6 to 10 carbon atoms.
The invention provides a preparation method of the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence, which comprises the following steps:
mixing polyglycol, diisocyanate, dimethylol carboxylic acid and an organic metal catalyst, and performing a first-step polymerization reaction to obtain a first-step prepolymer;
mixing the prepolymer in the first step with bridged azobenzene containing amino, and carrying out a second polymerization reaction to obtain a prepolymer in the second step; the amino-containing bridged azobenzene has a structure represented by formula 2:
performing addition reaction on the prepolymer in the second step and aminofluorescein, and adding a neutralizing agent for neutralization to obtain a polyurethane prepolymer;
and mixing the polyurethane prepolymer with water and an aqueous solution of a primary ammonia chain extender, and performing chain extension reaction to obtain the aqueous polyurethane with visible light photochromic and ultraviolet light excited fluorescence.
Preferably, the polyglycols include polyether glycol and/or polyester glycol;
the diisocyanate comprises one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexyl diisocyanate and trimethylhexamethylene diisocyanate;
the dimethylol carboxylic acid comprises one or two of dimethylol propionic acid and dimethylol butyric acid;
the primary amino chain extender comprises one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentanediamine, hexamethylenediamine, isophoronediamine and ethylenediamine sodium ethanesulfonate.
Preferably, the ratio of the amount of the hydroxyl group-containing substance in the polyglycol, the amount of the hydroxyl group-containing substance in the dimethylol carboxylic acid, the amount of the isocyanate-containing substance in the diisocyanate, the amount of the primary amino group-containing substance in the bridged azobenzene, the amount of the primary amino group-containing substance in the aminofluorescein, and the amount of the primary amino group-containing substance in the chain extender is 0.2 to 0.4:0.2 to 0.3:1:0.002 to 0.1:0.002 to 0.1:0.1 to 0.3.
Preferably, the first polymerization step further comprises adding a ketone solvent to adjust the viscosity of the reaction system.
Preferably, the temperature of the first polymerization step is 75-85 ℃ and the time is 3.5-5.5 h;
the temperature of the second polymerization reaction is 10-25 ℃ and the time is 0.2-1 h;
the temperature of the addition reaction is 10-25 ℃ and the time is 0.2-1 h;
the temperature of the chain extension reaction is 10-25 ℃ and the time is 0.5-2 h.
The invention provides application of the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence in anti-counterfeiting ink.
The invention provides anti-counterfeiting ink which comprises the following components in percentage by mass:
the aqueous polyurethane comprises the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence.
Preferably, the filler is one or more of precipitated white carbon black, active calcium carbonate and silica micropowder; the mesh number of the filler is more than or equal to 1000 meshes;
the rheological agent is hydroxyethyl cellulose and/or hydrophobic association polyurethane emulsion;
the film forming auxiliary agent is one or more of ethylene glycol butyl ether, propylene glycol methyl ether and propylene glycol butyl ether;
the pH value regulator is one or more of sodium dihydrogen phosphate, sodium bicarbonate, sodium carbonate and sodium phosphate.
The invention provides a water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, which has a structure shown in a formula 1. Wherein the bridged azobenzene group undergoes a cis-to-trans configuration transition under blue light irradiation and a light yellow-to-red transition in color. The fluorescein group emits yellow fluorescence under ultraviolet excitation. In the aqueous polyurethane molecular chain provided by the invention, the bridging azo phenyl group and the fluorescein group are bonded through covalent bonds, and the proportion of the two groups is adjusted, so that the color change and fluorescence emission are respectively presented under blue light and ultraviolet light, thereby realizing double anti-counterfeiting of the ink. The waterborne polyurethane provided by the invention has the dual optical characteristics of visible light photochromism and ultraviolet light excited fluorescence, and has the characteristics of anti-counterfeiting compared with single photochromism or fluorescence. According to the aqueous polyurethane provided by the invention, the visible photochromic group and the fluorescent group are bonded on the polyurethane molecular chain through chemical bonds, so that the phase separation between the photochromic substance and the fluorescent substance and the connecting resin is eliminated, the phenomena of decolorization, fading and the like are reduced, and the stable anti-counterfeiting ink coating is formed.
The invention provides the preparation method of the water-based polyurethane with the visible light color change and ultraviolet light fluorescence excitation, which is simple to operate, low in cost and easy to realize industrialized mass production.
Drawings
FIG. 1 is a graph showing the discoloration of the ink prepared in example 6 under different light conditions.
Detailed Description
The invention provides a water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, which has the following characteristics of
The structure shown in formula 1:
in formula 1, R 2 Is alkylene, cycloalkyl or aralkyl;
in formula 1, R 3 The structure of (1) is that
R 3 Wherein R is 1 Is alkylene, cycloalkyl or aralkyl, R 4 Is methyl or ethyl. R is R 3 In,representing the repeating units of the reaction product obtained after polycondensation of the polyglycol and the diisocyanate.
In the present invention, the R 1 、R 2 The alkylene group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkyl group having 3 to 4 carbon atoms; the cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, more preferably a cycloalkyl group having 6 to 8 carbon atoms; the aralkyl group is preferably an aralkyl group having 6 to 10 carbon atoms, more preferably an aralkyl group having 7 to 8 carbon atoms.
In the present invention, n in formula 1 represents a repeating unit, n=1 to 100; preferably, n=10 to 80; more preferably, n=20 to 60; more preferably, n=30 to 50.
The invention provides a preparation method of the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence, which comprises the following steps:
mixing polyglycol, diisocyanate, dimethylol carboxylic acid and an organic metal catalyst, and performing a first-step polymerization reaction to obtain a first-step prepolymer;
mixing the prepolymer in the first step with bridged azobenzene containing amino, and carrying out a second polymerization reaction to obtain a prepolymer in the second step; the amino-containing bridged azobenzene has a structure represented by formula 2:
performing addition reaction on the prepolymer in the second step and aminofluorescein, and adding a neutralizing agent for neutralization to obtain a polyurethane prepolymer;
and mixing the polyurethane prepolymer with water and an aqueous solution of a primary ammonia chain extender, and performing chain extension reaction to obtain the aqueous polyurethane with visible light photochromic and ultraviolet light excited fluorescence.
In the invention, R in the aqueous polyurethane with the structure shown in the formula 1 and fluorescence excited by visible light and ultraviolet light 1 The structure is derived from diisocyanate, R 4 The structure is derived from dimethylol carboxylic acid, R 2 The structure is derived from primary amine chain extenders.
The invention mixes polyglycol, diisocyanate, dimethylol carboxylic acid and organic metal catalyst, and carries out a first polymerization reaction to obtain a first prepolymer. In the present invention, the polyglycol preferably includes polyether glycol and/or polyester glycol; in the present invention, the molecular weight of the polyether glycol is preferably 1000 to 3000Da, more preferably 2000Da, and the molecular weight of the polyester glycol is preferably 1000 to 3000Da, more preferably 2000Da.
In the present invention, the diisocyanate preferably includes one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexyl diisocyanate, trimethylhexane diisocyanate. In the present invention, the ratio of the amount of the hydroxyl group-containing substance in the polyglycol to the amount of the isocyanate group-containing substance in the diisocyanate is preferably 0.2 to 0.4:1, more preferably 0.3:1.
In the present invention, the dimethylol carboxylic acid preferably includes one or both of dimethylol propionic acid and dimethylol butyric acid. In the present invention, the mass ratio of the dimethylol carboxylic acid to the diisocyanate is preferably 0.2 to 0.3:1.
In the present invention, the organometallic catalyst is preferably an organometallic tin catalyst and/or an organometallic bismuth catalyst. In the present invention, the organometallic catalyst is preferably 0.001 to 0.1% by mass, more preferably 0.01 to 0.05% by mass of the diisocyanate.
In the present invention, the temperature of the first polymerization step is preferably 75 to 85 ℃, more preferably 80 ℃; the time is preferably 3.5 to 5.5 hours.
In the present invention, the mixing is preferably performed in a reaction kettle, and the mixing is preferably stirring mixing.
In the invention, the first polymerization step further comprises the step of adding a ketone solvent to adjust the viscosity of the reaction system. In the present invention, the ketone solvent preferably includes one or more of acetone, butanone and cyclohexanone. After the raw materials are added, the reaction is preferably carried out for 1.5 hours at the temperature of 75-85 ℃, the ketone solvent is added to adjust the viscosity, and the reaction is continued for 2-4 hours. In the present invention, the viscosity of the reaction system after the addition of the ketone solvent is preferably 100 to 10000 mPas, more preferably 200 to 1000 mPas.
After the first-step prepolymer is obtained, the first-step prepolymer is mixed with bridged azobenzene containing amino group, and a second-step polymerization reaction is carried out to obtain a second-step prepolymer. In the present invention, the amount ratio of the amino group-containing bridged azobenzene to diisocyanate is preferably 0.002 to 0.1:1, more preferably 0.005 to 0.01:1.
In the present invention, the temperature of the second polymerization step is preferably 10 to 25℃and the time is preferably 0.2 to 1 hour, more preferably 0.5 to 0.8 hour.
After the second-step prepolymer is obtained, the second-step prepolymer and amino fluorescein are subjected to addition reaction, and a neutralizing agent is added for neutralization, so that the polyurethane prepolymer is obtained. In the present invention, the aminofluorescein preferably includes one or more of 5-aminofluorescein, 6-aminofluorescein and isomers thereof. In the present invention, the ratio of the amount of the substance of the primary amino group contained in the aminofluorescein to the amount of the substance of the isocyanate contained in the diisocyanate is preferably 0.002 to 0.1:1, more preferably 0.005 to 0.01:1.
In the present invention, the temperature of the addition reaction is preferably 10 to 25 ℃, and the time is preferably 0.2 to 1h, more preferably 0.5 to 0.8h.
In the present invention, the neutralizing agent preferably includes triethylamine and/or triethanolamine; in the present invention, the mass ratio of the neutralizing agent to the dimethylol carboxylic acid is preferably 0.6 to 0.95:1, more preferably 0.7 to 0.8:1.
After the polyurethane prepolymer is obtained, the polyurethane prepolymer is mixed with water and an aqueous solution of a primary ammonia chain extender for chain extension reaction, so that the visible light photochromic and ultraviolet light excited fluorescent aqueous polyurethane is obtained. In the present invention, the primary amine chain extender preferably includes one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentylenediamine, hexamethylenediamine, isophoronediamine, and sodium ethylenediamine-ethanesulfonate (a 95). In the present invention, the mass ratio of the primary amine chain extender to the diisocyanate is preferably 0.1 to 0.3:1, more preferably 0.2:1.
In the present invention, the temperature of the water is preferably 2 to 20 ℃.
In the present invention, the temperature of the chain extension reaction is preferably 10 to 25℃and the time is preferably 0.5 to 2 hours, more preferably 1 hour.
After the chain extension reaction, the invention also preferably removes ketone solvents in the chain extension reaction system. In the present invention, the manner of removing the ketone solvent in the chain extension reaction system is preferably distillation, and the solid content of the aqueous polyurethane obtained is preferably 30 to 50% by weight, more preferably 35 to 45% by weight.
The invention provides application of the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence in anti-counterfeiting ink.
The invention provides anti-counterfeiting ink which comprises the following components in percentage by mass:
the aqueous polyurethane is the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence.
The anti-counterfeiting ink provided by the invention comprises 50-70% of aqueous polyurethane, preferably 55-65%, and more preferably 60% by mass. The main chain of the waterborne polyurethane contains a bridging azo phenyl group, the end group of the waterborne polyurethane contains a fluorescein group, the bridging azo phenyl group is converted from cis-form to trans-form under the irradiation of blue light, and the color is converted from pale yellow to red. The fluorescein group emits yellow fluorescence under ultraviolet excitation. In the aqueous polyurethane molecular chain, bridging azo phenyl groups and fluorescein groups are bonded through covalent bonds, and the proportion of the two groups is adjusted, so that the color change and fluorescence emission are respectively shown under blue light and ultraviolet light, and double anti-counterfeiting of the ink is realized.
The anti-counterfeiting ink provided by the invention comprises 0.1-1% of bactericide, preferably 0.5% by mass. In the present invention, the bactericide is preferably a pinocembrane preservative.
The anti-counterfeiting ink provided by the invention comprises 0.1-1% of defoamer, preferably 0.5% by mass. In the present invention, the antifoaming agent is preferably a silicone antifoaming agent.
The anti-counterfeiting ink provided by the invention comprises 5-20% of filler, preferably 10-15% of filler by mass percent. In the invention, the filler is preferably one or more of precipitated white carbon black, activated calcium carbonate and silica micropowder; the particle size of the filler is preferably more than or equal to 1000 meshes.
The anti-counterfeiting ink provided by the invention comprises 5-10% of color paste, and more preferably 6-8% of color paste by mass percent. In the invention, the color paste is preferably resin type water-based titanium white paste which contains more than or equal to 50% of titanium dioxide and has fineness less than or equal to 20 mu m and no APE.
The anti-counterfeiting ink provided by the invention comprises 0-2% of pH value regulator, preferably 0.5-1.5% by mass. In the invention, the pH value regulator is one or more of sodium dihydrogen phosphate, sodium bicarbonate, sodium carbonate and sodium phosphate. In the invention, the pH value of the anti-counterfeiting ink is preferably 6-8 after the pH value is regulated.
The anti-counterfeiting ink provided by the invention comprises 0.2-2% of rheological agent, preferably 0.5-1.5%, and more preferably 1% by mass. In the present invention, the rheology agent is preferably hydroxyethylcellulose and/or a hydrophobically associative polyurethane emulsion.
The anti-counterfeiting ink provided by the invention comprises 1-2% of film forming auxiliary agent, preferably 1.5% by mass. In the invention, the film forming auxiliary agent is preferably one or more of ethylene glycol butyl ether, propylene glycol methyl ether and propylene glycol butyl ether.
The anti-counterfeiting ink provided by the invention preferably comprises 5-20% of water by mass percent. In the present invention, the water is preferably deionized water.
In the present invention, the preparation method of the anti-counterfeit ink preferably includes the following steps:
adding the visible light-induced color change and ultraviolet light-induced fluorescence water-based polyurethane, a bactericide and a defoaming agent according to the weight ratio of the formula, and performing high-speed dispersion;
adding filler and color paste under low-speed dispersion;
and then adding the pH regulator, the flatting agent, the film forming auxiliary agent and deionized water, stirring, and regulating the viscosity to obtain the anti-counterfeiting ink.
In the present invention, the rate of the high-speed dispersion is preferably 100 to 500rpm, and the time is preferably 5 to 10 minutes;
the rate of the low-speed dispersion is preferably 20 to 100rpm, and the time is preferably 1 to 4 hours, more preferably 2 to 3 hours.
In the present invention, the viscosity of the anti-forgery ink is preferably 20 to 300mpa·s.
In the present invention, after the anti-forgery ink is obtained, the present invention is also preferably subjected to filtration and packaging.
The following describes the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence, the preparation method and the application in anti-counterfeiting ink in detail by combining the examples, but the aqueous polyurethane is not to be interpreted as limiting the protection scope of the invention.
Example 1
Dried polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong) 5000 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 201 g and 2.0 g bismuth catalyst (MC-710, beijing Baiyuan chemical) are added into a reaction kettle, stirred evenly, heated to 75 ℃ for reaction for 2 hours, acetone 600 g is added, the reaction is continued for 2 hours, cooled to room temperature, p-diaminoazobenzene bridged azobenzene (Z) -11, 12-dihydrodibenzo [ c, g ] [1,2] azooctane-3, 8-diamine 21 g and 100 g acetone mixture solution are added, the reaction is continued for 20 minutes, 6-aminofluorescein 17 g and 50 g acetone mixture solution are added, the reaction is continued for 20 minutes, triethylamine 150 g is added, and stirring is continued for 5 minutes to uniformity, thus obtaining polyurethane prepolymer.
The polyurethane prepolymer was rapidly added to 12000 g of purified water at 5℃and stirred at 500rpm for 3 minutes, 110 g of a 50% aqueous ethylenediamine solution was added dropwise thereto under stirring at 3 minutes, and stirred at 50rpm for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous polyurethane dispersion.
Example 2
Dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Da) 4000 g, polyester glycol (XCP-2000N, molecular weight 2000Da, with the chemicals of sunk) 1000 g, isophorone diisocyanate 889 g, toluene diisocyanate 174 g, dimethylol propionic acid 201 g and 1.0 g dibutyl tin dilaurate were added to the reaction kettle, stirred well, heated to 75 ℃ for 2 hours, added with acetone 600 g, reacted for 2 hours, cooled to room temperature, added with bridged azobenzene (Z) -11, 12-dihydrodibenzo [ c, g ] [1,2] azooctane-3, 8-diamine 21 g and 100 g acetone mixture solution, reacted for 20 minutes continuously, added with 6-amino fluorescein 17 g and 50 g acetone mixture solution, reacted for 20 minutes continuously, cooled to room temperature, added with triethylamine 150 g, stirred for 5 minutes until uniform, to obtain polyurethane prepolymer.
The polyurethane prepolymer was rapidly added to 12000 g of purified water at 5℃and stirred at 500rpm for 3 minutes, 110 g of a 50% aqueous ethylenediamine solution was added dropwise thereto under stirring at 3 minutes, and stirred at 50rpm for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous polyurethane dispersion.
Example 3
Dried polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong) 5000 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 201 g and 2.0 g bismuth catalyst (MC-710, beijing Baiyuan chemical) are added into a reaction kettle, stirred evenly, heated to 75 ℃ for reaction for 2 hours, acetone 600 g is added, the reaction is continued for 2 hours, cooled to room temperature, bridged azobenzene (Z) -11, 12-dihydrodibenzo [ c, g ] [1,2] azoaromatics octane-3, 8-diamine 21 g and 100 g acetone mixture solution are added, the reaction is continued for 20 minutes, 6-aminofluorescein 35 g and 50 g acetone mixture solution are added, the reaction is continued for 20 minutes, triethylamine 150 g is added, and stirring is continued for 5 minutes to be uniform, thus obtaining polyurethane prepolymer.
The polyurethane prepolymer was rapidly added to 12000 g of purified water at 5℃and stirred at 500rpm for 3 minutes, 110 g of a 50% aqueous ethylenediamine solution was added dropwise thereto under stirring at 3 minutes, and stirred at 50rpm for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous polyurethane dispersion.
Example 4
Dried polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong) 5000 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 201 g and 2.0 g bismuth catalyst (MC-710, beijing Baiyuan chemical) are added into a reaction kettle, stirred evenly, heated to 75 ℃ for reaction for 2 hours, acetone 600 g is added, the reaction is continued for 2 hours, cooled to room temperature, bridged azobenzene (Z) -11, 12-dihydrodibenzo [ c, g ] [1,2] azoaromatics octane-3, 8-diamine 11 g and 100 g acetone mixture solution are added, the reaction is continued for 20 minutes, 6-aminofluorescein 18 g and 50 g acetone mixture solution are added, the reaction is continued for 20 minutes, the temperature is reduced to room temperature, triethylamine 150 g is added, and stirring is continued for 5 minutes to uniformity, thus obtaining polyurethane prepolymer.
The polyurethane prepolymer was rapidly added to 12000 g of purified water at 5℃and stirred at 500rpm for 3 minutes, 110 g of a 50% aqueous ethylenediamine solution was added dropwise thereto under stirring at 3 minutes, and stirred at 50rpm for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous polyurethane dispersion.
Example 5
Adding 1500 g of the aqueous polyurethane synthesized in the embodiment 1,2 g of the kasong bactericide, 300 g of 2000-mesh precipitated white carbon black and 8 g of AFE-3168 defoamer into a dispersing kettle, dispersing for 40 minutes at a speed of 500rpm, adding 200 g of titanium white color paste under 50rpm stirring, uniformly stirring, then adding 3 g of sodium carbonate, 5 g of Haimas RHEOLATE299 rheologic agent, 25 g of propylene glycol methyl ether and 100 g of deionized water, stirring, defoaming, adjusting the viscosity, and filtering and packaging to obtain the aqueous anti-counterfeiting ink.
Example 6
Adding 1500 g of the aqueous polyurethane synthesized in the embodiment 4, 2 g of the kasong bactericide, 400 g of 2000-mesh precipitated white carbon black and 8 g of AFE-3168 defoamer into a dispersing kettle, dispersing for 40 minutes at a speed of 500rpm, adding 100 g of titanium white color paste under low-speed stirring, uniformly stirring, then adding 3 g of sodium carbonate, 5 g of Haimas RHEOLATE299 rheologic agent, 25 g of propylene glycol methyl ether and 100 g of deionized water, stirring, defoaming, adjusting the viscosity, and filtering and packaging to obtain the aqueous anti-counterfeiting ink. The ink prepared in example 6 shows the color change of the ink under different illumination conditions as shown in FIG. 1.
Comparative example 1
Dried polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong) 5000 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 201 g and 2.0 g bismuth catalyst (MC-710, beijing Baiyuan chemical) are added into a reaction kettle, stirred evenly, heated to 75 ℃ for 2 hours, acetone 600 g is added, the reaction is continued for 2 hours, cooled to room temperature, bridged azobenzene (Z) -11, 12-dihydrodibenzo [ c, g ] [1,2] azoaromatics octane-3, 8-diamine 21 g and 100 g acetone mixture solution are added, the reaction is continued for 20 minutes, triethylamine 150 g is added, and stirring is continued for 5 minutes to uniformity, thus obtaining polyurethane prepolymer.
The polyurethane prepolymer was rapidly added to 12000 g of purified water at 5℃and stirred at 500rpm for 3 minutes, 110 g of a 50% aqueous ethylenediamine solution was added dropwise thereto under stirring at 3 minutes, and stirred at 50rpm for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous polyurethane dispersion.
Comparative example 2
Dried polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong) 5000 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 201 g and 2.0 g bismuth catalyst (MC-710, beijing Baiyuan chemical) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for 2 hours, added with acetone 600 g, reacted for 2 hours, cooled to room temperature, added with a mixture solution of 6-aminofluorescein 17 g and 50 g acetone, reacted for 20 minutes, added with triethylamine 150 g, stirred for 5 minutes until uniform, and finally polyurethane prepolymer is obtained.
The polyurethane prepolymer was rapidly added to 12000 g of purified water at 5℃and stirred at 500rpm for 3 minutes, 110 g of a 50% aqueous ethylenediamine solution was added dropwise thereto under stirring at 3 minutes, and stirred at 50rpm for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous polyurethane dispersion.
Comparative example 3
Dried polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong) 5000 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 201 g and 2.0 g bismuth catalyst (MC-710, beijing Baiyuan chemical) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for 2 hours, added with acetone 600 g, reacted for 2 hours, cooled to room temperature, added with a mixture solution of 6-aminofluorescein 17 g and 50 g acetone, reacted for 20 minutes, added with triethylamine 150 g, stirred for 5 minutes until uniform, and finally polyurethane prepolymer is obtained.
The polyurethane prepolymer was rapidly added to 12000 g of purified water at 5℃and stirred at 500rpm for 3 minutes, 110 g of a 50% aqueous ethylenediamine solution was added dropwise thereto under stirring at 3 minutes, and stirred at 50rpm for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous polyurethane dispersion.
Comparative example 4
Adding 1500 g of the aqueous polyurethane synthesized in the comparative example 1,2 g of a kasong bactericide, 300 g of 2000-mesh precipitated white carbon black and 8 g of an AFE-3168 defoamer into a dispersing kettle, stirring at a speed of 500rpm for 40 minutes, adding 200 g of titanium white color paste under 50rpm stirring, uniformly stirring, then adding 3 g of sodium carbonate, 5 g of a Haimas RHEOLATE299 rheologic agent, 25 g of propylene glycol methyl ether and 100 g of deionized water, stirring for defoaming, adjusting the viscosity, and filtering and packaging to obtain the aqueous scratch ink.
Comparative example 5
Adding 1500 g of the aqueous polyurethane synthesized in the comparative example 2, 2 g of a kasong bactericide, 300 g of 2000-mesh precipitated white carbon black and 8 g of an AFE-3168 defoamer into a dispersing kettle, stirring at a speed of 500rpm for 40 minutes, adding 200 g of titanium white color paste under 50rpm stirring, uniformly stirring, then adding 3 g of sodium carbonate, 5 g of a Haimas RHEOLATE299 rheologic agent, 25 g of propylene glycol methyl ether and 100 g of deionized water, stirring for defoaming, adjusting the viscosity, and filtering and packaging to obtain the aqueous ink.
Comparative example 6
Adding 1500 g of the aqueous polyurethane synthesized in the comparative example 3, 2 g of bactericide, 300 g of 2000-mesh precipitated white carbon black and 8 g of AFE-3168 defoamer into a dispersing kettle, stirring at a speed of 500rpm for 40 minutes, adding 200 g of titanium white color paste under 50rpm stirring, stirring uniformly, adding 3 g of sodium carbonate, 5 g of Haiman RHEOTATE 299 rheologic agent, 25 g of propylene glycol methyl ether and 100 g of deionized water, stirring for defoaming, adjusting viscosity, filtering and packaging to obtain the aqueous ink.
Test example 1
A certain amount of the aqueous polyurethane obtained in examples 1 to 4 and comparative examples 1 to 3 was placed in a polytetrafluoroethylene mold, left for 1 to 2 days, and dried naturally. The polyurethane film was then dried in a vacuum oven at 25 ℃ for 2 days, weighed, calculated for solids content, observed for color, and measured for 100% modulus. The dry film was irradiated with blue light and ultraviolet light at 25℃for 2 minutes, respectively, and the color thereof was observed. The results are shown in Table 1.
Table 1 waterborne polyurethane parameters
The results in Table 1 show that the aqueous polyurethanes obtained in examples 1 to 4 have properties of blue photochromic and ultraviolet light-excited fluorescence, and have similar mechanical properties to those of comparative example 1.
Test example 2
A certain amount of aqueous polyurethane ink of examples 5-6 and comparative examples 4-6 is coated on PET film, and the PET film is left for 1 day, dried naturally and observed to be color; the ink-coated PET film was irradiated with blue light for 1 minute or placed in an oven at 60℃for 10 minutes, and the color change was observed. The results are shown in Table 2.
TABLE 2 discoloration of anti-forgery ink
The results in Table 2 show that the aqueous inks of examples 5 and 6 have blue photochromic and ultraviolet light-excited fluorescent properties.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A visible light photochromic and ultraviolet light excited fluorescent aqueous polyurethane has a structure shown in a formula 1:
in the formula 1, n=1 to 100; r is R 2 Is alkylene, cycloalkyl or aralkyl;
R 3 the structure of (1) is that
R 3 Wherein R is 1 Is alkylene, cycloalkyl or aralkyl, R 4 Is methyl or ethyl.
2. The aqueous polyurethane of visible light-induced fluorescence and ultraviolet light-induced fluorescence according to claim 1, wherein R 1 、R 2 Wherein the alkylene group includes an alkylene group having 1 to 6 carbon atoms, the cycloalkyl group includes a cycloalkyl group having 5 to 10 carbon atoms, and the aralkyl group includes an aralkyl group having 6 to 10 carbon atoms.
3. The method for preparing the aqueous polyurethane with visible light color change and ultraviolet light fluorescence excitation according to claim 1 or 2, comprising the following steps:
mixing polyglycol, diisocyanate, dimethylol carboxylic acid and an organic metal catalyst, and performing a first-step polymerization reaction to obtain a first-step prepolymer;
mixing the prepolymer in the first step with bridged azobenzene containing amino, and carrying out a second polymerization reaction to obtain a prepolymer in the second step; the amino-containing bridged azobenzene has a structure represented by formula 2:
performing addition reaction on the prepolymer in the second step and aminofluorescein, and adding a neutralizing agent for neutralization to obtain a polyurethane prepolymer;
and mixing the polyurethane prepolymer with water and an aqueous solution of a primary ammonia chain extender, and performing chain extension reaction to obtain the aqueous polyurethane with visible light photochromic and ultraviolet light excited fluorescence.
4. A method of preparation according to claim 3, wherein the polyglycols comprise polyether glycol and/or polyester glycol;
the diisocyanate comprises one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexyl diisocyanate and trimethylhexamethylene diisocyanate;
the dimethylol carboxylic acid comprises one or two of dimethylol propionic acid and dimethylol butyric acid;
the primary amino chain extender comprises one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentanediamine, hexamethylenediamine, isophoronediamine and ethylenediamine sodium ethanesulfonate.
5. The method according to claim 3 or 4, wherein the ratio of the amount of the hydroxyl group-containing substance in the polyglycol, the amount of the hydroxyl group-containing substance in the dimethylol carboxylic acid, the amount of the isocyanate-containing substance in the diisocyanate, the amount of the primary amino group-containing substance in the bridged azobenzene, the amount of the primary amino group-containing substance in the aminofluorescein, and the amount of the primary amino group-containing substance in the chain extender is 0.2 to 0.4:0.2 to 0.3:1:0.002 to 0.1:0.002 to 0.1:0.1 to 0.3.
6. The method according to claim 3, wherein the first polymerization step further comprises adding a ketone solvent to adjust the viscosity of the reaction system.
7. The method according to claim 3 or 6, wherein the temperature of the first polymerization step is 75 to 85 ℃ and the time is 3.5 to 5.5 hours;
the temperature of the second polymerization reaction is 10-25 ℃ and the time is 0.2-1 h;
the temperature of the addition reaction is 10-25 ℃ and the time is 0.2-1 h;
the temperature of the chain extension reaction is 10-25 ℃ and the time is 0.5-2 h.
8. The application of the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence according to claim 1 or 2 or the aqueous polyurethane with visible light color change and ultraviolet light excited fluorescence prepared by the preparation method according to any one of claims 3 to 7 in anti-counterfeiting ink.
9. An anti-counterfeiting ink comprises the following components in percentage by mass:
the aqueous polyurethane comprises the aqueous polyurethane with visible light color change and ultraviolet light fluorescence excitation according to the claims 1 or 2 or the aqueous polyurethane with visible light color change and ultraviolet light fluorescence excitation prepared by the preparation method according to any one of the claims 3-7.
10. The anti-counterfeiting ink according to claim 9, wherein the filler is one or more of precipitated white carbon black, activated calcium carbonate and silica micropowder; the mesh number of the filler is more than or equal to 1000 meshes;
the rheological agent is hydroxyethyl cellulose and/or hydrophobic association polyurethane emulsion;
the film forming auxiliary agent is one or more of ethylene glycol butyl ether, propylene glycol methyl ether and propylene glycol butyl ether;
the pH value regulator is one or more of sodium dihydrogen phosphate, sodium bicarbonate, sodium carbonate and sodium phosphate.
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