CN106928774A - A kind of ageing-resistant Antiforge fluorescent ink and preparation method thereof - Google Patents

A kind of ageing-resistant Antiforge fluorescent ink and preparation method thereof Download PDF

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Publication number
CN106928774A
CN106928774A CN201710214325.3A CN201710214325A CN106928774A CN 106928774 A CN106928774 A CN 106928774A CN 201710214325 A CN201710214325 A CN 201710214325A CN 106928774 A CN106928774 A CN 106928774A
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ageing
resistant
phenyl
polynary
oil
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Inventor
姚瑞刚
王永捷
赵丽容
王秋菊
屈先立
张海涛
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BEIJING JINCHEN CICCONE SECURITY PRINTING Co Ltd
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BEIJING JINCHEN CICCONE SECURITY PRINTING Co Ltd
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Priority to CN201710214325.3A priority Critical patent/CN106928774A/en
Publication of CN106928774A publication Critical patent/CN106928774A/en
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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
    • 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
    • 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
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/02—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
    • 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
    • C09D11/02—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
    • C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
    • 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
    • C09D11/02—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
    • C09D11/104—Polyesters
    • 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
    • C09D11/02—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
    • C09D11/104—Polyesters
    • C09D11/105—Alkyd resins
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention provides a kind of ageing-resistant Antiforge fluorescent ink and preparation method thereof.Methods described includes ageing-resistant fluorescent material, pigment, binder, diluent, filler and auxiliary agent, and the weight proportion of each composition is in the anti-forgery ink：The ageing-resistant fluorescent material includes the ligand complex of europium 4 and polymer binder dielectric material with logical formula (I)；In the logical formula (I), RE is the compound rare-earth metal cation being made up of rare earth metal cations europium, and L is the beta diketone anion with logical formula (II), and Z is 1,10 quinoline Féraud beautiful jades, the L and the Z are complexed with molecular forms with the RE；The ageing-resistant fluorescent composition has ageing-resistant performance, and red fluorescence is produced under the irradiation that daylight, wavelength are 200~400nm ultraviolet lights or Ultra-Violet Laser；Z(RE)L4 (I)

Description

A kind of ageing-resistant Antiforge fluorescent ink and preparation method thereof
Technical field
The invention belongs to anti-counterfeiting printing technology field, more particularly to a kind of ageing-resistant Antiforge fluorescent ink, and one kind The preparation method of ageing-resistant Antiforge fluorescent ink.
Background technology
Fluorescein anti-forgery ink is had been widely used in various invoices, Hongkong and Macro's pass, passport, banknote, identity card, credit In the aspects such as card, lottery ticket, existing fluorescein anti-forgery ink has that ageing-resistant performance is low, light shine, the disadvantage of high temperature resistant difference, Often fluorescent weakening or it is wholly absent in a short period of time during use, the antiforge function to anti-fake product brings hidden danger, Therefore, strengthen the anti-fraud functional stability of anti-fake product and ageing-resistant performance is imperative.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of ageing-resistant Antiforge fluorescent ink and preparation method thereof, with complete Portion or part solve above-mentioned technical problem.
According to an aspect of the invention, there is provided a kind of ageing-resistant Antiforge fluorescent ink, including ageing-resistant fluorescent material, face Material, binder, diluent, filler and auxiliary agent, the weight proportion of each composition is in the anti-forgery ink：
The ageing-resistant fluorescent material includes the ligand complex of europium 4 and polymer binder medium material with logical formula (I) Material；
In the logical formula (I), RE is the compound rare-earth metal cation being made up of rare earth metal cations europium, L be with The beta diketone anion of logical formula (II), Z is 1,10- quinoline Féraud beautiful jades, and the L and the Z are complexed with molecular forms with the RE；
The ageing-resistant fluorescent composition has ageing-resistant performance, is 200~400nm ultraviolet lights or purple in daylight, wavelength Red fluorescence is produced under the irradiation of outer laser；
Z(RE)L4 (I)
Alternatively, according to the detection of standard GB/T/T 17001.1-2011, the light shine of the ageing-resistant fluorescent material and resistance to Heat reaches highest 5 grades.
Alternatively, content of the ligand complex of the europium 4 in the ageing-resistant fluorescent material is 5~20%.
Alternatively, in the L, functional group R is C1-C4 alkyl, phenyl, one of C1-C4 alkyl, unitary or polynary fluorine substitution First or polynary substituted phenyl, furyl, unitary or polynary substituted furyl, thienyl or unitary or polynary substituted thiophene Base；
Functional group R ' is C1-C4 alkyl, phenyl, the unitary or polynary substituted of C1-C4 alkyl, unitary or polynary fluorine substitution Phenyl, furyl, unitary or polynary substituted furyl, thienyl or unitary or polynary substituted thienyl.
Alternatively, the L is the base of trifluoromethyl thiophene-2-beta diketone anion.
Alternatively, the RE is in addition to including europium cation, also including one or more in lanthanum cation and neodymium cation.
Alternatively, the ageing-resistant fluorescent material also includes organic phosphorous oxides.
Alternatively, organic phosphorous oxides include with below formula (III)~oxide of logical formula (VIII) in One or more；
R1R2R3P=O (III)
R1R2(OR3) P=O (IV)
R1(OR2)(OR3) P=O (V)
(OR1)(OR2)(OR3) P=O (VI)
R1(R2O) (OH) P=O (VII)
(R1O)(R2O) (OH) P=O (VIII)
In formula, R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl；
R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl；
R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl.
Alternatively, the polymer binder dielectric material includes polystyrene, polymethyl methacrylate, gathers to benzene two One or more in formic acid class plastics, polypropylene and polyurethane；
The pigment includes one or more in organic pigment and inorganic pigment, the organic pigment include AZOpigments and One or more in phthalein green grass or young crops pigment mordant pigment, the inorganic pigment includes carbon black, barba hispanica, chrome yellow, lithopone, titanium dioxide and gold One or more in category pigment；
The binder includes phenolic resin, alkyd resin, polyvinyl resin, Corvic, polyacrylate tree One or more in fat, polyester resin, polyurethane resin, acrylic resin, epoxy resin and amino resins；
The diluent is included one or more in vegetable oil, mineral oil, deionized water and ultraviolet curing monomer, described Vegetable oil includes at least one of castor oil, coconut oil, peanut oil, tea oil, soya-bean oil and rapeseed oil, and the mineral oil includes vapour At least one of oil, high-boiling point kerosene and lubricating oil, the ultraviolet curing monomer include monofunctional monomer, bifunctionality list At least one of body and polyfunctional monomer；
Described filler is included one or more in calcene, wax and aluminium soap；
The auxiliary agent includes plasticizer, removes stick, drier, diluent, anti-gelatinizing agent, antidesiccant, surfactant, anti- One or more in rotten agent, defoamer, initiator, ultra-violet absorber and wetting dispersing agent.
According to another aspect of the present invention, a kind of preparation method of above-mentioned ageing-resistant Antiforge fluorescent ink is additionally provided, Including：
Mix ageing-resistant fluorescent material, pigment and binder and stir into slurry, less than 15 μm are ground on three-roll grinder, Obtain component 1；
Mixed diluent, filler and auxiliary agent, are ground to less than 15 μm on the three-roll grinder, obtain component 2；
The component 1 and the component 2 are mixed through the three-roll grinder, the ageing-resistant fluorescence falsification preventing oil is obtained Ink.
Compared with prior art, the embodiment of the present invention is studied the component and component structure of fluorescent material, selection 1, 10- quinoline Féraud beautiful jades are used as complex ligands, the presence based on 1,10- quinoline Féraud beautiful jades so that by 1,10- quinoline Féraud beautiful jade, europium sun from The complex compound of son and beta diketone anion composition has the ageing-resistant performances such as preferable fast light, heat-resisting, moisture-proof, correspondingly by the network Compound mixes with other components, and the anti-forgery ink for obtaining also has preferable ageing-resistant performance and stability, expands false proof oil The scope of application of ink, effectively extends the service life of anti-forgery ink.
Meanwhile, ageing-resistant Antiforge fluorescent ink provided in an embodiment of the present invention has red fluorescence performance, in daylight, wavelength To produce red fluorescence, therefore the anti-forgery ink of gained also to have accordingly under the irradiation of 200~400nm ultraviolet lights or Ultra-Violet Laser Red fluorescence performance.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of a kind of ageing-resistant Antiforge fluorescent ink described in the embodiment of the present invention；
Fig. 2 is the fluorescence emission spectrogram of compound of a kind of ageing-resistant fluorescent material described in the embodiment of the present invention.
Specific embodiment
It is below in conjunction with the accompanying drawings and specific real to enable the above objects, features and advantages of the present invention more obvious understandable The present invention is further detailed explanation to apply mode.
Flow is described in detail to be realized to the method for the invention below by embodiment.
The embodiment of the invention provides a kind of ageing-resistant Antiforge fluorescent ink, including ageing-resistant fluorescent material, pigment, connection Material, diluent, filler and auxiliary agent, the weight proportion of each composition is in the anti-forgery ink：
The ageing-resistant fluorescent material includes the ligand complex of europium 4 and polymer binder medium material with logical formula (I) Material；
In the logical formula (I), RE is the compound rare-earth metal cation being made up of rare earth metal cations europium, L be with The beta diketone anion of logical formula (II), Z is 1,10- quinoline Féraud beautiful jades, and the L and the Z are complexed with molecular forms with the RE；
The ageing-resistant fluorescent composition has ageing-resistant performance, is 200~400nm ultraviolet lights or purple in daylight, wavelength Red fluorescence is produced under the irradiation of outer laser；
Z(RE)L4 (I)
The embodiment of the present invention is studied the component and component structure of fluorescent material, selects 1,10- quinoline Féraud beautiful jade conducts Complex ligands, the presence based on 1,10- quinoline Féraud beautiful jades so that by 1,10- quinoline Féraud beautiful jade, europium cation and beta diketone anion The complex compound of composition has the ageing-resistant performances such as preferable heat-resisting, moisture-proof, correspondingly mixes the complex compound with other components, obtains The anti-forgery ink for arriving also has preferable ageing-resistant performance and stability, expands the scope of application of anti-forgery ink, effectively extension The service life of anti-forgery ink.
Research finds that ageing-resistant Antiforge fluorescent ink provided in an embodiment of the present invention has red fluorescence performance, daylight, Wavelength be 200~400nm ultraviolet lights or Ultra-Violet Laser irradiation under produce the red fluorescence, therefore the anti-forgery ink of gained also to have Corresponding red fluorescence performance.
Above-mentioned ageing-resistant fluorescent material can be dissolved in organic solvent, obtain mixture, gained mixture can be used for Coating of objects, forms the fluorescence film with ageing-resistant performance and red fluorescence performance；Can also will be above-mentioned ageing-resistant glimmering Light powder is dispersed in high polymer or the copolymer with coordination ability, and the red fluorescence material with ageing-resistant performance is obtained.
Specifically, the organic solvent that can will be dissolved with above-mentioned ageing-resistant fluorescent material is attached to body surface, after drying To fluorescence film, the fluorescence film has ageing-resistant performance and under the ultraviolet light or UV light of 200~400nm Produce the performance of red fluorescence.
The organic solvent and non-water flow dynamic material mixing of above-mentioned ageing-resistant fluorescent material can will be dissolved with, for coating, Paint, plastics, fabric, press or fine arts field, the mixture of gained have ageing-resistant performance and 200~ The performance of red fluorescence is produced under the ultraviolet light or UV light of 400nm, preferably in the ultraviolet light or purple of 350~370nm The performance of the outer lower generation red fluorescence of laser irradiation.
The color of anti-forgery ink by controlling the component colors of other components in anti-forgery ink, can be made close to colourless, from And suitable for being used at the aspects such as various invoices, Hongkong and Macro's pass, passport, banknote, identity card, credit card, lottery ticket, printing is each The class sightless invisible-bar-number of naked eyes and picture and text, it is disguised strong, can effectively prevent from duplicating, counterfeit, identification is simple, resistance to ag(e)ing It is strong to be easy to promote.
The organic solvent that can will be dissolved with above-mentioned ageing-resistant fluorescent material mixes with pulverulent solids or solia particle, removes Solvent, forms powdered or microgranular composite fluorescent material, and resulting materials can be used for the interior/exterior decoration of construction industry, or In plastic products.Further, it is possible to the composite fluorescent material of gained is made into solid powder use, or added to solid or semi-fluid Used in dynamic property material, be such as used for luminescence display or as distinctive mark material.
Dissolve above-mentioned ageing-resistant fluorescent material organic solvent can include aromatic hydrocarbons, alkane, halogenated alkane, esters, alcohols and One or more in tetrahydrofuran.
Due to ageing-resistant fluorescent material provided in an embodiment of the present invention and the mixing material being made from it, in the purple of certain wavelength Under outer light or UV light, fluorescence can be all sent, and with preferable ageing-resistant performance, therefore the ageing-resistant fluorescent material tool There is application prospect widely, really convert uv light into visible ray, therefore can be widely used in luminous energy conversion.
Preferably, according to standard GB/T/T 17001.1-2011 detections, the light shine of the ageing-resistant fluorescent composition 5 grades of the superlative degree is reached with heat-resisting.
Preferably, in above-mentioned ageing-resistant fluorescent material, the ligand complex of the europium 4 containing in the ageing-resistant fluorescent material Measure is 5~20%.Under matching herein, the ageing-resistant fluorescent material of gained has the preferably performance such as heat-resisting and fast light.
Preferably, lead to formula (I) in, functional group R be C1-C4 alkyl, unitary or polynary fluorine substitution C1-C4 alkyl, phenyl, Unitary or polynary substituted phenyl, furyl, unitary or polynary substituted furyl, thienyl or unitary or polynary substituted thiophene Fen base.
Functional group R ' is C1-C4 alkyl, phenyl, the unitary or polynary substituted of C1-C4 alkyl, unitary or polynary fluorine substitution Phenyl, furyl, unitary or polynary substituted furyl, thienyl or unitary or polynary substituted thienyl.
Wherein, functional group R can be with identical with functional group R ', it is also possible to different.
Preferably, lead in formula (I), L is the base of trifluoromethyl thiophene-2-beta diketone anion.
Preferably, lead in formula (I), RE in addition to including europium cation, also including a kind of in lanthanum cation and neodymium cation or It is various.
Preferably, ageing-resistant fluorescent material provided in an embodiment of the present invention also includes organic phosphorous oxides.Organic phosphorus oxygen Content of the compound in ageing-resistant fluorescent material is preferably 0~6%.
Further, organic phosphorous oxides can include with below formula (III)~oxide of logical formula (VIII) in One or more；
R1R2R3P=O (III)
R1R2(OR3) P=O (IV)
R1(OR2)(OR3) P=O (V)
(OR1)(OR2)(OR3) P=O (VI)
R1(R2O) (OH) P=O (VII)
(R1O)(R2O) (OH) P=O (VIII)
In formula, R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl；
R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl；
R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl.
Wherein, R1With R2With R3Can be with identical, it is also possible to different.
Research finds that organic phosphorous oxides is added in fluorescent material can be effectively increased the luminous efficiency of fluorescent material, improves Fluorescent material performance.
Preferably, polymer binder dielectric material includes polystyrene, polymethyl methacrylate, poly terephthalic acid One or more in class plastics, polypropylene and polyurethane.
Preferably, the pigment includes that one or more in organic pigment and inorganic pigment, the organic pigment includes even One or more in nitrogen pigment and phthalein green grass or young crops pigment mordant pigment, the inorganic pigment includes carbon black, barba hispanica, chrome yellow, lithopone, titanium One or more in white powder and metallic pigments.
Preferably, the binder includes phenolic resin, alkyd resin, polyvinyl resin, Corvic, polypropylene One or more in acid ester resin, polyester resin, polyurethane resin, acrylic resin, epoxy resin and amino resins.
Preferably, the diluent includes one kind or many in vegetable oil, mineral oil, deionized water and ultraviolet curing monomer Kind.
Preferably, the vegetable oil includes one kind or many in castor oil, coconut oil, peanut oil, tea oil, soya-bean oil and rapeseed oil Kind.
Preferably, the mineral oil is included one or more in gasoline, high-boiling point kerosene and lubricating oil.
Preferably, the ultraviolet curing monomer includes monofunctional monomer, bifunctionality monomer and polyfunctional monomer At least one of.
Ultraviolet curing monomer in UV curing systems is mainly used to rheological characteristic, the stream of control system also known as UV diluents The crosslink density of dynamic property and cured film.Select which kind of monomer makees diluent depending on system viscosity drop low degree, curing rate, machine The factors such as tool performance, glass transition temperature, volatility, toxicity, smell and cost.
Being usually used in the monomer of UV curing systems can be divided into following 3 class：1) monofunctional monomer, such as acrylic acid-2-ethyl are Ester (EHA), hydroxy-ethyl acrylate (HEA) etc.；2) bifunctionality monomer, such as hexanediyl ester (HDDA), two three second of contracting Omega-diol diacrylate (TEG-DA), new the eleventh of the twelve Earthly Branches omega-diol diacrylate (NPGDA), tri (propylene glycol) diacrylate (TPGDA) etc.；3) polyfunctional monomer, such as trimethylolpropane trimethacrylate (TMPTA), season the eleventh of the twelve Earthly Branches tetrol triacrylate (PETA) etc..
In UV curing systems, conventional monofunctional monomer is fast to balance solidification with the mixture of difunctionality or polyfunctional monomer Degree, the performance such as crosslink density and pliability.The reactivity of photo-sensitive monomer is usually to be improved with the increase of degree of functionality, official Energy degree is more, and reactivity is bigger, and hardness is high；Conversely, reactivity reduction, pliability raising.Therefore, photonasty is being selected During monomer, be according to the design requirement of product, reasonable selection.
Preferably, described filler is included one or more in calcene, wax and aluminium soap.
Preferably, the auxiliary agent includes plasticizer, diluent, removes stick, drier, diluent, anti-gelatinizing agent, anti-dry One or more in agent, surfactant, preservative, defoamer, initiator, ultra-violet absorber and wetting dispersing agent.
The embodiment of the present invention additionally provides a kind of preparation method of above-mentioned ageing-resistant Antiforge fluorescent ink.Fig. 1 is this hair The flow chart of the preparation method of a kind of ageing-resistant Antiforge fluorescent ink described in bright embodiment, reference picture 1, methods described includes：
Step 101, the ageing-resistant fluorescent material of mixing, pigment and binder simultaneously stir into slurry, are ground on three-roll grinder Less than 15 μm, obtain component 1.
Step 102, mixed diluent, filler and auxiliary agent, are ground to less than 15 μm on three-roll grinder, obtain component 2.
Step 103, component 1 and component 2 are mixed through three-roll grinder, ageing-resistant Antiforge fluorescent ink is obtained.
Ageing-resistant Antiforge fluorescent ink provided in an embodiment of the present invention can be obtained according to the method described above.For preparation process In each material selection and material ratio, can refer to the above, the embodiment of the present invention will not be described here.
To make those skilled in the art more fully understand the present invention, this hair is illustrated below by way of multiple specific embodiments The ageing-resistant Antiforge fluorescent ink of bright embodiment.
Embodiment 1
The component and component ratio of ageing-resistant fluorescein Offset print anti-forgery ink are as follows：
Ageing-resistant fluorescent material is by polypropylene and the ligand complex Phen (Eu of europium 4 with logical formula (I)0.8Nd0.2) (TTA)4It is mixed to prepare, wherein polypropylene and Phen (Eu0.8Nd0.2)(TTA)4Weight ratio be 50:3.
The preparation of ageing-resistant fluorescein Offset print anti-forgery ink：
After above-mentioned substance is proportionally weighed, 30min is stirred in mixing tank, then rolled on three-roll grinder System grinding, detection particle size is 35~45 μm, and dress iron flask makes and finishes.
The present embodiment has carried out fluorometric investigation to the ageing-resistant fluorescent material for obtaining, and test result is as shown in Figure 1.In Fig. 1, Under the ultraviolet light of wavelength 200-400nm, preferably under the ultraviolet light of wavelength 365nm, this kind of ageing-resistant fluorescent material exists Strong, bright-coloured red fluorescence is produced at 613nm.
Ageing-resistant performance of the embodiment of the present invention also to the anti-forgery ink of gained is tested.National anti-fake product instruction Supervisory detection center is to the ageing-resistant red Offset print anti-forgery ink of colorless fluorescent provided in an embodiment of the present invention and common colorless fluorescent Red Offset print anti-forgery ink carries out contrasting detection, test basis《Anti-counterfeiting technology production licensing detailed rules for the implementation (three) (anti-forged bill Card product section) annex 6》I.e.《False-proof ticket technical conditions》It is required that, press《GB/T 17001.1-2011 anti-forgery inks the 1st Point：Ultraviolet excited fluorescence anti-forgery ink》Detection, weatherability test instrument is placed in by sample, and irradiating 8h with 5kw xenon lamps takes out, and picks up survey Change in fluorescence, the ageing-resistant performance of existing common sample is 3 grades, fluorescence significant change decline, and the embodiment of the present invention is provided The ageing-resistant performance of product reach 5 grades, fluorescence is not changed in, and illustrates that the resistance to ag(e)ing of the product is strong.
Embodiment 2
Ageing-resistant fluorescein water-base gravure anti-forgery ink component and component ratio are as follows:
Ageing-resistant fluorescent material is by polypropylene and the ligand complex Phen (Eu of europium 4 with logical formula (I)0.9La0.1) (TTA)4It is mixed to prepare, wherein polypropylene and Phen (Eu0.9La0.1)(TTA)4Weight ratio be 4:1.
The preparation of ageing-resistant fluorescein water-base gravure anti-forgery ink：
The specific production process of ageing-resistant fluorescein water-base gravure anti-forgery ink is as follows：Every batch of production anti-forgery ink 20 is public Jin, loads ball mill grinding and processes in above recipe ingredient ratio, and Ball-milling Time is more than 24h, and detection particle size is 10~25 μ M, packing making is finished.
Embodiment 3
The component and component ratio of ageing-resistant fluorescein Offset print anti-forgery ink are as follows：
Ageing-resistant fluorescent material is by polystyrene, the ligand complex Phen (Eu of europium 4 with logical formula (I)0.7Nd0.3) (TTA)4And Triphenylphospine oxide is mixed to prepare, wherein polystyrene, Phen (Eu0.7Nd0.3)(TTA)4With Triphenylphospine oxide Weight ratio be 94:5:1.
The preparation of ageing-resistant fluorescein Offset print anti-forgery ink：
After above-mentioned substance is proportionally weighed, 30min is stirred in mixing tank, then rolled on three-roll grinder System grinding, detection particle size is 35~45 μm, and dress iron flask makes and finishes.
Embodiment 4
Ageing-resistant fluorescein UV Offset print anti-forgery inks component and component ratio are as follows：
Ageing-resistant fluorescent material is by polystyrene and the ligand complex Phen (Eu of europium 4 with logical formula (I)0.9La0.1) (TTA)4It is mixed to prepare, wherein polystyrene and Phen (Eu0.9La0.1)(TTA)4Weight ratio be 9:1.
The preparation of ageing-resistant fluorescein UV Offset print anti-forgery inks：
After above-mentioned substance is proportionally weighed, 30min is stirred in mixing tank, then rolled on three-roll grinder System grinding, detection particle size is 35~45 μm, and dress iron flask makes and finishes.
Above to a kind of ageing-resistant Antiforge fluorescent ink provided by the present invention and a kind of ageing-resistant Antiforge fluorescent ink Preparation method be described in detail, specific case used herein is explained principle of the invention and implementation method State, the explanation of above example is only intended to help and understands the method for the present invention and its core concept；Simultaneously for this area Those skilled in the art, according to thought of the invention, will change in specific embodiments and applications, to sum up institute State, this specification content should not be construed as limiting the invention.

Claims (10)

1. a kind of ageing-resistant Antiforge fluorescent ink, it is characterised in that including ageing-resistant fluorescent material, pigment, binder, diluent, Filler and auxiliary agent, the weight proportion of each composition is in the anti-forgery ink：
The ageing-resistant fluorescent material includes the ligand complex of europium 4 and polymer binder dielectric material with logical formula (I)；
In the logical formula (I), RE is the compound rare-earth metal cation being made up of rare earth metal cations europium, and L is with formula (II) beta diketone anion, Z is 1,10- quinoline Féraud beautiful jades, and the L and the Z are complexed with molecular forms with the RE；
The ageing-resistant fluorescent composition has ageing-resistant performance, is 200~400nm ultraviolet lights or ultraviolet sharp in daylight, wavelength Red fluorescence is produced under the irradiation of light；
Z(RE)L4 (I)
2. anti-forgery ink according to claim 1, it is characterised in that according to standard GB/T/T17001.1-2011 inspections Survey, the light shine of the ageing-resistant fluorescent material and heat-resisting reach highest 5 grades.
3. anti-forgery ink according to claim 1, it is characterised in that the ligand complex of the europium 4 is described ageing-resistant glimmering Content in light powder is 5~20%.
4. anti-forgery ink according to claim 1, it is characterised in that in the L, functional group R is C1-C4 alkyl, unitary Or C1-C4 alkyl, phenyl, unitary or polynary substituted phenyl, furyl, unitary or the polynary substituted furans that polynary fluorine replaces Base, thienyl or unitary or polynary substituted thienyl；
Functional group R ' is C1-C4 alkyl, phenyl, unitary or the polynary substituted benzene of C1-C4 alkyl, unitary or polynary fluorine substitution Base, furyl, unitary or polynary substituted furyl, thienyl or unitary or polynary substituted thienyl.
5. anti-forgery ink according to claim 4, it is characterised in that the L is the cloudy base of trifluoromethyl thiophene-2-beta diketone Ion.
6. anti-forgery ink according to claim 1, it is characterised in that the RE in addition to including europium cation, also including lanthanum One or more in cation and neodymium cation.
7. anti-forgery ink according to claim 1, it is characterised in that the ageing-resistant fluorescent material also includes organic phosphorus oxidation Thing.
8. anti-forgery ink according to claim 7, it is characterised in that organic phosphorous oxides includes thering is below formula (III) one or more in the oxide of~logical formula (VIII)；
R1R2R3P=O (III)
R1R2(OR3) P=O (IV)
R1(OR2)(OR3) P=O (V)
(OR1)(OR2)(OR3) P=O (VI)
R1(R2O) (OH) P=O (VII)
(R1O)(R2O) (OH) P=O (VIII)
In formula, R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl；
R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl；
R1It is C1-C4 alkyl, phenyl, mono-substituted benzenes base or polynary substituted-phenyl.
9. anti-forgery ink according to claim 1, it is characterised in that：
The polymer binder dielectric material include polystyrene, polymethyl methacrylate, poly terephthalic acid class plastics, One or more in polypropylene and polyurethane；
The pigment includes one or more in organic pigment and inorganic pigment that the organic pigment includes that AZOpigments and phthalein are blue or green One or more in pigment mordant pigment, the inorganic pigment includes carbon black, barba hispanica, chrome yellow, lithopone, titanium dioxide and metal face One or more in material；
The binder includes phenolic resin, alkyd resin, polyvinyl resin, Corvic, polyacrylate resin, poly- One or more in ester resin, polyurethane resin, acrylic resin, epoxy resin and amino resins；
The diluent includes one or more, the plant in vegetable oil, mineral oil, deionized water and ultraviolet curing monomer Oil includes at least one of castor oil, coconut oil, peanut oil, tea oil, soya-bean oil and rapeseed oil, and the mineral oil includes gasoline, height At least one of boiling point kerosene and lubricating oil, the ultraviolet curing monomer include monofunctional monomer, bifunctionality monomer and At least one of polyfunctional monomer；
Described filler is included one or more in calcene, wax and aluminium soap；
The auxiliary agent includes plasticizer, removes stick, drier, diluent, anti-gelatinizing agent, antidesiccant, surfactant, anti-corrosion One or more in agent, defoamer, initiator, ultra-violet absorber and wetting dispersing agent.
10. the preparation method of a kind of ageing-resistant Antiforge fluorescent ink as described in claim any one of 1-9, it is characterised in that Including：
Mix ageing-resistant fluorescent material, pigment and binder and stir into slurry, less than 15 μm are ground on three-roll grinder, obtain Component 1；
Mixed diluent, filler and auxiliary agent, are ground to less than 15 μm on the three-roll grinder, obtain component 2；
The component 1 and the component 2 are mixed through the three-roll grinder, the ageing-resistant Antiforge fluorescent ink is obtained.
CN201710214325.3A 2017-04-01 2017-04-01 A kind of ageing-resistant Antiforge fluorescent ink and preparation method thereof Pending CN106928774A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108229983A (en) * 2018-02-06 2018-06-29 佛山市南方数据科学研究院 A kind of invisible two dimensional barcode anti-counterfeiting system
CN108912841A (en) * 2018-07-17 2018-11-30 芜湖倍思科创园有限公司 A kind of fluorescent ink and preparation method thereof
CN108948866A (en) * 2018-08-07 2018-12-07 长春吉星印务有限责任公司 One kind becoming special printing inks and preparation method thereof for the aqueous light of intaglio plate green
CN109206973A (en) * 2018-09-03 2019-01-15 安庆市航海印务有限公司 A kind of paper products printing ink
CN109825130A (en) * 2019-01-16 2019-05-31 广东轻工职业技术学院 A kind of multiple response type fluorescent ink and preparation method
CN110452580A (en) * 2019-07-29 2019-11-15 北京金辰西维科安全印务有限公司 A kind of anti-forgery ink and preparation method thereof with particular spectral lines feature
CN113004884A (en) * 2021-03-01 2021-06-22 广东美纳防伪科技有限公司 Invisible anti-counterfeiting material composition, preparation process and application thereof
CN113150339A (en) * 2021-04-22 2021-07-23 大连工业大学 SrSi2O2N2Preparation method and application of green light information storage fluorescent film
CN113580797A (en) * 2021-07-16 2021-11-02 硕包科技(扬州)有限公司 Film multilayer three-dimensional pattern anti-counterfeiting printing process with prism refraction function

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062917A (en) * 1990-12-30 1992-07-22 北京大学 A kind of rare-earth fluorescent composition and uses thereof
CN1737068A (en) * 2005-07-28 2006-02-22 中国印钞造币总公司 Black fluorescent ink
CN103254337A (en) * 2013-05-07 2013-08-21 常州大学 Beta-diketone rare earth complex and preparation method thereof
CN106479480A (en) * 2015-08-28 2017-03-08 中国科学院长春光学精密机械与物理研究所 A kind of Nano microsphere preparation method with core/shell type composite construction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062917A (en) * 1990-12-30 1992-07-22 北京大学 A kind of rare-earth fluorescent composition and uses thereof
CN1737068A (en) * 2005-07-28 2006-02-22 中国印钞造币总公司 Black fluorescent ink
CN103254337A (en) * 2013-05-07 2013-08-21 常州大学 Beta-diketone rare earth complex and preparation method thereof
CN106479480A (en) * 2015-08-28 2017-03-08 中国科学院长春光学精密机械与物理研究所 A kind of Nano microsphere preparation method with core/shell type composite construction

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108229983A (en) * 2018-02-06 2018-06-29 佛山市南方数据科学研究院 A kind of invisible two dimensional barcode anti-counterfeiting system
CN108912841A (en) * 2018-07-17 2018-11-30 芜湖倍思科创园有限公司 A kind of fluorescent ink and preparation method thereof
CN108948866A (en) * 2018-08-07 2018-12-07 长春吉星印务有限责任公司 One kind becoming special printing inks and preparation method thereof for the aqueous light of intaglio plate green
CN109206973A (en) * 2018-09-03 2019-01-15 安庆市航海印务有限公司 A kind of paper products printing ink
CN109825130A (en) * 2019-01-16 2019-05-31 广东轻工职业技术学院 A kind of multiple response type fluorescent ink and preparation method
WO2020147632A1 (en) * 2019-01-16 2020-07-23 广东轻工职业技术学院 Multiple-response fluorescent ink and preparation method
CN110452580A (en) * 2019-07-29 2019-11-15 北京金辰西维科安全印务有限公司 A kind of anti-forgery ink and preparation method thereof with particular spectral lines feature
CN113004884A (en) * 2021-03-01 2021-06-22 广东美纳防伪科技有限公司 Invisible anti-counterfeiting material composition, preparation process and application thereof
CN113004884B (en) * 2021-03-01 2021-09-28 广东美纳防伪科技有限公司 Invisible anti-counterfeiting material composition, preparation process and application thereof
CN113150339A (en) * 2021-04-22 2021-07-23 大连工业大学 SrSi2O2N2Preparation method and application of green light information storage fluorescent film
CN113580797A (en) * 2021-07-16 2021-11-02 硕包科技(扬州)有限公司 Film multilayer three-dimensional pattern anti-counterfeiting printing process with prism refraction function
CN113580797B (en) * 2021-07-16 2023-03-07 硕包科技(扬州)有限公司 Film multilayer three-dimensional pattern anti-counterfeiting printing process with prism refraction function

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