CN108660852B - Preparation method of stress-induced paper anti-counterfeiting coating and product thereof - Google Patents

Preparation method of stress-induced paper anti-counterfeiting coating and product thereof Download PDF

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CN108660852B
CN108660852B CN201810378753.4A CN201810378753A CN108660852B CN 108660852 B CN108660852 B CN 108660852B CN 201810378753 A CN201810378753 A CN 201810378753A CN 108660852 B CN108660852 B CN 108660852B
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stress
water
paper
asa
counterfeiting
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CN108660852A (en
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于得海
王慧丽
侯夫庆
戴仁刚
崔杰东
王肖肖
郭文艳
刘温霞
李国栋
宋兆萍
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LIAONING XINGDONG TECHNOLOGY Co.,Ltd.
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Qilu University of Technology
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46—Non-macromolecular organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46—Non-macromolecular organic compounds
    • D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)

Abstract

The invention provides a preparation method of a stress induction type paper anti-counterfeiting coating, which comprises the following steps: (1) adding HAuCl4Dissolving PVP-DADMAN in water, boiling, adding a reducing agent, stirring in the dark for reaction, centrifuging, and drying the supernatant in vacuum to obtain modified gold nanoparticles; (2) PEOS was diluted in ASA as the oil phase; dissolving the modified nano-gold prepared in the step (1) in water, and adjusting the pH to be acidic to be used as a water phase; and ultrasonically stirring the water phase and the oil phase under the heating condition, and standing to obtain an oil-in-water ASA Pickering emulsion, namely the stress-induced anti-counterfeiting paper coating. The invention can obtain the stable oil-in-water ASA Pickering emulsion, can effectively reduce coalescence among ASA oil drops, greatly improves the stability of the emulsion, stabilizes the emulsion for months, separates out an anhydrous phase and an oil phase, and does not need to add any surfactant or other modifiers.

Description

Preparation method of stress-induced paper anti-counterfeiting coating and product thereof
Technical Field
The invention belongs to the field of application of nano materials in papermaking, and particularly relates to a preparation technology of a stress-induced Alkenyl Succinic Anhydride (ASA) paper anti-counterfeiting emulsion.
Background
The anti-counterfeiting coating can be applied to commodity packaging and trademark design to prevent products from being damaged by counterfeiting, and provides a powerful means for distinguishing the authenticity of commodities for product producers, consumers and distributors. The application of the anti-counterfeiting coating generally has the following conditions: the color change is reversible, the color change is triggered at normal temperature, and the like, the color change is stable, accurate and bright, and the paint does not contain heavy metals, toxic substances and corrosive acidic and basic substances. The anti-counterfeiting coating cannot be put into the market as a common commodity, and an enterprise generally has monopoly production right or use right for the anti-counterfeiting coating, so that the anti-counterfeiting coating with more varieties and performances is required to be researched to meet the requirements of more different commodities. Generally, anti-counterfeiting coatings developed based on color-changing pigments can only be used for initial application and functions, but the development direction of the anti-counterfeiting coatings and anti-counterfeiting agents is to use anti-counterfeiting ink which can change color, change temperature and the like along with temperature change, illumination intensity, pH change, magnetic field change or other change factors to cause induction characteristics, and the anti-counterfeiting ink is used for printing trademarks, specifications and the like of products. The color change of the prior anti-counterfeiting coating is closely related to the environmental humidity, and under the condition of very low humidity, the coating can lose crystal water and change color even if not heated. When the environmental humidity is high, the crystal water may be lost at a high temperature to show the color change, and at present, the coating film is generally closed in order to prevent the influence of the environmental humidity. There is a need for hydrophobic anti-counterfeit coating preparation technology to compensate for this limitation.
Disclosure of Invention
Aiming at the problems of large influence of the current environmental humidity on the anti-counterfeiting coating and the like, the invention provides a preparation method of a stress-induced Alkenyl Succinic Anhydride (ASA) anti-counterfeiting coating, which does not need to add other surfactants, and the obtained anti-counterfeiting coating has good stability to the humidity.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a stress-induced paper anti-counterfeiting coating comprises the following steps:
(1) adding HAuCl4Dissolving (tetrachloroauric acid) and PVP-DADMAN (poly (diallyl dimethyl-ammonium nitrate) vinyl pyrrolidone) in water, boiling, adding a reducing agent, stirring for reaction in the dark, centrifuging, and drying the supernatant in vacuum to obtain modified gold nanoparticles;
(2) PEOS (polyethoxysiloxane) was diluted in ASA (alkenyl succinic anhydride) as the oil phase; dissolving the modified nano-gold prepared in the step (1) in water, and adjusting the pH to be acidic to be used as a water phase; and ultrasonically stirring the water phase and the oil phase under the heating condition, and standing to obtain an oil-in-water ASA Pickering emulsion, namely the stress-induced anti-counterfeiting paper coating.
The weight average molecular weight M of the PVP-DADMANwFrom 55 to 68kg/mol, more preferably 60 kg/mol.
The HAuCl4And PVP-DADMAN at a mass ratio of 60:1 to 20:1, preferably 35: 1. The HAuCl4Is preferably 1 × 10-2-1×10-4M, more preferably 3 × 10-3M, the concentration of PVP-DADMAN is preferably 1 × 10-7-1×10-5M, more preferably 6 × 10-6M。
The reducing agent is selected from ascorbic acid or thiourea; ascorbic acid is preferred.
The HAuCl4The mass ratio of the reducing agent to the reducing agent is 3:1-1:5, preferably 1: 2.
In the step (1), the boiling time is 1 h; the temperature of the reduction reaction is 98 ℃, and the reaction time is 1 h; the centrifugation speed is 5000-.
In the step (1), the modified nano gold particles are in a shape of a nearly hexagon; the average particle diameter is 15 to 65nm, preferably 30 to 45 nm.
The weight average molecular weight M of the PEOSwIs 1 to 3kg/mol, more preferably 1.3 kg/mol.
In the step (2), the mass ratio of the PEOS to the ASA is 1:3-1: 10; more preferably 1: 6.
In the step (2), the mass ratio of the PEOS to the modified nano-gold is 1:2-5:1, preferably 2: 1.
In the step (2), the mass percentage concentration of the modified nano-gold solution is 0.4-1.2%.
In the step (2), the pH is 1-4; preferably 2. The acid for adjusting the pH can be inorganic acid or organic acid; preferably selected from hydrochloric acid or citric acid.
In the step (2), the volume ratio of the oil phase to the water phase is 1:5-1:1, preferably 1: 2. Mixing the oil phase with the water phase can be adding the water phase into the oil phase or adding the oil phase into the water phase; preferably, the aqueous phase is added to the oil phase.
In the step (2), the heating temperature is 65-80 ℃; preferably 70 deg.c. The standing time is 2-5 days.
A paper prepared by adopting the stress induction type paper anti-counterfeiting coating.
In the invention, PVP-DADMAN and HAuCl are used4Carrying out reduction reaction to graft the diallyl dimethyl-ammonium nitrate long skeleton on the surface of the nanogold, and modifying the nanogold to improve the lipophilicity of the nanogold; then the modified nano-gold is embedded by PEOS, so that the oleophylic property of the modified nano-gold is further improved, and the modified nano-gold can further be compatible with ASA. The PEOS embedded modified nanogold charge repulsion is reduced by adjusting the pH value, compact and stable bulk emulsifier particles are formed, ASA is wrapped, and stable Pickering emulsion is formed.
The invention has the following advantages:
the invention can effectively improve the lipophilicity of the gold nanoparticles by the diallyl dimethyl-ammonium nitrate long skeleton grafting and PEOS embedding in PVP-DADMAN; the Pickering emulsion obtained has a three-phase contact angle close to 90 degrees and a zeta potential of about 0; the stable oil-in-water ASA Pickering emulsion is obtained, coalescence among ASA oil drops can be effectively reduced, the emulsion stability is greatly improved, an anhydrous phase and an oil phase are separated out after the emulsion is stable for months, any surfactant and other modifiers do not need to be added, and the method is simple in steps and easy to operate.
Drawings
FIG. 1 is a transmission electron microscope image of modified gold nanoparticles;
FIG. 2 is a Pickering emulsion microscope picture of ASA.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Example 1
(1) 60 parts by weight of HAuCl4And 1 part by weight of MwPVP-DADMAN was dissolved in water at 68kg/mol to give a concentration of 1 × 10-2HAuCl of M4Solution and concentration of 5 × 10-6Mixing solutions of PVP-DADMAN of M, boiling for 1h, adding 50 parts by weight of ascorbic acid, stirring in a dark place at 98 ℃ for reaction for 1h, and centrifuging at 8000rpm for 15min to obtain a supernatant; drying the supernatant in vacuum to obtain modified nano gold particles with the average particle size of 65 nm;
(2) 1 part by weight of MwPEOS at 1kg/mol was dissolved in 3 parts by weight of ASA as an oil phase; dispersing 2 parts by weight of the modified nano-gold prepared in the step (1) in water to prepare a solution with the mass percentage concentration of 0.4%, and dropwise adding dilute hydrochloric acid to adjust the pH value to 1 to be used as a water phase; and adding the water phase into the oil phase, wherein the volume ratio of the oil phase to the water phase is 1:5, performing ultrasonic stirring for 15min at room temperature, standing for 2 days to obtain an oil-in-water ASA Pickering emulsion, namely the ASA paper anti-counterfeiting coating, wherein the average particle size of the sizing agent emulsion is 1.8 mu m, and the emulsion is unchanged after being placed for 24h and has good stability.
Sizing paper performance test of ASA paper anti-counterfeiting coating:
hydrophobic anti-counterfeiting performance: the tested paper is prepared by performing surface sizing on the ASA paper anti-counterfeiting coating, wherein the dosage of the sizing agent is 8 per mill (the proportion of ASA to absolutely dry paper pulp, the same below), the surface of the sized paper is light blue, the surface sizing degree is 1427 seconds (GB/T5405-.
Strain-induced anti-counterfeiting performance: stretching induction, namely placing the sizing paper on the surface of transparent glass, clamping the paper by using a pliers, slowly stretching, observing the color change of the sizing paper by using an optical microscope, and gradually changing the color of the film from light blue to pink and finally to red along with the stretching of the paper; the sizing paper is subjected to mechanical force impact induction, wherein the sizing surface of the sizing paper is upward and horizontally spread, 200g of iron blocks are suspended above the sizing paper, free fall is carried out according to different heights and falls onto the sizing paper, the color change of the sizing paper after the sizing paper is impacted by the iron blocks is observed and recorded by an optical microscope, and the impact point positions of the sizing paper impacted by the iron blocks respectively show light blue, pink, light purple and red changes along with the gradual rise of the falling height of the iron blocks; perforation response, paper that carries out the mechanical force to ASA paper anti-counterfeit paint glueing with paper hole puncher and punches, and the bore hole is observed to the bore hole, can see glueing paper perforation edge and can demonstrate different colours, and the colour change by far away and near apart from the hole edge does: light blue, light pink, light purple, and red.
The sizing paper of the ASA paper anti-counterfeiting coating has obvious hydrophobic and strain induction properties, can distinguish obvious color change by naked eyes, and has good anti-counterfeiting property.
Example 2
(1) 55 parts by weight of HAuCl4And 1 part by weight of MwPVP-DADMAN was dissolved in water at 68kg/mol to give a concentration of 1 × 10-2HAuCl of M4Solution and concentration of 5 × 10-6Mixing solutions of PVP-DADMAN of M, boiling for 1h, adding 70 parts by weight of ascorbic acid, stirring in a dark place at 98 ℃ for reacting for 1h, centrifuging for 15min at 10000rpm to obtain supernatant, and obtaining a TEM picture of the supernatant as shown in figure 1; drying the supernatant in vacuum to obtain modified nano gold particles with the average particle size of 40 nm;
(2) 2 parts by weight of MwPEOS at 1kg/mol was dissolved in 12 parts by weight of ASA as an oil phase; dispersing 2 parts by weight of the modified nano-gold prepared in the step (1) in water to prepare a solution with the mass percentage concentration of 0.8%, and dropwise adding dilute hydrochloric acid to adjust the pH value to 2 to be used as a water phase; adding the aqueous phase to the oil phase, the oil phase and the aqueous phaseThe volume ratio of the ASA powder to the ASA powder is 1:2, ultrasonic stirring is carried out for 15min at room temperature, standing is carried out for 5 days, and then an oil-in-water type ASA Pickering emulsion, namely the ASA paper anti-counterfeiting coating, is obtained, wherein a micrograph is shown in figure 2: the average grain diameter of the sizing agent emulsion is 2 mu m, the emulsion is not changed after being placed for 24h, and the stability is good.
Testing the anti-counterfeiting performance of sizing paper of the ASA paper anti-counterfeiting coating:
hydrophobic anti-counterfeiting performance: the tested paper is prepared by performing surface sizing on the ASA paper anti-counterfeiting coating, wherein the dosage of the sizing agent is 8 per mill, the surface of the sized paper is light blue, the surface sizing degree is 1227 seconds, the contact angle with water is 159 degrees, the paper belongs to a super-hydrophobic surface, and the paper has hydrophobicity.
Strain-induced anti-counterfeiting performance: stretching induction, namely placing the sizing paper on the surface of transparent glass, clamping the paper by using a pliers, slowly stretching, observing the color change of the sizing paper by using an optical microscope, and gradually changing the color of the film from light blue to light pink, light purple and finally red along with the stretching of the paper; the sizing paper is subjected to mechanical force impact induction, wherein the sizing surface of the sizing paper is upward and horizontally spread, 200g of iron blocks are suspended above the sizing paper, free fall is carried out according to different heights and falls onto the sizing paper, the color change of the sizing paper after the sizing paper is impacted by the iron blocks is observed and recorded by an optical microscope, and the impact point positions of the sizing paper impacted by the iron blocks respectively show the change trends of blue, light pink and red along with the gradual rise of the falling height of the iron blocks; perforation response punches (round hole) to the glueing paper with paper puncher, and the bore hole is observed to the bore hole, and glueing paper perforation edge can demonstrate different colours, and the colour change by far away and near apart from the hole edge does: blue, light blue, pink, light purple, and red.
The sizing paper of the ASA paper anti-counterfeiting coating has obvious hydrophobic and strain induction properties, can distinguish obvious color change by naked eyes, and has good anti-counterfeiting property.
Example 3
(1) 20 parts by weight of HAuCl4And 1 part by weight of MwPVP-DADMAN was dissolved in water at 68kg/mol to give a concentration of 1 × 10-2HAuC of Ml4Solution and concentration of 5 × 10-6Mixing solutions of PVP-DADMAN of M, boiling for 1h, adding 100 parts by weight of ascorbic acid, stirring in a dark place at 98 ℃ for reaction for 1h, and centrifuging at 20000rpm for 25min to obtain a supernatant; drying the supernatant in vacuum to obtain modified nano gold particles with the average particle size of 18 nm;
(2) mixing 5 parts by weight of MwPEOS at 1kg/mol was dissolved in 100 parts by weight of ASA as an oil phase; dispersing 1 part by weight of the modified nano-gold prepared in the step (1) in water to prepare a solution with the mass percentage concentration of 1.2%, and dropwise adding dilute hydrochloric acid to adjust the pH value to 4 to be used as a water phase; and adding the water phase into the oil phase, wherein the volume ratio of the oil phase to the water phase is 1:1, performing ultrasonic stirring for 15min at room temperature, standing for 4 days to obtain an oil-in-water ASA Pickering emulsion, namely the ASA paper anti-counterfeiting coating, wherein the average particle size of the sizing agent emulsion is 3 mu m, and the emulsion is unchanged after being placed for 24 hours and has good stability.
Testing the anti-counterfeiting performance of sizing paper of the ASA paper anti-counterfeiting coating:
hydrophobic anti-counterfeiting performance: the surface sizing is carried out on the tested paper by ASA paper anti-counterfeiting coating, the dosage of the sizing agent is 8 per mill, the surface of the sized paper is light blue, the surface sizing degree is 1379 seconds, the contact angle with water is 163 degrees, and the paper belongs to a super-hydrophobic surface.
Strain-induced anti-counterfeiting performance: stretching induction, namely placing the sizing paper on the surface of transparent glass, clamping the paper by using a pliers, slowly stretching, observing the color change of the sizing paper by using naked eyes or an optical microscope, and gradually changing the color of the film from light blue to light pink and finally to red along with the stretching of the paper; sensing mechanical impact force, namely, enabling the sizing paper to be horizontally spread with the sizing surface facing upwards, suspending a 1kg iron block above the sizing paper, freely dropping according to different heights and dropping onto the sizing paper, observing and recording the color change of the sizing paper after being impacted by the iron block by using an optical microscope, and respectively presenting light blue, light pink and red change trends at the impact point position of the sizing paper impacted by the iron block along with the gradual rise of the dropping height of the iron block; perforation response punches (round hole) to the glueing paper with paper puncher, and the bore hole is observed to the bore hole, and glueing paper perforation edge can demonstrate different colours, and the colour change by far away and near apart from the hole edge does: blue, light pink and red; the sizing paper of the ASA paper anti-counterfeiting coating has obvious hydrophobic and strain induction properties, can distinguish color change by naked eyes, and has good anti-counterfeiting property.

Claims (8)

1. A stress induction type paper anti-counterfeiting coating is characterized in that the preparation method comprises the following steps:
(1) adding HAuCl4Dissolving PVP-DADMAN in water, boiling, adding a reducing agent, stirring in the dark for reaction, centrifuging, and drying the supernatant in vacuum to obtain modified gold nanoparticles;
(2) PEOS was diluted in ASA as the oil phase; dissolving the modified nano-gold prepared in the step (1) in water, and adjusting the pH to be acidic to be used as a water phase; and ultrasonically stirring the water phase and the oil phase under the heating condition, and standing to obtain an oil-in-water ASA Pickering emulsion, namely the stress-induced anti-counterfeiting paper coating.
2. The stress-sensitive paper anti-counterfeiting coating according to claim 1, wherein the PVP-DADMAN has a weight average molecular weight Mw55-68kg/mol, and the concentration of PVP-DADMAN is 1 × 10-7-1×10-5M; the HAuCl4The mass ratio of PVP to DADMAN is 60:1-20: 1; the HAuCl4Has a concentration of 1 × 10-2-1×10-4M。
3. The stress-sensitive paper security coating of claim 1, wherein the reducing agent is selected from ascorbic acid or thiourea; the HAuCl4The mass ratio of the reducing agent to the reducing agent is 3:1-1: 5.
4. The stress-sensitive paper anti-counterfeiting coating according to claim 1, wherein in the step (1), the modified nano-gold particles are in the shape of a nearly hexagon; the average particle diameter is 15-65 nm.
5. The stress-sensitive paper security coating of claim 1, wherein the PEOS has a weight average molecular weight MwIs 1-3 kg/mol; the mass ratio of the PEOS to the ASA is 1:3-1: 10; the mass ratio of the PEOS to the modified nano-gold is 1:2-5: 1; the mass percentage concentration of the modified nano-gold solution is 0.4-1.2%.
6. The stress-sensitive paper anti-counterfeiting coating according to claim 1, wherein in the step (2), the pH is 1-4; the volume ratio of the oil phase to the water phase is 1:5-1: 1.
7. The stress-sensitive paper anti-counterfeiting coating according to claim 1, wherein in the step (1), the boiling time is 1 h; the temperature of the reduction reaction is 98 ℃, and the reaction time is 1 h; the centrifugation speed is 5000-; in the step (2), the heating temperature is 65-80 ℃; the standing time is 2-5 days.
8. A paper prepared using the stress-sensitive paper security coating of claim 1.
CN201810378753.4A 2018-04-25 2018-04-25 Preparation method of stress-induced paper anti-counterfeiting coating and product thereof Active CN108660852B (en)

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CN102268839A (en) * 2011-07-25 2011-12-07 华南理工大学 Method for preparing Pickering emulsion type alkenyl succinic anhydrides (ASA) papermaking sizing agent
CN105056830A (en) * 2015-07-16 2015-11-18 齐鲁工业大学 Biodegradable solid particle emulsifier and papermaking sizing agent
CN106694039A (en) * 2016-09-19 2017-05-24 安徽师范大学 Preparation method and application of carbon sphere/Au nanometer composite material

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CN102268839A (en) * 2011-07-25 2011-12-07 华南理工大学 Method for preparing Pickering emulsion type alkenyl succinic anhydrides (ASA) papermaking sizing agent
CN105056830A (en) * 2015-07-16 2015-11-18 齐鲁工业大学 Biodegradable solid particle emulsifier and papermaking sizing agent
CN106694039A (en) * 2016-09-19 2017-05-24 安徽师范大学 Preparation method and application of carbon sphere/Au nanometer composite material

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