CN116102923A - Temperature-changing anti-counterfeiting coating and preparation method thereof - Google Patents
Temperature-changing anti-counterfeiting coating and preparation method thereof Download PDFInfo
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- CN116102923A CN116102923A CN202211709831.7A CN202211709831A CN116102923A CN 116102923 A CN116102923 A CN 116102923A CN 202211709831 A CN202211709831 A CN 202211709831A CN 116102923 A CN116102923 A CN 116102923A
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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
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/06—Copolymers with styrene
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to the technical field of anti-counterfeiting paint, in particular to temperature-changing anti-counterfeiting paint and a preparation method thereof, wherein the temperature-changing anti-counterfeiting paint comprises the following raw materials in parts by weight: 10-20 parts of temperature-changing capsules, 3-7 parts of resin color developing agent, 10-20 parts of adhesive, 1-3 parts of color-changing fiber, 1-5 parts of dispersing agent, 1-3 parts of defoaming agent and 30-50 parts of deionized water, wherein the resin color developing agent is benzyl zinc salicylate. The temperature-changing anti-counterfeiting coating has the advantage of wider color-changing temperature range, and the temperature-changing temperature can be arbitrarily selected in a certain range; the main solvent is water, is an environment-friendly pseudo-paint, and does not recover the primary color after the temperature is reduced after the color is changed; the color is bright, can be used for displaying whether the article exceeds the monitoring temperature, and plays an irreversible intelligent temperature indication and anti-counterfeiting role; and after coating, the paint has good adhesive force, friction resistance, chemical resistance and water resistance, bright color saturation and good tone level reproducibility.
Description
Technical Field
The invention relates to the technical field of anti-counterfeiting paint, in particular to temperature-changing anti-counterfeiting paint and a preparation method thereof.
Background
Generally, anti-counterfeiting technology refers to technology for preventing counterfeiting and imitation, and is mainly aimed at protecting enterprise brands, markets and legal rights of consumers. Paper is used as a packaging material of the product, is easy to identify authenticity and has relatively low cost, and can effectively prevent the circulation of counterfeit goods. There are many reports on paper anti-counterfeiting treatment, and the reports mainly comprise anti-counterfeiting and anti-counterfeiting paint of paper.
The temperature-changing anti-counterfeiting coating in the anti-counterfeiting coating is one of the most effective high-tech anti-counterfeiting coatings at present, and has the advantages of wide application range, no toxicity or radiation, simple use method, good durability, convenient identification and the like. The principle of thermochromic is that a special thermosensitive material is added into the paint and coated on the surface of anti-counterfeiting paper, when the paint is heated to a certain temperature, the molecules of the thermosensitive material in the paint change correspondingly in structure or form, and the color of the paint changes accordingly, so that the temperature can be indicated.
At present, thermochromic paint is widely applied to the aspects of safety warning, chemical anti-counterfeiting and the like, but most of the existing thermochromic paint changes color at high temperature, and the research of low-temperature thermochromic paint is less. Meanwhile, most of low-temperature color-changing materials are organic materials, and are greatly influenced by the pH value of the surrounding environment.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the temperature-changing anti-counterfeiting coating which has the advantage of wider color-changing temperature range and can be arbitrarily selected in a certain range; the main solvent is water, is an environment-friendly anti-counterfeiting coating, and does not recover the primary color after the temperature is reduced after the color is changed; the color is bright, can be used for displaying whether the article exceeds the monitoring temperature, and plays an irreversible intelligent temperature indication and anti-counterfeiting role; and after coating, the adhesive force, the friction resistance, the chemical resistance and the water resistance are good, the color saturation is bright, and the tone level reproducibility is good.
The invention aims to provide a preparation method of a temperature-changing anti-counterfeiting coating, which is simple and efficient, convenient to operate and control, high in quality of produced products, low in cost and convenient for industrial production.
The aim of the invention is achieved by the following technical scheme: the temperature-changing anti-counterfeiting coating comprises the following raw materials in parts by weight: 10-20 parts of temperature-changing capsules, 3-7 parts of resin color developing agent, 10-20 parts of adhesive, 1-3 parts of color-changing fiber, 1-5 parts of dispersing agent, 1-3 parts of defoaming agent and 30-50 parts of deionized water, wherein the resin color developing agent is benzyl zinc salicylate.
The temperature-changing anti-counterfeiting coating prepared by adopting the raw materials has the advantage of wider color-changing temperature range, and the temperature-changing temperature can be arbitrarily selected in a certain range; the main solvent is water, is an environment-friendly pseudo-paint, and does not recover the primary color after the temperature is reduced after the color is changed; the color is bright, can be used for displaying whether the article exceeds the monitoring temperature, and plays an irreversible intelligent temperature indication and anti-counterfeiting role; and after coating, the paint has good adhesive force, friction resistance, chemical resistance and water resistance, bright color saturation and good tone level reproducibility. The adopted temperature-changing capsules have the advantage of wider color-changing temperature range, can arbitrarily select the temperature-changing temperature in a certain range, avoid the defect that the traditional coating cannot realize color change when the temperature is higher than 50 ℃, and can enable the color-developing temperature range of the temperature-changing anti-counterfeiting coating to be wider; the resin color developing agent has the advantages of high low-temperature color developing speed, high whiteness of the coating, good color developing density and good light aging resistance, and further improves the color developing rate and the color developing effect of the temperature-changing anti-counterfeiting coating. The adhesive has better ageing resistance, higher cohesive force and conjunctival strength, good mechanical and chemical stability, good fluidity and storage stability, and further improves the comprehensive performance of the temperature-change anti-counterfeiting coating in an auxiliary way. The color-changing fiber is easy to see color fibers with various colors in the anti-counterfeiting paper due to the diversity and the distribution flexibility of the fiber, so that the anti-counterfeiting purpose is achieved, and meanwhile, the coating can be endowed with excellent mechanical property and good storage stability.
Preferably, the temperature-changing capsule comprises a wall material and a core material, wherein the mass ratio of the wall material to the core material is 1:1.8-2.4.
Preferably, the temperature-changing capsule takes tetradecanol, a color former and a color former as core materials, and the mass ratio of the tetradecanol, the color former and the color former is 1-3:0.4-0.8:0.8-1.2.
Preferably, the wall material consists of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio of 0.5-1.0:0.4-0.8:0.6-1.0:0.3-0.7.
According to the invention, the temperature-changing capsule of the core-shell mechanism is adopted, tetradecyl alcohol, a color former and a color former are used as core materials, and a mixture of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin is used as a wall material, so that the prepared temperature-changing capsule has the advantage of wider color-changing temperature range, the temperature-changing temperature can be arbitrarily selected within a certain range, the defect that the color-changing cannot be realized when the temperature of the traditional coating is higher than 50 ℃ is avoided, and the color-developing temperature range of the temperature-changing anti-counterfeiting coating is wider; wherein the mass ratio of tetradecanol, the color former and the color former used in the core material is 1-3:0.4-0.8:0.8-1.2, which can ensure the high color change sensitivity of the core material; cetyl alcohol is critical for low temperature discoloration, and the use of other solvents can cause the discoloration temperature to be too high or too low to monitor the temperature range of 39-45 ℃. The wall material overcomes the defects of the traditional capsule prepared by other modes by adopting the raw materials, and has the advantages of strong controllability, proper microcapsule size, uniform particle size and good temperature change effect; the larger the core wall ratio is, the thinner the capsule wall is, the time required for color changing and color compounding is short, and the color changing sensitivity is high; however, too large a core wall ratio may result in a low coating rate, with some of the color-changing material not being coated. When the core material is wrapped in the wall material, the core material is not contacted with the external environment, so that the influence of the pH value of the surrounding environment on substances in the core material is avoided, and the service life of the thermochromic anti-counterfeiting coating is prolonged.
Preferably, the color former is at least one of crystal violet lactone, thermosensitive green or thermosensitive red paste.
Preferably, the color-developing agent is at least one of phthalic acid, calcium chloride or benzenediol.
The color-developing agent adopted in the invention has good color-developing effect, wherein the temperature-changing anti-counterfeiting coating prepared by combining the benzene diphenol and the thermosensitive green or thermosensitive red paste in the color-developing agent has obvious color-changing effect in the use process.
Preferably, the adhesive is a mixture composed of styrene-butadiene latex, carboxymethyl color-changing fiber, polyvinyl alcohol and acrylic emulsion according to the mass ratio of 0.8-1.2:0.4-0.8:0.6-1.0:0.1-0.5.
The adhesive adopted in the invention exerts the synergistic advantages of various adhesive resins, so that the mixed adhesive has better anti-aging capability, higher cohesive force and conjunctival strength, good mechanical and chemical stability, good fluidity and storage stability, and further improves the comprehensive performance of the temperature-change anti-counterfeiting coating in an auxiliary way; the styrene-butadiene latex adopted has better anti-aging capability, and also has higher cohesive force and conjunctival strength; in addition, the adopted acrylic emulsion has good water resistance, alkali resistance and dirt resistance, and has good adhesion to the surfaces of various materials.
Preferably, the dispersing agent is at least one of sodium polyacrylate, sodium pyrophosphate and polyacrylamide.
The coating system of the invention can uniformly disperse the rest raw materials in the slurry under the action of the dispersing agent.
Preferably, the defoaming agent is at least one of emulsified silicone oil, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.
The foam generated by the dispersing agent can be eliminated by adding the defoaming agent, so that the dispersing time is shortened; meanwhile, the bubble flaws in the coating can be eliminated by adding the defoaming agent, so that the coating is convenient to coat, and the coating film is uniform.
The invention also provides a preparation method of the temperature-changing anti-counterfeiting coating, which is prepared by the following steps:
s1, adding tetradecanol into a color former and a color former according to a mass ratio, heating to 50-90 ℃, and keeping for 0.5-2h after complete dissolution to obtain a nuclear material for later use;
s2, mixing polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio to obtain a wall material, adding the wall material into a core material, heating to 70-90 ℃, stirring for reaction for 1-3h, cooling, and filtering to obtain a temperature-changing capsule for later use;
s3, adding the resin color developing agent, the adhesive, the color-changing fiber, the dispersing agent and the defoaming agent into deionized water according to parts by weight, mixing, and dispersing to obtain a pre-dispersion for later use;
s4, adding the temperature-changing capsules into the pre-dispersion, mixing, heating to 60-80 ℃ and stirring for 20-40min, cooling and standing to obtain the temperature-changing anti-counterfeiting coating.
The invention has the beneficial effects that: the temperature-changing anti-counterfeiting coating has the advantage of wider color-changing temperature range, and the temperature-changing temperature can be arbitrarily selected in a certain range; the main solvent is water, is an environment-friendly pseudo-paint, and does not recover the primary color after the temperature is reduced after the color is changed; the color is bright, can be used for displaying whether the article exceeds the monitoring temperature, and plays an irreversible intelligent temperature indication and anti-counterfeiting role; and after coating, the paint has good adhesive force, friction resistance, chemical resistance and water resistance, bright color saturation and good tone level reproducibility.
The preparation method of the temperature-changing anti-counterfeiting coating is simple and efficient, convenient to operate and control, high in quality of produced products, low in cost and convenient for industrial production.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1
The temperature-changing anti-counterfeiting coating comprises the following raw materials in parts by weight: 10 parts of temperature-change capsules, 3 parts of resin color-developing agent, 10 parts of adhesive, 1 part of color-change fiber, 1 part of dispersing agent, 1 part of defoaming agent and 30 parts of deionized water; wherein the resin color developing agent is benzyl zinc salicylate.
Wherein, the temperature-changing capsule comprises a wall material and a core material, and the mass ratio of the wall material to the core material is 1:1.8.
Wherein, the temperature-changing capsule takes tetradecanol, a color former and a color former as core materials, and the mass ratio of the tetradecanol, the color former and the color former is 1:0.4:0.8.
Wherein the wall material consists of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio of 0.5:0.4:0.6:0.3; wherein the urethane acrylate is selected from the group consisting of Basfuside, such as Marromer PR 9000.
Wherein the color former is crystal violet lactone and the color former is phthalic acid.
Wherein the adhesive is a mixture composed of styrene-butadiene latex, carboxymethyl color-changing fiber, polyvinyl alcohol and acrylic emulsion according to the mass ratio of 0.8:0.4:0.6:0.1; wherein styrene-butadiene latex is produced by Shanghai Jin Lang rubber and plastic technology Co., ltd, and acrylic emulsion is aqueous acrylic emulsion with the brand sy101 produced by Dongguan Shuangyi new materials Co., ltd.
Wherein the dispersing agent is sodium polyacrylate, and the defoaming agent is emulsified silicone oil.
The temperature-changing anti-counterfeiting coating is prepared by the following steps:
s1, adding tetradecanol into a color former and a color former according to a mass ratio, heating to 50 ℃, and keeping for 0.5h after complete dissolution to obtain a nuclear material for later use;
s2, mixing polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio to obtain a wall material, adding the wall material into a core material, heating to 70 ℃, stirring for reaction for 1h, cooling, and filtering to obtain a temperature-changing capsule for later use;
s3, adding the resin color developing agent, the adhesive, the color-changing fiber, the dispersing agent and the defoaming agent into deionized water according to parts by weight, mixing, and dispersing to obtain a pre-dispersion for later use;
s4, adding the temperature-changing capsules into the pre-dispersion, mixing, heating to 60 ℃ and stirring for 20min, cooling and standing to obtain the temperature-changing anti-counterfeiting coating.
Example 2
The temperature-changing anti-counterfeiting coating comprises the following raw materials in parts by weight: 13 parts of temperature-change capsules, 4 parts of resin color-developing agent, 13 parts of adhesive, 1.5 parts of color-change fiber, 2 parts of dispersing agent, 1.5 parts of defoamer and 35 parts of deionized water; wherein the resin color developing agent is benzyl zinc salicylate.
Wherein, the temperature-changing capsule comprises a wall material and a core material, and the mass ratio of the wall material to the core material is 1:2.0.
Wherein, the temperature-changing capsule takes tetradecanol, a color former and a color former as core materials, and the mass ratio of the tetradecanol, the color former and the color former is 1.5:0.5:0.9.
Wherein the wall material consists of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio of 0.6:0.5:0.7:0.4; wherein the urethane acrylate is selected from the group consisting of Basfuside, such as Marromer PR 9000.
Wherein the color former is thermosensitive green, and the color former is calcium chloride.
Wherein the adhesive is a mixture composed of styrene-butadiene latex, carboxymethyl color-changing fiber, polyvinyl alcohol and acrylic emulsion according to the mass ratio of 0.9:0.5:0.7:0.2; wherein styrene-butadiene latex is produced by Shanghai Jin Lang rubber and plastic technology Co., ltd, and acrylic emulsion is aqueous acrylic emulsion with the brand sy101 produced by Dongguan Shuangyi new materials Co., ltd.
Wherein the dispersant is sodium pyrophosphate, and the defoamer is polyoxyethylene polyoxypropylene pentaerythritol ether.
The temperature-changing anti-counterfeiting coating is prepared by the following steps:
s1, adding tetradecanol into a color former and a color former according to a mass ratio, heating to 60 ℃, and keeping for 0.8h after complete dissolution to obtain a nuclear material for later use;
s2, mixing polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio to obtain a wall material, adding the wall material into a core material, heating to 75 ℃, stirring for reaction for 1.5 hours, cooling, and filtering to obtain a temperature-changing capsule for later use;
s3, adding the resin color developing agent, the adhesive, the color-changing fiber, the dispersing agent and the defoaming agent into deionized water according to parts by weight, mixing, and dispersing to obtain a pre-dispersion for later use;
s4, adding the temperature-changing capsules into the pre-dispersion, mixing, heating to 65 ℃ and stirring for 25min, cooling and standing to obtain the temperature-changing anti-counterfeiting coating.
Example 3
The temperature-changing anti-counterfeiting coating comprises the following raw materials in parts by weight: 15 parts of temperature-change capsules, 5 parts of resin color-developing agents, 15 parts of adhesives, 2 parts of color-change fibers, 3 parts of dispersing agents, 2 parts of defoaming agents and 40 parts of deionized water; wherein the resin color developing agent is benzyl zinc salicylate.
Wherein, the temperature-changing capsule comprises a wall material and a core material, and the mass ratio of the wall material to the core material is 1:2.1.
The temperature-changing capsule takes tetradecanol, a color former and a color former as core materials, and the mass ratio of the tetradecanol, the color former and the color former is 2:0.6:1.0.
Wherein the wall material consists of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio of 0.7:0.6:0.8:0.5; wherein the urethane acrylate is selected from the group consisting of Basfuside, such as Marromer PR 9000.
Wherein the color former is a mixture of crystal violet lactone and thermal green according to the mass ratio of 0.7:0.6.
Wherein the color developing agent is a mixture of phthalic acid and calcium chloride according to the mass ratio of 0.5:0.6.
Wherein the adhesive is a mixture composed of styrene-butadiene latex, carboxymethyl color-changing fiber, polyvinyl alcohol and acrylic emulsion according to the mass ratio of 1.0:0.6:0.8:0.3; wherein styrene-butadiene latex is produced by Shanghai Jin Lang rubber and plastic technology Co., ltd, and acrylic emulsion is aqueous acrylic emulsion with the brand sy101 produced by Dongguan Shuangyi new materials Co., ltd.
Wherein the dispersing agent is sodium polyacrylate, and the defoaming agent is polyoxyethylene polyoxypropylene amine ether.
The temperature-changing anti-counterfeiting coating is prepared by the following steps:
s1, adding tetradecanol into a color former and a color former according to a mass ratio, heating to 70 ℃, and keeping for 1.3 hours after complete dissolution to obtain a nuclear material for later use;
s2, mixing polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio to obtain a wall material, adding the wall material into a core material, heating to 80 ℃, stirring for reaction for 2 hours, cooling, and filtering to obtain a temperature-changing capsule for later use;
s3, adding the resin color developing agent, the adhesive, the color-changing fiber, the dispersing agent and the defoaming agent into deionized water according to parts by weight, mixing, and dispersing to obtain a pre-dispersion for later use;
s4, adding the temperature-changing capsules into the pre-dispersion, mixing, heating to 70 ℃ and stirring for 30min, cooling and standing to obtain the temperature-changing anti-counterfeiting coating.
Example 4
The temperature-changing anti-counterfeiting coating comprises the following raw materials in parts by weight: 18 parts of temperature-changing capsules, 6 parts of resin color-developing agent, 18 parts of adhesive, 2.5 parts of color-changing fiber, 4 parts of dispersing agent, 2.5 parts of defoaming agent and 45 parts of deionized water; wherein the resin color developing agent is benzyl zinc salicylate.
Wherein, the temperature-changing capsule comprises a wall material and a core material, and the mass ratio of the wall material to the core material is 1:2.3.
Wherein, the temperature-changing capsule takes tetradecanol, a color former and a color former as core materials, and the mass ratio of the tetradecanol, the color former and the color former is 2.5:0.7:1.1.
Wherein the wall material consists of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio of 0.9:0.7:0.9:0.6; wherein the urethane acrylate is selected from the group consisting of Basfuside, such as Marromer PR 9000.
Wherein the color former is crystal violet lactone and the color former is phthalic acid.
Wherein the adhesive is a mixture composed of styrene-butadiene latex, carboxymethyl color-changing fiber, polyvinyl alcohol and acrylic emulsion according to the mass ratio of 1.1:0.7:0.9:0.4; wherein styrene-butadiene latex is produced by Shanghai Jin Lang rubber and plastic technology Co., ltd, and acrylic emulsion is aqueous acrylic emulsion with the brand sy101 produced by Dongguan Shuangyi new materials Co., ltd.
Wherein the dispersing agent is sodium polyacrylate, and the defoaming agent is polyoxypropylene glycerol ether.
The temperature-changing anti-counterfeiting coating is prepared by the following steps:
s1, adding tetradecanol into a color former and a color former according to a mass ratio, heating to 80 ℃, and keeping for 1.6 hours after complete dissolution to obtain a nuclear material for later use;
s2, mixing polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio to obtain a wall material, adding the wall material into a core material, heating to 85 ℃, stirring for reacting for 2.5 hours, cooling, and filtering to obtain a temperature-changing capsule for later use;
s3, adding the resin color developing agent, the adhesive, the color-changing fiber, the dispersing agent and the defoaming agent into deionized water according to parts by weight, mixing, and dispersing to obtain a pre-dispersion for later use;
s4, adding the temperature-changing capsules into the pre-dispersion, mixing, heating to 75 ℃ and stirring for 35min, cooling and standing to obtain the temperature-changing anti-counterfeiting coating.
Example 5
The temperature-changing anti-counterfeiting coating comprises the following raw materials in parts by weight: 20 parts of temperature-change capsules, 7 parts of resin color-developing agents, 20 parts of adhesives, 3 parts of color-change fibers, 5 parts of dispersing agents, 3 parts of defoaming agents and 50 parts of deionized water; wherein the resin color developing agent is benzyl zinc salicylate.
Wherein, the temperature-changing capsule comprises a wall material and a core material, and the mass ratio of the wall material to the core material is 1:2.4.
Wherein, the temperature-changing capsule takes tetradecanol, a color former and a color former as core materials, and the mass ratio of the tetradecanol, the color former and the color former is 3:0.8:1.2.
Wherein the wall material consists of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio of 1.0:0.8:1.0:0.7; wherein the urethane acrylate is selected from the group consisting of Basfuside, such as Marromer PR 9000.
Wherein the color former is crystal violet lactone and the color former is phthalic acid.
Wherein the adhesive is a mixture composed of styrene-butadiene latex, carboxymethyl color-changing fiber, polyvinyl alcohol and acrylic emulsion according to the mass ratio of 1.2:0.8:1.0:0.5; wherein styrene-butadiene latex is produced by Shanghai Jin Lang rubber and plastic technology Co., ltd, and acrylic emulsion is aqueous acrylic emulsion with the brand sy101 produced by Dongguan Shuangyi new materials Co., ltd.
Wherein the dispersing agent is sodium polyacrylate, and the defoaming agent is polyoxypropylene polyoxyethylene glyceryl ether.
The temperature-changing anti-counterfeiting coating is prepared by the following steps:
s1, adding tetradecanol into a color former and a color former according to a mass ratio, heating to 90 ℃, and keeping for 2 hours after complete dissolution to obtain a nuclear material for later use;
s2, mixing polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio to obtain a wall material, adding the wall material into a core material, heating to 90 ℃, stirring for reaction for 3 hours, cooling, and filtering to obtain a temperature-changing capsule for later use;
s3, adding the resin color developing agent, the adhesive, the color-changing fiber, the dispersing agent and the defoaming agent into deionized water according to parts by weight, mixing, and dispersing to obtain a pre-dispersion for later use;
s4, adding the temperature-changing capsules into the pre-dispersion, mixing, heating to 80 ℃ and stirring for 40min, cooling and standing to obtain the temperature-changing anti-counterfeiting coating.
Comparative example 1
This comparative example differs from example 3 above in that: the raw materials of the temperature-changing anti-counterfeiting coating of the comparative example are not added with the temperature-changing capsules. The remainder of this comparative example is the same as in example 3 and will not be described here again.
Comparative example 2
This comparative example differs from example 3 above in that: the raw materials of the temperature-changing anti-counterfeiting coating of the comparative example are not added with a resin color developing agent and color-changing fibers. The remainder of this comparative example is the same as in example 3 and will not be described here again.
The temperature-variable anti-counterfeiting coatings prepared in example 3 and comparative examples 1-2 were subjected to performance test, and the results are shown in Table 1:
the viscosity of the paint is measured at the temperature of (23+/-2) DEG C (4 cups of paint, s/25 ℃) according to the requirement of GB/T1723-93;
the initial dryness of the paint is measured according to the requirements of GB/T13217.5-2008;
the adhesive force of the paint is measured according to the requirement of GB/T9286-2021;
the water resistance of the coating is that the printing product is cut into 25 samples with the length of 1cm multiplied by 1cm, and the samples are placed in a beaker filled with deionized water for 30min at normal temperature (28 ℃ +/-2 ℃) to observe whether the color is lost;
the weather resistance of the coating is that the printing product is placed in a constant temperature and humidity box, the temperature is 40 ℃, the humidity is 80 percent, and whether the color is changed or not is observed after the placing time is 100 hours; the prints were placed in an oven at a predetermined temperature for 5min and the color change temperature was recorded.
TABLE 1
| Project | Example 3 | Comparative example 1 | Comparative example 2 |
| Adhesion force | 3 grade | Level 2 | Level 1 |
| Viscosity of 4 cup(s) coating | 36 | 31 | 24 |
| Primary drying (s, 28 ℃ C.) | 14 | 18 | 25 |
| Water resistance (28 ℃,30 min) | Does not fade | Does not fade | Does not fade |
| Weather resistance (100 h) | Does not fade | Does not fade | Does not fade |
| Color change temperature (. Degree. C.) | 110-180 | Does not change color | Does not change color |
The temperature-changing anti-counterfeiting coating prepared by the invention has the advantages of better adhesive force, low viscosity and other mechanical properties, quicker initial drying, stronger water resistance, weather resistance and the like as shown in the example 3.
As can be seen from the comparison of the embodiment 3 and the comparative examples 1-2, the addition of the heating variable capsules, the resin color-developing agent and the color-changing fibers in the formula under the same conditions can lead the prepared temperature variable anti-counterfeiting coating to have the advantages of better adhesive force, better initial drying property, wider color-changing temperature and the like, and has wide market prospect and application value.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (10)
1. A temperature-changing anti-counterfeiting coating is characterized in that: the material comprises the following raw materials in parts by weight: 10-20 parts of temperature-changing capsules, 3-7 parts of resin color developing agent, 10-20 parts of adhesive, 1-3 parts of color-changing fiber, 1-5 parts of dispersing agent, 1-3 parts of defoaming agent and 30-50 parts of deionized water, wherein the resin color developing agent is benzyl zinc salicylate.
2. The temperature-variable anti-counterfeiting coating according to claim 1, wherein: the temperature-changing capsule comprises a wall material and a core material, wherein the mass ratio of the wall material to the core material is 1:1.8-2.4.
3. The temperature-variable anti-counterfeiting coating according to claim 2, wherein: the temperature-changing capsule takes tetradecanol, a color former and a color former as core materials, and the mass ratio of the tetradecanol to the color former is 1-3:0.4-0.8:0.8-1.2.
4. A temperature-variable anti-counterfeiting coating according to claim 3, wherein: the wall material consists of polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio of 0.5-1.0:0.4-0.8:0.6-1.0:0.3-0.7.
5. A temperature-variable anti-counterfeiting coating according to claim 3, wherein: the color former is at least one of crystal violet lactone, thermosensitive green or thermosensitive red paste.
6. A temperature-variable anti-counterfeiting coating according to claim 3, wherein: the color developing agent is at least one of phthalic acid, calcium chloride or benzenediol.
7. The temperature-variable anti-counterfeiting coating according to claim 1, wherein: the adhesive is a mixture composed of styrene-butadiene latex, carboxymethyl color-changing fiber, polyvinyl alcohol and acrylic emulsion according to the mass ratio of 0.8-1.2:0.4-0.8:0.6-1.0:0.1-0.5.
8. The temperature-variable anti-counterfeiting coating according to claim 1, wherein: the dispersing agent is at least one of sodium polyacrylate, sodium pyrophosphate and polyacrylamide.
9. The temperature-variable anti-counterfeiting coating according to claim 1, wherein: the defoaming agent is at least one of emulsified silicone oil, high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.
10. A method for preparing a temperature-variable anti-counterfeiting coating as claimed in any one of claims 4 to 9, which is characterized by: the preparation method comprises the following steps:
s1, adding tetradecanol into a color former and a color former according to a mass ratio, heating to 50-90 ℃, and keeping for 0.5-2h after complete dissolution to obtain a nuclear material for later use;
s2, mixing polyurethane acrylic ester, polyvinyl alcohol, ethylene glycol diacrylate and urea resin according to the mass ratio to obtain a wall material, adding the wall material into a core material, heating to 70-90 ℃, stirring for reaction for 1-3h, cooling, and filtering to obtain a temperature-changing capsule for later use;
s3, adding the resin color developing agent, the adhesive, the color-changing fiber, the dispersing agent and the defoaming agent into deionized water according to parts by weight, mixing, and dispersing to obtain a pre-dispersion for later use;
s4, adding the temperature-changing capsules into the pre-dispersion, mixing, heating to 60-80 ℃ and stirring for 20-40min, cooling and standing to obtain the temperature-changing anti-counterfeiting coating.
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