CN109098042B - Anti-counterfeiting thermal sensitive paper and preparation method thereof - Google Patents
Anti-counterfeiting thermal sensitive paper and preparation method thereof Download PDFInfo
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- CN109098042B CN109098042B CN201811052465.6A CN201811052465A CN109098042B CN 109098042 B CN109098042 B CN 109098042B CN 201811052465 A CN201811052465 A CN 201811052465A CN 109098042 B CN109098042 B CN 109098042B
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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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
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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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
Abstract
The application discloses anti-counterfeiting thermal sensitive paper and a preparation method thereof, wherein the anti-counterfeiting thermal sensitive paper comprises: base paper; the anti-counterfeiting back coating is arranged on one surface of the base paper and is formed by coating anti-counterfeiting coating, wherein the anti-counterfeiting coating comprises leuco dye microcapsules and a spacing substrate, the leuco dye microcapsules comprise first leuco dyes, and the first leuco dyes are leuco dyes for displaying blue, red, black or other colors; the base coat is arranged on the other surface of the base paper, which is opposite to the back coat; and the top coating is arranged on one surface of the bottom coating, which faces away from the base paper, and is formed by coating a top coating paint, wherein the top coating paint contains a color developing agent. Through the mode, the thermal paper has the anti-counterfeiting performance, and the cost of the anti-counterfeiting thermal paper is effectively reduced.
Description
Technical Field
The application relates to the technical field of papermaking, in particular to anti-counterfeiting thermal sensitive paper and a preparation method thereof.
Background
Thermal paper is a thermal recording material that does not require consumables such as ribbon, ink, toner, etc., and produces a printed image by direct application of heat thereto, and generally consists of a substrate, an undercoat layer, and a thermal coating layer containing a thermal-sensitive chromogenic chemical.
At present, the anti-counterfeiting purpose is achieved in the market by printing anti-counterfeiting watermarks, anti-counterfeiting ink or anti-counterfeiting safety lines and other post-processing modes on thermal paper. However, the thermal sensitive paper prepared by the processing method does not have anti-counterfeiting performance, and the processing method has more processing steps and needs additional production equipment, so that the cost of the anti-counterfeiting thermal sensitive paper is higher.
Disclosure of Invention
The anti-counterfeiting thermal paper mainly solves the technical problem of providing the anti-counterfeiting thermal paper and the preparation method thereof, and the anti-counterfeiting thermal paper has anti-counterfeiting performance, so that the cost of the anti-counterfeiting thermal paper is effectively reduced.
In order to solve the technical problem, the application adopts a technical scheme that: provided is forgery-preventing thermal paper including: base paper; the anti-counterfeiting back coating is arranged on one surface of the base paper and is formed by coating anti-counterfeiting coating, wherein the anti-counterfeiting coating comprises leuco dye microcapsules and a spacing substrate, the leuco dye microcapsules comprise first leuco dyes, and the first leuco dyes are leuco dyes for displaying blue, red, black or other colors; the base coat is arranged on the other surface of the base paper, which is opposite to the back coat; and the top coating is arranged on one surface of the bottom coating, which faces away from the base paper, and is formed by coating a top coating paint, wherein the top coating paint contains a color developing agent.
In order to solve the above technical problem, another technical solution adopted by the present application is: the preparation method of the anti-counterfeiting thermal paper is used for preparing the anti-counterfeiting thermal paper, and comprises the following steps: providing a base paper; coating an anti-counterfeiting coating on one surface of base paper to form an anti-counterfeiting back coating, wherein the anti-counterfeiting coating comprises a leuco dye microcapsule and a spacing substrate, the leuco dye microcapsule comprises a first leuco dye, the first leuco dye is a leuco dye for displaying blue, red, black or other colors, and the coating weight of the anti-counterfeiting coating is 5-13 g/m2(ii) a Coating a primer on the other surface of the base paper, which faces away from the anti-counterfeiting back coating, to form a primer layer, wherein the coating weight of the primer is 5-15 g/m2(ii) a Coating a surface coating on one surface of the bottom coating opposite to the base paper to form a surface coating, wherein the surface coating comprises a color developing agent, and the coating weight of the surface coating is 3-12 g/m2(ii) a And drying the base paper with the surface coating layer formed to obtain the anti-counterfeiting thermal sensitive paper.
The beneficial effect of this application is: in contrast to the prior art, the thermal security paper of the present application includes a base paper, wherein one surface of the base paper is coated with a security coating containing leuco dye microcapsules, the leuco dye microcapsules contain a first leuco dye which develops color when encountering a color developer, and the base paper has a base coating layer and a top coating layer on the other surface thereof in this order, and the top coating layer forming the top coating layer contains a color developer which develops color of the first leuco dye. Through the mode, the anti-counterfeiting thermal sensitive paper only needs to contact the two surfaces and apply pressure to the paper surface in the using process, so that the leuco dye microcapsules are broken and flow out of the leuco dye, and the leuco dye is developed to realize an anti-counterfeiting function when meeting a color developing agent. Therefore, the thermosensitive paper has the anti-counterfeiting performance, the anti-counterfeiting function can be realized without post processing, the thermosensitive paper can be produced on the basis of the existing coating equipment, the investment of extra equipment cost can be avoided, and the cost of the anti-counterfeiting thermosensitive paper is effectively reduced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts. Wherein:
FIG. 1 is a schematic structural diagram of an embodiment of the anti-counterfeiting thermal paper of the present application;
FIG. 2 is a schematic flow chart of an embodiment of a method for preparing the anti-counterfeiting thermal paper;
FIG. 3 is a schematic flow chart of another embodiment of the method for preparing the anti-counterfeiting thermal paper;
FIG. 4 is a schematic flow chart of another embodiment of the method for preparing the anti-counterfeiting thermal paper;
fig. 5 is a schematic flow chart of a further embodiment of the preparation method of the anti-counterfeiting thermal paper.
FIG. 6 is a schematic structural diagram of a first anti-counterfeiting performance testing method for anti-counterfeiting thermal paper according to the present application;
fig. 7 is a schematic structural diagram of a second anti-counterfeiting performance testing method for the anti-counterfeiting thermal paper.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Fig. 1 is a schematic structural diagram of an embodiment of the anti-counterfeiting thermal paper. The application provides a forgery-prevention thermal paper 100, and the forgery-prevention thermal paper 100 comprises a stacked structure of: the anti-counterfeiting back coating comprises an anti-counterfeiting back coating 104, base paper 101, a bottom coating 102 and a top coating 103.
The anti-counterfeiting back coating 104 is arranged on one surface of the base paper 101, and the anti-counterfeiting back coating 104 is formed by coating anti-counterfeiting paint. The anti-counterfeiting coating comprises a leuco dye microcapsule and a small amount of spacing matrix, wherein the leuco dye microcapsule comprises a first leuco dye, and the first leuco dye is a leuco dye for displaying blue, red, black or other colors. The addition of the spacer matrix is intended to avoid the leuco dye from having capsules exposed to external forces, such as: the extrusion and collision in the transportation process cause the premature rupture, so that when the anti-counterfeiting test is required, the leuco dye microcapsule is ruptured in advance, and the anti-counterfeiting function is lost. The spacing matrix can be at least one of starch, polyolefin, polymethyl methacrylate and paraffin, and the particle size range is 5-10 micrometers. The base coat layer 102 is disposed on the other surface of the base paper 101 facing away from the back coat layer, the top coat layer 103 is disposed on the surface of the base coat layer 102 facing away from the base paper 101, and the top coat layer 103 is formed by coating a top coat paint containing a color developer.
Specifically, the base paper 101 may be double-sided offset paper, carbon-free base paper, thermal base paper, plastic paper, synthetic paper, or other base materials that can be used as a coating carrier. The anti-counterfeiting principle of the anti-counterfeiting thermal paper 100 is as follows: the security thermal paper 100 comprises two surfaces (first side, second side), the first side being a security back coating 104 comprising leuco dye microcapsules and the second side comprising a colour developer. The first surface and the second surface of the anti-counterfeiting thermal paper 100 are at least partially overlapped, and under the action of external force, for example, the anti-counterfeiting thermal paper 100 is rubbed, so that the leuco dye in the leuco dye microcapsule of the first surface overflows, at the moment, the leuco dye is contacted with the color developing agent on the second surface, and a color developing reaction is generated on the second surface, so that a specific color is displayed, and the anti-counterfeiting effect is achieved. The leuco dye is a special dye and can be encapsulated by microcapsules with the particle size of 2.0-6.0 micrometers (such as 2.0 micrometers, 3.0 micrometers, 4.0 micrometers, 5.0 micrometers and 6.0 micrometers), the microcapsules can be crushed by friction, the leuco dye flows out to be in contact with a color developing agent, and a chemical reaction is carried out to present colored pictures and texts, so that the anti-counterfeiting purpose is achieved.
Unlike the prior art, the forgery-preventing thermal paper 100 of the present application includes a base paper 101, wherein one surface of the base paper 101 is coated with a forgery-preventing coating material containing leuco dye microcapsules containing a first leuco dye that develops color when encountering a color developer, and a base coating layer 102 and a top coating layer 103 are sequentially disposed on the other surface of the base paper 101, and the top coating material forming the top coating layer 103 contains a color developer that develops color of the first leuco dye. In this way, the anti-counterfeiting thermal sensitive paper 100 of the present application only needs to contact the two surfaces and apply pressure to the paper surface during use, so that the leuco dye microcapsules are broken and flow out of the leuco dye, and the leuco dye is developed to realize the anti-counterfeiting function when encountering a color developing agent. Therefore, the thermal paper has anti-counterfeiting performance, can realize the anti-counterfeiting function without post processing, can be produced on the basis of the existing coating equipment, can avoid extra equipment cost investment, and effectively reduces the cost of the anti-counterfeiting thermal paper 100.
The leuco dye microcapsules are an important component of the anti-counterfeiting thermal paper 100, and largely affect the quality of the anti-counterfeiting thermal paper 100. The leuco dye microcapsule is usually prepared by coating uniformly dispersed solid particles, liquid or gas with natural or synthetic polymer film-forming material to form tiny solid particles. The leuco dye microcapsule further comprises a wall material, i.e. a coating film outside the leuco dye microcapsule is referred to as wall material. The wall material of the leuco dye microcapsule may be at least one of acacia, gelatin-acacia, chitosan, polyurethane, polystyrene, urea resin, polyurea resin, melamine-formaldehyde resin, polyamide, diisocyanate, polyisocyanate, polycarbonate, and polymethyl methacrylate.
In one embodiment, the topcoat coating composition comprises at least a leuco dye dispersion comprising a second leuco dye and polyvinyl alcohol. The mass of the second leuco dye is 70% to 90% (e.g., 70%, 80%, 90%) of the mass of the leuco dye dispersion on a dry weight basis, and the mass of the polyvinyl alcohol is 10% to 30% (e.g., 10%, 20%, 30%) of the mass of the leuco dye dispersion on a dry weight basis. The second leuco dye is a leuco dye for exhibiting blue, red, black, or other colors.
Note that the mass of the leuco dye dispersion in dry weight in the present embodiment is the mass of the leuco dye dispersion when no aqueous solvent or oil solvent is added.
Specifically, when printing using a thermal printer or a thermal facsimile machine, heat is directly applied to the second side. At this time, the second leuco dye on the second side chemically reacts with the developer to generate color to develop characters and images. In order to achieve a distinction between printed images appearing at the second side and security images appearing at the first side, the second leuco dye may be used to display a different color than the first leuco dye.
Wherein, of the first leuco dye and the second leuco dye, the leuco dye for exhibiting blue color is at least one of 10-benzoyl-3, 7-bis (dimethylamino) phenothiazine, 7- [4- (diethylamino) -2- (hexyloxy) phenyl ] -7- (1-ethyl-2-methyl-1H-indol-3-yl) furo [3,4-B ] pyridin-5 (7H) -one, 3- (4-dimethylaminophenyl) -3- (4-methylethylaminophenyl) -6-dimethylaminophthalide, 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalide. Leuco dyes for exhibiting a black color are 2-phenylamino-3-methyl-6-diethylaminofluoran, 2-phenylamino-3-methyl-6-dibutylamino fluoran, 3-N-isopentyl-N-ethylamino-6-methyl-7-phenylamino fluoran, 6'- [ 3-ethoxypropyl) ethylamino ] -3' -methyl-2 '- (phenylamino) -spiro [ isobenzofuran-1- (3H),9' - [9H ] xanthen ] -3-one, 3-bis [2- [4- (dimethylamino) phenyl ] -2- (4-methoxyphenyl) vinyl ] -4, at least one of 5,6, 7-tetrachlorophthalide. The leuco dye for exhibiting a red color is at least one of 2 '-chloro-6' - (diethylamino) fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-bis (N-octyl-2-methylindole) phthalide, 9- [ ethyl (3-methylbutyl) amino ] -spiro [ 12H-benzo [ a ] xanthene-12, 1'(3' H) -isobenzofuran ] -3 '-one, 6' - [ ethyl (4-methylphenyl) amino ] -2 '-methyl-spiro [ isobenzofuran-1 (3H),9' - (9H) xanthene ] -3-one.
In one embodiment, the primer layer 102 is formed by applying a primer coating. The base coating comprises a first filler and a first adhesive, wherein the first filler accounts for 65-85% (such as 65%, 75% and 85%) of the dry weight of the base coating in terms of mass fraction, and the first adhesive accounts for 15-35% (such as 15%, 25% and 35%) of the dry weight of the base coating in terms of mass fraction.
Note that the dry weight quality of the undercoat paint in the present embodiment is the quality of the undercoat paint when no aqueous solvent or oil solvent is added.
The first filler can be at least one of light calcium carbonate, heavy calcium carbonate, calcined kaolin, washing kaolin, aluminum hydroxide, hollow plastic pigment and silicon dioxide, and in order to avoid the influence of too rough paper surface on the quality of thermal printing, the first filler comprises a first fine particle size filler, the first fine particle size filler accounts for 80-100% of the dry weight of the first filler, and the particle size of the first fine particle size filler is less than or equal to 2 microns. The first adhesive can be at least one of biological latex, acrylic latex, styrene-butadiene latex, carboxylic styrene-butadiene latex and polyvinyl alcohol, wherein the biological latex can be starch, and the starch can be biological latex prepared from coating-grade starch such as tapioca starch, corn starch, potato starch and the like; the starch of the biological latex can be native starch, acidified starch and esterified starch.
Wherein, in one embodiment, the top-coat paint further comprises a second filler, a second adhesive, a developer solution, a sensitizer solution and a lubricant, wherein the mass of the second filler accounts for 30-60% (e.g. 30%, 40%, 50%, 60%) of the dry mass of the top-coat paint, the mass of the second adhesive accounts for 10-25% (e.g. 10%, 15%, 20%, 25%) of the dry mass of the top-coat paint, the mass of the developer solution accounts for 20-45% (e.g. 25%, 30%, 35%, 45%) of the dry mass of the top-coat paint, the mass of the leuco dye dispersion accounts for 10-35% (e.g. 10%, 15%, 25%, 35%) of the dry mass of the top-coat paint, the mass of the sensitizer solution accounts for 0-30% (e.g. 0%, 15%, 25%, 30%) of the dry mass of the top-coat paint, and the mass of the lubricant accounts for 0-15% (e.g. 0%, (e.g. 0%) of the dry mass of the top-coat paint, 5%, 10%, 15%).
Note that the dry weight quality of the top-coat paint in the present embodiment is the quality of the top-coat paint when no aqueous solvent or oil solvent is added.
The developer solution comprises a developer and polyvinyl alcohol, wherein the mass of the developer accounts for 70-90% (such as 70%, 80%, 90%) of the dry weight of the developer solution, and the mass of the polyvinyl alcohol accounts for 10-30% (such as 10%, 15%, 25%, 30%) of the dry weight of the developer solution. The sensitizer solution comprises a sensitizer and polyvinyl alcohol, wherein the mass of the sensitizer accounts for 70-90% (e.g. 70%, 80%, 90%) of the dry weight of the sensitizer solution, and the mass of the polyvinyl alcohol accounts for 10-30% (e.g. 10%, 15%, 25%, 30%) of the dry weight of the sensitizer solution.
Note that the dry weight mass of the developer solution in the present embodiment is the mass of the developer solution when no aqueous solvent or oily solvent is added. The dry weight of the sensitizer solution is the weight of the sensitizer solution when no aqueous solvent or oil solvent is added.
The second filler can be at least one of light calcium carbonate, heavy calcium carbonate, calcined kaolin, washing kaolin, aluminum hydroxide, hollow plastic pigment and silicon dioxide, and in order to avoid the influence of too rough paper surface on the quality of thermal printing, the second filler comprises a second fine particle size filler, the second fine particle size filler accounts for 80-100% of the dry weight of the second filler, and the particle size of the second fine particle size filler is less than or equal to 2 microns. The second adhesive may be: the biological latex can be starch, and the starch type can be biological latex prepared from coating-grade starch such as cassava starch, corn starch, potato starch and the like; the starch of the biological latex can be native starch, acidified starch and esterified starch. The lubricant of the top coat 103 can be at least one of calcium stearate, zinc stearate, aluminum stearate and paraffin wax, wherein the particle size of the lubricant is 2-6 micrometers. The color developer of the topcoat 103 may be 2, 2-bis (4-hydroxyphenyl) propane, 2, 4-dihydroxydiphenyl sulfone, 4' -dihydroxydiphenyl sulfone, 3' -diallyl-4, 4' -sulfonylphenol, 4- [ [4- (2-allyloxy) phenyl ] sulfonyl ] phenol, 4-hydroxy-4 ' -isopropoxydiphenyl sulfone, bis (2-chloroethyl) ether-4, 4' -dihydroxydiphenyl sulfone copolymer, 3' -diallyl-4, 4' -sulfonylphenol, 3' -diallyl-4, 4' -dihydroxydiphenyl sulfone, N- (p-toluenesulfonyl) -N ' -3- (p-toluenesulfonyl hydroxyphenyl) urea. Alternatively, the developer may be a single compound. The sensitizer of the top coat 103 may be at least one of 1, 2-diphenoxyethane, 2-naphthol benzyl ether, 1, 2-di-m-tolyloxyethane, diphenyl sulfone, di-p-chlorobenzyl oxalate, p-methylbenzyl alcohol oxalate, dibenzyl oxalate, vinyl bis stearamide, stearic acid amide, stearyl aniline, vinyl bis stearamide, acetoaceto-toluidine, and tetramethyl diphenylethane.
Referring to fig. 1 and fig. 2, a flow chart of an embodiment of a method for manufacturing the thermal security paper 100 of the present application is schematically illustrated, and the method for manufacturing the thermal security paper 100 is used for manufacturing the thermal security paper 100 as described above. The preparation method comprises the following steps:
step S21: a base paper 101 is provided.
Step S22: an anti-counterfeiting coating is coated on one surface of the base paper 101 to form an anti-counterfeiting back coating 104.
The anti-counterfeiting coating comprises a leuco dye microcapsule, the leuco dye microcapsule comprises a first leuco dye, the first leuco dye is a leuco dye for displaying blue, red, black or other colors, and the coating weight of the anti-counterfeiting coating is 5-13 g/m2. The preferable coating weight is 6-10 g/m2E.g. 6g/m2、8g/m2、10g/m2。
Step S23: the base coating is applied on the other surface of the base paper 101 facing away from the forgery-preventing back coating 104 to form a base coating 102.
The coating weight of the prime coating is 5-15 g/m2. The preferable coating weight is 6-10 g/m2E.g. 6g/m2、8g/m2、10g/m2。
Step S24: a surface of the base coat layer 102 facing away from the base paper 101 is coated with a coating material to form a top coat layer 103.
The top-coat paint contains a color-developing agent, and the coating weight of the top-coat paint is 3-12 g/m2. Preferably, the coating weight is 5 to 9g/m2E.g. 5g/m2、7g/m2、9g/m2。
Step S25: and drying the base paper 101 with the top coating 103 to obtain the anti-counterfeiting thermal paper 100.
In contrast to the prior art, the forgery-preventing thermal paper 100 prepared by the present application includes a base paper 101, wherein one surface of the base paper 101 is coated with a forgery-preventing coating containing leuco dye microcapsules containing a first leuco dye that develops color when exposed to a developer, and the other surface of the base paper 101 is sequentially provided with an undercoat layer 102 and a topcoat layer 103, and the topcoat layer forming the topcoat layer 103 contains a developer that develops color of the first leuco dye. In this way, the anti-counterfeiting thermal sensitive paper 100 of the present application only needs to contact the two surfaces and apply pressure to the paper surface during use, so that the leuco dye microcapsules are broken and flow out of the leuco dye, and the leuco dye is developed to realize the anti-counterfeiting function when encountering a color developing agent. Therefore, the thermal paper has anti-counterfeiting performance, can realize the anti-counterfeiting function without post processing, can be produced on the basis of the existing coating equipment, can avoid extra equipment cost investment, and effectively reduces the cost of the anti-counterfeiting thermal paper 100.
In one embodiment, before step S23, the preparation method further includes preparing a primer coating including: weighing the first filler, the first adhesive and water according to a first preset proportion, and uniformly mixing to prepare the primer coating with the concentration of 22% -40% (such as 22%, 30%, 35%, 40%).
Specifically, the base coating comprises a first filler and a first adhesive, wherein the mass of the first filler accounts for 65-85% (for example, 65%, 75% and 85%) of the dry mass of the base coating, and the mass of the first adhesive accounts for 15-35% (for example, 15%, 25% and 35%) of the dry mass of the base coating. Uniformly stirring the first filler, the first adhesive and water at a high speed to prepare the primer coating with the concentration of 22-40%.
Uniformly coating the primary coating on the second surface of the base paper by a coating machine, wherein the coating weight is 5-15 g/m2Preferably, the coating weight is 8 to 12g/m2E.g. 8g/m2、10g/m2、12g/m2. The coating machine may be a bar coater, a knife coater, an air knife coater, a single or multiple layer curtain coater, a single or multiple layer slide curtain coater (or a slide curtain coater), or other coating equipment that can be used for coating.
In one embodiment, before step S24, the preparation method further includes preparing a topcoat paint including: weighing the second filler, the second adhesive, the color developing agent solution, the sensitizer solution, the leuco dye dispersion, the lubricant and water according to a second preset proportion, and uniformly mixing to prepare the surface coating with the concentration of 25-45% (such as 25%, 30%, 35% and 45%).
Specifically, the top coat contains a second filler, a second adhesive, a color developing agent solution, a sensitizer solution, a leuco dye dispersion, a lubricant and water. Wherein the mass of the second filler is 30% to 60% (e.g., 30%, 40%, 50%, 60%) of the dry mass of the topcoat coating, the mass of the second binder is 10% to 25% (e.g., 10%, 15%, 20%, 25%) of the dry mass of the topcoat coating, the mass of the developer solution is 20% to 45% (e.g., 25%, 30%, 35%, 45%) of the dry mass of the topcoat coating, the mass of the leuco dye dispersion is 10% to 35% (e.g., 10%, 15%, 25%, 35%) of the dry mass of the topcoat coating, the mass of the sensitizer solution is 0% to 30% (e.g., 0%, 15%, 25%, 30%) of the dry mass of the topcoat coating, and the mass of the lubricant is 0% to 15% (e.g., 0%, 5%, 10%, 15%) of the dry mass of the topcoat coating. The components and water are evenly stirred at a high speed to prepare the surface coating with the concentration of 25-45%.
Coating the top coating on the bottom coating by a coating machine, wherein the coating weight is 3-12 g/m2E.g. 3g/m2、7g/m2、13g/m2Preferably, the coating weight is 5 to 9g/m2E.g. 5g/m2、7g/m2、9g/m2. The coating machine may be a bar coater, a knife coater, an air knife coater, a single or multiple layer curtain coater, a single or multiple layer slide curtain coater (or a slide curtain coater), or other coating equipment that may be used for coating.
Referring to fig. 3, fig. 3 is a schematic flow chart of another embodiment of the method for preparing the anti-counterfeiting thermal paper of the present application. The preparation of the developer solution comprises the following steps:
step S31: weighing the color developing agent, the polyvinyl alcohol and the water according to a third preset proportion, and uniformly mixing to prepare a color developing agent crude solution with the concentration of 35% -50% (such as 35%, 40%, 45% and 50%).
Step S32: the developer crude solution is ground by a wet grinder to obtain a developer solution having a particle size of 0.3 to 1.8 micrometers (e.g., 0.3 micrometers, 0.8 micrometers, 1.3 micrometers, 1.8 micrometers).
Referring to fig. 4, fig. 4 is a schematic flow chart of another embodiment of the method for preparing the anti-counterfeiting thermal paper of the present application. The preparation of the sensitizer solution comprises the following steps:
step S41: weighing the sensitizer, the polyvinyl alcohol and the water according to a fourth preset proportion, and uniformly mixing to prepare a sensitizer crude solution with the concentration of 35% -50% (such as 35%, 40%, 45% and 50%).
Step S42: the sensitizer crude solution is ground by a wet grinder to obtain a sensitizer solution with a particle size of 0.5-2.0 micrometers (e.g., 0.5 micrometers, 1.0 micrometers, 1.5 micrometers, 2.0 micrometers).
Referring to fig. 5, fig. 5 is a schematic flow chart of a further embodiment of the method for preparing the anti-counterfeiting thermal paper of the present application. The preparation of the leuco dye dispersion comprises the following steps:
step S51: weighing the second leuco dye, the polyvinyl alcohol and the water according to a fifth preset proportion, and uniformly mixing to prepare a leuco dye crude dispersion with the concentration of 35% -50% (for example, 35%, 40%, 45%, 50%).
Step S52: the leuco dye crude dispersion is ground by a wet grinder to obtain a leuco dye dispersion having a particle size of 0.5 to 1.0 micron (e.g., 0.5 micron, 0.7 micron, 0.9 micron, 1.0 micron).
The anti-counterfeiting thermal paper of the invention is further explained by the following specific examples.
Example 1
Preparing a base coating: according to the mass fraction, mixing the light calcium carbonate and the calcined kaolin in a ratio of 1:2, wherein the addition amount of the light calcium carbonate and the calcined kaolin is 84% of the dry weight of the base coating. The addition amount of the polyvinyl alcohol is 16 percent of the dry weight of the base coating. Adding a certain amount of water, and stirring at high speed to prepare the 38% primer coating. Coating the base coating on the second surface of the base paper by a coating machine, wherein the coating weight is 11g/m2。
Preparing a color developing agent solution: according to the mass fraction, the adding amount of the 2, 4-dihydroxy diphenyl sulfone is 72 percent of the dry weight mass of the developer solution, and the adding amount of the polyvinyl alcohol is 28 percent of the dry weight mass of the developer solution. Adding a certain amount of water, stirring at high speed to obtain developer coarse solution with concentration of 37%, and grinding in a wet grinder to obtain developer solution with particle size of 0.8 μm.
Preparing a sensitizer solution: the addition amount of stearic acid amide is 86% of the dry weight of the sensitizer solution, and the addition amount of polyvinyl alcohol is 14% of the dry weight of the sensitizer solution. Adding a certain amount of water, stirring at high speed to obtain a sensitizer crude solution with a concentration of 41%, and grinding in a wet grinding machine to obtain a sensitizer solution with a particle size of 1.2 microns.
Preparation of a leuco dye dispersion: according to the mass fraction, the adding amount of the 2-phenylamino-6-dibutylamino-3-methyl-fluoran is 86% of the dry weight of the leuco dye dispersion, and the adding amount of the polyvinyl alcohol is 14% of the dry weight of the leuco dye dispersion. Adding a certain amount of water, stirring at high speed to prepare a leuco dye solution with a concentration of 41%, and grinding to obtain a leuco dye solution with a particle size of 1.2 microns in a wet grinding machine.
Preparing a top coating: mixing water-washed kaolin and aluminum hydroxide in a ratio of 1:1 by mass, and adding the water-washed kaolin and the aluminum hydroxideThe amount was 42% by mass of the dry weight of the topcoat coating. The addition amount of the carboxylated styrene-butadiene latex is 7 percent of the dry weight of the top-coating paint. The addition amount of the developer solution is 30% of the dry weight of the top-coat paint. The addition amount of the sensitizer solution is 5% of the dry weight of the top-coat paint. The addition amount of the leuco dye solution was 14% by dry weight of the top-coat paint. The addition amount of calcium stearate is 2% of the dry weight of the top-coat paint. Adding a certain amount of water, and uniformly stirring at a high speed to prepare the top coating with the concentration of 30%. The above top-coating paint was applied to the undercoat layer with a coater in an amount of 8.5g/m2。
Anti-counterfeiting coating: the leuco dye microcapsule containing 3- (4-dimethylamino phenyl) -3- (4-methyl ethyl amino phenyl) -6-dimethylamino phthalide has a particle size of 5 μm, and the anti-counterfeiting coating is coated on the first surface of the base paper by a coating machine at a coating weight of 9g/m2。
Example 2
Preparing a base coating: according to the mass fraction, the light calcium carbonate, the calcined kaolin and the plastic pigment are mixed in a ratio of 1:1:1, and the addition amount of the light calcium carbonate, the calcined kaolin and the plastic pigment is 75% of the dry weight of the base coating. Mixing styrene-butadiene acid latex and polyvinyl alcohol in a ratio of 2:1, wherein the addition amount of the styrene-butadiene acid latex and the polyvinyl alcohol is 25% of the dry weight of the base coating. Adding a certain amount of water, and stirring at high speed to prepare the 28% primer coating. Coating the base coating on the second surface of the base paper by a coating machine, wherein the coating weight is 9.8g/m2。
Preparing a color developing agent solution: according to the mass fraction, the adding amount of the 3,3 '-diallyl-4, 4' -dihydroxy diphenyl sulfone is 85% of the dry weight of the developer solution, and the adding amount of the polyvinyl alcohol is 15% of the dry weight of the developer solution. Adding a certain amount of water, stirring at high speed to obtain developer coarse solution with concentration of 43%, and grinding in a wet grinder to obtain developer solution with particle size of 0.8 μm.
Preparation of a leuco dye dispersion: according to the mass fraction, the adding amount of the 3-N-isoamyl-N-ethylamino-6-methyl-7-phenylaminofluorane is 78% of the dry weight of the leuco dye dispersion, and the adding amount of the polyvinyl alcohol is 22% of the dry weight of the leuco dye dispersion. Adding a certain amount of water, stirring at high speed to obtain 48% leuco dye solution, and grinding to obtain 0.8 μm leuco dye solution in a wet grinder.
Preparing a top coating: according to the mass fraction, the light calcium carbonate and the silicon dioxide are mixed in a ratio of 4:1, and the addition amount of the light calcium carbonate and the silicon dioxide is 50% of the dry weight of the top-coat paint. The amount of the acrylic latex added was 6% by dry weight of the top-coat paint. The amount of the developer solution added was 22% by dry weight of the top-coat paint. The addition amount of the sensitizer solution is 10% of the dry weight of the top coating paint. The addition amount of the leuco dye solution was 14% by dry weight of the top-coat paint. According to the mass fraction, the paraffin wax and the aluminum stearate are mixed in a ratio of 1:2, and the addition amount of the paraffin wax and the aluminum stearate is 12 percent of the dry weight of the surface coating paint. Adding a certain amount of water, and uniformly stirring at a high speed to prepare the top coating with the concentration of 45%. The above top-coating paint was applied to the undercoat layer with a coater in an amount of 8.2g/m2。
Anti-counterfeiting coating: the leuco dye microcapsule containing 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalide has a particle size of 5 microns, and the anti-counterfeiting coating is coated on the first surface of the base paper by a coating machine, wherein the coating weight is 10.0g/m2。
Example 3
Preparing a base coating: according to the mass fraction, the heavy calcium carbonate, the calcined kaolin and the plastic pigment are mixed in a ratio of 2:1:1, and the addition amount of the heavy calcium carbonate, the calcined kaolin and the plastic pigment is 67 percent of the dry weight of the base coating. The addition amount of the acrylic latex is 23 percent of the dry weight of the base coating. Adding a certain amount of water, and stirring at high speed to prepare the primer coating with the concentration of 23%. Coating the base coating on the second surface of the base paper by a coating machine, wherein the coating weight is 7.8g/m2。
Preparing a color developing agent solution: according to the mass fraction, the adding amount of the 3,3 '-diallyl-4, 4' -dihydroxy diphenyl sulfone is 85% of the dry weight of the developer solution, and the adding amount of the polyvinyl alcohol is 15% of the dry weight of the developer solution. Adding a certain amount of water, stirring at high speed to obtain developer coarse solution with concentration of 43%, and grinding in a wet grinder to obtain developer solution with particle diameter of 1.2 μm.
Preparing a sensitizer solution: according to the mass fraction, the adding amount of the 2-naphthol benzyl ether is 72 percent of the dry weight of the sensitizer solution, and the adding amount of the polyvinyl alcohol is 28 percent of the dry weight of the sensitizer solution. Adding a certain amount of water, stirring at high speed to obtain a sensitizer crude solution with a concentration of 36%, and grinding in a wet grinding machine to obtain a sensitizer solution with a particle size of 0.7 micrometer.
Preparation of a leuco dye dispersion: according to the mass fraction, the adding amount of the 3-N-isoamyl-N-ethylamino-6-methyl-7-phenylaminofluorane is 78% of the dry weight of the leuco dye dispersion, and the adding amount of the polyvinyl alcohol is 22% of the dry weight of the leuco dye dispersion. Adding a certain amount of water, stirring at high speed to obtain a 48% leuco dye solution, and grinding to obtain a 1.0 micrometer leuco dye solution in a wet grinding machine.
Preparing a top coating: the addition amount of the light calcium carbonate is 43 percent of the dry weight of the top-coat paint in mass fraction. The addition amount of the acrylic latex was 8% by dry weight of the top-coat paint. The amount of the developer solution added was 22% by dry weight of the top-coat paint. The addition amount of the sensitizer solution is 10% of the dry weight of the top coating paint. The addition amount of the leuco dye solution was 12% by dry weight of the top-coat paint. According to the mass fraction, calcium stearate and aluminum stearate are mixed in a ratio of 1:2, and the addition amount of paraffin and aluminum stearate is 5% of the dry weight of the surface coating paint. Adding a certain amount of water, and stirring at high speed to prepare the top coating with the concentration of 43%. The above top-coating paint was applied to the undercoat layer with a coater in an amount of 7.6g/m2。
Anti-counterfeiting coating: the leuco dye microcapsule containing 2 '-chloro-6' - (diethylamino) fluorane and having a particle size of 4.5 μm was applied to the first surface of base paper in an amount of 8.5g/m by means of a coater2。
Example 4
Preparing a base coating: the calcined kaolin was added in an amount of 83% by mass based on the dry weight of the undercoat paint. The addition amount of the biological latex is 17 percent of the dry weight of the priming paint. Adding a certain amount of water, and stirring at high speed to prepare the primer coating with the concentration of 40%. Coating the base coating on the second surface of the base paper by a coating machine, wherein the coating weight is 9.0g/m2。
Preparing a color developing agent solution: according to the mass fraction, the adding amount of the 3,3 '-diallyl-4, 4' -sulfonylphenol is 80% of the dry weight of the developer solution, and the adding amount of the polyvinyl alcohol is 20% of the dry weight of the developer solution. Adding a certain amount of water, stirring at high speed to obtain 40% developer solution, and grinding in a wet grinder to obtain developer solution with particle diameter of 1.0 μm.
Preparing a sensitizer solution: according to the mass fraction, the adding amount of the 1, 2-m-tolyloxy ethane is 75% of the dry weight of the sensitizer solution, and the adding amount of the polyvinyl alcohol is 25% of the dry weight of the sensitizer solution. Adding a certain amount of water, stirring at high speed to obtain a sensitizer crude solution with the concentration of 38%, and grinding to obtain a sensitizer solution with the particle size of 1.2 microns in a wet grinding machine.
Preparation of a leuco dye dispersion: according to the mass fraction, the adding amount of 3- (4-dimethylaminophenyl) -3- (4-methylethylaminophenyl) -6-dimethylaminophthalide is 78% of the dry weight mass of the leuco dye dispersion, and the adding amount of polyvinyl alcohol is 22% of the dry weight mass of the leuco dye dispersion. Adding a certain amount of water, stirring at high speed to obtain a leuco dye solution with a concentration of 46%, and grinding to obtain a leuco dye solution with a particle size of 1.5 μm in a wet grinding machine.
Preparing a top coating: the amount of the light calcium carbonate mixed with the aluminum hydroxide in a ratio of 1:1 by mass is 43% of the dry weight of the top-coat paint. The addition amount of the acrylic latex was 8% by dry weight of the top-coat paint. The amount of the developer solution added was 22% by dry weight of the top-coat paint. The addition amount of the sensitizer solution was 12% by dry weight of the top-coat paint. The addition amount of the leuco dye solution was 15% by dry weight of the top-coat paint. The amount of paraffin added was 7% by dry weight of the top-coat paint. Adding a certain amount of water, and stirring at high speed to prepare the top coating with the concentration of 28%. The above top-coating paint was applied to the undercoat layer with a coater in an amount of 7.6g/m2。
Anti-counterfeiting coating: the leuco dye microcapsule containing 2-phenylamino-3-methyl-6-diethylaminofluorane has a particle size of 3.8 μm, and the anti-counterfeiting coating is coated on the first surface of base paper by a coating machine at a coating weight of 7.2g/m2。
Example 5
Preparing a base coating: and mixing the heavy calcium carbonate and the calcined kaolin in a ratio of 1:2 by mass, wherein the addition amount of the heavy calcium carbonate and the calcined kaolin is 80% of the dry weight of the base coating. The addition amount of the biological latex is 20 percent of the dry weight mass of the priming paint. Adding a certain amount of water, and stirring at high speed to prepare the primer coating with the concentration of 36%. Coating the base coating on the second surface of the base paper by a coating machine, wherein the coating weight is 10.0g/m2。
Preparing a color developing agent solution: according to the mass fraction, the addition amount of the 2, 2-bis (4-hydroxyphenyl) propane is 85 percent of the dry weight mass of the developer solution, and the addition amount of the polyvinyl alcohol is 15 percent of the dry weight mass of the developer solution. Adding a certain amount of water, stirring at high speed to obtain a developer coarse solution with a concentration of 45%, and grinding in a wet grinder to obtain a developer solution with a particle size of 1.2 microns.
Preparing a sensitizer solution: according to the mass fraction, the adding amount of the 2-naphthol benzyl ether is 70 percent of the dry weight of the sensitizer solution, and the adding amount of the polyvinyl alcohol is 30 percent of the dry weight of the sensitizer solution. Adding a certain amount of water, stirring at high speed to obtain a sensitizer crude solution with the concentration of 35%, and grinding to obtain a sensitizer solution with the particle size of 0.8 micron in a wet grinding machine.
Preparation of a leuco dye dispersion: according to the mass fraction, the adding amount of the 3-diethylamino-6-methyl-7-chlorofluorane is 86 percent of the dry weight mass of the leuco dye dispersion liquid, and the adding amount of the polyvinyl alcohol is 14 percent of the dry weight mass of the leuco dye dispersion liquid. Adding a certain amount of water, stirring at high speed to obtain 42% leuco dye solution, and grinding to obtain 0.7 μm leuco dye solution in a wet grinder.
Preparing a top coating: according to the mass fraction, the adding amount of the light calcium carbonate and the aluminum hydroxide mixed in a ratio of 1:1 is 37 percent of the dry weight of the top-coat paint. The biological latex and the acrylic latex are mixed in a ratio of 2:1, and the addition amount of the biological latex and the acrylic latex is 8% of the dry weight of the top coating. The addition amount of the developer solution is 25% of the dry weight of the top coating paint. The addition amount of the sensitizer solution is 15% of the dry weight of the top coating paint. The addition amount of the leuco dye solution was 14% by dry weight of the top-coat paint. The amount of paraffin added was 7% by dry weight of the top-coat paint. Adding a certain amount of water, and stirring at high speed to prepare the top coating with the concentration of 28%. The above top-coating paint was applied to the undercoat layer with a coater in an amount of 8.5g/m2。
Anti-counterfeiting coating: the leuco dye microcapsule containing 3-N-isoamyl-N-ethylamino-6-methyl-7-phenylaminofluorane has a particle size of 3.0 microns, and the anti-counterfeiting coating is coated on the first surface of the base paper by a coating machine, wherein the coating weight is 9.0g/m2。
Comparative example 1
Preparing a base coating: the addition amount of the water-washed kaolin is 78 percent of the dry weight of the base coating according to the mass fraction. The addition amount of the styrene-butadiene latex is 22 percent of the dry weight of the base coating. Adding a certain amount of water, and stirring at high speed to prepare the primer coating with the concentration of 36%. Coating the base coating on the second surface of the base paper by a coating machine, wherein the coating weight is 10.0g/m2。
Preparing a color developing agent solution: according to the mass fraction, the addition amount of the 2, 2-bis (4-hydroxyphenyl) propane is 85 percent of the dry weight mass of the developer solution, and the addition amount of the polyvinyl alcohol is 15 percent of the dry weight mass of the developer solution. Adding a certain amount of water, stirring at high speed to obtain a developer coarse solution with a concentration of 45%, and grinding in a wet grinder to obtain a developer solution with a particle size of 1.2 microns.
Preparing a sensitizer solution: according to the mass fraction, the adding amount of the 2-naphthol benzyl ether is 72 percent of the dry weight of the sensitizer solution, and the adding amount of the polyvinyl alcohol is 28 percent of the dry weight of the sensitizer solution. Adding a certain amount of water, stirring at high speed to obtain a sensitizer crude solution with a concentration of 34%, and grinding in a wet grinding machine to obtain a sensitizer solution with a particle size of 0.7 micrometer.
Preparation of a leuco dye dispersion: according to the mass fraction, the addition amount of the 2-phenylamino-3-methyl-6-diethylaminofluorane is 88 percent of the dry weight mass of the leuco dye dispersion liquid, and the addition amount of the polyvinyl alcohol is 12 percent of the dry weight mass of the leuco dye dispersion liquid. Adding a certain amount of water, stirring at high speed to obtain a leuco dye solution with a concentration of 43%, and grinding to obtain a leuco dye solution with a particle size of 1.0 μm in a wet grinding machine.
Preparing a top coating: the light calcium carbonate accounts for 37 percent of the dry weight of the top coating according to the mass fraction. The addition amount of the biological latex is 8 percent of the dry weight mass of the top coating. The addition amount of the developer solution was 23% by dry weight of the top-coat paint. The addition amount of the sensitizer solution was 14% by dry weight of the top-coat paint. The addition amount of the leuco dye solution was 14% by dry weight of the top-coat paint. The amount of the paraffin wax added is 6% of the dry weight of the top-coat paint. Adding a certain amount of water, and stirring at high speed to prepare the top coating with the concentration of 28%. The above top-coating paint was applied to the undercoat layer with a coater in an amount of 8.0g/m2。
Comparative example 2
Preparing a base coating: according to the mass fraction, the light calcium carbonate and the hollow plastic pigment are mixed in a ratio of 2:1, and the addition amount of the light calcium carbonate and the hollow plastic pigment is 80% of the dry weight of the base coating. The addition amount of the styrene-butadiene latex is 20 percent of the dry weight of the base coating. Adding a certain amount of water, and stirring at high speed to prepare the 38% primer coating. Coating the base coating on the second surface of the base paper by a coating machine, wherein the coating weight is 8.5g/m2。
Preparing a color developing agent solution: according to the mass fraction, the adding amount of the 3,3 '-diallyl-4, 4' -sulfonylphenol is 80% of the dry weight of the developer solution, and the adding amount of the polyvinyl alcohol is 20% of the dry weight of the developer solution. Adding a certain amount of water, stirring at high speed to obtain 40% developer solution, and grinding in a wet grinder to obtain developer solution with particle diameter of 1.0 μm.
Preparing a sensitizer solution: according to the mass fraction, the adding amount of the 1, 2-m-tolyloxy ethane is 75% of the dry weight of the sensitizer solution, and the adding amount of the polyvinyl alcohol is 25% of the dry weight of the sensitizer solution. Adding a certain amount of water, stirring at high speed to obtain a sensitizer crude solution with the concentration of 38%, and grinding to obtain a sensitizer solution with the particle size of 1.2 microns in a wet grinding machine.
Preparation of a leuco dye dispersion: according to the mass fraction, the addition amount of 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalide is 72% of the mass of the leuco dye dispersion on a dry basis, and the addition amount of polyvinyl alcohol is 28% of the mass of the leuco dye dispersion on a dry basis. Adding a certain amount of water, stirring at high speed to obtain a 36% leuco dye solution, and grinding to obtain a 1.3 micrometer leuco dye solution in a wet grinding machine.
Preparing a top coating: the aluminum hydroxide was 36% by mass of the dry weight of the topcoat coating. The addition amount of the carboxylated styrene-butadiene latex is 9 percent of the dry weight of the top-coating paint. The addition amount of the developer solution is 24% of the dry weight of the top-coat paint. The addition amount of the sensitizer solution was 12% by dry weight of the top-coat paint. The addition amount of the leuco dye solution was 14% by dry weight of the top-coat paint. The amount of the paraffin wax added is 5% of the dry weight of the top-coat paint. Adding a certain amount of water, and stirring at high speed to prepare the top coating with the concentration of 28%. The above top-coating paint was applied to the undercoat layer with a coater in an amount of 7.5g/m2。
The anti-counterfeiting performance of the anti-counterfeiting thermal paper in the above embodiment of the present application is tested below.
The anti-counterfeiting thermal papers of examples 1 to 5 and the ordinary thermal papers of comparative examples 1 to 2 were subjected to a front-side conventional image-text printing test using an EPSONTM-88IV thermal POS printer, respectively. And the above examples 1 to 5 were compared with comparative examples 1 to 2, respectively, for the forgery prevention test.
Referring to fig. 6, two pieces of thermal paper 100 and 100' having different thermal coloration and forgery prevention coloration are taken.
Assume 100 that a forgery-preventing thermal paper includes: base paper 101, a bottom coating 102, a top coating 103 containing a color developer, and a forgery prevention coating 104. 100' is a forgery-preventing thermal paper comprising: base paper 101 ', base coat layer 102', color developer-containing top coat layer 103 ', security coating layer 104'.
At this time, the forgery prevention coating layer 104 of the forgery prevention thermal paper 100 is stacked in contact with the color developer-containing top coat layer 103 'of the forgery prevention thermal paper 100'. Then, a forgery prevention performance test was performed by scratching from the position where the color developer-containing top coat layer 103 of the upper thermal paper 100 was stacked or from the position where the forgery prevention coating layer 104 ' of the lower thermal paper 100 ' was stacked, and forgery prevention performance was confirmed based on the color development of the color developer-containing top coat layer 103 ' of the thermal paper, which is the contact surface between the two thermal papers.
(II) assume 100 is a forgery-preventing thermal paper comprising: base paper 101, a bottom coating 102, a top coating 103 containing a color developer, and a forgery prevention coating 104. 100' is a plain thermal paper comprising: base paper 101 ', undercoat layer 102 ', and developer-containing topcoat layer 103 ' (no 104 ' in the case of 100 ' being a plain thermal paper).
At this time, the forgery prevention coating layer 104 of the thermal paper 100 is stacked in contact with the color developer-containing top coating layer 103 'of the plain thermal paper 100'. Then, a forgery prevention performance test was performed by scratching from the position of the color developer-containing top coat layer 103 of the stacked upper thermal paper 100 or from the position of the base paper 101 of the stacked lower thermal paper 100 ', and forgery prevention performance was confirmed based on the color development of the color developer-containing top coat layer 103 ' of the thermal paper, which is the contact surface between the two thermal papers 100, 100 '.
Referring to fig. 7, a piece of thermal paper 100 and a piece of thermal paper 200 with different thermal coloration from the anti-counterfeiting coloration of the thermal paper 100 are taken.
Assume 100 that a forgery-preventing thermal paper includes: base paper 101, a bottom coating 102, a top coating 103 containing a color developer, and a forgery prevention coating 104. 200 is a plain thermal paper comprising: base paper 201, an undercoat layer 202, and a heat-sensitive layer 203.
The forgery-preventing coating 104 of the thermal paper 100 to be tested is stacked in contact with the color developer-containing top coating 203 of any thermal paper. Then, a forgery prevention performance test was performed by scratching from the position of the color developer-containing top coat layer 103 of the stacked upper thermal paper 100 or from the position of the base paper 201 of the stacked lower thermal paper 200, and forgery prevention performance was confirmed based on the color development of the contact surface between the two thermal papers, i.e., the color developer-containing top coat layer 203.
(II) assume 100 is a forgery-preventing thermal paper comprising: base paper 101, a bottom coating 102, a top coating 103 containing a color developer, and a forgery prevention coating 104. 200 is a forgery prevention thermal paper, which comprises: the base paper 201, the bottom coating 202, the top coating 203 containing the color developing agent, and the forgery prevention coating (not shown), when 200 is the forgery prevention thermal paper, the forgery prevention coating is provided on the side of the base paper 201 opposite to the bottom coating 202.
The forgery-preventing coating 104 of the thermal paper 100 to be tested is stacked in contact with the color developer-containing top coating 203 of any thermal paper. Then, a forgery prevention performance test is performed by scratching from the position of the top coat layer 103 containing a developer on the upper thermal paper 100 or from the position of the forgery prevention coating layer 204 on the lower thermal paper 200, and forgery prevention performance is confirmed based on the color development of the contact surface between the two thermal papers 100 and 200, i.e., the top coat layer 203 containing a developer.
See table 1 for specific experimental results:
TABLE 1 anti-counterfeiting test comparison experiment results
According to the test results, the anti-counterfeiting thermal paper provided by the application can be used for developing the color on the front side in a scraping mode to provide anti-counterfeiting performance after the front sides and the back sides of two pieces of thermal paper are in contact and stacked. Compared with the comparative example, the thermal paper has no anti-counterfeiting coating on the back surface, and the front surface of the thermal paper cannot develop color by scraping, so that the anti-counterfeiting performance cannot be provided.
The above embodiments are merely examples and are not intended to limit the scope of the present disclosure, and all modifications, equivalents, and flow charts using the contents of the specification and drawings of the present disclosure or those directly or indirectly applied to other related technical fields are intended to be included in the scope of the present disclosure.
Claims (10)
1. A forgery-preventing thermal paper, comprising:
base paper;
the anti-counterfeiting back coating is arranged on one surface of the base paper and is formed by coating anti-counterfeiting coating, wherein the anti-counterfeiting coating comprises leuco dye microcapsules and a spacing substrate, the leuco dye microcapsules comprise first leuco dyes, and the first leuco dyes are leuco dyes for displaying blue, red, black or other colors;
the base coating is arranged on the other surface of the base paper, which faces away from the back coating;
the top coating is arranged on one surface of the bottom coating, which is opposite to the base paper, and is formed by coating top coating paint;
wherein the top coating comprises a color developing agent, and the anti-counterfeiting back coating does not comprise the color developing agent; when the anti-counterfeiting back coating layer is in contact with the top coating layer, the leuco dye microcapsules can break under pressure to flow out of the first leuco dye, so that the first leuco dye and the color developing agent are in contact for color development, and an anti-counterfeiting function is realized;
the top coating paint at least comprises a leuco dye dispersion liquid, the leuco dye dispersion liquid comprises a second leuco dye and polyvinyl alcohol, and the second leuco dye can chemically react with the color developing agent to generate a color under the action of heat.
2. A forgery-preventing thermal paper as claimed in claim 1,
the leuco dye microcapsule also comprises a wall material, and the particle size of the leuco dye microcapsule is 2.0-6.0 microns;
the spacing matrix is at least one of starch, polyolefin, polymethyl methacrylate and paraffin, and the particle size of the spacing matrix is 5.0-10.0 micrometers;
wherein the mass of the second leuco dye accounts for 70-90% of the mass of the leuco dye dispersion by dry weight; the mass of the polyvinyl alcohol accounts for 10-30% of the dry weight of the leuco dye dispersion liquid; the second leuco dye is a leuco dye for exhibiting blue, red, black, or other colors;
the second leuco dye is adapted to exhibit a color different from a color exhibited by the first leuco dye.
3. A forgery-preventing thermal paper as claimed in claim 2,
the base coat is formed by coating a base coat, wherein the base coat comprises a first filler and a first adhesive, and the mass of the first filler accounts for 65-85% of the dry weight of the base coat; the first adhesive accounts for 15% -35% of the dry weight of the base coating;
the first filler comprises a first fine particle size filler, the first fine particle size filler accounts for 80-100% of the dry weight of the first filler, and the particle size of the first fine particle size filler is less than or equal to 2 microns.
4. A forgery-preventing thermal paper as claimed in claim 2,
the top-coat paint also comprises a second filler, a second adhesive, a color-developing agent solution, a sensitizer solution and a lubricant, wherein the mass of the second filler accounts for 30-60% of the dry weight of the top-coat paint, the mass of the second adhesive accounts for 10-25% of the dry weight of the top-coat paint, the mass of the color-developing agent solution accounts for 20-45% of the dry weight of the top-coat paint, the mass of the leuco dye dispersion accounts for 10-35% of the dry weight of the top-coat paint, the mass of the sensitizer solution accounts for 0-30% of the dry weight of the top-coat paint, and the mass of the lubricant accounts for 0-15% of the dry weight of the top-coat paint;
the second filler comprises a second fine particle size filler, the second fine particle size filler accounts for 80-100% of the dry weight of the second filler, and the particle size of the second fine particle size filler is less than or equal to 2 microns;
the color developing agent solution comprises the color developing agent and polyvinyl alcohol, wherein the weight of the color developing agent accounts for 70-90% of the dry weight of the color developing agent solution; the mass of the polyvinyl alcohol accounts for 10-30% of the dry weight of the color developing agent solution;
the sensitizer solution comprises a sensitizer and polyvinyl alcohol, wherein the mass of the sensitizer accounts for 70-90% of the dry weight of the sensitizer solution, and the mass of the polyvinyl alcohol accounts for 10-30% of the dry weight of the sensitizer solution.
5. A forgery-preventing thermal paper as claimed in claim 2,
the leuco dye for exhibiting blue color is at least one of 10-benzoyl-3, 7-bis (dimethylamino) phenothiazine, 7- [4- (diethylamino) -2- (hexyloxy) phenyl ] -7- (1-ethyl-2-methyl-1H-indol-3-yl) furo [3,4-B ] pyridin-5 (7H) -one, 3- (4-dimethylaminophenyl) -3- (4-methylethylaminophenyl) -6-dimethylaminophthalide, 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalide;
said leuco dyes for exhibiting a black color are 2-phenylamino-3-methyl-6-diethylaminofluoran, 2-phenylamino-3-methyl-6-dibutylaminofluoran, 3-N-isopentyl-N-ethylamino-6-methyl-7-anilinofluoran, 6'- [ 3-ethoxypropyl) ethylamino ] -3' -methyl-2 '- (phenylamino) -spiro [ isobenzofuran-1- (3H),9' - [9H ] xanthen ] -3-one, 3-bis [2- [4- (dimethylamino) phenyl ] -2- (4-methoxyphenyl) vinyl ] -4, at least one of 5,6, 7-tetrachlorophthalide;
the leuco dye for exhibiting a red color is at least one of 2 '-chloro-6' - (diethylamino) fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-bis (N-octyl-2-methylindole) phthalide, 9- [ ethyl (3-methylbutyl) amino ] -spiro [ 12H-benzo [ a ] xanthene-12, 1'(3' H) -isobenzofuran ] -3 '-one, 6' - [ ethyl (4-methylphenyl) amino ] -2 '-methyl-spiro [ isobenzofuran-1 (3H),9' - (9H) xanthene ] -3-one.
6. A method for preparing forgery-preventing thermal paper, which is used for preparing forgery-preventing thermal paper according to any one of claims 1 to 5, the method comprising:
providing a base paper;
the anti-counterfeiting paper is characterized in that anti-counterfeiting coating is coated on one surface of base paper to form an anti-counterfeiting back coating, wherein the anti-counterfeiting coating comprises leuco dye microcapsules and a spacing matrix and does not contain a color developing agent, the leuco dye microcapsules comprise first leuco dye, the first leuco dye is leuco dye for displaying blue, red, black or other colors, and the coating weight of the anti-counterfeiting coating is 5-13 g/m2；
Coating a primer on the other surface of the base paper, which faces away from the anti-counterfeiting back coating, so as to form a base coating, wherein the coating weight of the primer is 5-15 g/m2；
Coating a surface coating on one surface of the bottom coating, which faces away from the base paper, to form a surface coating, wherein the surface coating comprises the color developing agent, and the coating weight of the surface coating is 3-12 g/m2；
Drying the base paper with the surface coating formed to prepare the anti-counterfeiting thermal sensitive paper;
when the anti-counterfeiting back coating layer is in contact with the top coating layer, the leuco dye microcapsules can be broken by pressure to flow out of the first leuco dye, so that the first leuco dye and the color developing agent are in contact for color development, and an anti-counterfeiting function is realized;
before the surface of the base coat opposite to the base paper is coated with the coating, the preparation method further comprises the following steps: preparing the topcoat coating;
the preparing the topcoat coating comprises: weighing a second filler, a second adhesive, a color developing agent solution, a sensitizer solution, a leuco dye dispersion, a lubricant and water according to a second preset proportion, and uniformly mixing to prepare the surface coating with the concentration of 25-45%;
the preparation method further comprises the following steps: preparing the leuco dye dispersion;
the preparing the leuco dye dispersion includes: weighing the second leuco dye, polyvinyl alcohol and water according to a fifth preset proportion, and uniformly mixing to prepare a leuco dye crude dispersion liquid with the concentration of 35% -50%;
grinding the crude leuco dye dispersion by a wet grinder to obtain the leuco dye dispersion with the particle size of 0.5-1.0 micron;
wherein the second leuco dye is capable of chemically reacting with the color developer to produce a color under the action of heat.
7. The method for preparing the anti-counterfeiting thermal paper as claimed in claim 6, wherein before the primer coating is coated on the other surface of the base paper, which faces away from the anti-counterfeiting back coating, the method further comprises the following steps: preparing the base coating;
the preparation of the base coating comprises the following steps: weighing a first filler, a first adhesive and water according to a first preset proportion, and uniformly mixing to prepare the base coating with the concentration of 22-40%;
wherein the first filler is at least one of light calcium carbonate, heavy calcium carbonate, calcined kaolin, water-washed kaolin, aluminum hydroxide, a hollow plastic pigment and silicon dioxide;
the first adhesive is at least one of biological latex, acrylic latex, styrene-butadiene latex, carboxylic styrene-butadiene latex and polyvinyl alcohol.
8. The method for producing forgery-preventing thermal paper as claimed in claim 6,
the second filler is at least one of light calcium carbonate, heavy calcium carbonate, calcined kaolin, water-washed kaolin, aluminum hydroxide, hollow plastic pigment and silicon dioxide;
the second adhesive is at least one of biological latex, acrylic latex, styrene-butadiene latex, carboxylic styrene-butadiene latex and polyvinyl alcohol;
the lubricant is at least one of calcium stearate, zinc stearate, aluminum stearate and paraffin.
9. The method for preparing forgery-preventing thermal paper according to claim 8, further comprising: preparing the color developing agent solution;
the preparing the developer solution includes: weighing the color developing agent, polyvinyl alcohol and water according to a third preset proportion, and uniformly mixing to prepare a color developing agent crude solution with the concentration of 35-50%;
grinding the coarse color developing agent solution by using a wet grinder to prepare the color developing agent solution with the particle size of 0.3-1.8 microns;
the preparation method further comprises the following steps: preparing the sensitizer solution;
the preparing the sensitizer solution comprises: weighing the sensitizer, the polyvinyl alcohol and the water according to a fourth preset proportion, and uniformly mixing to prepare a sensitizer crude solution with the concentration of 35% -50%;
and grinding the sensitizer crude solution by adopting a wet grinding machine to prepare the sensitizer solution with the particle size of 0.5-2.0 microns.
10. The method for producing forgery-preventing thermal paper as claimed in claim 8,
the developer is at least one of 2, 2-bis (4-hydroxyphenyl) propane, 2, 4-dihydroxydiphenyl sulfone, 4 '-dihydroxydiphenyl sulfone, 3' -diallyl-4, 4 '-sulfonylphenol, 4- [ [4- (2-allyloxy) phenyl ] sulfonyl ] phenol, 4-hydroxy-4' -isopropoxydiphenyl sulfone, bis (2-chloroethyl) ether-4, 4 '-dihydroxydiphenyl sulfone copolymer, 3' -diallyl-4, 4 '-sulfonylphenol, 3' -diallyl-4, 4 '-dihydroxydiphenyl sulfone, and N- (p-toluenesulfonyl) -N' -3- (p-toluenesulfonyl hydroxyphenyl) urea;
the sensitizer is at least one of 1, 2-diphenoxy ethane, 2-naphthol benzyl ether, 1, 2-di-m-tolyloxy ethane, diphenyl sulfone, di-p-chlorobenzyl oxalate, p-methyl benzyl alcohol oxalate diester, dibenzyl oxalate, vinyl bis stearamide, stearic acid amide, stearyl aniline, vinyl bis stearamide, acetoaceto-toluidine and tetramethyl diphenylethane.
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Families Citing this family (8)
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|---|---|---|---|---|
| CN109594398B (en) * | 2018-12-29 | 2021-07-30 | 粤港（广州）智能印刷有限公司 | Production process of waterproof thermal sensitive paper |
| DE102019005551A1 (en) * | 2019-08-07 | 2021-02-11 | Giesecke+Devrient Currency Technology Gmbh | Manufacturing process for a security paper and thus obtainable security paper |
| CN114164706A (en) * | 2020-09-10 | 2022-03-11 | 金华盛纸业（苏州工业园区）有限公司 | Thermal paper and preparation method thereof |
| CN113005812B (en) * | 2021-02-24 | 2022-04-22 | 宁波卓洋印务有限公司 | Thermochromic anti-counterfeiting coating and thermochromic anti-counterfeiting paper |
| CN115748297A (en) * | 2021-05-26 | 2023-03-07 | 刘兴发 | Carbon paper with flame retardant property |
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| CN114960274A (en) * | 2022-06-21 | 2022-08-30 | 理光感热技术（无锡）有限公司 | High-stability thermal sensitive paper and preparation method thereof |
| CN115897291A (en) * | 2022-10-20 | 2023-04-04 | 康爱特维迅（蓬莱）化学有限公司 | Thermosensitive recording composite material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193878A (en) * | 1987-02-06 | 1988-08-11 | Fuji Photo Film Co Ltd | Multicolor recording material |
| JPS63218392A (en) * | 1987-03-06 | 1988-09-12 | Fuji Photo Film Co Ltd | Multicolor recording material |
| KR20050101628A (en) * | 2004-04-19 | 2005-10-25 | 삼성전자주식회사 | Heat-sensitive and pressure-sensitive color recording medium and process |
| CN102493278A (en) * | 2011-12-08 | 2012-06-13 | 广东冠豪高新技术股份有限公司 | Two-color anti-counterfeiting carbonless CB (coated back)/CFB (coated front and back) paper and production process for same |
| CN202742838U (en) * | 2012-05-23 | 2013-02-20 | 曹志雄 | Anti-counterfeiting heat-sensitive paper |
| CN103321095A (en) * | 2013-07-03 | 2013-09-25 | 金华盛纸业（苏州工业园区）有限公司 | Fluorescent falsification-preventing carbonless copy paper coating and application thereof |
| CN106120430A (en) * | 2016-06-28 | 2016-11-16 | 金华盛纸业（苏州工业园区）有限公司 | A kind of heat-sensitive paper of mechanical resistant slurry |
| CN106904014A (en) * | 2017-01-22 | 2017-06-30 | 上海固尔建工贸有限公司 | A kind of false-proof ticket heat-sensitive paper and preparation method thereof |
-
2018
- 2018-09-10 CN CN201811052465.6A patent/CN109098042B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193878A (en) * | 1987-02-06 | 1988-08-11 | Fuji Photo Film Co Ltd | Multicolor recording material |
| JPS63218392A (en) * | 1987-03-06 | 1988-09-12 | Fuji Photo Film Co Ltd | Multicolor recording material |
| KR20050101628A (en) * | 2004-04-19 | 2005-10-25 | 삼성전자주식회사 | Heat-sensitive and pressure-sensitive color recording medium and process |
| CN102493278A (en) * | 2011-12-08 | 2012-06-13 | 广东冠豪高新技术股份有限公司 | Two-color anti-counterfeiting carbonless CB (coated back)/CFB (coated front and back) paper and production process for same |
| CN202742838U (en) * | 2012-05-23 | 2013-02-20 | 曹志雄 | Anti-counterfeiting heat-sensitive paper |
| CN103321095A (en) * | 2013-07-03 | 2013-09-25 | 金华盛纸业（苏州工业园区）有限公司 | Fluorescent falsification-preventing carbonless copy paper coating and application thereof |
| CN106120430A (en) * | 2016-06-28 | 2016-11-16 | 金华盛纸业（苏州工业园区）有限公司 | A kind of heat-sensitive paper of mechanical resistant slurry |
| CN106904014A (en) * | 2017-01-22 | 2017-06-30 | 上海固尔建工贸有限公司 | A kind of false-proof ticket heat-sensitive paper and preparation method thereof |
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