CN112428632B - Fluorescent interlayer anti-counterfeiting material and application thereof - Google Patents
Fluorescent interlayer anti-counterfeiting material and application thereof Download PDFInfo
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- CN112428632B CN112428632B CN202011426744.1A CN202011426744A CN112428632B CN 112428632 B CN112428632 B CN 112428632B CN 202011426744 A CN202011426744 A CN 202011426744A CN 112428632 B CN112428632 B CN 112428632B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/14—Printing or colouring
- B32B38/145—Printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
- B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
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- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Printing Methods (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a fluorescent interlayer anti-counterfeiting material and application thereof. The fluorescent sandwich anti-counterfeiting material is formed by pressing a fluorescent material between two layers of biological cellulose films. The invention adopts the biological cellulose membrane with the microscopic superfine reticular structure as the base material of the fluorescent material, and the fluorescent material can be firmly fixed in the reticular structure after being pressed, so that the fluorescent pattern of the prepared anti-counterfeiting material has the technical effect of completely not falling off after being used for a long time, and meanwhile, the printing and the printing can adopt various known printing methods, such as offset printing, gravure printing, flexographic printing, silk screen printing and the like. The method has the technical effects that the printing mode is flexible, the fluorescent material is not limited, and the anti-counterfeiting pattern design can be more complicated and accurate.
Description
Technical Field
The invention relates to the technical field of anti-counterfeiting safety, in particular to a fluorescent interlayer anti-counterfeiting material and application thereof.
Background
The anti-counterfeiting technology is a technology which is adopted for achieving the anti-counterfeiting purpose and is convenient for a user to distinguish true from false, can accurately distinguish true from false within a certain range and is not easy to copy and duplicate. The technology is simple, and the technology is used for preventing counterfeiting and counterfeit. The method is a precautionary technical measure which is adopted for protecting enterprise brands, protecting markets and protecting the legitimate rights and interests of consumers. The anti-counterfeiting technologies are various, and mainly include printing anti-counterfeiting technologies, chemical material anti-counterfeiting technologies, physical anti-counterfeiting technologies, digital information anti-counterfeiting technologies, structure and package anti-counterfeiting technologies, human body and biological characteristic anti-counterfeiting technologies and the like.
The fluorescent anti-counterfeiting material is more applied at present, is colorless under the irradiation of common visible light, and has the luminescent colors of red, yellow, green, blue and the like under the irradiation of a 365/254nm ultraviolet lamp. However, when the fluorescent anti-counterfeiting material is used, the defects that the anti-counterfeiting pattern is single (such as a safety line), the fluorescent anti-counterfeiting material can only be added in a dispersed state (such as plastic injection) in a novel material, or the anti-counterfeiting pattern is easy to fall off and deform, and the like exist. .
Disclosure of Invention
In order to overcome the technical defects, the invention provides a fluorescent interlayer anti-counterfeiting material and application thereof. The anti-counterfeiting pattern has the advantages that the anti-counterfeiting pattern can be designed according to requirements, the pattern is complex, the attachment is firm, the anti-counterfeiting pattern is not easy to fall off, and the like.
The invention relates to a fluorescent sandwich anti-counterfeiting material, which is formed by laminating a fluorescent material between two layers of biological cellulose membranes. Biocellulose (biocelluose), also known as Bacterial Cellulose (BC), is a cellulose synthesized by certain microorganisms of the species acetobacter, agrobacterium, rhizobium, and the like. Unlike plant cellulose, biocellulose is not a structural component of bacterial cell walls, but a product secreted outside cells by bacteria, is in the form of independent filamentous fibers, is cellulose obtained by simple polycondensation of glucose, has an extremely high cellulose content, is not doped with other polysaccharide impurities such as lignin and hemicellulose, and has a microfiber pattern that is much different from that of plant cellulose. Common strains of the biological cellulose producing bacteria are acetobacter xylinum, acetobacter gluconicum and the like. The ultra-pure cellulose structure of the biological cellulose gel makes the appearance of the biological cellulose gel have the characteristics and the appearance of gel, and the biological cellulose gel has high crystallinity (up to 95 percent) and high polymerization degree (DP value is 2000-8000); has hyperfine reticular structure and tensile strength, and also has excellent water holding capacity, high biocompatibility and degradability. Has been widely applied to various fields such as food, medicine and the like.
The invention adopts the biological cellulose membrane as the attachment base material of the fluorescent material, can design and manufacture various known fluorescent materials, such as fluorescent ink, rare earth fluorescent material, quantum dot fluorescent material and the like, into various anti-counterfeiting patterns according to the requirements of anti-counterfeiting users, such as safety lines, safety codes, commodity marks, commodity logos, commodity production places, commodity source tracing codes and the like, and transfers the fluorescent anti-counterfeiting patterns onto the biological fiber membrane by a printing method, and then covers a layer of biological cellulose membrane on the biological fiber membrane, thereby having better fixing and protecting effects. According to the fluorescent sandwich anti-counterfeiting material, the biological cellulose membrane with the micro superfine mesh structure is used as the base material of the fluorescent material, and the fluorescent material can be firmly fixed in the mesh structure after being pressed, so that the prepared anti-counterfeiting material has the technical effect that the fluorescence can not fall off after being used for a long time, and meanwhile, the printing can be realized by adopting various known printing methods, such as offset printing, gravure printing, flexographic printing, silk screen printing and the like. The method has the technical effects that the printing mode is flexible, the fluorescent material is not limited, and the anti-counterfeiting pattern design can be more complicated and accurate.
The fluorescent sandwich anti-counterfeiting material provided by the invention has the advantages that the thickness of the biological cellulose membrane is preferably 0.1-20 mm, and the water content of the biological cellulose membrane is below 30 wt%. The biological fiber membrane can reduce the water content to below 30wt% by adopting a mechanical compression or hot air drying dehydration mode, and then is cut into the required thickness according to the use requirement.
Further, the fluorescent interlayer anti-counterfeiting material provided by the invention is prepared by soaking the biological cellulose membrane in 10-25wt% of sodium hydroxide solution or potassium hydroxide solution at 80-100 ℃ for 2-8 hours before pressing. The research of the invention finds that the biological cellulose membrane treated by proper alkali has more active hydroxyl groups on the surface, and fluorescent particles of the fluorescent material can be well combined and adsorbed and fixed when the fluorescent material is pressed in the biological cellulose membrane. The invention further prepares the fluorescent interlayer anti-counterfeiting material by soaking the biological cellulose membrane in alkali, and tests show that the fluorescent particle attachment firmness is improved. The anti-counterfeiting pattern (such as a holographic image) with a very complex pattern can be firmly fixed, and the anti-counterfeiting information cannot be lost due to friction falling in the using process.
The fluorescent sandwich anti-counterfeiting material is characterized in that the biological cellulose is prepared by statically fermenting biological cellulose producing bacteria in a fermentation culture medium, wherein the biological cellulose producing bacteria comprise acetobacter xylinum or acetobacter gluconicum. The fermentation medium contains a proper amount of carbon source, nitrogen source and trace elements, wherein the carbon source comprises one or more of glucose, sucrose, maltose and lactose; the nitrogen source comprises beef extract or peptone, and glacial acetic acid or citric acid is used for adjusting the pH value of the culture medium to 3.5-5.0; the fermentation medium is preferably supplied with coconut water as the carbon source, preferably 80-90% coconut water by volume.
According to a preferred embodiment of the present invention, the method for preparing the fluorescent sandwich anti-counterfeiting material according to the present invention may comprise the steps of:
1) Soaking the biological cellulose membrane prepared by fermentation in 10-25wt% sodium hydroxide solution or potassium hydroxide solution at 80-100 ℃ for 2-8 hours;
2) Mechanically compressing and dehydrating or drying and dehydrating the soaked biological cellulose membrane by hot air until the water content is below 30wt%, and cutting the biological cellulose membrane into a thin membrane with the thickness of 0.1mm-20 mm;
3) Pressing the fluorescent material between the two layers of the biological cellulose films;
4) Pressing at 100-180 deg.C for 30-600 min.
According to the preparation method, the fluorescent material comprises fluorescent ink, a rare earth fluorescent material, a quantum dot fluorescent material and the like. The fluorescent material can be designed into various anti-counterfeiting patterns according to the needs of users, such as a security line, a security code, a commodity identification, a commodity logo, a commodity origin, a commodity tracing code, a holographic image and the like, the fluorescent material designed into the anti-counterfeiting patterns is printed on one layer of the biological cellulose membrane in a printing mode, and then the other layer of the biological cellulose membrane is covered on the layer of the biological cellulose membrane and is pressed for 60-120 minutes preferably under the condition of 120-150 ℃. A better print fixing effect can be obtained.
The fluorescent interlayer anti-counterfeiting material obtained by the invention can be widely applied to tickets, anti-counterfeiting marks and warning marks and is used for verifying authenticity, source and the like of the tickets and the anti-counterfeiting marks; because the fluorescent material can not be directly seen in visible light, ultraviolet light detection equipment is required to be adopted for detection in verification, and related anti-counterfeiting information can be checked under specific conditions. The anti-counterfeiting material can be directly used on a commodity tag, a ticket part structure or an object needing warning in an embedded mode, and can be processed into other modes needing using according to requirements.
Detailed Description
To further illustrate the present invention, reference is made to the following examples:
the wet biological cellulose membrane of the present invention is prepared by the prior art, such as static tray fermentation or dynamic fermenter fermentation, and one preparation method of the wet biological cellulose membrane involved in the examples is as follows: preparing a biological cellulose fermentation culture medium, wherein the culture medium contains a proper amount of carbon sources such as glucose and sucrose, a proper amount of nitrogen sources and trace elements are added, the pH value is adjusted to be 3.5-5.0, 10% (volume ratio) of fermentation bacteria are inoculated into the culture medium after sterilization, and the fermentation bacteria can be acetobacter xylinum or acetobacter xylinum; fermenting in tray at 34 deg.C for 7 days to obtain biocellulose hydrogel film with thickness of at least 20mm on the tray surface. Washing with ethanol or water.
Example 1: preparation of fluorescent sandwich anti-counterfeiting material
The preparation method comprises the following steps:
1) Soaking the biological cellulose membrane prepared by fermentation in 20wt% sodium hydroxide solution at 90 ℃ for 6 hours;
2) Mechanically compressing and dehydrating or drying and dehydrating the soaked biological cellulose membrane by hot air until the water content is below 20wt%, and cutting the biological cellulose membrane into a thin membrane with the thickness of 6-8 mm;
3) Printing the designed anti-counterfeiting pattern on one layer of biological cellulose film by using fluorescent ink, and covering the layer of biological cellulose film with another layer of biological cellulose film;
4) Pressing at 150 deg.C for 60 min.
The anti-counterfeiting pattern can be designed into various forms, such as a security line, a security code, a commodity identification, a commodity logo, a commodity origin, a commodity source tracing code, a holographic image and the like. The prepared anti-counterfeiting material is transparent and colorless under visible light, and can show a fluorescent anti-counterfeiting pattern therein under the irradiation of ultraviolet light.
Example 2: preparation of fluorescent sandwich anti-counterfeiting material
The preparation method comprises the following steps:
1) Soaking the biological cellulose membrane prepared by fermentation in 15wt% potassium hydroxide solution at 80 ℃ for 8 hours;
2) Mechanically compressing and dehydrating the soaked biological cellulose membrane or drying and dehydrating the biological cellulose membrane by hot air until the water content is below 25wt%, and cutting the biological cellulose membrane into a thin membrane with the thickness of 8-10 mm;
3) Printing the designed anti-counterfeiting pattern on one layer of biological cellulose membrane by using a rare earth fluorescent material, and then covering the biological cellulose membrane with the other layer of biological cellulose membrane;
4) Pressing at 120 deg.C for 120 min.
The anti-counterfeiting pattern can be designed into various forms, such as a safety line, a safety code, a commodity identification, a commodity logo, a commodity origin, a commodity source tracing code, a holographic image and the like. The prepared anti-counterfeiting material is transparent and colorless under visible light, and can show a fluorescent anti-counterfeiting pattern therein under the irradiation of ultraviolet light.
Example 3: preparation of fluorescent sandwich anti-counterfeiting material
The preparation method comprises the following steps:
1) Soaking the biological cellulose membrane prepared by fermentation in 10wt% sodium hydroxide solution at 100 ℃ for 4 hours;
2) Mechanically compressing and dehydrating or drying and dehydrating the soaked biological cellulose membrane by hot air until the water content is below 15wt%, and cutting the biological cellulose membrane into a thin membrane with the thickness of 2-4 mm;
3) Printing the designed anti-counterfeiting pattern on one layer of biological cellulose membrane by using a quantum dot fluorescent material, and then covering the biological cellulose membrane with another layer of biological cellulose membrane;
4) Pressing for 30 minutes under the condition of 180 degrees.
The anti-counterfeiting pattern can be designed into various forms, such as a safety line, a safety code, a commodity identification, a commodity logo, a commodity origin, a commodity source tracing code, a holographic image and the like. The prepared anti-counterfeiting material is transparent and colorless under visible light, and can show a fluorescent anti-counterfeiting pattern therein under the irradiation of ultraviolet light.
Comparative example 1:
only one layer of the biological cellulose film is used in the step 3), and the other layer is not used for pressing. Namely, the fluorescent ink anti-counterfeiting pattern of the example 1 is directly printed on a layer of the biological cellulose film.
Comparative example 2:
the fluorescent ink security device of example 1 was printed on 300 grams of coated paper.
Comparative example 3:
the fluorescent ink security device of comparative example 2 was further covered with a thermoplastic film.
Experimental example: the product of the above embodiment is used for fastness test, and the test process is as follows:
a: the sample was taken and put on the portion printed with the anti-counterfeit pattern with the thumb, and wiped back and forth 30 times with a force of about 3 KGF.
B: the sample was taken and wiped with a piece of white cotton gauze dipped in 75% alcohol back and forth 30 times over the area printed with the anti-counterfeiting pattern.
C: the sample was taken and wiped with a piece of 95% alcohol-dipped cotton gauze back and forth 30 times over the area printed with the anti-counterfeit pattern.
D: the sample was taken and wiped back and forth 30 times with a piece of white cotton gauze dipped in a small amount of gasoline on the portion printed with the anti-counterfeiting pattern.
Results of the experiment
And (3) observing the anti-counterfeiting pattern of the sample under the irradiation of an ultraviolet lamp, wherein the pattern is not notched, broken lines, poor ink adhesion and the like. The observations were as follows:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| A | Clear pattern without deformation | Clear pattern without deformation | Clear pattern without deformation | Clear pattern without deformation | Broken line with notch at pattern edge | Clear pattern without deformation |
| B | Clear pattern without deformation | Clear pattern without deformation | Clear pattern without deformation | Broken line with notch at pattern edge | The whole pattern is not clear | Clear pattern without deformation |
| C | Clear pattern without deformation | Clear pattern without deformation | Clear pattern without deformation | The whole pattern is unclear | The whole pattern is unclear | Slight notch broken line of pattern |
| D | Clear pattern without deformation | Clear pattern without deformation | Clear pattern without deformation | The whole pattern is unclear | Pattern falling off as a whole | Unclear patternAnd the whole has ink falling |
From the above experiments, it can be seen that the fluorescent sandwich anti-counterfeiting material of the invention adopts the biological cellulose membrane with the microscopic ultrafine mesh structure as the base material of the fluorescent material, and the fluorescent material can be firmly fixed in the mesh structure after being pressed, so that the fluorescent pattern of the prepared anti-counterfeiting material has the technical effect of being completely prevented from falling off after being used for a long time, and meanwhile, the printing and printing can adopt various known printing methods, such as offset printing, gravure printing, flexographic printing, silk screen printing and the like. The method has the technical effects that the printing mode is flexible, the fluorescent material is not limited, and the anti-counterfeiting pattern design can be more complicated and accurate.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention made by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (11)
1. The fluorescent sandwich anti-counterfeiting material is characterized in that the fluorescent material is pressed between two layers of biological cellulose membranes, the fluorescent material is printed on one layer of biological cellulose membrane in a printing mode, and the other layer of biological cellulose membrane is covered on the fluorescent sandwich anti-counterfeiting material.
2. The fluorescent sandwich anti-counterfeiting material according to claim 1, wherein the thickness of the biological cellulose membrane is between 0.1mm and 20mm, and the water content of the biological cellulose membrane is below 30 wt%.
3. The fluorescent sandwich anti-counterfeiting material according to claim 1 or 2, wherein the fluorescent material comprises fluorescent ink, rare earth fluorescent material and quantum dot fluorescent material.
4. The fluorescent sandwich anti-counterfeiting material according to claim 1 or 2, wherein the biological cellulose membrane is soaked in 10-25wt% sodium hydroxide solution or potassium hydroxide solution at a temperature of 80-100 ℃ for 2-8 hours before pressing.
5. The fluorescent sandwich anti-counterfeiting material according to claim 1, wherein the biological cellulose is prepared by static fermentation of biological cellulose producing bacteria in a fermentation medium, and the biological cellulose producing bacteria comprise acetobacter xylinum or acetobacter gluconicum.
6. The fluorescent sandwich anti-counterfeiting material according to claim 5, wherein the fermentation medium contains appropriate amounts of carbon source, nitrogen source and trace elements, and the carbon source comprises one or more of glucose, sucrose, maltose and lactose; the nitrogen source comprises beef extract or peptone, and glacial acetic acid or citric acid is used for adjusting the pH value of the culture medium to 3.5-5.0.
7. The fluorescent sandwich security material of claim 5, wherein the fermentation medium is supplied with coconut water as a carbon source, wherein the coconut water is 80-90% by volume.
8. The preparation method of the fluorescent sandwich anti-counterfeiting material as claimed in claim 1, which is characterized by comprising the following steps:
(1) Soaking the biological cellulose membrane prepared by fermentation in 10-25wt% sodium hydroxide solution or potassium hydroxide solution at 80-100 deg.C for 2-8 hr;
(2) Mechanically compressing and dehydrating or drying and dehydrating the soaked biological cellulose membrane by hot air until the water content is below 30wt%, and cutting the biological cellulose membrane into a thin membrane with the thickness of 0.1mm-20 mm;
(3) Pressing the fluorescent material between the two layers of biological cellulose films, namely printing the fluorescent material on one layer of biological cellulose film in a printing mode, and covering the other layer of biological cellulose film thereon;
(4) Pressing at 100-180 deg.C for 30-600 min.
9. The method for preparing the fluorescent sandwich anti-counterfeiting material according to claim 8, wherein the fluorescent material comprises fluorescent ink, rare earth fluorescent material and quantum dot fluorescent material.
10. The method for preparing the fluorescent sandwich anti-counterfeiting material according to claim 8, wherein the step (4) is carried out for 60-120 minutes under the condition of 120-150 ℃.
11. The fluorescent sandwich anti-counterfeiting material according to claim 1 is applied to tickets, anti-counterfeiting marks and warning marks.
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