CN108752580A - A kind of double anti-forge material, antifalsification label and preparation method and false-proof detection method - Google Patents

Abstract

The invention relates to a double anti-counterfeit material, an anti-counterfeit label, a preparation method and an anti-counterfeit detection method. The material has a fluorescent effect under ultraviolet light irradiation, and a shape memory effect at 50-120 ° C. The structural formula is: R is any one or a combination of hydrocarbon groups, alkyl groups, cycloalkyl groups, and aryl groups; R ₁ is any one or more combination of alkyl groups, alkenyl groups, and aryl groups; 5≤n≤ 1000, and n is an integer. Use a tablet press to press the material into a plate with a set raised pattern or text on the surface under the condition of vacuuming and 180-240°C, and then roll the plate in an environment slightly higher than the glass transition temperature of the material. After rolling An anti-counterfeiting label with a flat surface and a thickness of 0.1-1.5mm is formed. The double anti-counterfeiting material and the anti-counterfeiting label of the present invention have double anti-counterfeiting functions of fluorescence anti-counterfeiting and shape memory anti-counterfeiting, and the anti-counterfeiting effect is better. In addition, the preparation method and detection method of the present invention are simple.

Description

A double anti-counterfeit material, anti-counterfeit label, preparation method and anti-counterfeit detection method

technical field

The invention belongs to the technical field of anti-counterfeiting materials, and in particular relates to a double anti-counterfeiting material, an anti-counterfeiting label, a preparation method and an anti-counterfeiting detection method.

Background technique

With the continuous progress of society and the development of industry and agriculture, a variety of commodities of different grades not only promote the rapid development of the commodity economy, but also meet the needs of people's continuously improving material living standards. However, nasty fakes have also entered the circulation market in a mixed manner. Counterfeit coins, counterfeit notes, counterfeit products under the cover of counterfeit trademarks and counterfeit certificates often make people deceived and suffer losses. Anti-counterfeiting materials have been widely used in certificates, currency, labels and important documents. The essence of anti-counterfeiting materials lies in their inimitability and easy identification, and are favored by the general public. Today, anti-counterfeiting materials have become one of the most important and hottest research fields. Scientists have successfully prepared various anti-counterfeiting materials, such as fluorescent anti-counterfeiting materials, laser anti-counterfeiting materials, shape memory anti-counterfeiting materials and so on.

Fluorescent anti-counterfeiting materials can respond to different fluorescent effects after external stimuli, with high technological content, good color concealment, and certain aesthetics. Laser anti-counterfeiting refracts different colors or patterns through observation from different angles, with good anti-counterfeiting effect and beautiful colors. Shape memory material is currently a new type of anti-counterfeiting material. Its shape will change to a certain extent after external stimulation, and the process of shape change is controllable and editable. Anti-counterfeiting labels made of shape memory anti-counterfeiting materials are simple and reliable in inspection methods, and shape memory anti-counterfeiting materials are favored by enterprises and consumers for their easy identification, difficulty in imitation and moderate price. However, with the rapid development of science and technology, the high profits brought by counterfeiting and shoddy products make the counterfeiting technology more able to confuse the real ones, which brings great challenges to anti-counterfeiting materials.

Contents of the invention

In order to solve the above technical problems, the present invention provides a double anti-counterfeiting material, an anti-counterfeiting label, a preparation method and an anti-counterfeiting detection method.

In order to realize the purpose of the present invention, the present invention has adopted following technical scheme:

A double anti-counterfeiting material, the material has a fluorescent effect under the irradiation of ultraviolet light, and the material has a shape memory effect under the condition of 50-120°C. The structural formula of the material is as follows:

Wherein, R is any group or _a combination of groups in hydrocarbon group, alkyl group, cycloalkyl group and aryl group; R is any group or group in alkyl group, alkenyl group and aryl group A combination of groups; 5≤n≤1000, and n is an integer.

Further technical solution: the glass transition temperature of the material is 45-120°C, the degradation temperature is 260-300°C; the breaking strength of the material is 30-110MPa, the elongation at break is 5-15%, and the toughness after moisture absorption is 36 ~52MJ/m ³ .

An anti-counterfeit label made of the double anti-counterfeit material, which is obtained through the following processing steps:

Step 1. Use a tablet press to press the material into a plate with a set raised pattern or text on the surface under the condition of vacuuming and 180-240°C. The thickness of the plate is 0.1-2mm, and the raised pattern Or text height 0.1 ~ 1mm;

Step 2. Rolling the plate in an environment slightly higher than the glass transition temperature of the material, and forming a film with a flat surface and a thickness of 0.1-1.5 mm after rolling, and the film constitutes the anti-counterfeiting label.

A preparation method of the double anti-counterfeiting material, comprising the following steps:

Step 1, heating and dissolving 35-156 parts by weight of dimethyl ester compounds and 28-87 parts by weight of alcohol ammonia compounds and stirring uniformly to form a reaction solution; the structural formula of the dimethyl ester compounds is The structural formula of the alcohol ammonia compound is

Step 2, adding 0.1-0.3 parts by weight of a basic catalyst to the reaction liquid, sealing and heating to 60-80°C for 2-24 hours;

Step 3, heating the reaction liquid described in step 2 to 95-105°C, and pumping the water pump to react for 1-3 hours;

Step 4, heating the reaction liquid described in step 3 to 145-155°C, and vacuuming the reaction with an oil pump for 0.5-1.5 hours;

Step 5. Heating the reaction solution in step 4 to 210-230° C., and vacuuming the mixture with an oil pump for 0.5-1.5 hours to obtain the double anti-counterfeiting material.

Further technical scheme: the catalyst is any one of sodium methoxide solution, potassium methoxide solution and sodium ethoxide solution.

An anti-counterfeit detection method of the anti-counterfeit label, heating the anti-counterfeit label at 50-120°C for 10-30 seconds, then placing the anti-counterfeit label under ultraviolet light, and observing the shape and color change of the anti-counterfeit label; When the surface of the anti-counterfeit label has a raised pattern or text and emits the expected fluorescent effect, it means that the anti-counterfeit label is genuine, otherwise it is false.

A further technical solution: the anti-counterfeiting label is directly heated by soaking in hot air or hot water.

The beneficial effects of the present invention are:

(1) The double anti-counterfeiting material of the present invention has good thermal stability and excellent mechanical properties. The double anti-counterfeit material of the present invention and the anti-counterfeit label made of the double anti-counterfeit material shrink after heating, the surface shape changes, and at the same time produce obvious fluorescent colors under ultraviolet irradiation, thereby giving people a strong tactile and visual difference , the anti-counterfeiting effect is remarkable, and the detection operation is simple and convenient. Since the double anti _- counterfeiting material composed of different groups R and R1 will emit different fluorescent colors, it is difficult to imitate, that is, the anti-counterfeiting effect of the double anti-counterfeiting material of the present invention is better.

(2) The double anti-counterfeiting material of the present invention is obtained by synthesizing dimethyl ester compounds and alcohol ammonia compounds without adding solvents, the synthesis method is simple, no pollution to the environment, the product does not need to be purified and removed, and the recovery is simple .

The chemical reaction formula of dimethyl ester compound and alcohol ammonia compound described in the present invention is as follows:

During the preparation process of the double anti-counterfeiting material of the present invention, the function of the water pump to vacuumize is to remove impurities in the reaction system; the function of the oil pump to vacuumize is to prevent the reaction system from being oxidized, and to gradually increase the molecular weight of the product and improve the overall performance. it is good.

(3) During the preparation process of the anti-counterfeiting label of the present invention, the shape of the plate is a permanent memory shape, and the shape of the film formed after rolling is a temporary memory shape. When the anti-counterfeiting label is detected by the anti-counterfeiting detection method, it will be It will change from a temporary memory shape to a permanent memory shape. At this time, the raised pattern or text on the surface of the anti-counterfeiting label will reappear, which is more conducive to realizing the shape memory anti-counterfeiting function.

Description of drawings

Figure 1 is a schematic diagram of the shape memory effect produced by the double anti-counterfeiting material in Example 1. It can be seen from Figure 1 that the flat temporary memory shape of the double anti-counterfeiting material in Example 1 gradually returns to the folded permanent memory shape after being heated at a temperature slightly higher than the glass transition temperature.

Fig. 2 is a schematic diagram of the fluorescent effect produced by the double anti-counterfeiting material in Examples 1, 2, and 3. As can be seen from Figure 2, the double anti-counterfeiting materials of Examples 1, 2, and 3 produce fluorescent effects of different colors under the irradiation of 365nm ultraviolet light. Example 1 produces blue fluorescence, example 2 produces green fluorescence, and example 3 produces yellow fluorescence.

3 is a schematic diagram of an anti-counterfeit detection method for a double anti-counterfeit label in Example 1. It can be seen from Figure 3 that the anti-counterfeit detection method of the double anti-counterfeit label of Example 1: it will emit blue fluorescence under heating and ultraviolet irradiation, and two raised characters on the genuine product will appear on the surface.

Fig. 4 is the fluorescence spectrum obtained by the double anti-counterfeiting material in Example 1 produced by the fluorescence effect. It can be seen from Fig. 4 that the fluorescence spectrum of the double anti-counterfeiting material of Example 1, the peak of fluorescence is mainly in the spectral range of blue light, indicating that the material of Example 1 emits blue fluorescence after being excited by ultraviolet light.

Detailed ways

Below in conjunction with embodiment technical solution of the present invention is made more specific description:

Example 1

Take 9.5 g of dimethyl sebacate and 3.7 g of 1,3 diamino-2-propanol and mix them uniformly at 70°C, add 250 μL of sodium methoxide solution (concentration: 5 mol/L), seal and heat at 70°C for 12 hours. Connect the water pump to evacuate and heat to 100°C for 2 hours until there is no liquid in the reaction system. Replace the water pump with an oil pump to evacuate and heat to 150°C for 1 hour. Finally, the oil pump is vacuumed and heated to 220°C for 1 hour to obtain a double anti-counterfeiting material.

The glass transition temperature of the double anti-counterfeiting material is 50°C, and the degradation temperature is 280°C; the breaking strength of the material is 70MPa, the breaking elongation is 8%, and the toughness after moisture absorption is 45MJ/m ³ .

Using a tablet press, the tablet press mold is designed with a variety of shapes or characters, and a certain distance is set between the shapes or characters (the distance is set according to the degree of thinning of the sheet, the thinner the sheet is rolled, the greater the distance). Use a mold to press the above double anti-counterfeiting material into a plate with a pattern or text corresponding to the mold on the surface under high temperature and vacuum conditions. The thickness of the plate is 0.1mm, and the shape or text is raised by 0.1mm. The plate is heated, and the heated plate is pressed into a flat film of 0.1mm by using a three-roller calender. When using a flat film as an anti-counterfeiting label, heat it with a hair dryer or soak it in boiling water, the film will shrink and show patterns or characters, and when the film is irradiated with an ultraviolet pen or placed under a banknote detector, the irradiated area will be It emits obvious blue fluorescence and obtains a double anti-counterfeiting label.

Example 2

Take 13.5 g of dimethyl malonate and 9.3 g of 1,3 diamino-2-propanol and mix them uniformly at 70°C, add 650 μL of sodium methoxide solution (concentration: 5 mol/L), seal and heat at 70°C for 10 hours. Connect the water pump to evacuate and heat to 100°C for 1 hour until there is no liquid in the reaction system. Replace the water pump with an oil pump to evacuate and heat to 150°C for 0.8 hours. Finally, the oil pump vacuumizes and heats to 220°C for 1 hour to prepare a double anti-counterfeiting material .

The glass transition temperature of the double anti-counterfeiting material is 120°C, and the degradation temperature is 300°C; the breaking strength of the material is 110MPa, the breaking elongation is 5%, and the toughness after moisture absorption is 52MJ/m ³ .

Using a tablet press, the tablet press mold is designed with a variety of shapes or characters, and a certain distance is set between the shapes or characters (the distance is set according to the degree of thinning of the sheet, the thinner the sheet is rolled, the greater the distance). Use a mold to press the above double anti-counterfeiting material into a plate with a pattern or text corresponding to the mold on the surface under high temperature and vacuum conditions. The thickness of the plate is 1mm, and the shape or text is raised by 0.5mm. The plate is heated, and the heated plate is pressed into a flat film of 0.8mm by using a three-roller calender. When using a flat film as an anti-counterfeiting label, heat it with a hair dryer or soak it in boiling water, the film will shrink and show patterns or characters, and when the film is irradiated with an ultraviolet pen or placed under a banknote detector, the irradiated area will be It emits obvious green fluorescence and obtains double anti-counterfeiting labels.

Example 3

Take 5.9 g of dimethyl terephthalate and 2.8 g of 1,3 diamino-2-propanol and mix them uniformly at 70°C, add 190 μL of sodium methoxide solution (concentration: 5 mol/L), seal and heat at 70°C for 10 hours. Connect the water pump to evacuate and heat to 100°C for 1.5h until there is no liquid in the reaction system. Replace the water pump with an oil pump to evacuate and heat to 150°C for 0.5h. Finally, the oil pump is evacuated and heated to 220°C for 0.8h to prepare a double Anti-counterfeiting material.

The glass transition temperature of the double anti-counterfeiting material is 90°C, and the degradation temperature is 290°C; the breaking strength of the material is 100MPa, the breaking elongation is 7%, and the toughness after moisture absorption is 43MJ/m ³ .

Using a tablet press, the tablet press mold is designed with a variety of shapes or characters, and a certain distance is set between the shapes or characters (the distance is set according to the degree of thinning of the sheet, the thinner the sheet is rolled, the greater the distance). Use a mold to press the above double anti-counterfeiting material into a plate with a pattern or text corresponding to the mold on the surface under high temperature and vacuum conditions. The thickness of the plate is 2mm, and the shape or text is raised by 1mm. The plate is heated, and the heated plate is pressed into a flat film of 1.5 mm by a three-roll calender. When using a flat film as an anti-counterfeiting label, heat it with a hair dryer or soak it in boiling water, the film will shrink and show patterns or characters, and when the film is irradiated with an ultraviolet pen or placed under a banknote detector, the irradiated area will be It emits obvious yellow fluorescence and obtains a double anti-counterfeiting label.

Example 4

Take 2.6 g of dimethyl terecanedicarboxylate and 1.9 g of 1,3 diamino-2-propanol and mix well at 60°C, add 100 μL of sodium methoxide solution (concentration: 5 mol/L), seal and heat at 60°C for 24 hours. Connect the water pump to evacuate and heat to 95°C to react for 3 hours until there is no liquid in the reaction system. Replace the water pump with an oil pump to evacuate and heat to 155°C to react for 0.5h. Finally, the oil pump is evacuated and heated to 210°C for 1.5h to prepare a double anti-counterfeiting product. Material.

The glass transition temperature of the double anti-counterfeiting material is 45°C, and the degradation temperature is 260°C; the breaking strength of the material is 30MPa, the breaking elongation is 15%, and the toughness after moisture absorption is 36MJ/m ³ .

Using a tablet press, the tablet press mold is designed with a variety of shapes or characters, and a certain distance is set between the shapes or characters (the distance is set according to the degree of thinning of the sheet, the thinner the sheet is rolled, the greater the distance). Use a mold to press the above double anti-counterfeiting material into a plate with a pattern or text corresponding to the mold on the surface under high temperature and vacuum conditions. The thickness of the plate is 2mm, and the shape or text is raised by 1mm. The plate is heated, and the heated plate is pressed into a flat film of 1.5 mm by a three-roll calender. When using a flat film as an anti-counterfeiting label, heat it with a hair dryer or soak it in boiling water, the film will shrink and show patterns or characters, and when the film is irradiated with an ultraviolet pen or placed under a banknote detector, the irradiated area will be It emits a distinct bright blue color fluorescence and obtains a double anti-counterfeiting label.

Example 5

Take 7.0 g of dimethyl tereadipate and 3.7 g of 1,3 diamino-2-propanol and mix them uniformly at 60°C, add 250 μL of sodium methoxide solution (concentration: 5 mol/L), seal and heat at 65°C for 14 hours. Connect the water pump to evacuate and heat to 100°C for 1.5h until there is no liquid in the reaction system. Replace the water pump with an oil pump to evacuate and heat to 155°C for 0.8h. Finally, the oil pump is evacuated and heated to 215°C for 1.2h to prepare a double Anti-counterfeiting material.

The glass transition temperature of the double anti-counterfeiting material is 82°C, and the degradation temperature is 287°C; the breaking strength of the material is 85MPa, the breaking elongation is 7%, and the toughness after moisture absorption is 46MJ/m ³ .

Using a tablet press, the tablet press mold is designed with a variety of shapes or characters, and a certain distance is set between the shapes or characters (the distance is set according to the degree of thinning of the sheet, the thinner the sheet is rolled, the greater the distance). Use a mold to press the above double anti-counterfeiting material into a plate with a pattern or text corresponding to the mold on the surface under high temperature and vacuum conditions. The thickness of the plate is 2mm, and the shape or text is raised by 1mm. The plate is heated, and the heated plate is pressed into a flat film of 1.5 mm by a three-roll calender. When using a flat film as an anti-counterfeiting label, heat it with a hair dryer or soak it in boiling water, the film will shrink and show patterns or characters, and when the film is irradiated with an ultraviolet pen or placed under a banknote detector, the irradiated area will be It emits obvious light blue color fluorescence, and obtains a double anti-counterfeiting label.

Example 6

Take 3.7 g of dimethyl tartrate and 1.9 g of 1,3 diamino-2-propanol and mix them uniformly at 65 °C, add 130 μL of sodium methoxide solution (concentration 5 mol/L), seal and heat at 75 °C for 12 hours. Connect the water pump to evacuate and heat to 105°C for 2 hours until there is no liquid in the reaction system. Replace the water pump with an oil pump to evacuate and heat to 150°C for 1.2 hours. Finally, the oil pump is vacuumed and heated to 220°C for 1 hour to prepare a double anti-counterfeiting material .

The glass transition temperature of the double anti-counterfeiting material is 92°C, and the degradation temperature is 285°C; the breaking strength of the material is 105MPa, the breaking elongation is 5%, and the toughness after moisture absorption is 39MJ/m ³ .

Using a tablet press, the tablet press mold is designed with a variety of shapes or characters, and a certain distance is set between the shapes or characters (the distance is set according to the degree of thinning of the sheet, the thinner the sheet is rolled, the greater the distance). Use a mold to press the above double anti-counterfeiting material into a plate with a pattern or text corresponding to the mold on the surface under high temperature and vacuum conditions. The thickness of the plate is 2mm, and the shape or text is raised by 1mm. The plate is heated, and the heated plate is pressed into a flat film of 1.5 mm by a three-roll calender. When using a flat film as an anti-counterfeiting label, heat it with a hair dryer or soak it in boiling water, the film will shrink and show patterns or characters, and when the film is irradiated with an ultraviolet pen or placed under a banknote detector, the irradiated area will be It emits obvious light yellow fluorescence and obtains double anti-counterfeiting labels.

Example 7

Take 7.4 g of dimethyl furandicarboxylate and 3.7 g of 1,3 diamino-2-propanol and mix them uniformly at 65 °C, add 260 μL of sodium methoxide solution (concentration: 5 mol/L), seal and heat at 70 °C for 15 h. Connect the water pump to evacuate and heat to 110°C for 2.5 hours until there is no liquid in the reaction system. Replace the water pump with an oil pump to evacuate and heat to 150°C for 1 hour. Finally, the oil pump is vacuumed and heated to 225°C for 1.5 hours to prepare a double anti-counterfeiting product. Material.

The glass transition temperature of the double anti-counterfeiting material is 95°C, and the degradation temperature is 295°C; the breaking strength of the material is 107MPa, the breaking elongation is 6%, and the toughness after moisture absorption is 49MJ/m ³ .

Using a tablet press, the tablet press mold is designed with a variety of shapes or characters, and a certain distance is set between the shapes or characters (the distance is set according to the degree of thinning of the sheet, the thinner the sheet is rolled, the greater the distance). Use a mold to press the above double anti-counterfeiting material into a plate with a pattern or text corresponding to the mold on the surface under high temperature and vacuum conditions. The thickness of the plate is 2mm, and the shape or text is raised by 1mm. The plate is heated, and the heated plate is pressed into a flat film of 1.5 mm by a three-roll calender. When using a flat film as an anti-counterfeiting label, heat it with a hair dryer or soak it in boiling water, the film will shrink and show patterns or characters, and when the film is irradiated with an ultraviolet pen or placed under a banknote detector, the irradiated area will be It emits obvious dark green fluorescence and obtains a double anti-counterfeiting label.

The above examples are only used to illustrate the implementation of the present invention, and are not intended to limit the protection scope of the present invention. Improvements and adjustments made by skilled personnel according to the present invention in practical applications still belong to the protection scope of the present invention.

Claims (7)

1. a kind of double anti-forge material, it is characterised in that：The material has fluorescent effect under ultraviolet light, and the material is 50 There is shape memory effect under the conditions of~120 DEG C, the structural formula of the material is as follows：

Wherein, R is the combination of any one of alkyl, alkyl, naphthenic base, aromatic radical group or a variety of groups；R₁For alkyl, alkene The combination of any one of base, aromatic radical group or a variety of groups；5≤n≤1000, and n is integer.

2. double anti-forge material as described in claim 1, it is characterised in that：The glass transition temperature of the material 45~ 120 DEG C, degradation temperature is 260~300 DEG C；The fracture strength of the material is 30~110MPa, and elongation at break is 5~15%, 36~52MJ/m of toughness after moisture absorption³。

3. a kind of antifalsification label made of double anti-forge material as claimed in claim 1 or 2：It is characterized in that the label passes through Following procedure of processing obtains：

Step 1 has setting vacuumizing and the material is pressed into surface under the conditions of 180~240 DEG C by tablet press machine The pattern of protrusion or the plank of word, the 0.1~2mm of plate thickness, 0.1~1mm of pattern or word height of the protrusion；

Step 2 rolls the plank in the environment of the slightly above material glass transition temperature, and surface is formed after calendering Smooth and thickness is the film of 0.1~1.5mm, and the film constitutes the antifalsification label.

4. a kind of preparation method of double anti-forge material as claimed in claim 1 or 2, it is characterised in that include the following steps：

Step 1 dissolves by heating the alcohol ammoniac compounds of 35~156 parts by weight dimethyl ester compounds and 28~87 parts by weight simultaneously It stirs evenly to form reaction solution；The structural formula of the dimethyl ester compound isThe alcohol ammoniac compounds Structural formula be

0.1~0.3 parts by weight basic catalyst, heated sealed to 60~80 DEG C of reactions 2 are added into the reaction solution for step 2 ~for 24 hours；

Reaction solution described in step 2 is heated to 95~105 DEG C by step 3, and water pump vacuumizes reaction 1~3 hour；

Reaction solution described in step 3 is heated to 145~155 DEG C by step 4, and oil pump vacuumizes reaction 0.5~1.5 hour；

Reaction solution described in step 4 is heated to 210~230 DEG C by step 5, and oil pump vacuumizes reaction 0.5~1.5 hour, obtains The double anti-forge material.

5. the preparation method of double anti-forge material as claimed in claim 4, it is characterised in that：The catalyst is that sodium methoxide is molten Any one of liquid, methanol potassium solution, alcohol sodium solution.

6. a kind of false-proof detection method of antifalsification label as claimed in claim 3, it is characterised in that：By the antifalsification label 50 It is heated under the conditions of~120 DEG C 10~30 seconds, the antifalsification label is placed under ultraviolet light later, observes the shape of antifalsification label And color change；When the pattern or word that the antifalsification label surface has setting raised and send out expected fluorescent effect, then it represents that The antifalsification label is true, is otherwise false.

7. the false-proof detection method of antifalsification label as claimed in claim 6, it is characterised in that：The antifalsification label heating Directly use hot wind or hot-water soak.