Preparation method of pulp molding material with anti-counterfeiting function

Abstract

The invention discloses a method for preparing a pulp molding material with an anti-counterfeiting function, which specifically comprises the following steps: step 1, performing red-blue light modification on cotton fibers; step 2, performing green-red light modification on cotton fibers; step 3, performing blue-green light modification on cotton fibers; step 4, preparing optical anti-counterfeiting fibers according to the products obtained in steps 1 to 3; and step 5, preparing a pulp molding anti-counterfeiting material according to the product obtained in step 4. In the preparation method of the invention, anti-counterfeiting particles are embedded in the interior of pulp molding products, so that the anti-counterfeiting performance of the prepared material is greatly improved, and the difficulty and cost of counterfeiting are increased.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a method for preparing a pulp molding material with anti-counterfeiting function. Background Art

[0002] With the rapid development of social economy, product packaging can be seen everywhere, and the role of packaging is becoming more and more important. The most basic function of packaging is to protect products from wear and damage during transportation. Compared with traditional petroleum-based packaging materials, the raw materials of pulp molded products are green and renewable, and the fibers used can be recycled for a second time, making them more and more important in the packaging field. Pulp molded products are based on papermaking pulp, and a series of additives such as water retaining agents and reinforcing agents are added, and further compression molded on a special mesh mold to form a type of three-dimensional paper product. With the widespread application of pulp molded products, how to conveniently and quickly identify and high-level anti-counterfeiting on the outer packaging of pulp molded products has become a key issue in current research; up to now, the anti-counterfeiting of packaging materials mainly involves printing and spraying anti-counterfeiting inks to apply anti-counterfeiting materials on the surface of pulp molded products, which belongs to the post-processing anti-counterfeiting of packaging materials, but the cost and difficulty of imitation of this post-processing anti-counterfeiting are relatively low, so it is difficult to play an effective anti-counterfeiting function; if the anti-counterfeiting process is moved forward, embedding anti-counterfeiting particles into the interior of pulp molded products will greatly increase the cost and difficulty of imitation. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing a pulp molded material with anti-counterfeiting function. The method embeds anti-counterfeiting particles into the interior of a pulp molded product, thereby greatly improving the anti-counterfeiting performance of the prepared material and increasing the difficulty and cost of counterfeiting.

[0004] The technical solution adopted by the present invention is a method for preparing a pulp molding material with anti-counterfeiting function, which specifically comprises the following steps:

[0005] Step 1, red-blue light modification of cotton fibers;

[0006] Step 2, green-red light modification of cotton fibers;

[0007] Step 3, modifying the cotton fiber with blue-green light;

[0008] Step 4, preparing an optical anti-counterfeiting fiber according to the products obtained in steps 1 to 3;

[0009] Step 5, preparing a pulp molded anti-counterfeiting material according to the product obtained in step 4.

[0010] The present invention is also characterized in that:

[0011] The specific process of step 1 is:

[0012] Step 1.1, take 3-6 cotton yarns with a length of 1-2 meters and a specification of 60 / 4 male yarn, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2"-terpyridine, add 3-6 mL of triethylamine dropwise, raise the reaction temperature to 180-220° C. under a nitrogen atmosphere, and wash them with 300-600 mL of deionized water 3 times after the reaction to obtain terpyridine-modified cotton fibers;

[0013] Step 1.2, the terpyridine modified cotton fiber obtained in step 1.1 is placed in 1-2L deionized water, 2-4g of reactive red R-2BF dye and 2-4g of sodium sulfate are added, the temperature is raised to 40-60°C, and after reacting for 30-60min, the temperature is raised to 60-80°C, 1.5-3g of sodium carbonate is added and reacted for 30min, and after the reaction is completed, it is washed with soaping agent HM-900 until no pigment fades, thereby obtaining red-blue light modified cotton fiber.

[0014] The specific process of step 2 is:

[0015] Step 2.1, take 3-6 cotton yarns with a length of 1-2 meters and a specification of 60 / 4 male yarn, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2"-terpyridine, add 3-6 mL of triethylamine dropwise, raise the reaction temperature to 180-220° C. under a nitrogen atmosphere, and wash them with 300-600 mL of deionized water 3 times after the reaction to obtain terpyridine-modified cotton fibers;

[0016] Step 2.2, putting the terpyridine modified cotton fiber obtained in step 2.1 into 1-2L deionized water, adding 2-4g of direct green BE dye and 2-4g of sodium sulfate, raising the temperature to 40-60°C, reacting for 30-60min, raising the temperature to 60-80°C, adding 1.5-3g of sodium carbonate and reacting for 30-60min, and washing with soaping agent HM-900 after the reaction is completed until no pigment fades;

[0017] Step 2.3, put the cotton fiber obtained after the treatment in step 2.2 into 100-200 mL of deionized water, then add 3-6 g of hexafluoroacetylacetone, 2-3 g of europium chloride and 1-2 mL of triethylamine in sequence, heat the temperature to 60-80 ° C for 1-3 hours, wash three times with 300-600 mL of deionized water to obtain green-red light modified cotton fiber.

[0018] The specific process of step 3 is:

[0019] Step 3.1, take 3-6 cotton yarns with a length of 1-2 meters and a specification of 60 / 4 male yarn, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2"-terpyridine, add 3-6 mL of triethylamine dropwise, raise the reaction temperature to 180-220° C. under a nitrogen atmosphere, and wash them three times with 300-600 mL of deionized water after the reaction is completed to obtain terpyridine-modified cotton fibers;

[0020] Step 3.2, putting the terpyridine modified cotton fiber obtained in step 3.1 into 1-2L deionized water, adding 2-4g of active dark blue R-2GLN dye and 2-4g of sodium sulfate, raising the temperature to 40-60°C, reacting for 30-60min, raising the temperature to 60-80°C, adding 1.5-3g of sodium carbonate and reacting for 30-60min, and washing with soaping agent HM-900 after the reaction is completed until no pigment fades;

[0021] Step 3.3, put the cotton fiber treated in step 3.2 into 100-200 mL of deionized water, then add 3-6 g of hexafluoroacetylacetone, 2-3 g of terbium chloride and 1-2 mL of triethylamine in sequence, heat the temperature to 60-80 ° C for 1-3 hours, wash three times with 300-600 mL of deionized water to obtain green-red light modified cotton fiber.

[0022] The specific process of step 4 is:

[0023] Step 4.1, immersing 1-3 red-blue light modified cotton fibers, 1-3 green-red light modified cotton fibers, and 1-3 blue-green light modified cotton fibers in a UV adhesive solution for 2-10 seconds respectively;

[0024] Step 4.2, winding the cotton fiber impregnated with UV adhesive obtained in step 4.1 on the surface of a circular column with a diameter of 5-10 cm in a spiral winding form, and irradiating it with ultraviolet light for 20-40 seconds to obtain an optical anti-counterfeiting fiber.

[0025] In step 4.1, the preparation process of the UV adhesive is as follows: 40-59 g of ethylene glycol acrylate, 40-59 g of butyl acrylate and 1-10 g of azobisisobutyronitrile are uniformly mixed to obtain the UV adhesive.

[0026] The specific process of step 5 is:

[0027] Step 5.1, taking 100-200 g of pulp, the pulp is selected from any one or more of bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, straw pulp, crushing at 25° C. for 10-20 min, adjusting the beating concentration to 8-12%, and the beating degree after beating to 50-60° SR;

[0028] Step 5.2, adding 1-2 g of cyclopropane acrylic acid resin, 2-3 g of polyvinyl alcohol, 0.2-0.4 g of polyacrylamide and 0.5-1 g of optical anti-counterfeiting fiber having a width of 0.1-1 mm and a length of 1-3 mm to the slurry obtained in step 5.1 to obtain a mixed slurry;

[0029] Step 5.3, introduce the mixed slurry obtained in step 5.2 into the mold of a micro pulp molding machine and filter the water to a moisture content of 55-60%, then demold after extrusion molding at 5-6 MPa, and then dry in a drying oven at 70-80°C for 4-5 hours, and finally transfer to a flat vulcanizer for hot pressing and shaping, controlling the temperature to 100-110°C, the pressure to 5.5-6 MPa, and the time to 2-3 minutes to obtain a pulp molded anti-counterfeiting material.

[0030] The beneficial effects of the present invention are as follows:

[0031] 1. The present invention designs fibrous anti-counterfeiting particles, and a single fiber realizes red, green and blue colors that can be identified by the naked eye. In addition, blue, red and green luminescence can be obtained under 254nm excitation. The length of the anti-counterfeiting fiber can be simply adjusted by single, double or triple arrangement. The anti-counterfeiting fiber is dispersed in the slurry, and pulp molded products are further prepared. The combination of three colors and three luminescences greatly improves the anti-counterfeiting performance.

[0032] 2. The present invention constructs three colors and three luminous anti-counterfeiting fibers; most dyes have their own colors and fluorescence emission when excited at 365nm, which has a great influence on the anti-counterfeiting color and luminous anti-counterfeiting.

[0033] 3. The fluorescence excitation of the anti-counterfeiting fiber constructed by the present invention is 254nm, which avoids the influence of ultraviolet excitation of the pigment on the luminescence performance. At the same time, the three colors of red, green and blue match the three luminescences of blue, red and green, avoiding the overlap of the absorption wavelength of the pigment and the luminescence wavelength, which affects the luminescence performance; the anti-counterfeiting fiber can be evenly dispersed with the slurry, and the prepared pulp molding contains anti-counterfeiting particles inside, which is different from the surface printing process of traditional anti-counterfeiting particles, and increases the difficulty of imitation. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a process diagram for preparing anti-counterfeiting fibers in the method for preparing pulp molding materials with anti-counterfeiting functions of the present invention;

[0035] Figure 2 This is a graph of the ultraviolet light intensity at 254nm of red-blue light modified cotton fiber, green-red light modified cotton fiber, and blue-green light modified cotton fiber obtained in Example 1 of the method for preparing a pulp molding material with anti-counterfeiting function of the present invention. DETAILED DESCRIPTION

[0036] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0037] The method for preparing the pulp molding material with anti-counterfeiting function of the present invention specifically comprises the following steps:

[0038] Step 1, red-blue light modification of cotton fiber, specifically: take 3-6 cotton yarns, 1-2 meters long, with a specification of 60 / 4 male, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2"-terpyridine, add 3-6 mL of triethylamine dropwise, and raise the reaction temperature to 180-220 ° C under a nitrogen atmosphere. After the reaction is completed, wash with 300-600 mL of deionized water for 3 times , to obtain terpyridine modified cotton fiber; further put the terpyridine modified cotton fiber into 1-2L deionized water, add 2-4g of reactive red R-2BF dye and 2-4g of sodium sulfate, increase the temperature to 40-60°C, react for 30-60min, further heat to 60-80°C, add 1.5-3g of sodium carbonate and react for 30min, wash with soap detergent HM-900 after the reaction, until no pigment fades, to obtain red-blue light modified cotton fiber.

[0039] Step 2, green-red light modification of cotton fiber, specifically: take 3-6 cotton yarns, 1-2 meters long, and with a specification of 60 / 4 male, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2"-terpyridine, add 3-6 mL of triethylamine dropwise, and raise the reaction temperature to 180-220 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300-600 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1-2 L of deionized water, add 2-4 g of direct green BE Dye and sodium sulfate 2-4g, temperature raised to 40-60℃, reacted for 30-60min, further heated to 60-80℃, added sodium carbonate 1.5-3g and reacted for 30-60min, washed with soaping agent HM-900 after the reaction, until no pigment faded. The obtained cotton fiber was further placed in 100-200mL deionized water, and then 3-6g hexafluoroacetylacetone, 2-3g europium chloride and 1-2mL triethylamine were added in sequence, the temperature was heated to 60-80℃ and reacted for 1-3h, and washed three times with deionized water 300-600mL to obtain green-red light modified cotton fiber.

[0040] Step 3, blue-green light modification of cotton fiber, specifically: take 3-6 cotton yarns, 1-2 meters long, and with a specification of 60 / 4 male, put them into 200-300mL of dimethyl sulfoxide solution, then add 20-40g of 4'-chloro-2,2':6',2"-terpyridine, add 3-6mL of triethylamine dropwise, and raise the reaction temperature to 180-220°C under a nitrogen atmosphere. After the reaction is completed, wash it with 300-600mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1-2L of deionized water, add 2-4g of active dark blue R-2G LN dye and sodium sulfate 2-4g, the temperature is raised to 40-60℃, after reacting for 30-60min, further heated to 60-80℃, added sodium carbonate 1.5-3g to react for 30-60min, washed with soaping agent HM-900 after the reaction, until no pigment fades. The obtained cotton fiber is further placed in 100-200mL of deionized water, and then 3-6g of hexafluoroacetylacetone, 2-3g of terbium chloride and 1-2mL of triethylamine are added in sequence, the temperature is heated to 60-80℃ to react for 1-3h, and washed three times with deionized water 300-600mL to obtain blue-green light modified cotton fiber.

[0041] Step 4, preparation of optical anti-counterfeiting fiber, specifically: Figure 1 As shown, red-blue light modified cotton fibers (1-3), green-red light modified cotton fibers (1-3), and blue-green light modified cotton fibers (1-3) are immersed in a UV adhesive solution for 2-10 seconds, wherein the UV adhesive components are ethylene glycol acrylate (40-59g), butyl acrylate (40-59g) and azobisisobutyronitrile (1-10g). The cotton fibers impregnated with the UV adhesive are wound in a spiral form on the surface of a circular column with a diameter of 5-10cm, and irradiated with a 45W, 365nm ultraviolet lamp for 20-40 seconds. Finally, a laser cutting machine is used to cut and obtain an optical anti-counterfeiting fiber with a width of 0.1-1mm and a length of 1-3mm.

[0042] Step 5, preparation of pulp molding anti-counterfeiting material, specifically: take 100-200g of pulp, and select any one or more of bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, and straw pulp, crush for 10-20min at 25°C, adjust the pulping concentration to 8-12%, and the beating degree after pulping is 50-60°SR. Then add acrylic cyclopropane resin (1-2g), polyvinyl alcohol (2-3g), polyacrylamide (0.2-0.4g) and optical anti-counterfeiting fiber (0.5-1g) with a width of 0.1-1mm and a length of 1-3mm to obtain a mixed pulp. The mixed slurry is then introduced into the mold of a micro pulp molding machine and filtered to a moisture content of 55-60%. It is then demolded after extrusion molding at 5-6 MPa, and then dried in a drying oven at 70-80°C for 4-5 hours. Finally, it is transferred to a flat vulcanizer for hot pressing and shaping, with the temperature controlled at 100-110°C, the pressure at 5.5-6 MPa, and the time being 2-3 minutes to obtain a pulp molded anti-counterfeiting material.

[0043] Example 1

[0044] Step 1, red-blue light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male count, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180°C under a nitrogen atmosphere. After the reaction, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of reactive red R-2BF dye and 2 g of sodium sulfate, raise the temperature to 40°C, react for 30 minutes, further heat to 60°C, add 1.5 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0045] Step 2, green-red light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of direct Take green BE dye and 2g of sodium sulfate, raise the temperature to 40℃, react for 30min, then further heat to 60℃, add 1.5g of sodium carbonate and react for 30min, wash with soap detergent HM-900 after the reaction, until no pigment fades. Further put the obtained cotton fiber into 100mL of deionized water, then add 3g of hexafluoroacetylacetone, 2g of europium chloride and 1mL of triethylamine in sequence, heat the temperature to 60℃ and react for 1h, wash three times with 300mL of deionized water to obtain green-red light modified cotton fiber.

[0046] Step 3, blue-green light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of active deep Blue R-2GLN dye and 2g of sodium sulfate, the temperature was raised to 40℃, reacted for 30min, then further heated to 60℃, added 1.5g of sodium carbonate and reacted for 30min, and washed with soaping agent HM-900 after the reaction until no pigment faded. The obtained cotton fiber was further placed in 100mL of deionized water, and then 3g of hexafluoroacetylacetone, 2g of terbium chloride and 1mL of triethylamine were added in sequence, the temperature was heated to 60℃ and reacted for 1h, and washed three times with 300mL of deionized water to obtain blue-green light modified cotton fiber.

[0047] Step 4, preparation of optical anti-counterfeiting fiber, specifically: Figure 1As shown, red-blue light modified cotton fiber (1 piece), green-red light modified cotton fiber (1 piece), and blue-green light modified cotton fiber (1 piece) were immersed in a UV adhesive solution for 10 seconds, wherein the UV adhesive components were ethylene glycol acrylate (40g, butyl acrylate (59g) and azobisisobutyronitrile (1g). The cotton fiber impregnated with the UV adhesive was spirally wound on the surface of a circular column with a diameter of 5cm, and irradiated with a 45W, 365nm ultraviolet lamp for 20 seconds. Finally, a laser cutting machine was used to cut the optical anti-counterfeiting fiber with a width of 0.1mm and a length of 1mm.

[0048] Step 5, preparation of pulp molding anti-counterfeiting material, specifically: take 100g of pulp, select bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, straw pulp, any one or more, crush at 25℃ for 10min, adjust the pulping concentration to 8%, and the beating degree after pulping is 50°SR. Then add acrylic cyclopropane resin (1g), polyvinyl alcohol (2g), polyacrylamide (0.2g) and optical anti-counterfeiting fiber (0.5g) with a width of 0.1mm and a length of 1mm to obtain a mixed slurry. Then the mixed slurry is introduced into the mold of a micro-pulp molding machine to filter water to a moisture content of 55%, then demolded after extrusion molding at 5MPa, then in a drying oven, the drying time is 4h at 70℃, and finally transferred to a flat vulcanizer for hot pressing shaping, controlling the temperature to 100℃, the pressure to 5.5MPa, and the time to 2min to obtain a pulp molding anti-counterfeiting material.

[0049] Comparative Example 1 (Compared with Example 1, the beta-diketone ligand hexafluoroacetylacetone was replaced with 2-thenoyltrifluoroacetone, the anti-counterfeiting fiber lacked green, and the red light was weak under 254 excitation)

[0050] Step 1, red-blue light modification of cotton fiber, specifically: take 3 cotton yarns of 1 meter in length and specification model 60 / 4 male count, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180°C under a nitrogen atmosphere. After the reaction, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of reactive red R-2BF dye and 2 g of sodium sulfate, raise the temperature to 40°C, react for 30 minutes, further heat to 60°C, add 1.5 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0051] Step 2, green-red light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of direct green BE dye and 2g sodium sulfate, the temperature is raised to 40℃, after reacting for 30min, it is further heated to 60℃, 1.5g sodium carbonate is added to react for 30min, and after the reaction, it is washed with soaping agent HM-900 until the pigment fades. The obtained cotton fiber is further placed in 100mL of deionized water, and then 3g of 2-thenoyltrifluoroacetone, 2g of europium chloride and 1mL of triethylamine are added in sequence, the temperature is heated to 60℃ to react for 1h, and washed three times with 300mL of deionized water to obtain green-red light modified cotton fiber.

[0052] Step 3, blue-green light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of active dark blue R- 2GLN dye and 2g sodium sulfate, the temperature is raised to 40℃, after reacting for 30min, it is further heated to 60℃, 1.5g sodium carbonate is added to react for 30min, and after the reaction, it is washed with soaping agent HM-900 until the pigment fades. The obtained cotton fiber is further placed in 100mL of deionized water, and then 3g of 2-thenoyltrifluoroacetone, 2g of terbium chloride and 1mL of triethylamine are added in sequence, the temperature is heated to 60℃ to react for 1h, and washed three times with 300mL of deionized water to obtain blue-green light modified cotton fiber.

[0053] Step 4, preparation of optical anti-counterfeiting fiber, specifically: red-blue light modified cotton fiber (1), green-red light modified cotton fiber (1), blue-green light modified cotton fiber (1) are immersed in UV adhesive solution for 10s, wherein the UV adhesive component is ethylene glycol acrylate (40g), butyl acrylate (59g) and azobisisobutyronitrile (1g). The cotton fiber impregnated with UV adhesive is wound on the surface of a circular column with a diameter of 5cm in the form of spiral winding, and irradiated with a 45W, 365nm ultraviolet lamp for 20s. Finally, a laser cutting machine is used to cut the optical anti-counterfeiting fiber with a width of 0.1mm and a length of 1mm.

[0054] Step 5, preparation of pulp molding anti-counterfeiting material, specifically: take 100g of pulp, and select bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, straw pulp, any one or more of them, and crush them for 10min at 25℃, adjust the pulping concentration to 8%, and the beating degree after pulping is 50°SR. Then add acrylic cyclopropane resin (1g), polyvinyl alcohol (2g), polyacrylamide (0.2g) and optical anti-counterfeiting fiber (0.5g) with a width of 0.1mm and a length of 1mm to obtain a mixed slurry. Then the mixed slurry is introduced into the mold of a micro-pulp molding machine, filtered to a moisture content of 55%, and then demolded after extrusion molding at 5MPa, and then in a drying oven, the drying time is 4h at 70℃, and finally transferred to a flat vulcanizer for hot pressing shaping, controlling the temperature to 100℃, the pressure to 5.5MPa, and the time to 2min to obtain a pulp molding anti-counterfeiting material.

[0055] Comparative Example 2 (Compared with Example 1, during the preparation of green-red light modified cotton fiber and blue-green light modified cotton fiber, Eu and Tb ions were exchanged, the pulp molded anti-counterfeiting fiber had no green light, and the position of the red light changed)

[0056] Step 1, red-blue light modification of cotton fiber, specifically: take 3 cotton yarns of 1 meter in length and specification model 60 / 4 male count, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180°C under a nitrogen atmosphere. After the reaction, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of reactive red R-2BF dye and 2 g of sodium sulfate, raise the temperature to 40°C, react for 30 minutes, further heat to 60°C, add 1.5 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0057] Step 2, green-red light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of Direct green BE dye and 2g of sodium sulfate, the temperature was raised to 40℃, reacted for 30min, then further heated to 60℃, added 1.5g of sodium carbonate and reacted for 30min, and washed with soaping agent HM-900 after the reaction until no pigment faded. The obtained cotton fiber was further placed in 100mL of deionized water, and then 3g of hexafluoroacetylacetone, 2g of terbium chloride and 1mL of triethylamine were added in sequence, the temperature was heated to 60℃ and reacted for 1h, and washed three times with 300mL of deionized water to obtain green-red light modified cotton fiber.

[0058] Step 3, blue-green light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further, put it into 1 L of deionized water, add 2 g of active Dark blue R-2GLN dye and 2g of sodium sulfate, the temperature was raised to 40℃, after reacting for 30min, it was further heated to 60℃, 1.5g of sodium carbonate was added to react for 30min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 100mL of deionized water, and then 3g of hexafluoroacetylacetone, 2g of europium chloride and 1mL of triethylamine were added in sequence, the temperature was heated to 60℃ to react for 1h, and it was washed three times with 300mL of deionized water to obtain blue-green light modified cotton fiber.

[0059] Step 4, immerse the red-blue light modified cotton fiber (1), green-red light modified cotton fiber (1), and blue-green light modified cotton fiber (1) in a UV adhesive solution for 10 seconds, wherein the UV adhesive component is ethylene glycol acrylate (40 parts), butyl acrylate (59 parts) and azobisisobutyronitrile (1 part). The cotton fiber impregnated with the UV adhesive is wound on the surface of a circular column with a diameter of 5 cm in a spiral winding form, and irradiated with a 45W, 365nm ultraviolet lamp for 20 seconds. Finally, a laser cutting machine is used to cut and obtain an optical anti-counterfeiting fiber with a width of 0.1 mm and a length of 1 mm.

[0060] Step 5, take 100g of pulp, and the pulp is selected from bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, and straw pulp, and is crushed for 10min at 25°C, and the pulping concentration is adjusted to 8%, and the beating degree after pulping is 50°SR. Then add acrylic cyclopropane resin (1g), polyvinyl alcohol (2g), polyacrylamide (0.2g) and optical anti-counterfeiting fiber (0.5g) with a width of 0.1mm and a length of 1mm to obtain a mixed slurry. Then the mixed slurry is introduced into the mold of a micro-pulp molding machine, filtered to a moisture content of 55%, and then demolded after extrusion molding at 5MPa, and then in a drying oven, the drying time is 4h at 70°C, and finally transferred to a flat vulcanizer for hot pressing shaping, and the temperature is controlled to be 100°C, the pressure is 5.5MPa, and the time is 2min to obtain a pulp molding anti-counterfeiting material.

[0061] Comparative Example 3 (Compared with Example 1, when preparing red-blue light and blue-green light modified cotton fibers, the red and blue dyes are exchanged, the pulp molded anti-counterfeiting fiber has no blue light, and the blue and red positions are interchanged)

[0062] Step 1, red-blue light modification of cotton fiber, specifically: take 3 cotton yarns of 1 meter in length and specification model 60 / 4 male count, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180°C under a nitrogen atmosphere. After the reaction, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of active dark blue R-2GLN dye and 2 g of sodium sulfate, raise the temperature to 40°C, react for 30 minutes, further heat to 60°C, add 1.5 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0063] Step 2, green-red light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of direct Take green BE dye and 2g of sodium sulfate, raise the temperature to 40℃, react for 30min, then further heat to 60℃, add 1.5g of sodium carbonate and react for 30min, wash with soap detergent HM-900 after the reaction, until no pigment fades. Further put the obtained cotton fiber into 100mL of deionized water, then add 3g of hexafluoroacetylacetone, 2g of europium chloride and 1mL of triethylamine in sequence, heat the temperature to 60℃ and react for 1h, wash three times with 300mL of deionized water to obtain green-red light modified cotton fiber.

[0064] Step 3, blue-green light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine, and raise the reaction temperature to 180 ° C under nitrogen atmosphere. After the reaction is completed, wash with 300 mL of deionized water for 3 times. Further put the cotton fiber into 1 L of deionized water, add 2 g of reactive red R-2BF dye and sulfur 2g of sodium bispyribac acid was added, the temperature was raised to 40°C, and after reacting for 30min, it was further heated to 60°C, 1.5g of sodium carbonate was added and reacted for 30min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 100mL of deionized water, and then 3g of hexafluoroacetylacetone, 2g of terbium chloride and 1mL of triethylamine were added in sequence, the temperature was heated to 60°C and reacted for 1h, and washed three times with 300mL of deionized water to obtain blue-green light modified cotton fiber.

[0065] Step 4, immerse the red-blue light modified cotton fiber (1), green-red light modified cotton fiber (1), and blue-green light modified cotton fiber (1) in a UV adhesive solution for 10 seconds, wherein the UV adhesive component is ethylene glycol acrylate (40g), butyl acrylate (59g) and azobisisobutyronitrile (1g). The cotton fiber impregnated with the UV adhesive is wound on the surface of a circular column with a diameter of 5cm in a spiral winding form, and irradiated with a 45W, 365nm ultraviolet lamp for 20 seconds. Finally, a laser cutting machine is used to cut and obtain an optical anti-counterfeiting fiber with a width of 0.1mm and a length of 1mm.

[0066] Step 5, take pulp, and select 100g of any one or more of bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, and straw pulp, crush it at 25℃ for 10min, adjust the pulping concentration to 8%, and the beating degree after pulping is 50°SR. Then add acrylic cyclopropane resin (1g), polyvinyl alcohol (2g), polyacrylamide (0.2g) and optical anti-counterfeiting fiber (0.5g) with a width of 0.1mm and a length of 1mm to obtain a mixed slurry. Then introduce the mixed slurry into the mold of a micro-pulp molding machine, filter the water to a moisture content of 55%, then demold after extrusion molding at 5MPa, and then in a drying oven, dry for 4h at 70℃, and finally transfer to a flat vulcanizer for hot pressing and shaping, control the temperature to 100℃, the pressure to 5.5MPa, and the time to 2min to obtain a pulp molding anti-counterfeiting material. ,

[0067] Comparative Example 4 (Compared with Example 1, the water-retaining agent cyclopropane acrylic acid resin was replaced with sodium alginate, and the multi-color luminescence of the anti-counterfeiting fiber was changed to a single blue light)

[0068] Step 1, red-blue light modification of cotton fiber, specifically: take 3 cotton yarns of 1 meter in length and specification model 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180°C under a nitrogen atmosphere. After the reaction, wash it 3 times with 300 mL of deionized water to obtain terpyridine-modified cotton fiber, further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of reactive red R-2BF dye and 2 g of sodium sulfate, raise the temperature to 40°C, react for 30 minutes, further heat to 60°C, add 1.5 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades to obtain red-blue light modified cotton fiber.

[0069] Step 2, green-red light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of direct Take green BE dye and 2g of sodium sulfate, raise the temperature to 40℃, react for 30min, then further heat to 60℃, add 1.5g of sodium carbonate and react for 30min, wash with soap detergent HM-900 after the reaction, until no pigment fades. Further put the obtained cotton fiber into 100mL of deionized water, then add 3g of hexafluoroacetylacetone, 2g of europium chloride and 1mL of triethylamine in sequence, heat the temperature to 60℃ and react for 1h, wash three times with 300mL of deionized water to obtain green-red light modified cotton fiber.

[0070] Step 3, blue-green light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of active dark blue R-2GLN dye and 2g of sodium sulfate, the temperature was raised to 40°C, after reacting for 30min, it was further heated to 60°C, 1.5g of sodium carbonate was added to react for 30min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 100mL of deionized water, and then 3g of hexafluoroacetylacetone, 2g of terbium chloride and 1mL of triethylamine were added in sequence, the temperature was heated to 60°C to react for 1h, and it was washed three times with 300mL of deionized water to obtain blue-green light modified cotton fiber.

[0071] Step 4, immerse the red-blue light modified cotton fiber (1), green-red light modified cotton fiber (1), and blue-green light modified cotton fiber (1) in a UV adhesive solution for 10 seconds, wherein the UV adhesive component is ethylene glycol acrylate (40g), butyl acrylate (59g) and azobisisobutyronitrile (1g). The cotton fiber impregnated with the UV adhesive is wound on the surface of a circular column with a diameter of 5cm in a spiral winding form, and irradiated with a 45W, 365nm ultraviolet lamp for 20 seconds. Finally, a laser cutting machine is used to cut and obtain an optical anti-counterfeiting fiber with a width of 0.1mm and a length of 1mm.

[0072] Step 5, take 100g of pulp, the pulp is selected from any one or more of bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, and straw pulp, and is crushed for 10min at 25°C, and the pulping concentration is adjusted to 8%, and the beating degree after pulping is 50°SR. Then add sodium alginate (1g), polyvinyl alcohol (2g), polyacrylamide (0.2g) and optical anti-counterfeiting fiber (0.5g) with a width of 0.1mm and a length of 1mm to obtain a mixed slurry. Then the mixed slurry is introduced into the mold of a micro-pulp molding machine, filtered to a moisture content of 55%, and then demolded after extrusion molding at 5MPa, and then in a drying oven, the drying time is 4h at 70°C, and finally transferred to a flat vulcanizer for hot pressing shaping, and the temperature is controlled to be 100°C, the pressure is 5.5MPa, and the time is 2min to obtain a pulp molding anti-counterfeiting material.

[0073] Comparative Example 5 (Compared with Example 1, the reinforcing agent polyvinyl alcohol was replaced with carboxymethyl cellulose, and the multi-color luminescence of the anti-counterfeiting fiber was changed to a single blue light)

[0074] Step 1, red-blue light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male count, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180°C under a nitrogen atmosphere. After the reaction, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of reactive red R-2BF dye and 2 g of sodium sulfate, raise the temperature to 40°C, react for 30 minutes, further heat to 60°C, add 1.5 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0075] Step 2, green-red light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of direct Take green BE dye and 2g of sodium sulfate, raise the temperature to 40℃, react for 30min, then further heat to 60℃, add 1.5g of sodium carbonate and react for 30min, wash with soap detergent HM-900 after the reaction, until no pigment fades. Further put the obtained cotton fiber into 100mL of deionized water, then add 3g of hexafluoroacetylacetone, 2g of europium chloride and 1mL of triethylamine in sequence, heat the temperature to 60℃ and react for 1h, wash three times with 300mL of deionized water to obtain green-red light modified cotton fiber.

[0076] Step 3, blue-green light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of active dark blue R-2GLN dye and 2g of sodium sulfate, the temperature was raised to 40°C, after reacting for 30min, it was further heated to 60°C, 1.5g of sodium carbonate was added to react for 30min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 100mL of deionized water, and then 3g of hexafluoroacetylacetone, 2g of terbium chloride and 1mL of triethylamine were added in sequence, the temperature was heated to 60°C to react for 1h, and it was washed three times with 300mL of deionized water to obtain blue-green light modified cotton fiber.

[0077] Step 4, immerse the red-blue light modified cotton fiber (1), the green-red light modified cotton fiber (1), and the blue-green light modified cotton fiber (1) in a UV adhesive solution for 10 seconds, wherein the UV adhesive component is ethylene glycol acrylate (40 parts), butyl acrylate (59 parts) and azobisisobutyronitrile (1 part). The cotton fiber impregnated with the UV adhesive is wound in a spiral form on the surface of a circular column with a diameter of cm, and irradiated with a 45W, 365nm ultraviolet lamp for 20 seconds. Finally, a laser cutting machine is used to cut and obtain an optical anti-counterfeiting fiber with a width of 0.1 mm and a length of 1 mm.

[0078] Step 5, take 100g of pulp, the pulp is selected from any one or more of bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, and straw pulp, and is crushed for 10min at 25°C, and the pulping concentration is adjusted to 8%, and the beating degree after pulping is 50°SR. Then add acrylic cyclopropane resin (1g), carboxymethyl cellulose (2g), polyacrylamide (0.2g) and optical anti-counterfeiting fiber (0.5g) with a width of 0.1mm and a length of 1mm to obtain a mixed slurry. Then the mixed slurry is introduced into the mold of a micro-pulp molding machine and filtered to a moisture content of 55%, then demolded after extrusion molding at 5MPa, then in a drying oven, the drying time is 4h at 70°C, and finally transferred to a flat vulcanizer for hot pressing shaping, the temperature is controlled to be 100°C, the pressure is 5.5MPa, and the time is 2min, to obtain a pulp molding anti-counterfeiting material.

[0079] Comparative Example 6 (Compared with Example 1, during the preparation of the optical anti-counterfeiting fiber, ethylene glycol acrylate was not added to the UV adhesive, and the prepared anti-counterfeiting fiber could not be dispersed in pulp molding)

[0080] Step 1, red-blue light modification of cotton fiber, specifically: take 3 cotton yarns of 1 meter in length and specification model 60 / 4 male count, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180°C under a nitrogen atmosphere. After the reaction, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of reactive red R-2BF dye and 2 g of sodium sulfate, raise the temperature to 40°C, react for 30 minutes, further heat to 60°C, add 1.5 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0081] Step 2, green-red light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of direct Take green BE dye and 2g of sodium sulfate, raise the temperature to 40℃, react for 30min, then further heat to 60℃, add 1.5g of sodium carbonate and react for 30min, wash with soap detergent HM-900 after the reaction, until no pigment fades. Further put the obtained cotton fiber into 100mL of deionized water, then add 3g of hexafluoroacetylacetone, 2g of europium chloride and 1mL of triethylamine in sequence, heat the temperature to 60℃ and react for 1h, wash three times with 300mL of deionized water to obtain green-red light modified cotton fiber.

[0082] Step 3, blue-green light modification of cotton fiber, specifically: take 3 cotton yarns, 1 meter long, with a specification of 60 / 4 male, put them into 200 mL of dimethyl sulfoxide solution, then add 20 g of 4'-chloro-2,2':6',2"-terpyridine, add 3 mL of triethylamine dropwise, and raise the reaction temperature to 180 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 300 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1 L of deionized water, add 2 g of active deep Blue R-2GLN dye and 2g of sodium sulfate, the temperature was raised to 40℃, reacted for 30min, then further heated to 60℃, added 1.5g of sodium carbonate and reacted for 30min, and washed with soaping agent HM-900 after the reaction until no pigment faded. The obtained cotton fiber was further placed in 100mL of deionized water, and then 3g of hexafluoroacetylacetone, 2g of terbium chloride and 1mL of triethylamine were added in sequence, the temperature was heated to 60℃ and reacted for 1h, and washed three times with 300mL of deionized water to obtain blue-green light modified cotton fiber.

[0083] Step 4, preparation of optical anti-counterfeiting fiber, specifically: red-blue light modified cotton fiber (1), green-red light modified cotton fiber (1), blue-green light modified cotton fiber (1) are immersed in UV adhesive solution for 10s, wherein the UV adhesive component is butyl acrylate (99g) and azobisisobutyronitrile (1g). The cotton fiber impregnated with UV adhesive is wound on the surface of a circular column with a diameter of cm in the form of spiral winding, and irradiated with a 45W, 365nm ultraviolet lamp for 20s. Finally, a laser cutting machine is used to cut the optical anti-counterfeiting fiber with a width of 0.1mm and a length of 1mm.

[0084] Results and Discussion

[0085] like Figure 1 As shown, the preparation process of anti-counterfeiting fiber mainly involves adhesive impregnation, spiral winding, UV curing, and laser cutting. Red-blue light modified cotton fiber, green-red light modified cotton fiber, and blue-green light modified cotton fiber can be arranged to form red, green, and blue single fibers, whose colors can be seen by the naked eye, and their blue, red, and green light can be seen under 254nm ultraviolet light. Similarly, red-blue light modified cotton fiber, green-red light modified cotton fiber, and blue-green light modified cotton fiber can be arranged in sequence to form a red, green, and blue double-root arrangement; red-blue light modified cotton fiber, green-red light modified cotton fiber, and blue-green light modified cotton fiber can be arranged in sequence to form a red, green, and blue three-root arrangement. The fiber color and color arrangement can be used as an anti-counterfeiting password.

[0086] like Figure 2 As shown, the red-blue light modified cotton fiber, green-red light modified cotton fiber, and blue-green light modified cotton fiber prepared in Example 1 can detect 430nm blue light emission, 613nm red light emission, and 547nm green light emission under 254nm ultraviolet light irradiation. Among them, the broad peak of 430nm of the red-blue light modified cotton fiber is the fluorescence emission peak of the terpyridine functional group. The red light emission of 613nm of the green-red light modified cotton fiber is a narrow linear spectrum, which is obviously the rare earth ion Eu 3+ The green light emission of the blue-green light modified cotton fiber is also a narrow linear spectrum, which can be attributed to the characteristic luminescence of the rare earth Tb3+ ions. It should be pointed out that the pigment used in dyeing the veil itself will also emit light under the excitation of 365nm ultraviolet light, which has the fluorescent anti-counterfeiting performance of the anti-counterfeiting fiber. The present invention adopts conjugated small hexafluoroacetylacetone as the main ligand, which can not only sensitize Tb and Eu ions at the same time under 254nm ultraviolet excitation, but also reduce the influence of the luminescence of the pigment on the fluorescent anti-counterfeiting performance.

[0087] Table 1 Three-stage color and three-stage luminescence of anti-counterfeiting fibers in pulp molding under natural light and ultraviolet light 254

[0088]

[0089] As shown in Table 1, the pulp molded internal anti-counterfeiting fiber in Example 1 can be seen in red, green and blue under natural light, and the three colors are arranged in the same order. In addition, blue, red and green luminescence of 430, 613 and 547 nm can be observed under 254 nm irradiation.

[0090] In Comparative Example 1, during the preparation of green-red light modified cotton fiber and blue-green light modified cotton fiber, the beta-diketone ligand hexafluoroacetylacetone was replaced with 2-thenoyltrifluoroacetone, and the anti-counterfeiting fiber in pulp molding lacked green, and the red light was weak under 254 excitation. This is because 2-thenoyltrifluoroacetone has a large conjugation, and its most suitable wavelength for exciting Eu3+ ions is 365nm. Therefore, when 254nm ultraviolet secondary is used, the red light of the green-red light modified cotton fiber is weak, and due to the influence of energy level matching, 2-thenoyltrifluoroacetone cannot effectively sensitize Tb ions, resulting in the blue-green light modified cotton fiber having no green light, and can only emit residual blue light of the terpyridine ligand. However, the blue-green light modified cotton fiber has a strong absorption of blue light by the blue dye, and luminescence cannot be observed.

[0091] In Comparative Example 2, Eu and Tb ions were exchanged during the preparation of green-red light cotton fiber and blue-green light cotton fiber, and the anti-counterfeiting fiber obtained had no green light, and the position of red light changed. This is because after the Eu and Tb ions were exchanged, the Tb ions in the green-red light cotton fiber can emit green light, but are affected by the absorption of the green pigment, and the green light cannot be observed. The blue-green light cotton fiber emits red light from Eu ions, which is not affected by the blue dye, and the red light can be observed. Therefore, in pulp molding, the three-segment color of red, green and blue can be seen. When excited by 254nm ultraviolet light, the three-segment luminescence is 430nm, no green light, and 613nm respectively.

[0092] In Comparative Example 3, when preparing red-blue light and blue-green light modified cotton fibers, when the red and blue dyes are exchanged, the pulp molded anti-counterfeiting fiber has no blue light, and the blue and red positions are interchanged. Due to the exchange of red and blue dyes, the color position changes under natural light and becomes blue, green, and red three-stage colors (although the red, green, and blue three-stage colors of the anti-counterfeiting fiber in the pulp molding are the same as the blue, green, and red three-stage colors, and the color position change cannot be judged, but the position color change can be judged by the luminous order of the anti-counterfeiting fiber).

[0093] In Comparative Example 4, the water-retaining agent polyacrylic acid cyclopropane resin is replaced with sodium alginate, and in Comparative Example 5, the reinforcing agent polyvinyl alcohol is replaced with carboxymethyl cellulose, which will result in a large number of carboxyl functional groups in the pulp molding. Since the rare earth ions Eu3+ and Tb3+ have strong coordination reaction ability with the carboxyl group, the coordination structure between the rare earth and hexafluoroacetylacetone is destroyed, and the luminescence is quenched. Therefore, in Comparative Examples 4 and 5, the luminescence of rare earth ions cannot be observed under 254nm ultraviolet excitation, and only the luminescence of the terpyridine group can be observed. The three-segment luminescence of the anti-counterfeiting fiber in the pulp molding is 430, 430, 430nm.

[0094] In the preparation process of the anti-counterfeiting fiber of Comparative Example 6, ethylene glycol acrylate is not added to the UV adhesive. The surface of the prepared anti-counterfeiting fiber is coated with hydrophobic polybutyl acrylate, which cannot be dispersed in the aqueous solution of the pulp molding slurry and ultimately cannot be dispersed in the pulp molding.

[0095] Example 2

[0096] Step 1, red-blue light modification of cotton fiber, specifically: take 4 cotton yarns with a length of 1.5 meters and a specification of 60 / 4 male count, put them into 250 mL of dimethyl sulfoxide solution, then add 30 g of 4'-chloro-2,2':6',2"-terpyridine, add 4 mL of triethylamine dropwise, and raise the reaction temperature to 200°C under a nitrogen atmosphere. After the reaction, wash it three times with 400 mL of deionized water to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1.5 L of deionized water, add 3 g of reactive red R-2BF dye and 3 g of sodium sulfate, raise the temperature to 50°C, react for 40 minutes, further heat to 70°C, add 2 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0097] Step 2, green-red light modification of cotton fiber, specifically: take 4 cotton yarns, 1.5 meters long, with a specification of 60 / 4 male, put them into 250mL of dimethyl sulfoxide solution, then add 30g of 4'-chloro-2,2':6',2"-terpyridine, add 4mL of triethylamine dropwise, and raise the reaction temperature to 200°C under a nitrogen atmosphere. After the reaction is completed, wash it with 400mL of deionized water three times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 1.5L of deionized water, add 3g of Direct green BE dye and 3g of sodium sulfate, the temperature was raised to 50℃, after reacting for 40min, it was further heated to 70℃, 2g of sodium carbonate was added to react for 40min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 150mL of deionized water, and then 4g of hexafluoroacetylacetone, 2.5g of europium chloride and 1.5mL of triethylamine were added in sequence, the temperature was heated to 70℃ to react for 2h, and it was washed three times with 400mL of deionized water to obtain green-red light modified cotton fiber.

[0098] Step 3, blue-green light modification of cotton fiber, specifically: take 4 cotton yarns, 1.5 meters long, with a specification of 60 / 4 male, put them into 250mL of dimethyl sulfoxide solution, then add 30g of 4'-chloro-2,2':6',2"-terpyridine, add 4mL of triethylamine dropwise, and raise the reaction temperature to 200°C under a nitrogen atmosphere. After the reaction is completed, wash it with 400mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 1.5L of deionized water, add 3g of active deep Blue R-2GLN dye and 3g sodium sulfate, the temperature was raised to 50℃, after reacting for 40min, it was further heated to 70℃, 2g sodium carbonate was added to react for 40min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 150mL of deionized water, and then 4g of hexafluoroacetylacetone, 2.5g of terbium chloride and 1.5mL of triethylamine were added in sequence, the temperature was heated to 70℃ to react for 1.5h, and it was washed three times with 400mL of deionized water to obtain green-red light modified cotton fiber.

[0099] Step 4, preparation of optical anti-counterfeiting fiber, specifically: red-blue light modified cotton fiber (2 pieces), green-red light modified cotton fiber (2 pieces), blue-green light modified cotton fiber (2 pieces) are immersed in UV adhesive solution for 8 seconds, wherein the UV adhesive component is ethylene glycol acrylate (50g, butyl acrylate (45g) and azobisisobutyronitrile (5g). The cotton fiber impregnated with UV adhesive is wound on the surface of a circular column with a diameter of 8cm in the form of spiral winding, and irradiated with a 45W, 365nm ultraviolet lamp for 30s. Finally, a laser cutting machine is used to cut the optical anti-counterfeiting fiber with a width of 0.8mm and a length of 2mm.

[0100] Step 5, preparation of pulp molding anti-counterfeiting material, specifically: take 100g of pulp, and select any one or more of bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, straw pulp, crush for 15min at 25°C, adjust the pulping concentration to 10%, and the beating degree after pulping is 55°SR. Then add acrylic cyclopropane resin (1.5g), polyvinyl alcohol (2.5g), polyacrylamide (0.3g) and optical anti-counterfeiting fiber (0.8g) with a width of 0.8mm and a length of 2mm to obtain a mixed pulp. The mixed slurry is then introduced into the mold of a micro pulp molding machine and filtered to a moisture content of 58%. It is then extruded and molded at 5.5 MPa and demolded. It is then dried in a drying oven at 75°C for 4.5 hours. Finally, it is transferred to a flat vulcanizer for hot pressing and shaping, with the temperature controlled at 105°C, the pressure at 5.8 MPa, and the time at 2.5 minutes to obtain a pulp molded anti-counterfeiting material.

[0101] Example 3

[0102] Step 1, red-blue light modification of cotton fiber, specifically: take 6 cotton yarns with a length of 2 meters and a specification of 60 / 4 male, put them into 300 mL of dimethyl sulfoxide solution, then add 40 g of 4'-chloro-2,2':6',2"-terpyridine, add 6 mL of triethylamine dropwise, and raise the reaction temperature to 220°C under a nitrogen atmosphere. After the reaction, wash it with 600 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 2L of deionized water, add 4 g of reactive red R-2BF dye and 4 g of sodium sulfate, raise the temperature to 60°C, react for 60 minutes, further heat to 80°C, add 3 g of sodium carbonate and react for 30 minutes, and wash it with soaping agent HM-900 after the reaction until no pigment fades, to obtain red-blue light modified cotton fiber.

[0103] Step 2, green-red light modification of cotton fiber, specifically: take 6 cotton yarns of 2 meters in length and 60 / 4 male yarn, put them into 300 mL of dimethyl sulfoxide solution, then add 40 g of 4'-chloro-2,2':6',2"-terpyridine, add 6 mL of triethylamine dropwise, and raise the reaction temperature to 220 ° C under a nitrogen atmosphere. After the reaction is completed, wash it with 600 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the terpyridine-modified cotton fiber into 2 L of deionized water, add 4 g of Direct green BE dye and 4g of sodium sulfate, the temperature was raised to 60℃, after reacting for 60min, it was further heated to 80℃, 3g of sodium carbonate was added to react for 60min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 200mL of deionized water, and then 6g of hexafluoroacetylacetone, 3g of europium chloride and 2mL of triethylamine were added in sequence, the temperature was heated to 80℃ and reacted for 3h, and washed three times with 600mL of deionized water to obtain green-red light modified cotton fiber.

[0104] Step 3, blue-green light modification of cotton fiber, specifically: take 6 cotton yarns of 2 meters in length and 60 / 4 male yarn, put them into 300 mL of dimethyl sulfoxide solution, then add 40 g of 4'-chloro-2,2':6',2"-terpyridine, add 6 mL of triethylamine dropwise, and raise the reaction temperature to 220 ° C under nitrogen atmosphere. After the reaction is completed, wash it with 600 mL of deionized water for 3 times to obtain terpyridine-modified cotton fiber; further put the obtained terpyridine-modified cotton fiber into 2 L of deionized water, add 4 g of active Dark blue R-2GLN dye and 4g of sodium sulfate, the temperature was raised to 60℃, after reacting for 60min, it was further heated to 80℃, 3g of sodium carbonate was added to react for 60min, and after the reaction, it was washed with soaping agent HM-900 until the pigment faded. The obtained cotton fiber was further placed in 200mL of deionized water, and then 6g of hexafluoroacetylacetone, 3g of terbium chloride and 2mL of triethylamine were added in sequence, the temperature was heated to 80℃ and reacted for 3h, and washed three times with 600mL of deionized water to obtain green-red light modified cotton fiber.

[0105] Step 4, preparation of optical anti-counterfeiting fiber, specifically: red-blue light modified cotton fiber (3 pieces), green-red light modified cotton fiber (3 pieces), blue-green light modified cotton fiber (3 pieces) are immersed in UV adhesive solution for 8 seconds, wherein the UV adhesive component is ethylene glycol acrylate (59g, butyl acrylate (40g) and azobisisobutyronitrile (10g). The cotton fiber impregnated with UV adhesive is wound on the surface of a circular column with a diameter of 10cm in the form of spiral winding, and irradiated with a 45W, 365nm ultraviolet lamp for 40s. Finally, a laser cutting machine is used to cut the optical anti-counterfeiting fiber with a width of 1mm and a length of 3mm.

[0106] Step 5, preparation of pulp molding anti-counterfeiting material, specifically: take 100g of pulp, the pulp is selected from bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp, straw pulp, any one or more, crushed at 25°C for 20min, adjust the pulping concentration to 12%, and the beating degree after pulping is 60°SR. Then add acrylic cyclopropane resin (2g), polyvinyl alcohol (3g), polyacrylamide (0.4g) and optical anti-counterfeiting fiber (1g) with a width of 1mm and a length of 3mm to obtain a mixed slurry. Then the mixed slurry is introduced into the mold of a micro-pulp molding machine and filtered to a moisture content of 60%, then demolded after extrusion molding at 6MPa, then in a drying oven, the drying time is 5h at 80°C, and finally transferred to a flat vulcanizer for hot pressing shaping, the temperature is controlled to be 110°C, the pressure is 6MPa, and the time is 3min, to obtain a pulp molding anti-counterfeiting material.

Claims

1. A method for preparing a pulp molding material with anti-counterfeiting function, characterized in that: The specific steps include: Step 1, red-blue light modification of cotton fibers; Step 2, green-red light modification of cotton fibers; Step 3, modifying the cotton fiber with blue-green light; Step 4, preparing an optical anti-counterfeiting fiber according to the products obtained in steps 1 to 3; Step 5, preparing a pulp molded anti-counterfeiting material according to the product obtained in step 4; The specific process of step 5 is as follows: Step 5.1, taking 100-200 g of pulp, crushing it at 25° C. for 10-20 min, adjusting the pulping concentration to 8-12%, and the beating degree after pulping to 50-60° SR; Step 5.2, adding 1-2 g of cyclopropane acrylic acid resin, 2-3 g of polyvinyl alcohol, 0.2-0.4 g of polyacrylamide and 0.5-1 g of optical anti-counterfeiting fiber having a width of 0.1-1 mm and a length of 1-3 mm to the slurry obtained in step 5.1 to obtain a mixed slurry; Step 5.3, introducing the mixed slurry obtained in step 5.2 into the mold of a micro pulp molding machine, filtering the water to a moisture content of 55-60%, then demolding after extrusion molding at 5-6 MPa, and then drying in a drying oven at 70-80°C for 4-5 hours, and finally transferring to a flat vulcanizer for hot pressing and shaping, controlling the temperature to 100-110°C, the pressure to 5.5-6 MPa, and the time to 2-3 minutes, to obtain a pulp molded anti-counterfeiting material.

2. The method for preparing a pulp molding material with anti-counterfeiting function according to claim 1, characterized in that: The specific process of step 1 is as follows: Step 1.1, take 3-6 cotton yarns with a length of 1-2 meters and a specification of 60 / 4 male yarn, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2''-terpyridine, add 3-6 mL of triethylamine dropwise, raise the reaction temperature to 180-220° C. under a nitrogen atmosphere, and wash with 300-600 mL of deionized water 3 times after the reaction to obtain terpyridine-modified cotton fiber; Step 1.2, the terpyridine modified cotton fiber obtained in step 1.1 is placed in 1-2L deionized water, 2-4g of reactive red R-2BF dye and 2-4g of sodium sulfate are added, the temperature is raised to 40-60°C, and after reacting for 30-60min, the temperature is raised to 60-80°C, 1.5-3g of sodium carbonate is added and reacted for 30min, and after the reaction is completed, it is washed with soaping agent HM-900 until no pigment fades, thereby obtaining red-blue light modified cotton fiber.

3. The method for preparing a pulp molding material with anti-counterfeiting function according to claim 1, characterized in that: The specific process of step 2 is as follows: Step 2.1, take 3-6 cotton yarns with a length of 1-2 meters and a specification of 60 / 4 male yarn, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2''-terpyridine, add 3-6 mL of triethylamine dropwise, raise the reaction temperature to 180-220° C. under a nitrogen atmosphere, and wash with 300-600 mL of deionized water 3 times after the reaction to obtain terpyridine-modified cotton fiber; Step 2.2, putting the terpyridine modified cotton fiber obtained in step 2.1 into 1-2L deionized water, adding 2-4g of direct green BE dye and 2-4g of sodium sulfate, raising the temperature to 40-60°C, reacting for 30-60min, raising the temperature to 60-80°C, adding 1.5-3g of sodium carbonate and reacting for 30-60min, and washing with soaping agent HM-900 after the reaction is completed until no pigment fades; Step 2.3, put the cotton fiber obtained after the treatment in step 2.2 into 100-200 mL of deionized water, then add 3-6 g of hexafluoroacetylacetone, 2-3 g of europium chloride and 1-2 mL of triethylamine in sequence, heat the temperature to 60-80 ° C for 1-3 hours, wash three times with 300-600 mL of deionized water to obtain green-red light modified cotton fiber.

4. The method for preparing a pulp molding material with anti-counterfeiting function according to claim 1, characterized in that: The specific process of step 3 is as follows: Step 3.1, take 3-6 cotton yarns with a length of 1-2 meters and a specification of 60 / 4 male yarn, put them into 200-300 mL of dimethyl sulfoxide solution, then add 20-40 g of 4'-chloro-2,2':6',2''-terpyridine, add 3-6 mL of triethylamine dropwise, raise the reaction temperature to 180-220° C. under a nitrogen atmosphere, and wash them three times with 300-600 mL of deionized water after the reaction is completed to obtain terpyridine-modified cotton fibers; Step 3.2, putting the terpyridine modified cotton fiber obtained in step 3.1 into 1-2L deionized water, adding 2-4g of active dark blue R-2GLN dye and 2-4g of sodium sulfate, raising the temperature to 40-60°C, reacting for 30-60min, raising the temperature to 60-80°C, adding 1.5-3g of sodium carbonate and reacting for 30-60min, and washing with soaping agent HM-900 after the reaction is completed until no pigment fades; Step 3.3, put the cotton fiber treated in step 3.2 into 100-200 mL of deionized water, then add 3-6 g of hexafluoroacetylacetone, 2-3 g of terbium chloride and 1-2 mL of triethylamine in sequence, heat the temperature to 60-80 ° C for 1-3 hours, wash three times with 300-600 mL of deionized water to obtain blue-green light modified cotton fiber.

5. The method for preparing a pulp molding material with anti-counterfeiting function according to claim 1, characterized in that: The specific process of step 4 is as follows: Step 4.1, immersing 1-3 red-blue light modified cotton fibers, 1-3 green-red light modified cotton fibers, and 1-3 blue-green light modified cotton fibers in a UV adhesive solution for 2-10 seconds respectively; Step 4.2, winding the cotton fiber impregnated with UV adhesive obtained in step 4.1 on the surface of a circular column with a diameter of 5-10 cm in a spiral winding form, and irradiating it with ultraviolet light for 20-40 seconds to obtain an optical anti-counterfeiting fiber.

6. The method for preparing a pulp molding material with anti-counterfeiting function according to claim 5, characterized in that: In the step 4.1, the preparation process of the UV adhesive is as follows: 40-59 g of ethylene glycol acrylate, 40-59 g of butyl acrylate and 1-10 g of azobisisobutyronitrile are uniformly mixed to obtain the UV adhesive.

7. The method for preparing a pulp molding material with anti-counterfeiting function according to claim 1, characterized in that: The pulp can be any one or more of bamboo pulp, sugarcane pulp, wood pulp, waste corrugated paper pulp, newspaper pulp and straw pulp.

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