CN103343486B - Preparation method of paper with magnetic characteristic and luminescent characteristic - Google Patents

Abstract

The invention discloses a preparation method of paper with magnetic characteristic and luminescent characteristic. Specific papers with magnetic characteristic and luminescent characteristic are produced through combining luminous inorganic strong magnetic characteristic material with common paper pulp. The prepared paper has not only a series of advantages of non-electric conductivity, high temperature resistance, excellent chemical performance and aging resistance of an inorganic material but also excellent mechanical property and less possibility of combustion; the thickness of the paper is reduced by 20-30% than the thickness of common paper under the same mechanical property; the prepared paper also has special characteristics of strong paramagnetism and red glow. The paper prepared by utilizing the method has the magnetic characteristics such as magnetic response and magnetic recording so as to be used for high anti-counterfeiting special paper products such as register papers, wrapping papers and calligraphic papers which require special identification. The method does not need special equipment in a papermaking process and is simple to operate and easy for industrial production; the paper has permanent magnetism, is unlikely to be demagnetized, has strong hidden property and is unlikely to counterfeit.

Description

A preparation method of paper with magnetic properties and luminescent properties

technical field

The invention relates to a method for manufacturing paper, in particular to a method for preparing paper with magnetic and luminescent properties.

Background technique

With the development of science and technology, various counterfeit and counterfeit products emerge in an endless stream. Special paper products such as bills, product packaging, calligraphy, and paintings can bring huge profits to counterfeiters, so they do not hesitate to use various cutting-edge new technologies (such as computer graphics processing software, color printing, high-precision scanning, digital printing, etc.) to imitate , so that the original anti-counterfeiting is easy to lose its unique secrecy. Therefore, it is urgent to develop and research various new special and efficient anti-counterfeiting technologies. CN1609919 discloses a kind of anti-counterfeit film inner label sticker and its preparation method and application, comprising a label paper layer (2) printed with an anti-counterfeit label layer (1) on the surface, and an adhesive film layer ( 3), the film layer (3) has embossing (4). It overcomes the shortcomings of the existing label paper, and has a complete anti-counterfeiting function, and does not need to be labeled after molding. However, the prepared stickers are not resistant to high temperature and have poor strength. CN101381975 provides a transparent fiber exhibiting light transmittance in paper, a preparation method of the transparent fiber and a paper product containing the transparent fiber. The transparent fiber is a synthetic fiber obtained by dry spinning or wet spinning of raw materials comprising the following composition: polyvinyl alcohol: 75-97%, chitosan: 1-15%, carboxymethyl cellulose : 0.5‐10%. Equally, the prepared paper is not resistant to high temperature, and the anti-counterfeiting durable effect is poor.

Compared with other recording forms, the biggest advantage of magnetic paper is that there are a large number of useful records stored in the invisible magnetic layer, which is highly concealed, and it is particularly convenient to carry and use, and the feedback is rapid (insert into the machine, display or action in just a few seconds). From the perspective of confidentiality, its application fields will be more expanded, such as production management, communication, business sales, anti-theft and explosion-proof, etc. At present, most of the magnetic materials used in the preparation of magnetic paper are ferrite including Fe ₃ O ₄ (Yang Xin. Research on the preparation of magnetic paper by cell cavity filling method [D]. Jiangnan University, 2008.; Li Haifeng. In-situ composite method for magnetic paper Preparation and magnetic properties of [D]. Jiangnan University, 2008.), γ‐Fe ₂ O ₃ (Tang Aimin, Zhang Hongwei, Chen Gang, etc. Preparation and properties of magnetic nanocomposite fibers and magnetic paper [J]. South China University of Technology University Journal (Natural Science Edition), 2009, 37(3):75‐80.), Mn _1‐x Zn _x Fe ₂ O ₄ (Yu Gang, Duan Mingzhu, Lu Jian. Intracellular filling method to prepare fibers for magnetic paper [J]. Shanghai Paper, 2008, 39(1): 32‐35.), etc. However, the ferrite material has low resistance, is not resistant to acid and alkali, and cannot transmit light, and the whiteness of the prepared paper is relatively low, which has certain limitations in printing and other aspects. CN102587215A discloses a method for preparing paper with magnetic properties, specifically filling the cell cavity of pulp fibers with magnetic inorganic materials to prepare paper with magnetic properties. The paper prepared by the method has only magnetic anti-counterfeiting properties, and the anti-counterfeiting function is single. CN102587194A discloses a method for preparing high-strength magnetic paper. By adding an inorganic non-metallic high-temperature resistant amorphous material to the paper, the paper with magnetic properties is prepared. The prepared inorganic non-metallic high-temperature-resistant amorphous material has a simple preparation process, has optical isotropy, excellent chemical stability, non-conductivity, excellent mechanical properties and strong magnetism. Artificial wire drawing is used to avoid the crystallization and devitrification of inorganic fibers during the wire drawing process. Although the prepared paper of this invention patent has high strength, it still has the single shortcoming of anti-counterfeiting.

At present, for some special-purpose papers, such as RMB paper, the paper can emit specific light when excited by light of a specific wavelength, such as red and yellow-green light after being excited by ultraviolet light, which greatly increases the anti-counterfeiting of RMB. strength. However, most of the currently used anti-counterfeiting luminescent materials are organic luminescent materials, which are only printed on the surface of banknotes by printing, and the preparation process is complicated and the cost is high. However, there are few reports on paper that has both magnetic properties and luminous properties, and has excellent mechanical properties, non-conductivity, high temperature resistance, aging resistance, and high anti-counterfeiting strength. CN2695469 discloses a kind of light-storing luminescent paper. The surface of imported high-grade pure white paper with back glue is sprayed with a luminescent layer with ultra-long afterglow luminescence performance. Composition, the four kinds of raw materials are mixed evenly according to a certain proportion, and then sprayed on the surface of pure white paper four times. The paper prepared by the method has the disadvantages of poor abrasion resistance, low bonding strength between the light-storing material and the paper, and the like. CN2856114 discloses a kind of anti-counterfeiting paper with light storage and light emitting function. Its cross section has a layered structure. The layered structure is composed of a paper bottom layer, a light storage material layer, an intention mark layer, an adhesive layer and a transparent protective layer. The paper prepared by the method has the disadvantages of poor abrasion resistance, low bonding strength between the light-storing material and the paper, single anti-counterfeit property and the like. CN201546123U discloses a kind of luminescent paper that can be excited rapidly, and a glass microbead layer (2) is added between the matrix layer (1) and the luminescent material coating (3), and the thickness of the luminescent material coating (3) is smaller than that of the glass microbeads. The thickness of the bead layer, the luminous paper with this structure, by improving the light extraction efficiency of the luminous paper, can achieve the effect of rapid excitation under the condition that the excitation performance of the self-luminous material does not change. The paper prepared by the method has poor abrasion resistance, single anti-counterfeiting property and complex preparation process. CN102174784A discloses a light-storing and luminescent anti-counterfeiting paper as well as a manufacturing method and application thereof. It is uniformly coated with light-storing and luminescent ink in a printing manner on ordinary paper. The light-storing pigment is phosphorescent zinc sulfide ZnS:Cu. The paper prepared by the method has the disadvantages of poor abrasion resistance, low bonding strength between the light-storing material and the paper, short service life of the light-emitting material, single anti-counterfeiting property and the like.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, and provide a method for preparing paper that is non-conductive, acid and alkali resistant, light-transmitting, high-temperature resistant, anti-aging, and has good magnetic and luminous properties.

For achieving above object, technical scheme of the present invention is:

Include the following steps:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 12-20% of GeO2, 18-25% of Al2O3, 8-12% of B2O3, 35-40% of Tb4O7, 3-5% of Eu2O3, 0.1-2% of Dy2O3, 2-3% ZnO, 3-5% Na2SiF6, 0.2-0.5% CeO2, 0.3-0.5% ZrO2 are weighed and put into an agate emulsion mortar for grinding and mixing to form a batch;

2) Next, keep warm at the melting temperature of 1380-1410°C for 1-2 hours, put in the stirring paddle to continue stirring and melting, and keep the temperature at 1380-1410°C during the stirring process to obtain the melt;

3) Then, after the stirring in step 2), take out the stirring paddle, and cool the melt to 1350°C to obtain a melt;

4) Then, pour the melt into a copper mold, and make a sample rod after the melt is solidified. After the mold is opened, put the sample rod in an annealing furnace at 650°C to cool to room temperature;

5) Then, put the obtained sample rod into a wire drawing machine, heat and draw it into a fiber with a diameter of 20-30 μm, and coat the fiber surface with a softening sizing agent;

6) Finally, dry the fiber coated with the softening sizing agent and cut it into a fiber with a length of 2-5 mm to prepare a luminous inorganic strong magnetic material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, according to the mass fraction, take 1% to 3% hardwood dry pulp, 5% to 10% luminous inorganic strong magnetic material, 0.6% to 1.5% retention and drainage aid, and the balance is distilled water;

Add dry hardwood pulp into distilled water and stir evenly to obtain stirring liquid A;

2) Next, add a luminescent inorganic strong magnetic material to the stirring liquid A, and stir evenly to obtain the stirring liquid B;

3) Then, add retention and drainage aids to the stirring liquid B, and stir evenly to obtain the stirring liquid C;

4) Then, move the stirring solution B to the sheet copying machine to make sheets of 0.1-0.3mm;

5) Finally, after the paper sheet is baked, it is naturally cooled to obtain a paper with magnetic and luminous properties.

In step 3) of the first step, after the stirring blade is taken out, the melt is cooled to 1350° C. at a cooling rate of 10° C./min.

The circular sample rod has a diameter of 5 mm.

The step 1) in the second step is to stir evenly in a mixer at 500-1000 rpm.

Step 2) in the second step is to stir evenly in a mixer at 400-600 rpm.

Step 3) in the second step is uniformly stirred in a mixer at 800-1500 rpm.

The paper sheet is formed after pressing with a pressure of 4-6 MPa for 3-15 minutes.

The paper sheet is dried, and drying is to put the paper sheet into an oven at 105-110° C. for drying.

The retention and drainage aid is one or more of CPAM, PEI, and PEO.

The softening sizing agent is to weigh the mass ratio of paraffin: vaseline: stearic acid: water = 1:1:1:30, first melt the paraffin, vaseline and stearic acid, then add water, mix well configured later.

The beneficial effects of the present invention are:

The invention prepares special paper with both magnetic and luminous properties by compounding luminescent inorganic strong magnetic material and common pulp. The prepared paper not only has a series of advantages such as non-conductive inorganic materials, high temperature resistance, excellent chemical properties, anti-aging, etc., but also has excellent mechanical properties, and the inorganic fiber material is firmly combined with the paper fiber, which is not easy to burn; Under mechanical properties, the thickness is 20-30% less than that of ordinary paper. At the same time, the prepared paper also exhibits special properties of strong paramagnetism and red light emission. The paper prepared according to the preparation method of the present invention has magnetic properties such as magnetic response and magnetic recording, and can be used for special paper products such as receipt paper, wrapping paper, and calligraphy paper that require special identification. The invention does not need special equipment in the paper preparation process, is simple to operate, and is easy to industrialized production; and the magnetism is permanent, difficult to demagnetize, strong in concealment, and difficult to be copied.

Description of drawings

Fig. 1 is the luminescent spectrogram of the paper with magnetic properties and luminescent properties prepared in Example 1, wherein the abscissa is the wavelength of emitted light, and the ordinate is the intensity of emitted light;

Fig. 2 is the hysteresis loop of the paper with magnetic properties and luminous properties prepared in Example 1, wherein the abscissa is the magnetic field strength, and the ordinate is the magnetization;

Fig. 3 is a photo of the paper with magnetic properties and luminescent properties prepared in Example 1 under a scanning electron microscope.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings.

Example 1:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 19% GeO ₂ , 20% Al ₂ O ₃ , 10% B ₂ O ₃ , 38% Tb ₄ O ₇ , 4% Eu ₂ O ₃ , 1% Dy ₂ O ₃ , 3% ZnO, 4% Na ₂ SiF ₆ , 0.5% CeO ₂ , 0.5% ZrO ₂ were weighed and put into an agate emulsion mortar and mixed until the uniformity was greater than 98%. , forming a batch;

2) Next, add the batch material into the platinum crucible at 1410°C, and keep it at the melting temperature of 1410°C for 1 hour, then put in the stirring paddle and continue to stir and melt for 3 hours. During the stirring process, the temperature is always kept at 1410°C;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a copper mold at 600°C, and make a sample rod with a diameter of 5mm after the melt is solidified. After the mold is opened, put the sample rod into an annealing furnace at 650°C. After heat preservation for 2 hours, cool to room temperature with the furnace;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, draw the sample rod into a fiber with a diameter of 20-30 μm, and coat the fiber surface with a softening sizing agent;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 2 hours, dry the water, and cut it into a fiber with a length of 2-5mm to prepare a luminous inorganic strong magnetic property Material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 5g of dry hardwood pulp, add it to 500ml of distilled water, and stir it in a mixer at 1000 rpm for 50min to obtain stirring solution A;

2) Next, add 10 g of the prepared luminescent inorganic ferromagnetic material to the obtained stirring solution A, and then stir at 600 rpm for 50 minutes to obtain the stirring solution B;

3) Then, add 1.5g of retention and drainage aid CPAM (cationic polyacrylamides, cationic polyacrylamide) to the obtained stirred liquid B, and continue to stir at 1500 rpm for 80 minutes to obtain stirred liquid C;

4) Then, move the obtained stirring solution C to a sheet machine to sheet, press with a pressure of 6 MPa for 15 minutes, and form a sheet of 0.1 mm;

5) Finally, put the paper in an oven at 105°C, dry for 30 minutes, and cool naturally to obtain paper with magnetic and luminescent properties.

Referring to Figure 1, it is the photoluminescence spectrum of the prepared paper with magnetic and luminescent properties at an excitation wavelength of 378nm, where the abscissa is the wavelength of emitted light, and the ordinate is the intensity of emitted light. It can be seen from Figure 1 that the strongest emission wavelength of the prepared paper is 617.4nm, and the intensity is close to 1200 units, while the emission intensity at 580.2nm, 593.2nm, 656.2nm, and 705.4nm is very weak.

Referring to Figure 2, it is the hysteresis loop of the prepared paper with magnetic and luminescent properties in the range of -2000-3000Oe. It can be seen from the figure that the prepared paper has certain paramagnetism.

Referring to accompanying drawing 3, it is the SEM photograph of the prepared paper with magnetic and luminous properties under 1K magnification. It can be seen from the figure that the inorganic fibers in the prepared paper are closely combined with the paper fibers and present a uniform distribution.

Example 2:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 14.5% GeO ₂ , 25% Al ₂ O ₃ , 11% B ₂ O ₃ , 37% Tb ₄ O ₇ , 3% Eu ₂ O ₃ , 2% Dy ₂ O ₃ , 2% ZnO, 5% Na ₂ SiF ₆ , 0.2% CeO ₂ , 0.3% ZrO ₂ were weighed and put into agate emulsion, ground and mixed until the uniformity was greater than 98%, and formed Batch materials;

2) Next, add the batch material into the platinum crucible at 1410°C, and keep it warm at the melting temperature of 1410°C for 2 hours, then put in the stirring paddle and continue stirring and melting for 2 hours, and the temperature is always kept at 1410°C during the stirring process;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a copper mold at 600°C to make a sample rod with a diameter of 10mm. After the melt is solidified, open the mold and put the sample rod into an annealing furnace at 650°C for heat preservation. Cool to room temperature with the furnace after 2h;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, and draw the sample rod into a fiber with a diameter of 30 μm, and apply a softening sizing agent on the surface of the fiber in time;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 2 hours, dry the water, and cut it to a length of 2-5 mm to prepare a luminescent inorganic strong magnetic material ;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 4g of dry hardwood pulp, add it to 400ml of distilled water, and stir it in a mixer at 700 rpm for 40min to obtain stirring solution A;

2) Next, add 8 g of the prepared luminescent inorganic ferromagnetic fiber to the obtained stirring liquid A, and then stir at 500 rpm for 40 minutes to obtain the stirring liquid B;

3) Then, add 1.2g of retention and drainage aid PEI (Polyetherimide, polyetherimide) to the stirring liquid B, and continue stirring at 1000 rpm for 60 minutes to obtain the stirring liquid C;

4) Then, move the agitated liquid C to the sheet machine for sheeting, press with a pressure of 5 MPa for 11 minutes, and form a sheet of 0.2 mm;

5) Finally, put the paper sheet in an oven at 110°C, dry it for 20 minutes, and cool it naturally to obtain paper with magnetic and luminescent properties.

Example 3:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 16% GeO ₂ , 24% Al ₂ O ₃ , 9.5% B ₂ O ₃ , 36% Tb ₄ O ₇ , 5% Eu ₂ O ₃ , 2% Dy ₂ O ₃ , 2% ZnO, 5% Na ₂ SiF ₆ , 0.3% CeO ₂ , 0.2% ZrO ₂ were weighed and put into agate emulsion, ground and mixed until the uniformity was greater than 98%, and formed Batch materials;

2) Next, add the batch material into the platinum crucible at 1400°C, and keep it warm at the melting temperature of 1400°C for 2 hours, then put in the stirring paddle and continue stirring and melting for 2 hours, and the temperature is always kept at 1400°C during the stirring process;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a 600°C copper mold to make a sample rod with a diameter of 5mm. After the melt is solidified, open the mold and put the sample rod into an annealing furnace at 650°C for heat preservation. Cool to room temperature with the furnace after 2h;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, and draw the sample rod into a fiber with a diameter of 20-30 μm, and apply a softening sizing agent on the surface of the fiber in time;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 2 hours, dry the water, and cut it into a fiber with a length of 2-5mm to prepare a luminous inorganic strong magnetic property Material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 3g of dry hardwood pulp, add it to 300ml of distilled water, and stir it in a mixer at 600 rpm for 50min to obtain stirring solution A;

2) Next, add 6g of the prepared luminous inorganic strong magnetic fiber to the stirring liquid A, and then stir at 600 rpm for 20 minutes to obtain the stirring liquid B;

3) Then, add 0.9g of retention and drainage aid PEO (polyethylene oxide) to the stirring liquid B, and continue stirring at 900 rpm for 80 minutes to obtain the stirring liquid C;

4) Then, move the stirred liquid C to the sheet machine for sheeting, and press it with a pressure of 4 MPa for 15 minutes to form a 0.1mm sheet;

5) Finally, put the paper in an oven at 105°C, dry for 30 minutes, and cool naturally to obtain paper with magnetic and luminescent properties.

Example 4:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 17.4% GeO ₂ , 19% Al ₂ O ₃ , 12% B ₂ O ₃ , 40% Tb ₄ O ₇ , 3% Eu ₂ O ₃ , 1% Dy ₂ O ₃ , 3% ZnO, 4% Na ₂ SiF ₆ , 0.3% CeO ₂ , 0.3% ZrO ₂ were weighed and put into agate emulsion, ground and mixed until the uniformity was greater than 98%, and formed Batch materials;

2) Next, add the batch material into the platinum crucible at 1380°C, and keep it warm at the melting temperature of 1380°C for 2 hours, then put in the stirring paddle and continue stirring and melting for 3 hours, and the temperature is always kept at 1380°C during the stirring process;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a 600°C copper mold to make a sample rod with a diameter of 5mm. After the melt is solidified, open the mold and put the sample rod into an annealing furnace at 650°C for heat preservation. Cool to room temperature with the furnace after 2h;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, and draw the sample rod into fibers with a diameter of 20-30 μm, and coat the softening sizing agent on the surface of the sample fiber in time ;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 2 hours, dry the water, and cut it into a fiber with a length of 2-5mm to prepare a luminous inorganic strong magnetic property Material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 5g of dry hardwood pulp, add it to 500ml of distilled water, and stir it in a mixer at 1000 rpm for 50min to obtain stirring solution A;

2) Next, add 10 g of the prepared luminescent inorganic ferromagnetic material to the stirring liquid, and then stir at 600 rpm for 20 minutes to obtain the stirring liquid B;

3) Then, add 0.6g of retention and drainage aids CPAM and PEI to the stirring liquid B, and continue stirring at 8000 rpm for 80 minutes to obtain the stirring liquid C;

4) Then, move the agitated liquid C to the sheet copying machine for sheeting, press with a pressure of 6 MPa for 3 minutes, and form a 0.1mm sheet;

5) Finally, put the paper sheet in an oven at 110°C, dry it for 10 minutes, and cool it naturally to obtain paper with magnetic and luminescent properties.

Example 5:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 18.5% GeO ₂ , 20% Al ₂ O ₃ , 11% B ₂ O ₃ , 39% Tb ₄ O ₇ , 4% Eu ₂ O ₃ , 2% Dy ₂ O ₃ , 2% ZnO, 3% Na ₂ SiF ₆ , 0.2% CeO ₂ , 0.3% ZrO ₂ were weighed and put into agate emulsion, ground and mixed until the uniformity was greater than 98%, and formed Batch materials;

2) Next, add the batch material into the platinum crucible at 1390°C, and keep it at the melting temperature of 1390°C for 2 hours, then put in the stirring paddle and continue stirring and melting for 3 hours, and the temperature is always kept at 1390°C during the stirring process;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a 600°C copper mold to make a sample rod with a diameter of 5mm. After the melt is solidified, open the mold and put the sample rod into an annealing furnace at 650°C for heat preservation. Cool to room temperature with the furnace after 2h;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, and draw the sample into a fiber with a diameter of 20-30 μm, and apply a softening sizing agent on the surface of the fiber in time;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 2 hours, dry the water, and cut it into a fiber with a length of 2-5mm to prepare a luminescent inorganic strong magnetic property Material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 4g of dry hardwood pulp, add it to 400ml of distilled water, and stir it in a mixer at 700 rpm for 40min to obtain stirring solution A;

2) Next, add 7g of the prepared luminescent inorganic ferromagnetic fiber to the stirring liquid A, and then stir at 500 rpm for 30 minutes to obtain the stirring liquid B;

3) Then, add 1.0 g of retention and drainage aids CPAM, PEI and PEO to the stirring liquid B, and continue stirring at 1100 rpm for 50 minutes to obtain the stirring liquid C;

4) Then, move the stirred liquid C to the sheet machine for sheeting, and press it for 10 minutes with a pressure of 5 MPa to form a sheet of 0.2mm;

5) Finally, put the paper sheet in an oven at 105°C, dry it for 20 minutes, and cool it naturally to obtain paper with magnetic and luminescent properties.

Embodiment 6:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 15% GeO ₂ , 19.3% Al ₂ O ₃ , 11% B ₂ O ₃ , 40% Tb ₄ O ₇ , 5% Eu ₂ O ₃ , 2% Dy ₂ O ₃ , 3% ZnO, 4% Na ₂ SiF ₆ , 0.3% CeO ₂ , 0.4% ZrO ₂ were weighed and put into agate emulsion, ground and mixed until the uniformity was greater than 98%, and formed Batch materials;

2) Next, add the batch material into the platinum crucible at 1400°C, and keep it at the melting temperature of 1400°C for 1 hour, then put in the stirring paddle and continue to stir and melt for 3 hours, and the temperature is always kept at 1400°C during the stirring process;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a 600°C copper mold to make a sample rod with a diameter of 5mm. After the melt is solidified, open the mold and put the sample rod into an annealing furnace at 650°C for heat preservation. Cool to room temperature with the furnace after 2h;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, and draw the sample rod into a fiber with a diameter of 20-30 μm, and apply a softening sizing agent on the surface of the fiber in time;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 1 hour, dry the water, and cut it into a fiber with a length of 2-5mm to prepare a luminous inorganic strong magnetic property Material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 5g of dry hardwood pulp, add it to 500ml of distilled water, and stir it in a mixer at 1000 rpm for 50min to obtain stirring solution A;

2) Next, add 8 g of the prepared luminescent inorganic ferromagnetic material to the stirring liquid A, and then stir at 500 rpm for 40 minutes to obtain the stirring liquid B;

3) Then, add 1.4g of retention and drainage aids PEI and PEO to the stirring solution B, and continue stirring at 1200 rpm for 70 minutes to obtain the stirring solution C;

4) Then, move the agitated liquid C to the sheet machine for sheeting, and press it with a pressure of 6 MPa for 7 minutes to form a sheet of 0.15 mm;

5) Finally, put the paper in an oven at 105°C, dry for 30 minutes, and cool naturally to obtain paper with magnetic and luminous properties.

Embodiment 7:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 12% GeO ₂ , 18% Al ₂ O ₃ , 8% B ₂ O ₃ , 35% Tb ₄ O ₇ , 4% Eu ₂ O ₃ , 0.1% Dy ₂ O ₃ , 2.5% ZnO, 4% Na ₂ SiF ₆ , 0.4% CeO ₂ , and 0.3% ZrO ₂ were weighed and put into agate emulsion, ground and mixed until the uniformity was greater than 98%, and formed Batch materials;

2) Next, add the batch material into the platinum crucible at 1380°C, and keep it warm at the melting temperature of 1380°C for 2 hours, then put in the stirring paddle and continue stirring and melting for 3 hours, and the temperature is always kept at 1380°C during the stirring process;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a 600°C copper mold to make a sample rod with a diameter of 5mm. After the melt is solidified, open the mold and put the sample rod into an annealing furnace at 650°C for heat preservation. Cool to room temperature with the furnace after 1h;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, and draw the sample rod into fibers with a diameter of 20-30 μm, and coat the softening sizing agent on the surface of the sample fiber in time ;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 1 hour, dry the water, and cut it into a fiber with a length of 2-5mm to prepare a luminous inorganic strong magnetic property Material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 5g of dry hardwood pulp, add it to 500ml of distilled water, and stir it in a mixer at 1000 rpm for 50min to obtain stirring solution A;

2) Next, add 8 g of the prepared luminescent inorganic ferromagnetic material to the stirring liquid A, and then stir at 500 rpm for 40 minutes to obtain the stirring liquid B;

3) Then, add 1.4 g of retention and drainage aids CPAM and PEI to the stirring liquid B, and continue stirring at 1200 rpm for 70 minutes to obtain the stirring liquid C;

4) Then, move the agitated liquid C to the sheet machine for sheeting, and press it with a pressure of 6 MPa for 7 minutes to form a sheet of 0.15 mm;

5) Finally, put the paper in an oven at 105°C, dry for 30 minutes, and cool naturally to obtain paper with magnetic and luminescent properties.

Embodiment 8:

Step 1: Preparation and processing of luminescent inorganic strong magnetic materials

1) First, according to the mass fraction, 20% GeO ₂ , 22% Al ₂ O ₃ , 12% B ₂ O ₃ , 35% Tb ₄ O ₇ , 3% Eu ₂ O ₃ , 0.5% Dy ₂ O ₃ , 2.5% ZnO, 5% Na ₂ SiF ₆ , 0.5% CeO ₂ , and 0.5% ZrO ₂ were weighed and put into agate emulsion, ground and mixed until the uniformity was greater than 98%, and formed Batch materials;

2) Next, add the batch material into the platinum crucible at 1410°C, and keep it at the melting temperature of 1410°C for 1 hour, then put in the stirring paddle and continue stirring and melting for 2 hours, and the temperature is always kept at 1410°C during the stirring process;

3) Then, after the stirring is completed, take out the stirring blade, cool the melt to 1350°C at a cooling rate of 10°C/min, and keep it at 1350°C for 30 minutes to obtain a melt;

4) Then, pour the molten melt into a 600°C copper mold to make a sample rod with a diameter of 5mm. After the melt is solidified, open the mold and put the sample rod into an annealing furnace at 650°C for heat preservation. Cool to room temperature with the furnace after 2h;

5) Then, put the obtained sample rod into a wire drawing machine, heat it to 1350°C, and draw the sample rod into fibers with a diameter of 20-30 μm, and coat the softening sizing agent on the surface of the sample fiber in time ;

6) Finally, put the fiber coated with the softening sizing agent into an oven at 110°C, keep it warm for 1 hour, dry the water, and cut it into a fiber with a length of 2-5mm to prepare a luminous inorganic strong magnetic property Material;

Step 2: Preparation of paper with magnetic and luminescent properties

1) First, take 5g of dry hardwood pulp, add it to 500ml of distilled water, and stir it in a mixer at 1000 rpm for 50min to obtain stirring solution A;

2) Next, add 8 g of the prepared luminescent inorganic ferromagnetic material to the stirring liquid A, and then stir at 500 rpm for 40 minutes to obtain the stirring liquid B;

3) Then, add 1.4g of retention and drainage aid CPAM to the stirring liquid B, and continue stirring at 1200 rpm for 70 minutes to obtain the stirring liquid C;

4) Then, move the agitated liquid C to the sheet machine for sheeting, and press it with a pressure of 6 MPa for 7 minutes to form a sheet of 0.15 mm;

5) Finally, put the paper in an oven at 105°C, dry for 30 minutes, and cool naturally to obtain paper with magnetic and luminescent properties.

It should be noted that GeO ₂ , Al ₂ O ₃ , B ₂ O ₃ , Tb ₄ O ₇ , Eu ₂ O ₃ , Dy ₂ O ₃ , ZnO, Na ₂ SiF ₆ , CeO ₂ , ZrO ₂ were introduced by analytically pure germanium oxide, aluminum hydroxide, boric acid, terbium oxide, europium oxide, dysprosium oxide, zinc oxide, sodium fluorosilicate, cerium oxide, and zirconium oxide.

The invention prepares special paper with both magnetic and luminous properties by compounding luminous inorganic strong magnetic properties material with common pulp. The prepared paper not only has a series of advantages such as non-conductive inorganic materials, high temperature resistance, excellent chemical properties, anti-aging, etc., but also has excellent mechanical properties and is not easy to burn; under the same mechanical properties, the thickness is thicker than ordinary paper The thickness is reduced by 20-30%. At the same time, the prepared paper also exhibits special properties of strong paramagnetism and red light emission. The paper prepared according to the preparation method of the present invention has magnetic properties such as magnetic response and magnetic recording, and can be used for special paper products such as bill paper, wrapping paper, calligraphy paper and the like that require special identity certificates and high anti-counterfeiting. The invention does not need special equipment in the paper preparation process, is simple to operate, and is easy to industrialized production; and the magnetism is permanent, difficult to demagnetize, strong in concealment, and difficult to be copied.

Claims (10)

1. A method for preparing paper with magnetic properties and luminescent properties, characterized in that it may further comprise the steps: Step 1: Preparation and processing of luminescent inorganic strong magnetic materials 1) First, according to the mass fraction, 12-20% of GeO ₂ , 18-25% of Al ₂ O ₃ , 8-12% of B ₂ O ₃ , 35-40% of Tb ₄ O ₇ , 3- 5% Eu ₂ O ₃ , 0.1-2% Dy ₂ O ₃ , 2-3% ZnO, 3-5% Na ₂ SiF ₆ , 0.2-0.5% CeO ₂ , 0.3-0.5% ZrO ₂ After weighing, put it into an agate emulsion mortar and grind and mix to form a batch; 2) Next, keep warm at the melting temperature of 1380-1410°C for 1-2 hours, put in the stirring paddle to continue stirring and melting, and keep the temperature at 1380-1410°C during the stirring process to obtain the melt; 3) Then, after step 2) the stirring is completed, take out the stirring paddle, and cool the melt to 1350° C. to obtain the melt; 4) Then, pour the melt into a copper mold, and make a sample rod after the melt is solidified. After the mold is opened, put the sample rod into an annealing furnace at 650° C. to cool to room temperature; 5) Then, put the obtained sample rod into a wire drawing machine, heat and draw it into a fiber with a diameter of 20-30 μm, and coat the fiber surface with a softening sizing agent; 6) Finally, after drying the fiber coated with the softening sizing agent, cut it into a fiber with a length of 2-5 mm, and then prepare a luminescent inorganic strong magnetic material; Step 2: Preparation of paper with magnetic and luminescent properties 1) First, according to the mass fraction, take 1% to 3% dry hardwood pulp, 5% to 10% luminescent inorganic strong magnetic material, 0.6% to 1.5% retention and drainage aid, and the balance is distilled water; Add dry hardwood pulp into distilled water and stir evenly to obtain stirring liquid A; 2) Next, add the luminescent inorganic strong magnetic material into the stirring liquid A, and carry out uniform stirring to obtain the stirring liquid B; 3) Then, add the retention and drainage aid to the stirring liquid B, and stir evenly to obtain the stirring liquid C; 4) Then, move the stirring solution B to the sheet copying machine to make sheets of 0.1-0.3 mm; 5) Finally, after the paper sheet is baked, it is naturally cooled to obtain paper with magnetic and luminescent properties. 2. A method for preparing paper with magnetic and luminescent properties according to claim 1, characterized in that, after step 3) in the first step is taken out of the stirring paddle, the molten Liquid cooling to 1350°C. 3. A method for preparing paper with magnetic and luminous properties according to claim 1, wherein the diameter of the sample rod is 5 mm. 4. A method for preparing paper with magnetic and luminous properties according to claim 1, characterized in that, in the second step, step 1) uniformly stirs in a stirrer at 500-1000 rpm. 5. A method for preparing paper with magnetic and luminous properties according to claim 1, characterized in that, in the second step, step 2) uniformly stirs in a stirrer at 400-600 rpm. 6. A method for preparing paper with magnetic and luminous properties according to claim 1, characterized in that, in the second step, step 3) uniformly stirs in a stirrer at 800-1500 rpm. 7 . The method for preparing paper with magnetic and luminous properties according to claim 1 , wherein the paper sheet is formed after pressing for 3 to 15 minutes with a pressure of 4 to 6 MPa. 8 . The method for preparing paper with magnetic and luminous properties according to claim 1 , wherein the paper is dried in an oven at 105-110° C. for drying. 9. A method for preparing paper with magnetic and luminescent properties according to claim 1, wherein the retention and drainage aid is one or more of CPAM, PEI, and PEO. 10. A kind of preparation method with magnetic property and luminescent property paper according to claim 1, is characterized in that, described softening sizing agent is paraffin: vaseline: stearic acid: water=1:1:1: After weighing with a mass ratio of 30, first melt paraffin, vaseline and stearic acid, then add water, mix well and prepare.