Preparation method and application of recyclable visible light printing paper

Abstract

The application discloses a preparation method and application of a recyclable visible light printing paper, and the visible light printing paper is prepared by the following steps: firstly, using a free radical polymerization method to prepare a visible light response polymer by taking a polymerizable monomer, a functional monomer and a visible light response monomer as raw materials, and then coating the visible light response polymer on ordinary paper to obtain the visible light printing paper. The visible light printing paper can be used for at least 100 times, and can be used in combination with a visible light printer to print without ink, and has the advantages of simple structure, low investment cost, environmental friendliness, no pollution and the like, and is suitable for application in life scenes such as table card printing, movie ticket printing and number taking sheet printing, and has a huge application prospect in the printing market.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of functional materials and printing technology, and in particular relates to a preparation method and application of a recyclable visible light printing paper. BACKGROUND

[0002] With the continuous development of the national economy, people's demand for printing market is expanding, and the consumption of paper in China is also increasing year by year, reaching 120 million tons in 2022. Although the types and printing methods of current printers are diversified, there are still problems such as expensive printing consumables, high energy consumption, environmental pollution, and non-recyclable printing paper, especially the environmental problems caused by paper resource consumption.

[0003] In order to improve the resource consumption problem caused by paper waste, scientists have been committed to seeking new solutions, such as paper recycling and optimization and upgrading of printing technology. Although these technologies can slow down the consumption of paper to some extent, they still cannot effectively solve the above problems. Therefore, how to reuse paper is very necessary to reduce resource consumption, which requires the development of new printing technology, especially the recyclable inkless printing technology of paper. At present, light as a green and pollution-free external stimulus means has the advantages of green, pollution-free, high spatial and temporal resolution, and is widely used to construct stimulus-responsive systems. Among them, the response system based on visible light stimulus is concerned. Therefore, the combination of light response and printing technology can realize light printing under non-contact conditions, which is more in line with the requirements of low-carbon energy saving and green environmental protection of the country.

[0004] Unlike conventional ultraviolet light-responsive materials, visible light-responsive materials can well avoid the harm of ultraviolet light to human health and structural damage to materials, thereby realizing the multiple recycling of printed paper. In addition, low-energy visible light is more green and safe, and has better recycling performance. Although there have been related reports on the development of new visible light switch polymers for light erasable, information anti-counterfeiting encryption (CN202211567167.7, CN202311833788.X). However, so far, there has been no report on the application of visible light-responsive materials in the printing field. Therefore, it is of great practical significance and application prospect to invent a "inkless, recyclable paper, green and environmentally friendly" light printing paper and supporting light printing equipment. SUMMARY

[0005] The technical problems to be solved by the present application are to overcome the shortcomings of the prior art and provide a recyclable visible light printing paper preparation method and application. The visible light printing paper is first prepared by using a polymerizable monomer, a functional monomer, and a visible light responsive monomer as raw materials to prepare a visible light responsive polymer (CN202211567167.7, CN202311833788.X), and then coated on ordinary paper to prepare the required visible light printing paper. The visible light printing paper can be printed at least 100 times. The printing process does not require the use of ink, and the visible light printing paper can be recycled, which is low-carbon and environmentally friendly.

[0006] To solve the above technical problems, the basic idea of the technical solution adopted by the present application is:

[0007] The present application provides a recyclable visible light printing paper preparation method, which specifically comprises the following steps:

[0008] (1) The preparation of the visible light responsive polymer is prepared by using a polymerizable monomer, an initiator, a functional monomer, and a visible light responsive monomer as raw materials by one-step free radical copolymerization;

[0009] (2) A certain amount of visible light responsive polymer is dissolved in dichloromethane and then put into paper;

[0010] (3) After soaking for a period of time, the filter paper is taken out and dried at 40 degrees to obtain a recyclable visible light printing paper.

[0011] Preferably, the polymerizable monomer can be selected from one or a combination of the following molecular structures.

[0012] In the formula, 30≥n≥1.

[0013] The content of the polymerizable monomer in the polymer is 94-99.99 wt%, preferably 98-99.9 wt%.

[0014] Preferably, the functional monomer can be selected from one or a combination of the following molecular structures.

[0015] In the formula, 30≥n≥0.

[0016] The content of the functional monomer in the polymer is 0~5 wt%, preferably 0.1~1wt%.

[0017] The present application contains a large amount of structures that can form multiple hydrogen bond structures, hydroxyl groups, carboxyl groups, amino groups, and sulfonic acid groups in the growth material, which can effectively combine with the paper and achieve uniform distribution of the polymer.

[0018] Preferably, the visible light responsive monomer can be selected from one or a combination of the following molecular structures.

[0019] , wherein 30≥n≥0.

[0020] The content of the visible light responsive monomer in the polymer is 0.01-1 wt%, preferably 0.05-0.1 wt%.

[0021] The red open ring state of the visible light responsive monomer is converted into the colorless closed ring state under the stimulation of visible light. Since the closed ring state is a non-stable state, it can be converted into the red non-closed ring state under heating conditions, as follows:

[0022]

[0023] The application of the visible light printing paper prepared by the above method in visible light printing. The visible light printing paper is used in conjunction with a visible light printer, which comprises a laser pen, a controller, a mechanical arm, a distance sensor, and a housing.

[0024] The mechanical arm comprises a first support, a second support, a third support, a first motor, a second motor, and a third motor. The housing bottom plate is provided with an X-axis guide rail, the first support is in sliding connection with the X-axis guide rail, one end of the second support is connected with the first support, the second support is provided with a Y-axis guide rail, the third support is in sliding connection with the Y-axis guide rail, the third support is provided with a Z-axis guide rail, the laser pen is in sliding connection with the Z-axis guide rail, the X-axis guide rail, the Y-axis guide rail, and the Z-axis guide rail are perpendicular to each other, the first motor drives the first support to move along the X-axis guide rail, the second motor drives the third support to move along the Y-axis guide rail, and the third motor drives the laser pen to move along the Z-axis guide rail.

[0025] The distance sensor is mounted on the third support, and the controller is in electrical connection with the laser pen, the first motor, the second motor, the third motor, and the distance sensor.

[0026] The controller can control the position, speed, and other parameters of the mechanical arm. The movement of the mechanical arm drives the laser pen, the distance between the laser pen and the paper is adjusted by the distance sensor, and the switch of the laser pen power supply is controlled, so as to leave a track on the paper and realize the writing of characters.

[0027] Compared with the prior art, the present application has the following beneficial effects.

[0028] (1) The visible light printing paper can be tested to be recycled at least 100 times, and has excellent recycling performance.

[0029] (2) The visible light printing paper can determine the storage time of information by controlling the temperature, and has strong controllability.

[0030] (3) Compared with the traditional printer, the light printer adopts inkless intelligent printing, and the visible light printing paper can be recycled, which not only saves the consumable cost of ink, paper and the like, but also has the ecological benefits of low carbon and environmental protection.

[0031] (4) The visible light printing paper of the application can be widely applied in the fields of supermarket small tickets, movie tickets, table cards, dining shop meal taking numbers, large-scale sports event tickets and bank number taking sheets.

[0032] The specific embodiments of the application will be further described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0033] The accompanying drawings, which are part of the present application, serve to provide a further understanding of the application, and the schematic embodiments of the application and the description thereof serve to explain the application, but do not constitute an improper limitation on the application. Obviously, the accompanying drawings in the following description are only some embodiments, and other drawings can be obtained by those skilled in the art without creative labor. In the drawings:

[0034] Figure 1 It is a schematic diagram for the preparation of the polymer.

[0035] Figure 2 It is a molecular weight distribution diagram of the polymer.

[0036] Figure 3 It is a real object diagram before and after the preparation of the light printing paper.

[0037] Figure 4 It is a schematic diagram and a real object diagram of the light printer; in the diagram, 1, X-axis guide rail; 2, distance sensor; 3, laser pen; 4, third support; 5, second support.

[0038] Figure 5 It is an effect diagram of visible light printing.

[0039] It should be noted that these drawings and written descriptions are not intended to limit the scope of the concept of the application in any way, but to illustrate the concept of the application to those skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical scheme and advantages of the embodiments of the application more clear, the technical scheme in the embodiments will be described clearly and completely below with reference to the drawings in the embodiments of the application, and the following embodiments are used to illustrate the application, but not to limit the scope of the application.

[0041] Embodiment 1: Preparation of visible light responsive polymer, the specific steps are as follows:

[0042] Butyl acrylate 1.12 g, azobisisobutyronitrile 4.8 mg, 1,2-(((6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)pyrimidinone)hexyl)carbamoyl)oxy)methyl acrylate 3.8 mg and 2-((acryloyloxy)methyl)-6-((E)-2-((1R,3r,8S)-4-methyl-4-azatricyclo[4.3.1.13,8]undec-4-ene-4-ium-5-yl)vinyl)-4-nitrophenolate 11.8 mg were dissolved in 2.5 mL of refined N,N-dimethylformamide, vacuumed and filled with nitrogen for three times, stirred at 70 degrees Celsius under nitrogen protection for 12 h. After the reaction was completed, the reaction solution was rapidly cooled in an ice water bath, precipitated in methanol, and the obtained precipitate was dried to obtain visible light responsive polymer 1. Its molecular weight was 31.7 kilodaltons Figure 2 .

[0043] Example 2: Preparation of visible light responsive polymer, the specific steps are as follows:

[0044] Butyl acrylate 1.12 g, azobisisobutyronitrile 4.8 mg, 1,2-(((6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)pyrimidinone)hexyl)carbamoyl)oxy)methyl acrylate 3.2 mg and 2-((acryloyloxy)methyl)-6-((E)-2-((1R,3r,8S)-4-methyl-4-azatricyclo[4.3.1.13,8]undec-4-ene-4-ium-5-yl)vinyl)-4-nitrophenolate 9.8 mg were dissolved in 2 mL of refined N,N-dimethylformamide, vacuumed and filled with nitrogen for three times, stirred at 60 degrees Celsius under nitrogen protection for 18 h. After the reaction was completed, the reaction solution was rapidly cooled in an ice water bath, precipitated in methanol, and the obtained precipitate was dried to obtain visible light responsive polymer 2.

[0045] Example 3: Preparation of visible light responsive polymer, the specific steps are as follows:

[0046] Butyl acrylate 1.12 g, azobisisobutyronitrile 4.8 mg, 1,2-(((6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)pyrimidinone)hexyl)carbamoyl)oxy)methyl acrylate 6.6 mg and 2-((acryloyloxy)methyl)-6-((E)-2-((1R,3r,8S)-4-methyl-4-azatricyclo[4.3.1.13,8]undec-4-en-4-ium-5-yl)vinyl)-4-nitrophenolate 12.2 mg were dissolved in 4 mL of refined N,N-dimethylformamide, vacuumed and filled with nitrogen three times, and stirred at 80 degrees Celsius under nitrogen protection for 10 hours. After the reaction was completed, the reaction solution was rapidly cooled in an ice water bath, precipitated in methanol, and the obtained precipitate was dried to obtain a visible light responsive polymer 3.

[0047] Example 4: Preparation of a recyclable visible light printing paper, the specific steps are as follows:

[0048] Take 240 mg of visible light responsive polymer 1 and dissolve it in 4 mL of dichloromethane, then soak the ordinary printing paper in the mixed solution, take out the filter paper after 30 minutes, and dry it at 40 degrees Celsius to obtain a recyclable visible light printing paper 1. The changes before and after printing paper are shown in Figure 3 .

[0049] Example 5: Preparation of a recyclable visible light printing paper, the specific steps are as follows:

[0050] Take 200 mg of visible light responsive polymer 2 and dissolve it in 2 mL of dichloromethane, then soak the ordinary printing paper in the mixed solution, take out the filter paper after 30 minutes, and dry it at 30 degrees Celsius to obtain a recyclable visible light printing paper 2.

[0051] Example 6: Preparation of a recyclable visible light printing paper, the specific steps are as follows:

[0052] Take 280 mg of visible light responsive polymer 3 and dissolve it in 6 mL of dichloromethane, then soak the ordinary printing paper in the mixed solution, take out the filter paper after 30 minutes, and dry it at 50 degrees Celsius to obtain a recyclable visible light printing paper 3.

[0053] Example 7: Printing process of an intelligent automatic light printer, the specific steps are as follows:

[0054] Take the visible light printing paper 1 prepared in Example 4 and place it in the machine Figure 4), and a TOF ranging module is fixed on the third support to measure the height of the TOF ranging module from the bottom writing paper. The machine is started, parameters are set on the computer or the mobile phone, and a word or a figure to be printed is input. Printing is started, the controller controls the movement of the mechanical arm in combination with the feedback result of the TOF ranging module, the mechanical arm moves with the green laser pen, and writing on the paper is completed. The printing effect is as shown in Figure 5 The printed information can be eliminated by heating or storage in the dark, and the paper can be reused.

[0055] The above merely describes the preferred embodiments of the present application and is not intended to limit the present application in any form. Although the present application has been disclosed as above with the preferred embodiments, the present application is not intended to be limited. Any person skilled in the art can make some changes or modifications to the above-mentioned technical content without departing from the technical solution of the present application, and any simple modification, equivalent change and modification of the above-mentioned embodiments according to the technical essence of the present application still belong to the scope of the present application.

Claims

1. A method for preparing recyclable visible light printing paper, characterized in that, Using polymerizable monomers, functional monomers, and visible light-responsive monomers as raw materials, a visible light-responsive polymer is prepared, and then coated onto ordinary printing paper to obtain recyclable visible light printing paper; the specific steps include: (1) The polymerizable monomer, initiator, functional monomer and visible light responsive monomer are dissolved in purified N,N-dimethylformamide, vacuumed and nitrogen-blown three times, and stirred under nitrogen protection. After the reaction is completed, the reaction solution is rapidly cooled in an ice-water bath and precipitated in methanol. The precipitate is dried to obtain the visible light responsive polymer. Among them, the polymerizable monomer is butyl acrylate; the initiator is azobisisobutyronitrile; the functional monomer is 1,2-(((6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)pyrimidinone)hexyl)carbamoyl)oxy)ethyl methacrylate; and the visible light responsive monomer is 2-((acryloyloxy)methyl)-6-((E)-2-((1R,3r,8S)-4-methyl-4-azatricyclo[4.3.1.13,8]undecyl-4-en-4-onthium-5-yl)vinyl)-4-nitrophenolate ester; (2) Weigh a certain amount of visible light responsive polymer, dissolve it in dichloromethane, and then put it into paper; (3) After soaking for a period of time, remove the filter paper and dry it at 30-50℃ to obtain reusable visible light printing paper.

2. The method for preparing recyclable visible light printing paper according to claim 1, characterized in that, The content of the functional monomer in the polymer is 0-5 wt%; the content of the visible light responsive monomer in the polymer is 0.01-1 wt%; and the content of the polymerizable monomer in the polymer is 94-99.99 wt%.

3. The method for preparing recyclable visible light printing paper according to claim 1, characterized in that, The mass ratio of the visible light responsive polymer to dichloromethane is (100-140):(1-3).

4. The application of the visible light printing paper prepared by any one of the methods described in claims 1-3 in visible light printing.

5. The application according to claim 4, characterized in that, Visible light printing paper is used in conjunction with a visible light printer, which includes a laser pointer, a controller, a robotic arm, a distance sensor, and a housing. The robotic arm includes a first support, a second support, a third support, a first motor, a second motor, and a third motor. An X-axis guide rail is provided on the base plate of the housing. The first support is slidably connected to the X-axis guide rail. One end of the second support is connected to the first support. A Y-axis guide rail is provided on the second support. The third support is slidably connected to the Y-axis guide rail and a Z-axis guide rail is provided on the third support. A laser pointer is slidably connected to the Z-axis guide rail. The X-axis, Y-axis, and Z-axis guide rails are perpendicular to each other. The first motor drives the first support to move along the X-axis guide rail, the second motor drives the third support to move along the Y-axis guide rail, and the third motor drives the laser pointer to move along the Z-axis guide rail. The distance sensor is mounted on the third bracket, and the controller is electrically connected to the laser pointer, the first motor, the second motor, the third motor, and the distance sensor.

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