Preparation method and application of printing plate capable of printing different patterns

Abstract

The invention discloses a preparation method and application of a printing plate capable of printing different patterns, according to the method for printing multiple patterns through a multi-surface-energy printing plate based on one-plate multi-printing, surface energy difference regulation and control of the printing plate can be utilized, multiple colors and multiple materials can be printed through one printing plate, and the method has the advantages that the preparation process is simple and convenient, the requirement for an ink solution is low, the cost is low, and the like. The method has a series of advantages of simple equipment, simplicity and convenience in operation, low preparation cost, wider application range and the like, greatly reduces the use of printing plates in the whole printing process, saves time, reduces cost and reduces resource loss. The method for printing the multiple patterns through the multi-surface-energy printing plate based on one-plate multi-printing has wide application prospects in the fields of surface patterning, functional device printing, biological analysis and detection, selective chemical reaction and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of material interface wetting, and relates to a preparation method and application of a printing plate capable of printing different patterns, and in particular to a method for preparing a multi-surface energy printing plate by regional selective patterning regulation. Background Art

[0002] Printing technology has broad application prospects in the fields of publishing, flexible electronics, photovoltaic materials, etc. due to its high precision, simplicity and high sensitivity. Among them, the printing plate plays a key role in the printing process as a medium for regulating ink distribution and pattern transfer. In order to achieve patterned printing of ink in a limited area, the processing of the printing plate mainly includes the use of boundary effects (such as reported in Thompson, PA, Troian, SM Nature 1997, 389, 360-362; Liao WS, Cheunkar S, Cao HH, Science 2012, 337, 1517-1521.), surface wettability regulation (such as reported in Li X, Liu J, Qu R, Nat. Commun. 2021, 12, 80.) and the use of physical structure (such as reported in patents CN207772580U and CN108454223A). However, the current printing method is mainly based on "one plate one print", where one plate corresponds to one pattern / material, and multiple plates are required to assist in printing multiple colors / materials. This method will result in a large amount of plate consumption, which will exponentially increase printing time, cost, and resource consumption. For small batches of multiple types of printing, it is difficult to achieve fast, cost-saving, and low-consumption printing using current technology. Summary of the invention

[0003] In order to improve the above technical problems, the present invention provides a method for realizing multi-pattern printing using one printing plate by utilizing surface energy differences, wherein an ultra-low surface energy substrate is obtained by physical treatment and chemical modification, and a printing plate with patterned different surface energies is obtained by patterned ultraviolet treatment. When inks with different surface tensions come into contact with the printing plates with patterned different surface energies, different patterns can be presented and "one plate, multiple prints" can be realized.

[0004] In order to achieve the above-mentioned invention object, the present invention adopts the following technical scheme:

[0005] The present invention provides a method for preparing a multi-surface energy printing plate, comprising the following steps:

[0006] 1) Treat the surface of the printing plate substrate to construct a printing plate with a micro-nano structure;

[0007] 2) Performing hydrophobic treatment on the surface of the printing plate having the micro-nano structure to obtain a printing plate having an ultra-low surface energy surface;

[0008] 3) The printing plate with ultra-low surface energy is subjected to hydrophilic treatment to obtain a multi-surface energy printing plate.

[0009] According to an embodiment of the present invention, the method further comprises the following steps:

[0010] 4) Immersing the multi-surface energy printing plate in inks with different surface tensions, distributing the ink on the surface of the multi-surface energy printing plate by pulling, and obtaining a patterned multi-surface energy printing plate.

[0011] According to an embodiment of the present invention, in step 1), the printing plate substrate is selected from one or more of metals (such as aluminum sheets), metal oxides and non-metals (such as silicon sheets).

[0012] According to an embodiment of the present invention, in step 1), the surface of the printing plate substrate is treated by one or more of chemical etching, photolithography, electron beam etching, laser etching, chemical deposition and printing to construct a printing plate with a micro-nano structure. For example, the etching solution used in the chemical etching method is an acid mixed solution. Preferably, the acid mixed solution is a mixed solution of hydrochloric acid, hydrofluoric acid and water, wherein the volume ratio of hydrochloric acid, hydrofluoric acid and water is (10-20):1:(1-10), exemplarily 16:1:5. For another example, the etching time can be 1-30s, exemplarily 10s.

[0013] In one embodiment of the present invention, the concentration of the hydrofluoric acid is 10-50%, and exemplarily 40%.

[0014] In one embodiment of the present invention, the concentration of the hydrochloric acid is 10-50%, and exemplarily 37%.

[0015] According to an embodiment of the present invention, in step 2), the superphobicity of the ultra-low surface energy surface of the printing plate is that the contact angle of water is greater than 100°, preferably the contact angle of water is 150-180°, exemplified by 150°, 160°, 170°.

[0016] According to an embodiment of the present invention, in step 2), the superphobicity of the ultra-low surface energy surface of the printing plate is that the contact angle of hexadecane is greater than 100°, preferably 140-160°, and exemplified by 140°, 145°, 150°, and 160°.

[0017] According to an embodiment of the present invention, in step 2), the hydrophobic treatment is to treat the printing plate with micro-nano structure by one or more of vapor phase modification, liquid phase modification, spin coating, spray coating, electrospinning, printing and electrochemical corrosion. For example, the vapor phase modification method is achieved by vacuum drying. For example, the temperature of the vacuum drying method is 100-150°C, exemplarily 110°C; the time of the vacuum drying method is 1-10h, exemplarily 5h.

[0018] According to an embodiment of the present invention, in step 2), the material used for the hydrophobic treatment is selected from one or more of polydimethylsiloxane, polystyrene, polytetrafluoroethylene, polyperfluoropropylene, hydrophobic nanoparticles, silane, fluorosilane (such as perfluorodecyltrimethoxysilane), chlorosilane, fluorosilicone, chlorosiloxane and polyvinyl chloride.

[0019] According to an embodiment of the present invention, in step 3), the hydrophilic treatment is to treat the ultra-low surface energy surface of the printing plate under a photomask by one or more of ultraviolet exposure, laser treatment, plasma treatment, printing and spraying to construct a multi-surface energy printing plate.

[0020] In one embodiment of the present invention, the photomask can have at least one of any geometric pattern (including regular patterns and irregular patterns; for example, it can be one or more of a triangle, a quadrilateral (square, rectangle), a heart shape and a hexagon), and a font structure (Chinese characters, letters, numbers, etc.).

[0021] For example, the intensity of the UV exposure method is 10 to 20 mw / cm 2 , exemplified by 18mw / cm 2 ; The time of the ultraviolet exposure method is 5 to 120 minutes, exemplified by 5 minutes, 15 minutes, 50 minutes or 120 minutes.

[0022] According to an embodiment of the present invention, in step 4), the ink is a liquid with a surface tension between 27.8-72.8 mN / m; for example, the ink is selected from at least one of water, ethanol, ethylene glycol, soybean oil, hexadecane, an inorganic salt solution, a nanoparticle solution, a cell solution and a protein solution.

[0023] In one embodiment of the present invention, the nanoparticles are selected from one or more of conductive materials (such as platinum nanoparticles, gold nanoparticles, copper nanoparticles, silver nanoparticles, nickel nanoparticles, gold nanowires, silver nanowires, copper nanowires, silver nanosheets, liquid metals, carbon nanotubes, graphene, graphyne, fullerenes, 3,4-ethylenedioxythiophene, poly-3,4-ethylenedioxythiophene / polystyrene sulfonate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3-hexylthiophene-2,5-diyl), tetrakis[N,N-di(4-methoxyphenyl)amino]spirobifluorene and phthalocyanine blue or [6,6]-phenyl C61 butyric acid methyl ester; the liquid metal is selected from one or more of gallium-tin alloys, gallium-aluminum alloys, gallium-indium alloys, gallium-zinc alloys and gallium-indium-tin alloys.), luminescent materials (such as ZnS), dielectric materials (such as Ba), semiconductor materials (such as IDT-BT), etc.

[0024] In one embodiment of the present invention, the ink is a mixed solution of water and ethanol. Preferably, the mixed volume ratio of ethanol to water is (0.10-0.65):(0.35-0.90), preferably (0.12-0.63):(0.37-0.88), and exemplarily 0.12:0.88, 0.32:0.68, and 0.63:0.37.

[0025] The present invention also provides a multi-surface energy printing plate prepared by the above method, specifically, a patterned multi-surface energy printing plate.

[0026] According to an embodiment of the present invention, the patterned structure of the patterned multi-surface energy printing plate can be at least one of any geometric pattern (including regular patterns and irregular patterns; for example, it can be one or more of a triangle, a quadrilateral (square, rectangle), a heart shape and a hexagon), a font structure (Chinese characters, letters, numbers, etc.).

[0027] The present invention also provides the application of the above-mentioned multi-surface energy printing plate, especially the patterned multi-surface energy printing plate in the fields of biological analysis and detection, chemical reaction, electronic devices, water-oil separation, education (such as printing of Chinese characters, letters, numbers, etc.).

[0028] The present invention also provides a device, which contains the functional layer obtained by printing the multi-surface energy printing plate.

[0029] According to an embodiment of the present invention, the device may be a light-emitting flexible device, a transistor, and the like.

[0030] The present invention also provides a method for printing Chinese characters, which adopts the multi-surface energy printing plate.

[0031] Beneficial effects of the present invention:

[0032] The method of printing multiple patterns with a multi-surface energy printing plate based on "one plate for multiple prints" adopted by the present invention can utilize the surface energy difference of the printing plate to control and realize printing multiple colors and multiple materials with one printing plate, and has a series of advantages such as simple preparation process, low requirements for ink solution, simple equipment, simple operation, low preparation cost, wider application range, etc., and greatly reduces the use of printing plates in the entire printing process, saving time, reducing costs, and reducing resource loss. The method of printing multiple patterns with a multi-surface energy printing plate based on "one plate for multiple prints" described in the present invention has broad application prospects in the fields of surface patterning, printing functional devices, biological analysis and detection, selective chemical reactions, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a schematic diagram of the preparation process of the multi-surface energy printing plate based on "one plate for multiple prints" in the present invention.

[0034] Figure 2 It is a schematic diagram and a physical picture of the "one plate, multiple prints" single printing plate with multiple patterns in the present invention.

[0035] Figure 3 It is a schematic diagram and a physical picture of the process of preparing a heart-shaped light-emitting device by “one plate, multiple prints” in Example 3. DETAILED DESCRIPTION

[0036] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0037] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0038] Example 1

[0039] The "ICCAS" pattern with multiple surface energy states is prepared on the surface of the extremely low surface energy printing plate. The specific steps are as follows:

[0040] 1) Clean the aluminum sheet: ultrasonically clean the aluminum sheet three times with acetone and ethanol respectively (each cleaning for 15 minutes), rinse it with deionized water, and blow it dry with nitrogen. Then etch the aluminum sheet with an acid mixed solution, which is a mixed solution of hydrochloric acid, hydrofluoric acid, and water, wherein the volume ratio of hydrochloric acid (concentration of 37%), hydrofluoric acid (concentration of 40%), and water is 16:1:5. After etching for 10 seconds, clean the etched aluminum sheet with ethanol and water respectively, and blow it dry with nitrogen.

[0041] 2) Plasma-treat the aluminum sheet etched in step (1) for 300 s (the power of plasma treatment is 200 w), place it in a dryer, place a glass slide in it (the glass slide and the aluminum sheet do not touch), and drop 1 mL of perfluorodecyltrimethoxysilane on the glass slide (75 mm x 26 mm). Then use an oil pump to evacuate the vacuum dryer for 10 minutes. Then place the dryer in an oven at 110 °C for 5 hours. After taking it out, the static water contact angle on the surface of the etched aluminum sheet is 154°, and an extremely low surface energy printing plate is obtained (relying on the gas-phase deposition method, at high temperature, silane will be vaporized, and fluorosilane molecules crosslink with the hydroxyl groups on the surface of the etched aluminum sheet to form a hydrophobic layer to reduce the surface energy of the aluminum sheet surface).

[0042] 3) Then perform the treatment of the patterned surface energy region. Place the extremely low surface energy printing plate obtained in step 2) under a photomask with the pattern "ICCAS", and then expose it under an ultraviolet lamp. The ultraviolet intensity is 18 mw / cm 2 , and expose it for 5 min, 15 min, 50 min, and 120 min respectively when the mask patterns are "ICCAS", "ICCA", "ICC", and "I", to obtain surface energy states that can wet hexadecane (surface energy is 1.17 mJ / m 2 ), soybean oil (surface energy is 1.7 mJ / m 2 ), ethylene glycol (surface energy is 4.5 mJ / m 2 ), and water (surface energy is 41.1 mJ / m 2 ) respectively.

[0043] 4) Immerse the printing plate into the hexadecane-based ink (the ink is ethanol:water = 0.63:0.37 by volume ratio) for 10 s, soybean oil-based ink (the ink is ethanol:water = 0.32:0.68 by volume ratio) for 10 s, ethylene glycol-based ink (the ink is ethanol:water = 0.12:0.88 by volume ratio) for 10 s, and water-based ink for 10 s respectively, to obtain the patterns of "ICCAS", "ICCA", "ICC", and "I" respectively.

[0044] Example 2

[0045] Print Chinese characters on the multi-surface energy printing plate of "one plate, multiple prints" and combine radicals to form new Chinese characters. Taking the Chinese characters "Song" and "Yu" as examples. After obtaining the extremely low surface energy printing plate (the preparation of the extremely low surface energy printing plate is the same as that in Example 1), perform the treatment of the patterned surface energy region. Place the extremely low surface energy printing plate under a photomask with the pattern "Song", and place it under an ultraviolet lamp for exposure. The ultraviolet intensity is 18 mw / cm 2, in the case where the mask pattern is "Song" and "宀", expose for 5 minutes and 120 minutes respectively to obtain surface energy states that can wet hexadecane and water respectively. Immerse the printing plate into inks based on hexadecane and water respectively to obtain the patterns of "Song" and "宀".

[0046] The same is true for "竽". Under the same ultraviolet intensity of 18 mw / cm 2 , place the ultra-low surface energy printing plate under the photomasks with the patterns of "竽" and "于" and expose for 5 minutes and 120 minutes respectively to obtain surface energy states that can wet hexadecane and water respectively. Immerse the printing plate (dip-coating method, just immerse it into the ink and then slowly lift it out, there is no requirement for the lifting speed) into inks based on hexadecane (the ink is ethanol:water = 0.63:0.37 by volume ratio) and water respectively to obtain the patterns of "竽" and "于".

[0047] When the printing plate with the four patterns is imprinted on paper, the four patterns of "Song", "宀", "竽" and "于" can be obtained. When "宀" and "于" are combined, a new pattern "宇" can also be obtained, saving the use of new printing plates.

[0048] Example 3

[0049] Printing a light-emitting flexible device with a multi-surface energy printing plate of "one plate, multiple prints". Taking a heart-shaped light-emitting device as an example to illustrate ( Figure 3 ). After obtaining the ultra-low surface energy printing plate (the preparation of the ultra-low surface energy printing plate is the same as that in Example 1), perform the treatment of the patterned surface energy region. Place the ultra-low surface energy printing plate under the photomasks with the patterns of square and heart shape, and expose it under an ultraviolet lamp. The ultraviolet intensity is 18 mw / cm 2, respectively exposed for 5min and 120min, to obtain the surface energy states that can be wetted by hexadecane and water respectively. The light-emitting device consists of four layers, including a flexible ITO layer, a light-emitting layer (ZnS), a dielectric layer (Ba) and a conductive layer (AgNWs silver nanowires, with a particle size of 50nm), in which the shape of the light emission is mainly determined by the conductive layer. Therefore, by adjusting the surface tension of the ink used, the surface tension of the ink of the light-emitting layer (ZnS) and the dielectric layer (Ba) can be made close to the surface tension of hexadecane, while the conductive layer (AgNWs silver nanowires, with a particle size of 50nm) can be made close to the surface tension of water. The printing plate after the above exposure for 5 minutes was immersed (pulling method, immersing in the ink and then slowly pulling it out, no requirement for the pulling speed) in the ink of the light-emitting layer (1g ZnS dissolved in a mixed solvent of 3mL ethanol and water (volume ratio of ethanol: water = 0.63:0.37)) to obtain a square pattern printing plate, which was imprinted on the surface of ITO / PET and heated on a hot stage at 120°C for 20min. Then the printing plate was immersed (pulling method, immersing in the ink and then slowly pulling it out, no requirement for the pulling speed) in the ink of the dielectric layer (1g Ba dissolved in a mixed solution of 3mL ethanol and water (volume ratio of ethanol: water = 0.63:0.27)) to obtain the same square pattern, which was imprinted on the upper layer of the light-emitting layer and heated at 120°C for 20min. Finally, the printing plate is immersed (pulling method, immersing in the ink and then slowly pulling it out, there is no requirement for the pulling speed) into the ink of the conductive layer (20 mg / mL AgNWs silver nanowire aqueous solution) to obtain a heart-shaped pattern, which is imprinted on the surface of the dielectric layer, heated at 80°C for 10 minutes, and powered on to obtain a luminous flexible device (the device can still maintain a stable current (current of 32 mA) under the condition of more than 100 bends at a bending angle of 120°).

[0050] Example 4

[0051] "One plate, multiple prints" multi-surface energy printing plate prints high-density transistors. Take a 10×10 organic transistor array as an example. After obtaining an extremely low surface energy printing plate (the preparation of the extremely low surface energy printing plate is the same as in Example 1), the patterned surface energy area is processed. The extremely low surface energy printing plate is placed under a photomask with a square and rectangular array pattern, and exposed under a UV lamp with an UV intensity of 18mw / cm 2 , respectively, exposure for 5min and 120min, and obtain the surface energy states that can be wetted by hexadecane and water respectively. The transistor has a total of 3 layers, including a silicon / silicon dioxide layer (the SiO 2 / p+Si type, where the thickness of the silicon dioxide layer is 300nm), semiconductor layer (IDT-BT) and source-drain electrode layer (AgNWs silver nanowire, particle size is 50nm), the surface tension of the ink used can be adjusted to achieve the printing of the semiconductor layer (IDT-BT) and the source-drain electrode layer (the width and length of the printed source-drain layer are 300μm and 50μm). By adjusting the surface tension of the semiconductor layer (IDT-BT) and the source-drain electrode layer (AgNWs silver nanowire, particle size is 50nm), the ratio of the two inks is close to hexadecane and water, respectively. The printing plate (made of silicon / silicon dioxide layer (used is SiO 2 / p+Si type, wherein the thickness of the silicon dioxide layer is 300nm) is immersed (pulling method, immersing in the ink and then slowly pulling it out, and there is no requirement for the pulling speed) in the ink of the semiconductor layer (IDT-BT in o-dichlorobenzene with a concentration of 2.5mg / mL), and heated on a hot stage at 160°C for 10min to obtain a square array pattern, which is imprinted on the surface of the silicon / silicon dioxide. Then, the printing plate is immersed (pulling method, immersing in the ink and then slowly pulling it out, and there is no requirement for the pulling speed) in the ink of the source and drain electrode layer (20mg / mL of AgNWs silver nanowire aqueous solution), and then heated at 70°C for 10min to obtain a rectangular array pattern, which is imprinted on the upper layer of the semiconductor layer. Finally, the obtained transistor was immersed in a 0.13% (v / v) isopropanol solution of pentafluorothiophenol for 5 min to improve the transistor performance (high integration, more than 17,000 transistors were integrated on an 8-inch silicon wafer, with an average mobility of 0.05 cm 2 V -1 s -1 , the switching ratio is 10 6 ).

[0052] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a multi-surface energy printing plate, characterized in that: The steps include: 1) Treat the surface of the printing plate substrate to construct a printing plate with a micro-nano structure; 2) Performing hydrophobic treatment on the surface of the printing plate having the micro-nano structure to obtain a printing plate having an ultra-low surface energy surface; 3) The printing plate with ultra-low surface energy is subjected to hydrophilic treatment to obtain a multi-surface energy printing plate.

2. The preparation method according to claim 1, characterized in that The method further comprises the following steps: 4) immersing the multi-surface energy printing plate into inks with different surface tensions by a pulling method, distributing the ink on the surface of the multi-surface energy printing plate by pulling, and obtaining a patterned multi-surface energy printing plate. Preferably, in step 1), the printing plate substrate is selected from one or more of metals (such as aluminum sheets), metal oxides and non-metals (such as silicon sheets). Preferably, in step 1), the surface of the printing plate substrate is processed by one or more of chemical etching, photolithography, electron beam etching, laser etching, chemical deposition and printing to construct a printing plate with a micro-nano structure.

3. The preparation method according to claim 1, characterized in that: In step 2), the superphobicity of the ultra-low surface energy surface of the printing plate is that the contact angle of water is greater than 100°, preferably the contact angle of water is 150-180°. Preferably, in step 2), the ultra-low surface energy surface of the printing plate has a superphobicity such that the contact angle of hexadecane is greater than 100°, preferably 140-160°.

4. The preparation method according to any one of claims 1 to 3, characterized in that: In step 2), the hydrophobic treatment is to treat the printing plate with the micro-nano structure by one or more of the following methods: gas phase modification, liquid phase modification, spin coating, spray coating, electrospinning, printing and electrochemical etching. Preferably, the gas phase modification method is achieved by vacuum drying. For example, the temperature of the vacuum drying method is 100 to 150° C. and the time of the vacuum drying method is 1 to 10 hours. Preferably, in step 2), the material used for the hydrophobic treatment is selected from one or more of polydimethylsiloxane, polystyrene, polytetrafluoroethylene, polyperfluoropropylene, hydrophobic nanoparticles, silane, fluorosilane (such as perfluorodecyltrimethoxysilane), chlorosilane, fluorosilicone, chlorosiloxane and polyvinyl chloride.

5. The preparation method according to any one of claims 1 to 4, characterized in that: In step 3), the hydrophilic treatment is to treat the ultra-low surface energy surface of the printing plate under a photomask by one or more of ultraviolet exposure, laser treatment, plasma treatment, printing and spraying to construct a multi-surface energy printing plate. Preferably, the photomask may have at least one of any geometric pattern (including regular and irregular patterns; for example, one or more of a triangle, a quadrilateral (square, rectangle), a heart shape and a hexagon), or a font structure (Chinese characters, letters, numbers, etc.). Preferably, the intensity of the UV exposure method is 10-20 mw / cm 2 ; The time of the ultraviolet exposure method is 5 to 120 minutes.

6. The preparation method according to any one of claims 1 to 5, characterized in that: In step 4), the ink is a liquid having a surface tension between 27.8-72.8 mN / m; for example, the ink is selected from at least one of water, ethanol, ethylene glycol, soybean oil, hexadecane, an inorganic salt solution, a nanoparticle solution, a cell solution and a protein solution. Preferably, the ink is a mixed solution of water and ethanol. Preferably, the mixing volume ratio of ethanol and water is (0.10-0.65):(0.35-0.90), preferably (0.12-0.63):(0.37-0.88). Preferably, the printing plate substrate is selected from one or more of metals (such as aluminum sheets) and metal oxides.

7. A multi-surface energy printing plate prepared by the preparation method according to any one of claims 1 to 6.

8. Application of the multi-surface energy printing plate described in claim 7 in the fields of biological analysis and detection, chemical reaction, electronic devices, water-oil separation, education, etc.

9. A device, characterized in that It contains the functional layer obtained by printing on the multi-surface printing plate as claimed in claim 7.

10. A method for printing Chinese characters, using the multi-surface energy printing plate described in any one of claims 1 to 6.

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