CN109004107B - A kind of paper light-emitting structure and preparation method based on full printing process - Google Patents

Abstract

The invention discloses paper luminous structures and a preparation method based on a full printing process, wherein the paper luminous structures relate to materials used by each functional layer of paper, a printing mode and a paper processing method.

Description

A kind of paper light-emitting structure and preparation method based on full printing process

technical field

The invention relates to the fields of paper, printing and paper-based materials, and relates to a preparation method of an organic light-emitting structure of paper, in particular to a paper light-emitting structure and a preparation method based on a full printing process.

Background technique

Electro-organic light-emitting devices have unique advantages such as planar auto-luminescence, fast response, wide viewing angle, thin and light volume, and the ability to fabricate bendable, rollable and even foldable devices, and are known as the most promising next-generation light-emitting and display technologies. At present, some electro-organic light-emitting devices have been successfully used in mobile phones, tablet computers, TVs, wearable devices, etc. In the preparation of existing organic light-emitting devices, the choice of substrates is basically based on glass substrates, or polyethylene terephthalate (PET), polyethylene naphthalate ( PEN), polyethersulfone resin (PES) plastic film and other materials are the main materials, but these petroleum-based materials are not cheap in cost, and at the same time, they mainly have problems such as being difficult to degrade and not environmentally friendly, which brings a lot to the subsequent degradation treatment. environmental issues. In contrast, paper or paper-based materials, which are naturally biodegradable fiber-based materials, have fast and efficient biodegradation characteristics, and it takes about two weeks to complete the biodegradation of paper fibers. The price of paper by area is about 1/20 of the price of films such as PET/PEN/PES. Therefore, using paper-based materials as organic light-emitting substrates will undoubtedly make organic light-emitting products and technologies develop in a more environmentally friendly and cost-effective direction. In addition, in the preparation process of organic light-emitting devices, evaporation and spin coating are usually used to prepare various functional layers of the device on the above-mentioned substrates, including conductive anode, hole injection layer, hole transport layer, light-emitting layer, Preparation of electron transport layer, electron layer injection layer, cathode, etc. However, these methods cannot realize the preparation of large-scale functional layers. Benefiting from the development of solutionization of organic light-emitting functional layer materials, printing has become an effective way to prepare functional layers of organic light-emitting devices. Therefore, using more environmentally friendly fibrous paper-based materials (paper) as substrates and preparing electro-organic light-emitting devices by printing is one of the most advantageous ways, and it is also one of the most advantageous ways to realize the pattern and display of paper-based printing and packaging products. potentially powerful approach.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a paper luminous structure and a preparation method based on a full printing process, so as to overcome the problems existing in the prior art, the present invention adopts the full printing method to realize the production of the paper luminous structure, which is a paper-based printing and packaging product Local lighting and luminescence provide reliable fabrication methods.

To achieve the above object, the present invention adopts the following technical solutions:

A paper light-emitting structure, comprising a paper base, a filling layer, an improvement layer, a blocking layer, a paper surface coating, a printing varnish layer, a conductive anode layer, a hole transport layer, a light-emitting layer, and an electron injection layer sequentially distributed from bottom to top and a conductive cathode layer;

The preparation raw material of the filling layer is a heavy calcium carbonate coating; the preparation raw material of the improvement layer is a kaolin coating with a flake structure; the preparation raw material of the barrier layer is a composite coating of heavy calcium carbonate and acrylic emulsion; the preparation of the paper surface coating The raw material is a composite coating of kaolin or talc powder and acrylic emulsion; the preparation raw material of the printing varnish layer is water-based varnish; the preparation raw material of the conductive anode layer is poly-3,4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution, methanol and dimethyl sulfoxide; the raw material for the preparation of the hole transport layer is N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl- The mixed solution obtained by dissolving 4,4'-diamine and polycarbonate in chloroform; the raw material for the preparation of the light-emitting layer is a mixture of conjugated polymer Superyellow, tetrahydrofuran and toluene; the raw material for the preparation of the electron injection layer is epoxy resin adhesive A mixed solution obtained by dissolving poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] in methanol; the preparation material of the conductive cathode layer is nano-silver Conductive ink.

Further, the mass concentration of the ground calcium carbonate coating is 5%, and at least 90% of the ground calcium carbonate in the ground calcium carbonate coating has a particle size of less than 2 μm;

The mass ratio of heavy calcium carbonate and acrylic acid emulsion in the preparation raw materials of the barrier layer is 100:12;

The mass ratio of kaolin or talc to acrylic emulsion in the preparation raw material of the paper surface coating is 100:8.

Further, the mass fraction of the poly-3,4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution in the preparation raw materials of the conductive anode layer is 1.3%, and the poly-3,4-ethylenedioxythiophene-polystyrene sulfonate The volume ratio of the aqueous solution to methanol is 1:1, and the volume of dimethyl sulfoxide is 5% of the sum of the volume of the poly-3,4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and methanol;

The raw materials for the preparation of the hole transport layer are N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine and polycarbonate The sum of the mass of the lipid is 13.6% of the mass of chloroform, and N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diphenyl The mass ratio of amine to polycarbonate was 1:1.

Further, the mass concentration of the conjugated polymer Super yellow in the preparation raw material of the light-emitting layer is 5g/L, and the volume ratio of tetrahydrofuran and toluene is 4:1;

The mass ratio of epoxy resin binder to poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] in the preparation raw materials of the electron injection layer is 11: 2, and the mass of the epoxy resin adhesive and poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] accounts for 0.04% of the mass of the mixture .

A method for preparing a paper light-emitting structure based on a full printing process, comprising the following steps:

Step 1: Fill the surface of the pore structure of the paper substrate with heavy calcium carbonate coating to form a filling layer on the paper surface;

Step 2: coating the filling layer in step 1 with a kaolin coating with a flaky structure to form an improved layer;

Step 3: use the composite coating of heavy calcium carbonate and acrylic emulsion to coat on the improvement layer in step 2 to form a barrier layer;

Step 4: use a composite coating of kaolin or talc and acrylic emulsion to coat the barrier layer in step 3, and perform calendering treatment to form a paper surface coating;

Step 5: apply water-based varnish for printing on the paper surface coating in step 4 to form a printing varnish layer;

Step 6: On the printing varnish layer in Step 5, print a mixed solution of poly-3,4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution, methanol and dimethyl sulfoxide, and print two layers to form paper luminous The conductive anode layer of the structure;

Step 7: On the conductive anode layer from Step 6, print N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl dissolved in chloroform The mixed solution of -4,4'-diamine and polycarbonate forms the hole transport layer of the paper light-emitting structure;

Step 8: printing the mixture of conjugated polymer Super yellow, tetrahydrofuran and toluene on the hole transport layer in step 7 to form the light-emitting layer of the paper light-emitting structure;

Step 9: Print epoxy resin adhesive and poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] on the light-emitting layer in step 8 The mixture in methanol, the electron injection layer that forms the light-emitting structure of the paper;

Step 10: Print a nano-silver layer on the electron injection layer in Step 9 to form a conductive cathode layer of the paper light-emitting structure.

Further, step 6, step 7, step 8 and step 9 are all performed by screen printing, and step 10 is performed by inkjet printing.

Further, in step 1, at least 90% of the particle size of the ground calcium carbonate is less than 2 μm;

In step 2, the coating amount is 8-10 g/m ² , and after coating is completed, the surface roughness of the paper is 300-500 nm;

In step 3, at least 90% of the particle size of the ground calcium carbonate is less than 2 μm, the mass ratio of the ground calcium carbonate and the acrylic emulsion in the composite coating of the ground calcium carbonate and the acrylic emulsion is 100:12, and the coating weight is 0.5-20g /m ² , the coating thickness is 2-28 μm, and after the coating is completed, the surface roughness of the paper is 200-300 nm.

Further, in step 4, the mass ratio of kaolin or talc and acrylic emulsion in the composite coating of kaolin or talc and acrylic emulsion is 100:8, the coating weight is 20-25g/m ² , and the coating thickness is 0.8-6 μm , After the coating is completed, the surface roughness of the paper is 50-150nm;

In step 5, the water-based varnish is a water-based UV varnish, the coating weight is 3-6g/m ² , and the coating thickness is 25 μm. After the coating is completed, the UVA lamp is used to irradiate, and the irradiation time is 3-5min to make it dry and solidify.

Further, in step 6, the mass fraction of the poly-3,4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution is 1.3%, and the mass fraction of the poly-3,4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and methanol is The volume ratio is 1:1, and the volume of dimethyl sulfoxide is 5% of the sum of the volume of poly-3,4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and methanol;

In step 7, the mass sum of N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine and polycarbonate is 13.6% of the mass of chloroform, and N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine and polycarbonate The mass ratio is 1:1.

Further, the mass concentration of conjugated polymer Super yellow in step 8 is 5g/L, and the volume ratio of tetrahydrofuran and toluene is 4:1;

In step 9, the mass ratio of the epoxy resin adhesive to poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] is 11:2, and the ring The mass of oxygen resin binder and poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] and 0.04% of the mass of the mixed solution were completed after printing Then irradiate in a UV curing oven for 2 minutes, the output power of the UV curing oven is 30mW/cm ² , and then anneal at 65°C for 30 minutes;

After the printing is completed in step 10, it will be dried at 80°C in a vacuum drying oven to remove the solvent in the electronic ink, and then annealed at 140°C for 30 minutes to sinter the nano-silver particles to make the cathode line conductive.

Compared with the prior art, the present invention has the following beneficial technical effects:

The paper light-emitting structure of the present invention mainly obtains a light-emitting device substrate with a smooth and flat surface by using an effective surface modification technology on a paper-based material. Through the printing technology that can realize large-scale production, the preparation and film formation of the light-emitting functional layer of the paper-based material is realized, and the structure of a green, environmentally friendly, and rapidly degradable paper light-emitting device is formed.

The method of the invention utilizes multiple paper surface coating methods, and through the interaction between the coatings, the surface of the paper is effectively improved and modified, and the modified surface meets the requirements for film formation of light-emitting devices, which is conducive to subsequent light emission Efficient cumulative film formation of functional layers. On this basis, through the design of the formula of the luminescent functional layer and the printing and film formation, the preparation of organic light-emitting paper is realized, which is an environment-friendly, low-cost method for preparing organic light-emitting devices, which can be applied to paper product packaging products. , beautify and lighten the packaging.

Description of drawings

Fig. 1 is the structure diagram of paper surface coating and modification;

2 is a structural diagram of a paper luminescent structure prepared by a full printing process;

Fig. 3 is the printing process corresponding to the functional layer of the paper light-emitting structure;

FIG. 4 is a luminous effect diagram of paper prepared by the full printing process in Example 1. FIG.

Among them, 1. paper substrate, 2. filling layer, 3. improvement layer, 4. barrier layer, 5. paper surface coating, 6. printing varnish layer, 7. conductive anode layer, 8. hole transport layer, 9. Light-emitting layer, 10. Electron injection layer, 11. Conductive cathode layer.

Detailed ways

Below in conjunction with accompanying drawing, the present invention is described in further detail:

The invention relates to a paper light-emitting structure and a preparation method based on a full printing process. The surface roughness and porosity of the paper are changed by modifying the surface of the paper, and the light-emitting device functional layer is prepared by printing.

The surface modification of the paper, combined with Figure 1, is carried out according to the following steps:

Step 1: Generally, uncoated paper (surface uncoated) is selected as the paper base of the device, and the basis weight of the paper is generally selected to be greater than or equal to 80 g/m ² . Use a low concentration (5%) fine ground calcium carbonate coating (90% of the ground calcium carbonate particle size should be less than 2μm), fill the surface of the paper by bar coating, form a filling layer on the surface, and fill the holes on the paper surface structure to ensure a flat and smooth surface. This step can be omitted if coated paper is used as the paper base. After the coating is completed, it is fully dried in an oven at a drying temperature of 80-100°C to form a filling layer.

Step 2: In order to further improve the surface roughness, on the basis of the above, the kaolin coating with a sheet-like structure is applied by bar coating, and the coating amount is about 8-10g/m ² . After the coating is completed, it is fully dried in an oven , the drying temperature is 80-100 ℃, the surface roughness (EMS) of the paper is located in the range of 300-500nm, and the improvement layer is formed.

Step 3: On the basis of the above, apply a composite coating of ground calcium carbonate (90% of the particle size of ground calcium carbonate should be less than 2 μm) and acrylic emulsion by rod coating. In the composite coating, ground calcium carbonate and acrylic acid The mass ratio of the emulsion is 100:12, the coating weight is 0.5-20g/m ² , and the coating thickness is 2-28 μm. After the coating is completed, it is fully dried in an oven at a drying temperature of 80-100 ° C to make the paper The surface roughness (EMS) is in the range of 200-300 nm, forming the barrier layer.

Step 4: On the basis of the foregoing, a composite coating of kaolin or talc and acrylic emulsion is applied by rod coating. In the composite coating, the mass ratio of kaolin or talc and acrylic emulsion is 100:8, and the coating amount is 20 -25g/m ² , the coating thickness is 0.8-6μm, after the coating is completed, it is fully dried in an oven, the drying temperature is 80-100 ° C, and the calendering treatment is performed on a calender to make the surface roughness of the paper (EMS ) in the 50-150 nm range, forming a smooth paper coating.

Step 5: On the basis of the above, coat the water-based UV varnish for printing with a coating weight of 3-6g/m ² and a coating thickness of 25 μm. After the coating is completed, use a UVA (wavelength 320-400nm) lamp to illuminate, The irradiation time is 3-5min, and it is dried and solidified to form a printing varnish layer.

The finally formed paper surface coating and modified structure are shown in Figure 1.

After the paper-based surface is treated, the printing of the paper-based organic light-emitting structure functional layer is completed according to the following steps and structures:

Step 6: Printing an aqueous solution of 1.3% poly-3,4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS), methanol and high boiling point by mass percentage on the varnish layer of the above paper by screen printing The mixed solution of dimethyl sulfoxide (DMSO), the mass percentage of 1.3% PEDOT:PSS aqueous solution and methanol were mixed in a volume ratio of 1:1, and the volume fraction of dimethyl sulfoxide (DMSO) was PEDOT:PSS aqueous solution and methanol Mix 5% of the volume of the solution, and print 2 layers. After the printing is completed, fully dry in an oven, and the drying temperature is 80-100 °C. A conductive anode layer of the organic light emitting structure is formed.

Step 7: Printing by screen printing on the anode layer of the above device, printing N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1 dissolved in chloroform, A mixed solution of 1'-biphenyl-4,4'-diamine (TPD) and polycarbonate, the mass of the solute in the mixed solution is 13.6% of the mass of the solvent, and the mass ratio of polycarbonate and TPD is 1:1 , after the printing is completed, fully dry in an oven at a drying temperature of 80-100° C. to form a hole transport layer of an organic light-emitting structure.

Step 8: by screen printing, the conjugated polymer Super yellow (pharmaceutical trade name) luminescent material is dissolved in a mixed solution of tetrahydrofuran and toluene at a concentration of 5 g/L, and printed on the hole transport layer of the above device, The volume ratio of tetrahydrofuran and toluene in the mixed solution is 4:1, and after printing is completed, it is fully dried in an oven at a drying temperature of 80-100° C. to form a light-emitting layer of an organic light-emitting structure.

Step 9: Using screen printing on the light-emitting layer, the epoxy resin adhesive and poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl) Fluorene](PFNR ₂ ) was dissolved in methanol at a mass ratio of 11:2 to form a 0.04% (w/w) mixed solution, screen printed on the light-emitting layer, and irradiated in a UV curing oven for 2 min after the printing was completed. (The output power is 30 mW/cm ² ), followed by annealing at a low temperature of 65° C. for 30 minutes, that is, the electron injection layer of the organic light-emitting structure is formed.

Step 10: On the basis of the device electron injection layer, the nano-silver layer is printed with nano-silver electronic ink by inkjet printing. After the cathode printing is completed, it is dried in a vacuum drying box at 80 ° C to remove the electronic ink. The solvent is then annealed at 140° C. for 30 minutes to sinter the nano-silver particles to make the cathode line conduct, that is, to form a conductive cathode of the organic light-emitting structure.

The luminous structure of the paper prepared by the final full-printing process is shown in Figure 2.

Below in conjunction with embodiment, the present invention is described in detail:

Example 1

A method for preparing paper luminescence based on a full printing process, which is specifically implemented according to the following steps:

Finishing the paper:

(1) Generally, uncoated paper (uncoated on the surface) is selected as the base material of the device, and copy paper of 80 g/m ² is selected in this embodiment. With low concentration (5%) fine ground ground calcium carbonate paint (90% of the ground calcium carbonate particle size is less than 2μm), the paper surface is filled by rod coating to form a filling layer on the surface, filling the paper surface. The pore structure was dried in an oven at 90 °C for 1 h, and the surface of the paper was smooth to form a filling layer on the surface.

(2) On the basis of the above, a kaolin coating with a sheet-like structure was applied by means of bar coating, and the coating weight was 9g/m ² . (EMS) was 482 nm, and an improvement layer was formed.

(3) On the basis of the foregoing, a composite coating of ground calcium carbonate (the particle size of ground calcium carbonate is 90% less than 2 μm) and acrylic emulsion is coated by rod coating. In the composite coating, ground calcium carbonate and acrylic acid The mass ratio of the emulsion is 100:12, the coating weight is 10g/m ² , and the coating thickness is 25μm. It is used to improve the barrier properties of paper to humidity, grease and oxygen. After coating, dry it in an oven at 90°C for 1 hour. , the surface roughness (EMS) of the paper is 266nm, forming a barrier layer.

(4) On the basis of the foregoing, a composite coating of kaolin or talc and acrylic emulsion is applied by rod coating. In the composite coating, the mass ratio of kaolin or talc and acrylic emulsion is 100:8, and the coating amount is It is 23g/m ² and the coating thickness is 3μm. After the coating is completed, it is dried in an oven at 90°C for 1 hour and calendered on a calender. The surface roughness of the paper is about 105nm, forming a smooth paper coating .

(5) On the basis of the above, apply water-based UV varnish for printing, the coating amount is 5g/m ² , the coating thickness is 25 μm, and after the coating is completed, use a UVA (wavelength 320-400 nm) lamp to irradiate for 4 minutes to make It dries and solidifies to form a printing varnish layer.

After the surface of the paper is treated, the printing of the organic light-emitting structure functional layer of the paper is completed according to the following steps and structures:

(1) The conductive anode was printed on the varnish layer of the above-mentioned paper by screen printing, using a nylon wire mesh, the mesh number of the mesh was 400 meshes, and the wire diameter was 18 μm. A solution with a mass percentage of 1.3% poly-3,4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS) aqueous solution and methanol in a volume ratio of 1:1 was used, and then dimethyl sulfoxide ( The volume of DMSO) is 5% of the volume of the mixed solution, then stirred with a stirrer for 20 min, and sonicated for 1 h; screen-printed a layer of grids, dried in an oven at 90 °C for 30 min, and then screen-printed a second layer of grids , the two-layer mesh forms the conductive anode layer.

(2) A hole transport layer is printed on the above-mentioned conductive anode layer by screen printing. The wire mesh used is a 120-mesh nylon wire mesh with a wire diameter of 60 μm. N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-dissolved in chloroform For the mixed solution of biphenyl-4,4'-diamine (TPD) and polycarbonate, the mass of the solute is 13.6% of the mass of the solvent, and the mass ratio of polycarbonate and TPD is 1:1. The mixture was stirred for 6 hours, and then screen-printed. After the printing was completed, it was dried in an oven at 90° C. for 30 min to form a light-emitting hole transport layer.

(3) The light-emitting layer is printed on the above-mentioned hole transport layer by screen printing. The nylon wire mesh was used, the mesh number was 200, and the wire diameter was 48 μm. The conjugated polymer Super yellow (pharmaceutical trade name) luminescent material was dissolved in a mixed solution of tetrahydrofuran and toluene at a concentration of 5 g/L. The volume ratio of toluene and toluene is 4:1. After stirring evenly, screen printing is performed on the hole transport layer. After the printing is completed, it is dried in an oven at 90 °C for 30 min to form a light-emitting layer with an organic light-emitting structure.

(4) The method of screen printing is adopted on the above-mentioned light-emitting layer, and the screen is made of 120-mesh nylon screen, and the wire diameter is 60 μm. Poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene], which acts as a high-efficiency electron injection layer between the organic light-emitting layer and the high work function cathode, both It can ensure the efficient injection of electrons, and at the same time can effectively block the erosion of the conductive nano-silver electronic ink solvent. The epoxy resin adhesive and poly-PFNR ₂ are dissolved in methanol at a mass ratio of 11:2 to make up 0.04% (w/ w) mixed solution, screen-printed the mixed solution on the light-emitting layer, after the printing was completed, irradiated in a UV curing oven for 2min (output power was 30mW/cm ² ), and then annealed at a low temperature of 65°C for 30min to form Electron injection layer of organic light emitting structure.

(5) On the basis of the above electron injection layer, the nano-silver conductive ink is printed by inkjet printing to form the cathode of the device. After the cathode printing is completed, it is dried at 80°C in a vacuum drying box to remove the electronic ink. and then annealed at 140° C. for 30 minutes to sinter the nano-silver particles to make the cathode line conduct, that is, to form a conductive cathode of the organic light-emitting structure.

The luminous structure of the finally formed paper is shown in Figure 2. Driven by a DC voltage of 7V, under the current efficiency of 1.2cd/A, the luminous effect with a uniform brightness of 130cd/m ² is shown in Figure 4.

Example 2

A method for preparing paper luminescence based on a full printing process, which is specifically implemented according to the following steps:

Finishing the paper:

(1) Generally, uncoated paper (uncoated on the surface) is selected as the base material of the device, and copy paper of 80 g/m ² is selected in this embodiment. With low concentration (5%) fine ground ground calcium carbonate paint (90% of the ground calcium carbonate particle size is less than 2μm), the paper surface is filled by rod coating to form a filling layer on the surface, filling the paper surface. The pore structure was dried in an oven at 100 °C for 1 h, and the surface of the paper was smooth, forming a filling layer on the surface.

(2) On the basis of the above, a kaolin coating with a sheet-like structure was applied by means of bar coating, and the coating weight was 10 g/m ² . (EMS) was 356 nm, and an improvement layer was formed.

(3) On the basis of the foregoing, a composite coating of ground calcium carbonate (the particle size of ground calcium carbonate is 90% less than 2 μm) and acrylic emulsion is coated by rod coating. In the composite coating, ground calcium carbonate and acrylic acid The mass ratio of the emulsion is 100:12, the coating weight is 0.5g/m ² , and the coating thickness is 2μm. It is used to improve the barrier properties of paper to humidity, grease and oxygen. After coating, dry it in an oven at 80°C For 1 h, the surface roughness (EMS) of the paper was 296 nm, and a barrier layer was formed.

(4) On the basis of the foregoing, a composite coating of kaolin or talc and acrylic emulsion is applied by rod coating. In the composite coating, the mass ratio of kaolin or talc and acrylic emulsion is 100:8, and the coating amount is It is 20g/m ² and the coating thickness is 0.8μm. After the coating is completed, it is dried in an oven at 80°C for 1 hour, and calendered on a calender. The surface roughness of the paper is about 55nm, forming a smooth paper surface coating. Floor.

(5) On the basis of the above, apply water-based UV varnish for printing, the coating amount is 3g/m ² , the coating thickness is 25 μm, and after the coating is completed, use a UVA (wavelength 320-400nm) lamp to irradiate for 3 minutes to make It dries and solidifies to form a printing varnish layer.

After the surface of the paper is treated, the printing of the organic light-emitting structure functional layer of the paper is completed according to the following steps and structures:

(1) The conductive anode was printed on the varnish layer of the above-mentioned paper by screen printing, using a nylon wire mesh, the mesh number of the mesh was 400 meshes, and the wire diameter was 18 μm. A solution with a mass percentage of 1.3% poly-3,4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS) aqueous solution and methanol in a volume ratio of 1:1 was used, and then dimethyl sulfoxide ( The volume of DMSO) is 5% of the volume of the mixed solution, then stirred with a stirrer for 20 min, and sonicated for 1 h; screen-printed a layer of grids, dried in an oven at 80 °C for 30 minutes, and then screen-printed a second layer of grids , the two-layer mesh forms the conductive anode layer.

(2) A hole transport layer is printed on the above-mentioned conductive anode layer by screen printing. The wire mesh used is a 120-mesh nylon wire mesh with a wire diameter of 60 μm. N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-dissolved in chloroform For the mixed solution of biphenyl-4,4'-diamine (TPD) and polycarbonate, the mass of the solute is 13.6% of the mass of the solvent, and the mass ratio of polycarbonate and TPD is 1:1. The mixture was stirred for 6 hours, and then screen-printed. After the printing was completed, it was dried in an oven at 80° C. for 30 min to form a light-emitting hole transport layer.

(3) The light-emitting layer is printed on the above-mentioned hole transport layer by screen printing. The nylon wire mesh was used, the mesh number was 200, and the wire diameter was 48 μm. The conjugated polymer Super yellow (pharmaceutical trade name) luminescent material was dissolved in a mixed solution of tetrahydrofuran and toluene at a concentration of 5 g/L. The volume ratio of toluene and toluene is 4:1. After stirring evenly, screen printing is performed on the hole transport layer. After the printing is completed, it is dried in an oven at 80 °C for 30 min to form a light-emitting layer with an organic light-emitting structure.

(4) The method of screen printing is adopted on the above-mentioned light-emitting layer, and the screen is made of 120-mesh nylon screen, and the wire diameter is 60 μm. Poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene], which acts as a high-efficiency electron injection layer between the organic light-emitting layer and the high work function cathode, both It can ensure the efficient injection of electrons and at the same time can effectively block the erosion of the conductive nano-silver electronic ink solvent. The epoxy resin adhesive and poly-PFNR ₂ are dissolved in methanol at a mass ratio of 11:2 to make up 0.04% (w/ w) mixed solution, screen-printed the mixed solution on the light-emitting layer, after the printing was completed, irradiated in a UV curing oven for 2min (output power was 30mW/cm ² ), and then annealed at a low temperature of 65°C for 30min to form Electron injection layer of organic light emitting structure.

(5) On the basis of the above electron injection layer, the nano-silver conductive ink is printed by inkjet printing to form the cathode of the device. After the cathode printing is completed, it is dried at 80°C in a vacuum drying box to remove the electronic ink. and then annealed at 140° C. for 30 minutes to sinter the nano-silver particles to make the cathode line conduct, that is, to form a conductive cathode of the organic light-emitting structure.

Example 3

A method for preparing paper luminescence based on a full printing process, which is specifically implemented according to the following steps:

Finishing the paper:

(1) Generally, uncoated paper (uncoated on the surface) is selected as the base material of the device, and copy paper of 80 g/m ² is selected in this embodiment. With low concentration (5%) fine ground ground calcium carbonate paint (90% of the ground calcium carbonate particle size is less than 2μm), the paper surface is filled by rod coating to form a filling layer on the surface, filling the paper surface. The pore structure was dried in an oven at 80 °C for 1 h, and the surface of the paper was smooth to form a filling layer on the surface.

(2) On the basis of the above, a kaolin coating with a sheet-like structure was applied by means of bar coating, and the coating weight was 8g/m ² . (EMS) was 312 nm, and an improvement layer was formed.

(3) On the basis of the foregoing, a composite coating of ground calcium carbonate (the particle size of ground calcium carbonate is 90% less than 2 μm) and acrylic emulsion is coated by rod coating. In the composite coating, ground calcium carbonate and acrylic acid The mass ratio of the emulsion is 100:12, the coating weight is 20g/m ² , and the coating thickness is 28μm. It is used to improve the barrier properties of paper to humidity, grease and oxygen. After coating, dry it in an oven at 100°C for 1h. , the surface roughness (EMS) of the paper is 212nm, forming a barrier layer.

(4) On the basis of the foregoing, a composite coating of kaolin or talc and acrylic emulsion is applied by rod coating. In the composite coating, the mass ratio of kaolin or talc and acrylic emulsion is 100:8, and the coating amount is It is 25g/m ² and the coating thickness is 6μm. After the coating is completed, it is dried in an oven at 100 ° C for 1 hour and calendered on a calender. The surface roughness of the paper is about 146nm, forming a smooth paper coating .

(5) On the basis of the above, coat the water-based UV varnish for printing, the coating weight is 6g/m ² , the coating thickness is 25 μm, and after the coating is completed, use a UVA (wavelength 320-400 nm) lamp to irradiate for 5 minutes to make It dries and solidifies to form a printing varnish layer.

After the surface of the paper is treated, the printing of the organic light-emitting structure functional layer of the paper is completed according to the following steps and structures:

(1) The conductive anode was printed on the varnish layer of the above-mentioned paper by screen printing, using a nylon wire mesh, the mesh number of the mesh was 400 meshes, and the wire diameter was 18 μm. A solution with a mass percentage of 1.3% poly-3,4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS) aqueous solution and methanol in a volume ratio of 1:1 was used, and then dimethyl sulfoxide ( The volume of DMSO) is 5% of the volume of the mixed solution, then stirred with a stirrer for 20 min, and sonicated for 1 h; first screen-printed a layer of grids, dried in an oven at 100 ° C for 30 minutes, and then screen-printed a second layer of grids , the two-layer mesh forms the conductive anode layer.

(2) A hole transport layer is printed on the above-mentioned conductive anode layer by screen printing. The wire mesh used is a 120-mesh nylon wire mesh with a wire diameter of 60 μm. N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-dissolved in chloroform For the mixed solution of biphenyl-4,4'-diamine (TPD) and polycarbonate, the mass of the solute is 13.6% of the mass of the solvent, and the mass ratio of polycarbonate and TPD is 1:1. The mixture was stirred for 6 hours, and then screen-printed. After the printing was completed, it was dried in an oven at 100° C. for 30 min to form a light-emitting hole transport layer.

(3) The light-emitting layer is printed on the above-mentioned hole transport layer by screen printing. The nylon wire mesh was used, the mesh number was 200, and the wire diameter was 48 μm. The conjugated polymer Super yellow (pharmaceutical trade name) luminescent material was dissolved in a mixed solution of tetrahydrofuran and toluene at a concentration of 5 g/L. The volume ratio of toluene and toluene is 4:1. After stirring evenly, screen printing is performed on the hole transport layer. After printing, it is dried in an oven at 100 °C for 30 min to form a light-emitting layer with an organic light-emitting structure.

(4) The method of screen printing is adopted on the above-mentioned light-emitting layer, and the screen is made of 120-mesh nylon screen, and the wire diameter is 60 μm. Poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene], which acts as a high-efficiency electron injection layer between the organic light-emitting layer and the high work function cathode, both It can ensure the efficient injection of electrons and at the same time can effectively block the erosion of the conductive nano-silver electronic ink solvent. The epoxy resin adhesive and poly-PFNR ₂ are dissolved in methanol at a mass ratio of 11:2 to make up 0.04% (w/ w) mixed solution, screen-printed the mixed solution on the light-emitting layer, after the printing was completed, irradiated in a UV curing oven for 2min (output power was 30mW/cm ² ), and then annealed at a low temperature of 65°C for 30min to form Electron injection layer of organic light emitting structure.

(5) On the basis of the above electron injection layer, the nano-silver conductive ink is printed by inkjet printing to form the cathode of the device. After the cathode printing is completed, it is dried at 80°C in a vacuum drying box to remove the electronic ink. and then annealed at 140° C. for 30 minutes to sinter the nano-silver particles to make the cathode line conduct, that is, to form a conductive cathode of the organic light-emitting structure.

Claims (6)

1. The method for preparing the paper light-emitting structure based on the full printing process is characterized in that the paper light-emitting structure comprises a paper substrate (1), a filling layer (2), an improvement layer (3), a barrier layer (4), a paper surface coating (5), a printing gloss oil layer (6), a conductive anode layer (7), a hole transport layer (8), a light-emitting layer (9), an electron injection layer (10) and a conductive cathode layer (11) which are sequentially distributed from bottom to top;

   the raw material for preparing the filling layer (2) is heavy calcium carbonate paint; the raw material for preparing the improvement layer (3) is a kaolin coating with a sheet structure; the barrier layer (4) is prepared from a composite coating of heavy calcium carbonate and acrylic emulsion; the preparation raw material of the paper surface coating (5) is kaolin or composite paint of talcum powder and acrylic emulsion; the preparation raw material of the printing gloss oil layer (6) is water-based gloss oil; the preparation raw material of the conductive anode layer (7) is a mixed solution of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and methanol and dimethyl sulfoxide; the hole transport layer (8) is prepared from a mixed solution of N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine and polycarbonate dissolved in chloroform; the preparation raw material of the luminous layer (9) is a mixture of a conjugated polymer Superyellow, tetrahydrofuran and toluene; the electron injection layer (10) is prepared from a mixed solution of an epoxy resin adhesive and poly [9, 9-dioctylfluorene-9, 9-bis (N, N-dimethylaminopropyl) fluorene ] dissolved in methanol; the raw material for preparing the conductive cathode layer (11) is nano-silver conductive ink;

   the method comprises the following steps:

   step 1: filling the surface of the pore structure of the paper substrate (1) with heavy calcium carbonate coating to form a filling layer (2) on the paper surface;

   step 2: coating a kaolin coating with a sheet structure on the filling layer (2) in the step 1 to form an improved layer (3);

   and step 3: coating the improved layer (3) in the step 2 with a composite coating of heavy calcium carbonate and acrylic emulsion to form a barrier layer (4);

   and 4, step 4: coating the composite coating of kaolin or talcum powder and acrylic emulsion on the barrier layer (4) in the step (3), and performing calendaring treatment to form a paper surface coating (5);

   and 5: coating aqueous gloss oil for printing on the paper surface coating (5) in the step 4 to form a printing gloss oil layer (6);

   step 6: printing a mixed solution of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and methanol and dimethyl sulfoxide on the printing gloss oil layer (6) in the step 5, and printing two layers to form a conductive anode layer (7) of the paper light-emitting structure;

   and 7: printing a mixed solution of N, N '-diphenyl-N, N' -di (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine and polycarbonate dissolved in chloroform on the conductive anode layer (7) in the step 6 to form a hole transport layer (8) of a paper light-emitting structure;

   and 8: printing a mixture of a conjugated polymer of Super yellow, tetrahydrofuran and toluene on the hole transport layer (8) in the step 7 to form a light emitting layer (9) of the paper light emitting structure;

   and step 9: printing a mixture of an epoxy resin adhesive and poly [9, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl aminopropyl) fluorene ] in methanol on the luminescent layer (9) in the step 8, namely forming an electron injection layer (10) of the paper luminescent structure;

   step 10: and printing a nano silver layer on the electron injection layer in the step 9 to form a conductive cathode layer (11) of the paper light-emitting structure.
2. 2. The method for preparing paper luminous structure based on full printing process, wherein, step 6, step 7, step 8 and step 9 are all printed by screen printing, and step 10 is printed by ink jet printing.
3. 3. The method for preparing paper luminescent structure based on full printing process as claimed in claim 1, wherein at least 90% of the heavy calcium carbonate particles in step 1 have a particle size less than 2 μm;

   the coating amount in the step 2 is 8-10g/m²After coating, the surface roughness of the paper is 300-500 nm;

   in the step 3, at least 90 percent of the heavy calcium carbonate has the particle size less than 2 mu m, the mass ratio of the heavy calcium carbonate to the acrylic emulsion in the composite coating of the heavy calcium carbonate and the acrylic emulsion is 100:12, and the coating weight is 0.5-20g/m²The thickness of the coating is 2-28 μm, and after the coating is finished, the surface roughness of the paper is 200-300 nm.
4. 4. The method for preparing paper luminous structures based on full printing process as claimed in claim 1, wherein the mass ratio of kaolin or talc to acrylic emulsion in the composite coating of kaolin or talc to acrylic emulsion in step 4 is 100:8, and the coating weight is 20-25g/m²The thickness of the coating is 0.8-6 μm, and after the coating is finished, the surface roughness of the paper is 50-150 nm;

   the water-based gloss oil in the step 5 is water-based UV gloss oil, and the coating weight is 3-6g/m²The coating thickness is 25 μm, and after coating, UVA lamp is used for irradiation for 3-5min to dry and cure.
5. 5. The method for preparing paper luminescent structure based on full printing process, according to claim 1, wherein the mass fraction of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution in step 6 is 1.3%, the volume ratio of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution to methanol is 1:1, and the volume of dimethyl sulfoxide is 5% of the sum of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and methanol;

   the sum of the mass of N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine and polycarbonate in step 7 was 13.6% of the mass of chloroform, and the mass ratio of N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine and polycarbonate was 1: 1.
6. 6. The method for preparing paper luminescent structure based on full printing process, according to claim 1, wherein the mass concentration of the conjugated polymer Superyellow in step 8 is 5g/L, and the volume ratio of tetrahydrofuran to toluene is 4: 1;

   in step 9, the epoxy resin adhesive and poly [9, 9-dioctylfluorene-9, 9-bis (N, N-dimethylaminopropyl) fluorene]In a mass ratio of 11:2, and the epoxy resin binder and poly [9, 9-dioctylfluorene-9, 9-bis (N, N-dimethylaminopropyl) fluorene]The mass of the mixed solution is 0.04 percent of the mass of the mixed solution, the mixed solution is irradiated in an ultraviolet curing furnace for 2min after the printing is finished, and the output power of the ultraviolet curing furnace is 30mW/cm²Then annealing at 65 ℃ for 30 min;

   after the printing in the step 10 is finished, drying the electronic ink in a vacuum drying oven at 80 ℃, removing the solvent in the electronic ink, and then annealing the electronic ink at 140 ℃ for 30min to sinter the nano silver particles to conduct the cathode wire.

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