CN111155350A - Preparation method of cellulose-based film-forming resin for positive photoresist - Google Patents
Preparation method of cellulose-based film-forming resin for positive photoresist Download PDFInfo
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- CN111155350A CN111155350A CN202010029380.7A CN202010029380A CN111155350A CN 111155350 A CN111155350 A CN 111155350A CN 202010029380 A CN202010029380 A CN 202010029380A CN 111155350 A CN111155350 A CN 111155350A
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- cellulose
- forming resin
- dissolving pulp
- based film
- positive photoresist
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biochemistry (AREA)
- Inorganic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of cellulose-based film-forming resin for positive photoresist. The key point of the method is that dissolving pulp cellulose is used as a basic raw material, and esterification modification is carried out on the dissolving pulp cellulose to prepare the environment-friendly cellulose-based film-forming resin for the positive photoresist. The dissolving pulp cellulose is introduced into the raw materials for preparing the film-forming resin for the positive photoresist, so that the raw material range is expanded, the production cost of the film-forming resin for the positive photoresist is reduced on the basis of ensuring the good performance of the film-forming resin, and the economic benefit is improved; simultaneously, the biodegradability of the film-forming resin product is improved, and the film-forming resin has good economic and social benefits.
Description
Technical Field
The invention relates to a preparation method of film-forming resin, in particular to a preparation method of cellulose-based film-forming resin for positive photoresist, belonging to the technical field of organic high polymer materials.
Background
In the last half century, the microelectronic technology has become the most potential technology in this century by virtue of rapid development speed and strong vitality, has entered into various fields of human society, and has become an industry of competitive development of countries in the world. Developed countries such as the united states and japan continue to view microelectronics as a preferred industry. The microelectronic technology has become the core competitiveness of the information society at present and becomes an important mark for measuring the national technological progress and the comprehensive national strength. Integrated circuits are at the heart of microelectronic fabrication technology. Photoresists, also known as photoresists, are key materials for fine patterning in microelectronics. The photoresist consists of resin, photosensitizer, solvent and additive. Positive photoresist is one of them, and the solubility of the exposed portion is greatly improved after exposure. At present, the most applied positive photoresist in the market is mainly phenolic resin-diazonaphthoquinone, and linear phenolic resin is used as film-forming resin; the raw materials of the phenolic resin are mainly derived from petrochemical products, so that the photoresist has high cost, is not biodegradable and has great harm to the environment. Because petroleum resources are limited and non-renewable, and greenhouse effect is increasingly serious, the preparation of environment-friendly novel film-forming resin for positive photoresist by using natural organic high molecular compounds is becoming a trend.
Cellulose is the most abundant renewable resource on the earth, is rich in active hydroxyl, and is convenient for reactions such as oxidation, etherification, esterification, crosslinking and the like. The dissolving pulp board has high cellulose content, low lignin and other impurity content, high whiteness and excellent reaction performance. At present, China is the country with the largest consumption of dissolving pulp in the world. The dissolving pulp in China is mainly used for producing and preparing viscose fibers and is used in the field of textiles. The resource source is wide, the price is low, and the method is applied to the production of green photoresist, so that the production cost can be reduced, the application field of dissolving pulp is expanded, the environmental protection is facilitated, and the national sustainable development road is met. The cellulose-based film-forming resin for the environment-friendly positive photoresist is prepared by grafting and modifying dissolving pulp cellulose, wherein a cellulose semi-rigid chain is used as a framework, so that the production cost of the film-forming resin for the photoresist can be greatly reduced and the economic benefit is improved while good application performance is ensured; the utilization of dissolving pulp cellulose can shorten the degradation period of the cellulose base film-forming resin product for the positive photoresist in natural environment, and has important economic and social benefits.
Cellulose for photoresistThe Chinese patent CN 109739070A, a 3D printing type positive photoresist for a high-resolution high-transmittance semiconductor, provides a preparation method of the 3D printing type positive photoresist for the high-resolution high-transmittance semiconductor, which has good fluidity, high polymerization degree and excellent anti-etching performance and is suitable for 193nm deep ultraviolet light; chinese patent CN109776756A 'double modified epoxy acrylate and photoresist thereof' to nano SiO2Performing surface modification, preparing epoxy acrylate from epoxy resin, and reacting the epoxy acrylate and the epoxy resin to synthesize the film-forming resin for the dual-modified epoxy acrylate photoresist; the acrylic ester film-forming resin containing the cubane, which is provided by Chinese patent CN 109679020A, "acrylic ester film-forming resin containing the cubane and ArF photoresist and a preparation method and a photoetching method thereof," is obtained by copolymerizing 20-60% of unit monomer I and 40-80% of unit monomer II by mass fraction. Until now, no related process technology for preparing a film-forming resin for an environment-friendly positive photoresist by chemical modification using dissolving pulp cellulose has appeared.
The dissolving pulp has wide source and low price, is beneficial to expanding the application field of dissolving pulp fiber and can improve the added value of products; the method can reduce the production cost of the film-forming resin for the photoresist, improve the economic benefit, shorten the degradation period of the film-forming resin for the photoresist in the natural environment and have important economic and social benefits while ensuring good photoetching performance.
Disclosure of Invention
In order to overcome the problems of limited resources, non-regeneration, poor biodegradability, large harm to the environment and the like existing in the traditional film-forming resin for the positive photoresist, the invention aims to provide a preparation method of cellulose-based film-forming resin for the positive photoresist.
In order to achieve the purpose, the technical scheme of the invention adopts the following steps:
1) crushing the dissolving pulp board by a miniature plant crusher, and screening to obtain dissolving pulp cellulose with the size of 0.04-0.07 mm;
2) dissolving 1g of the dissolved pulp cellulose with the size of 0.04-0.07mm obtained in the step 1) in a solvent, and mechanically stirring for 2-4h at the temperature of 100-120 ℃ to uniformly disperse the dissolved pulp cellulose to obtain a dissolved pulp cellulose suspension;
3) cooling the cellulose suspension of the dissolving pulp obtained in the step 2) to 90 ℃, adding 4-6g of an inorganic salt system, and naturally cooling to room temperature under mechanical stirring to obtain a homogeneous cellulose solution of the dissolving pulp;
4) sequentially adding 4-8mmol of 4-dimethylaminopyridine and 6-9mmol of monomer into the cellulose homogeneous solution of the dissolving pulp obtained in the step 3), and mechanically stirring for 30 hours at the temperature of 25-60 ℃ to obtain a reaction mixed solution;
5) soaking the reaction mixed solution obtained in the step 4) with absolute ethyl alcohol, standing, and removing supernatant to obtain a precipitation solution;
6) washing the precipitation solution obtained in the step 5) with absolute ethyl alcohol, and centrifuging for 3 times to obtain white fibrous slurry;
7) and (3) drying the white fibrous slurry obtained in the step 6) at 20 ℃ for 32h in vacuum, and grinding to obtain white powder, namely the cellulose-based film-forming resin for the positive photoresist.
The dissolving pulp board is one of a moso bamboo dissolving pulp board, a birch dissolving pulp board, a pinus sylvestris dissolving pulp board and a spruce dissolving pulp board.
The solvent is one of n-heptane, tetrahydrofuran, toluene and dipropyl alcohol.
The inorganic salt system is one of a lithium chloride single system, an aluminum chloride single system and a lithium chloride-aluminum chloride composite system.
The monomer is one of di-tert-butyl dicarbonate and trifluoroacetic anhydride.
Compared with the background art, the invention has the beneficial effects that:
the film-forming resin for the positive photoresist is prepared by taking the dissolving pulp plate as a basic raw material, so that sustainable development is facilitated, and the utilization efficiency of cellulose resources can be improved really; the prepared cellulose-based film-forming resin for the positive photoresist can reduce the production cost and improve the biodegradability and ecological sustainability in the natural environment while ensuring good performance.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
1) pulverizing the moso bamboo dissolving pulp board by a miniature plant pulverizer, and sieving to obtain moso bamboo dissolving pulp cellulose with the size of 0.04 mm;
2) dissolving 1g of the moso bamboo dissolving pulp cellulose with the size of 0.04mm obtained in the step 1) in n-heptane, and mechanically stirring for 4h at 100 ℃ to uniformly disperse the cellulose to obtain a moso bamboo dissolving pulp cellulose suspension;
3) cooling the cellulose suspension of the moso bamboo dissolving pulp obtained in the step 2) to 90 ℃, adding 4g of lithium chloride single inorganic salt system, and naturally cooling to room temperature under mechanical stirring to obtain a homogeneous cellulose solution of the moso bamboo dissolving pulp;
4) sequentially adding 4mmol of 4-dimethylaminopyridine and 6mmol of di-tert-butyl dicarbonate into the cellulose homogeneous solution of the moso bamboo dissolving pulp obtained in the step 3), and mechanically stirring for 30 hours at 60 ℃ to obtain a reaction mixed solution;
5) soaking the reaction mixed solution obtained in the step 4) with absolute ethyl alcohol, standing, and removing supernatant to obtain a precipitation solution;
6) washing the precipitation solution obtained in the step 5) with absolute ethyl alcohol, and centrifuging for 3 times to obtain white fibrous slurry;
7) drying the white fibrous slurry obtained in the step 6) at 20 ℃ for 32h in vacuum, and grinding to obtain white powder, namely the cellulose-based film-forming resin (a) for the positive photoresist.
Example 2:
1) crushing the birch dissolving pulp board by a miniature plant crusher, and screening to obtain birch dissolving pulp cellulose with the size of 0.07 mm;
2) dissolving 1g of birch dissolving pulp cellulose with the size of 0.07mm obtained in the step 1) in tetrahydrofuran, and mechanically stirring for 2h at 120 ℃ to uniformly disperse the birch dissolving pulp cellulose suspension;
3) cooling the birch dissolving pulp cellulose suspension obtained in the step 2) to 90 ℃, adding 4g of aluminum chloride single inorganic salt system, and naturally cooling to room temperature under mechanical stirring to obtain a birch dissolving pulp cellulose homogeneous solution;
4) sequentially adding 6mmol of 4-dimethylaminopyridine and 9mmol of di-tert-butyl dicarbonate into the homogeneous cellulose solution of the birch dissolving pulp obtained in the step 3), and mechanically stirring for 30 hours at the temperature of 30 ℃ to obtain a reaction mixed solution;
5) soaking the reaction mixed solution obtained in the step 4) with absolute ethyl alcohol, standing, and removing supernatant to obtain a precipitation solution;
6) washing the precipitation solution obtained in the step 5) with absolute ethyl alcohol, and centrifuging for 3 times to obtain white fibrous slurry;
7) drying the white fibrous slurry obtained in the step 6) at 20 ℃ for 32h in vacuum, and grinding to obtain white powder, namely the cellulose-based film-forming resin (b) for the positive photoresist.
Example 3:
1) crushing the pinus sylvestris dissolving pulp plate by a miniature plant crusher, and screening to obtain 0.06mm pinus sylvestris dissolving pulp cellulose;
2) dissolving 1g of 0.06mm pinus sylvestris dissolving pulp cellulose obtained in the step 1) in toluene, and mechanically stirring for 3h at 110 ℃ to uniformly disperse the cellulose to obtain pinus sylvestris dissolving pulp cellulose suspension;
3) cooling the pinus sylvestris dissolving pulp cellulose suspension obtained in the step 2) to 90 ℃, adding a composite inorganic salt system of 3g of lithium chloride and 3g of aluminum chloride, and naturally cooling to room temperature under mechanical stirring to obtain a pinus sylvestris dissolving pulp cellulose homogeneous phase solution;
4) sequentially adding 8mmol of 4-dimethylaminopyridine and 6mmol of trifluoroacetic anhydride into the cellulose homogeneous solution of the pinus sylvestris dissolving pulp obtained in the step 3), and mechanically stirring for 30 hours at 40 ℃ to obtain a reaction mixed solution;
5) soaking the reaction mixed solution obtained in the step 4) with absolute ethyl alcohol, standing, and removing supernatant to obtain a precipitation solution;
6) washing the precipitation solution obtained in the step 5) with absolute ethyl alcohol, and centrifuging for 3 times to obtain white fibrous slurry;
7) drying the white fibrous slurry obtained in the step 6) at 20 ℃ for 32h in vacuum, and grinding to obtain white powder, namely the cellulose-based film-forming resin (c) for the positive photoresist.
Example 4:
1) pulverizing the spruce dissolving pulp board by a miniature plant pulverizer, and sieving to obtain 0.05mm spruce dissolving pulp cellulose;
2) dissolving 1g of the spruce dissolving pulp cellulose with the size of 0.05mm obtained in the step 1) in dipropyl alcohol, and mechanically stirring for 3 hours at 120 ℃ to uniformly disperse the cellulose to obtain a spruce dissolving pulp cellulose suspension;
3) cooling the cellulose suspension of the spruce dissolving pulp obtained in the step 2) to 90 ℃, adding 6g of aluminum chloride single inorganic salt system, and naturally cooling to room temperature under mechanical stirring to obtain a cellulose homogeneous solution of the spruce dissolving pulp;
4) sequentially adding 8mmol of 4-dimethylaminopyridine and 9mmol of trifluoroacetic anhydride into the cellulose homogeneous phase solution of the spruce dissolving pulp obtained in the step 3), and mechanically stirring for 30 hours at 25 ℃ to obtain a reaction mixed solution;
5) soaking the reaction mixed solution obtained in the step 4) with absolute ethyl alcohol, standing, and removing supernatant to obtain a precipitation solution;
6) washing the precipitation solution obtained in the step 5) with absolute ethyl alcohol, and centrifuging for 3 times to obtain white fibrous slurry;
7) drying the white fibrous slurry obtained in the step 6) at 20 ℃ for 32h in vacuum, and grinding to obtain white powder, namely the cellulose-based film-forming resin (d) for the positive photoresist.
The positive photoresist prepared in examples 1, 2, 3 and 4 was subjected to photoresist compounding, spin coating, baking and photolithography with cellulose-based film-forming resin, and the film thickness, sensitivity (20 μm film thickness gauge), imaging resolution and biodegradability in soil extract for 90 days were measured; table 1 shows the performance parameters of the cellulose-based film-forming resin for positive photoresists prepared in examples 1, 2, 3 and 4. As can be seen from Table 1, the cellulose-based film-forming resin for a positive photoresist produced had a sensitivity (20 μm film thickness) of 50 to 75mJ/cm-2The imaging resolution is 2-5 μm, which shows thatThe film resin material has better photosensitivity and higher resolution; the biodegradation rate in the soil extracting solution is 59.4-64.3% in 90 days, which shows that the soil extracting solution has good environmental friendliness in natural environment.
TABLE 1
The foregoing lists merely illustrate specific embodiments of the invention. The present invention is not limited to the above embodiments, and many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. A preparation method of cellulose-based film-forming resin for positive photoresist is characterized by comprising the following steps:
1) crushing the dissolving pulp board by a miniature plant crusher, and screening to obtain dissolving pulp cellulose with the size of 0.04-0.07 mm;
2) dissolving 1g of the dissolved pulp cellulose with the size of 0.04-0.07mm obtained in the step 1) in a solvent, and mechanically stirring for 2-4h at the temperature of 100-120 ℃ to uniformly disperse the dissolved pulp cellulose to obtain a dissolved pulp cellulose suspension;
3) cooling the cellulose suspension of the dissolving pulp obtained in the step 2) to 90 ℃, adding 4-6g of an inorganic salt system, and naturally cooling to room temperature under mechanical stirring to obtain a homogeneous cellulose solution of the dissolving pulp;
4) sequentially adding 4-8mmol of 4-dimethylaminopyridine and 6-9mmol of monomer into the cellulose homogeneous solution of the dissolving pulp obtained in the step 3), and mechanically stirring for 30 hours at the temperature of 25-60 ℃ to obtain a reaction mixed solution;
5) soaking the reaction mixed solution obtained in the step 4) with absolute ethyl alcohol, standing, and removing supernatant to obtain a precipitation solution;
6) washing the precipitation solution obtained in the step 5) with absolute ethyl alcohol, and centrifuging for 3 times to obtain white fibrous slurry;
7) and (3) drying the white fibrous slurry obtained in the step 6) at 20 ℃ for 32h in vacuum, and grinding to obtain white powder, namely the cellulose-based film-forming resin for the positive photoresist.
2. The method of claim 1, wherein the cellulose-based film-forming resin comprises: the dissolving pulp board is one of a moso bamboo dissolving pulp board, a birch dissolving pulp board, a pinus sylvestris dissolving pulp board and a spruce dissolving pulp board.
3. The method of claim 1, wherein the cellulose-based film-forming resin comprises: the solvent is one of n-heptane, tetrahydrofuran, toluene and dipropyl alcohol.
4. The method of claim 1, wherein the cellulose-based film-forming resin comprises: the inorganic salt system is one of a lithium chloride single system, an aluminum chloride single system and a lithium chloride-aluminum chloride composite system.
5. The method of claim 1, wherein the cellulose-based film-forming resin comprises: the monomer is one of di-tert-butyl dicarbonate and trifluoroacetic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010029380.7A CN111155350A (en) | 2020-01-13 | 2020-01-13 | Preparation method of cellulose-based film-forming resin for positive photoresist |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010029380.7A CN111155350A (en) | 2020-01-13 | 2020-01-13 | Preparation method of cellulose-based film-forming resin for positive photoresist |
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| CN111155350A true CN111155350A (en) | 2020-05-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115185160A (en) * | 2022-09-09 | 2022-10-14 | 之江实验室 | Laser direct-writing photoresist composition based on cellulose derivative and patterning method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020068236A1 (en) * | 2000-10-16 | 2002-06-06 | Genji Imai | Positive photosensitive resin composition, positive photosensitive dry film and method of forming pattern |
| CN1630551A (en) * | 2001-04-11 | 2005-06-22 | 科莱恩金融(Bvi)有限公司 | Process for producing film forming resins for photoresist compositions |
| US20070248913A1 (en) * | 2006-04-24 | 2007-10-25 | Rahman M Dalil | Process for producing film forming resins for photoresist compositions |
| US20170115567A1 (en) * | 2015-10-27 | 2017-04-27 | Shin-Etsu Chemical Co., Ltd. | Chemically Amplified Positive Resist Composition and Patterning Process |
-
2020
- 2020-01-13 CN CN202010029380.7A patent/CN111155350A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020068236A1 (en) * | 2000-10-16 | 2002-06-06 | Genji Imai | Positive photosensitive resin composition, positive photosensitive dry film and method of forming pattern |
| CN1630551A (en) * | 2001-04-11 | 2005-06-22 | 科莱恩金融(Bvi)有限公司 | Process for producing film forming resins for photoresist compositions |
| US20070248913A1 (en) * | 2006-04-24 | 2007-10-25 | Rahman M Dalil | Process for producing film forming resins for photoresist compositions |
| US20170115567A1 (en) * | 2015-10-27 | 2017-04-27 | Shin-Etsu Chemical Co., Ltd. | Chemically Amplified Positive Resist Composition and Patterning Process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115185160A (en) * | 2022-09-09 | 2022-10-14 | 之江实验室 | Laser direct-writing photoresist composition based on cellulose derivative and patterning method |
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Application publication date: 20200515 |