CN109811586B - Method for preparing super-hydrophobic coating by laser printing - Google Patents
Method for preparing super-hydrophobic coating by laser printing Download PDFInfo
- Publication number
- CN109811586B CN109811586B CN201910082352.9A CN201910082352A CN109811586B CN 109811586 B CN109811586 B CN 109811586B CN 201910082352 A CN201910082352 A CN 201910082352A CN 109811586 B CN109811586 B CN 109811586B
- Authority
- CN
- China
- Prior art keywords
- super
- hydrophobic
- carbon powder
- preparing
- hydrophobic coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Carbon And Carbon Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a method for preparing a super-hydrophobic coating by laser printing, which comprises the steps of firstly preparing a super-hydrophobic nano compound by hydrolyzing and condensing organosilane and nano particles; then mixing and ball-milling the super-hydrophobic nano composite, the resin and the carbon powder to obtain uniform super-hydrophobic carbon powder; and then loading the super-hydrophobic carbon powder into a selenium drum of a laser printer, and printing the super-hydrophobic carbon powder on common printing paper by the laser printer to obtain the super-hydrophobic coating. The invention prints the super-hydrophobic coating by the laser printer, has high speed and high precision, can quickly print the super-hydrophobic coating with a complex structure (such as a complex shape, gradient wettability and the like) by computer design, has excellent performance (the contact angle of a 5 mu L water drop is more than 155 degrees, and the rolling angle is less than 8 degrees) of the printed and prepared super-hydrophobic coating, and lays a foundation for large-scale application.
Description
Technical Field
The invention relates to a preparation method of a super-hydrophobic coating, in particular to a method for preparing the super-hydrophobic coating by printing the super-hydrophobic coating on common printing paper by laser printing.
Background
The super-hydrophobic surface refers to a surface of which the contact angle of a water drop on the surface is more than 150 degrees and the rolling angle is less than 10 degrees. Currently, there are two main approaches to preparing superhydrophobic surfaces: (1) modifying a low surface energy substance on the surface with the micro-nano rough structure; (2) micro-nano roughness structure is constructed on the surface of the substance with low surface energy. The micro-nano rough structure is constructed mainly by technical means such as plasma etching, electrostatic spinning, self-assembly, vapor deposition, electrochemical deposition and the like, but the technologies still have the problems of complex preparation method, higher cost, poor stability and the like. In patent CN108654960A, a laser etching method is used to perform microstructure pattern processing on the substrate surface, and then a fluorine-containing reagent is used to perform low-energy treatment on the substrate to obtain a super-hydrophobic surface. In patent CN106517821A, PDMS is used as a silicon source, and a multi-walled carbon nanotube is used as a template, a silicon nanotube coating is constructed on the glass surface, and then hydrophobic treatment is performed on the glass surface by using chemical vapor deposition cured PDMS, so as to obtain a super-hydrophobic coating. The methods have the problems of complex preparation process, large dependence on a substrate, poor hydrophobicity of the coating, unrelated stability of the coating and the like.
In recent years, how to construct a super-hydrophobic coating through a simple and efficient method is widely concerned, and a foundation is laid for the application of a super-hydrophobic surface. Patent CN108043482A discloses a super-wetting Janus paper or paper base super-wetting pattern and its application, which takes tetraethoxysilane and fluorosilane as raw materials, and synthesizes a specific sol solution in a mixed system of ethanol and water by an acid catalysis method. The sol solution was then deposited onto a filter paper substrate by ink jet printing to form a surface with good superhydrophobicity. However, the method still has the problems of environmental pollution, long time-consuming preparation process, high cost, incapability of large-scale application and the like.
The spray coating method and the ink jet printing method are simple, but have self-defects. For example, the spraying method for preparing the super-hydrophobic coating has large artificial influence factors and large coating performance fluctuation; after the super-hydrophobic modification, the stability of the ink-jet printing ink has a problem, and a spray head is easy to block. Therefore, how to prepare the super-hydrophobic coating by a simple, quick and high-precision method, especially quickly prepare the super-hydrophobic coating with a complex structure (such as a complex shape, gradient wettability and the like), is a problem which is urgently solved in the field.
Disclosure of Invention
The invention aims to solve the problems of complex and expensive preparation technology of the existing super-hydrophobic coating, particularly the problem of difficulty in preparing a super-hydrophobic sample with a complex structure, and provides a simple, quick and high-precision method for preparing the super-hydrophobic coating by laser printing.
The invention relates to a method for preparing a super-hydrophobic coating by laser printing, which comprises the steps of firstly preparing a super-hydrophobic nano compound by hydrolyzing and condensing organosilane and nano particles; then mixing and ball-milling the super-hydrophobic nano composite, the resin and the carbon powder to obtain uniform super-hydrophobic carbon powder; and then loading the super-hydrophobic carbon powder into a selenium drum of a laser printer, and printing the super-hydrophobic carbon powder on common printing paper by the laser printer to obtain the super-hydrophobic coating.
Preparing the super-hydrophobic nano composite: adding a catalyst, water, organosilane and nanoparticles into an alcohol solvent, and stirring and reacting at 25-100 ℃ for 1-72 hours; and (4) after the reaction is finished, centrifuging and drying to obtain the catalyst. The mass ratio of the organosilane to the nanoparticles is 1: 1-1: 50. The adding amount of the catalyst is 1-200 times of the mass of the organosilane. Wherein the organosilane is at least one of perfluorooctyltrichlorosilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorodecyltrichlorosilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyldimethylchlorosilane, perfluorooctyldimethylmethoxysilane, perfluorodecyldimethylchlorosilane, perfluorodecyldimethylmethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane and hexadecyltrimethoxysilane. The nano particles are at least one of carbon nano tubes, graphene oxide, silicon dioxide, titanium dioxide, zinc oxide, nano silver, montmorillonite, attapulgite, sepiolite, halloysite, hydrotalcite, vermiculite, mica, kaolinite, hectorite, bacterial cellulose, polystyrene and polytetrafluoroethylene. The catalyst is at least one of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, benzenesulfonic acid, ammonia water, ethylenediamine, triethylamine and butylamine. The alcohol solvent is at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, and glycerol.
In the preparation of the super-hydrophobic carbon powder, the mass ratio of the super-hydrophobic nano composite to the carbon powder is 1: 5-1: 0.2, and the mass ratio of the super-hydrophobic nano composite to the resin is 1: 0.05-1: 0.5; the mixing and ball milling time is 2-36 h. Wherein the resin comprises at least one of polystyrene, polybutyl acrylate, polyethyl acrylate, poly-n-hexyl acrylate, poly-2-ethylhexyl acrylate, polylauryl acrylate, polymethyl methacrylate, polyethyl methacrylate, poly-n-butyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate and poly-n-hexyl methacrylate.
When the laser printer prints, patterns can be designed according to requirements, and the computer controls and prints the super-hydrophobic coating with a complex structure.
The invention prints the super-hydrophobic coating by the laser printer, has high speed and high precision, can quickly print the super-hydrophobic coating with a complex structure (such as a complex shape, gradient wettability and the like) by computer design, has excellent performance (the contact angle of a 5 mu L water drop is more than 155 degrees, and the rolling angle is less than 8 degrees) of the printed and prepared super-hydrophobic coating, and lays a foundation for large-scale application.
Detailed Description
The preparation method and properties of the laser printing super-hydrophobic coating prepared by the invention are further explained by the following specific examples.
Example 1
18.0 g of SiO 100 nm in diameter are weighed out2Adding the nano particles into a 1000 mL wide-mouth bottle, respectively measuring 800 mL of propanol, 80 mL of oxalic acid and 40 mL of deionized water, magnetically stirring for 10 min, and ultrasonically treating for 3 min by using a cell crusher. Then measuring 5.0 mL of tetraethoxysilane and 16.0 mL of perfluorodecyl dimethylchlorosilane, adding the tetraethoxysilane and the perfluorodecyl dimethylchlorosilane into a wide-mouth bottle, and stirring the mixture at room temperature for reaction for 2 hours to obtain uniform super-hydrophobic SiO2And (3) suspension. Then centrifuging at 10000 rpm for 10 min to collect precipitate, and drying at 60 deg.C for 6 h to obtain super-hydrophobic SiO2(ii) a Secondly, adding super-hydrophobic SiO2Mixing the powder with carbon powder in a mass ratio of 1:1 and 5.0 g of polystyrene, ball-milling for 24 hours to obtain uniform super-hydrophobic carbon powder, further sieving the super-hydrophobic carbon powder by a 300-mesh sieve, weighing 50 g of the super-hydrophobic carbon powder, filling the super-hydrophobic carbon powder into a selenium drum of a laser printer, and printing a computer-designed pattern on common printing paper by laser printing to obtain the patternAnd (3) a super-hydrophobic coating.
Measuring a contact angle and a rolling angle by using 5 muL water drops: water contact angle =166 °, roll angle =5 °.
Example 2
Weighing 15.0 g of attapulgite, adding into a 1000 mL wide-mouth bottle, respectively weighing 660 mL of isopropanol, 60 mL of hydrochloric acid and 30 mL of deionized water, magnetically stirring for 10 min, and ultrasonically treating with a cell crusher for 3 min. Then 4.0 mL of aminopropyltriethoxysilane and 12.0 mL of perfluorooctyltriethoxysilane were measured and added to a jar, and the mixture was stirred at room temperature for 2 hours to obtain a homogeneous super-hydrophobic attapulgite suspension. Centrifuging at 8000 rpm for 15 min, collecting precipitate, and drying at 80 deg.C for 5 hr to obtain super-hydrophobic attapulgite; secondly, mixing and ball-milling 4.0 g of polybutyl acrylate powder and 3:1 by mass ratio of super-hydrophobic attapulgite and carbon powder for 36 hours to obtain uniform super-hydrophobic carbon powder, further sieving the super-hydrophobic carbon powder by a 300-mesh sieve, weighing 50 g of the super-hydrophobic carbon powder, filling the powder into a selenium drum of a laser printer, and then printing a pattern designed by a computer on common printing paper by laser printing to obtain a super-hydrophobic coating.
Measuring a contact angle and a rolling angle by using 5 muL water drops: water contact angle =155 °, roll angle =7 °.
Example 3
Weighing 10.0 g of halloysite, adding into a 1000 mL wide-mouth bottle, respectively weighing 440 mL of methanol, 40 mL of acetic acid and 20 mL of deionized water, magnetically stirring for 10 min, and ultrasonically treating for 3 min by using a cell crusher. Then 3.0 mL of gamma-glycidoxypropyltrimethoxysilane and 8.0 mL of perfluorodecyltrichlorosilane were measured and added to a wide-mouth bottle and stirred at room temperature for 2 hours to obtain a uniform super-hydrophobic halloysite suspension. Centrifuging at 9000 rpm for 12 min to collect precipitate, and drying at 70 deg.C for 6 hr to obtain superhydrophobic halloysite; secondly, mixing and ball-milling the super-hydrophobic halloysite and carbon powder in a mass ratio of 1:3 for 30 h to obtain uniform super-hydrophobic carbon powder, further sieving the super-hydrophobic carbon powder by a 300-mesh sieve, weighing 50 g of the super-hydrophobic carbon powder, filling the powder into a selenium drum of a laser printer, and then printing a computer-designed pattern on common printing paper by laser printing to obtain the super-hydrophobic coating.
Measuring a contact angle and a rolling angle by using 5 muL water drops: water contact angle =156 °, roll angle =10 °.
Example 4
Weighing 12.0 g of sepiolite, adding into a 1000 mL wide-mouth bottle, respectively weighing 520 mL of ethylene glycol, 50 mL of ammonia water and 30 mL of deionized water, magnetically stirring for 10 min, and ultrasonically treating for 3 min by using a cell crusher. Then 4.0 mL of methyltriethoxysilane and 10.0 mL of perfluorodecyltriethoxysilane were measured and added to a jar, and the reaction was stirred at room temperature for 2 hours to obtain a homogeneous suspension of super-hydrophobic sepiolite. Centrifuging at 10000 rpm for 10 min, collecting precipitate, and drying at 100 deg.C for 4 hr to obtain super-hydrophobic sepiolite; secondly, mixing and ball-milling 10.0 g of poly-n-hexyl acrylate powder and 1:1 by mass ratio of the super-hydrophobic sepiolite to the carbon powder for 16 h to obtain uniform super-hydrophobic carbon powder, further sieving the super-hydrophobic carbon powder by a 300-mesh sieve, weighing 50 g of the super-hydrophobic carbon powder, filling the super-hydrophobic carbon powder into a selenium drum of a laser printer, and printing a pattern designed by a computer on common printing paper by laser printing to obtain the super-hydrophobic coating.
Measuring a contact angle and a rolling angle by using 5 muL water drops: water contact angle =158 °, roll angle =8 °.
Claims (6)
1. A method for preparing a super-hydrophobic coating by laser printing comprises the steps of firstly preparing a super-hydrophobic nano compound by carrying out hydrolysis and condensation reaction on organosilane and nano particles; then mixing and ball-milling the super-hydrophobic nano composite, the resin and the carbon powder to obtain uniform super-hydrophobic carbon powder; then loading the super-hydrophobic carbon powder into a selenium drum of a laser printer, and printing the super-hydrophobic carbon powder on common printing paper by the laser printer to obtain a super-hydrophobic coating;
preparing a super-hydrophobic nano composite: adding a catalyst, water, organosilane and nanoparticles into an alcohol solvent, and stirring and reacting at 25-100 ℃ for 1-72 hours; centrifuging and drying after the reaction is finished to obtain the product;
the resin is at least one of polystyrene, polybutyl acrylate, polyethyl acrylate, poly-n-hexyl acrylate, poly-2-ethylhexyl acrylate, polylauryl acrylate, polymethyl methacrylate, polyethyl methacrylate, poly-n-butyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate and poly-n-hexyl methacrylate;
in the preparation of the super-hydrophobic carbon powder, the mass ratio of the super-hydrophobic nano composite to the carbon powder is 1: 5-1: 0.2, and the mass ratio of the super-hydrophobic nano composite to the resin is 1: 0.05-1: 0.5; the mixing and ball milling time is 2-36 h;
when the laser printer prints, the super-hydrophobic carbon powder is printed on the common printing paper according to the designed pattern.
2. The method for preparing the super-hydrophobic coating by laser printing as claimed in claim 1, wherein: the organosilane is at least one of perfluorooctyltrichlorosilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorodecyltrichlorosilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyldimethylchlorosilane, perfluorooctyldimethylmethoxysilane, perfluorodecyldimethylchlorosilane, perfluorodecyldimethylmethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane and hexadecyltrimethoxysilane.
3. The method for preparing the super-hydrophobic coating by laser printing as claimed in claim 1, wherein: the nano particles are at least one of carbon nano tubes, graphene oxide, silicon dioxide, titanium dioxide, zinc oxide, nano silver, montmorillonite, attapulgite, sepiolite, halloysite, hydrotalcite, vermiculite, mica, kaolinite, hectorite, bacterial cellulose, polystyrene and polytetrafluoroethylene.
4. The method for preparing the super-hydrophobic coating by laser printing as claimed in claim 1, wherein: the mass ratio of the organosilane to the nanoparticles is 1: 1-1: 50.
5. The method for preparing the super-hydrophobic coating by laser printing as claimed in claim 1, wherein: the catalyst is at least one of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, benzenesulfonic acid, ammonia water, ethylenediamine, triethylamine and butylamine, and the addition amount of the catalyst is 1-200 times of the mass of the organosilane.
6. The method for preparing the super-hydrophobic coating by laser printing as claimed in claim 1, wherein: the alcohol solvent is at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, and glycerol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910082352.9A CN109811586B (en) | 2019-01-28 | 2019-01-28 | Method for preparing super-hydrophobic coating by laser printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910082352.9A CN109811586B (en) | 2019-01-28 | 2019-01-28 | Method for preparing super-hydrophobic coating by laser printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109811586A CN109811586A (en) | 2019-05-28 |
| CN109811586B true CN109811586B (en) | 2021-07-13 |
Family
ID=66605572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910082352.9A Active CN109811586B (en) | 2019-01-28 | 2019-01-28 | Method for preparing super-hydrophobic coating by laser printing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109811586B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113338047A (en) * | 2021-05-25 | 2021-09-03 | 青岛大学 | TiO on surface of cotton fabric2-BC/PDMS hydrophobic coating and preparation method thereof |
| CN113457954B (en) * | 2021-07-14 | 2022-07-12 | 宁波齐云新材料技术有限公司 | System and method for processing super-hydrophobic surface by laser |
| SE545404C2 (en) | 2022-06-22 | 2023-08-01 | Organograph Ab | An electron conducting coating |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789124A (en) * | 2014-12-30 | 2015-07-22 | 中国科学院兰州化学物理研究所 | A preparing method of a stable superamphiphobic surface |
| CN105440888A (en) * | 2015-12-17 | 2016-03-30 | 中国科学院兰州化学物理研究所 | Preparation method of stable superhydrophobic hot liquid coating |
| CN106394044A (en) * | 2015-08-12 | 2017-02-15 | 北京天合映像科技有限公司 | Laser printing method and laser printing film |
| CN106752133A (en) * | 2016-12-07 | 2017-05-31 | 上海交通大学 | The super-hydrophobic coat prepared using Graphene three-dimensional aggregates and its synthetic method and application |
| CN106800885A (en) * | 2016-12-21 | 2017-06-06 | 中国科学院兰州化学物理研究所 | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating |
| CN107315328A (en) * | 2017-08-07 | 2017-11-03 | 湖北远东卓越科技股份有限公司 | A kind of magnetic carbon powder and preparation method thereof |
| CN108912873A (en) * | 2017-04-13 | 2018-11-30 | 江苏华信新材料股份有限公司 | A kind of adaptation ink-jet and the multifunctional membrane coating fluid of laser printing and preparation method thereof |
-
2019
- 2019-01-28 CN CN201910082352.9A patent/CN109811586B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789124A (en) * | 2014-12-30 | 2015-07-22 | 中国科学院兰州化学物理研究所 | A preparing method of a stable superamphiphobic surface |
| CN106394044A (en) * | 2015-08-12 | 2017-02-15 | 北京天合映像科技有限公司 | Laser printing method and laser printing film |
| CN105440888A (en) * | 2015-12-17 | 2016-03-30 | 中国科学院兰州化学物理研究所 | Preparation method of stable superhydrophobic hot liquid coating |
| CN106752133A (en) * | 2016-12-07 | 2017-05-31 | 上海交通大学 | The super-hydrophobic coat prepared using Graphene three-dimensional aggregates and its synthetic method and application |
| CN106800885A (en) * | 2016-12-21 | 2017-06-06 | 中国科学院兰州化学物理研究所 | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating |
| CN108912873A (en) * | 2017-04-13 | 2018-11-30 | 江苏华信新材料股份有限公司 | A kind of adaptation ink-jet and the multifunctional membrane coating fluid of laser printing and preparation method thereof |
| CN107315328A (en) * | 2017-08-07 | 2017-11-03 | 湖北远东卓越科技股份有限公司 | A kind of magnetic carbon powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109811586A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109811586B (en) | Method for preparing super-hydrophobic coating by laser printing | |
| CN111019482B (en) | Preparation and application of super-hydrophobic/oleophobic coating with excellent performance | |
| CN106862039B (en) | Durable hydrophilic-super-hydrophobic bipolar self-cleaning composite membrane and preparation method thereof | |
| Chujo | Organic—inorganic hybrid materials | |
| CN108587447B (en) | Preparation method of durable transparent super-hydrophobic coating suitable for various substrates | |
| CN106800885A (en) | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating | |
| CN105694711B (en) | A kind of ultra-smooth self-cleaning coat and preparation method thereof | |
| KR101724603B1 (en) | Hollow silica particles, method of manufacturing the same, composition including the same and sheet with inner cavities | |
| CN104910656B (en) | A kind of method that super-hydrophobic silica powder and super-hydrophobic coat are prepared with compound silicon source | |
| CN110205025B (en) | Super-hydrophilic coating taking organic polysilazane as anchor molecule and preparation method thereof | |
| CN104789124A (en) | A preparing method of a stable superamphiphobic surface | |
| CN113372814B (en) | Cage-shaped polysilsesquioxane-based super-hydrophilic functional coating and preparation method thereof | |
| CN108912754A (en) | A kind of super-hydrophobic SiO2The preparation method and application of nano functional liquid | |
| CN114133772A (en) | Durable super-amphiphobic thin film material with gradient structure and preparation method thereof | |
| CN107088366A (en) | A kind of method for preparing organic-inorganic nanocomposite film | |
| CN113881323A (en) | Preparation method and application of super-hydrophobic coating | |
| CN113578706B (en) | Method for preparing corrosion-resistant composite coating by using layer-by-layer self-assembly technology | |
| CN115216170A (en) | Water-based epoxy resin anticorrosive paint and preparation method thereof | |
| CN107059469A (en) | A kind of super-hydrophobic/superoleophobic paper and preparation method thereof | |
| CN106700662A (en) | Preparation method of acid-base-resistant anticorrosive aluminum pigment | |
| Guo et al. | Research progress on titanium-containing organic–inorganic hybrid protective coatings | |
| CN113823467A (en) | Anti-pollution flashover porcelain insulator and preparation method thereof | |
| CN114350261A (en) | Durable multifunctional bionic super-hydrophobic coating and preparation method thereof | |
| JP7317203B2 (en) | SELF-HEALING OR REPEATABLE PRODUCTS, PRODUCTION METHOD AND APPLICATION THEREOF | |
| CN111978514B (en) | Preparation method of high-temperature-resistant nonionic waterborne epoxy curing agent emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |