CN111471214B - Method for recycling epoxy molding compound waste - Google Patents
Method for recycling epoxy molding compound waste Download PDFInfo
- Publication number
- CN111471214B CN111471214B CN201910189349.7A CN201910189349A CN111471214B CN 111471214 B CN111471214 B CN 111471214B CN 201910189349 A CN201910189349 A CN 201910189349A CN 111471214 B CN111471214 B CN 111471214B
- Authority
- CN
- China
- Prior art keywords
- molding compound
- epoxy molding
- compound waste
- waste
- epoxy
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention provides a method for recycling epoxy molding compound waste. The method of the invention extracts the silicon dioxide filler by removing the epoxy resin in the epoxy molding compound waste. The silica filler extracted by the present process can be used to reinforce polymers. The process of the present invention also includes thermally processing the extracted silica filler to produce a polymer composite, also referred to as a filled polymer. The method of the invention is efficient and does not produce any toxic substances harmful to the environment.
Description
Technical Field
The present invention relates to a method of recycling molded packaging materials, and more particularly to a method of recycling thermoset materials such as epoxy molding compounds from electronic packaging waste.
Background
Epoxy molding compounds are widely used as packaging materials in integrated circuits and semiconductors due to their high mechanical strength, excellent thermal and moisture insulation capabilities, and low manufacturing cost. Epoxy molding compounds are used in almost all electronic devices and products, including cell phones, personal computers, digital cameras, video game consoles, household appliances, and the like. The range of applications of epoxy molding compounds is expanding year by year. In semiconductors, epoxy molding compounds are used to protect semiconductor chips from external damage, such as external physical impact and pressure, moisture, heat, or ultraviolet light, and to maintain electrical insulation properties and to facilitate the mounting of packages on printed circuit boards.
The epoxy molding compound consists of about 70% silica filler and about 10% epoxy resin; additives such as hardener resins, colorants, flame retardants and coupling agents constitute the remaining components thereof. The epoxy resin is a cured crosslinked structure and is hardly melted by heating or dissolved by a solvent. Therefore, it is very difficult to remove the epoxy resin from the epoxy molding compound, and many of the epoxy molding compounds are simply thrown into a landfill or incinerated at a very high temperature.
Attempts have been made to extract the silica filler, the major component of epoxy molding compounds, by various thermal cracking methods and to use it for the preparation of polymer composites. The extraction operation requires the isolation of the thermosetting epoxy resin fused with the inorganic silica filler. These epoxy resins are crosslinked and therefore cannot be fluidized or separated directly by conventional heat treatment methods. Extremely high temperatures above 600 ℃ are required to decompose the epoxy resin or disrupt the crosslinked network. Thus, the existing epoxy molding compound recycling methods are time consuming, cost inefficient and difficult to perform. The existing epoxy molding compound recycling method also generates harmful toxic substances. In view of the large amount of epoxy molding compound waste entering a landfill, and the reuse value of the silica filler in the epoxy molding compound waste, there is a need to provide an improved method for recycling the epoxy molding compound waste and converting it into a reusable material.
Disclosure of Invention
The invention provides a method for recycling epoxy molding compound waste. The method extracts the silicon dioxide filler by removing the epoxy resin in the epoxy molding compound waste material. According to the present invention, epoxy resin is removed from epoxy molding compound waste by a supercritical solvolysis decrosslinking process at a specific temperature and pressure. The silica filler extracted by the process of the invention can be used to reinforce other polymers and to produce polymer composites by thermal processing. The method of the invention is efficient and does not produce any toxic substances harmful to the environment.
Drawings
FIG. 1 is an SEM image of cleaned and broken epoxy molding compound waste (left) and modified epoxy molding compound according to the present invention.
Detailed Description
The present invention provides methods for recycling epoxy molding compound waste and producing polymer composites. The method comprises (1) cleaning waste epoxy molding compound; (2) crushing the waste epoxy molding compound; (3) modifying the epoxy molding compound waste to remove epoxy resin and extracting silica filler from the epoxy molding compound waste; (4) the extracted silica filler is thermally processed to produce a polymer composite. The epoxy molding compound waste of the present invention refers to epoxy molding compounds present in discarded electronic devices including, but not limited to, mobile phones, personal computers, digital cameras, home appliances, and the like.
Step (1) -cleaning waste epoxy molding compound
Epoxy molding compound waste is cleaned to ensure removal of contaminants such as soil, paper, metal residues. Physical separation techniques known in the art may be employed in this step. Solid contaminants can be removed from the epoxy molding compound waste by ultrasonic water bath plus detergent or by adding salt to the water bath to separate solid impurities from the epoxy molding compound based on density differences. Filters and screens with appropriate pore sizes are used to separate solid contaminants of different sizes. Epoxy molding compound waste may have few contaminants but negligible impact on the quality of the final recycled product. The cleaned epoxy molding compound waste is dried in an oven (e.g., above 80 ℃) for the next recycling process. The epoxy molding compound in the step can effectively remove most pollutants in the waste epoxy molding compound so as to obtain a high-quality recycled material.
Step (2) -crushing the waste epoxy molding compound
After the epoxy molding compound waste is cleaned and dried, the epoxy molding compound waste is crushed or ground to a suitable size for the subsequent modification step. It is important to break the epoxy molding compound to the proper size to achieve effective modification of the epoxy molding compound waste. In one embodiment, the epoxy molding compound waste is shredded into powder form. The epoxy molding compound may be crushed to the appropriate size by physical methods known in the art. For example, a plastic crusher may be used. In one embodiment, the epoxy molding compound waste is crushed to an average particle size of 20 to 200 mesh.
Step (3) -modification of epoxy molding compound waste
The modification step removes the epoxy resin from the epoxy molding compound waste and extracts the useful silica filler. The clean and broken waste epoxy molding compound is subjected to subcritical/supercritical fluid reaction. The sub/supercritical fluid reaction state is achieved in a sealed autoclave reactor by the selected solvents, additives, temperature and pressure. The sub/supercritical fluid state destroys the cross-linked structure of the thermosetting component in the epoxy molding compound waste. In one embodiment, the temperature of the sub/supercritical fluid state is from 100 ℃ to 300 ℃; the pressure is from 10 bar to 150 bar. In one embodiment, the reaction medium of the modification step may be recycled and reused. For example, any residue or precipitate at the end of the modification step may be filtered or distilled to recover the reaction medium (i.e., solvent). The reaction medium may be methanol, ethanol, isopropanol, and acetone, or a combination thereof. Additives include, but are not limited to, KH-550, KH-560, KH-570, and KH-590. The precipitate at the end of the modification reaction is silica filler extracted from the epoxy molding compound waste, which is then subjected to subsequent manufacturing steps to yield other useful products. In one embodiment, the silica filler is cleaned and dried into a useful polymer composite prior to subsequent manufacturing steps.
Step (4) -Heat treatment of silica Filler recovered from epoxy Molding Compound waste
Silica fillers recovered from epoxy molding compound waste are thermally processed to produce useful materials, such as polymer composites. In one embodiment, the silica filler is thermally compounded with the thermoplastic for reinforcement. In one embodiment, other additives may be added to the extracted silica filler to produce the desired polymer composite.
Examples
Example 1
The epoxy molding compound waste was cleaned with a mixture of deionized water, ethanol and detergent in an ultrasonic bath at 20 ℃ for 20 minutes. And separating large solid pollutants from the epoxy molding compound waste by using a sieve with the size of 10 mm. The cleaned epoxy molding compound waste was dried in an oven at 60 ℃ for 2 hours and comminuted by means of a plastics shredder to 100-mesh particles.
Example 2
In a 500ml autoclave reactor, 18g of the disintegrated epoxy molding compound were charged with 110ml of ethanol solvent. The reactor was then sealed and heated to 260 ℃ for 0.5 hour with the internal pressure stabilized at around 78 bar. The reactor was then cooled to room temperature, taking about 10 minutes. The modified epoxy molding material was cleaned with ethanol and acetone and then dried at 60 ℃ for 12 hours.
Example 3
In a 500ml autoclave reactor, 30g of the clean epoxy molding material were charged and 100ml of ethanol solvent were charged. The reactor was sealed and heated to 260 ℃ for 0.5 hour, the internal pressure also stabilized at around 78 bar. Then, the reactor was gradually cooled, taking about 10 minutes. The modified epoxy molding material was cleaned with ethanol and acetone and then dried at 60 ℃ for 12 hours.
Example 4
In a 500ml autoclave reactor, 30g of the clean epoxy molding material were charged and 100ml of ethanol solvent were charged. The reactor was sealed and heated to 160 ℃ for 0.5 hour, the internal pressure also being stabilized at around 78 bar. Then, the reactor was gradually cooled, and it took about 10 min. The modified epoxy molding material was cleaned with ethanol and acetone and then completely dried at 60 ℃ for 12 hours.
Example 5
In a 500ml autoclave reactor, 16g of the clean epoxy molding material were charged and 100ml of ethanol solvent were charged. The reactor was sealed and heated to 260 ℃ for 0.5 hour, the internal pressure also stabilized at around 78 bar. Then, the reactor was gradually cooled, taking about 10 minutes. The modified epoxy molding material was cleaned with ethanol and acetone and then dried at 60 ℃ for 12 hours.
Example 6 (existing method 1)
To compare the present invention with existing recycling methods, the epoxy molding compound waste is continuously heated and refluxed in an organic solvent at atmospheric pressure. In a 250ml round-bottom flask, 9g of crushed epoxy molding compound were added and 90ml of ethanol were charged. The solution was heated to about 60 ℃ with continuous stirring. The epoxy molding compound is modified for about 5 hours and a silane additive such as KH-550 may be added. The flask was then cooled to ambient temperature and the modified epoxy molding compound was washed with deionized water, ethanol and acetone and then dried at 60 ℃ for 12 hours.
Example 7 (existing method 2)
In order to compare the present invention with the existing recycling method, the waste epoxy molding compound is also recycled by glycolysis (glycolysis) of the waste epoxy molding compound in polyethylene glycol (PEG) solvent. This was done at atmospheric pressure with continuous reflux and stirring. In a 250ml round bottom flask, 4g of crushed epoxy molding compound was added and charged with 40ml of PEG-200. The round bottom flask was heated to about 160 ℃ with continuous stirring and reflux. The reaction was continued for 4 hours. The flask was then cooled to ambient temperature. The modified epoxy molding material was washed with deionized water, ethanol and acetone and then dried at 60 ℃ for 12 hours.
Table 1 below summarizes the reaction conditions of examples 2-5 and examples 6-7 (existing recovery methods) according to the present invention
TABLE 1
The broken epoxy molding compounds and the modified epoxy molding compounds (i.e.the uncrosslinked epoxy molding compound scrap) were characterized by Scanning Electron Microscopy (SEM). Fig. 1 clearly reveals that the thermosetting epoxy resin in the epoxy molding compound waste is significantly removed by the sub/supercritical fluid solvolysis reaction of the present invention. The modified epoxy molding compound waste can be reused as a substitute for pure silica for the manufacture of polymer composites. In the modified epoxy molding compound, the crosslinking of the epoxy resin is broken, so that the epoxy resin in the epoxy molding compound waste can be easily removed to obtain the silica filler.
The silica filler recovered by the process of the invention is useful for compounding with other polymers for reinforcement. The recycled silica filler may be thermally compounded with a thermoplastic, such as High Density Polyethylene (HDPE), to produce a polymer composite. In one embodiment, the manufacturing process involves thermal compounding by a twin screw extruder at 160 ℃ and a screw speed of 50rpm, followed by injection molding to formulate a product having a specific shape. Additives such as polyethylene wax or PE-g-MA may be incorporated to facilitate compounding. The thermal properties of the samples prepared with the epoxy molding compound/HDPE composite are set forth in Table 2.
TABLE 2 thermal Properties of the recycled epoxy Molding Compound/HDPE composite (fixed content of epoxy Molding Compound waste)
10％）
| Thermal performance | Virgin HDPE | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Melting Point (. degree.C.) | 133.07 | 129.98 | 130.14 | 129.45 | 129.37 | 129.71 | 128.04 |
| Heat of fusion (J/g) | 196.40 | 88.97 | 97.95 | 71.16 | 171.3 | 63.32 | 133.5 |
| Decomposition temperature (. degree.C.) | 472.42 | 482.84 | 465.92 | 475.23 | 476.88 | 477.09 | 485.90 |
The tensile properties of the recycled epoxy molding compound composites made by injection molding techniques were tested according to ASTM D638. As is clear from table 3 below, the recycled epoxy molding compound/HDPE composite of example 3 has a significantly improved tensile strength compared to virgin HDPE, despite a reduced elongation at break. However, for comparative example 6, both tensile strength and elongation at break were much lower compared to the polymer composite of the invention (example 3) and virgin HDPE. These results further demonstrate that the epoxy molding compound recovery process of the present invention is capable of producing better quality recycled silica fillers than conventional recovery processes (e.g., addition of coupling agents or glycolysis reaction at atmospheric pressure).
TABLE 3 tensile Properties of virgin HDPE and recycled epoxy Molding Compound/HDPE composites
| Tensile Properties | Virgin HDPE | Example 3 | Comparative example 6 |
| Tensile Strength (MPa) | 23.36 | 25.32 | 20.85 |
| Elongation at Break (%) | >800 | 250 | 115 |
It should be apparent to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the present disclosure. Moreover, in interpreting the disclosure, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms "comprises" and "comprising" should be interpreted as referring to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced.
The publication:
Xu, W. J., & Lu, S. Y. (2010). Recycling of waste cured epoxy molding compound as a filler in poly (vinyl chloride) composites. 2010 International Conference on Chemistry and Chemical Engineering.
Lu, W. J. (2011). Recycling of Thermosetting Epoxy Molding Compound Waste into PVC Composites: Effect of Silane Coupling Agent on Morphology and Physical Properties. Advanced Materials Research, 311-313, 1496-1500.
Christelle Morin, A. L.-S. (2012). Near- and supercritical solvolysis of carbon fibre reinforced polymers (CFRPs) for recycling carbon fibers as a valuable resource: State of the art. The Journal of Supercritical Fluids(66), 232-240.
CN 102744827A-production process for recovering waste epoxy molding compound by physical blending method.
CN 103522450A-production process of waste epoxy molding compound recovered from polypropylene.
US7851514B2–Process for producing regenerated resin, regenerated resin, processing recovered matter from resin composition, regenerated resin composition and method of regenerating resin composition.
Claims (10)
1. A method for recycling epoxy molding compound waste, the method comprising:
cleaning the epoxy molding compound waste to remove any contaminants;
crushing the epoxy molding compound waste material to a suitable particle size;
decrosslinking the epoxy molding compound waste by a solvent dissociation reaction in a sub/supercritical fluid state, the solvent being selected from methanol, ethanol, isopropanol, acetone or mixtures thereof, the ratio of mass of the epoxy molding compound waste to volume of solvent being 0.05 to 0.5;
thermally compounding the uncrosslinked epoxy molding compound waste with a thermoplastic.
2. The method of claim 1, wherein the epoxy molding compound waste is cleaned using one or more solvents selected from the group consisting of water, methanol, ethanol, isopropanol, acetone, or combinations thereof.
3. The method of claim 1, wherein the epoxy molding compound waste is cleaned at a temperature of 20 ℃ to 80 ℃.
4. The method of claim 1, wherein the suitable particle size of the epoxy molding compound waste is 20 mesh to 200 mesh.
5. The method of claim 1, wherein the sub/supercritical fluid state has a predetermined ratio of temperature, pressure, reaction solvent, additive, and epoxy molding compound mass to solvent volume.
6. The method of claim 1, wherein the thermal compounding step is selected from extrusion, injection molding, compression molding, or a combination thereof.
7. The method of claim 5, wherein the predetermined temperature is 100 ℃ to 300 ℃.
8. The method of claim 5, wherein the predetermined pressure is in the range of 10 bar to 150 bar.
9. The method according to claim 5, wherein the additive is a silane coupling agent, wherein the silane coupling agent is selected from the group consisting of KH-550, KH-560, KH-570, KH-590, or mixtures thereof.
10. The method of claim 1, further comprising removing epoxy resin from the uncrosslinked epoxy molding compound waste.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201962795567P | 2019-01-23 | 2019-01-23 | |
| US62/795567 | 2019-01-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111471214A CN111471214A (en) | 2020-07-31 |
| CN111471214B true CN111471214B (en) | 2022-07-29 |
Family
ID=71744829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910189349.7A Active CN111471214B (en) | 2019-01-23 | 2019-03-13 | Method for recycling epoxy molding compound waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111471214B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181071A (en) * | 2011-04-22 | 2011-09-14 | 中国科学院宁波材料技术与工程研究所 | Method for reclaiming carbon fiber reinforced epoxy resin composite material |
| CN103415561A (en) * | 2011-03-08 | 2013-11-27 | 松下电器产业株式会社 | Epoxy resin hardened material and decomposition method for same |
| CN106496631A (en) * | 2016-11-03 | 2017-03-15 | 南京工程学院 | The method that overcritical fluid-mixing reclaims carbon fiber enhancement resin base composite material |
-
2019
- 2019-03-13 CN CN201910189349.7A patent/CN111471214B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103415561A (en) * | 2011-03-08 | 2013-11-27 | 松下电器产业株式会社 | Epoxy resin hardened material and decomposition method for same |
| CN102181071A (en) * | 2011-04-22 | 2011-09-14 | 中国科学院宁波材料技术与工程研究所 | Method for reclaiming carbon fiber reinforced epoxy resin composite material |
| CN106496631A (en) * | 2016-11-03 | 2017-03-15 | 南京工程学院 | The method that overcritical fluid-mixing reclaims carbon fiber enhancement resin base composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111471214A (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6500872B1 (en) | Method for recycling waste styrene resin | |
| ES2879933T3 (en) | Procedure for the treatment of waste containing synthetic materials | |
| US7435772B2 (en) | Method and apparatus for removing additives from thermoplastic resin composition | |
| CN111471214B (en) | Method for recycling epoxy molding compound waste | |
| JP2017136816A (en) | Method for reusing waste of polypropylene resin molded body | |
| JP4979753B2 (en) | Decomposition of thermosetting resin and recovery method of decomposition product | |
| JP2004042461A (en) | Separation method for waste plastic material, and separating device for waste plastic material | |
| WO2001021694A1 (en) | Method of treating thermoplastic resin composition containing flame retardant | |
| JP5669072B2 (en) | Molded body for laying | |
| JP4350756B2 (en) | Processing device for thermoplastic resin composition containing additives | |
| KR100917856B1 (en) | Reproducing method of wast e.p.s | |
| JP4518153B2 (en) | Recycling method of waste polystyrene resin | |
| JP2004043648A (en) | Method and apparatus for separating plastic waste | |
| JP2006225409A (en) | Method for treating waste plastic containing flame retardant | |
| JP4400596B2 (en) | How to recycle alcohol | |
| JP2953412B2 (en) | Regeneration method of inorganic filler | |
| JP2004043649A (en) | Method and apparatus for separating plastic waste | |
| JP2005126669A (en) | Method for recycling plastic, treated and recovered plastic, thermosetting resin-forming material and recycled plastic | |
| JP2004359880A (en) | Method for extracting plasticizer from flexible polyvinyl chloride resin moldings | |
| JP2004148787A (en) | Thermoplastic resin composition containing additive and processing method thereof | |
| JP2005054137A (en) | Flame retardant-removing device | |
| JP2005314462A (en) | Apparatus for removing flame retardant | |
| JP2005238463A (en) | Fire retardant separating method | |
| JP2005307105A (en) | Apparatus for removing flame retardant | |
| JP2003305722A (en) | Method for highly purifying resin |
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 |