CN110054889B - Flame-retardant bio-based PA56 composite material and preparation method thereof - Google Patents
Flame-retardant bio-based PA56 composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110054889B CN110054889B CN201810050126.8A CN201810050126A CN110054889B CN 110054889 B CN110054889 B CN 110054889B CN 201810050126 A CN201810050126 A CN 201810050126A CN 110054889 B CN110054889 B CN 110054889B
- Authority
- CN
- China
- Prior art keywords
- bio
- flame
- composite material
- flame retardant
- retardant
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a flame-retardant bio-based PA56 composite material and a preparation method thereof, wherein the flame-retardant bio-based PA56 composite material comprises 100 parts of bio-based PA56, 5-10 parts of long-chain bio-based PA510, 3-5 parts of a compatibilizer, 10-25 parts of a flame retardant, 3-5 parts of a flame-retardant synergist and 10-30 parts of a reinforcing agent. The flame-retardant bio-based PA56 composite material has high relative tracking index and glow wire temperature, and also has good mechanical properties.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a flame-retardant bio-based PA56 composite material and a preparation method thereof.
Background
Polyamides are often used in automobile parts, parts of electric and electronic equipment, and other many applications because of their excellent mechanical properties and moldability. The polyamide has good flame retardance, belongs to a self-extinguishing material, has good electrical insulation performance (comparative tracking index CTI 600), and is widely applied to electronic and electrical equipment. In electronic and electrical appliance applications, in order to maintain better mechanical properties and flame retardance, glass fibers are generally added into a polyamide matrix for reinforcement modification and a halogen flame retardant is used, based on the premise of meeting ROHS & Reach instruction requirements, the halogen flame retardant is a halogen polymer, generally Brominated Polystyrene (BPS), and compared with phosphorus flame retardants and nitrogen flame retardants, the brominated polystyrene enables a polyamide composite material to have excellent mechanical properties, but due to the addition of the glass fibers and the use of the BPS, the relative electric leakage tracking index and glow wire temperature of the material are reduced. In addition, in these electric and electronic parts, requirements for glow wire properties and arc tracking resistance, as represented by the european IEC specification, are increasing. In particular, with regard to connector parts, the required level of Glow Wire Ignition Temperature (GWIT) in the IEC 60695-2-13 specification has recently been revised from 725 ℃ or higher to 775 ℃ or higher, and sometimes the relative tracking index (CTI) is required to be more than 400V, so that it is necessary to consider a polyamide material that achieves both a high relative tracking index and a high glow wire temperature, as well as good mechanical properties.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the flame-retardant bio-based PA56 composite material with high relative tracking index, high glow wire temperature and good mechanical property, and renewable energy is used as a production raw material, so that the environment is protected.
In order to achieve the above purpose, the solution of the invention is as follows:
a flame retardant bio-based PA56 composite, comprising: bio-based PA56, long-chain bio-based PA510, a compatibilizer, a flame retardant synergist and a reinforcing agent.
In a preferred embodiment of the invention, the relative viscosity of the bio-based PA56 is 2.0-4.0, and the mass part is as follows: 100 parts.
In a preferred embodiment of the present invention, the long-chain bio-based PA510 has a relative viscosity of 2.9, parts by mass: 5-10 parts.
In a preferred embodiment of the invention, the compatibilizer is maleic anhydride grafted polyolefin elastomer MAH-g-POE, and the mass parts are as follows: 3-5 parts.
In a preferred embodiment of the invention, the flame retardant is brominated polystyrene, and the mass parts are as follows: 10-25 parts.
In a preferred embodiment of the invention, the flame-retardant synergist is antimony trioxide, and the mass portion is as follows: 3-5 parts.
In a preferred embodiment of the invention, the reinforcing agent is alkali-free glass fiber, and the mass parts are as follows: 10-30 parts.
In a preferred embodiment of the invention, the flame retardant bio-based PA56 composite material may further include other processing aids, which may be selected from any one or more of compatibilizers, antioxidants, lubricants, and dispersants.
The flame-retardant bio-based PA56 composite material has a Comparative Tracking Index (CTI) of 350-400V and a Glow Wire Ignition Temperature (GWIT) of 800-850 ℃.
The preparation method of the flame-retardant bio-based PA56 composite material comprises the following steps:
1) premixing at least raw material components of a bio-based PA56, a long-chain bio-based PA510, a compatibilizer, a flame retardant and a flame retardant synergist to obtain a first premix;
2) adding the first premix into a double-screw extruder from a main feeding port of the double-screw extruder and adding the reinforcing agent into the double-screw extruder from a side feeding port of the double-screw extruder respectively to obtain a second premix, wherein the length-diameter ratio of a screw of the double-screw extruder is 1:40, the rotating speed of the screw is 200-500 rpm, the temperature of each zone of the double-screw extruder is set to be 80 +/-10 ℃, 220 +/-15 ℃, 250 +/-5 ℃, 270 +/-10 ℃, 280 +/-5 ℃, 280 +/-10 ℃ and 275 +/-15 ℃ from the feeding port to a die orifice in sequence, and the temperature of the die orifice is 270 +/-10 ℃;
3) adding the second premix into a melt mixing machine for melt mixing, wherein the melt mixing temperature is 30-50 ℃ higher than the melting point of the bio-based PA56, and the melt mixing time is 0.25-5 minutes, so as to obtain a melt mixed material;
4) and extruding the molten and mixed material from a nozzle of a melting and mixing machine to obtain a strand material, wherein the temperature of the strand material is 230-350 ℃, then cooling the strand material in water, and cutting the cooled strand material in a granulator to obtain the flame-retardant bio-based PA56 composite material.
Among them, since the strands cannot be cut and rolled directly by a pelletizer, it is necessary to cool them to below the melting point of bio-based PA56 using cooling water.
Experiments show that the polyamide flame-retardant material has good mechanical properties while the relative tracking index and the high glow-wire temperature of the polyamide flame-retardant material can be improved by adding the long-chain polyamide and the maleic anhydride grafted polyolefin elastomer into the existing flame-retardant polyamide system for blending.
The invention has the beneficial effects that:
the invention provides a flame-retardant bio-based PA56 composite material which has high Comparative Tracking Index (CTI) and glow wire temperature and good mechanical properties.
Detailed Description
The invention provides a flame-retardant bio-based PA56 composite material and a preparation method thereof.
[ Bio-based PA56]
PA56 uses at least pentanediamine (biomass source) and adipic acid as production raw materials. Pentanediamines are made by biological fermentation (e.g., by decarboxylation of lysine under the action of a decarboxylase) and contain organic carbon of renewable origin that at least partially meets the ASTM D6866 standard. Specifically, the bio-based polyamide is bio-based PA56, the relative viscosity is 2.0-4.0 and is lower than 2.0, the mechanical property of the material is poor, the relative viscosity is higher than 4.0, the material is difficult to process and form by adopting the existing equipment, and the mass part of the bio-based PA56 is 100 parts.
[ Long-chain Bio-based PA510]
The relative viscosity of the long-chain bio-based PA510 is 2.0-4.0, and in order to obtain a good mixing effect, the ratio of the relative viscosity of the long-chain bio-based PA510 to the relative viscosity of the bio-based PA56 is 1.1: 1-1.3: 1 according to the principle that the equal relative viscosity is easier to disperse and mix.
[ compatibilizers ]
The compatibilizer was a maleic anhydride grafted polyolefin elastomer MAH-g-P0E available from Ningbo energy, Inc. (N406).
[ flame retardant ]
The flame retardant is brominated polystyrene which is purchased from Yabao company (HP-3010) in America, and the mass portion of the flame retardant is 10-25 parts.
[ flame retardant synergist ]
The flame-retardant synergist is antimony trioxide, which is purchased from Huaxinxing antimony Co., Ltd (environment-friendly, content is 99.50%).
[ enhancer ]
The reinforcing agent was alkali-free glass fiber, available from boulder corporation, china (568H).
The present invention will be further described with reference to the following specific examples.
< methods for characterizing Properties >
The following methods were used for performance characterization:
1. determination of the relative viscosity of the polyamides:
measured according to ISO 307.
2. Tensile strength:
measured according to ISO 527-2.
3. Impact strength:
the measurement was carried out according to ISO 180/1A.
4. Relative tracking index (CTI):
test pieces having a length of 100mm, a width of 100mm and a thickness of 3mm were prepared and measured by the method of IEC 60112.
5. Glow Wire (GWIT):
test pieces having a length of 80mm, a width of 80mm and a thickness of 3mm were prepared and measured by the method of IEC 60695-2-13.
6. And (3) testing vertical combustion performance:
test pieces having a length of 12.7mm, a width of 12.7mm and a thickness of 0.8mm were produced and tested in accordance with UL94 specification.
< raw materials for production >
The raw materials for the following examples were as follows:
bio-based PA 56: kaiser (Jinxiang) biomaterial, Inc., having a relative viscosity of 2.7(98 wt% concentrated sulfuric acid process);
long-chain bio-based PA 510: kaiser (Jinxiang) biomaterial, Inc., having a relative viscosity of 3.0(98 wt% concentrated sulfuric acid process);
maleic anhydride grafted polyolefin elastomer (MAH-g-POE): ningbo optical fiber Inc. (N406);
alkali-free glass fiber: china giant stone corporation (568H);
brominated Polystyrene (BPS): yabao corporation, USA (HP-3010);
antimony trioxide (Sb)2O3): huaxing antimony industries, Inc. of Lou bottom of Hunan province (environmental protection type, content is 99.50%).
The preparation method of the flame retardant bio-based PA56 composite material in the examples and the comparative examples comprises the following steps:
1) mixing biological group PA56, long-chain biological group PA510, maleic anhydride grafted polyolefin elastomer MAH-g-POE, brominated polystyrene BPS and antimony trioxide Sb2O3Premixing according to the mixture ratio of the table 1 to obtain a first premix;
2) adding the first premix into a double-screw extruder from a main feeding port of the double-screw extruder and adding alkali-free glass fibers into the double-screw extruder from a side feeding port of the double-screw extruder respectively to obtain a second premix, wherein the length-diameter ratio of a screw of the double-screw extruder is 1:40, the temperature of each zone is set from the feeding port to a die orifice to be 80 ℃, 220 ℃, 250 ℃, 270 ℃, 280 ℃, 275 ℃ and 270 ℃, the temperature of the die orifice is 270 ℃, kneading the first premix in the double-screw extruder (manufactured by Nanjing Kogyo chemical engineering plant complete set Co., Ltd., type SK-40) at the rotating speed of 480rpm to obtain a melt-kneaded mixture, and the time of melt-kneading is 4 minutes;
3) the melt-kneaded material was extruded from a nozzle of a melt kneader into strands, the strands were cooled to a temperature not higher than the melting point of bio-based PA56 using water as a cooling medium, the cooled strands were cut in a pelletizer to obtain a flame-retardant bio-based PA56 composite material, and then the mechanical properties and combustion properties of the flame-retardant bio-based PA56 composite material were measured, and the measurement results are shown in table 2.
The twin-screw extruder is one of melt kneaders, and kneading in the twin-screw extruder is a kneading process.
Table 1 addition ratio table
TABLE 2 Performance results Table
As shown in Table 2, compared with the comparative examples, the long-chain bio-based PA510 and the MAH-g-POE elastomer play a synergistic role in improving the Comparative Tracking Index (CTI) and the Glow Wire Ignition Temperature (GWIT) of the flame-retardant bio-based PA56 composite material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A flame-retardant bio-based PA56 composite material, characterized in that: the flame-retardant bio-based PA56 composite material comprises:
the compatibilizer is MAH-g-POE;
the flame retardant comprises brominated polystyrene.
2. The flame retardant bio-based PA56 composite material of claim 1, wherein: the relative viscosity of the bio-based PA56 is 2.0-4.0.
3. The flame retardant bio-based PA56 composite material of claim 1, wherein: the relative viscosity of the long-chain bio-based PA510 is 2.0-4.0.
4. The flame retardant bio-based PA56 composite material of claim 1, wherein: the flame retardant synergist comprises antimony trioxide.
5. The flame retardant bio-based PA56 composite material of claim 1, wherein: the reinforcing agent comprises alkali-free glass fibers.
6. The flame retardant bio-based PA56 composite material of claim 1, wherein: the flame-retardant bio-based PA56 composite material further comprises other processing aids;
the other processing aids are selected from any one or more of antioxidants, lubricants and dispersants.
7. A process for preparing a flame retardant bio-based PA56 composite according to any of claims 1-6, wherein: the method comprises the following steps:
1) premixing at least raw material components of a bio-based PA56, a long-chain bio-based PA510, a compatibilizer, a flame retardant and a flame retardant synergist to obtain a first premix;
2) adding the first premix into a double-screw extruder from a main feeding port of the double-screw extruder and adding the reinforcing agent into the double-screw extruder from a side feeding port of the double-screw extruder respectively to obtain a second premix, wherein the length-diameter ratio of a screw of the double-screw extruder is 1:40, the rotating speed of the screw is 200-500 rpm, the temperature of each area of the double-screw extruder is set to be 80 +/-10 ℃, 220 +/-15 ℃, 250 +/-5 ℃, 270 +/-10 ℃, 280 +/-5 ℃, 280 +/-10 ℃ and 275 +/-15 ℃ from the feeding port to a die orifice in sequence, and the temperature of the die orifice is 270 +/-10 ℃;
3) adding the second premix into a melt mixing machine for melt mixing, wherein the melt mixing temperature is 30-50 ℃ higher than the melting point of the bio-based PA56, and the melt mixing time is 0.25-5 minutes, so as to obtain a melt mixed material;
4) and extruding the molten and mixed material from a nozzle of a molten and mixed machine to obtain a strand material, wherein the temperature of the strand material is 230-350 ℃, then cooling the strand material in water, and cutting the cooled strand material in a granulator to obtain the flame-retardant bio-based PA56 composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810050126.8A CN110054889B (en) | 2018-01-18 | 2018-01-18 | Flame-retardant bio-based PA56 composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810050126.8A CN110054889B (en) | 2018-01-18 | 2018-01-18 | Flame-retardant bio-based PA56 composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110054889A CN110054889A (en) | 2019-07-26 |
| CN110054889B true CN110054889B (en) | 2021-09-07 |
Family
ID=67315211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810050126.8A Active CN110054889B (en) | 2018-01-18 | 2018-01-18 | Flame-retardant bio-based PA56 composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110054889B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117233B (en) * | 2019-12-31 | 2022-07-12 | 会通新材料(上海)有限公司 | Polyamide 56 composition resistant to corrosion of automobile coolant and preparation method and application thereof |
| CN113232384A (en) * | 2021-05-31 | 2021-08-10 | 上海凯赛生物技术股份有限公司 | Continuous long fiber reinforced thermoplastic composite board and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010031179A (en) * | 2008-07-30 | 2010-02-12 | Toray Ind Inc | Polyamide resin composition |
| JP5299051B2 (en) * | 2009-02-16 | 2013-09-25 | 三菱化学株式会社 | Conductive polyamide resin composition, process for producing conductive polyamide resin composition, injection-molded product and extrusion-molded product |
| CN102395626B (en) * | 2009-04-20 | 2013-07-24 | 三菱化学株式会社 | Conductive thermoplastic resin composition, conductive polyamide resin compositions, and conductive polyamide film |
| CN106883603B (en) * | 2017-02-24 | 2021-09-07 | 上海凯赛生物技术股份有限公司 | Antistatic reinforced flame-retardant polyamide composite material and preparation method thereof |
-
2018
- 2018-01-18 CN CN201810050126.8A patent/CN110054889B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110054889A (en) | 2019-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101649088B (en) | Halogen-free intumescent flame-retardant polypropylene/ethylene vinyl acetate cable material | |
| CN108587145B (en) | High-glow-wire high-CTI-value halogen-free flame-retardant glass fiber reinforced PA6 composite material and preparation method thereof | |
| CN101812202B (en) | Halogen-free low-smoke flame-retardant polypropylene/polyamide composite material and preparation method | |
| CN104194161A (en) | Precipitation resistant, toughening and flame-retardant polypropylene composite material and preparation method thereof | |
| CN103351525B (en) | A kind of high-glossiness flame-retardant polypropylene composite and preparation method thereof | |
| CN102604375A (en) | Low-cost high-flame-retardant reinforced polyamide and preparation method for same | |
| CN107541049B (en) | Graphene-continuous glass fiber reinforced halogen-free flame-retardant weather-resistant PPO/HIPS alloy material and preparation method thereof | |
| CN111484739A (en) | Flame-retardant reinforced polyamide composition and preparation method thereof | |
| CN110054889B (en) | Flame-retardant bio-based PA56 composite material and preparation method thereof | |
| CN108250606B (en) | Ultra-low temperature resistant ASA composite material and preparation method thereof | |
| CN109504078B (en) | Efficient enhanced halogen-free flame-retardant heat-conducting shading multifunctional master batch for direct injection molding of nylon resin and preparation method thereof | |
| CN112745642B (en) | Low-mold-fouling flame-retardant reinforced PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof | |
| KR100877392B1 (en) | Tube extrudable polyamide composition with a good flammability and long term heat stability | |
| CN108624008A (en) | A kind of flame-retardant enhanced PBT material and preparation method thereof | |
| CN110903642B (en) | Halogen-free flame-retardant resin and preparation method thereof | |
| CN104086971A (en) | High-flowability and flame-retardant polycarbonate and polystyrene composition and preparation method thereof | |
| CN112391024A (en) | Anti-cracking TPE sheath material for charging cable and preparation and application thereof | |
| CN103483689A (en) | Preparation method of modified polypropylene composite material | |
| CN110054890B (en) | Bio-based PA56 composite material with high flame retardance and preparation method thereof | |
| CN112552677B (en) | Modified nylon 66 composition and preparation method thereof | |
| CN109486154B (en) | Efficient halogen-free enhanced flame-retardant functional master batch for direct injection molding of PC-ABS (polycarbonate-acrylonitrile butadiene styrene) alloy and preparation method thereof | |
| CN114133691A (en) | Halogen-free flame-retardant antibacterial ABS material and preparation method thereof | |
| CN114106522A (en) | Brominated flame-retardant PBT (polybutylene terephthalate) material as well as preparation method and application thereof | |
| CN113563663A (en) | Fire-resistant low-smoke halogen-free soft material and preparation method thereof | |
| CN112029260A (en) | Fibrilia-reinforced PC/ABS composite material, and preparation method and application thereof |
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 | ||
| CB02 | Change of applicant information |
Address after: No.5 Building, 1690 Cailun Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CATHAY INDUSTRIAL BIOTECH Ltd. Address before: 200120 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 5 No. 1690 Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. |
|
| CB02 | Change of applicant information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191010 Address after: No.5 Building, 1690 Cailun Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CIBT USA Address before: 201203 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 5 No. 1690 Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210817 Address after: 201203 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 5 No. 1690 Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CIBT USA Applicant after: CATHAY (WUSU) BIOMATERIAL Co.,Ltd. Address before: No.5 Building, 1690 Cailun Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai, 200120 Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CIBT USA |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |