CN109181290B - Flame-retardant nylon/polyphenylene sulfide alloy material and preparation method and application thereof - Google Patents
Flame-retardant nylon/polyphenylene sulfide alloy material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109181290B CN109181290B CN201811160440.8A CN201811160440A CN109181290B CN 109181290 B CN109181290 B CN 109181290B CN 201811160440 A CN201811160440 A CN 201811160440A CN 109181290 B CN109181290 B CN 109181290B
- Authority
- CN
- China
- Prior art keywords
- parts
- polyphenylene sulfide
- flame
- alloy material
- retardant nylon
- 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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- 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 nylon/polyphenylene sulfide alloy material and a preparation method and application thereof, belonging to the technical field of new materials, wherein the flame-retardant nylon/polyphenylene sulfide alloy material comprises the following components in parts by weight: 32.5-49.8 parts of PA6 resin; 10-20 parts of PPS resin; 10-20 parts of graphene nanoplatelets; 20-30 parts of asphalt-based carbon fiber; 5-10 parts of diethyl aluminum phosphinate; 0.2-0.5 part of antioxidant; 0.2-1 part of lubricant; 1-2 parts of black master batch. The flame-retardant nylon/polyphenylene sulfide alloy material provided by the invention has high heat conductivity coefficient, and simultaneously keeps good mechanical properties, processability, flame retardance and low odor.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a flame-retardant nylon/polyphenylene sulfide alloy material and a preparation method and application thereof.
Background
The heat-conducting plastic has the high heat-conducting performance of metal and ceramic, simultaneously retains the advantages of common plastic in design, performance and cost, and is widely applied to the LED illumination industry. With the increasing power of LED lighting devices, heat dissipation has become an important factor affecting the service life of the LED lighting devices, and there is an urgent need to develop a heat-conductive polymer material with high reliability and excellent heat-conductive combination property.
In order to meet the requirements of LED lighting lamps on use safety, the flame retardant grade of plastic shell materials is generally required to reach UL94v-0 grade, and the current common practice is to add brominated flame retardants, antimony trioxide, red phosphorus and other flame retardants into the materials, wherein the brominated flame retardants may generate harmful substances when being combusted, and the brominated flame retardants may be released from the materials and enter ecological environment and food chain. The red phosphorus flame retardant has the problems of clearness and large odor in the processing process.
Disclosure of Invention
In order to solve the defects and problems in the prior art, the invention provides the flame-retardant nylon/polyphenylene sulfide alloy material and the preparation method and application thereof, wherein the novel material provided by the invention has high heat conductivity coefficient, keeps good mechanical property, processability, flame retardance and low odor, and is simple to prepare, strong in operability and easy to implement.
The invention provides a flame-retardant nylon/polyphenylene sulfide alloy material which comprises the following components in parts by weight:
further, the components according to the weight ratio comprise:
further, the PA6 resin is selected to have the viscosity of 2.0-2.4 Pa.s; the PPS resin is selected to have a melt index of 500-1000 g/min.
Furthermore, the graphene microchip has a lamella diameter of 7-10 μm and a thickness of less than 100 nm.
Furthermore, the pitch-based carbon fiber is chopped carbon fiber with the diameter of 7 μm, the chopped length of 4.5-6mm, the tensile strength of 2.0-5Gpa and the thermal conductivity of 500-700W/(m.k).
Further, the molecular formula of the aluminum diethylphosphinate is Al (PO2C4H10)3, the aluminum diethylphosphinate is white powder in appearance, and the average particle size is 15-20 mu m.
Further, the antioxidant is prepared by compounding a hindered phenol antioxidant 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) and a phosphite antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite) which is 1010/168 of 1: 1.
Further, the lubricant is one or both of an E wax and a montan wax of Kelaien; the black master batch adopts a PA carrier, and the content of carbon black is 30-40%.
The invention also provides a preparation method of the flame-retardant nylon/polyphenylene sulfide alloy material, which comprises the following steps:
step one, adding PA6 resin, PPS resin, graphene nanoplatelets, an antioxidant, a lubricant and diethyl aluminum phosphinate in a certain weight ratio into a mixer, and mixing for 5-10min to obtain a premixed material;
secondly, adding the premixed material into a double-screw extruder through a main feeding port, adding the asphalt-based carbon fiber into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder;
and step three, adopting a water-cooling brace and grain cutting mode, and then screening and dehydrating to obtain the flame-retardant nylon/polyphenylene sulfide alloy material.
The invention also provides application of the flame-retardant nylon/polyphenylene sulfide alloy material prepared by any one of the flame-retardant nylon/polyphenylene sulfide alloy materials or the method in the aspect of LED lighting products.
According to the invention, graphene, aluminum diethylphosphinate and PPS are added for compounding and are synergistic, so that the material reaches a flame-retardant V-0 grade, and the compound system can reduce the odor in the processes of processing, using and fire burning.
Among them, the high thermal conductivity of graphene itself means that local heat is conducted to the rest of the material and dispersed, making the fire difficult to spread. And the graphene will remain in the material combustion front on combustion creating a labyrinth effect where the heat and combustion gases must follow a tortuous path to the fuel and this effectively prevents the spread of the flame.
The added carbon fibers can act counter-currently, destroying the occlusion of the carbon layer and the fibers can cause the wick effect, i.e. similar to the wick of a candle, because the effect of surface tension is to migrate the fuel continuously to the combustion front, the addition of aluminum diethylphosphinate is intended to carbonize the polymer, destroying the channels of polymer migration, while the aluminum diethylphosphinate catalyzes the carbon formation of the polymer to act together with the graphene to occlude the carbon layer, isolating oxygen. Aluminum diethylphosphinate also acts as a gas phase flame retardant by removing free radicals from the high energy zone of combustion. In addition to the flame retardant effect, the graphene and aluminum diethylphosphinate interact to promote polymer char formation to bond with the graphene, and the foamed carbon layer has a very high surface area, which can adsorb flammable organic volatiles and prevent their release and diffusion during combustion, reducing the odor and toxicity of the combustion process.
The PPS resin has extremely high limiting oxygen index, and the flame retardant degree of the material can be improved as a whole. The invention also well solves the problems that the graphene is easy to peel off from the surface of the material and the material is brittle because the material cannot well coat the graphene microchip by adding the polyphenylene sulfide material. Because the acting force between graphene sheets is very small, when graphene is not coated by plastic, the graphene is easy to peel off, and similar to scratching on paper by using a pencil, the PPS is used for coating the graphene by using the PPS with low molecular weight and high fluidity, so that the condition is improved, and the impact strength of the material is improved.
The preparation method of the flame-retardant nylon/polyphenylene sulfide alloy material is simple in preparation, strong in operability and easy to implement, can realize large-scale industrial production by means of the conventional mature-technology double-screw extruder, and has a very wide application prospect.
According to the application of the flame-retardant nylon/polyphenylene sulfide alloy material in the aspect of LED lighting products, the shrinkage rate and warpage of the material are reduced by adding the carbon fiber and the graphene. The LED industry at present generally adopts the form of wrapping the aluminum substrate by the plastic shell to realize heat dissipation design, when the shrinkage rate of a plastic material is larger than the shrinkage rate of the aluminum substrate and warping occurs, the aluminum substrate is easy to separate from the plastic, poor heat dissipation is caused, the shrinkage rate of the plastic can be reduced by adding the needle-shaped carbon fibers, the shrinkage rates in the flow direction and the direction perpendicular to the flow direction are inconsistent due to the orientation effect of the needle-shaped fibers in the injection molding process, warping deformation is caused, the addition of the sheet-shaped graphene material can simultaneously inhibit the deformation in the two directions, warping is reduced, and the integral flatness is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The flame-retardant nylon/polyphenylene sulfide alloy material provided by the invention is shown in examples 1-4 (the components are in weight ratio) in Table 1:
TABLE 1
In order to prove the coordination effect among the components provided by the invention for comparison, the invention also provides comparative examples 1-4 (the components are in weight ratio) as shown in Table 2:
TABLE 2
The following are the preparation methods of the above examples and comparative examples (the components of each example are weighed according to the weight percentages in tables 1 and 2):
firstly, drying PA6 resin and PPS resin for 3 hours at the temperature of 110 ℃, then adding the dried PA6 resin, PPS resin, graphene nanoplatelets, aluminum diethylphosphinate, black master batch, an antioxidant and a lubricant into a high-speed mixer, mixing for 5 minutes at the rotating speed of the mixer of 300r/min, and uniformly mixing in the mixer to obtain a premixed material;
secondly, adding the premixed material into a double-screw extruder from a main feeding port, adding the asphalt-based carbon fiber into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder;
and thirdly, adopting a water-cooling brace and grain cutting mode, and then sieving and dehydrating to obtain the flame-retardant nylon/polyphenylene sulfide alloy material.
In the second step, the pitch-based carbon fiber is added through a lateral feeding system in the fifth section to the sixth section of the cylinder of the double-screw extruder, so that the pitch-based carbon fiber is directly mixed with the melted plastic, and the retention strength of the fiber in the material is improved finally.
Specifically, the length-diameter ratio of a screw of the double-screw extruder is 40:1, the rotating speed of a main machine is 400r/min, the temperature of each reaction section from a feeding section to a machine head in the double-screw extruder is 250 ℃, 260 ℃, 270 ℃, 280 ℃, 270 ℃, 275 ℃, 280 ℃ and the temperature of a die head is 280 ℃.
The flame-retardant nylon/polyphenylene sulfide alloy materials prepared in examples 1-4 and comparative examples 1-4 were injection molded at a temperature of 270-300 ℃ to obtain test specimens, and the relevant performance tests and test methods of the test specimens are detailed in tables 3 and 4.
Table 3: test data for examples 1-4
Table 4: test data for comparative examples 1-4
The above experimental data show that: the asphalt-based carbon fiber is reasonably added into the graphene heat-conducting nylon to replace part of graphene, so that the addition amount of the graphene in the high heat-conducting plastic is reduced, the mechanical strength of the material is improved, the melt index of the material can be improved by processing the high-flow PPS, the processing is improved, and the impact strength of the material is improved; the graphene is added to be matched with the asphalt-based carbon fiber for use, so that the flow direction shrinkage rate is reduced, the transverse flow direction shrinkage rate is reduced, the material and aluminum substrate laminating capacity is improved, and the integral heat dissipation uniformity of the LED radiator is ensured.
The addition of the diethyl aluminum phosphinate can effectively ensure that the flame retardant grade of the material is V-0 grade. The black master batch is added in the sense of ensuring the color consistency of the material and avoiding fluctuation caused by the fluctuation of the components of the formula.
In addition, the inventors experimentally compared examples 1 to 4 in preparation methods, one in which pitch-based carbon fibers and other components were directly fed from a main feeding port into a twin-screw extruder (preparation method a); alternatively, pitch-based carbon fibers were added to the premix material via a side feed system in sections five through six of the barrel of a twin screw extruder (preparation method B). The experimental result shows that the average value of the impact strength performance index of the preparation method A is 4.8KJ/m2The average value of the impact strength performance index by the preparation method B is 3.3KJ/m2Therefore, the preparation method A adopted by the inventor effectively improves the retention strength of the fiber in the material finally.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The flame-retardant nylon/polyphenylene sulfide alloy material is characterized by comprising the following components in parts by weight:
32.5-49.8 parts of PA6 resin
10-20 parts of PPS resin
10-20 parts of graphene nanoplatelets
20-30 parts of asphalt-based carbon fiber
5-10 parts of aluminum diethylphosphinate
0.2 to 0.5 portion of antioxidant
0.2 to 1 portion of lubricant
1-2 parts of black master batch;
the PPS resin is selected to have a melt index of 500-1000 g/min;
the pitch-based carbon fiber is short carbon fiber with the diameter of 7 mu m, the short length of 4.5-6mm, the tensile strength of 2.0-5Gpa and the heat conductivity of 500-700W/(m.k);
the graphene microchip is characterized in that the diameter of a sheet layer is 7-10 mu m, and the thickness of the sheet layer is less than 100 nm.
2. The flame-retardant nylon/polyphenylene sulfide alloy material as claimed in claim 1, wherein the flame-retardant nylon/polyphenylene sulfide alloy material comprises the following components in parts by weight:
32.5 parts of PA6 resin
PPS resin 20 parts
20 parts of graphene nanoplatelets
20 portions of asphalt-based carbon fiber
Diethyl aluminum phosphinate 5 parts
0.5 part of antioxidant
0.2 portion of lubricant
And 2 parts of black master batch.
3. The flame retardant nylon/polyphenylene sulfide alloy material according to claim 1 or 2, wherein: the PA6 resin is selected to have a viscosity of 2.0-2.4 Pa.s.
4. The flame retardant nylon/polyphenylene sulfide alloy material according to claim 1 or 2, wherein: the molecular formula of the diethyl aluminum phosphinate is Al (PO2C4H10)3, the diethyl aluminum phosphinate is white powder in appearance, and the average particle size is 15-20 mu m.
5. The flame retardant nylon/polyphenylene sulfide alloy material according to claim 1 or 2, wherein: the antioxidant is prepared by compounding a hindered phenol antioxidant 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) and a phosphite antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite) in a ratio of 1:1 of 1010/168.
6. The flame retardant nylon/polyphenylene sulfide alloy material according to claim 1 or 2, wherein: the lubricant is one or two of Kelaien E wax and montan wax; the black master batch adopts a PA carrier, and the content of carbon black is 30-40%.
7. The preparation method of the flame-retardant nylon/polyphenylene sulfide alloy material as claimed in any one of claims 1-6, characterized by comprising the following steps:
step one, adding PA6 resin, PPS resin, graphene nanoplatelets, an antioxidant, a lubricant and diethyl aluminum phosphinate in a certain weight ratio into a mixer, and mixing for 5-10min to obtain a premixed material;
secondly, adding the premixed material into a double-screw extruder through a main feeding port, adding the asphalt-based carbon fiber into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder;
and step three, adopting a water-cooling brace and grain cutting mode, and then screening and dehydrating to obtain the flame-retardant nylon/polyphenylene sulfide alloy material.
8. Use of the flame retardant nylon/polyphenylene sulfide alloy material according to any one of claims 1-6 or prepared by the method according to claim 7 in LED lighting products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811160440.8A CN109181290B (en) | 2018-09-30 | 2018-09-30 | Flame-retardant nylon/polyphenylene sulfide alloy material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811160440.8A CN109181290B (en) | 2018-09-30 | 2018-09-30 | Flame-retardant nylon/polyphenylene sulfide alloy material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109181290A CN109181290A (en) | 2019-01-11 |
| CN109181290B true CN109181290B (en) | 2021-04-16 |
Family
ID=64946534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811160440.8A Active CN109181290B (en) | 2018-09-30 | 2018-09-30 | Flame-retardant nylon/polyphenylene sulfide alloy material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109181290B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138851B (en) * | 2019-12-18 | 2022-08-30 | 南京聚隆科技股份有限公司 | Flame-retardant reinforced micro-foaming nylon material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017070880A1 (en) * | 2015-10-29 | 2017-05-04 | Hewlett-Packard Development Company, L.P. | Composite structure, preparation method thereof and articles comprising the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725004B (en) * | 2013-12-06 | 2016-06-29 | 四川大学 | A kind of polyphenylene sulfide ether heat-conductive composite material and preparation method thereof |
| CN106675029A (en) * | 2015-11-06 | 2017-05-17 | 余姚市爱佟塑料制品厂 | Novel material for reducing LED junction temperature and preparation method of novel material |
| CN106589741A (en) * | 2016-11-30 | 2017-04-26 | 安徽电气集团股份有限公司 | High-toughness and high-thermal-conductivity high-molecular material |
-
2018
- 2018-09-30 CN CN201811160440.8A patent/CN109181290B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017070880A1 (en) * | 2015-10-29 | 2017-05-04 | Hewlett-Packard Development Company, L.P. | Composite structure, preparation method thereof and articles comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109181290A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103102669B (en) | Thermal-resistant light-smoke halogen-free flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN110591350B (en) | Smoke-inhibiting polyamide composition and preparation method thereof | |
| CN112778741B (en) | Flame-retardant polycarbonate composition and preparation method thereof | |
| CN104031374B (en) | Polycarbonate compositions and preparation method thereof | |
| CN113372676B (en) | Flame-retardant high impact polystyrene composition and preparation method thereof | |
| CN106009585A (en) | Halogen-free flame retardation polycarbonate material and preparation method thereof | |
| WO2020098593A1 (en) | Polyphenylene sulfide composite material, preparation method therefor and application thereof | |
| CN109627568A (en) | Polyolefine cable sheath material and preparation method thereof | |
| KR101170533B1 (en) | Resin composition for polycarbonate flame-retarded film, method of manufacturing flame-retarded polycarbonate film using the resin composition and flame-retarded polycarbonate film manufactured the method | |
| WO2021114752A1 (en) | Flame-retardant polyethylene cable material and preparation method therefor | |
| CN106751808A (en) | A kind of fire-retardant non-reinforcing PA66 composites of GWIT high CTI high | |
| CN103013081A (en) | Heat-resistant scratch-resistant halogen-free anti-flaming polycarbonate thin film | |
| CN109181290B (en) | Flame-retardant nylon/polyphenylene sulfide alloy material and preparation method and application thereof | |
| CN109749372A (en) | A kind of fire-retardant reinforced PBT composite material and preparation method thereof | |
| CN102367317A (en) | Flame retardant polypropylene (PP) material and its preparation method | |
| CN101062992A (en) | Halogen-free flame-proof highly anti-flush polyphenylacetylene composition and method of making the same | |
| CN108059824B (en) | Transparent flame-retardant high-temperature nylon and preparation method thereof | |
| CN113861550A (en) | B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material and preparation method thereof | |
| CN110698854B (en) | Thermal-oxidative-aging-resistant low-precipitation MCA flame-retardant PA66 composite material and application thereof | |
| CN104130505B (en) | Halogen-free flame-retardant crosslinked polypropylene as well as preparation method and application thereof | |
| KR20210033591A (en) | Halogen-free flame-retardant polycarbonate/ABS composite material | |
| CN113845771A (en) | Halogen-free flame-retardant PA66 composite material and preparation method thereof | |
| CN113462068B (en) | Flame-retardant oxygen-barrier layer material and preparation method thereof | |
| CN114989602A (en) | Laser-markable halogen-free flame-retardant polyamide material and preparation method thereof | |
| CN104693720A (en) | Phosphorus-nitrogen halogen-free flame-retardant modified PC/PET composite material, and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |