CN115678160A - Composition with laser marking function - Google Patents
Composition with laser marking function Download PDFInfo
- Publication number
- CN115678160A CN115678160A CN202211280744.4A CN202211280744A CN115678160A CN 115678160 A CN115678160 A CN 115678160A CN 202211280744 A CN202211280744 A CN 202211280744A CN 115678160 A CN115678160 A CN 115678160A
- Authority
- CN
- China
- Prior art keywords
- composition
- parts
- mass
- boron nitride
- heat conducting
- 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.)
- Granted
Links
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a composition with a laser marking function, which comprises the following components in parts by mass: 100 parts of polypropylene and developer dodecaphenyl polyhedral silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of an inducer, 1-3 parts of decabromodiphenylethane and 1-3 parts of a heat conducting agent; the heat conducting agent is a titanium dioxide surface modified boron nitride nanosheet, wherein the sum G2 of the mass G1 of the dodecaphenyl polyhedral silsesquioxane, the mass of decabromodiphenylethane and the heat conducting agent meets the following condition that G1: G2= 1.5-2. The composition may also contain a compatibilizer, antioxidant, toughener, coupling agentAt least one of the agents; the composition has high blackness and high definition of laser marks, and ensures that the appearance marks of the final laser marked product are not easy to damage. The composition has good application prospect in various containers, especially medical container shells.
Description
Technical Field
The invention relates to the field of plastics, in particular to a composition with a laser marking function.
Background
A laser marking method of recording (so-called laser printing) on various packaging containers for storing foods, beverages, medicines, quasi-drugs, cosmetics, and the like, packaging materials such as various packaging materials including films, papers, and the like, by irradiating a laser beam to an object is generally used.
The principle of the laser marking technology is that a high-energy laser beam is used for irradiating the surface of a material or a workpiece to vaporize or develop color, so that a predetermined pattern or characters are displayed on the surface of the material or the workpiece. The laser marking technology has certain requirements on the material or the added auxiliary agent, namely the surface of the material is required to be melted, gasified or carbonized at the high-energy laser beam irradiation part, and the surrounding part is not changed, or the added auxiliary agent in the material has a color development effect, the part under the beam irradiation is developed, and the other surrounding parts are not developed. For the material which can be marked by laser, the material molecule is required to have certain thermal stability, and under the action of laser beam, the illumination part is carbonized to display graphic characters; other materials need to be modified correspondingly, and the molecules of the base materials which can be used for modification need to have certain stability and assistant compatibility; the laser marking method has the following advantages because it is a so-called non-contact method: high-precision recording can be performed; high-speed recording can be performed; recording can be performed on various surface shapes of the object. Further, the laser marking method has an advantage that it can provide recording that is difficult to erase, compared with recording by a thermal imprint method or an ink jet method.
Disclosure of Invention
The invention provides a composition with a laser marking function, which comprises the following components in parts by mass: 100 parts of polypropylene and developer dodecaphenyl polyhedral silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of an inducer decabromodiphenylethane 1-3 parts, and a heat conducting agent 1-3 parts; the heat conducting agent is a titanium dioxide surface modified boron nitride nanosheet, wherein the sum G2 of the mass G1 of the dodecaphenyl polyhedral silsesquioxane, the mass of decabromodiphenylethane and the heat conducting agent meets the following condition that G1: G2= 1.5-2. The composition can also comprise at least one of a compatilizer, an antioxidant, a toughening agent and a coupling agent; the composition has high blackness and high definition of laser marks, and ensures that the appearance marks of the final laser marked product are not easy to damage. The composition has wide application prospect in various pipe bodies, container shells, particularly biomedical materials, consumable materials and other related fields.
The specific scheme comprises the following steps:
a composition with a laser marking function comprises the following components in parts by mass: 100 parts of polypropylene and developer dodecaphenyl polyhedral silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of an inducer, 1-3 parts of decabromodiphenylethane and 1-3 parts of a heat conducting agent; the heat conducting agent is a titanium dioxide surface-modified boron nitride nanosheet, wherein the sum G2 of the mass G1 of the dodecaphenyl polyhedral silsesquioxane, the mass of decabromodiphenylethane and the heat conducting agent meets the requirement that G1: G2= 1.
Further, the composition also comprises 10-12 parts of a compatilizer, wherein the compatilizer is selected from at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl ester grafted polyethylene, glycidyl ester grafted polypropylene, maleic anhydride grafted polypropylene, an ethylene-acrylic acid copolymer, an ethylene-acrylate copolymer, an ethylene-vinyl alcohol copolymer and an ethylene-vinyl acetate copolymer.
Further, the composition also comprises at least one of an antioxidant, a toughening agent and a coupling agent.
Further, the antioxidant is 0.2 to 0.8 part by mass, and is selected from at least one of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 4' -thiobis (6-tert-butyl-3-methylphenol), tris (2, 4-di-tert-butylphenyl) phosphite, and tetrakis (2, 4-di-tert-butylphenol) -4, 4-biphenyldiphosphite.
Further, the toughening agent is 0.5-3.0 parts by mass, and the toughening agent is selected from at least one of polyoctene-maleic anhydride graft, ethylene-ethyl acrylate copolymer, polycaprolactone and poly (butyl adipate-terephthalate).
Further, the coupling agent is 0.2-1 part by mass and is selected from at least one of silane coupling agent KH550, gamma-aminopropyl triethoxysilane and phenylaminomethyl trimethoxysilane.
Further, the composition may further comprise a color toner, wherein the color refers to a single common color of red, blue, orange, yellow, cyan, green, purple, or various mixed colors of the above colors.
Further, the titanium dioxide surface modified boron nitride nanosheet is prepared by the following method, 2.5g of tetraisopropyl titanate is dissolved in 200ml of a mixed solvent of ethanol and dimethylformamide in a volume ratio of 1, 10g of boron nitride nanosheet is added, the mixture is placed in a hydrothermal reaction kettle, an inner tank body of the reaction kettle is a polytetrafluoroethylene sealed tank, the inner tank body is sealed, hydrothermal reaction is carried out for 4-6 hours at 120 ℃, precipitation is obtained by filtration, and the precipitate is washed by ethanol and deionized water respectively and dried to obtain the titanium dioxide surface modified boron nitride nanosheet.
Further, the particle size of the boron nitride nanosheet is 300-500nm.
The invention has the beneficial technical effects
1) Dodecaphenyl polyhedral silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) The material is colorless in visible light and can be added into polypropylene plastics with any color, and the material has higher blackness value and high identifiability after carbonization in the heating process;
2) Decabromodiphenylethane can absorb laser and promote carbonization of dodecylphenyl polyhedral silsesquioxane, blackness of laser marks is improved, meanwhile, titanium dioxide in boron nitride nanosheets modified on the surfaces of the titanium dioxide can absorb the laser and generate heat, and the boron nitride nanosheets serve as good thermal conductors, so that rapid carbonization of laser irradiation positions is promoted, and black marks with high contrast and definition are generated on the surfaces.
Detailed Description
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples within the scope not exceeding the gist thereof.
A composition with a laser marking function comprises the following components in parts by mass: 100 parts of polypropylene and developer dodecaphenyl polyhedral silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of an inducer decabromodiphenylethane 1-3 parts, and a heat conducting agent 1-3 parts; the heat conducting agent is titanium dioxideSurface-modified boron nitride nanosheets, wherein the sum G2 of the mass G1 of the dodecylphenyl polyhedral silsesquioxane, the mass of decabromodiphenylethane and the thermal conductive agent satisfies G1: G2= 1.5-2.
Further, the content of the compatibilizer is not particularly limited, preferably 10 to 12 parts, and the type of the compatibilizer is not particularly limited, and may be at least one selected from the group consisting of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl ester grafted polyethylene, glycidyl ester grafted polypropylene, maleic anhydride grafted polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl acetate copolymer.
Further, the composition also comprises at least one of an antioxidant, a toughening agent and a coupling agent.
Further, the content of the antioxidant is not particularly limited, and is preferably 0.2 to 0.8 part by mass, and the kind of the antioxidant is not particularly limited, and may be at least one selected from n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 4' -thiobis (6-tert-butyl-3-methylphenol), tris (2, 4-di-tert-butylphenyl) phosphite, and tetrakis (2, 4-di-tert-butylphenol) -4, 4-biphenyldiphosphite.
Further, the content of the toughening agent is not particularly limited, and is preferably 0.5 to 3.0 parts by mass, and the type of the toughening agent is not particularly limited, and may be at least one selected from the group consisting of polyoctene-maleic anhydride graft, ethylene-ethyl acrylate copolymer, polycaprolactone, and polybutyl terephthalate adipate.
Further, the content of the coupling agent is not particularly limited, and is preferably 0.2 to 1 part by mass, and the kind of the coupling agent is not particularly limited, and may be at least one selected from the group consisting of a silane coupling agent KH550, γ -aminopropyltriethoxysilane, and phenylaminomethyltrimethoxysilane.
Further, the composition may further comprise a color toner, wherein the color refers to a single common color of red, blue, orange, yellow, cyan, green, purple, or various mixed colors of the above colors.
Further, the titanium dioxide surface modified boron nitride nanosheet is prepared by the following method, 2.5g of tetraisopropyl titanate is dissolved in 200ml of a mixed solvent of ethanol and dimethylformamide in a volume ratio of 1, 10g of boron nitride nanosheet is added, the mixture is placed in a hydrothermal reaction kettle, an inner tank body of the reaction kettle is a polytetrafluoroethylene sealed tank, the inner tank body is sealed, hydrothermal reaction is carried out for 4-6 hours at 120 ℃, precipitation is obtained by filtration, and the precipitate is washed by ethanol and deionized water respectively and dried to obtain the titanium dioxide surface modified boron nitride nanosheet. The particle size of the boron nitride nanosheet is 300-500nm.
The following specific examples only test the visual performance of three components, namely the color reagent dodecaphenyl polyhedral silsesquioxane, the inducer decabromodiphenylethane and the heat conducting agent titanium dioxide surface-modified boron nitride nanosheet, on laser marking, and do not perform further tests on the performance in the aspect of mechanics.
The titanium dioxide surface modified boron nitride nanosheet is prepared by the following method, 2.5g of tetraisopropyl titanate is dissolved in 200ml of a mixed solvent of ethanol and dimethylformamide in a volume ratio of 1, 10g of boron nitride nanosheets with the particle size of 400nm are added, the boron nitride nanosheets are placed in a hydrothermal reaction kettle, an inner tank body of the reaction kettle is made of polytetrafluoroethylene, the inner tank body is sealed, the hydrothermal reaction is carried out for 6 hours at 120 ℃, precipitates are obtained by filtration, the boron nitride nanosheets are washed with ethanol and deionized water for 3 times respectively, and the mixture is heated to 350 ℃ and dried for 1 hour, so that the titanium dioxide surface modified boron nitride nanosheet is obtained.
In the examples and the comparative examples, the mass parts of the color reagent, namely the dodecylbenzene polyhedral silsesquioxane, the inducer, namely the decabromodiphenylethane, and the heat conducting agent, namely the titanium dioxide surface-modified boron nitride nanosheet are shown in table 1, the contents of other components are the same, and the components are not shown in table 1, wherein the mass parts of the polypropylene are 100 parts;
TABLE 1
Data and results
The compositions of the examples and comparative examples were injection molded into high gloss plaques and then laser marked to make test specimens. The laser wavelength is 1064nm, the speed is 1000mm/s, the laser energy is 8W, the laser frequency is 80kHz, the definition and the blackness of laser printing marks of the laser printer are respectively evaluated by adopting a 15-time magnifier, and the laser printer is divided into 10 grades according to the definition of the laser marks: from very clear to unclear, which correspond to the number of levels 10 to 1, respectively. And respectively detecting the blackness of the black powder by using a spectrophotometer.
As shown in table 2 below.
TABLE 2
As can be seen from Table 2, when G2/G1 is between 1.5 and 2, a very clear contrast can be obtained, the edge is clear, the contrast is high, and the obtained blackness value is good, when G2/G1 is lower than 1.5, the blackness value is reduced, and the contrast is reduced along with the reduction of G2; however, when G2/G1 is higher than 2, the blackness value is hardly changed, but the contrast is remarkably lowered.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (9)
1. A composition having a laser marking function, characterized by comprising, in parts by mass: 100 parts of polypropylene and developer dodecaphenyl polyhedral silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of inducer decabromodiphenylethane1-3 parts of heat conducting agent; the heat conducting agent is a titanium dioxide surface-modified boron nitride nanosheet, wherein the sum G2 of the mass G1 of the dodecaphenyl polyhedral silsesquioxane, the mass of decabromodiphenylethane and the heat conducting agent meets the requirement that G1: G2= 1.
2. The composition of claim 1, further comprising 10-12 parts of a compatibilizer selected from at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl ester grafted polyethylene, glycidyl ester grafted polypropylene, maleic anhydride grafted polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl acetate copolymer.
3. The composition of claim 2, further comprising at least one of an antioxidant, a toughening agent, and a coupling agent.
4. The composition according to claim 3, wherein the antioxidant is 0.2 to 0.8 parts by mass and is at least one member selected from the group consisting of n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 4' -thiobis (6-tert-butyl-3-methylphenol), tris (2, 4-di-tert-butylphenyl) phosphite, and tetrakis (2, 4-di-tert-butylphenol) -4, 4-biphenyldiphosphite.
5. The composition of claim 3, wherein the toughening agent is 0.5-3.0 parts by mass, and the toughening agent is at least one selected from the group consisting of polyoctene-maleic anhydride graft, ethylene-ethyl acrylate copolymer, polycaprolactone, and poly (butyl adipate terephthalate).
6. The composition according to claim 3, wherein the coupling agent is 0.2-1 part by mass and is at least one selected from silane coupling agents KH550, gamma-aminopropyltriethoxysilane, and phenylaminomethyltrimethoxysilane.
7. The composition of claim 1, further comprising a color toner other than black.
8. The composition of claim 1, wherein the titanium dioxide surface modified boron nitride nanosheet is prepared by dissolving 2.5g of tetraisopropyl titanate in 200ml of a mixed solvent of ethanol and dimethylformamide in a volume ratio of 1, adding 10g of boron nitride nanosheet, placing the mixture in a hydrothermal reaction kettle, wherein an inner tank body of the reaction kettle is a polytetrafluoroethylene sealed tank, sealing the inner tank body, carrying out hydrothermal reaction at 120 ℃ for 4-6h, filtering to obtain a precipitate, washing with ethanol and deionized water respectively, and drying to obtain the titanium dioxide surface modified boron nitride nanosheet.
9. The composition of claim 7, the boron nitride nanoplates having a particle size of 300-500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211280744.4A CN115678160B (en) | 2022-10-19 | 2022-10-19 | Composition with laser marking function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211280744.4A CN115678160B (en) | 2022-10-19 | 2022-10-19 | Composition with laser marking function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115678160A true CN115678160A (en) | 2023-02-03 |
| CN115678160B CN115678160B (en) | 2023-07-14 |
Family
ID=85066574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211280744.4A Active CN115678160B (en) | 2022-10-19 | 2022-10-19 | Composition with laser marking function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115678160B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020155291A1 (en) * | 2000-11-21 | 2002-10-24 | Vijay Daga | Pigments and compositions for use in laser marking |
| KR20070004624A (en) * | 2004-01-16 | 2007-01-09 | 테크노 폴리머 가부시키가이샤 | Multi-color coloring laser marking-use chromatic color colorant, multi-color coloring laser marking-use composition and molding containing it, multi-color marking-carrying molding and laser marking method |
| CN101519529A (en) * | 2009-03-26 | 2009-09-02 | 上海交通大学 | Polycarbonate composition and preparation method thereof |
| CN103289188A (en) * | 2013-02-25 | 2013-09-11 | 金发科技股份有限公司 | Polypropylene compound, its preparation method and application |
| CN103289365A (en) * | 2012-03-01 | 2013-09-11 | 党晓容 | Polyamide composition capable of being marked by laser |
| CN107345029A (en) * | 2017-06-23 | 2017-11-14 | 广东圆融新材料有限公司 | Laser carving master batch, can laser marking be high flows high brilliant black polypropene composition and preparation method thereof |
| CN109880308A (en) * | 2019-01-21 | 2019-06-14 | 宁波华腾首研新材料有限公司 | A kind of bromine/stibium flame retardancy enhancing PBT composite and preparation method thereof |
| CN113150449A (en) * | 2021-04-02 | 2021-07-23 | 南京聚隆科技股份有限公司 | Low-shrinkage laser-weldable polypropylene modified composite material and preparation method thereof |
| CN114058176A (en) * | 2021-08-24 | 2022-02-18 | 广东思汗新材料有限公司 | Laser-marking anti-aging nylon glass fiber reinforced flame-retardant composite material |
| CN114561079A (en) * | 2022-01-18 | 2022-05-31 | 国家能源集团宁夏煤业有限责任公司 | Polyformaldehyde composition, polyformaldehyde material capable of being marked by laser and preparation method of polyformaldehyde material |
-
2022
- 2022-10-19 CN CN202211280744.4A patent/CN115678160B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020155291A1 (en) * | 2000-11-21 | 2002-10-24 | Vijay Daga | Pigments and compositions for use in laser marking |
| KR20070004624A (en) * | 2004-01-16 | 2007-01-09 | 테크노 폴리머 가부시키가이샤 | Multi-color coloring laser marking-use chromatic color colorant, multi-color coloring laser marking-use composition and molding containing it, multi-color marking-carrying molding and laser marking method |
| CN101519529A (en) * | 2009-03-26 | 2009-09-02 | 上海交通大学 | Polycarbonate composition and preparation method thereof |
| CN103289365A (en) * | 2012-03-01 | 2013-09-11 | 党晓容 | Polyamide composition capable of being marked by laser |
| CN103289188A (en) * | 2013-02-25 | 2013-09-11 | 金发科技股份有限公司 | Polypropylene compound, its preparation method and application |
| CN107345029A (en) * | 2017-06-23 | 2017-11-14 | 广东圆融新材料有限公司 | Laser carving master batch, can laser marking be high flows high brilliant black polypropene composition and preparation method thereof |
| CN109880308A (en) * | 2019-01-21 | 2019-06-14 | 宁波华腾首研新材料有限公司 | A kind of bromine/stibium flame retardancy enhancing PBT composite and preparation method thereof |
| CN113150449A (en) * | 2021-04-02 | 2021-07-23 | 南京聚隆科技股份有限公司 | Low-shrinkage laser-weldable polypropylene modified composite material and preparation method thereof |
| CN114058176A (en) * | 2021-08-24 | 2022-02-18 | 广东思汗新材料有限公司 | Laser-marking anti-aging nylon glass fiber reinforced flame-retardant composite material |
| CN114561079A (en) * | 2022-01-18 | 2022-05-31 | 国家能源集团宁夏煤业有限责任公司 | Polyformaldehyde composition, polyformaldehyde material capable of being marked by laser and preparation method of polyformaldehyde material |
Non-Patent Citations (1)
| Title |
|---|
| 张平;林远开;张钊鹏;: "一种优异激光打标效果的750℃灼热丝环保阻燃增强改性PBT的研究", 广东化工, vol. 45, no. 18, pages 59 - 61 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115678160B (en) | 2023-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107459871B (en) | 3D inkjet printings photocuring transparent ink and preparation method thereof | |
| JP4533205B2 (en) | Active energy ray-curable water-based ink, ink jet recording method, ink cartridge, recording unit and ink jet recording apparatus using the same | |
| EP1696008B1 (en) | Dispersion, inkjet ink, method of manufacturing the dispersion, method of manufacturing the inkjet ink | |
| JP5227733B2 (en) | Bismuth oxide additive for laser marking and method for producing the same | |
| US9475950B2 (en) | Radiation-curable inkjet ink set and inkjet recording method | |
| JP2010275561A (en) | White heat-hardening resin composition, printed-wiring board with the hardened material, and reflection board for light emitting element formed of the hardened material | |
| JPH02235686A (en) | Laser tinted marking of plastic material | |
| CN100540619C (en) | Dispersion, ink for ink-jet print, the method for making of the two and printed matter | |
| CN116157474B (en) | Photo-curable ink composition for inkjet printing | |
| JP2007314610A (en) | Active energy ray-curable aqueous ink, ink-jet printing method, ink cartridge, printing unit, and ink-jet printer | |
| CN114031972B (en) | Composite ink for OLED packaging and application method thereof | |
| CN115678160A (en) | Composition with laser marking function | |
| KR102270109B1 (en) | White thermosetting resin composition, cured product thereof and display member using the same | |
| CN109135425A (en) | Laser labelling ink composition and packaging material | |
| JP2008266635A (en) | Active energy ray-curable type liquid composition and liquid cartridge | |
| JP5670533B1 (en) | Thermosetting resin composition, cured product thereof, and display member using the same | |
| JP2007314611A (en) | Active energy ray-curable aqueous ink, ink-jet printing method, ink cartridge, printing unit, and ink-jet printer | |
| JP6653362B2 (en) | Ink for ink jet | |
| JP7069674B2 (en) | Method for manufacturing UV-curable printed matter and UV-curable printed matter | |
| JP2019073667A (en) | Colorant and aqueous pigment dispersion | |
| CN115298272B (en) | Photo-curable ink composition for inkjet printing | |
| JP3479698B2 (en) | Resin composition for laser marking | |
| JP5805896B1 (en) | Thermosetting resin composition, cured product thereof, and display member using the same | |
| CN115536943B (en) | Polypropylene plastic capable of being marked by laser | |
| TW201529760A (en) | Ink composition for pad printing |
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 |