CN107502341B - Piezoluminescence material crystals and preparation method and application - Google Patents
Piezoluminescence material crystals and preparation method and application Download PDFInfo
- Publication number
- CN107502341B CN107502341B CN201710685932.8A CN201710685932A CN107502341B CN 107502341 B CN107502341 B CN 107502341B CN 201710685932 A CN201710685932 A CN 201710685932A CN 107502341 B CN107502341 B CN 107502341B
- Authority
- CN
- China
- Prior art keywords
- carbazole
- base
- anthraquinone
- crystal
- alkyl halide
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
- B42D25/405—Marking
- B42D25/415—Marking using chemicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The invention belongs to technical field of organic luminescence materials, more particularly to piezoluminescence material crystals and preparation method and application, 2- carbazole -9- base-anthraquinone crystal is used for piezoluminescence material for the first time by the present invention, and 2- carbazole -9- base-anthraquinone crystal can be used for alkyl halide detection or anti-fake material;Two different colors of 2- carbazole -9- base-anthraquinone crystal prepared by the present invention, under environmental stimuli such as external force, temperature and solvent action, luminescent color is substantially change, and can be mutually converted, i.e., with the property of piezoluminescence;The method that the present invention prepares two different colors of 2- carbazole -9- base-anthraquinone crystal has determined solvent, the ratio of solvent and the temperature condition of solvent flashing of recrystallization by the selection of a large amount of condition experiments, has obtained above two 2- carbazole -9- base-anthraquinone crystal.
Description
Technical field
The invention belongs to technical field of organic luminescence materials, and in particular to piezoluminescence material crystals and preparation method and answer
With.
Background technique
Piezoluminescence off-color material refers in environmental stimuli such as external force (such as milling, pressure, shearing force, drawing force), temperature
Under degree, solvent and electric field action, luminescent color is substantially change and reversible a kind of luminescent material;This kind of material is being sent out
The fields such as optical device, strain gauge, detection, anti-fake, memory chip, data storage, optical writing have boundless answer
Use prospect.
So far, piezoluminescence material category and few, the piezoluminescence material largely haveing excellent performance has to be developed;Mesh
The piezoluminescence material of preceding report mainly have divinyl anthracene derivate (Dong Y et al.Angew.Chem.Int.Ed.,
2012,51,10782-10785), diphenyl sulfone derivative (Xu S et al.Angew.Chem.Int.Ed., 2015;127:874-
878), benzophenone derivative (Xie Z et al.Angew.Chem.Int.Ed., 2015,127:7181-7184), dibenzo pheno
Oxazine derivatives (Okazaki M et al.Chem.Sci., 2017,8:2677-2686) etc.;Anthraquinone derivatives cause hair as pressure
The example of luminescent material is actually rare;Chinese patent CN 201610712691.7 reports anthraquinone derivative 2- carbazole -9- base-anthracene
Quinone has aggregation-induced emission and hot activation delayed fluorescence performance, and is applied to luminescent device and makes, but 2- carbazole -9- base-anthracene
The crystal of quinone is used as piezoluminescence material, and there has been no relevant reports.
Summary of the invention
The present invention provides 2- carbazole -9- base-anthraquinone two kinds of crystal, preparation method and its answering in piezoluminescence material
With.
Technical scheme is as follows:
2- carbazole -9- base-anthraquinone crystal can be used as piezoluminescence material, 2- carbazole -9- base-anthraquinone ring such as formula (I) institute
Show:
Preferably, 2- carbazole -9- base-anthraquinone crystal is used for alkyl halide detection or anti-fake material.
Preferably, the 2- carbazole -9- base-anthraquinone crystal includes red acicular crystal or yellow rhabdolith,
The parameter of the mono-crystalline structures of the red acicular crystal are as follows:
The parameter of the mono-crystalline structures of the yellow rhabdolith are as follows:
2- carbazole -9- base-anthraquinone crystal preparation method comprising the steps of:
By 2- carbazole -9- base-anthraquinone solid, carried out with alkyl halide, N-alkanes 1:100~200:150 in mass ratio~300
Mixed dissolution, room temperature solvent flashing obtain the red acicular crystal.
Preferably, the alkyl halide is dichloromethane or chloroform, and the N-alkanes is pentane, n-hexane, positive heptan
Alkane or petroleum ether (60-90 DEG C of boiling range).
Another preparation method of 2- carbazole -9- base-anthraquinone crystal comprising the steps of:
By 2- carbazole -9- base-anthraquinone solid, mixed with alkyl halide, alcohol 1:100~200:200~500 in mass ratio
Dissolution, 50-75 DEG C of solvent flashing obtain the yellow rhabdolith.
Preferably, the alkyl halide is any one in dichloromethane or chloroform, and the alcohol is methanol, ethyl alcohol, different
Propyl alcohol or propyl alcohol.
2- carbazole -9- base-anthraquinone crystal is used for alkyl halide detection, detection method are as follows: use the yellow rhabdolith
Alkyl halide steam is smoked, becomes the red acicular crystal in 1 minute.
Preferably, the alkyl halide is methylene chloride, chloroform, carbon tetrachloride, 1,1- dichloroethanes or 1,2- dichloro
Ethane.
Compared with the existing technology, advantages of the present invention is as follows,
2- carbazole -9- base-anthraquinone crystal is used as piezoluminescence material for the first time by the present invention, can be by 2- carbazole -9- base-anthraquinone
Crystal is detected for alkyl halide or anti-fake material;
Two different colors of 2- carbazole -9- base-anthraquinone crystal prepared by the present invention, in environmental stimuli such as external force, temperature
Under solvent action, luminescent color is substantially change, and can be mutually converted, i.e., with the property of piezoluminescence;
The method that the present invention prepares two different colors of 2- carbazole -9- base-anthraquinone crystal is selected by a large amount of condition experiments
The ratio of solvent, solvent that recrystallization has been determined and the temperature condition of solvent flashing are selected, above two 2- carbazole -9- is obtained
Base-anthraquinone crystal;This method is easy to operate, and raw material is easy to get, and is easy to be prepared on a large scale.
Detailed description of the invention
Fig. 1 is the structure cell accumulation graph of yellow single crystal;
Fig. 2 is the structure cell accumulation graph of red monocrystalline.
Specific embodiment
Embodiment 1: the preparation of red piezoluminescence material crystals
A group: 2- carbazole -9- base-anthraquinone solid is mixed with methylene chloride, pentane 1:100:150 in mass ratio
Dissolution, room temperature solvent flashing obtain red acicular crystal.
B group: 2- carbazole -9- base-anthraquinone solid is mixed with chloroform, normal heptane 1:150:200 in mass ratio
Dissolution, room temperature solvent flashing obtain red acicular crystal.
C group: 2- carbazole -9- base-anthraquinone solid is mixed with chloroform, n-hexane 1:200:300 in mass ratio
Dissolution, room temperature solvent flashing obtain red acicular crystal.
D group: by 2- carbazole -9- base-anthraquinone solid, and methylene chloride, petroleum ether (60-90 DEG C of boiling range) in mass ratio 1:
200:300 carries out mixed dissolution, and room temperature solvent flashing obtains red acicular crystal.
E group: 2- carbazole -9- base-anthraquinone solid mix with methylene chloride, n-hexane 1:30:30 in mass ratio molten
Solution, room temperature solvent flashing obtain red powder.
F group: by 2- carbazole -9- base-anthraquinone solid, and methylene chloride, petroleum ether (60-90 DEG C of boiling range) in mass ratio 1:
40:40 carries out mixed dissolution, and room temperature solvent flashing obtains red powder.
G group: 2- carbazole -9- base-anthraquinone solid is mixed with methylene chloride, n-hexane 1:300:50 in mass ratio
Dissolution, room temperature solvent flashing obtain red powder.
H group: 2- carbazole -9- base-anthraquinone solid is mixed with chloroform, n-hexane 1:50:500 in mass ratio
Dissolution, room temperature solvent flashing obtain red powder.
F group: 2- carbazole -9- base-anthraquinone solid is mixed with chloroform, normal heptane 1:150:200 in mass ratio
Dissolution, 50 DEG C of solvent flashings obtain red powder.
Embodiment 2: the preparation of yellow piezoluminescence material crystals
A group: 2- carbazole -9- base-anthraquinone solid mix with methylene chloride, ethyl alcohol 1:100:200 in mass ratio molten
Solution, 75 DEG C of solvent flashings obtain yellow rhabdolith.
B group: 2- carbazole -9- base-anthraquinone solid mix with chloroform, methanol 1:200:500 in mass ratio molten
Solution, 50 DEG C of solvent flashings obtain yellow rhabdolith.
C group: 2- carbazole -9- base-anthraquinone solid mix with methylene chloride, propyl alcohol 1:100:500 in mass ratio molten
Solution, 60 DEG C of solvent flashings obtain yellow rhabdolith.
D group: 2- carbazole -9- base-anthraquinone solid mix with methylene chloride, propyl alcohol 1:100:500 in mass ratio molten
Solution, 75 DEG C of solvent flashings obtain yellow rhabdolith.
E group: 2- carbazole -9- base-anthraquinone solid is mixed with chloroform, isopropanol 1:100:300 in mass ratio
Dissolution, 75 DEG C of solvent flashings obtain yellow rhabdolith.
F group: 2- carbazole -9- base-anthraquinone solid mix with methylene chloride, ethyl alcohol 1:50:100 in mass ratio molten
Solution, 60 DEG C of solvent flashings obtain red powder.
G group: 2- carbazole -9- base-anthraquinone solid mix with methylene chloride, ethyl alcohol 1:300:100 in mass ratio molten
Solution, 60 DEG C of solvent flashings obtain red powder.
H group: 2- carbazole -9- base-anthraquinone solid mix with methylene chloride, ethyl alcohol 1:50:600 in mass ratio molten
Solution, 75 DEG C of solvent flashings obtain red powder.
F group: 2- carbazole -9- base-anthraquinone solid mix with chloroform, methanol 1:200:500 in mass ratio molten
Solution, 40 DEG C of solvent flashings obtain red powder.
G group: 2- carbazole -9- base-anthraquinone solid mix with chloroform, methanol 1:200:500 in mass ratio molten
Solution, 85 DEG C of solvent flashings obtain red powder.
Embodiment 3: the parameter of mono-crystalline structures
The single crystal parameters of the red acicular crystal of embodiment 1 (A-D group) preparation:
The single crystal parameters of the yellow rhabdolith of embodiment 2 (A-E group) preparation:
Embodiment 4: yellow piezoluminescence material crystals are transformed into red crystals
Yellow crystals made from embodiment 2 (A-E group) are smoked with different alkyl halide steams respectively, become in 1 minute red
Color crystal, alkyl halide are methylene chloride, chloroform, carbon tetrachloride, 1,1- dichloroethanes or 2- dichloroethanes;It is detected, it should
The mono-crystalline structures of red crystals are identical as red acicular crystal mono-crystalline structures made from embodiment 1 (A-D group).
Yellow crystals made from embodiment 2 (A-E group) are placed on surface plate, is milled with steel spoon, is become in 30 minutes
Red crystals;Through detecting, red acicular crystal monocrystalline knot made from the mono-crystalline structures and embodiment 1 (A-D group) of the red crystals
Structure is identical.
Embodiment 5: red piezoluminescence material crystals are transformed into yellow crystals
Red crystals made from embodiment 1 (A-D group) are placed on glass slide, 200 DEG C is heated to, becomes in 5 minutes
Yellow crystals;Through detecting, red acicular crystal monocrystalline knot made from the mono-crystalline structures and embodiment 2 (A-E group) of the yellow crystals
Structure is identical.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (6)
1.2- carbazole -9- base-application of the anthraquinone crystal in piezoluminescence material.
2. application as described in claim 1, which is characterized in that the 2- carbazole -9- base-anthraquinone crystal detect in alkyl halide or
Application in anti-fake material.
3. application as described in claim 1, which is characterized in that the 2- carbazole -9- base-anthraquinone crystal includes red needle-shaped crystalline substance
Body or yellow rhabdolith,
The parameter of the mono-crystalline structures of the red acicular crystal are as follows:
The parameter of the mono-crystalline structures of the yellow rhabdolith are as follows:
4. 2- carbazole -9- base-anthraquinone crystal preparation method as described in claim any one of 1-3, which is characterized in that comprising with
Lower step:
By 2- carbazole -9- base-anthraquinone solid, mixed with alkyl halide, N-alkanes 1:100~200:150~300 in mass ratio
Dissolution, room temperature solvent flashing obtain red acicular crystal;
The alkyl halide be dichloromethane or chloroform, the N-alkanes be pentane, n-hexane, normal heptane or petroleum ether,
The boiling range of the petroleum ether is 60-90 DEG C.
5. 2- carbazole -9- base-anthraquinone crystal preparation method as described in claim any one of 1-3, which is characterized in that comprising with
Lower step:
By 2- carbazole -9- base-anthraquinone solid, mix with alkyl halide, alcohol 1:100~200:200~500 in mass ratio molten
Solution, 50-75 DEG C of solvent flashing obtain yellow rhabdolith;
The alkyl halide is dichloromethane or chloroform, and the alcohol is methanol, ethyl alcohol, isopropanol or propyl alcohol.
6. 2- carbazole -9- base-anthraquinone crystal as claimed in claim 3 is used for the detection method of alkyl halide detection, feature exists
In the detection method are as follows: smoke the yellow rhabdolith with alkyl halide steam, the red for becoming described in 1 minute is needle-shaped
Crystal;The alkyl halide is methylene chloride, chloroform, carbon tetrachloride, 1,1- dichloroethanes or 1,2- dichloroethanes.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710685932.8A CN107502341B (en) | 2017-08-11 | 2017-08-11 | Piezoluminescence material crystals and preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710685932.8A CN107502341B (en) | 2017-08-11 | 2017-08-11 | Piezoluminescence material crystals and preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107502341A CN107502341A (en) | 2017-12-22 |
CN107502341B true CN107502341B (en) | 2019-10-18 |
Family
ID=60689132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710685932.8A Active CN107502341B (en) | 2017-08-11 | 2017-08-11 | Piezoluminescence material crystals and preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107502341B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201504392A (en) * | 2013-06-21 | 2015-02-01 | Univ Kyushu Nat Univ Corp | Red light-emitting material, organic electroluminescence device and compound |
CN105199711A (en) * | 2015-09-08 | 2015-12-30 | 河南师范大学 | Application of carbazole derivative as triboluminescence material to manufacturing of pressure-sensitive luminophor or pressure sensor |
CN106083694A (en) * | 2016-05-30 | 2016-11-09 | 山西大学 | A kind of 3,6 2 (anthraquinone 2 vinyl) N ethyl carbazole and preparation method thereof |
CN106367061A (en) * | 2016-08-23 | 2017-02-01 | 江苏第二师范学院 | Aggregation-induced light emission red delay material, preparation method and application thereof |
-
2017
- 2017-08-11 CN CN201710685932.8A patent/CN107502341B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201504392A (en) * | 2013-06-21 | 2015-02-01 | Univ Kyushu Nat Univ Corp | Red light-emitting material, organic electroluminescence device and compound |
CN105199711A (en) * | 2015-09-08 | 2015-12-30 | 河南师范大学 | Application of carbazole derivative as triboluminescence material to manufacturing of pressure-sensitive luminophor or pressure sensor |
CN106083694A (en) * | 2016-05-30 | 2016-11-09 | 山西大学 | A kind of 3,6 2 (anthraquinone 2 vinyl) N ethyl carbazole and preparation method thereof |
CN106367061A (en) * | 2016-08-23 | 2017-02-01 | 江苏第二师范学院 | Aggregation-induced light emission red delay material, preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN107502341A (en) | 2017-12-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | An ESIPT-based fluorescent switch with AIEE, solvatochromism, mechanochromism and photochromism | |
Zhang et al. | Fine-tuning the mechanofluorochromic properties of benzothiadiazole-cored cyano-substituted diphenylethene derivatives through D–A effect | |
CN107082753B (en) | A kind of compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property, preparation and application | |
CN105968377B (en) | A kind of luminescent metal organic frame compound and its preparation method and application | |
CN107200709B (en) | Fluorescent compound with aggregation-induced emission property and application thereof in cell fluorescence imaging field | |
CN106867503B (en) | Reversible force/heat/solvent multiple stimulation responsive materials and preparation method thereof that cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed | |
CN104073250A (en) | Application of light-emitting metal organic frame in detection on trace phenylamine pollutant | |
CN110483371A (en) | A kind of AIE compound and preparation method thereof with reversible force mutagens color property | |
CN107502341B (en) | Piezoluminescence material crystals and preparation method and application | |
CN104370927A (en) | Schiff base type fluorescent probe compound and preparation method thereof | |
CN108003859B (en) | A kind of piezallochromy fluorescent molecule and its preparation method and application | |
CN106588981A (en) | Temperature-sensitive fluorescent photochromic material with high quantum yield | |
CN109095445B (en) | Preparation method of hollowed-out nanobelt, hollowed-out nanobelt and application | |
CN106632063A (en) | Compound I and compound II based on phenanthroimidazole, and preparation method and applications thereof | |
CN102936498B (en) | Zirconium phosphate-based elastic stress luminescent material and preparation method thereof | |
Zhang et al. | Dependence of mechanofluorochromic property at room temperature on alkyl chain structure for β-diketone boron complex and its polymer blend film | |
CN104927841A (en) | Near infrared organic fluorescent dye with mechanical responsiveness | |
CN112662394A (en) | Thermal stimulation fluorescence/visible light color dual-response capsule and synthesis method thereof | |
CN105713598B (en) | Five substituted-tetrahydro pyrimidine derivatives are preparing the application in causing fluorescence off-color material with pressure | |
CN104807794A (en) | Application of transition metal organic zinc complex in trace nitroaromatic pollutant detection | |
CN104741108A (en) | Low-temperature preparation method for gamma crystalline phase bismuth oxide (gamma-Bi2O3) photocatalyst | |
CN106905365B (en) | Based on triaryl phosphoric-oxygenic compound and its preparation method and application | |
CN105754557A (en) | Low-temperature phase-change compound and preparation method and application thereof | |
CN109180958A (en) | A kind of Zn (II) coordination polymer and preparation method thereof based on pyrazole ring | |
CN109081784A (en) | A kind of triphenylamine derivative and its preparation method and application |
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 |