CN111574504A - Organic compound based on aza-benzene and dicarboxyl diamine derivative and application thereof - Google Patents
Organic compound based on aza-benzene and dicarboxyl diamine derivative and application thereof Download PDFInfo
- Publication number
- CN111574504A CN111574504A CN201910122163.XA CN201910122163A CN111574504A CN 111574504 A CN111574504 A CN 111574504A CN 201910122163 A CN201910122163 A CN 201910122163A CN 111574504 A CN111574504 A CN 111574504A
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- general formula
- group
- organic compound
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
- C09K2211/1007—Non-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
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- 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
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an organic compound based on aza-benzene and dicarboximide derivatives and application thereof, belonging to the technical field of semiconductors. The structure of the compound provided by the invention is shown as a general formula (1):
the invention also discloses application of the compound. The compound of the invention has higher glass transition temperatureAnd molecular thermal stability; the refractive index in the visible light field is high, and the light extraction efficiency of the OLED device can be effectively improved after the light extraction material is applied to a CPL layer of the OLED device; the compound also has a deep HOMO energy level and high electron mobility, can be used as a hole blocking/electron transport layer material of an OLED device, and can effectively block holes or energy from being transferred from a light emitting layer to one side of an electron layer, so that the recombination efficiency of the holes and electrons in the light emitting layer is improved, and the light emitting efficiency and the service life of the OLED device are improved.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to an organic compound based on an aza-benzene and a dicarboxyl diamine derivative and application thereof.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and further will be expanded to the large-size application fields of televisions and the like. However, since there is a great gap between the external quantum efficiency and the internal quantum efficiency of the OLED, the development of the OLED is greatly restricted. Therefore, how to improve the light extraction efficiency of the OLED becomes a hot point of research. Total reflection occurs at the interface between the ITO thin film and the glass substrate and at the interface between the glass substrate and the air, the light emitted to the front external space of the OLED device accounts for about 20% of the total amount of the organic material thin film EL, and the remaining about 80% of the light is mainly confined in the organic material thin film, the ITO thin film and the glass substrate in the form of guided waves. It can be seen that the light extraction efficiency of the conventional OLED device is low (about 20%), which severely restricts the development and application of the OLED. How to reduce the total reflection effect in the OLED device and improve the ratio of light coupled to the forward external space of the device (light extraction efficiency) has attracted much attention.
Currently, the improvement of OLED external quantum efficiency is realizedOne important class of methods is to form structures such as corrugations, photonic crystals, microlens arrays (mLA) and the addition of surface coatings on the light exit surface of the substrate. The first two structures can influence the radiation spectrum angle distribution of the OLED, the third structure is complex in manufacturing process, the surface covering layer is simple in using process, the luminous efficiency is improved by more than 30%, and people pay particular attention to the structure. According to the optical principle, when light is transmitted through the material with the refractive index n1To a refractive index of n2When (n) is1＞n2) Only in arcsin (n)2/n1) Can be incident within an angle of n2The absorbance B can be calculated by the following formula:
let n1＝nOrganic materials for OLEDs in general＝1.70，n2＝nGlassWhen 1.46, 2B is 0.49. Assuming that the light propagating outward is totally reflected by the metal electrode, only 51% of the light can be guided by the high refractive index organic film and the ITO layer, and the transmittance of the light when it is emitted from the glass substrate to the air can be calculated as well. So that only about 17% of the light emitted from the organic layer is visible to humans when it exits the exterior of the device. Therefore, in view of the current situation that the light extraction efficiency of the OLED device is low, a CPL layer, that is, a light extraction material needs to be added in the device structure, and according to the principles of optical absorption and refraction, the refractive index of the surface covering layer material should be as high as possible.
Current research into improving the performance of OLED light emitting devices includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the photoelectric functional material of the OLED are required to create the functional material of the OLED with higher performance.
Disclosure of Invention
It is an object of the present invention to provide organic compounds based on azabenzene and dicarboximide derivatives. The compound has higher glass transition temperature and high refractive index in the field of visible light, and can effectively improve the light extraction efficiency of the OLED device after being applied to a CPL layer of the OLED device.
The technical scheme for solving the technical problems is as follows: an organic compound based on an azabenzene and a dicarboximide derivative, the structure of the organic compound being represented by the general formula (1):
in the general formula (1), Z represents N atom, C atom or C-H, and at least one represents nitrogen atom;
x represents the number 1, 2 or 3;
R1represents substituted or unsubstituted 5-60 membered aryl, substituted or unsubstituted 5-60 membered heteroaryl containing one or more heteroatoms, 5-60 membered aryl or 5-60 membered heteroaryl substituted amino; r1Not represented as anthracene;
R2、R3independently represent a structure shown in a general formula (2), a general formula (3) or a general formula (4);
R1、R2、R3not simultaneously expressed as the structure shown in the general formula (2) or the general formula (3);
Ar1、Ar2and Ar3Each independently represents a single bond, substituted or unsubstituted C6-C30Arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms, and when R is2And R3When it is represented by the general formula (2) or the general formula (3), Ar2And Ar3Is not represented as a single bond;
in the general formula (4), R4Is represented by substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms;
the substituent of the substituent group is one or more selected from cyano, halogen atom, C1-10 alkyl, C6-30 aryl and 5-to 30-membered heteroaryl containing one or more heteroatoms;
the hetero atoms in the heteroaryl and the heteroarylene are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms.
The structure of the organic compound contains two rigid groups of aza-benzene and dicarboxyl diamine derivatives, so that the structural stability is improved; in the spatial structure, the organic compound contains strong-electron aza-benzene and dicarboximide derivative groups, and 3 groups are mutually crossed and separated to avoid free rotation of the groups, so that the organic compound has higher density and higher refractive index; at the same time, has a very high Tg. The evaporation temperature in the vacuum state is generally less than 350 ℃, so that the organic compound is not decomposed in mass production for a long time, and the influence of heat radiation of the evaporation temperature on the deformation of evaporation MASK is reduced.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, Ar is1、Ar2And Ar3Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted furylene group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted pyridazylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted N-phenylcarbazolyl group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group and a substituted or unsubstituted naphthyridine group.
Further, R is1Represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted N-benzeneCarbazolyl, substituted or unsubstituted diphenylamine group, general formula (2), general formula (3) or general formula (4).
Further, the organic compound based on the aza-benzene and the dicarboximide derivative is characterized in that R is4Is represented by one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furyl and substituted or unsubstituted fluorenylidene.
Further, the structure of the organic compound is represented by any one of general formula (5), general formula (6), and general formula (7):
wherein the symbols and indices used have the meanings given above.
Further, the specific structural formula of the organic compound is as follows:
The second object of the present invention is to provide the use of the organic compounds based on the derivatives of azabenzenes and dicarboximides in the preparation of organic electroluminescent devices. The organic compound has deep HOMO energy level and high electron mobility, and can effectively prevent holes or energy from being transferred from the light-emitting layer to one side of the electron layer, so that the recombination efficiency of the holes and electrons in the light-emitting layer is improved, the light-emitting efficiency of the OLED device is improved, and the service life of the OLED device is prolonged.
The technical scheme for solving the technical problems is as follows: use of the above-mentioned organic compounds based on an azabenzene and a dicarboximide derivative for the preparation of an organic electroluminescent device.
It is a further object of the present invention to provide an organic electroluminescent device. The compound has good application effect in OLED luminescent devices and good industrialization prospect.
The technical scheme for solving the technical problems is as follows: an organic electroluminescent device comprising at least one functional layer containing the above organic compound based on an azabenzene and a dicarboximide derivative.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the functional layer is a hole blocking layer/an electron transport layer.
Further, the functional layer is a CPL layer.
The adoption of the further beneficial effects is as follows: after the organic compound is applied to a CPL layer of an OLED device, the light extraction efficiency of the OLED device can be effectively improved.
The fourth object of the present invention is to provide a display device. The organic electroluminescent device can be applied to display elements, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
The technical scheme for solving the technical problems is as follows: a display element comprising the above organic electroluminescent device.
The invention has the beneficial effects that:
1. the structure of the organic compound contains two rigid groups of the aza-benzene and the dicarboxyl diamine derivative, so that the structural stability is improved; in the spatial structure, the organic compound contains strong-electron aza-benzene and dicarboximide derivative groups, and 3 groups are mutually crossed and separated to avoid free rotation of the groups, so that the organic compound has higher density and higher refractive index; at the same time, has a very high Tg. The evaporation temperature in the vacuum state is generally less than 350 ℃, so that the organic compound is not decomposed in mass production for a long time, and the influence of heat radiation of the evaporation temperature on the deformation of evaporation MASK is reduced.
2. The organic compound disclosed by the invention is applied to a CPL layer in an OLED device, does not participate in electron and hole transmission of the device, and has very high requirements on thermal stability, film crystallinity and light transmission (high refractive index). As analyzed above, the derivatives of the azabenzene and the dicarboximide are rigid groups, and the stability is improved; the high Tg ensures that the film is not crystallized; the low evaporation temperature is the premise of being applicable to mass production; the high refractive index is the most important factor that can be applied to the CPL layer.
3. The organic compound has deep HOMO energy level and high electron mobility, and can effectively prevent holes or energy from being transferred from the light-emitting layer to one side of the electron layer, so that the recombination efficiency of the holes and electrons in the light-emitting layer is improved, the light-emitting efficiency of the OLED device is improved, and the service life of the OLED device is prolonged. After the organic compound is applied to a CPL layer of an OLED device, the light extraction efficiency of the OLED device can be effectively improved.
4. The compound contains the structure of the aza-benzene and the dicarboxyl diamine derivative, has higher glass transition temperature and molecular thermal stability, has low absorption and high refractive index in the field of visible light, and can effectively improve the light extraction efficiency of an OLED device after being applied to a CPL layer of the OLED device; and the aza-benzene and dicarboxyl diamine derivatives have deep HOMO energy level and wide forbidden band (Eg) energy level, so that the aza-benzene and dicarboxyl diamine derivatives can be used as a hole blocking/electron transport layer material of an OLED device, block holes from being transferred from a light emitting layer to one side of an electron layer, improve the recombination degree of the holes and the electrons in the light emitting layer, and further improve the light emitting efficiency and the service life of the OLED device.
In conclusion, the compound disclosed by the invention has good application effect and industrialization prospect in OLED light-emitting devices.
Drawings
Fig. 1 is a schematic structural diagram of the application of the materials enumerated in the present invention to an OLED device, wherein the components represented by the respective reference numerals are as follows:
the OLED device comprises an OLED device substrate 1, an OLED device substrate 2, an anode layer 3, a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole blocking layer/electron transport layer 7, an electron injection layer 8, a cathode layer 9 and a CPL layer.
FIG. 2 is a graph showing refractive index measurements of Compound 1 of the present invention.
FIG. 3 shows Compound 1 of the present invention and Alq which is a known material3Comparative film acceleration experiments. Wherein, the figure a is a surface morphology diagram of the material after the film formation of the compound 1. FIG. b shows a known material Alq3Surface morphology of the material after film formation. FIG. c is a surface morphology of the material 72 hours after the experiment with Compound 1. FIG. d shows a known material Alq3After 72 hours of the experimentThe material surface morphology map of (1). FIG. e is a surface morphology of the material 600 hours after the experiment with Compound 1.
Fig. 4 is a graph of efficiency of the device measured at different temperatures.
Detailed Description
The present invention will now be described with reference to the accompanying drawings, which are given by way of illustration only and are not intended to limit the scope of the present invention.
Example 1: synthesis of intermediate M
Introducing nitrogen into a 250mL three-necked flask, adding 0.02mol of the raw material A, dissolving the raw material A in 100mL Tetrahydrofuran (THF), adding 0.024mol of the raw material B, 0.0002mol of (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.05mol of potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 80 ℃ for 5 hours; after the reaction was complete, cool and add 100mL of water, and the mixture was filtered and dried in a vacuum oven. The residue obtained was isolated and purified by means of a silica gel column to give intermediate M.
Ar-corresponds to (R) in the general formula (1)1)x-Ar1-、R2-Ar2-or R3-Ar3-any of the above.
Synthesis example of intermediate M-1:
introducing nitrogen into a 250mL three-necked flask, adding 0.02mol of raw material A-1, dissolving in 100mL Tetrahydrofuran (THF), adding 0.024mol of raw material B, 0.0002mol of (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.05mol of potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 80 ℃ for 5 hours; after the reaction was complete, cool and add 100mL of water, and the mixture was filtered and dried in a vacuum oven. The residue obtained was isolated and purified by means of a silica gel column to give intermediate M-1.
Intermediate M was prepared according to the procedure for the preparation of intermediate M-1 in example 1, using the following table 1 for the corresponding substitution of the starting materials:
TABLE 1
Example 2: synthesis of Compound 1
A250 mL three-necked flask was purged with nitrogen, charged with 0.02mol of the starting material C, 150mL of DMF, 0.048mol of the intermediate M-1 and 0.0004mol of palladium acetate, stirred, and then charged with 6mL of 0.01mol/mL of K3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 10 hours, sampling a sample, and completely reacting. After cooling naturally, 80mL of water were added, the mixture was filtered and dried in a vacuum oven, and the resulting residue was purified by silica gel column to give intermediate N-1.
In a 250mL three-necked flask, nitrogen was purged, 0.02mol of intermediate N-1, 150mL of DMF, 0.024mol of intermediate M-7 and 0.0002mol of palladium acetate were added, followed by stirring, and 3mL of 0.01mol/mL K was added3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 10 hours, sampling a sample, and completely reacting. After cooling naturally, 50mL of water was added, the mixture was filtered and dried in a vacuum oven, and the resulting residue was purified by a silica gel column to give Compound 1. Elemental analysis Structure (molecular formula C)41H25N5O4): theoretical value C, 75.57; h, 3.87; n, 10.75; test values are: c, 75.58; h, 3.89; n, 10.76. ESI-MS (M/z) (M +): theoretical value is 651.19, found 651.21.
Example 3: synthesis of Compound 3
The synthetic procedure for compound 3 was identical to that of example 2, except that intermediate M-7 in the second step was replaced with intermediate M-6. Elemental analysis Structure (molecular formula C)41H24N6O4): theoretical value C, 74.09; h, 3.64; n, 12.64; test values are: c, 74.11; h, 3.65; and N, 12.66. ESI-MS (M/z) (M +): theoretical value is 664.19, found 664.18.
Example 4: synthesis of Compound 9
The synthetic procedure for compound 9 was identical to that of example 2, except that intermediate M-1 in the first step was replaced with intermediate M-2. Elemental analysis Structure (molecular formula C)49H29N5O4): theoretical value C, 78.28; h, 3.89; n, 9.32; test values are: c, 78.29; h, 3.91; n, 9.33. ESI-MS (M/z) (M +): theoretical value is 751.22, found 751.23.
Example 5: synthesis of Compound 10
The synthetic procedure for compound 10 was identical to that of example 2, except that intermediate M-1 in the first reaction step was replaced with intermediate M-2, and intermediate M-7 in the second reaction step was replaced with intermediate M-5. Elemental analysis Structure (molecular formula C)43H25N5O4): theoretical value C, 76.43; h, 3.73; n, 10.36; test values are: c, 76.44; h, 3.75; n, 10.37. ESI-MS (M/z) (M +): theoretical value is 675.19, found 675.21.
Example 6: synthesis of Compound 13
Synthesis step of Compound 13The procedure was identical to example 2, except that intermediate M-1 in the first reaction step was replaced with intermediate M-3. Elemental analysis Structure (molecular formula C)49H29N5O4): theoretical value C, 78.28; h, 3.89; n, 9.32; test values are: c, 78.29; h, 3.88; n, 9.33. ESI-MS (M/z) (M +): theoretical value is 751.22, found 751.23.
Example 7: synthesis of Compound 53
The synthetic procedure for compound 53 was identical to that of example 2, except that intermediate M-1 in the first reaction step was replaced with intermediate M-4. Elemental analysis Structure (molecular formula C)39H23N7O4): theoretical value C, 71.66; h, 3.55; n, 15.00; test values are: c, 71.67; h, 3.57; and N, 15.01. ESI-MS (M/z) (M +): theoretical value is 653.18, found 653.20.
Example 8: synthesis of Compound 61
The synthetic procedure for compound 61 was identical to that of example 2, except that intermediate M-1 in the first reaction step was replaced with intermediate M-9. Elemental analysis Structure (molecular formula C)47H27N7O4): theoretical value C, 74.89; h, 3.61; n, 13.01; test values are: c, 74.89; h, 3.61; and N, 13.01. ESI-MS (M/z) (M +): theoretical value is 753.21, found 753.23.
Example 9: synthesis of Compound 78
The synthetic procedure for compound 78 was identical to that of example 2, except that intermediate M-1 in the first reaction step was replaced with intermediate M-2, and intermediate M-7 in the second reaction step was replaced with intermediate M-8. Elemental analysis structure(formula C)42H24N6O4): theoretical value C, 74.55; h, 3.58; n, 12.42; test values are: c, 74.56; h, 3.59; n, 12.43. ESI-MS (M/z) (M +): theoretical value is 676.19, found 676.21.
Example 10: synthesis of Compound 97
A250 mL three-necked flask was purged with nitrogen, charged with 0.02mol of the starting material C, 150mL of DMF, 0.048mol of the intermediate M-1 and 0.0006mol of palladium acetate, stirred, and then charged with 9mL of 0.01mol/mL of K3PO4Heating the aqueous solution to 150 ℃, carrying out reflux reaction for 10 hours, sampling a sample, carrying out complete reaction, and directly putting the obtained intermediate into the next reaction; intermediate M-10 is used to replace intermediate M-1 and a second coupling reaction is carried out with the intermediate obtained in the previous step, the reaction process is similar to the first step, and compound 97 is obtained. Elemental analysis Structure (molecular formula C)41H24N6O4): theoretical value C, 74.09; h, 3.64; n, 12.64; test values are: c, 74.11; h, 3.65; n, 12.65; . ESI-MS (M/z) (M +): theoretical value is 664.19, found 664.21.
Example 11: synthesis of Compound 100
The synthetic procedure for compound 100 was identical to that of example 10, except that intermediate M-1 was replaced with intermediate M-2. Elemental analysis Structure (molecular formula C)49H28N6O4): theoretical value C, 76.95; h, 3.69; n, 10.99; test values are: c, 76.96; h, 3.68; n, 10.98. ESI-MS (M/z) (M +): theoretical value is 764.22, found 764.24.
Example 12: synthesis of Compound 132
The synthetic procedure for compound 132 was identical to that of example 10, except that intermediate M-1 in the first reaction step was replaced with intermediate M-9 and intermediate M-10 in the second reaction step was replaced with intermediate M-11. Elemental analysis Structure (molecular formula C)46H27N9O4): theoretical value C, 71.77; h, 3.54; n, 16.38; test values are: c, 71.78; h, 3.56; n, 16.39. ESI-MS (M/z) (M +): theoretical value is 769.22, found 769.24.
Example 13: synthesis of Compound 148
The synthetic procedure for compound 148 was identical to that of example 10, except that starting material C was replaced with starting material D and intermediate M-10 was replaced with intermediate M-11. Elemental analysis Structure (molecular formula C)42H27N5O4): theoretical value C, 75.78; h, 4.09; n, 10.52; test values are: c, 75.78; h, 4.09; n, 10.52. ESI-MS (M/z) (M +): theoretical value is 665.71, found 665.73.
Example 14: synthesis of Compound 151
The synthetic procedure for compound 151 was identical to that of example 10, except that intermediate M-1 in the first reaction step was replaced with intermediate M-12 and starting material C was replaced with starting material G. Elemental analysis Structure (molecular formula C)57H34N6O4): theoretical value C, 78.97; h, 3.95; n, 9.69; test values are: c, 78.96; h, 3.93; and N, 9.68. ESI-MS (M/z) (M +): theoretical value is 866.26, found 866.24.
Example 15: synthesis of Compound 180
The procedure for the synthesis of compound 180 is identical to that of example 2, except thatAnd replacing the intermediate M-1 in the one-step reaction with an intermediate M-2, and replacing the raw material C with a raw material D. Elemental analysis Structure (molecular formula C)50H30N4O4): theoretical value C, 79.99; h, 4.03; n, 7.46; test values are: c, 79.98; h, 4.04; and N, 7.46. ESI-MS (M/z) (M +): theoretical value is 750.23, found 750.24.
The organic compounds of the present invention are useful as CPL layer materials in light emitting devices, having high Tg (glass transition temperature) and high refractive index. The thermal properties and refractive index of the compounds of the present invention and the conventional materials were measured, respectively, and the results are shown in Table 2. The refractive index test chart of compound 1 is shown in fig. 2.
TABLE 2
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the refractive index was measured by an ellipsometer (U.S. J.A. Woollam Co. model: ALPHA-SE) and measured as an atmospheric environment.
As can be seen from the data in Table 2, the Alq applied at present is compared3The organic compound has high glass transition temperature and high refractive index, and simultaneously, because the organic compound contains rigid groups of the aza-benzene and the dicarboxyl diamine derivatives, the thermal stability of the material is ensured. Therefore, after the organic material taking the aza-benzene and the dicarboximide derivative as the core is applied to the CPL layer of the OLED device, the light extraction efficiency of the device can be effectively improved, and the long service life of the OLED device is ensured.
The application effect of the synthesized OLED material of the present invention in the device is detailed by device examples 1-15 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 15 and the device comparative example 1 of the present invention have the same manufacturing process, and adopt the same substrate material and electrode material, the film thickness of the electrode material is also kept consistent, except that the device embodiments 2 to 13 change the CPL layer material in the device; device examples 14-15 were prepared by changing the hole blocking or electron transport layer materials of the devices, and the results of performance testing of the devices obtained from each example are shown in table 3.
Device example 1: as shown in fig. 1, an electroluminescent device is prepared by the steps of:
a) cleaning an ITO anode layer 2 on a transparent OLED device substrate 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3; c) evaporating a hole transport material HT-1 on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material HT-1 is 80nm, and the hole transport layer is a hole transport layer 4; d) and (2) evaporating a light-emitting layer 5, GH-2 and GH-1 as host materials and GD-1 as doping materials on the hole transport layer 4, wherein the mass ratio of GH-2 to GH-1 to GD-1 is 45: 45: 10, thickness of 30 nm; e) evaporating electron transport materials ET-1 and Liq on the light emitting layer 5 in a vacuum evaporation mode, wherein the mass ratio is 1:1, the thickness is 40nm, and the organic material of the layer is used as a hole blocking/electron transport layer 6; f) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 6, wherein the layer is an electron injection layer 7; g) on the electron injection layer 7, a cathode Mg: an Ag layer, wherein the doping ratio of Mg to Ag is 9:1, the thickness of the Ag layer is 15nm, and the Ag layer is a cathode layer 8; h) on the cathode layer 8, the CPL material compound 3 was deposited by vacuum deposition to a thickness of 60nm, and this layer of organic material was used as the CPL layer 9. After the electroluminescent device was fabricated according to the above procedure, the current efficiency and lifetime of the device were measured, and the results are shown in table 6. The molecular mechanism formula of the related material is as follows:
device example 2: the CPL layer material of the electroluminescent device becomes compound 3 of the present invention.
Device example 3: the CPL layer material of the electroluminescent device becomes compound 9 of the present invention.
Device example 4: the CPL layer material of the electroluminescent device becomes the compound 10 of the present invention.
Device example 5: the CPL layer material of the electroluminescent device becomes compound 21 of the present invention.
Device example 6: the CPL layer material of the electroluminescent device becomes the compound 152 of the present invention.
Device example 7: the CPL layer material of the electroluminescent device becomes the compound 120 of the present invention.
Device example 8: the CPL layer material of the electroluminescent device becomes the compound 79 of the present invention.
Device example 9: the CPL layer material of the electroluminescent device was changed to compound 189 of the present invention.
Device example 10: the CPL layer material of the electroluminescent device becomes the compound 190 of the present invention.
Device example 11: the CPL layer material of the electroluminescent device becomes the compound 217 of the present invention.
Device example 12: the CPL layer material of the electroluminescent device becomes the compound 220 of the present invention.
Device example 13: the CPL layer material of the electroluminescent device becomes the compound 223 of the present invention.
Device example 14: the hole-blocking or electron-transporting layer material of the electroluminescent device is changed into the compound 180 of the invention, and the CPL layer material is changed into the known material Alq3。
Device example 15: the hole-blocking or electron-transporting layer material of the electroluminescent device is changed into the compound 205 of the invention, and the CPL layer material is changed into the known material Alq3。
Device comparative example 1: CPL layer material of electroluminescent device is changed into known material Alq3. The inspection data of the obtained electroluminescent device are shown in Table 3.
TABLE 3
The results in table 3 show that, when the organic compound with the core of the aza-benzene and the dicarboximide derivative of the present invention is applied to the fabrication of an OLED light-emitting device, compared with comparative device example 1, the light extraction is significantly improved, the device luminance and the device efficiency are both improved under the same current density, and as the luminance and the efficiency are improved, the power consumption of the OLED device at a constant luminance is relatively reduced, and the service life is also improved.
In order to illustrate the phase crystallization stability of the material film of the invention, the material compound 1 of the invention and the known material Alq are mixed3A film accelerated crystallization experiment was performed: respectively adding the compound 1 and Alq by vacuum evaporation3The film was deposited on alkali-free glass, sealed in a glove box (water oxygen content < 0.1ppm), the sealed sample was placed under conditions of double 85 (temperature 85 ℃, humidity 85%), the crystalline state of the material film was observed periodically with a microscope (LEICA, DM8000M, 5 × 10 magnification), the experimental results are shown in table 4, and the material surface morphology is shown in fig. 3:
TABLE 4
| Name of | Compound | 1 | Alq3 |
| After the material is formed into film | The surface shape is smooth and even | The surface shape is smooth and even | |
| After 72 hours of the experiment | The surface shape is smooth, even and no crystal | The surface forms a plurality of scattered circular crystal planes | |
| After 600 hours of the experiment | The surface shape is smooth, even and no crystal | Surface cracking |
The experiments show that the film crystallization stability of the material is far higher than that of the known material, and the material has a beneficial effect on the service life after being applied to an OLED device.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 2, 7 and 11 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 5 and the figure 4.
TABLE 5
As can be seen from the data in table 5 and fig. 4, device examples 2, 7, and 11 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An organic compound based on an azabenzene and a dicarboximide derivative, characterized in that the structure of the organic compound is represented by general formula (1):
in the general formula (1), Z represents N atom, C atom or C-H, and at least one represents N atom;
x represents the number 1, 2 or 3;
R1represents substituted or unsubstituted 5-60 membered aryl, substituted or unsubstituted 5-60 membered heteroaryl containing one or more heteroatoms, 5-60 membered aryl or 5-60 membered heteroaryl substituted amino; r1Not represented as anthracene;
R2、R3independently represent a structure shown in a general formula (2), a general formula (3) or a general formula (4);
R1、R2、R3not simultaneously expressed as the structure shown in the general formula (2) or the general formula (3);
Ar1、Ar2and Ar3Each independently represents a single bond, substituted or unsubstituted C6-C30Arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms, and when R is2And R3When it is represented by the general formula (2) or the general formula (3), Ar2And Ar3Is not represented as a single bond;
in the general formula (4), R4Is represented by substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms;
the above-mentioned substituent for the substitutable group is optionally selected from a cyano group, a halogen atom, C1-10Alkyl radical, C6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the hetero atoms in the heteroaryl and the heteroarylene are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms.
2. An organic compound based on an azepine and a dicarboxamide derivative according to claim 1 characterised in that said Ar is1、Ar2And Ar3Are independent of each otherIs represented by a single bond, or one of a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted furylene group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted pyridazylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted N-phenylcarbazolyl group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted naphthyrylene group, and when R is2And R3When it is represented by the general formula (2) or the general formula (3), Ar2And Ar3Not represented as a single bond.
3. An organic compound based on an azepine and a dicarboxamide derivative according to claim 1, characterised in that said R is1The compound is represented by one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furyl, substituted or unsubstituted fluorenylidene, substituted or unsubstituted N-phenyl carbazolyl, substituted or unsubstituted diphenylamine, general formula (2), general formula (3) and general formula (4).
4. An organic compound based on an azepine and a dicarboxamide derivative according to claim 1, characterised in that said R is4Is represented by one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furyl and substituted or unsubstituted fluorenylidene.
5. The organic compound based on an azepine and a dicarboximide derivative according to claim 1, wherein the structure of the organic compound is represented by any one of general formula (5), general formula (6), and general formula (7):
wherein the symbols and indices used have the meanings given in claim 1.
6. An organic compound based on an azepine and a dicarboximide derivative according to any one of claims 1 to 3 wherein the organic compound has the following specific structural formula:
7. Use of an organic compound based on an azepine and a dicarboximide derivative according to any one of claims 1 to 5 in the preparation of an organic electroluminescent device.
8. An organic electroluminescent device comprising at least one functional layer containing the organic compound based on an azepine and a dicarboximide derivative according to any one of claims 1 to 5.
9. An organic electroluminescent device according to claim 7, wherein the functional layer is a hole blocking layer or an electron transporting layer.
10. An organic electroluminescent device according to claim 7, wherein the functional layer is a CPL layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910122163.XA CN111574504A (en) | 2019-02-19 | 2019-02-19 | Organic compound based on aza-benzene and dicarboxyl diamine derivative and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910122163.XA CN111574504A (en) | 2019-02-19 | 2019-02-19 | Organic compound based on aza-benzene and dicarboxyl diamine derivative and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111574504A true CN111574504A (en) | 2020-08-25 |
Family
ID=72122512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910122163.XA Pending CN111574504A (en) | 2019-02-19 | 2019-02-19 | Organic compound based on aza-benzene and dicarboxyl diamine derivative and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111574504A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11760764B2 (en) | 2020-05-22 | 2023-09-19 | Aligos Therapeutics, Inc. | Methods and compositions for targeting PD-L1 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004032716A2 (en) * | 2002-10-08 | 2004-04-22 | Massachusetts Institute Of Technology | Compounds for modulation of cholesterol transport |
| US20070203236A1 (en) * | 2006-01-11 | 2007-08-30 | Smith Jeffrey W | Novel antagonists of the human fatty acid synthase thioesterase |
| CN101489542A (en) * | 2006-03-09 | 2009-07-22 | 塞尼科斯生物科学股份有限公司 | Use of inhibitors of scavenger receptor class proteins for the treatment of infectious diseases |
| CN107417668A (en) * | 2017-05-11 | 2017-12-01 | 江苏三月光电科技有限公司 | A kind of organic compound based on pyridine and benzimidazole and its application on OLED |
-
2019
- 2019-02-19 CN CN201910122163.XA patent/CN111574504A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004032716A2 (en) * | 2002-10-08 | 2004-04-22 | Massachusetts Institute Of Technology | Compounds for modulation of cholesterol transport |
| US20070203236A1 (en) * | 2006-01-11 | 2007-08-30 | Smith Jeffrey W | Novel antagonists of the human fatty acid synthase thioesterase |
| CN101489542A (en) * | 2006-03-09 | 2009-07-22 | 塞尼科斯生物科学股份有限公司 | Use of inhibitors of scavenger receptor class proteins for the treatment of infectious diseases |
| CN107417668A (en) * | 2017-05-11 | 2017-12-01 | 江苏三月光电科技有限公司 | A kind of organic compound based on pyridine and benzimidazole and its application on OLED |
Non-Patent Citations (1)
| Title |
|---|
| LEI, RUI等: "Novel Sulfonated Polyimide Ionomers by Incorporating Pyridine Functional Group in the Polymer Backbone", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11760764B2 (en) | 2020-05-22 | 2023-09-19 | Aligos Therapeutics, Inc. | Methods and compositions for targeting PD-L1 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109824659B (en) | Organic compound based on heteroaryl amine structure and application thereof | |
| CN109761967B (en) | Organic compound based on heteroaryl amine structure and application thereof in OLED | |
| CN109206420B (en) | Triazine-based organic compound and application thereof in organic electroluminescent device | |
| CN109449304B (en) | Organic compound based on triazine and benzimidazole and application of organic compound in organic electroluminescent device | |
| CN110229145B (en) | Azabenzene-based organic compound and application thereof in OLED | |
| CN107417668B (en) | Organic compound based on azabenzene and benzimidazole and application of organic compound to OLED | |
| WO2019114478A1 (en) | Organic compound based on triazine and benzoxazole and use thereof in organic electroluminescent device | |
| CN111253332A (en) | Organic compound, preparation method thereof and application of organic compound in OLED | |
| CN110878091B (en) | Organic compound based on triazine and anthrone structure and application thereof | |
| CN109912431B (en) | Triarylamine organic compound containing naphthalene and application thereof | |
| WO2019061796A1 (en) | Organic compound with triazine and quinoxaline as core and application thereof in oled | |
| CN110872286B (en) | Organic compound based on azabenzene and benzoxadiazole and application thereof | |
| CN106220649B (en) | Diaryl ketone-based compound and application thereof in organic electroluminescent device | |
| CN111808085B (en) | Compound and application thereof, and organic electroluminescent device comprising compound | |
| CN110526901A (en) | A kind of luminous organic material and its application for preparing organic electroluminescence device | |
| CN110964038A (en) | Organic compound based on triazine and benzimidazolone structure and application of organic compound to organic electroluminescent device | |
| CN106467458B (en) | A kind of compound based on diaryl ketone and its application on organic electroluminescence device | |
| CN110642732B (en) | Organic compound containing spirofluorene anthrone structure and application thereof | |
| CN110835304A (en) | Compound with spirofluorene structure as core, preparation method and application thereof | |
| CN110885338A (en) | Organic compound with triarylamine as core, preparation method and application thereof | |
| CN111253382B (en) | Organic compound with ketone derivative as core, preparation method and application thereof | |
| CN110734446A (en) | organic compound and application thereof | |
| CN107056763A (en) | A kind of electroluminescent organic material and its application using xanthene as core | |
| CN110577523B (en) | Compound containing triarylamine structure and organic electroluminescent device prepared from compound | |
| CN109912592B (en) | Compound containing pyridoindole and application of compound in organic electroluminescent device |
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: 214112 No.210 Xinzhou Road, Wuxi City, Jiangsu Province Applicant after: Jiangsu March Technology Co.,Ltd. Address before: 214112 No.210 Xinzhou Road, New District, Wuxi City, Jiangsu Province Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200825 |
|
| WD01 | Invention patent application deemed withdrawn after publication |