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WO2020077633A1 - Organic magnetic molecule, film packaging structure and preparation method therefor, and display apparatus - Google Patents

Organic magnetic molecule, film packaging structure and preparation method therefor, and display apparatus Download PDF

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Publication number
WO2020077633A1
WO2020077633A1 PCT/CN2018/111081 CN2018111081W WO2020077633A1 WO 2020077633 A1 WO2020077633 A1 WO 2020077633A1 CN 2018111081 W CN2018111081 W CN 2018111081W WO 2020077633 A1 WO2020077633 A1 WO 2020077633A1
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group
substrate
organic
magnetic
alkyl
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PCT/CN2018/111081
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French (fr)
Chinese (zh)
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汪少安
陈龙
陈羿恺
赵小虎
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深圳市柔宇科技有限公司
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Priority to PCT/CN2018/111081 priority Critical patent/WO2020077633A1/en
Publication of WO2020077633A1 publication Critical patent/WO2020077633A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings

Definitions

  • the invention relates to the technical field of materials, in particular to organic magnetic molecules, a thin-film encapsulation structure, a preparation method thereof, and a display device.
  • OLED Organic Light Emitting Diode
  • its devices have wide application prospects due to their advantages of fast response, high contrast and flexibility.
  • the OLED device will exhibit corrosion damage. Therefore, choosing a better packaging method is particularly important for OLED devices.
  • thin film packaging is a packaging method widely used in the production of OLED displays, that is, an inorganic-organic stack structure is used to cover the OLED device to achieve the effects of blocking water and oxygen, stress release, and planarization.
  • the invention aims to provide an organic magnetic molecule, a thin-film encapsulation structure, a preparation method and a display device thereof, and the thin-film encapsulation structure prepared by using the organic magnetic molecule can have good water-oxygen barrier ability, bending resistance and tensile resistance Performance improves the performance of the display device.
  • the invention proposes an organic magnetic molecule.
  • the organic magnetic molecule includes: a host group; a linking group; and a magnetic group, the host group and the magnetic group are connected through the linking group.
  • the inventor connects the magnetic group on the host group through a linking group, so that the molecule containing the magnetic group has magnetism and can be aligned under the guidance of magnetic guidance.
  • the organic polymer material formed after curing has strong water-oxygen barrier ability, good tensile resistance and good bending property.
  • the above organic magnetic molecules may also have the following additional technical features:
  • the magnetic group has a molecular structure as shown below or is a C 1-8 heterocyclic group, the hetero atom is at least N atom, and the N atom and the oxygen atom form a nitroxide radical,
  • M is selected from metal ions.
  • the metal ions include iron ions, cobalt ions, or nickel ions.
  • the C 1-8 heterocyclic group has a molecular structure of at least one of the following:
  • the host group is selected from groups that can undergo polymerization under at least one condition of heating and light to form a polymer.
  • the host group is selected from at least one of the following: acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane group Acrylic group, siloxane group and silazinyl group; wherein, the acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane acrylic group , Siloxane group or silazane group can be optionally selected from one or more of F, Cl, Br, I, -OH, -NO 2 , -NH 2 , -CN, C 1-6 alkyl , Halogenated C 1-6 alkyl, C 1-6 alkoxy C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, alkylamino C 1-6 alkyl, C 3 ⁇ 6 cycloalkyl, C 3-6 cycloalkyl C
  • the linking group is selected from at least one of the following: C 1-6 alkyl, halogenated C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 2-6 alkenyl C 1-6 alkyl, C 2-6 alkynyl C 1-6 alkyl, C 1 ⁇ 6 alkylamino C 1-6 alkyl, amido C 1-6 alkyl, carboxy C 1-6 alkyl and carbonyl C 1-6 alkyl.
  • the organic magnetic molecule has one of the following molecular structures:
  • the present invention provides a thin film packaging structure.
  • the thin film packaging structure includes: a first substrate; an organic layer covering the surface of the first substrate; and a second substrate covering the second substrate The organic layer is away from the surface of the first substrate; wherein, the organic layer includes at least a polymer formed of the organic magnetic molecules described above.
  • the organic magnetic molecules of the present invention have magnetism, and after being applied on the first substrate, they are aligned under the guidance of magnetic guidance, and after curing, form a thin film with a regular arrangement structure, making the thin film encapsulation structure water and oxygen Strong barrier ability, tensile resistance, good bending performance and long service life of the protected device.
  • the present invention provides a method for preparing the aforementioned thin film packaging structure.
  • the method includes: providing the first substrate; applying a mixed solution containing the organic magnetic molecules and an initiator on the surface of the first substrate; A magnetic force generating device is provided on the surface side of the bottom for magnetic guidance to form a thin layer of liquid organic magnetic molecules aligned; and curing the thin layer of liquid organic magnetic molecules to form the organic layer.
  • the method further includes: forming a second substrate on a surface of the organic layer away from the first substrate, so as to obtain the thin film packaging structure.
  • the magnetic force generating device is selected from at least one of an electromagnet and a permanent magnet.
  • a method of curing the thin layer of liquid organic magnetic molecules includes at least one of heating and light irradiation.
  • the initiator is selected from free radical initiators.
  • the invention proposes a display device.
  • the display device includes: a substrate to be packaged; and the thin film packaging structure described above, the thin film packaging structure covering the substrate to be packaged.
  • the display device according to the embodiment of the present invention has strong water and oxygen barrier capabilities and a long service life.
  • FIG. 1 shows a schematic diagram of an organic magnetic molecular structure according to an embodiment of the present invention
  • FIG. 2 shows a schematic diagram of a thin film packaging structure according to an embodiment of the present invention
  • FIG. 3 shows a schematic flowchart of a method for preparing a thin film packaging structure according to an embodiment of the present invention.
  • first and second are used for description purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features.
  • the features defined as “first” and “second” may explicitly or implicitly include one or more of the features.
  • the meaning of “plurality” is two or more.
  • the invention provides an organic magnetic molecule, a thin film packaging structure, a preparation method thereof and a display device, which will be described in detail below.
  • the invention proposes an organic magnetic molecule.
  • the organic magnetic molecule includes: a host group; a linking group; and a magnetic group, the host group and the magnetic group are connected by the linking group.
  • the inventor connects the magnetic group to the host group through a linking group, so that the molecules containing the magnetic group have magnetic properties and can be aligned under the guidance of magnetic guidance.
  • the organic polymer material formed after curing has better performance, for example, it is used in a thin-film encapsulation structure to make it have strong water-oxygen barrier ability, good resistance to stretching, good bending, and a long service life of the protected device.
  • an organic magnetic molecule is one or more atoms of a host group 100 (which can also be understood as a main chain) are replaced by a linking group 200, and one end of the linking group 200 is connected to the host group 100 Connected, one end is connected to the magnetic group 300.
  • the main group is a functional group, which endows the organic magnetic molecules with corresponding functions. For example, for the thin film encapsulation structure, it has the effects of flattening the inorganic material layer, bending resistance, and improving the water and oxygen barrier capabilities.
  • the magnetic group mainly gives the molecules With magnetic properties, it can drive the orientation of the main groups under the guidance of magnetic guidance, so that the organic polymer material formed after curing has better performance.
  • a host group may correspond to a linking group and a magnetic group, or a host group may correspond to multiple groups.
  • Each connecting group corresponds to one magnetic group, or one host group corresponds to multiple connecting groups, and each connecting group corresponds to multiple magnetic groups, which can be flexibly selected according to actual conditions.
  • the present invention does not strictly limit the polymerization degree of the polymer, and can be flexibly selected according to the actual situation. According to a specific embodiment of the present invention, the polymerization degree of the polymer is 2-200.
  • the magnetic group has a molecular structure as shown below or is a C 1-8 heterocyclic group, the hetero atom is at least N atom, and the N atom and the oxygen atom form a nitroxide radical,
  • M is selected from metal ions.
  • the metal ions include iron ions, cobalt ions, or nickel ions.
  • the C 1-8 heterocyclic group has a molecular structure of at least one of the following:
  • the inventor obtained the above-mentioned superior magnetic group through a large number of experiments, which is connected to the host group through the connecting group, so that the organic magnetic molecules can be aligned under the action of magnetic guidance, and the gap between the chains is small.
  • the magnetic group has little effect on the structure and function of the host group, and the magnetic group is easily connected to the linking group, which reduces the difficulty of synthesis and is suitable for large-scale production.
  • the host group is selected from groups that can undergo polymerization under at least one condition of heating and light to form a polymer.
  • the organic magnetic molecules can be cured under heating and / or light irradiation conditions to form a thin layer of organic magnetic molecules.
  • the present invention does not strictly limit the type of host group, and can be flexibly selected according to the actual film packaging structure requirements.
  • the host group is selected from at least one of the following: acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane acrylic group , Siloxane group and silazane group; among them, acrylate group, vinyl group, styrene group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane acrylate group, siloxane
  • the group or silazinyl group may be optionally selected from one or more selected from F, Cl, Br, I, -OH, -NO 2 , -NH 2 , -CN, C 1-6 alkyl, halogenated C 1 to 6 alkyl, C 1 to 6 alkoxy C 1 to 6 alkyl, C 2 to 6 alkenyl, C 2 to
  • the host group has a molecular structure of at least one of the following:
  • R is selected from C n H 2n + 1 and n is selected from an integer of 0-10.
  • the inventor obtained the above-mentioned superior host group through a lot of experiments.
  • the linking group and the magnetic group have little effect on the structure and function of the host group, and the host group is easily connected to the linking group, which reduces the difficulty of synthesis.
  • the organic magnetic molecules containing the host group can flatten the inorganic material layer, giving it properties such as resistance to bending and water and oxygen barriers.
  • the linking group is selected from at least one of the following: C 1-6 alkyl, halogenated C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy C 1 ⁇ 6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 2-6 alkenyl C 1-6 alkyl, C 2-6 alkynyl C 1-6 alkyl, C 1-6 alkane Amino C 1-6 alkyl, amido C 1-6 alkyl, carboxy C 1-6 alkyl and carbonyl C 1-6 alkyl.
  • the linking group has one of the following molecular structures:
  • n is selected from the integer of 0-10.
  • the organic magnetic molecule has one of the following molecular structures:
  • the inventors obtained the above-mentioned superior organic magnetic molecular structure through a large number of experiments.
  • the main group is connected to the magnetic group through the connecting group, so that the organic magnetic molecules are magnetic and can be aligned under the guidance of magnetic guidance to make the molecular packing more compact.
  • the gap between the chains is smaller, and the water-oxygen barrier ability, tensile resistance and bending resistance of the organic polymer material formed after curing have stronger advantages, and the service life of the protected device is also longer.
  • the connection between the three groups has little effect on their respective structures and functions, is easy to synthesize, and is suitable for large-scale production.
  • the present invention provides a thin film packaging structure.
  • the thin film packaging structure includes: a first substrate 10; an organic layer 20 covering the surface of the first substrate 10; and a second substrate 30, a second substrate The bottom 30 covers the surface of the organic layer 20 away from the first substrate 10; wherein, the organic layer 20 includes at least a polymer formed of the organic magnetic molecules described above.
  • the organic magnetic molecules of the present invention have magnetism, and after being applied on the first substrate, they are aligned under the guidance of magnetic guidance, so that the molecules are packed more closely, the gap between the chains is smaller, and the The mechanical properties of the film are stronger, which makes the film packaging structure have better water and oxygen barrier capabilities, good tensile resistance, bending resistance and long service life of the protected device.
  • the materials for forming the first substrate and the second substrate are not strictly limited, and can be flexibly selected according to actual conditions.
  • the first substrate and the second substrate are selected from inorganic layers.
  • it may be an inorganic layer formed of oxide, fluoride, and / or silicon nitride.
  • the present invention does not strictly limit the number of layers of the first substrate, the organic layer, and the second substrate in the thin film packaging structure, as long as the first substrate and the second substrate are relatively arranged on the organic layer Both sides are sufficient, for example, the first substrate / organic layer / second substrate / organic layer / first substrate / organic layer / second substrate, the first substrate / organic layer / second substrate / organic Layer / first substrate / organic layer / second substrate / organic layer / first substrate.
  • the present invention provides a method for preparing the aforementioned thin film packaging structure. According to an embodiment of the present invention, referring to FIG. 3, the method includes:
  • step S100 a first substrate is provided.
  • step S200 a mixed liquid containing organic magnetic molecules and an initiator is applied on the surface of the first substrate.
  • the initiator is selected from free radical initiators.
  • the initiator is selected from at least one of the following: benzoyl peroxide, lauroyl peroxide, cumene hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, Dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicycloperoxydicarbonate Hexyl ester, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptanonitrile, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexylbenzene Ketone, 2-methyl-2- (4-
  • the initiator is selected from 2,4,6-trimethylbenzoyl-diphenylphosphine oxide or ethyl 2,4,6-trimethylbenzoylphenylphosphonate.
  • the content of the initiator is 0.1-20% by volume based on the total volume of the mixed liquid.
  • applying the mixed liquid containing the organic magnetic molecules and the initiator includes using an inkjet printing method or a chemical vapor deposition method.
  • an inkjet printing method or a chemical vapor deposition method is easy to form a thin and uniform film.
  • step S300 a magnetic force generating device is provided on the surface side of the first substrate to perform magnetic guidance, so as to form a thin layer of liquid organic magnetic molecules aligned.
  • a magnetic force generating device is provided on the surface side of the first substrate for magnetic guidance, so as to form a thin layer of liquid organic magnetic molecules aligned.
  • the organic magnetic molecules of the present invention have magnetic properties, and by applying magnetic guidance, the organic magnetic molecules can be aligned.
  • the magnetic force generating device is selected from at least one of electromagnets and permanent magnets. According to another embodiment of the present invention, the magnetic force generated by the magnetic force generating device is 0.001 to 100T. Thereby, the organic magnetic molecules can be aligned and a thin layer of liquid organic magnetic molecules can be formed on the surface of the first substrate.
  • step S400 a thin layer of liquid organic magnetic molecules is cured to form an organic layer.
  • the organic magnetic molecules undergo a curing reaction to form a polymer, resulting in a thin film with a regular and ordered structure, which makes the film packaging structure strong in water and oxygen barriers, good in resistance to stretching and bending, and The protected device has a long service life.
  • a method of curing a thin layer of liquid organic magnetic molecules includes at least one of heating and light irradiation.
  • the method further includes forming a second substrate on the surface of the organic layer away from the first substrate, so as to obtain a thin film packaging structure.
  • the method of applying the mixed liquid containing the organic magnetic molecules and the initiator is not strictly limited, and can be flexibly selected according to the actual situation.
  • applying the mixed liquid containing the organic magnetic molecules and the initiator includes using an inkjet printing method or a chemical vapor deposition method.
  • a thin layer of liquid organic magnetic molecules can be formed on the surface of the first substrate, and the thickness of the thin layer is uniform.
  • the invention proposes a display device.
  • a display device includes: a substrate to be packaged; and the thin film packaging structure described above, the thin film packaging structure covering the substrate to be packaged. Therefore, the display device according to the embodiment of the present invention has such properties as strong water-oxygen barrier capability and long service life.
  • the surface of the first substrate or the second substrate away from the organic layer covers the substrate to be packaged.
  • Step 1 Synthesis of chloromethylferrocene.
  • the synthetic route is shown in formula (1a).
  • the specific synthesis steps are as follows: 1.6 g of paraformaldehyde, 4.0 g of anhydrous zinc chloride and 6 ml of concentrated hydrochloric acid are added to the three-necked flask, and heated and stirred. When the temperature rises to 60 degrees Celsius, add 2g of ferrocene, and quickly pass the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, and control the amount of the passed gas by the dripping acceleration of concentrated sulfuric acid. The excess gas is absorbed with water.
  • the reaction was completed after 6h, neutralized with a 5% sodium carbonate aqueous solution to a pH between 5-7, the reaction liquid was extracted with chloroform, the organic layer was collected and washed with 10% sodium carbonate solution twice and distilled water three times, then Dry with anhydrous sodium sulfate, filter, and the filtrate is slowly dropped into 500ml of methanol to precipitate a brown solid, which is dried by suction filtration, and the filter cake is placed in a vacuum drying oven at 60 ° C and dried in vacuum for 2h to obtain crude chloromethylferrocene The product is 1.4g without further purification.
  • Step 2 Synthesis of hydroxymethyl ferrocene, the synthetic route is shown in formula (1b).
  • the specific synthesis steps are as follows: Weigh 1g of the chloromethyl ferrocene prepared in the previous step into a round-bottom flask, add 30ml of toluene to dissolve, slowly pour 5ml of 20% aqueous sodium hydroxide solution into the round-bottom flask, heat and stir to reflux 12 hour.
  • Step 3 Synthesis of organic magnetic molecules (1), the synthetic route is shown in formula (1c).
  • the specific synthesis steps are as follows: Weigh 0.6g hydroxymethyl ferrocene into a round bottom flask, add 5ml of tetrahydrofuran, stir and dissolve it in an ice bath, wrap the round bottom flask with aluminum foil, and slowly drop 0.3ml of methacryloyl chloride, After 30min, the ice bath was removed, and the reaction was carried out at room temperature for 2h. After the reaction was completed, 30ml of water was added, followed by extraction with ether. The organic layer was collected and washed with 10% sodium carbonate solution twice, distilled water three times, and then dried over anhydrous sodium sulfate.
  • Step 1 Synthesis of chloromethyl nickelocene, the synthetic route is shown in formula (2a).
  • the specific synthesis steps are as follows: 1.6 g of paraformaldehyde, 4.0 g of anhydrous zinc chloride and 6 ml of concentrated hydrochloric acid are added to the three-necked flask, and heated and stirred. When the temperature rises to 60 degrees Celsius, 2g of nickelocene is added, and the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride is quickly introduced, and the amount of the introduced gas is controlled by the dripping speed of concentrated sulfuric acid. The excess gas is absorbed with water.
  • the reaction was completed after 6h, neutralized with 5% sodium carbonate aqueous solution to pH value between 5-7, extracted with chloroform, the organic layer was collected and washed with 10% sodium carbonate solution twice in sequence, washed with distilled water three times, and then Anhydrous sodium sulfate was dried, filtered, the filtrate was slowly dropped into 500ml of methanol, a brown solid was precipitated, dried by suction filtration, the filter cake was placed in a vacuum drying oven at 60 ° C and vacuum dried for 2h to obtain crude chloromethyl nickelocene 1.3g without further purification.
  • Step 2 Synthesis of hydroxymethyl nickelocene, the synthetic route is shown in formula (2b).
  • the specific synthesis steps are as follows: Weigh 1g of the chloromethyl nickelocene prepared in the previous step into a round bottom flask, add 30ml of toluene to dissolve, slowly pour 5ml of 20% sodium hydroxide aqueous solution into the round bottom flask, and stir and reflux 12 hours.
  • Step 3 Synthesis of intermediate 1, the synthetic route is shown in formula (2c).
  • the specific synthesis steps are as follows: Weigh 0.8g of hydroxymethyl nickelocene into a round bottom flask, add 10ml of boron trifluoride etherate complex, and pass ethylene oxide gas at 25-30 ° C with stirring. After passing through, the temperature is automatically increased to 38-45 ° C, and the resulting reaction solution is neutralized with potassium hydroxide-methanol solution to a pH value between 8-9. It was then extracted with ether. The organic layer was washed twice with 10% sodium carbonate solution and washed three times with distilled water, then dried over anhydrous sodium sulfate, and filtered.
  • Step 4 Synthesis of organic magnetic molecules (2), the synthetic route is shown in formula (2d).
  • the specific synthesis steps are as follows: Weigh 0.6g of intermediate 1 into a round bottom flask, add 5ml of tetrahydrofuran, stir and dissolve in an ice bath, wrap the round bottom flask with aluminum foil, slowly drop 0.3ml of methacryloyl chloride, and remove after 30min The reaction was performed in an ice bath at room temperature for 2h. After the reaction was completed, 30ml of water was added, followed by extraction with ether.
  • the organic layer was washed twice with 10% sodium carbonate solution and washed with distilled water three times, then dried over anhydrous sodium sulfate, filtered, and the filtrate was rotated
  • Step 1 Synthesis of chloromethylcobalocene.
  • the synthetic route is shown in formula (3a).
  • the specific synthesis steps are as follows: 1.6 g of paraformaldehyde, 4.0 g of anhydrous zinc chloride and 6 ml of concentrated hydrochloric acid are added to the three-necked flask, and heated and stirred. When the temperature rises to 60 degrees Celsius, add 2g of cobaltocene, and quickly pass the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, and control the amount of the passed gas by the dripping acceleration of concentrated sulfuric acid. The excess gas is absorbed with water.
  • the reaction was completed after 6h, neutralized with 5% sodium carbonate aqueous solution to pH value between 5-7, extracted with chloroform, the organic layer was collected and washed with 10% sodium carbonate solution twice in sequence, washed with distilled water three times, and then Anhydrous sodium sulfate was dried, filtered, the filtrate was slowly dropped into 500ml of methanol, a brown solid was precipitated, dried by suction filtration, the filter cake was placed in a vacuum drying oven at 60 ° C and dried in vacuum for 2h, to obtain a crude product of chloromethylcobalocene 1.6g without further purification.
  • Step 2 Synthesis of intermediate 2, the synthetic route is shown in formula (3b).
  • Step 3 Synthesis of organic magnetic molecules (3), the synthetic route is shown in formula (3c).
  • the specific synthesis steps are as follows: Weigh 0.6g of intermediate 2 into a round-bottom flask, add 5ml of tetrahydrofuran, stir and dissolve in an ice bath, wrap the round-bottom flask with aluminum foil, slowly drop 0.3ml of methacryloyl chloride, and remove after 30min The reaction was performed in an ice bath at room temperature for 2h. After the reaction was completed, 30ml of water was added, followed by extraction with ether.
  • the synthetic route is as shown in formula (4a).
  • the specific synthesis steps are as follows: Weigh 2g of raw material 1 into a round bottom flask, add 50ml of tetrahydrofuran, stir and dissolve it in an ice bath, wrap the round bottom flask with aluminum foil, and place 1.4ml of methacrylic acid The acid chloride was slowly added dropwise, the ice bath was removed after 30min, and the reaction was carried out at room temperature for 2h. After the reaction was completed, 100ml of water was added, followed by extraction with ether.
  • Step 1 Synthesis of intermediate 3, the synthetic route is shown in formula (5a).
  • the specific synthesis steps are as follows: Weigh 5g of zinc powder into a beaker, add 3mol / L hydrochloric acid 20mL, stir and wash at room temperature until no bubbles are generated (at this time the zinc powder color becomes bright), suction filter, wash with water until neutral, no Wash three times with water ethanol, three times with ether, and dry under vacuum. Then transfer the treated zinc powder to a round-bottom flask and pump it through nitrogen three times to ensure oxygen-free. Dissolve 2g of raw material 2 in 30ml of tetrahydrofuran, slowly drop it into a round bottom flask at -5 degrees Celsius to react with zinc powder. After 30min, the ice bath was removed, and the reaction was stirred at room temperature for 2h. After the reaction was completed, intermediate 3 was obtained and no longer separated.
  • Step 2 Preparation of organic magnetic molecules (5), the synthetic route is shown in formula (5b).
  • the organic magnetic molecules (1) to (5) obtained in Examples 1 to 5 are used respectively to prepare thin film encapsulation structures 1 to 5 according to the following method:
  • test group
  • the thin layer of liquid organic magnetic molecules undergoes a curing reaction to form a polymer, and an organic layer (thickness 4 to 10 ⁇ m) is formed on the surface of the silicon nitride inorganic material.
  • the polymer structures formed by the organic magnetic molecules of Examples 1 to 5 are as follows:
  • a silicon nitride inorganic layer (thickness 0.5-2 ⁇ m) is formed on the side of the organic layer away from the silicon nitride inorganic material to obtain a thin-film encapsulation structure.
  • Inkjet printing on the surface of silicon nitride inorganic materials contains compounds that are currently not commercially available without magnetic field induced alignment (product of kateeva company, model is FlexCap EXP-TFE-A1) and 2,4,6-trimethylbenzoyl -A mixture of diphenylphosphine oxide (based on the total volume of the mixture, the content is 10% by volume), and then subjected to ultraviolet light irradiation, the compound undergoes a curing reaction to form a polymer, and an organic layer is formed on the surface of the silicon nitride inorganic material;
  • a silicon nitride inorganic layer is formed on the side of the organic layer away from the silicon nitride inorganic material to obtain a thin film packaging structure.
  • the results are shown in Table 1. The results show that in the thin-film encapsulation structure of the present invention, due to the orientation of the polymer molecules forming the organic layer, the molecules are packed more closely and the gap between the chains is smaller, making the thin-film encapsulation structure's water-oxygen barrier ability, tensile resistance and bending The folding performance has a stronger advantage, and the service life of the protected OLED device is also longer.

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Abstract

An organic magnetic molecule, comprising: a main group (100); a connecting group (200); and a magnetic group (300). The main group (100) is connected to the magnetic group (300) by means of the connecting group (200). A film packaging structure and preparation method therefor. The film packaging structure comprises: a first substrate (10); an organic layer (20), the organic layer (20) covering the surface of the first substrate (10); and a second substrate (30), the second substrate (30) covering the surface of the organic layer (20) away from the first substrate (10), wherein the organic layer (20) at least comprises a polymer formed by the aforementioned organic magnetic molecule. A display apparatus comprises: a substrate to be packaged and the aforementioned film packaging structure. The film packaging structure covers the substrate to be packaged.

Description

有机磁性分子、薄膜封装结构及其制备方法和显示装置Organic magnetic molecule, thin film packaging structure, preparation method thereof and display device 技术领域Technical field
本发明涉及材料技术领域，具体涉及有机磁性分子、薄膜封装结构及其制备方法和显示装置。The invention relates to the technical field of materials, in particular to organic magnetic molecules, a thin-film encapsulation structure, a preparation method thereof, and a display device.
背景技术Background technique
OLED(有机发光二极管)及其装置由于具有快速响应、高对比度和可柔性化等优点，拥有广泛的应用前景。但是，由于OLED器件在水汽和氧气的作用下，会出现腐蚀损坏的现象。因此，选择较好的封装方式对OLED器件来说尤为重要。OLED (Organic Light Emitting Diode) and its devices have wide application prospects due to their advantages of fast response, high contrast and flexibility. However, due to the effects of water vapor and oxygen, the OLED device will exhibit corrosion damage. Therefore, choosing a better packaging method is particularly important for OLED devices.
目前，薄膜封装是一种广泛应用在OLED显示器制作中的封装方式，即采用无机有机堆叠结构对OLED器件进行覆盖，以达到阻隔水氧、应力释放和平坦化等效果。At present, thin film packaging is a packaging method widely used in the production of OLED displays, that is, an inorganic-organic stack structure is used to cover the OLED device to achieve the effects of blocking water and oxygen, stress release, and planarization.
然而，目前薄膜封装结构仍有待改进。However, the current thin film packaging structure still needs to be improved.
发明内容Summary of the invention
本发明旨在提供一种有机磁性分子、薄膜封装结构及其制备方法和显示装置，利用所述有机磁性分子制备的薄膜封装结构能够具有良好的水氧阻隔能力、耐弯折和抗拉伸的性能，提升了显示装置的性能。The invention aims to provide an organic magnetic molecule, a thin-film encapsulation structure, a preparation method and a display device thereof, and the thin-film encapsulation structure prepared by using the organic magnetic molecule can have good water-oxygen barrier ability, bending resistance and tensile resistance Performance improves the performance of the display device.
本发明的一个方面，本发明提出了一种有机磁性分子。根据本发明的实施例，所述有机磁性分子包括：主体基团；连接基团；以及磁性基团，所述主体基团与所述磁性基团通过所述连接基团相连。In one aspect of the invention, the invention proposes an organic magnetic molecule. According to an embodiment of the present invention, the organic magnetic molecule includes: a host group; a linking group; and a magnetic group, the host group and the magnetic group are connected through the linking group.
发明人在主体基团上通过连接基团连接磁性基团，使得含有该磁性基团的分子具有磁性，可以在磁引导的作用下定向排列。经固化后形成的有机聚合物材料的水氧阻隔能力强、抗拉伸、弯折性好。The inventor connects the magnetic group on the host group through a linking group, so that the molecule containing the magnetic group has magnetism and can be aligned under the guidance of magnetic guidance. The organic polymer material formed after curing has strong water-oxygen barrier ability, good tensile resistance and good bending property.
根据本发明的实施例，上述有机磁性分子还可以具有下列附加技术特征：According to the embodiments of the present invention, the above organic magnetic molecules may also have the following additional technical features:
根据本发明的实施例，所述磁性基团具有如下所示的分子结构或者为C 1～8杂环基，杂原子至少为N原子，并且N原子与氧原子形成氮氧自由基， According to an embodiment of the present invention, the magnetic group has a molecular structure as shown below or is a C 1-8 heterocyclic group, the hetero atom is at least N atom, and the N atom and the oxygen atom form a nitroxide radical,
Figure PCTCN2018111081-appb-000001
其中，M选自金属离子。
Figure PCTCN2018111081-appb-000001
Among them, M is selected from metal ions.
根据本发明的实施例，所述金属离子包括铁离子、钴离子或者镍离子。According to an embodiment of the present invention, the metal ions include iron ions, cobalt ions, or nickel ions.
根据本发明的实施例，所述C 1～8杂环基具有如下至少之一的分子结构： According to an embodiment of the present invention, the C 1-8 heterocyclic group has a molecular structure of at least one of the following:
Figure PCTCN2018111081-appb-000002
Figure PCTCN2018111081-appb-000002
根据本发明的实施例，所述主体基团选自可以在加热和光照至少一种条件下发生聚合反应形成聚合物的基团。According to an embodiment of the present invention, the host group is selected from groups that can undergo polymerization under at least one condition of heating and light to form a polymer.
根据本发明的实施例，所述主体基团选自下列至少之一：丙烯酸酯基、乙烯基、苯乙烯基、丙烯基、丙烯酸基、酰胺基、酰亚胺基、碳酸酯基、氨酯丙烯酸基、硅氧烷基和硅氮烷基；其中，所述丙烯酸酯基、乙烯基、苯乙烯基、丙烯基、丙烯酸基、酰胺基、酰亚胺基、碳酸酯基、氨酯丙烯酸基、硅氧烷基或者硅氮烷基均可任选地被一个或者多个选自F、Cl、Br、I、-OH、-NO 2、-NH 2、-CN、C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基C 1～6烷基、C 2～6烯基、C 2～6炔基、烷氨基C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 3～6环烷基C 2～6烯基、C 3～6环烷基C 2～6炔基或者C 3～6环烷基氧基C 2～6炔基的基团所取代。 According to an embodiment of the present invention, the host group is selected from at least one of the following: acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane group Acrylic group, siloxane group and silazinyl group; wherein, the acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane acrylic group , Siloxane group or silazane group can be optionally selected from one or more of F, Cl, Br, I, -OH, -NO 2 , -NH 2 , -CN, C 1-6 alkyl , Halogenated C 1-6 alkyl, C 1-6 alkoxy C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, alkylamino C 1-6 alkyl, C 3 ～ 6 cycloalkyl, C 3-6 cycloalkyl C 1-6 alkyl, C 3-6 cycloalkyl C 2-6 alkenyl, C 3-6 cycloalkyl C 2-6 alkynyl or C 3 ～ 6 cycloalkyloxy C 2-6 alkynyl groups are substituted.
根据本发明的实施例，所述连接基团选自下列至少之一：C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基、C 1～6烷氧基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 2～6烯基C 1～6烷基、C 2～6炔基C 1～6烷基、C 1～6烷氨基C 1～6烷基、酰胺基C 1～6烷基、羧基C 1～6烷基和羰基C 1～6烷基。 According to an embodiment of the present invention, the linking group is selected from at least one of the following: C 1-6 alkyl, halogenated C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 2-6 alkenyl C 1-6 alkyl, C 2-6 alkynyl C 1-6 alkyl, C 1 ～ 6 alkylamino C 1-6 alkyl, amido C 1-6 alkyl, carboxy C 1-6 alkyl and carbonyl C 1-6 alkyl.
根据本发明的实施例，所述有机磁性分子具有下列之一的分子结构：According to an embodiment of the present invention, the organic magnetic molecule has one of the following molecular structures:
Figure PCTCN2018111081-appb-000003
Figure PCTCN2018111081-appb-000003
Figure PCTCN2018111081-appb-000004
Figure PCTCN2018111081-appb-000004
在本发明的又一方面，本发明提出了一种薄膜封装结构。根据本发明的实施例，所述薄膜封装结构包括：第一衬底；有机层，所述有机层覆盖于所述第一衬底的表面；以及第二衬底，所述第二衬底覆盖于所述有机层远离所述第一衬底的表面；其中，所述有机层至少包括由前面所述有机磁性分子形成的聚合物。如前所述，本发明的有机磁性分子具有磁性，施加于第一衬底上后，在磁引导的作用下定向排列，经固化后形成规整有序排列结构的薄膜，使得薄膜封装结构水氧阻隔能力强、抗拉伸、弯折性好以及所保护的器件使用寿命长。In yet another aspect of the present invention, the present invention provides a thin film packaging structure. According to an embodiment of the present invention, the thin film packaging structure includes: a first substrate; an organic layer covering the surface of the first substrate; and a second substrate covering the second substrate The organic layer is away from the surface of the first substrate; wherein, the organic layer includes at least a polymer formed of the organic magnetic molecules described above. As mentioned above, the organic magnetic molecules of the present invention have magnetism, and after being applied on the first substrate, they are aligned under the guidance of magnetic guidance, and after curing, form a thin film with a regular arrangement structure, making the thin film encapsulation structure water and oxygen Strong barrier ability, tensile resistance, good bending performance and long service life of the protected device.
在本发明的又一方面，本发明提出了一种制备前面所述薄膜封装结构的方法。根据本发明的实施例，所述方法包括：提供所述第一衬底；在所述第一衬底的表面上施加含有所述有机磁性分子和引发剂的混合液；在所述第一衬底的表面一侧设置磁力产生装置进行磁引导，以便形成定向排列的液体有机磁性分子薄层；以及使所述液体有机磁性分子薄层固化，以便形成所述有机层。In yet another aspect of the present invention, the present invention provides a method for preparing the aforementioned thin film packaging structure. According to an embodiment of the present invention, the method includes: providing the first substrate; applying a mixed solution containing the organic magnetic molecules and an initiator on the surface of the first substrate; A magnetic force generating device is provided on the surface side of the bottom for magnetic guidance to form a thin layer of liquid organic magnetic molecules aligned; and curing the thin layer of liquid organic magnetic molecules to form the organic layer.
根据本发明的实施例，所述方法进一步包括：在所述有机层远离所述第一衬底的表面形成第二衬底，以便获得所述薄膜封装结构。According to an embodiment of the present invention, the method further includes: forming a second substrate on a surface of the organic layer away from the first substrate, so as to obtain the thin film packaging structure.
根据本发明的实施例，所述磁力产生装置选自电磁铁和永磁体的至少之一。According to an embodiment of the present invention, the magnetic force generating device is selected from at least one of an electromagnet and a permanent magnet.
根据本发明的实施例，使所述液体有机磁性分子薄层固化的方法包括加热和光照射中的至少之一。According to an embodiment of the present invention, a method of curing the thin layer of liquid organic magnetic molecules includes at least one of heating and light irradiation.
根据本发明的实施例，所述引发剂选自自由基引发剂。According to an embodiment of the present invention, the initiator is selected from free radical initiators.
在本发明的又一方面，本发明提出了一种显示装置。根据本发明的实施例，所述显示装置包括：待封装基板；以及前面所述的薄膜封装结构，所述薄膜封装结构覆盖所述待封装基板。由此，根据本发明实施例的显示装置水氧阻隔能力强以及使用寿命长。In yet another aspect of the invention, the invention proposes a display device. According to an embodiment of the present invention, the display device includes: a substrate to be packaged; and the thin film packaging structure described above, the thin film packaging structure covering the substrate to be packaged. Thus, the display device according to the embodiment of the present invention has strong water and oxygen barrier capabilities and a long service life.
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或者通过本发明的实践了解到。Additional aspects and advantages of the present invention will be partially given in the following description, and some will become apparent from the following description, or be learned through the practice of the present invention.
附图说明BRIEF DESCRIPTION
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:
图1显示了根据本发明一个实施例的有机磁性分子结构示意图；FIG. 1 shows a schematic diagram of an organic magnetic molecular structure according to an embodiment of the present invention;
图2显示了根据本发明一个实施例的薄膜封装结构示意图；2 shows a schematic diagram of a thin film packaging structure according to an embodiment of the present invention;
图3显示了根据本发明一个实施例的制备薄膜封装结构的方法的流程示意图。FIG. 3 shows a schematic flowchart of a method for preparing a thin film packaging structure according to an embodiment of the present invention.
具体实施方式detailed description
下面详细描述本发明的实施例。下面描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and cannot be construed as limiting the present invention.
需要说明的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或者暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。进一步地，在本发明的描述中，除非另有说明，“多个”的含义是两个或者两个以上。It should be noted that the terms “first” and “second” are used for description purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. Further, in the description of the present invention, unless otherwise stated, the meaning of "plurality" is two or more.
本发明提出了一种有机磁性分子、薄膜封装结构及其制备方法和显示装置，下面将分别对其进行详细描述。The invention provides an organic magnetic molecule, a thin film packaging structure, a preparation method thereof and a display device, which will be described in detail below.
有机磁性分子Organic magnetic molecules
为此，在本发明的一个方面，本发明提出了一种有机磁性分子。根据本发明的实施例，有机磁性分子包括：主体基团；连接基团；以及磁性基团，主体基团与磁性基团通过连接基团相连。To this end, in one aspect of the invention, the invention proposes an organic magnetic molecule. According to an embodiment of the present invention, the organic magnetic molecule includes: a host group; a linking group; and a magnetic group, the host group and the magnetic group are connected by the linking group.
发明人在主体基团上通过连接基团连接磁性基团，使得含有该磁性基团的分子具有磁 性，可以在磁引导的作用下定向排列。经固化后形成的有机聚合物材料具有较好性能，例如应用于薄膜封装结构中，使其水氧阻隔能力强、抗拉伸、弯折性好以及所保护的器件使用寿命长等。The inventor connects the magnetic group to the host group through a linking group, so that the molecules containing the magnetic group have magnetic properties and can be aligned under the guidance of magnetic guidance. The organic polymer material formed after curing has better performance, for example, it is used in a thin-film encapsulation structure to make it have strong water-oxygen barrier ability, good resistance to stretching, good bending, and a long service life of the protected device.
参见图1，本发明实施例的有机磁性分子为主体基团100(亦可理解为主链)的某一个或者多个原子被连接基团200所取代，连接基团200一端与主体基团100相连，一端与磁性基团300相连。主体基团为功能性基团，赋予有机磁性分子相应的功能，例如针对薄膜封装结构，起到使无机材料层平坦化、抗弯曲、提升水氧阻隔能力等效果，而磁性基团主要赋予分子以磁性，使其在磁引导的作用下带动主体基团定向排列，使经固化后形成的有机聚合物材料具有较好性能。Referring to FIG. 1, an organic magnetic molecule according to an embodiment of the present invention is one or more atoms of a host group 100 (which can also be understood as a main chain) are replaced by a linking group 200, and one end of the linking group 200 is connected to the host group 100 Connected, one end is connected to the magnetic group 300. The main group is a functional group, which endows the organic magnetic molecules with corresponding functions. For example, for the thin film encapsulation structure, it has the effects of flattening the inorganic material layer, bending resistance, and improving the water and oxygen barrier capabilities. The magnetic group mainly gives the molecules With magnetic properties, it can drive the orientation of the main groups under the guidance of magnetic guidance, so that the organic polymer material formed after curing has better performance.
需要说明的是，本发明对于连接基团和磁性基团的个数不作严格限定，例如，可以是一个主体基团对应一个连接基团和一个磁性基团，也可以是一个主体基团对应多个连接基团，每个连接基团对应一个磁性基团，还可以是一个主体基团对应多个连接基团，每个连接基团对应多个磁性基团，具体可以根据实际情况灵活选择。It should be noted that the present invention does not strictly limit the number of linking groups and magnetic groups. For example, a host group may correspond to a linking group and a magnetic group, or a host group may correspond to multiple groups. Each connecting group corresponds to one magnetic group, or one host group corresponds to multiple connecting groups, and each connecting group corresponds to multiple magnetic groups, which can be flexibly selected according to actual conditions.
另外，还需要说明的是，本发明对于聚合物的聚合度不作严格限定，可以根据实际情况灵活选择。根据本发明的具体实施例，聚合物的聚合度为2-200。In addition, it should be noted that the present invention does not strictly limit the polymerization degree of the polymer, and can be flexibly selected according to the actual situation. According to a specific embodiment of the present invention, the polymerization degree of the polymer is 2-200.
根据本发明的实施例，磁性基团具有如下所示的分子结构或者为C 1～8杂环基，杂原子至少为N原子，并且N原子与氧原子形成氮氧自由基， According to an embodiment of the present invention, the magnetic group has a molecular structure as shown below or is a C 1-8 heterocyclic group, the hetero atom is at least N atom, and the N atom and the oxygen atom form a nitroxide radical,
Figure PCTCN2018111081-appb-000005
其中，M选自金属离子。
Figure PCTCN2018111081-appb-000005
Among them, M is selected from metal ions.
根据本发明的实施例，金属离子包括铁离子、钴离子或者镍离子。According to an embodiment of the present invention, the metal ions include iron ions, cobalt ions, or nickel ions.
根据本发明的实施例，C 1～8杂环基具有如下至少之一的分子结构： According to an embodiment of the present invention, the C 1-8 heterocyclic group has a molecular structure of at least one of the following:
Figure PCTCN2018111081-appb-000006
Figure PCTCN2018111081-appb-000006
发明人经过大量实验得到上述较优磁性基团，其通过连接基团与主体基团相连，使得有机磁性分子可以在磁引导的作用下定向排列，链间空隙小。另外，磁性基团对于主体基团的结构和功能影响不大，而且，磁性基团容易与连接基团相连，降低了合成难度，适于 规模化生产。The inventor obtained the above-mentioned superior magnetic group through a large number of experiments, which is connected to the host group through the connecting group, so that the organic magnetic molecules can be aligned under the action of magnetic guidance, and the gap between the chains is small. In addition, the magnetic group has little effect on the structure and function of the host group, and the magnetic group is easily connected to the linking group, which reduces the difficulty of synthesis and is suitable for large-scale production.
根据本发明的实施例，主体基团选自可以在加热和光照至少一种条件下发生聚合反应形成聚合物的基团。由此，使得有机磁性分子能够在加热和/或光照射条件下发生固化，形成有机磁性分子薄层。According to an embodiment of the present invention, the host group is selected from groups that can undergo polymerization under at least one condition of heating and light to form a polymer. As a result, the organic magnetic molecules can be cured under heating and / or light irradiation conditions to form a thin layer of organic magnetic molecules.
需要说明的是，本发明对于主体基团的种类不作严格限定，可以根据实际的薄膜封装结构要求灵活选择。根据本发明的实施例，主体基团选自下列至少之一：丙烯酸酯基、乙烯基、苯乙烯基、丙烯基、丙烯酸基、酰胺基、酰亚胺基、碳酸酯基、氨酯丙烯酸基、硅氧烷基和硅氮烷基；其中，丙烯酸酯基、乙烯基、苯乙烯基、丙烯基、丙烯酸基、酰胺基、酰亚胺基、碳酸酯基、氨酯丙烯酸基、硅氧烷基或者硅氮烷基均可任选地被一个或者多个选自F、Cl、Br、I、-OH、-NO 2、-NH 2、-CN、C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 1～6烷氨基C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 3～6环烷基C 2～6烯基、C 3～6环烷基C 2～6炔基或者C 3～6环烷基氧基C 2～6炔基的基团所取代。 It should be noted that the present invention does not strictly limit the type of host group, and can be flexibly selected according to the actual film packaging structure requirements. According to an embodiment of the present invention, the host group is selected from at least one of the following: acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane acrylic group , Siloxane group and silazane group; among them, acrylate group, vinyl group, styrene group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane acrylate group, siloxane The group or silazinyl group may be optionally selected from one or more selected from F, Cl, Br, I, -OH, -NO 2 , -NH 2 , -CN, C 1-6 alkyl, halogenated C 1 to 6 alkyl, C 1 to 6 alkoxy C 1 to 6 alkyl, C 2 to 6 alkenyl, C 2 to 6 alkynyl, C 1 to 6 alkylamino C 1 to 6 alkyl, C 3 to 6 cycloalkyl, C 3-6 cycloalkyl C 1-6 alkyl, C 3-6 cycloalkyl C 2-6 alkenyl, C 3-6 cycloalkyl C 2-6 alkynyl or C 3 ～ The 6 cycloalkyloxy C 2-6 alkynyl group is substituted.
根据本发明的具体实施例，主体基团具有下列至少之一的分子结构：According to a specific embodiment of the present invention, the host group has a molecular structure of at least one of the following:
Figure PCTCN2018111081-appb-000007
Figure PCTCN2018111081-appb-000008
其中，R选自C nH 2n+1，n选自0～10的整数。
Figure PCTCN2018111081-appb-000007
Figure PCTCN2018111081-appb-000008
Wherein, R is selected from C n H 2n + 1 and n is selected from an integer of 0-10.
发明人经过大量实验得到上述较优主体基团，连接基团和磁性基团对于该主体基团的结构和功能影响不大，并且主体基团容易与连接基团相连，降低了合成难度，适于规模化生产。含有该主体基团的有机磁性分子可以使无机材料层平坦化，赋予其抗弯曲以及阻隔水氧等特性。The inventor obtained the above-mentioned superior host group through a lot of experiments. The linking group and the magnetic group have little effect on the structure and function of the host group, and the host group is easily connected to the linking group, which reduces the difficulty of synthesis. For large-scale production. The organic magnetic molecules containing the host group can flatten the inorganic material layer, giving it properties such as resistance to bending and water and oxygen barriers.
根据本发明的实施例，连接基团选自下列至少之一：C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基、C 1～6烷氧基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 2～6烯基C 1～6烷基、C 2～6炔基C 1～6烷基、C 1～6烷氨基C 1～6烷基、酰胺基C 1～6烷基、羧基C 1～6烷基和羰基C 1～6烷基。 According to an embodiment of the present invention, the linking group is selected from at least one of the following: C 1-6 alkyl, halogenated C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy C 1 ~ 6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 2-6 alkenyl C 1-6 alkyl, C 2-6 alkynyl C 1-6 alkyl, C 1-6 alkane Amino C 1-6 alkyl, amido C 1-6 alkyl, carboxy C 1-6 alkyl and carbonyl C 1-6 alkyl.
根据本发明的实施例，连接基团具有下列之一的分子结构：According to an embodiment of the present invention, the linking group has one of the following molecular structures:
Figure PCTCN2018111081-appb-000009
Figure PCTCN2018111081-appb-000009
其中，n选自0～10的整数。However, n is selected from the integer of 0-10.
根据本发明的实施例，有机磁性分子具有下列之一的分子结构：According to an embodiment of the present invention, the organic magnetic molecule has one of the following molecular structures:
Figure PCTCN2018111081-appb-000010
Figure PCTCN2018111081-appb-000010
发明人经过大量实验得到上述较优有机磁性分子结构，主体基团上通过连接基团连接磁性基团，使得有机磁性分子具有磁性，可以在磁引导的作用下定向排列，使分子堆积更紧密，链间的空隙更小，经固化后形成的有机聚合物材料的水氧阻隔能力、抗拉伸和弯折 性具有更强的优势，所保护的器件使用寿命也更长。并且，三个基团之间的连接对于各自的结构和功能影响不大，容易合成，适于规模化生产。The inventors obtained the above-mentioned superior organic magnetic molecular structure through a large number of experiments. The main group is connected to the magnetic group through the connecting group, so that the organic magnetic molecules are magnetic and can be aligned under the guidance of magnetic guidance to make the molecular packing more compact. The gap between the chains is smaller, and the water-oxygen barrier ability, tensile resistance and bending resistance of the organic polymer material formed after curing have stronger advantages, and the service life of the protected device is also longer. Moreover, the connection between the three groups has little effect on their respective structures and functions, is easy to synthesize, and is suitable for large-scale production.
薄膜封装结构Thin film packaging structure
在本发明的又一方面，本发明提出了一种薄膜封装结构。根据本发明的实施例，参见图2，薄膜封装结构包括：第一衬底10；有机层20，该有机层20覆盖于第一衬底10的表面；以及第二衬底30，第二衬底30覆盖于有机层20远离第一衬底10的表面；其中，有机层20至少包括由前面所述有机磁性分子形成的聚合物。如前所述，本发明的有机磁性分子具有磁性，施加于第一衬底上后，在磁引导的作用下定向排列，使分子堆积更紧密，链间的空隙更小，经固化后形成的薄膜力学性能更强，使得薄膜封装结构具有较好的水氧阻隔能力，抗拉伸、耐弯折性好以及所保护的器件使用寿命长等。In yet another aspect of the present invention, the present invention provides a thin film packaging structure. According to an embodiment of the present invention, referring to FIG. 2, the thin film packaging structure includes: a first substrate 10; an organic layer 20 covering the surface of the first substrate 10; and a second substrate 30, a second substrate The bottom 30 covers the surface of the organic layer 20 away from the first substrate 10; wherein, the organic layer 20 includes at least a polymer formed of the organic magnetic molecules described above. As mentioned above, the organic magnetic molecules of the present invention have magnetism, and after being applied on the first substrate, they are aligned under the guidance of magnetic guidance, so that the molecules are packed more closely, the gap between the chains is smaller, and the The mechanical properties of the film are stronger, which makes the film packaging structure have better water and oxygen barrier capabilities, good tensile resistance, bending resistance and long service life of the protected device.
需要说明的是，本发明对于形成第一衬底和第二衬底的材料不作严格限定，具体可以根据实际情况灵活选择。根据本发明的实施例，第一衬底和第二衬底选自无机层。例如，可以为氧化物、氟化物和/或氮化硅形成的无机层。It should be noted that, in the present invention, the materials for forming the first substrate and the second substrate are not strictly limited, and can be flexibly selected according to actual conditions. According to an embodiment of the invention, the first substrate and the second substrate are selected from inorganic layers. For example, it may be an inorganic layer formed of oxide, fluoride, and / or silicon nitride.
还需要说明的是，本发明对于薄膜封装结构中第一衬底、有机层和第二衬底的层数不作严格限定，只要保证是第一衬底和第二衬底相对地设置于有机层两侧即可，例如为第一衬底/有机层/第二衬底/有机层/第一衬底/有机层/第二衬底、第一衬底/有机层/第二衬底/有机层/第一衬底/有机层/第二衬底/有机层/第一衬底。It should also be noted that the present invention does not strictly limit the number of layers of the first substrate, the organic layer, and the second substrate in the thin film packaging structure, as long as the first substrate and the second substrate are relatively arranged on the organic layer Both sides are sufficient, for example, the first substrate / organic layer / second substrate / organic layer / first substrate / organic layer / second substrate, the first substrate / organic layer / second substrate / organic Layer / first substrate / organic layer / second substrate / organic layer / first substrate.
本领域技术人员能够理解的是，前面针对有机材料所描述的特征和优点，同样适用于该薄膜封装结构，在此不再赘述。Those skilled in the art can understand that the features and advantages described above for the organic materials are also applicable to the thin film packaging structure, and will not be repeated here.
制备薄膜封装结构的方法Method for preparing thin film packaging structure
在本发明的又一方面，本发明提出了一种制备前面所述薄膜封装结构的方法。根据本发明的实施例，参见图3，该方法包括：In yet another aspect of the present invention, the present invention provides a method for preparing the aforementioned thin film packaging structure. According to an embodiment of the present invention, referring to FIG. 3, the method includes:
步骤S100，提供第一衬底。In step S100, a first substrate is provided.
步骤S200，在第一衬底的表面上施加含有有机磁性分子和引发剂的混合液。In step S200, a mixed liquid containing organic magnetic molecules and an initiator is applied on the surface of the first substrate.
根据本发明的实施例，引发剂选自自由基引发剂。根据本发明的具体实施例，引发剂选自下列的至少之一：过氧化苯甲酰、过氧化月桂酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过氧化甲乙酮、过氧化环己酮、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯、过硫酸钾、过硫酸钠、过硫酸铵、偶氮二异丁腈、偶氮二异庚腈、2-羟基-2-甲基-1-苯基丙酮、1-羟基 环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、苯甲酰甲酸甲酯、氟化二苯基钛茂和双(五氟苯基)钛茂。According to an embodiment of the invention, the initiator is selected from free radical initiators. According to a specific embodiment of the present invention, the initiator is selected from at least one of the following: benzoyl peroxide, lauroyl peroxide, cumene hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, Dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicycloperoxydicarbonate Hexyl ester, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptanonitrile, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexylbenzene Ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl] -1-acetone, 2,4,6-trimethylbenzoyl- Diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-Butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] -1-acetone, methyl benzoylformate, fluorinated diphenyl titanium Mlocene and bis (pentafluorophenyl) titanocene.
根据本发明的优选实施例，引发剂选自2,4,6-三甲基苯甲酰基-二苯基氧化膦或者2,4,6-三甲基苯甲酰基苯基膦酸乙酯。According to a preferred embodiment of the present invention, the initiator is selected from 2,4,6-trimethylbenzoyl-diphenylphosphine oxide or ethyl 2,4,6-trimethylbenzoylphenylphosphonate.
根据本发明的实施例，基于混合液的总体积，引发剂的含量为0.1～20体积％。发明人经过大量实验得到上述较优配比，由此，以便于有机磁性分子在加热和/或光照条件下充分发生固化反应形成聚合物，得到具有规整有序排列结构的薄膜。According to an embodiment of the present invention, the content of the initiator is 0.1-20% by volume based on the total volume of the mixed liquid. The inventors obtained the above-mentioned optimal ratio through a large number of experiments, so that the organic magnetic molecules can sufficiently undergo a curing reaction to form a polymer under heating and / or light conditions, and a thin film with a regular and ordered structure can be obtained.
根据本发明的实施例，施加含有有机磁性分子和引发剂的混合液包括采用喷墨印刷法或者化学气相沉积法。由此，便于形成薄厚均一的薄膜。According to an embodiment of the present invention, applying the mixed liquid containing the organic magnetic molecules and the initiator includes using an inkjet printing method or a chemical vapor deposition method. Thus, it is easy to form a thin and uniform film.
步骤S300，在第一衬底的表面一侧设置磁力产生装置进行磁引导，以便形成定向排列的液体有机磁性分子薄层。In step S300, a magnetic force generating device is provided on the surface side of the first substrate to perform magnetic guidance, so as to form a thin layer of liquid organic magnetic molecules aligned.
在该步骤中，在第一衬底表面一侧设置磁力产生装置进行磁引导，以便形成定向排列的液体有机磁性分子薄层。如前所述，本发明的有机磁性分子具有磁性，通过施加磁引导，能够使得有机磁性分子定向排列。In this step, a magnetic force generating device is provided on the surface side of the first substrate for magnetic guidance, so as to form a thin layer of liquid organic magnetic molecules aligned. As mentioned above, the organic magnetic molecules of the present invention have magnetic properties, and by applying magnetic guidance, the organic magnetic molecules can be aligned.
根据本发明的实施例，磁力产生装置选自电磁铁和永磁体的至少之一。根据本发明的另一实施例，磁力产生装置所产生的磁力为0.001～100T。由此，能够使得有机磁性分子定向排列，在第一衬底表面形成液体有机磁性分子薄层。According to an embodiment of the present invention, the magnetic force generating device is selected from at least one of electromagnets and permanent magnets. According to another embodiment of the present invention, the magnetic force generated by the magnetic force generating device is 0.001 to 100T. Thereby, the organic magnetic molecules can be aligned and a thin layer of liquid organic magnetic molecules can be formed on the surface of the first substrate.
步骤S400，使液体有机磁性分子薄层固化，以便形成有机层。In step S400, a thin layer of liquid organic magnetic molecules is cured to form an organic layer.
通过对液体有机磁性分子薄层进行固化，有机磁性分子发生固化反应形成聚合物，得到具有规整有序排列结构的薄膜，使得薄膜封装结构水氧阻隔能力强，抗拉伸、弯折性好以及所保护的器件使用寿命长等。By curing a thin layer of liquid organic magnetic molecules, the organic magnetic molecules undergo a curing reaction to form a polymer, resulting in a thin film with a regular and ordered structure, which makes the film packaging structure strong in water and oxygen barriers, good in resistance to stretching and bending, and The protected device has a long service life.
需要说明的是，本发明对于使液体有机磁性分子薄层固化的方式不作严格限定，可以根据实际情况灵活选择。根据本发明的实施例，使液体有机磁性分子薄层固化的方法包括加热和光照射中的至少之一。It should be noted that, in the present invention, the method for curing the thin layer of liquid organic magnetic molecules is not strictly limited, and can be flexibly selected according to the actual situation. According to an embodiment of the present invention, a method of curing a thin layer of liquid organic magnetic molecules includes at least one of heating and light irradiation.
根据本发明的实施例，该方法进一步包括：在有机层远离第一衬底的表面形成第二衬底，以便获得薄膜封装结构。According to an embodiment of the present invention, the method further includes forming a second substrate on the surface of the organic layer away from the first substrate, so as to obtain a thin film packaging structure.
需要说明的是，本发明对于施加含有有机磁性分子和引发剂的混合液的方式不作严格限定，可以根据实际情况灵活选择。根据本发明的实施例，施加含有有机磁性分子和引发剂的混合液包括采用喷墨印刷法或者化学气相沉积法。由此，可以在第一衬底表面形成液 体有机磁性分子薄层，并且薄层厚度均一。It should be noted that, in the present invention, the method of applying the mixed liquid containing the organic magnetic molecules and the initiator is not strictly limited, and can be flexibly selected according to the actual situation. According to an embodiment of the present invention, applying the mixed liquid containing the organic magnetic molecules and the initiator includes using an inkjet printing method or a chemical vapor deposition method. Thus, a thin layer of liquid organic magnetic molecules can be formed on the surface of the first substrate, and the thickness of the thin layer is uniform.
本领域技术人员能够理解的是，前面针对薄膜封装结构所描述的特征和优点，同样适用于该制备薄膜封装结构的方法，在此不再赘述。Those skilled in the art can understand that the features and advantages described above for the thin-film encapsulation structure are also applicable to the method for preparing the thin-film encapsulation structure, which will not be repeated here.
显示装置Display device
在本发明的又一方面，本发明提出了一种显示装置。根据本发明的实施例，显示装置包括：待封装基板；以及前面所述的薄膜封装结构，薄膜封装结构覆盖待封装基板。由此，本发明实施例的显示装置具有水氧阻隔能力强以及使用寿命长等性能。In yet another aspect of the invention, the invention proposes a display device. According to an embodiment of the present invention, a display device includes: a substrate to be packaged; and the thin film packaging structure described above, the thin film packaging structure covering the substrate to be packaged. Therefore, the display device according to the embodiment of the present invention has such properties as strong water-oxygen barrier capability and long service life.
根据本发明的实施例，第一衬底或者第二衬底远离有机层的表面覆盖待封装基板。According to an embodiment of the present invention, the surface of the first substrate or the second substrate away from the organic layer covers the substrate to be packaged.
本领域技术人员能够理解的是，前面针对薄膜封装结构所描述的特征和优点，同样适用于该显示装置，在此不再赘述。Those skilled in the art can understand that the features and advantages described above for the thin-film encapsulation structure are also applicable to the display device and will not be repeated here.
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或者条件的，按照本领域内的文献所描述的技术或者条件或者按照产品说明书进行。所用试剂或者仪器未注明生产厂商者，均为可以通过市购获得的常规产品。The solution of the present invention will be explained below in conjunction with examples. Those skilled in the art will understand that the following embodiments are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. If no specific technology or conditions are indicated in the embodiments, the technology or conditions described in the literature in the art or the product specification shall be followed. The reagents or instruments used without indication of the manufacturer are conventional products that are commercially available.
实施例1Example 1
有机磁性分子(1)的制备路线：Preparation route of organic magnetic molecule (1):
Figure PCTCN2018111081-appb-000011
Figure PCTCN2018111081-appb-000011
步骤1：氯甲基二茂铁的合成，合成路线如式(1a)所示。具体合成步骤如下：在三颈烧瓶中加入多聚甲醛1.6g、无水氯化锌4.0g和浓盐酸6ml，加热搅拌。当温度升至60摄氏度时，加入二茂铁2g，并迅速通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加速度控制通入气体的量，多余气体用水吸收，反应6h后结束，用5％碳酸钠水溶液中和至pH介于5-7，利用三氯甲烷萃取反应液，收集有机层并依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，将滤液缓慢的滴入到500ml甲醇中，析出棕色固体，抽滤干燥，将滤饼放入真空干燥箱60℃真空干燥2h，得到氯甲基 二茂铁粗产品1.4g，无需进一步纯化。Step 1: Synthesis of chloromethylferrocene. The synthetic route is shown in formula (1a). The specific synthesis steps are as follows: 1.6 g of paraformaldehyde, 4.0 g of anhydrous zinc chloride and 6 ml of concentrated hydrochloric acid are added to the three-necked flask, and heated and stirred. When the temperature rises to 60 degrees Celsius, add 2g of ferrocene, and quickly pass the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, and control the amount of the passed gas by the dripping acceleration of concentrated sulfuric acid. The excess gas is absorbed with water. The reaction was completed after 6h, neutralized with a 5% sodium carbonate aqueous solution to a pH between 5-7, the reaction liquid was extracted with chloroform, the organic layer was collected and washed with 10% sodium carbonate solution twice and distilled water three times, then Dry with anhydrous sodium sulfate, filter, and the filtrate is slowly dropped into 500ml of methanol to precipitate a brown solid, which is dried by suction filtration, and the filter cake is placed in a vacuum drying oven at 60 ° C and dried in vacuum for 2h to obtain crude chloromethylferrocene The product is 1.4g without further purification.
Figure PCTCN2018111081-appb-000012
Figure PCTCN2018111081-appb-000012
步骤2：羟甲基二茂铁的合成，合成路线如式(1b)所示。具体合成步骤如下：称取1g上一步制备的氯甲基二茂铁加入到圆底烧瓶中，加入30ml甲苯溶解，缓慢将5ml 20％的氢氧化钠水溶液倒入圆底烧瓶，加热搅拌回流12小时。冷却后缓慢加入5％稀盐酸中和至pH值介于6-8，利用三氯甲烷萃取，收集有机层并依次用10％氯化钠水溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝10：1作为流动相，硅胶作为固定相，柱层析分离，收集产品。粗品加入10ml乙醇重结晶，得到橙色针状晶体，过滤后将滤饼放入真空干燥箱60℃真空干燥2h，得到羟甲基二茂铁0.86g。Step 2: Synthesis of hydroxymethyl ferrocene, the synthetic route is shown in formula (1b). The specific synthesis steps are as follows: Weigh 1g of the chloromethyl ferrocene prepared in the previous step into a round-bottom flask, add 30ml of toluene to dissolve, slowly pour 5ml of 20% aqueous sodium hydroxide solution into the round-bottom flask, heat and stir to reflux 12 hour. After cooling, slowly add 5% dilute hydrochloric acid to neutralize to pH value between 6-8, extract with chloroform, collect the organic layer and wash with 10% aqueous sodium chloride solution twice, distilled water three times, and then dry Sodium sulfate was dried, filtered, and the filtrate was removed with a rotary evaporator, using petroleum ether: ethyl acetate = 10: 1 as the mobile phase, silica gel as the stationary phase, column chromatography separation, and the product was collected. The crude product was recrystallized by adding 10ml of ethanol to obtain orange needle-like crystals. After filtration, the filter cake was placed in a vacuum drying oven at 60 ° C for 2 hours under vacuum to obtain 0.86g of hydroxymethylferrocene.
Figure PCTCN2018111081-appb-000013
Figure PCTCN2018111081-appb-000013
步骤3：有机磁性分子(1)的合成，合成路线如式(1c)所示。具体合成步骤如下：称取0.6g羟甲基二茂铁加入到圆底烧瓶中，加入5ml四氢呋喃，搅拌溶解后冰浴，用铝箔包裹圆底烧瓶，将0.3ml甲基丙烯酰氯缓慢滴入，30min后撤去冰浴，室温反应2h,反应结束，加入30ml水，然后用乙醚萃取，收集有机层并依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝15：1作为流动相，硅胶作为固定相，柱层析分离，收集产品，得到0.57g橙色透明油状液体有机磁性分子(1)。Step 3: Synthesis of organic magnetic molecules (1), the synthetic route is shown in formula (1c). The specific synthesis steps are as follows: Weigh 0.6g hydroxymethyl ferrocene into a round bottom flask, add 5ml of tetrahydrofuran, stir and dissolve it in an ice bath, wrap the round bottom flask with aluminum foil, and slowly drop 0.3ml of methacryloyl chloride, After 30min, the ice bath was removed, and the reaction was carried out at room temperature for 2h. After the reaction was completed, 30ml of water was added, followed by extraction with ether. The organic layer was collected and washed with 10% sodium carbonate solution twice, distilled water three times, and then dried over anhydrous sodium sulfate. Filtration, the filtrate was removed with a rotary evaporator, using petroleum ether: ethyl acetate = 15: 1 as the mobile phase, silica gel as the stationary phase, column chromatography separation, the product was collected, to obtain 0.57g orange transparent oily liquid organic magnetic molecules (1).
Figure PCTCN2018111081-appb-000014
Figure PCTCN2018111081-appb-000014
实施例2Example 2
有机磁性分子(2)的制备路线：Preparation route of organic magnetic molecule (2):
Figure PCTCN2018111081-appb-000015
Figure PCTCN2018111081-appb-000015
步骤1：氯甲基二茂镍的合成，合成路线如式(2a)所示。具体合成步骤如下：在三颈烧瓶中加入多聚甲醛1.6g、无水氯化锌4.0g和浓盐酸6ml，加热搅拌。当温度升至60摄氏度时，加入二茂镍2g，并迅速通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加速度控制通入气体的量，多余气体用水吸收，反应6h后结束，用5％碳酸钠水溶液中和至pH值介于5-7，利用三氯甲烷萃取，收集有机层并依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，将滤液缓慢地滴入到500ml甲醇中，析出棕色固体，抽滤干燥，将滤饼放入真空干燥箱60℃真空干燥2h，得到氯甲基二茂镍粗产品1.3g，无需进一步纯化。Step 1: Synthesis of chloromethyl nickelocene, the synthetic route is shown in formula (2a). The specific synthesis steps are as follows: 1.6 g of paraformaldehyde, 4.0 g of anhydrous zinc chloride and 6 ml of concentrated hydrochloric acid are added to the three-necked flask, and heated and stirred. When the temperature rises to 60 degrees Celsius, 2g of nickelocene is added, and the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride is quickly introduced, and the amount of the introduced gas is controlled by the dripping speed of concentrated sulfuric acid. The excess gas is absorbed with water. The reaction was completed after 6h, neutralized with 5% sodium carbonate aqueous solution to pH value between 5-7, extracted with chloroform, the organic layer was collected and washed with 10% sodium carbonate solution twice in sequence, washed with distilled water three times, and then Anhydrous sodium sulfate was dried, filtered, the filtrate was slowly dropped into 500ml of methanol, a brown solid was precipitated, dried by suction filtration, the filter cake was placed in a vacuum drying oven at 60 ° C and vacuum dried for 2h to obtain crude chloromethyl nickelocene 1.3g without further purification.
Figure PCTCN2018111081-appb-000016
Figure PCTCN2018111081-appb-000016
步骤2：羟甲基二茂镍的合成，合成路线如式(2b)所示。具体合成步骤如下：称取1g上一步制备的氯甲基二茂镍加入到圆底烧瓶中，加入30ml甲苯溶解，缓慢地将5ml 20％ 的氢氧化钠水溶液倒入圆底烧瓶，加热搅拌回流12小时。冷却后缓慢加入5％稀盐酸中和至pH值介于6-8，用三氯甲烷萃取，有机层依次用10％氯化钠水溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝10:1作为流动相，硅胶作为固定相，柱层析分离，收集产品。粗品加入10ml乙醇重结晶，得到墨绿色针状晶体，过滤后将滤饼放入真空干燥箱60℃真空干燥2h，得到羟甲基二茂镍0.83g。Step 2: Synthesis of hydroxymethyl nickelocene, the synthetic route is shown in formula (2b). The specific synthesis steps are as follows: Weigh 1g of the chloromethyl nickelocene prepared in the previous step into a round bottom flask, add 30ml of toluene to dissolve, slowly pour 5ml of 20% sodium hydroxide aqueous solution into the round bottom flask, and stir and reflux 12 hours. After cooling, slowly add 5% dilute hydrochloric acid to neutralize to pH value between 6-8, extract with chloroform, the organic layer was washed twice with 10% aqueous sodium chloride solution, washed three times with distilled water, and then with anhydrous sodium sulfate Dry, filter, and remove excess solvent by rotary evaporator. Use petroleum ether: ethyl acetate = 10: 1 as the mobile phase and silica gel as the stationary phase. Separate by column chromatography to collect the product. The crude product was recrystallized by adding 10 ml of ethanol to obtain dark green needle-like crystals. After filtration, the filter cake was placed in a vacuum drying oven at 60 ° C. for 2 hours under vacuum to obtain 0.83 g of hydroxymethyl nickelocene.
Figure PCTCN2018111081-appb-000017
Figure PCTCN2018111081-appb-000017
步骤3：中间体1的合成，合成路线如式(2c)所示。具体合成步骤如下：称取0.8g羟甲基二茂镍加入到圆底烧瓶中，加入10ml三氟化硼乙醚络合物中，在搅拌下于25-30℃通入环氧乙烷气体，通完后温度自动升至38-45℃，将所得反应液用氢氧化钾-甲醇溶液中和至pH值介于8-9。然后用乙醚萃取，有机层依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝8:1作为流动相，硅胶作为固定相，柱层析分离，收集产品，得到0.76g墨绿色油状液体中间体1。Step 3: Synthesis of intermediate 1, the synthetic route is shown in formula (2c). The specific synthesis steps are as follows: Weigh 0.8g of hydroxymethyl nickelocene into a round bottom flask, add 10ml of boron trifluoride etherate complex, and pass ethylene oxide gas at 25-30 ° C with stirring. After passing through, the temperature is automatically increased to 38-45 ° C, and the resulting reaction solution is neutralized with potassium hydroxide-methanol solution to a pH value between 8-9. It was then extracted with ether. The organic layer was washed twice with 10% sodium carbonate solution and washed three times with distilled water, then dried over anhydrous sodium sulfate, and filtered. The filtrate was removed with a rotary evaporator to remove excess solvent. Petroleum ether: ethyl acetate = 8: 1 as the mobile phase, silica gel as the stationary phase, column chromatography separation, and the product was collected to obtain 0.76 g of dark green oily liquid intermediate 1.
Figure PCTCN2018111081-appb-000018
Figure PCTCN2018111081-appb-000018
步骤4：有机磁性分子(2)的合成，合成路线如式(2d)所示。具体合成步骤如下：称取0.6g中间体1加入到圆底烧瓶中，加入5ml四氢呋喃，搅拌溶解后冰浴，用铝箔包裹圆底烧瓶，将0.3ml甲基丙烯酰氯缓慢滴入，30min后撤去冰浴，室温反应2h，反应结束，加入30ml水，然后用乙醚萃取，有机层依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝10:1作为流动相，硅胶作为固定相，柱层析分离，收集产品，得到0.52g墨绿色油状 液体有机磁性分子(2)。Step 4: Synthesis of organic magnetic molecules (2), the synthetic route is shown in formula (2d). The specific synthesis steps are as follows: Weigh 0.6g of intermediate 1 into a round bottom flask, add 5ml of tetrahydrofuran, stir and dissolve in an ice bath, wrap the round bottom flask with aluminum foil, slowly drop 0.3ml of methacryloyl chloride, and remove after 30min The reaction was performed in an ice bath at room temperature for 2h. After the reaction was completed, 30ml of water was added, followed by extraction with ether. The organic layer was washed twice with 10% sodium carbonate solution and washed with distilled water three times, then dried over anhydrous sodium sulfate, filtered, and the filtrate was rotated The evaporator removes the excess solvent, using petroleum ether: ethyl acetate = 10: 1 as the mobile phase, silica gel as the stationary phase, column chromatography separation, and collecting the product to obtain 0.52 g of dark green oily liquid organic magnetic molecules (2).
Figure PCTCN2018111081-appb-000019
Figure PCTCN2018111081-appb-000019
实施例3Example 3
有机磁性分子(3)的制备路线：Preparation route of organic magnetic molecule (3):
Figure PCTCN2018111081-appb-000020
Figure PCTCN2018111081-appb-000020
步骤1：氯甲基二茂钴的合成，合成路线如式(3a)所示。具体合成步骤如下：在三颈烧瓶中加入多聚甲醛1.6g、无水氯化锌4.0g和浓盐酸6ml，加热搅拌。当温度升至60摄氏度时，加入二茂钴2g，并迅速通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加速度控制通入气体的量，多余气体用水吸收，反应6h后结束，用5％碳酸钠水溶液中和至pH值介于5-7，采用三氯甲烷萃取，收集有机层并依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，将滤液缓慢的滴入到500ml甲醇中，析出棕色固体，抽滤干燥，将滤饼放入真空干燥箱60℃真空干燥2h，得到氯甲基二茂钴粗产品1.6g，无需进一步纯化。Step 1: Synthesis of chloromethylcobalocene. The synthetic route is shown in formula (3a). The specific synthesis steps are as follows: 1.6 g of paraformaldehyde, 4.0 g of anhydrous zinc chloride and 6 ml of concentrated hydrochloric acid are added to the three-necked flask, and heated and stirred. When the temperature rises to 60 degrees Celsius, add 2g of cobaltocene, and quickly pass the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, and control the amount of the passed gas by the dripping acceleration of concentrated sulfuric acid. The excess gas is absorbed with water. The reaction was completed after 6h, neutralized with 5% sodium carbonate aqueous solution to pH value between 5-7, extracted with chloroform, the organic layer was collected and washed with 10% sodium carbonate solution twice in sequence, washed with distilled water three times, and then Anhydrous sodium sulfate was dried, filtered, the filtrate was slowly dropped into 500ml of methanol, a brown solid was precipitated, dried by suction filtration, the filter cake was placed in a vacuum drying oven at 60 ° C and dried in vacuum for 2h, to obtain a crude product of chloromethylcobalocene 1.6g without further purification.
Figure PCTCN2018111081-appb-000021
Figure PCTCN2018111081-appb-000021
步骤2：中间体2的合成，合成路线如式(3b)所示。具体合成步骤如下：称取1g上一步的氯甲基二茂钴加入到圆底烧瓶中，加入30ml甲苯溶解，在搅拌下于80-100℃通入氨气，加热搅拌回流2小时。冷却后用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯：三乙胺＝100:10:1作为流动相，硅胶作为固定相，柱层析分离，收集产品，得到0.73g紫黑色中间体2。Step 2: Synthesis of intermediate 2, the synthetic route is shown in formula (3b). The specific synthesis steps are as follows: Weigh 1g of the previous step of chloromethylcobalocene into a round bottom flask, add 30ml of toluene to dissolve, pass ammonia gas under stirring at 80-100 ° C, heat and reflux for 2 hours. After cooling, the excess solvent was removed with a rotary evaporator. Petroleum ether: ethyl acetate: triethylamine = 100: 10: 1 was used as the mobile phase, silica gel was used as the stationary phase, column chromatography was separated, and the product was collected to obtain 0.73 g of purple black Intermediate 2.
Figure PCTCN2018111081-appb-000022
Figure PCTCN2018111081-appb-000022
步骤3：有机磁性分子(3)的合成，合成路线如式(3c)所示。具体合成步骤如下：称取0.6g中间体2加入到圆底烧瓶中，加入5ml四氢呋喃，搅拌溶解后冰浴，用铝箔包裹圆底烧瓶，将0.3ml甲基丙烯酰氯缓慢滴入，30min后撤去冰浴，室温反应2h，反应结束，加入30ml水，然后用乙醚萃取，收集有机层并依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝10:1作为流动相，硅胶作为固定相，柱层析分离，收集产品，得到0.52g紫黑色油状液体有机磁性分子(3)。Step 3: Synthesis of organic magnetic molecules (3), the synthetic route is shown in formula (3c). The specific synthesis steps are as follows: Weigh 0.6g of intermediate 2 into a round-bottom flask, add 5ml of tetrahydrofuran, stir and dissolve in an ice bath, wrap the round-bottom flask with aluminum foil, slowly drop 0.3ml of methacryloyl chloride, and remove after 30min The reaction was performed in an ice bath at room temperature for 2h. After the reaction was completed, 30ml of water was added, followed by extraction with ether. The organic layer was collected and washed with 10% sodium carbonate solution twice, distilled water three times, then dried over anhydrous sodium sulfate, filtered, and the filtrate The excess solvent was removed with a rotary evaporator, petroleum ether: ethyl acetate = 10: 1 as the mobile phase, silica gel as the stationary phase, column chromatography separation, and the product was collected to obtain 0.52g purple black oily liquid organic magnetic molecules (3) .
Figure PCTCN2018111081-appb-000023
Figure PCTCN2018111081-appb-000023
实施例4Example 4
有机磁性分子(4)的制备路线：Preparation route of organic magnetic molecules (4):
Figure PCTCN2018111081-appb-000024
Figure PCTCN2018111081-appb-000024
合成路线如式(4a)所示，具体合成步骤如下：称取2g原材料1加入到圆底烧瓶中，加入50ml四氢呋喃，搅拌溶解后冰浴，用铝箔包裹圆底烧瓶，将1.4ml甲基丙烯酰氯缓慢滴入，30min后撤去冰浴，室温反应2h，反应结束后，加入100ml水，然后用乙醚萃取，有机层依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝10:1作为流动相，硅胶作为固定相，柱层析分离，收集产品，得到无色油状液体1.2g有机磁性分子(4)。The synthetic route is as shown in formula (4a). The specific synthesis steps are as follows: Weigh 2g of raw material 1 into a round bottom flask, add 50ml of tetrahydrofuran, stir and dissolve it in an ice bath, wrap the round bottom flask with aluminum foil, and place 1.4ml of methacrylic acid The acid chloride was slowly added dropwise, the ice bath was removed after 30min, and the reaction was carried out at room temperature for 2h. After the reaction was completed, 100ml of water was added, followed by extraction with ether. The organic layer was washed twice with 10% sodium carbonate solution in sequence, washed with distilled water three times, and then anhydrous Sodium sulfate was dried, filtered, and the filtrate was removed with a rotary evaporator, using petroleum ether: ethyl acetate = 10: 1 as the mobile phase, silica gel as the stationary phase, column chromatography separation, and the product was collected to obtain a colorless oily liquid 1.2 g organic magnetic molecules (4).
Figure PCTCN2018111081-appb-000025
Figure PCTCN2018111081-appb-000025
实施例5Example 5
有机磁性分子(5)的制备路线：Preparation route of organic magnetic molecule (5):
Figure PCTCN2018111081-appb-000026
Figure PCTCN2018111081-appb-000026
步骤1：中间体3的合成，合成路线如式(5a)所示。具体合成步骤如下：称取5g锌粉加入烧杯中，加入3mol/L盐酸20mL，在室温下搅拌浸泡洗涤至无气泡产生(此时锌粉颜色变亮)，抽滤，水洗至中性，无水乙醇洗涤三次，乙醚洗涤三次，在真空下干燥。然后将处理好的锌粉转移到圆底烧瓶中，用氮气抽通三次，确保无氧。将2g原材料2溶解在30ml四氢呋喃中，-5摄氏度下缓慢滴入到圆底烧瓶中与锌粉反应，30min后撤去冰浴，室温搅拌反应2h，反应结束，得到中间体3，不再分离。Step 1: Synthesis of intermediate 3, the synthetic route is shown in formula (5a). The specific synthesis steps are as follows: Weigh 5g of zinc powder into a beaker, add 3mol / L hydrochloric acid 20mL, stir and wash at room temperature until no bubbles are generated (at this time the zinc powder color becomes bright), suction filter, wash with water until neutral, no Wash three times with water ethanol, three times with ether, and dry under vacuum. Then transfer the treated zinc powder to a round-bottom flask and pump it through nitrogen three times to ensure oxygen-free. Dissolve 2g of raw material 2 in 30ml of tetrahydrofuran, slowly drop it into a round bottom flask at -5 degrees Celsius to react with zinc powder. After 30min, the ice bath was removed, and the reaction was stirred at room temperature for 2h. After the reaction was completed, intermediate 3 was obtained and no longer separated.
Figure PCTCN2018111081-appb-000027
Figure PCTCN2018111081-appb-000027
步骤2：有机磁性分子(5)的制备，合成路线如式(5b)所示。具体合成步骤如下：向中间体3中缓慢滴入1.6ml原材料3，45摄氏度下反应8h，反应结束，小心的加入30ml稀盐酸终止反应，然后用乙醚萃取，有机层依次用10％碳酸钠溶液洗涤2次，蒸馏水洗涤3次，然后用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪除去多余的溶剂，以石油醚：乙酸乙酯＝15:1作为流动相，硅胶作为固定相，柱层析分离，收集产品，得到0.37g无色油状液体有机磁性分子(5)。Step 2: Preparation of organic magnetic molecules (5), the synthetic route is shown in formula (5b). The specific synthesis steps are as follows: 1.6ml of raw material 3 was slowly dropped into Intermediate 3, the reaction was completed at 45 degrees Celsius for 8h, the reaction was completed, carefully added 30ml of dilute hydrochloric acid to terminate the reaction, and then extracted with ether, the organic layer was sequentially used 10% sodium carbonate solution Wash 2 times, wash 3 times with distilled water, then dry over anhydrous sodium sulfate, filter, remove excess solvent with a rotary evaporator, use petroleum ether: ethyl acetate = 15: 1 as mobile phase, silica gel as stationary phase, column Chromatographic separation and collection of the product gave 0.37 g of colorless oily liquid organic magnetic molecules (5).
Figure PCTCN2018111081-appb-000028
Figure PCTCN2018111081-appb-000028
实施例6Example 6
在该实施例中，分别采用实施例1～5所得到的有机磁性分子(1)～(5)，按照下列方法制备薄膜封装结构1～5：In this example, the organic magnetic molecules (1) to (5) obtained in Examples 1 to 5 are used respectively to prepare thin film encapsulation structures 1 to 5 according to the following method:
实验组：test group:
1、在氮化硅无机材料表面(厚度0.5～2μm)喷墨打印含有实施例的有机磁性分子(1)～(5)和2,4,6-三甲基苯甲酰基-二苯基氧化膦(基于混合液的总体积，含量为10体积％)的混合液，并在表面一侧设置电磁铁进行磁引导，磁力为20T，形成液体有机磁性分子薄层；1. Inkjet printing on the surface of silicon nitride inorganic material (thickness 0.5 ～ 2μm) containing organic magnetic molecules (1) ～ (5) of the examples and 2,4,6-trimethylbenzoyl-diphenyl oxide A mixed liquid of phosphine (based on the total volume of the mixed liquid, the content is 10% by volume), and an electromagnet is provided on the surface side for magnetic guidance, and the magnetic force is 20T, forming a thin layer of liquid organic magnetic molecules;
2、对液体有机磁性分子薄层进行紫外光照射，液体有机磁性分子薄层发生固化反应形成聚合物，在氮化硅无机材料表面形成有机层(厚度4～10μm)，2. Irradiate the thin layer of liquid organic magnetic molecules with ultraviolet light, the thin layer of liquid organic magnetic molecules undergoes a curing reaction to form a polymer, and an organic layer (thickness 4 to 10 μm) is formed on the surface of the silicon nitride inorganic material.
其中，实施例1～5的有机磁性分子所形成的聚合物结构分别如下所示：Among them, the polymer structures formed by the organic magnetic molecules of Examples 1 to 5 are as follows:
Figure PCTCN2018111081-appb-000029
Figure PCTCN2018111081-appb-000029
Figure PCTCN2018111081-appb-000030
Figure PCTCN2018111081-appb-000030
3、在有机层远离氮化硅无机材料的一面形成氮化硅无机层(厚度0.5～2μm)，获得薄膜封装结构。3. A silicon nitride inorganic layer (thickness 0.5-2 μm) is formed on the side of the organic layer away from the silicon nitride inorganic material to obtain a thin-film encapsulation structure.
对照组：Control group:
1、在氮化硅无机材料表面喷墨打印含有目前商用不具备磁场诱导定向排列的化合物(kateeva公司产品，型号为FlexCap EXP-TFE-A1)和2,4,6-三甲基苯甲酰基-二苯基氧化膦(基于混合液的总体积，含量为10体积％)的混合液，然后进行紫外光照射，化合物发生固化反应形成聚合物，在氮化硅无机材料表面形成有机层；1. Inkjet printing on the surface of silicon nitride inorganic materials contains compounds that are currently not commercially available without magnetic field induced alignment (product of kateeva company, model is FlexCap EXP-TFE-A1) and 2,4,6-trimethylbenzoyl -A mixture of diphenylphosphine oxide (based on the total volume of the mixture, the content is 10% by volume), and then subjected to ultraviolet light irradiation, the compound undergoes a curing reaction to form a polymer, and an organic layer is formed on the surface of the silicon nitride inorganic material;
2、在有机层远离氮化硅无机材料的一面形成氮化硅无机层，获得薄膜封装结构。2. A silicon nitride inorganic layer is formed on the side of the organic layer away from the silicon nitride inorganic material to obtain a thin film packaging structure.
发明人对实验组和对照组的薄膜封装结构测试水汽透过。然后采用薄膜封装结构1～5和对照组的薄膜的封装结构对统一制备的性能无差别的绿光OLED器件进行薄膜封装，分别测试其在60℃、90％湿度调节下的器件使用寿命，测试结果如表1所示。结果表明，本发明的薄膜封装结构中，由于形成有机层的聚合物分子定向排列，使分子堆积更紧密，链间的空隙更小，使得薄膜封装结构的水氧阻隔能力、抗拉伸和弯折性能具有更强的优势，所保护的OLED器件使用寿命也更长。The inventor tested the water vapor transmission of the thin film packaging structure of the experimental group and the control group. Then, the thin film packaging structure 1 to 5 and the film packaging structure of the control group were used to perform thin film packaging on the uniformly prepared green OLED device with no difference in performance, and the device service life at 60 ° C and 90% humidity adjustment was tested respectively. The results are shown in Table 1. The results show that in the thin-film encapsulation structure of the present invention, due to the orientation of the polymer molecules forming the organic layer, the molecules are packed more closely and the gap between the chains is smaller, making the thin-film encapsulation structure's water-oxygen barrier ability, tensile resistance and bending The folding performance has a stronger advantage, and the service life of the protected OLED device is also longer.
表1 测试数据Table 1 Test data
Figure PCTCN2018111081-appb-000031
Figure PCTCN2018111081-appb-000031
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或者“一些示例”等的描述意指结合该实施例或者示例描述的具体特征、结构、材料或者者特点包含于本发明的至少一个实施例或者示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或者示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或者多个实施例或者示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或者示例以及不同实施例或者示例的特征进行结合和组合。In the description of this specification, the description referring to the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" means specific features described in conjunction with the embodiment or examples , Structure, material or characteristics are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. In addition, without contradicting each other, those skilled in the art may combine and combine different embodiments or examples and features of the different embodiments or examples described in this specification.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it should be understood that the above-mentioned embodiments are exemplary and cannot be construed as limitations to the present invention, and those of ordinary skill in the art may understand the above within the scope of the present invention. The embodiments are changed, modified, replaced, and modified.

Claims (20)

  1. 一种有机磁性分子，其特征在于，包括：An organic magnetic molecule, characterized in that it includes:
    主体基团；Host group
    连接基团；以及Linking group; and
    磁性基团，所述主体基团与所述磁性基团通过所述连接基团相连。A magnetic group, the host group and the magnetic group are connected through the linking group.
  2. 根据权利要求1所述的有机磁性分子，其特征在于，所述磁性基团具有如下所示的分子结构或者为C 1～8杂环基，杂原子至少为N原子，并且N原子与氧原子形成氮氧自由基，
    Figure PCTCN2018111081-appb-100001
    其中，M选自金属离子。     The organic magnetic molecule according to claim 1, wherein the magnetic group has a molecular structure as shown below or is a C 1-8 heterocyclic group, the hetero atom is at least N atom, and the N atom and the oxygen atom To form nitroxide radicals,
    Figure PCTCN2018111081-appb-100001
    Among them, M is selected from metal ions.
  3. 根据权利要求2所述的有机磁性分子，其特征在于，所述金属离子包括铁离子、钴离子或者镍离子。The organic magnetic molecule according to claim 2, wherein the metal ions include iron ions, cobalt ions, or nickel ions.
  4. 根据权利要求2所述的有机磁性分子，其特征在于，所述C 1～8杂环基具有如下至少之一的分子结构： The organic magnetic molecule according to claim 2, wherein the C 1-8 heterocyclic group has at least one of the following molecular structures:
    Figure PCTCN2018111081-appb-100002
    或者
    Figure PCTCN2018111081-appb-100003
    Figure PCTCN2018111081-appb-100002
    or
    Figure PCTCN2018111081-appb-100003
  5. 根据权利要求1所述的有机磁性分子，其特征在于，所述主体基团选自可以在加热和光照至少一种条件下发生聚合反应的基团。The organic magnetic molecule according to claim 1, wherein the host group is selected from groups that can undergo polymerization under at least one condition of heating and light irradiation.
  6. 根据权利要求5任一项所述的有机磁性分子，其特征在于，所述主体基团选自下列至少之一：丙烯酸酯基、乙烯基、苯乙烯基、丙烯基、丙烯酸基、酰胺基、酰亚胺基、碳酸酯基、氨酯丙烯酸基、硅氧烷基和硅氮烷基；The organic magnetic molecule according to any one of claims 5, wherein the host group is selected from at least one of the following: acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, Imide group, carbonate group, urethane acrylate group, siloxane group and silazane group;
    其中，所述丙烯酸酯基、乙烯基、苯乙烯基、丙烯基、丙烯酸基、酰胺基、酰亚胺基、碳酸酯基、氨酯丙烯酸基、硅氧烷基或者硅氮烷基均可任选地被一个或者多个选自F、Cl、Br、I、-OH、-NO 2、-NH 2、-CN、C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基C 1～6烷基、C 2～6 烯基、C 2～6炔基、C 1～6烷氨基C 1～6烷基、C 3～6环烷基、C 3～6环烷基C 1～6烷基、C 3～6环烷基C 2～6烯基、C 3～6环烷基C 2～6炔基或者C 3～6环烷基氧基C 2～6炔基的基团所取代。 Wherein, the acrylate group, vinyl group, styryl group, acryl group, acrylic group, amide group, imide group, carbonate group, urethane acrylic group, siloxane group or silazane group can Optionally, one or more are selected from F, Cl, Br, I, -OH, -NO 2 , -NH 2 , -CN, C 1-6 alkyl, halogenated C 1-6 alkyl, C 1 ～ 6 alkoxy C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkylamino C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 Cycloalkyl C 1-6 alkyl, C 3-6 cycloalkyl C 2-6 alkenyl, C 3-6 cycloalkyl C 2-6 alkynyl or C 3-6 cycloalkyloxy C 2 ～ 6 Alkynyl groups are substituted.
  7. 根据权利要求6所述的有机磁性分子，其特征在于，所述主体基团具有下列至少之一的分子结构：The organic magnetic molecule according to claim 6, wherein the host group has a molecular structure of at least one of the following:
    Figure PCTCN2018111081-appb-100004
    或者
    Figure PCTCN2018111081-appb-100005
    其中，所述R选自C nH 2n+1，n选自0～10的整数。
    Figure PCTCN2018111081-appb-100004
    or
    Figure PCTCN2018111081-appb-100005
    Wherein, said R is selected from C n H 2n + 1 and n is selected from an integer of 0-10.
  8. 根据权利要求1所述的有机磁性分子，其特征在于，所述连接基团选自下列至少之一：C 1～6烷基、卤代C 1～6烷基、C 1～6烷氧基、C 1～6烷氧基C 1～6烷基、C 2～6烯基、C 2～6炔基、C 2～6烯基C 1～6烷基、C 2～6炔基C 1～6烷基、C 1～6烷氨基C 1～6烷基、酰胺基C 1～6烷基、羧基C 1～6烷基和羰基C 1～6烷基。 The organic magnetic molecule according to claim 1, wherein the linking group is selected from at least one of the following: C 1-6 alkyl, halogenated C 1-6 alkyl, C 1-6 alkoxy , C 1-6 alkoxy C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 2-6 alkenyl C 1-6 alkyl, C 2-6 alkynyl C 1 -6 alkyl, C 1-6 alkylamino C 1-6 alkyl, amido C 1-6 alkyl, carboxy C 1-6 alkyl and carbonyl C 1-6 alkyl.
  9. 根据权利要求8所述的有机磁性分子，其特征在于，所述连接基团具有下列之一的分子结构：The organic magnetic molecule according to claim 8, wherein the linking group has one of the following molecular structures:
    Figure PCTCN2018111081-appb-100006
    Figure PCTCN2018111081-appb-100006
    其中，n选自0～10的整数。However, n is selected from the integer of 0-10.
  10. 根据权利要求1～9任一项所述的有机磁性分子，其特征在于，所述有机磁性分子具有下列之一的分子结构：The organic magnetic molecule according to any one of claims 1 to 9, wherein the organic magnetic molecule has one of the following molecular structures:
    Figure PCTCN2018111081-appb-100007
    Figure PCTCN2018111081-appb-100007
    Figure PCTCN2018111081-appb-100008
    或者
    Figure PCTCN2018111081-appb-100008
    or
    Figure PCTCN2018111081-appb-100009
    Figure PCTCN2018111081-appb-100009
  11. 一种薄膜封装结构，其特征在于，包括：A thin film packaging structure, which is characterized by comprising:
    第一衬底；First substrate
    有机层，所述有机层覆盖于所述第一衬底的表面；以及An organic layer covering the surface of the first substrate; and
    第二衬底，所述第二衬底覆盖于所述有机层远离所述第一衬底的表面；A second substrate, the second substrate covering the surface of the organic layer away from the first substrate;
    其中，所述有机层至少包括由权利要求1～10任一项所述有机磁性分子形成的聚合物。Wherein, the organic layer includes at least a polymer formed of the organic magnetic molecules according to any one of claims 1-10.
  12. 根据权利要求11所述的薄膜封装结构，其特征在于，所述第一衬底和第二衬底选自无机层。The thin film packaging structure according to claim 11, wherein the first substrate and the second substrate are selected from an inorganic layer.
  13. 一种薄膜封装结构的制备方法，其特征在于，包括以下步骤：A method for preparing a thin film packaging structure, characterized in that it includes the following steps:
    提供所述第一衬底；Providing the first substrate;
    在所述第一衬底的表面上施加含有所述有机磁性分子和引发剂的混合液；Applying a mixed solution containing the organic magnetic molecules and the initiator on the surface of the first substrate;
    在所述第一衬底的表面一侧设置磁力产生装置进行磁引导，以便形成定向排列的液体有机磁性分子薄层；以及A magnetic force generating device is provided on the surface side of the first substrate for magnetic guidance, so as to form a thin layer of liquid organic magnetic molecules aligned; and
    使所述液体有机磁性分子薄层固化，以便形成所述有机层。The thin layer of liquid organic magnetic molecules is cured to form the organic layer.
  14. 根据权利要求13所述的薄膜封装结构的制备方法，其特征在于，进一步包括：在所述有机层远离所述第一衬底的表面形成第二衬底，以便获得所述薄膜封装结构。The method for preparing a thin film packaging structure according to claim 13, further comprising: forming a second substrate on a surface of the organic layer away from the first substrate, so as to obtain the thin film packaging structure.
  15. 根据权利要求13所述的薄膜封装结构的制备方法，其特征在于，所述磁力产生装置选自电磁铁和永磁体的至少之一。The method for manufacturing a thin film packaging structure according to claim 13, wherein the magnetic force generating device is selected from at least one of an electromagnet and a permanent magnet.
  16. 根据权利要求13所述的薄膜封装结构的制备方法，其特征在于，使所述液体有机磁性分子薄层固化的方法包括加热和光照射中的至少之一。The method for preparing a thin film packaging structure according to claim 13, wherein the method for curing the thin layer of liquid organic magnetic molecules includes at least one of heating and light irradiation.
  17. 根据权利要求13所述的薄膜封装结构的制备方法，其特征在于，所述引发剂选自自由基引发剂。The method for preparing the thin film packaging structure according to claim 13, wherein the initiator is selected from free radical initiators.
  18. 根据权利要求17所述的薄膜封装结构的制备方法，其特征在于，基于所述混合液的总体积，所述引发剂的含量为0.1～20体积％。The method for preparing a thin-film encapsulation structure according to claim 17, wherein the content of the initiator is 0.1-20% by volume based on the total volume of the mixed solution.
  19. 根据权利要求13所述的薄膜封装结构的制备方法，其特征在于，所述在所述第一衬底的表面上施加含有所述有机磁性分子和引发剂的混合液包括：采用喷墨印刷法或者化学气相沉积法将所述混合液铺设在所述第一衬底的表面。The method for preparing a thin-film encapsulation structure according to claim 13, wherein the application of the mixed liquid containing the organic magnetic molecules and the initiator on the surface of the first substrate comprises: using an inkjet printing Alternatively, the chemical vapor deposition method lays the mixed solution on the surface of the first substrate.
  20. 一种显示装置，其特征在于，包括：A display device is characterized by comprising:
    待封装基板；以及Substrate to be packaged; and
    权利要求11或者12所述的薄膜封装结构，所述薄膜封装结构覆盖所述待封装基板。The thin film packaging structure according to claim 11 or 12, which covers the substrate to be packaged.
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