CN116288766B

CN116288766B - Electroluminescent fiber, yarn and fabric and preparation method thereof

Info

Publication number: CN116288766B
Application number: CN202111509616.8A
Authority: CN
Inventors: 陶光明; 李攀; 孙之惠
Original assignee: Wuhan Xinrunxing Material Technology Co ltd
Current assignee: Wuhan Xinrunxing Material Technology Co ltd
Priority date: 2021-12-10
Filing date: 2021-12-10
Publication date: 2025-01-24
Anticipated expiration: 2041-12-10
Also published as: CN116288766A

Abstract

The invention provides an electroluminescent fiber which is provided with more than two conductive layers and a luminescent layer arranged between the conductive layers, wherein the luminescent layer has the advantages of simple structure, reliable performance, good luminescent effect, firm combination of the luminescent layer and the conductive layers, and the optimal scheme can realize different colors or combinations of colors respectively or simultaneously. In addition, the invention also provides a method for preparing the electroluminescent fiber, which has the advantages of low production cost, simple operation, easy batch preparation, controllable wire diameter, controllable structure, environmental friendliness and the like, and the electroluminescent fiber/fabric is anti-bending, has the characteristics of excellent flame retardance, electromagnetic interference resistance, ultraviolet aging resistance, excellent wearability and the like, can keep stable display brightness in environments such as extreme temperature, PH and the like, and can keep stable luminous brightness in 5000 times of wear-resistant Martindale circulation.

Description

Electroluminescent fiber, yarn and fabric and preparation method thereof

Technical Field

The application relates to the field of functional fibers, in particular to electroluminescent fibers, yarns and fabrics and a preparation method thereof.

Background

With the improvement of life quality, the requirements of people on intelligent, functional and miniaturized devices are higher and higher, and intelligent wearable fabrics become an object of investigation which is tired for various nationologists, so that the demand market is gradually expanded. The research and development of the intelligent wearable fabric meets the requirements of people on different functions such as sensing, energy storage, heat management, color change and luminescence, and the luminescent fabric also has important and wide application value in the fields such as display, communication and intelligent robots. Common luminescent materials include photoluminescence, electroluminescence, ray luminescence, thermoluminescence, light-emission luminescence, radiation luminescence and the like, wherein electroluminescence is a phenomenon that a material emits light under the action of a direct current or alternating current electric field, and belongs to an electric control luminescence mode. Therefore, the electroluminescent fiber and the fabric thereof have the advantages of high response speed, high brightness, easy processing, easy control and the like.

At present, a plurality of processes for preparing electroluminescent fibers exist, for example, a Chinese patent No. CN108093535A discloses a preparation method of high-elasticity electroluminescent fibers, wherein a multi-channel parallel extrusion needle is designed, an extrusion luminous active layer wraps a fiber structure of two hydrogel electrodes which are arranged in parallel, but because the maximum luminous intensity point of the structure is positioned in the central area of the fiber, the brightness of the fiber is attenuated to a certain extent, the used base material is limited, the hydrogel electrodes are greatly influenced by environment and have high cost, and batch preparation is difficult to realize, and the Chinese patent No. CN1427652A discloses a preparation method of the electroluminescent fibers, which comprises a central electrode, a dielectric insulating layer, a luminous layer, a transparent electrode, an auxiliary electrode, an anti-aging filler, a protective sleeve and the like from inside to outside. The dielectric layer and the luminous layer are prepared by dip-coating and stretching methods, the transparent electrode is prepared by a reaction evaporation method, the preparation process is complex, the cost is high, and mass production is difficult to realize. Chinese patent CN107275498 a discloses a flexible electroluminescent device and its preparation method, which comprises a conductive nanofiber bundle, a luminescent layer coated on the surface of the conductive nanofiber bundle, and a transparent conductive film coated on the surface of the luminescent layer, wherein the transparent conductive film relates to electroplating, vapor deposition and other processes, and has high preparation cost and is difficult to mass production.

The Chinese patent No. 108505187A discloses a luminous fabric and a preparation method thereof, wherein the method comprises the steps of loading luminous active materials outside a flexible fiber conductor to obtain conductive luminous active fibers, assembling the conductive luminous active fibers and the conductive fibers, and finally packaging. The method for preparing the flexible electroluminescent fiber by adopting the electrostatic spinning method is also a current common method, and Chinese patent No. 106883852A discloses a method for preparing the rare earth erbium-doped titanium dioxide/silicon dioxide composite nanofiber by adopting polyvinylpyrrolidone (PVP) as a fiber forming material, N-N dimethylformamide as a solvent, tetrabutyl titanate, tetraethyl orthosilicate and Er nitrate as main raw materials, and adopting the electrostatic spinning method to prepare a precursor, and drying and calcining the precursor fiber; in addition, the preparation of luminescent raw materials by introducing an in-situ polymerization method is also a method which is developed and mature at present, and Chinese patent CN1234925C discloses a long afterglow luminescent polyamide fiber and a preparation method thereof, wherein the long afterglow luminescent polyamide fiber consists of polyamide fibers and an effective quantity of Eu ²⁺ activated alkali metal aluminate, and the simple preparation method comprises the following steps of directly carrying out melt spinning or blending with polyamide in a conventional manner by adopting the in-situ polymerization method to obtain the required long afterglow luminescent polyamide fiber. In the Chinese patent CN104674539B, a method with simple process and strong operability is disclosed, the method utilizes a sol-gel method to prepare europium and dysprosium co-doped strontium aluminate luminous powder with good luminous performance, and a uniform and compact luminous layer is deposited on the surfaces of fibers and fabrics by a radio frequency magnetron sputtering technology, but the sol-gel method used in the method needs low temperature or mild preparation conditions, and the production mode is limited. Therefore, a method with simple preparation process and mass production is urgently needed, and simultaneously, the characteristics of controllable wire diameter, controllable structure and the like are also needed in the process of preparing the fiber so as to meet the market demand for the electroluminescent fiber.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides the electroluminescent fiber which has the advantages of simple structure, reliable performance, realization of different colors or combinations of colors in real time respectively or simultaneously by an optimization scheme, low production cost, simple operation, easiness in batch preparation, controllable wire diameter, controllable structure, environmental friendliness and the like, and the invention also provides the electroluminescent fiber which is used for preparing the electroluminescent yarn and the electroluminescent fabric.

Specifically, the technical scheme of the invention is as follows:

1. an electroluminescent fiber comprising:

More than two conductive layers, and

And a light emitting layer disposed between the conductive layers.

2. The electroluminescent fiber of item 1, wherein the luminescent layer comprises a first polymeric material and an electroluminescent material.

3. The electroluminescent fiber according to item 1,

The first polymer material is selected from polymethyl methacrylate (PMMA), fluororesin, PMMA composite material doped with fluorinated polymer (F-PMMA), styrene dimethyl methyl acrylate copolymer (SMMA), cycloolefin copolymer (COC), cycloolefin polymer (COP), polycarbonate (PC), polyphenylene sulfone resin (PPSU), polyether sulfone resin (PES), polyethyleneimine (PEI), polystyrene (PS), polyethylene (PE), polypropylene (PP), polyamide (PA), polyimide (PI), polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), styrene-ethylene/butylene-styrene block copolymer (SEBS), polyurethane (PU), polyvinyl chloride (PVC), polystyrene (PS), polypropylene terephthalate (PTT), polyvinylidene chloride resin (PVDC), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene glycol (PEG), thermoplastic elastomer (TPE), low Density Polyethylene (LDPE), polyethylene glycol (PEG), high Density Polyethylene (HDPE), polyoxymethylene (POM), polyester (O), sodium metasulfonate, and acrylic acid ester copolymer, one or a combination of two or more kinds of polyvinyl acetal is preferably selected from polymethyl methacrylate (PMMA), fluororesin-modified polymethyl methacrylate (F-PMMA), cycloolefin copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-dimethyl methacrylate copolymer (SMMA), cycloolefin polymer (COP), and styrene-ethylene/butylene-styrene block copolymer (SEBS).

4. The electroluminescent fiber according to item 2,

The conductive layer comprises an inner conductive layer and an outer transparent conductive layer;

the inner conductive layer, the luminous layer and the outer transparent conductive layer are sequentially arranged from inside to outside.

5. The electroluminescent fiber of item 4, the material of the outer transparent conductive layer comprising an electronically transparent conductive material and/or an ionically transparent conductive material.

6. The electroluminescent fiber according to item 5,

The electronic transparent conductive material is a conductive polymer or polymer composite material;

The polymer composite material is formed by dispersing one or more than two of nanoscale inorganic nonmetallic materials, inorganic metallic materials and semiconductor materials in a second polymer material,

The conductive polymer comprises poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT/PSS);

The inorganic nonmetallic material is selected from one or more than two of graphene, carbon nano-tubes, carbon nano-rods and MXene;

the inorganic metal material is selected from one or more than two of nano silver wires, nano gold wires, nano copper wires, metal or oxide metal grids;

the semiconductor material is selected from one or more of Indium Tin Oxide (ITO), tin antimony oxide (ATO) and zinc oxide (ZTO), and/or,

The ionic transparent conductive material is a transparent solid polymer electrolyte, and is a lithium salt dissolved in a third polymer material, wherein the lithium salt is one or a combination of more than two of lithium hexafluorophosphate (LiPF ₆), lithium bis (trifluoromethanesulfonyl imide) (LiTFSI), lithium perchlorate (LiClO ₄), lithium tetrafluoroarsenate (LiAsF ₄) and lithium tetrafluoroborate (LiBF ₄).

7. The electroluminescent fiber according to item 6, wherein the second polymer material and the third polymer material are transparent thermoplastic polymer materials selected from one or more of polymethyl methacrylate (PMMA), fluororesin-modified polymethyl methacrylate (F-PMMA), cyclic Olefin Copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-methyl dimethacrylate copolymer (SMMA), cyclic Olefin Polymer (COP), and styrene-ethylene/butylene-styrene block copolymer (SEBS).

8. The electroluminescent fiber according to item 2, wherein two or more conductive layers are arranged in the light emitting layer, preferably the conductive layers are conductive filaments, further preferably the two or more conductive layers are arranged parallel to each other.

9. The electroluminescent fiber according to item 8,

The light-emitting layer comprises more than two light-emitting layer units which are axially arranged along the electroluminescent fiber;

At least one electroluminescent material between the luminescent layer unit and the other luminescent layer units has different luminescence bands;

the conductive layer is in contact with at least one light emitting layer unit.

10. The electroluminescent fiber according to item 8 or 9,

The conductive wire is a metal wire, the outer surface of the conductive wire is distributed with rugged defects, and/or the outer surface of the conductive wire is coated with a dielectric insulating layer with high dielectric constant;

Preferably, the dielectric insulating layer material with high dielectric constant is selected from nano paint of one or more than two of barium titanate (BaTiO ₃), lead titanate (PbTiO ₃), strontium titanate (SrTiO ₃) and titanium dioxide (TiO ₂).

11. The electroluminescent fiber according to any one of claims 1 to 10, wherein the outermost layer of the electroluminescent fiber is coated with a transparent protective layer, and the transparent protective layer is preferably a fourth polymer material.

12. The electroluminescent fiber according to item 11,

The fourth polymer material is a transparent thermoplastic polymer material and is selected from one or more than two of polymethyl methacrylate (PMMA), fluororesin modified polymethyl methacrylate (F-PMMA), cycloolefin copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene dimethyl methyl acrylate copolymer (SMMA), cycloolefin polymer (COP) and styrene-ethylene/butylene-styrene block copolymer (SEBS).

13. The electroluminescent fiber according to item 12, wherein the functional material is added to the transparent protective layer, and the functional material is uniformly distributed in the transparent protective layer.

14. The electroluminescent fiber according to item 13,

The functional material is selected from one or more than two of photoluminescent material, fluorescent material and scattering agent;

Preferably, the scattering agent is selected from one or a combination of more than two of TiO₂、BaSO₄、Al₂O₃、MgO、BeO、Y₂O₃、ZrO₂、GaAs、ZnS、ZnSe、MgF₂、CaF₂.

15. The electroluminescent fiber according to any one of the claims 2 to 14,

The electroluminescent material has a mass fraction in the luminescent layer of 0.1wt.% to 70wt.%, preferably 20wt.% to 50wt.%, and/or,

The concentration distribution of the electroluminescent material in the luminescent layer is kept unchanged or gradually decreases or increases gradually from inside to outside along the radial direction of the fiber.

16. The electroluminescent fiber according to any one of the claims 2 to 15,

The electroluminescent material is one or more than two of long afterglow material of sulfide system, sulfide material of alkaline earth metal sulfide and rare earth as activator, long afterglow material of aluminate system, long afterglow material of silicate system, long afterglow material of gallate system, silicon-based oxynitride series, stannate system, phosphate system, titanate system, rare earth doped or transition metal doped up-conversion luminescent material and luminescent quantum dot.

17. The electroluminescent fiber according to any one of the claim 16,

The long persistence material of the sulfide system comprises an overmetal sulfide selected from one or a combination of more than two of ZnS: cu ²⁺、ZnS:Mn²⁺、ZnS:Cu²⁺,Co²⁺, and/or,

The alkaline earth metal sulfide is selected from one or more than two of CaS, cu ²⁺、CaS:Ba³⁺、CaSrS:Ba³⁺, and/or,

The sulfide material of rare earth as activator is selected from one or more than two of Y₂O₂S:Eu³⁺,Mg²⁺,Ti⁴⁺、CaS:Eu²⁺,Pr³⁺、CaS:Eu²⁺,Tm³⁺, and/or,

The long afterglow material of aluminate system is one or more than two kinds of CaAl₂O₄:Eu²⁺,Nd³⁺、Sr₃Al₂O₄:Eu²⁺,Dy³⁺、Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺、CaAl₄O₇:Ce³⁺、MAlO₃:Mn⁴⁺,Ge⁴⁺(M＝La,Gd) and/or,

The long afterglow material of silicate system is one or more than two kinds selected from MgSiO₃:Mn²⁺,Eu²⁺,Dy³⁺、CdSiO₃:Mn²⁺、CdSiO₃:Sm²⁺、Ba₂ZrSi₃O₉:Eu²⁺,Pr³⁺ and/or,

The long afterglow material of the gallate (gallium germanic acid) system is selected from one or more than two of ZnGa₂O₄:Cr³⁺、Zn₃Ga₂Ge₂O₁₀:Cr³⁺、Zn₂Ga₂Ge₂O₁₀:Cr³⁺,Pr³⁺、Mg₄Ga₈Ge₂O₂₀:Cr³⁺ and/or,

The silicon-based oxynitride series includes LaSi ₃N₅:Ce³⁺, and/or,

The stannate system is selected from Sr ₂SnO₄:Sm³⁺ or CaSnO ₃:Pr³⁺, and/or,

The titanate system comprises CaTiO ₃:Pr³⁺, and/or,

The up-conversion luminescent material is selected from one or more of NaYF ₄、NaGdF₄、LiYF₄、YF₃、CaF₂ fluoride or Gd ₂O₃ oxide nanocrystals, such as NaYF ₄, er, yb, etc. and/or,

The luminescent quantum dot is selected from one or more than two of cadmium sulfide (CdS), cadmium selenide (CdSe) and cadmium telluride (CdTe).

18. The electroluminescent fiber according to any one of the above 1 to 17,

The electroluminescent fiber has a cross section of one of a circle, a triangle, a rectangle, an ellipse and a pentagram.

19. A method for preparing electroluminescent fiber, comprising the following steps:

compounding the first polymer material and the electroluminescent material to prepare an electroluminescent composite material;

Preparing a prefabricated rod from a transparent conductive material and an electroluminescent composite material, wherein the transparent conductive material is positioned on a cladding layer of the prefabricated rod, the electroluminescent composite material is positioned on a core layer of the prefabricated rod, and a hole structure is arranged in the electroluminescent composite material positioned on the core layer along the axial direction of the prefabricated rod;

and (3) penetrating the conductive layer through the pore structure of the preform, and preparing the composite structural fiber with the luminescent layer and the conductive layer through heat softening wire drawing.

20. The method according to item 19,

The transparent conductive material includes an electronic transparent conductive material and/or an ionic transparent conductive material.

21. The method of manufacturing according to item 20,

the inorganic metal material is selected from one or more than two of metallic materials such as nano silver wire/gold wire/copper wire, silver or copper and the like or oxide metal grids;

The semiconductor material is one or the combination of more than two of Indium Tin Oxide (ITO), tin antimony oxide (ATO) and zinc oxide (ZTO), and/or,

The ionic transparent conductive material is a transparent solid polymer electrolyte, and is a lithium salt dissolved in the third polymer material, wherein the lithium salt is one or more selected from lithium hexafluorophosphate (LiPF ₆), lithium bis (trifluoromethanesulfonyl imide) (LiTFSI), lithium perchlorate (LiClO ₄), lithium tetrafluoroarsenate (LiAsF ₄) and lithium tetrafluoroborate (LiBF ₄).

22. The method of producing a polypeptide according to item 21,

The second polymer material and the third polymer material are transparent thermoplastic polymer materials and are selected from one or more than two of polymethyl methacrylate (PMMA), fluororesin modified polymethyl methacrylate (F-PMMA), cycloolefin copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-dimethyl methyl acrylate copolymer (SMMA), cycloolefin polymer (COP) and styrene-ethylene/butylene-styrene block copolymer (SEBS).

23. A method for preparing electroluminescent fiber, comprising the following steps:

preparing an electroluminescent composite material into a preform, wherein a hole structure is arranged in the preform along the axial direction of the preform, and the hole structure comprises more than two holes along the axial direction of the preform, and preferably the more than two holes are parallel to each other;

respectively passing the conductive layers through more than two holes of the preform, and preparing and obtaining the electroluminescent fiber by a heat softening wire drawing method;

preferably, the conductive layer is a conductive wire.

24. The method of producing according to item 23,

The prefabricated rod is more than two electroluminescent composite materials arranged along the axial direction of the prefabricated rod, and at least one electroluminescent composite material and other electroluminescent composite materials have different luminous wave bands;

the aperture is in contact with at least one of the electroluminescent composites.

25. The method of producing according to item 23,

Preferably, the material of the dielectric insulating layer with high dielectric constant is a nano paint selected from one or more of barium titanate (BaTiO ₃), lead titanate (PbTiO ₃), strontium titanate (SrTiO ₃) and titanium dioxide (TiO ₂).

26. The production process according to any one of the claim 19 to 25,

The outer sleeve of the prefabricated rod is provided with a transparent material;

Preferably, the transparent material is a fourth polymer material, and more preferably, a functional material is added to the transparent material.

27. The method of manufacturing according to item 26,

28. The method of manufacturing according to item 26,

29. The method according to any one of claims 19 to 28,

The electroluminescent composite material is prepared by a physical blending method, a physical/chemical blending method or a solution blending method.

30. The method according to any one of claims 19 to 29,

The mass ratio of the electroluminescent material in the electroluminescent composite material is 0.1-70 wt%, preferably 20-50 wt%.

31. The method according to any one of the above 19 to 30,

The concentration distribution of the electroluminescent material in the electroluminescent composite material is kept unchanged or gradually decreases or increases from inside to outside along the radial direction of the preform.

32. The method according to any one of items 19 to 31,

The first polymer material is selected from polymethyl methacrylate (PMMA), fluororesin, PMMA composite material doped with fluorinated polymer (F-PMMA), styrene dimethyl methyl acrylate copolymer (SMMA), cycloolefin copolymer (COC), cycloolefin polymer (COP), polycarbonate (PC), polyphenylene sulfone resin (PPSU), polyether sulfone resin (PES), polyethyleneimine (PEI), polystyrene (PS), polyethylene (PE), polypropylene (PP), polyamide (PA), polyimide (PI), polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), styrene-ethylene/butylene-styrene block copolymer (SEBS), polyurethane (PU), polyvinyl chloride (PVC), polystyrene (PS), polytrimethylene terephthalate (PTT), polyvinylidene chloride resin (PVDC), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene glycol (PEG), thermoplastic elastomer (TPE), low Density Polyethylene (LDPE), polyethylene glycol (PEG), high Density Polyethylene (HDPE), polyoxymethylene (POM), polyester (O), sodium metasilicate sulfonate, sodium metasilicate, and acrylic resin, one or a combination of two or more kinds of polyvinyl acetal is preferably one or a combination of two or more kinds of polymethyl methacrylate (PMMA), fluororesin-modified polymethyl methacrylate (F-PMMA), cyclic Olefin Copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene dimethyl methacrylate copolymer (SMMA), cyclic Olefin Polymer (COP), styrene-ethylene/butylene-styrene block copolymer (SEBS).

33. The method according to any one of the claims 19 to 32,

34. An electroluminescent yarn made from more than two electroluminescent fibers twisted;

the electroluminescent fiber is selected from any one or more than two electroluminescent fibers in the items 1-18, and/or,

The electroluminescent fiber is selected from any one method or more than two methods in the items 19-33.

35. An electroluminescent textile fabric, which comprises a base layer,

The electroluminescent fabric contains electroluminescent fibers and/or electroluminescent yarns, or

The electroluminescent fabric comprises transparent conductive fibers and electroluminescent fibers and/or electroluminescent yarns;

the electroluminescent fiber is selected from any one or more than two electroluminescent fibers in the items 1-18, and/or the electroluminescent fiber is selected from any one method or more than two electroluminescent fibers prepared by any one method in the items 19-33;

The electroluminescent yarn is the electroluminescent yarn described in item 34.

The electroluminescent fiber has the characteristics of simple structure, simple preparation method, mass production, controllable wire diameter, unique structure and the like. The electroluminescent fiber has good luminous effect, the luminous layer and the conductive layer are firmly combined, the number and the distribution of holes are controlled, the multi-electrode luminous fiber can be prepared, the multi-electrode luminous fiber can control the luminous effect more accurately and stably, and meanwhile, the color of the electrochromic fiber (such as single-color electroluminescent fiber, double-color electroluminescent fiber and three-color electroluminescent fiber) can be regulated and controlled. In addition, the fabric can be further woven, is not easy to damage in a bending and folding state, and has the characteristics of excellent wearability and luminous effect. The electroluminescent fiber can be widely applied to the fields of clothes, decoration, industry, fishery, traffic and the like in the future.

The foregoing description is only an overview of the technical solutions of the present invention, to the extent that it can be implemented according to the content of the specification by those skilled in the art, and to make the above-mentioned and other objects, features and advantages of the present invention more obvious, the following description is given by way of example of the present invention.

Drawings

FIG. 1 is a schematic diagram of a first electroluminescent fiber structure according to the present invention;

FIG. 2 is a schematic diagram of a second electroluminescent fiber structure according to the present invention;

FIG. 3 is a schematic view of a third electroluminescent fiber structure according to the present invention;

FIG. 4 is a schematic diagram of a fourth electroluminescent fiber structure according to the present invention;

FIG. 5 is a schematic view of a fifth electroluminescent fiber structure according to the present invention;

FIG. 6 is a schematic view of a sixth electroluminescent fiber structure according to the present invention;

FIG. 7 is a schematic view of a seventh electroluminescent fiber structure according to the present invention;

FIG. 8 is a schematic view of an eighth electroluminescent fiber structure according to the present invention;

FIG. 9 is a schematic view of a ninth electroluminescent fiber structure according to the present invention;

FIG. 10 is a schematic view of a tenth electroluminescent fiber structure according to the present invention;

FIG. 11 is a schematic view of an electroluminescent fabric;

FIG. 12 is a schematic view of a fiber preparation process according to the present invention;

FIG. 13 is a chart showing the measurement of the electroluminescent fiber of example 12 according to the present invention by a visible-ultraviolet spectrometer.

The device comprises the following components of a conductive layer 1, a luminous layer 2, an outer transparent conductive layer 3, an outer transparent protective layer 4, a coil 5, a rod feeding device 6, a prefabricated rod 7, a heating furnace 8, a diameter measuring instrument 9, a coating device 10, an auxiliary traction device 11, a wire winding 12 and a wire winding.

Detailed Description

The following embodiments of the invention are merely illustrative of specific embodiments for carrying out the invention and are not to be construed as limiting the invention. Any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent arrangements which are within the scope of the invention.

The following are embodiments relating to electroluminescent fibers.

In one embodiment, an electroluminescent fiber is disclosed that includes two or more conductive layers and a luminescent layer disposed between the conductive layers.

The electroluminescent fiber provided by the embodiment has the advantages of simple structure and stable performance.

The "conductive layer" in the present invention is not limited to a laminar or lamellar structure, and the cross section of the conductive layer may be any shape such as a circle, a polygon, or the like, as long as an electric field can be formed between the conductive layers.

Also, the light-emitting layer is not limited to a layered or lamellar structure, and may have any cross-section as long as it emits light in an electric field between two or more conductive layers.

In one embodiment, the conductive layer is a conductive wire.

The embodiment provides a specific conductive layer, which is a conductive wire.

In one embodiment, the light emitting layer comprises a polymeric material and an electroluminescent material.

The embodiment provides a specific luminescent layer structure, and the material is an electroluminescent composite material, specifically an electroluminescent composite material obtained by compounding a first polymer material and an electroluminescent material.

In the invention, the electroluminescent material is a material which directly converts electric energy into light energy under the action of a direct current or alternating current electric field and by means of excitation of current and the electric field.

In a specific embodiment, the first polymer material is selected from polymethyl methacrylate (PMMA), fluororesin, fluorinated polymer doped PMMA composite (F-PMMA), styrene dimethyl methacrylate copolymer (SMMA), cyclic Olefin Copolymer (COC), cyclic Olefin Polymer (COP), polycarbonate (PC), polyphenylene sulfone resin (PPSU), polyether sulfone resin (PES), polyethylene imine (PEI), polystyrene (PS), polyethylene (PE), polypropylene (PP), polyamide (PA), polyimide (PI), polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), styrene-ethylene/butylene-styrene block copolymer (SEBS), polyurethane (PU), polyvinyl chloride (PVC), polystyrene (PS), polypropylene terephthalate (PTT), polyvinylidene chloride resin (PVDC), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene glycol (PEG), thermoplastic elastomer (TPE), low Density Polyethylene (LDPE), polyethylene glycol (PEG), high density polyethylene (m), polyoxymethylene copolymer (PP), sodium formaldehyde sulfonate, polyester, and sodium m-phenylene oxide copolymer (PPO) and polyphenylene oxide copolymer (PPO), one or a combination of two or more of vinyl acetate resin and polyvinyl acetal is preferably selected from polymethyl methacrylate (PMMA), fluororesin-modified polymethyl methacrylate (F-PMMA), cyclic Olefin Copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-dimethyl methyl acrylate copolymer (SMMA), cyclic Olefin Polymer (COP), and styrene-ethylene/butylene-styrene block copolymer (SEBS).

In this example, a specific type of first polymeric material is given.

In one embodiment, as shown in fig. 1, the conductive layers include an inner conductive layer, an outer transparent conductive layer 3;

The (inner) conductive layer 1, the light-emitting layer 2 and the outer transparent conductive layer 3 are sequentially arranged from inside to outside.

In this embodiment, as shown in fig. 1, the conductive layer is specifically divided into an (inner) conductive layer 1 and an outer transparent conductive layer 3, which form an electric field, so that the light-emitting layer 2 emits light, and the emitted light is emitted through the outer transparent conductive layer 3.

In a specific embodiment, the material of the outer transparent conductive layer 3 includes an electronic transparent conductive material and/or an ionic transparent conductive material.

The specific materials for the outer transparent conductive layer are given in this example.

In the invention, the electronic transparent conductive material refers to a transparent polymer material in which a first type of conductive material is distributed, a large number of freely movable electrons exist, and under the action of an external electric field, the electrons do directional movement to form obvious current.

In the invention, the ionic transparent conductive material refers to a transparent polymer material distributed with a second type of conductive material, a large number of freely movable ions exist in the second type of conductive material, and the ions perform directional diffusion movement under the action of an electric field.

In one embodiment, the electronically transparent conductive material is a conductive polymer or polymer composite;

The inorganic metal material is selected from one or more than two of metal materials such as nano silver wires, nano gold wires, nano copper wires and the like or a combination of metal grids;

The semiconductor material is selected from one or more of Indium Tin Oxide (ITO), tin antimony oxide (ATO) and zinc oxide (ZTO).

In the invention, the metal grid means that wires of conductive metals such as gold, silver or copper and oxides thereof are densely distributed on a transparent polymer base material to form a conductive network with a regular shape.

Further, since the inorganic nonmetallic material, the metallic material, and the semiconductor material are not transparent materials, they are dispersed in a polymer material, thereby obtaining the outer transparent conductive layer 3.

The embodiment shows a specific electronic transparent conductive material.

In a specific embodiment, the ionic transparent conductive material is a transparent solid polymer electrolyte, and is a lithium salt dissolved in the third polymer material, wherein the lithium salt is one or a combination of more than two of lithium hexafluorophosphate (LiPF ₆), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium perchlorate (LiClO ₄), lithium tetrafluoroarsenate (LiAsF ₄) and lithium tetrafluoroborate (LiBF ₄).

Specific ionic transparent conductive materials are given in this example.

In a specific embodiment, the second polymer material and the third polymer material are transparent thermoplastic polymer materials, and are selected from one or more than two of polymethyl methacrylate (PMMA), fluororesin modified polymethyl methacrylate (F-PMMA), cyclic Olefin Copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-dimethyl methyl acrylate copolymer (SMMA), cyclic Olefin Polymer (COP), and styrene-ethylene/butylene-styrene block copolymer (SEBS). Specific second and third polymeric materials are given in this example.

In a specific embodiment, as shown in fig. 2 to 10, two or more conductive layers are arranged in the light emitting layer along the axial direction of the electroluminescent fiber, preferably, the conductive layers are conductive filaments, and further preferably, the two or more conductive layers are disposed parallel to each other.

This example shows another structure of electroluminescent fiber.

Specifically, the luminescent layer comprises a pair of parallel conductive layers 1 (shown in fig. 2), three conductive layers 1 (shown in fig. 3 and 5) which are distributed in a triangular shape on the fiber section, three conductive layers 1 (shown in fig. 4) which are arranged on the same plane in parallel, four conductive layers 1 (shown in fig. 6-9) which are distributed in a quadrilateral shape on the fiber section, or four conductive layers in the luminescent layer, wherein one conductive layer is in the center of the luminescent layer, the other three conductive layers are uniformly distributed around the central conductive layer (shown in fig. 10, namely, on the fiber section), the three conductive layers are distributed in an equilateral triangle shape, and the other conductive layer is in the center of the equilateral triangle).

In addition, in the technical schemes of fig. 2 to 10, the two ends of the electroluminescent fiber can be rotated in opposite directions along the circumferential direction of the electroluminescent fiber, so that more than two conductive layers are spiral, and the technical effects can still be achieved. In short, two or more conductive layers do not intersect each other in the light-emitting layer, and an electric field may be formed between the two or more conductive layers.

In this embodiment, an electric field is formed between two or more conductive layers 1, so that the light-emitting layer 2 surrounding the conductive layers 1 emits light, and the emitted light is directly emitted from the light-emitting layer 2.

In a specific embodiment, the light-emitting layer includes more than two light-emitting layer units disposed along the axial direction of the electroluminescent fiber (as in fig. 4 to 10, light-emitting layer units with different color depths represent different light-emitting layer units, and more than two light-emitting layer units together form the light-emitting layer 2);

the conductive layer is in contact with at least one light emitting layer unit.

As shown in fig. 4,5, 10, at least one conductive layer 1 is in contact with each light emitting unit at the same time, while the other conductive layers are within each light emitting unit.

As shown in fig. 4 and 5, the light-emitting device specifically includes 2 light-emitting units, 3 conductive layers, 1 conductive layer being located on an interface between two light-emitting units, and the other 2 conductive layers being located in the two light-emitting units, respectively. When electric fields are formed between the middle conductive wires and any other conductive wires, different colors of light can be emitted respectively, and the electric fields can be formed among the three conductive wires, so that different lights can be emitted simultaneously, and the electric fields can be formed among the different conductive wires alternately, so that different lights can be emitted alternately.

Similarly, the electroluminescent fiber as shown in fig. 10 specifically includes 3 light emitting units and 4 conductive layers, wherein 1 conductive layer is located at the connection of 3 light emitting units, and the other 3 conductive layers are respectively located in 3 light emitting units. The electric field can be formed between the middle conductive layer and other conductive layers or between other conductive layers, so that mixed light emitting of more than two colors can be realized, and the above combinations can be alternatively used to alternately emit different lights.

As shown in fig. 6 and 7, the conductive layer may be located at the interface between the light emitting unit and the outer transparent protective layer 4, so long as an electric field may be formed between the conductive layers to make the electroluminescent composite emit light.

In addition, in the electroluminescent fiber, the conductive wires are positioned on the interface of the two light-emitting units. As shown in fig. 8 and 9, the light emitting units located at the upper and lower sides are the same type of light emitting unit. When electric fields are formed between different conductive wires, different colors of light can be emitted respectively, or electric fields can be formed between four conductive wires so as to emit different lights at the same time, or the combination can be used alternately so as to emit different lights alternately.

Therefore, this embodiment is a further improvement of the previous embodiment, and the conductive layers on both sides of the different types of light emitting units can be turned on to form different colors of light respectively, or of course, the electric fields can be formed between different conductive wires in any combination or between all conductive wires, so that different combinations form light with no color or different color combinations, or the combination can be changed continuously, so that light with different colors can be flashed. Therefore, the electroluminescent fiber of the invention can show different colors, different color combinations and different colors or color combinations to emit light alternately, so that the electroluminescent fiber of the invention can be applied to more scenes and the application range of the electroluminescent fiber of the invention is expanded.

In a specific embodiment, as shown in fig. 1-10, the conductive wire is a metal wire, and the surface of the metal wire is distributed with rugged defects. In this embodiment, the conductive layer 1 and the light emitting layer 2 can be more closely contacted by the uneven defects distributed on the surface of the metal wire, so that the adhesion between the conductive layer and the light emitting layer is increased.

In a specific embodiment, as shown in fig. 1-10, the conductive wire is a metal wire, and the surface of the conductive wire is coated with a dielectric insulating layer with a high dielectric constant (generally referred to as a relative dielectric constant, and the relative dielectric constant is free of units), preferably, the dielectric insulating layer with the high dielectric constant is a nano-coating containing one or more of barium titanate (BaTiO ₃), lead titanate (PbTiO ₃), strontium titanate (SrTiO ₃) and titanium dioxide (TiO ₂). In the invention, the high dielectric constant refers to a material or a composite material with a dielectric constant greater than 10, and when an electric field is externally applied, induced charges are generated to weaken the electric field, and the surface of the metal wire is coated with a dielectric insulating layer with a high dielectric constant, so that the luminescence layer can be prevented from being electrically broken down to generate fluorescence quenching.

In a specific embodiment, the light emitting layer is further covered with a transparent protective layer, and the transparent protective layer is preferably a fourth polymer material.

In a specific embodiment, the fourth polymer material is a transparent thermoplastic polymer material, and is selected from one or more than two of polymethyl methacrylate (PMMA), fluororesin-modified polymethyl methacrylate (F-PMMA), cyclic Olefin Copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-dimethyl methyl acrylate copolymer (SMMA), cyclic Olefin Polymer (COP), and styrene-ethylene/butylene-styrene block copolymer (SEBS).

The present example shows a specific fourth polymeric material.

Through setting up transparent protective layer on electroluminescent fiber surface, can make electroluminescent fiber more durable, outer transparent protective layer can prevent effectively that luminescent layer's electroluminescent material deliquescence from becoming invalid, still prevent the electric shock when people touch.

In one embodiment, the transparent protective layer is added with functional materials, and the functional materials are uniformly distributed in the transparent protective layer.

In the present invention, the functional material refers to a material having a specific function after the action of light, electricity, magnetism, heat, chemistry, biochemistry and the like, and particularly, a material which can emit light or can change the reflection angle of light under the light stimulation so as to scatter the light.

The transparent protective layer is added with functional materials, so that the transparent protective layer has the functions of corresponding functional materials.

In a specific embodiment, the functional material is selected from one or more than two of photoluminescent material, fluorescent material and scattering agent;

In the present invention, the photoluminescent material means a material that emits light when excited by an excitation source such as ultraviolet light or visible light. The addition of photoluminescent material in the transparent protective layer can regulate the light spectrum and brightness of electroluminescent fiber (light excitation with low energy and light with high energy is emitted).

In the present invention, the fluorescent material is a material that absorbs light of a certain wavelength and immediately emits light of a different wavelength. When the incident light disappears, the fluorescent material stops emitting light immediately, and the luminescent spectrum of the electroluminescent fiber can be adjusted by adding the fluorescent material into the transparent protective layer, so that the spectrum is widened in a limited electroluminescent spectrum range.

In the invention, the scattering agent refers to a material which can cause light rays to be emitted to the periphery (when the light beams pass through an uneven medium, part of the light beams are scattered and spread from the original direction), and the light-emitting scattering angle of the electroluminescent fiber can be adjusted by adding the scattering agent into the transparent protective layer, so that the light emission is more uniform and softer.

In a specific embodiment, the mass ratio of the electroluminescent material in the light-emitting layer is 0.1wt.% to 70wt.%, specifically may be 0.1wt.%, 1wt.%, 5wt.%, 10wt.%, 20wt.%, 30wt.%, 40wt.%, 50wt.%, 60wt.%, 70wt.%, and preferably 20wt.% to 50wt.%.

In this embodiment, the mass ratio of the electroluminescent material in the luminescent layer is 0.1wt.% to 70wt.%, in which the electroluminescent fiber can be prepared in batch and has excellent luminescence property, and above which the electroluminescent fiber is difficult to prepare, and especially, the mass ratio is preferably 20wt.% to 50wt.% and the mechanical property is superior under the condition that the luminescence property is ensured. Below 20wt.% concentration, the mechanical properties are good but the luminescent properties are poor, and above 50wt.% concentration the luminescent properties are good but the mechanical properties are poor.

In a specific embodiment, the concentration distribution of the electroluminescent material in the light-emitting layer is kept unchanged or gradually decreases or increases from inside to outside along the radial direction of the fiber.

When the concentration distribution in the luminous layer is kept unchanged from inside to outside along the radial direction of the fiber, the electroluminescent fiber can be prepared in batches and has excellent luminous performance.

When the concentration distribution in the luminous layer gradually increases along the radial direction of the fiber, the luminous performance of the electroluminescent fiber can be realized, and the mechanical performance of the electroluminescent fiber is simultaneously considered, compared with the concentration which is kept unchanged from inside to outside along the radial direction of the fiber (compared with the concentration of the outermost layer), the luminous performance is slightly weakened, but the mechanical performance is obviously improved.

When the concentration distribution in the luminous layer gradually decreases along the radial direction of the fiber, the luminous performance of the electroluminescent fiber can be realized, and meanwhile, the mechanical performance is simultaneously considered, and compared with the concentration which is kept unchanged from inside to outside along the radial direction of the fiber (compared with the concentration of the outermost layer), the luminous performance is obviously improved, but the mechanical performance is weakened.

In a specific embodiment, the electroluminescent material is one or more than two of a long afterglow material of a sulfide system, an alkaline earth sulfide, a sulfide material taking rare earth as an activator, a long afterglow material of an aluminate system, a long afterglow material of a silicate system, a long afterglow material of a gallate (gallium germanic acid) system, a long afterglow material of other systems such as silicon-based oxynitride systems, stannate systems, phosphate systems, titanate systems, rare earth doped or transition metal doped up-conversion luminescent materials, and luminescent quantum dots.

The kind of electroluminescent material is given in this example.

In one embodiment, the long persistence material of the sulfide system comprises a transition metal sulfide selected from one or a combination of two or more of ZnS: cu ²⁺、ZnS:Mn²⁺、ZnS:Cu²⁺,Co²⁺, and/or,

The silicon-based oxynitride series includes LaSi ₃N₅:Ce³⁺, and/or,

The titanate system comprises CaTiO ₃:Pr³⁺, and/or,

Specific electroluminescent materials are given in this example.

In a specific embodiment, the electroluminescent fiber has a cross section that is one of circular, triangular, rectangular, oval, and pentagram.

In the present embodiment, the electroluminescent fiber of the present invention may be any of a variety of cross-sectional shapes, and the cross-section of the electroluminescent fiber is not limited to the above-described ones.

The following are embodiments related to the method of making electroluminescent fibers.

In one embodiment, a method for preparing an electroluminescent fiber is disclosed, comprising the steps of:

and (3) penetrating the conductive layer through the pore structure of the preform, and preparing the electroluminescent fiber through heat softening wire drawing. This example shows a method for preparing an electroluminescent fiber by penetrating a conductive layer (in this embodiment, specifically, a conductive wire) into a pore structure of a preform prepared from an electroluminescent composite material, and then drawing the wire by heat softening, so that an electroluminescent fiber having a structure as shown in fig. 1 can be prepared. Namely, the conductive wires form a (inner) conductive layer 1, the transparent conductive material forms an outer transparent conductive layer 3, and the electroluminescent composite material forms a light-emitting layer 2.

The method has the advantages of low production cost, simple operation, easy batch preparation, controllable wire diameter, controllable structure, environmental friendliness and the like.

In one embodiment, the transparent conductive material comprises an electronic transparent conductive material and/or an ionic transparent conductive material.

This example illustrates several specific electronically transparent conductive materials.

In a specific embodiment, the ionic transparent conductive material is a transparent solid polymer electrolyte, and is a lithium salt dissolved in the third polymer material, wherein the lithium salt is one or a combination of two or more selected from lithium hexafluorophosphate (LiPF ₆), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium perchlorate (LiClO ₄), lithium tetrafluoroarsenate (LiAsF ₄) and lithium tetrafluoroborate (LiBF ₄).

This example illustrates several specific ionic transparent conductive materials.

In a specific embodiment, the second polymer material and the third polymer material are transparent thermoplastic polymer materials, and are selected from one or more than two of polymethyl methacrylate (PMMA), fluororesin modified polymethyl methacrylate (F-PMMA), cyclic Olefin Copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-dimethyl methyl acrylate copolymer (SMMA), cyclic Olefin Polymer (COP), and styrene-ethylene/butylene-styrene block copolymer (SEBS).

Specific second and third polymeric materials are given in this example.

In one embodiment, an electroluminescent composite is prepared by compounding a first polymeric material and an electroluminescent material;

preparing an electroluminescent composite material into a preform, wherein more than two holes (which can be double holes, three holes or four holes and the like) are arranged in the preform along the axial direction of the preform, and preferably, the more than two holes are parallel to each other;

And respectively passing the conductive layers through more than two holes of the preform, and preparing and obtaining the electroluminescent fiber by a heat softening wire drawing method, wherein the conductive layers are preferably conductive wires.

In this embodiment, another method for preparing electroluminescent fiber is provided, where the preform is made of an electroluminescent composite material, and two or more conductive filaments respectively pass through two or more holes, and then are subjected to heat softening wire drawing, so as to prepare the electroluminescent fiber with the structure shown in fig. 2 and 3, i.e. the two or more conductive filaments respectively form the conductive layer 1, and the electroluminescent composite material forms the luminescent layer 2.

In a specific embodiment, the preform is composed of more than two electroluminescent composite materials arranged along the axial direction of the preform, and at least one electroluminescent composite material and other electroluminescent composite materials have different light-emitting wave bands;

This embodiment is a preferred embodiment of the previous embodiment, and electroluminescent materials with different light emission bands can emit light of different colors. After heat softening and wire drawing, the different electroluminescent composite materials form luminescent layer units, and a plurality of luminescent layer units (luminescent layers in fig. 4-10 and the like distinguish different luminescent layer units through different color depths) form a luminescent layer 2. The conductive layers on two sides of different types of light-emitting units can be conducted, so that the electroluminescent composite materials containing the electroluminescent materials with different light-emitting wavebands can emit light with different colors, and the different electroluminescent composite materials can be promoted to emit light respectively, simultaneously or alternately.

In a specific embodiment, the conductive wire is a metal wire, and the surface of the conductive wire is distributed with the uneven defects, so that the conductive layer 1 and the light-emitting layer 2 can be in closer contact by the uneven defects distributed on the surface of the metal wire, and the adhesive force between the conductive layer and the light-emitting layer is increased.

In one specific embodiment, the conductive wire is a metal wire, and the surface of the conductive wire is coated with a dielectric insulating layer with high dielectric constant;

preferably, the material of the dielectric insulating layer with high dielectric constant is a nano paint containing one or more than two of barium titanate (BaTiO ₃), lead titanate (PbTiO ₃), strontium titanate (SrTiO ₃) and titanium dioxide (TiO ₂).

In this embodiment, by coating the surface of the wire with a dielectric insulating layer having a high dielectric constant, the light-emitting layer is prevented from being electrically broken down to cause fluorescence quenching.

In one embodiment, the preform is sheathed with a transparent material;

preferably, the transparent material is a fourth polymeric material.

After heat softening and wire drawing, the transparent material forms a transparent protective layer on the surface layer of the electroluminescent fiber, so that the luminescent layer 2 or the transparent conductive layer 3 can be protected, the durability of the electroluminescent fiber is improved, and meanwhile, the light emitted from the luminescent layer can be transmitted.

The present example shows a specific fourth polymeric material.

In one embodiment, a functional material is added to the transparent material.

The functional material refers to a material with specific functions after the actions of light, electricity, magnetism, heat, chemistry, biochemistry and the like. The addition of the functional material to the transparent material can give the transparent material the characteristics of the functional material, so that the formed outer transparent protective layer 4 can perform more functions.

When the functional material is a photoluminescent material, the photoluminescent material is contained in the outer protective layer of the surface layer of the electroluminescent fiber, so that the light-emitting spectrum (emitting light with different colors) and the light-emitting brightness of the electroluminescent fiber can be adjusted.

When the functional material is a fluorescent material, the outer protective layer on the surface layer of the prepared electroluminescent fiber contains the fluorescent material, so that the light-emitting spectrum of the electroluminescent fiber can be adjusted.

When the functional material is a scattering agent, the scattering agent is contained in the outer protective layer of the surface layer of the prepared electroluminescent fiber, so that the luminous scattering angle of the electroluminescent fiber can be adjusted, and the luminescence is more uniform and softer.

This example illustrates some of the types of electroluminescent materials that can be used in the method of the present application for making electroluminescent fibers.

In one embodiment, the long persistence material of the sulfide system comprises a transition metal sulfide selected from one or more of ZnS: cu ²⁺、ZnS:Mn²⁺ or ZnS: cu ²⁺,Co²⁺, and/or,

The alkaline earth metal sulfide is selected from one or more of CaS, cu ²⁺、CaS:Ba³⁺ or CaSrS and Ba ³⁺, and/or,

The long afterglow material of silicate system is one or more than two kinds selected from MgSiO₃:Mn²⁺,Eu²⁺,Dy³⁺、CdSiO₃:Mn²⁺、CdSiO₃:Sm²⁺、Ba₂ZrSi₃O₉:Eu²⁺,Pr³⁺, and/or,

The silicon-based oxynitride series includes LaSi ₃N₅:Ce³⁺, and/or,

The stannate system is selected from one or more than two of Sr ₂SnO₄:Sm³⁺、CaSnO₃:Pr³⁺, and/or,

The titanate system comprises CaTiO ₃:Pr³⁺, and/or,

The up-conversion luminescent material is selected from one or more of NaYF ₄、NaGdF₄、LiYF₄、YF₃、CaF₂ fluoride or Gd ₂O₃ oxide nanocrystals, such as NaYF ₄, er, yb, etc., and/or,

The luminescent quantum dot is selected from one or more of cadmium sulfide (CdS), cadmium selenide (CdSe) and cadmium telluride (CdTe).

In this example, electroluminescent materials are specifically exemplified, which can be used in the method of the present application for preparing electroluminescent fibers.

In one embodiment, the electroluminescent composite is prepared by a physical blending method, a physical/chemical blending method, or a solution blending method.

The physical blending method is to uniformly mix the polymer material and the electroluminescent material under the condition of heating and melting by a screw extruder, so as to prepare the electroluminescent composite material.

The physical/chemical blending method is that some chemical polymerization reaction occurs on the basis of physical blending, and the electroluminescent material does not participate in the chemical reaction, so that the physical properties of the polymer are enhanced, and the electroluminescent composite material is prepared.

The solution blending method is to fully dissolve the polymer material into solution by adopting chemical reagent, then add the electroluminescent material, and uniformly disperse by means of ultrasonic or magnetic stirrer, etc., the polymer material and the electroluminescent material do not react with the chemical reagent. And removing the chemical agent to prepare the electroluminescent composite material.

In a specific embodiment, the mass ratio of the electroluminescent material in the electroluminescent composite material is 0.1wt.% to 70wt.%, and specifically may be 0.1wt.%, 1wt.%, 5wt.%, 10wt.%, 20wt.%, 30wt.%, 40wt.%, 50wt.%, 60wt.%, 70wt.%. Preferably 20wt.% to 50wt.%.

In the embodiment, the mass ratio of the electroluminescent material in the electroluminescent composite material is 0.1wt.% to 70wt.%, in which the electroluminescent fiber can be prepared in batches and uniformly emits light, and beyond this range, the electroluminescent fiber is difficult to prepare, and especially, the mass ratio is preferably 20wt.% to 50wt.%, and the mechanical property is superior under the condition that the luminescence property is ensured. Below 20wt.% concentration, the mechanical properties are good but the luminescent properties are poor, and above 50wt.% concentration the luminescent properties are good but the mechanical properties are poor.

In one embodiment, the concentration profile of the electroluminescent material in the electroluminescent composite material is maintained constant or gradually decreases or increases from inside to outside along the radial direction of the preform.

According to the technical scheme, the luminous layer in the prepared electroluminescent fiber can be kept unchanged or gradually decreased or increased along the radial direction of the electroluminescent fiber. When the concentration distribution in the luminous layer is kept unchanged from inside to outside along the radial direction of the fiber, the electroluminescent fiber can be prepared in batches and has excellent luminous performance. When the concentration distribution in the luminous layer gradually increases along the radial direction of the fiber, the luminous performance of the electroluminescent fiber can be realized, and the mechanical performance of the electroluminescent fiber is simultaneously considered, compared with the concentration which is kept unchanged from inside to outside along the radial direction of the fiber (compared with the concentration of the outermost layer), the luminous performance is slightly weakened, but the mechanical performance is obviously improved. When the concentration distribution in the luminous layer gradually decreases along the radial direction of the fiber, the luminous performance of the electroluminescent fiber can be realized, and meanwhile, the mechanical performance is simultaneously considered, and compared with the concentration which is kept unchanged from inside to outside along the radial direction of the fiber (compared with the concentration of the outermost layer), the luminous performance is obviously improved, but the mechanical performance is weakened.

In a specific embodiment, the first polymeric material is selected from the group consisting of a polymer selected from the group consisting of polymethyl methacrylate (PMMA), a fluororesin, a PMMA composite doped with a fluorinated polymer (F-PMMA), a styrene dimethyl methacrylate copolymer (SMMA), a Cyclic Olefin Copolymer (COC), a Cyclic Olefin Polymer (COP), a Polycarbonate (PC), a polyphenylene sulfone resin (PPSU), a polyethersulfone resin (PES), a Polyethyleneimine (PEI), a Polystyrene (PS), a Polyethylene (PE), a polypropylene (PP), a Polyamide (PA), a Polyimide (PI), a polyethylene terephthalate (PET), a Polyacrylonitrile (PAN), a polyvinylidene fluoride (PVDF), a polyvinyl alcohol (PVA), a styrene-ethylene/butylene-styrene block copolymer (SEBS), a Polyurethane (PU), a polyvinyl chloride (PVC), a Polystyrene (PS), a polytrimethylene terephthalate (PTT), a polyvinylidene chloride resin (PVDC), an acrylonitrile-butadiene-styrene copolymer (ABS), a polyethylene glycol (PEG), a thermoplastic elastomer (TPE), a Low Density Polyethylene (LDPE), a polyethylene glycol (PEG), a High Density Polyethylene (HDPE), a polyoxymethylene (PP), a sodium m-formaldehyde copolymer (PP), and a sodium m-phthalate (PPO) polymer One or more of acrylic acid ester copolymer, vinyl acetate resin, and polyvinyl acetal is preferably polymethyl methacrylate (PMMA), fluororesin-modified polymethyl methacrylate (F-PMMA), cyclic Olefin Copolymer (COC), polyvinylidene fluoride (PVDF), polystyrene (PS), polycarbonate (PC), styrene-dimethyl methyl acrylate copolymer (SMMA), cyclic Olefin Polymer (COP), styrene-ethylene/butylene-styrene block copolymer (SEBS), or the like.

In this example, a specific type of first polymeric material is given.

The following are embodiments relating to electroluminescent yarns.

In one embodiment, an electroluminescent yarn is disclosed, the electroluminescent yarn being made from more than two electroluminescent fibers twisted;

the electroluminescent yarn is selected from any of the electroluminescent yarns described above, and/or,

The electroluminescent yarn is selected from electroluminescent yarns prepared by any one method or more than two methods respectively.

The yarn is a textile, and is processed into products with certain fineness by various textile fibers. The electroluminescent yarn of the embodiment is made by twisting more than two electroluminescent fibers, so that the electroluminescent yarn can be used for preparing fabrics later.

The following are embodiments relating to electroluminescent textiles.

In one specific embodiment, an electroluminescent fabric is disclosed, the electroluminescent fabric comprises electroluminescent fibers and/or electroluminescent yarns, or the electroluminescent fabric comprises transparent conductive fibers and electroluminescent fibers and/or electroluminescent yarns, wherein the electroluminescent fibers are selected from any one or more than two electroluminescent fibers, and/or the electroluminescent fibers are selected from electroluminescent fibers prepared by any one or more than two methods, respectively, and the electroluminescent yarns are selected from the electroluminescent yarns.

Specifically, the electroluminescent fabric of this embodiment may be woven from the electroluminescent fibers, or woven from the electroluminescent yarns, or woven from the electroluminescent fibers and the electroluminescent yarns, or woven from the transparent conductive fibers and the electroluminescent fibers, or woven from the transparent conductive fibers and the electroluminescent yarns, or woven from the transparent conductive fibers and the electroluminescent yarns, or the like, and the structure of the electroluminescent fabric prepared from the above combination may be as shown in fig. 11.

It is known in the art that the electroluminescent fiber/yarn can be controlled to emit light by controlling the electric field between the conductive layers in the electroluminescent fiber.

The invention provides an electroluminescent fiber which is provided with more than two conductive layers and a luminescent layer arranged between the conductive layers, wherein the luminescent layer has the advantages of simple structure, reliable performance, good luminescent effect, firm combination of the luminescent layer and the conductive layers, and the optimal scheme can realize different colors or combinations of colors respectively or simultaneously. In addition, the invention also provides a method for preparing the electroluminescent fiber, which has the advantages of low production cost, simple operation, easy batch preparation, controllable wire diameter, controllable structure, environmental friendliness and the like, and the electroluminescent fiber is used for preparing the electroluminescent yarn and the electroluminescent fabric, so that the electroluminescent fabric is not easy to damage in the bending and folding state, and has the characteristics of excellent wearability and luminous effect.

Examples

The experimental methods used below are conventional methods if no special requirements are imposed.

Materials, reagents and the like used in the following are commercially available unless otherwise specified.

The fluororesin used in the following examples was PVDF (model 2850-00).

Example 1 (electroluminescent fiber of electronic transparent conductive layer, electroluminescent material concentration in the light-emitting layer was 50 wt.%)

1. Preparation of electroluminescent composite materials

(1) 35G of polymethyl methacrylate (PMMA) and 15g of fluororesin are weighed, 200mL of polydimethyl acetamide (DMAC) is weighed by a beaker, the polymethyl methacrylate and the fluororesin are added into the beaker, mixed with the polydimethyl acetamide (DMAC), placed on a magnetic stirrer, heated in a water bath at 80 ℃ and stirred until particles are dissolved, and a uniform mixed solution is obtained;

(2) Adding 50g of electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent wave band 502 nm) into the mixed solution, stirring by a magnetic stirrer, and then placing into an ultrasonic device for ultrasonic dispersion for 15min to obtain a mixed solution of polymethyl methacrylate (PMMA), fluororesin, polydimethylacetamide (DMAC) and electroluminescent material (ZnS: cu);

(3) The mixed solution is coated into a film by a scraper, dried for 72 hours, crushed into powder, dried for 24 hours in a 50 ℃ ventilation oven, dried for 24 hours in a 50 ℃ vacuum drying oven, and removed solvent polydimethyl acetamide (DMAC) to obtain the electroluminescent composite material with the concentration of 50 wt.%.

2. Preparation of electronic transparent conductive material

(1) 49G of polymethyl methacrylate (PMMA) and 1g of nano silver wire were weighed out, and 200mL of polydimethyl acetamide (DMAC) was measured out in a beaker;

(2) Mixing polymethyl methacrylate (PMMA) and polydimethyl acetamide (DMAC), placing on a magnetic stirrer, heating in a water bath at 80 ℃ and stirring until particles are dissolved to obtain a uniform mixed solution;

(3) Adding 1g of nano silver wire into the mixed solution in the step (2), and fully dissolving;

(4) And (3) coating the mixed solution in the step (3) into a film by using a scraper, drying for 72 hours, crushing into powder, drying for 24 hours in a 50 ℃ ventilation oven, and drying for 24 hours in a 50 ℃ vacuum drying oven to remove solvent polydimethyl acetamide (DMAC) to obtain the electronic transparent conductive material.

3. Preparation of a preform

3.1 In this example, a preform was prepared by a hot pressing method, comprising the steps of:

(1) The electroluminescent composite material is placed in a mould with the length of 100mm multiplied by 22mm (length multiplied by width multiplied by height), the mould is a stainless steel groove, and the periphery of the groove is coated by a Teflon film to prevent the adhesion of a polymer material with the mould after heat softening.

(2) Stainless steel plates are covered on the upper side and the lower side of a die filled with the mixture materials, and the die is placed into a hot press to ensure uniform stress in the pressurizing process. The upper temperature of the hot press is set to be 120 ℃, the mixture in the die is preheated for 3min under the pressure of 1MPa, the pressure is increased by 5MPa, and the step is repeated until the preform is molded and marked as a No.1 preform, so that the width of the No.1 preform is 22mm.

(3) Taking out the prefabricated rod after the hot pressing, and then putting the prefabricated rod into a drying oven for standby.

(4) According to the above steps (1-3), an electronic transparent conductive material was prepared as an outer transparent conductive layer preform, denoted as No. 2 preform, differing only in the mold dimensions of 100mm×32mm (length×width×height), and thus the width of No. 2 preform was 32mm.

(5) The pure polymer material polymethyl methacrylate PMMA was prepared as an outer transparent protective layer preform, designated as preform No. 3, according to the above steps (1-3), except that the mold size was 100mm by 37mm (length by width by height), so that the width of preform No. 3 was 37mm.

3.2 Alternatively, the preform may be prepared by extrusion, which is only exemplary herein, comprising the steps of:

And (3) placing the electroluminescent composite material into a charging barrel, selecting a hollow structure die, wherein the outer diameter of the die is 25mm, the inner diameter of the hollow die is 22mm, the length of the hollow die is 100mm, setting the heating temperature to be 180 ℃, placing the charging barrel into an extruder, opening a rod feeding device, and performing melt extrusion to obtain the prefabricated rod in the shape of the die.

Those skilled in the art will appreciate that the corresponding preform No. 1, preform No. 2, or preform No. 3 may be produced by modifying the outer diameter, inner diameter, etc. of the mold.

4. Preparation of preform with pore Structure

(1) The prefabricated rod No. 1 prepared in 3.1 is placed in a lathe fixture, the prefabricated rod is processed through adjusting the rotating speed and the feeding distance, the rotating speed of the lathe is 150-300r/min, and the prefabricated rod is processed into a round shape with the cross section of 20mm and the length of 100mm through the lathe.

(2) And (3) axially punching the prefabricated rod machined by the lathe in the step (1) by using a drill floor, wherein the drill is directly 1mm, and the hollow prefabricated rod with the outer diameter of 20mm and the inner diameter of 1.5mm is obtained after machining by using the drill floor and is marked as a No. 1 prefabricated rod.

(3) According to the above steps (1-2), the preform No. 2 prepared in 3.1 was prepared as a hollow preform having an outer diameter of 30mm and an inner diameter of 20mm, and was designated as a preform No. 2'.

(4) According to the above-mentioned step (1-2), the preform No. 3 prepared in 3.1 was prepared as a hollow preform having an outer diameter of 35mm and an inner diameter of 30mm, and was designated as a 3' preform.

(5) And (3) combining the hollow structure prefabricated bars in the steps (2), 3 and 4) by adopting a sleeve method to obtain the prefabricated bar which is finally provided with a hole structure and is used for heat softening wire drawing, wherein the outer diameter is 35mm, the inner diameter is 1.5mm, namely the prefabricated bar with the hole structure is marked as a No. 4 prefabricated bar, and the lower end 5mm of the No. 4 prefabricated bar is radially perforated.

5. The No. 4 preform in step 4 is subjected to heat softening wire drawing, as shown in FIG. 12, comprising the steps of:

(1) And winding a copper wire with a wire diameter of 50 mu m on the annular receiving coil, enabling the free end of the copper wire to pass through a No. 4 prefabricated rod through hole with a hole structure, which is fixed on wire drawing equipment, enabling the lower end of the No. 4 prefabricated rod to radially penetrate into the metal wire, and simultaneously fixing a 20g weight at the lower ends of the metal wire and the copper wire.

(2) The heating furnace is turned on, the temperature of the upper temperature zone is set to 125 ℃, the temperature of the lower temperature zone is set to 235 ℃, and when the temperature of the heating zone reaches the preset temperature, the rod is fixed in length.

(3) After the preformed rod with the hole structure is heated and softened, the stub bar falls down and sequentially passes through the calliper 8, the auxiliary traction 10 is carried out, the rod feeding speed is set to be 0.1mm/min, and the stable wire collecting speed is set to be 0.25m/min.

Thus, an electroluminescent fiber (the electroluminescent material concentration in the light-emitting layer is 50 wt%) having an inner conductive layer diameter of 50 μm, a light-emitting layer thickness of 175 μm, an outer transparent conductive layer thickness of 100 μm, an outer transparent protective layer thickness of 50 μm and an overall filament diameter of 700 μm was obtained (the structure is shown in FIG. 1).

Example 2 (electroluminescent fiber of electronic transparent conductive layer, electroluminescent material concentration in the light-emitting layer was 70 wt.%)

In the electroluminescent fiber prepared in this example, the concentration of the electroluminescent material in the intermediate luminescent layer was 70wt.%, and the other steps were the same as in example 1, namely, the electroluminescent fiber was prepared in which the diameter of the inner conductive layer was 50. Mu.m, the thickness of the luminescent layer was 175. Mu.m, the thickness of the outer transparent conductive layer was 100. Mu.m, the thickness of the outer transparent protective layer was 50. Mu.m, and the overall filament diameter was 700. Mu.m (the concentration of the electroluminescent material in the luminescent layer was 70 wt.%).

Example 3 (electroluminescent fiber of electronic transparent conductive layer, electroluminescent material concentration in the inner layer of the luminescent layer was 70wt% and electroluminescent material concentration in the outer layer was 50 wt%)

In the electroluminescent fiber prepared in this embodiment, the concentration distribution of the electroluminescent material in the intermediate luminescent layer decreases from inside to outside along the radial direction of the fiber. The method specifically comprises the following steps:

1. Two electroluminescent composites were prepared as in step 1 of example 1

The first electroluminescent composite was prepared using 20g of polymethyl methacrylate (PMMA), 10g of fluororesin, 70g of electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 502 nm) at a concentration of 70 wt.%. .

The second electroluminescent composite was prepared at a concentration of 50wt.% using 35g polymethyl methacrylate (PMMA), 15g fluororesin, 50g electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 502 nm)

2. An electronic transparent conductive material was prepared according to step 2 in example 1.

3. Preparing a preform, comprising the steps of:

(1) According to the procedure of steps 3.1 (1) - (3) in example 1, a first electroluminescent composite material (concentration 70 wt.%) was prepared as an electroluminescent preform, denoted as preform No.1, differing only in the dimensions of the mold 100mm x 12mm (length x width x height), so that the width of preform No.1 was 12mm;

(2) The second electroluminescent composite (concentration 50 wt.%) was prepared as an electroluminescent preform, denoted as preform No. 2, following the procedure of steps 3.1 (1) - (3) in example 1, with the difference that the mould dimensions were 100mm x 22mm (length x width x height), so that the width of preform No. 2 was 22mm.

(3) The procedure of step 3.1 (4) in example 1 was followed to prepare an electronic transparent conductive material as an outer transparent conductive layer preform, denoted as No. 3 preform, differing only in the dimensions of the mold 100mm×32mm (length×width×height), and thus the width of No. 3 preform was 32mm.

(4) According to the procedure of step 3.1 (5) in example 1, a pure polymer material polymethyl methacrylate PMMA was prepared as an outer transparent protective layer preform, designated as a No. 4 preform, differing only in the mold dimensions of 100mm by 37mm (length by width by height), and thus the width of the No. 4 preform was 37mm.

4. A preform having a pore structure (sleeve method) is prepared, comprising the steps of:

(1) Step4 of example 1, processing the No.1 preform by a lathe drill floor to obtain a hollow structure preform with an outer diameter of 10mm and an inner diameter of 1.5mm, and marking the hollow structure preform as a No. 1' preform;

(2) Step 4 of example 1, processing the No. 2 preform by a lathe drill floor to obtain a hollow structure preform with an outer diameter of 20mm and an inner diameter of 10mm, and marking the hollow structure preform as a No. 2' preform;

(3) As in step 4 of example 1, a No. 3 preform was prepared as a hollow preform having an outer diameter of 30mm and an inner diameter of 20mm, and was designated as a No. 3' preform.

(4) As in step 4 of example 1, a No. 4 preform was prepared as a hollow preform having an outer diameter of 35mm and an inner diameter of 30mm, and was designated as a No. 4' preform.

(5) And (3) combining the hollow structure prefabricated bars in the steps (1), 2,3 and 4) by adopting a sleeve method to obtain the prefabricated bar which is finally provided with a hole structure and is used for heat softening wire drawing, wherein the outer diameter is 35mm, the inner diameter is 1.5mm, namely the prefabricated bar with the hole structure is marked as a No. 5 prefabricated bar, and the lower end of the No. 5 prefabricated bar is radially perforated at the position of 5 mm.

5. Performing heat softening wire drawing on the preformed rod with the hole structure,

The procedure is the same as in step 5 of example 1, the rod feeding speed is set to be 0.1mm/min, and the stable wire collecting speed is set to be 0.25m/min.

Thus, an electroluminescent fiber having an inner conductive layer diameter of 50 μm, a light-emitting layer thickness of 175 μm, an outer transparent conductive layer thickness of 100 μm, an outer transparent protective layer thickness of 50 μm and an overall filament diameter of 700 μm was obtained (70 wt% electroluminescent material concentration in the inner layer of the light-emitting layer, 50 wt% electroluminescent material concentration in the outer layer).

Example 4 (electroluminescent fiber of electronic transparent conductive layer, electroluminescent material concentration in the inner layer of the light-emitting layer was 50wt% and electroluminescent material concentration in the outer layer was 70 wt%)

In the electroluminescent fiber prepared in this embodiment, the concentration distribution of the electroluminescent material in the intermediate luminescent layer increases gradually from inside to outside along the radial direction of the fiber. The specific procedure was as in example 3, namely, an electroluminescent fiber having an inner conductive layer diameter of 50 μm, a light-emitting layer thickness of 175 μm, an outer transparent conductive layer thickness of 100 μm, an outer transparent protective layer thickness of 50 μm and an overall filament diameter of 700 μm was prepared (the concentration of electroluminescent material in the inner layer of the light-emitting layer was 50 wt.%, and the concentration of electroluminescent material in the outer layer was 70 wt.%).

Example 5 (Ionic transparent conductive layer electroluminescent fiber, electroluminescent Material concentration in the light-emitting layer was 70 wt%)

1. Preparing an electroluminescent composite material:

an electroluminescent composite was prepared according to step 1 of example 1, using 20g of polymethyl methacrylate (PMMA), 10g of fluororesin, 70g of electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 502 nm) at a concentration of 70 wt.%.

2. Preparation of an Ionic transparent conductive Material

(1) 50G of Polycarbonate (PC), 200g of acetonitrile, 18.75g of lithium perchlorate (LiClO ₄), 37.5g of polymethyl methacrylate (PMMA) are weighed out;

(2) Mixing polycarbonate and acetonitrile, placing on a magnetic stirrer, heating and stirring in a water bath at 80 ℃ until particles are dissolved, and obtaining a uniform mixed solution;

(3) Adding 18.75g of lithium perchlorate (LiClO ₄) into the mixed solution in the step (2), and fully dissolving;

(4) 37.5g of polymethyl methacrylate (PMMA) was slowly added to the solution in step (3) and placed on a magnetic stirrer at 1000rpm for 24 hours to dissolve thoroughly.

(5) And (3) coating the mixed solution in the step (4) into a film by using a scraper, drying for 72 hours, crushing into powder, drying for 24 hours in a 50 ℃ ventilation oven, and drying for 24 hours in a 50 ℃ vacuum drying oven to remove acetonitrile serving as a solvent, thereby obtaining the ionic transparent conductive material.

3. Preparation of a preform

(1) An electroluminescent composite (concentration of 70 wt.%) was prepared as an electroluminescent preform, denoted as preform 1, according to the procedure of steps 3.1 (1) - (3) in example 1, with the difference that the mould dimensions were 100mm x 22mm (length x width x height), so that the width of preform 1 was 22mm.

(2) The procedure of step 3.1 (4) in example 1 was followed to prepare an outer transparent conductive layer preform, designated as No. 2 preform, differing only in the dimensions of the mold 100mm×32mm (length×width×height), and thus the width of No. 3 preform was 32mm.

(3) According to the procedure of step 3.1 (5) in example 1, a pure polymer material polymethyl methacrylate PMMA was prepared as an outer transparent protective layer preform, designated as preform No. 3, differing only in the mold dimensions of 100mm by 37mm (length by width by height), and thus the width of preform No. 3 was 37mm.

4. Preparation of preform with pore Structure (sleeve method)

(1) Step4 of example 1, processing the No.1 preform by a lathe drill floor to obtain a hollow structure preform with an outer diameter of 20mm and an inner diameter of 1.5mm, and marking the hollow structure preform as a No. 1' preform;

(2) As in step 4 of example 1, a No. 2 preform was prepared as a hollow preform having an outer diameter of 30mm and an inner diameter of 20mm, and was designated as a No. 2 preform.

(3) As in step 4 of example 1, a No. 3 preform was prepared as a hollow preform having an outer diameter of 35mm and an inner diameter of 30mm, and was designated as a No. 3' preform.

(4) And (3) combining the hollow structure prefabricated bars in the steps (1), 2 and 3) by adopting a sleeve method to obtain the prefabricated bar which is finally provided with a hole structure and is used for heat softening wire drawing, wherein the outer diameter is 35mm, the inner diameter is 1.5mm, namely the prefabricated bar with the hole structure is marked as a No. 4 prefabricated bar, and the lower end 5mm of the No. 4 prefabricated bar is radially perforated.

5. Heat softening and drawing the preformed rod with hole structure

(1) And winding a copper wire with a wire diameter of 50 mu m on the annular receiving coil, enabling the free end of the copper wire to pass through a through hole of a preformed rod fixed on the wire drawing equipment, enabling the lower end of the preformed rod to radially penetrate into the metal wire, and simultaneously fixing a 20g weight at the lower ends of the metal wire and the copper wire.

(3) After the prefabricated rod is heated and softened, the stub bar falls down and sequentially passes through the diameter measuring instrument 8, the auxiliary traction 10 is carried out, the rod feeding speed is set to be 0.1mm/min, and the filament collecting speed is stabilized to be 0.25m/min.

In the electroluminescent fiber prepared in this example, the concentration of the electroluminescent material in the intermediate luminescent layer was 70wt.%, and the other steps were the same as in example 1, namely, an electroluminescent fiber (the concentration of the electroluminescent material in the luminescent layer was 70 wt.%) having a diameter of 50 μm for the inner conductive layer, a thickness of 175 μm for the luminescent layer, a thickness of 100 μm for the outer transparent conductive layer, a thickness of 50 μm for the outer transparent protective layer, and a total wire diameter of 700 μm was prepared

Example 6 (electroluminescent fiber with an Ionic transparent conductive layer, electroluminescent material concentration in the luminescent layer was 70wt%, conductive filaments were treated and coated with a dielectric insulating layer of barium titanate (BaTiO ₃) with a high dielectric constant)

In the electroluminescent fiber prepared in this example, the concentration distribution of the electroluminescent material in the luminescent layer was 70wt.%, and the specific procedure was the same as in example 5, except that the conductive metal wire was coated with a layer of high dielectric constant dielectric insulation layer barium titanate (BaTiO 3), i.e., the electroluminescent fiber was prepared with an inner conductive layer diameter of 50 μm, a luminescent layer thickness of 175 μm, an outer transparent conductive layer thickness of 100 μm, an outer transparent protective layer thickness of 50 μm, and an overall wire diameter of 700 μm.

Example 7 (parallel distribution of double electrodes)

1. Electroluminescent composites were prepared according to step 1 of example 1

An electroluminescent composite material was prepared at a concentration of 50wt.% using 35g polymethyl methacrylate (PMMA), 15g fluororesin, 50g electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 502 nm).

2. Preparation of a preform

(1) An electroluminescent composite material having a concentration of 50wt.% was prepared as a preform in the same manner as in steps 3.1 (1) - (3) of example 1, except that the dimensions of the mold were 100mm×26mm (length×width×height), and thus the electroluminescent preform had a width of 26mm and a length of 100mm, denoted as No. 1 preform;

(2) According to the procedure of step 3.1 (5) in example 1, a pure polymer material polymethyl methacrylate PMMA was prepared as an outer transparent protective layer preform, designated as preform No. 2, differing only in the mold dimensions of 100mm by 32mm (length by width by height), so that the width of preform No. 2 was 27mm

3. Preparation of hollow structural preform

(1) Step 4 of example 1, processing the No. 1 preform by a lathe drill floor to obtain a porous preform with an outer diameter of 24mm, wherein the inside of the preform is provided with two holes with the aperture of 1.5mm (the two holes are symmetrically distributed on two sides of the circle center), and marking the porous preform as a No. 1 preform;

(2) As in step 4 of example 1, a No. 2 preform was prepared as a hollow preform having an outer diameter of 30mm and an inner diameter of 24mm, and was designated as a No. 2 preform.

(4) And (3) combining the hollow structure prefabricated bars in the step (1) and the step (2) by adopting a sleeve method to obtain a prefabricated bar which is used for heat softening wire drawing and finally has a double-hole structure, wherein the outer diameter is 30mm, the aperture is 1.5mm, and the lower end of the obtained hollow prefabricated bar is radially perforated at a position of 5mm to obtain a prefabricated bar with the double-hole structure, which is marked as a No. 3 prefabricated bar.

4. Heat softening and wiredrawing the hollow electroluminescent prefabricated rod

(1) Winding a copper wire with a wire diameter of 50 mu m on two annular receiving coils, enabling the free end of the copper wire to pass through a preform through hole fixed on wire drawing equipment, enabling the lower end of the preform to radially penetrate into a metal wire, and simultaneously fixing 20g weights (two coils) at the lower ends of the metal wire and the copper wire;

(2) Opening the heating furnace, wherein the temperature of an upper temperature zone is set to be 125 ℃, the temperature of a lower temperature zone is set to be 235 ℃, and when the temperature of the heating zone reaches a preset temperature, fixing the length of a lower rod;

(3) After the prefabricated rod is heated and softened, the stub bar falls down and sequentially passes through the diameter measuring instrument 8, the auxiliary traction 10 is carried out, the rod feeding speed is set to be 0.1mm/min, and the filament collecting speed is stabilized to be 0.36m/min.

Thus, an electroluminescent fiber having a thickness of the outer transparent protective layer of 50 μm, a thickness of the light-emitting layer of 175 μm and a diameter of 500 μm was obtained, in which two inner conductive layers (copper wires) having a diameter of 50 μm were formed (the structure is shown in FIG. 2).

Example 8 (parallel distribution of double electrodes, addition of protective layer to functional Material)

The specific steps of this example are the same as those of example 7, except that in the prepared electroluminescent fiber, the concentration of the electroluminescent material in the light-emitting layer is 50wt.%, and in the outer transparent protective layer, a small amount of the scattering agent TiO ₂ (concentration is 2 wt.%) is added, namely, an electroluminescent fiber having an inner conductive layer diameter of 50 μm (two copper wires), a light-emitting layer thickness of 175 μm, an outer transparent protective layer thickness of 50 μm, and an overall filament diameter of 700 μm is prepared.

Example 9 (parallel distribution of double electrodes, carbon fiber electrodes)

The specific procedure of this example was the same as in example 7, except that, in the prepared electroluminescent fiber, two carbon fibers of the inner conductive layer having a diameter of 50 μm, the thickness of the luminescent layer was 175. Mu.m, the thickness of the outer transparent protective layer was 50. Mu.m, and the overall filament diameter was 700. Mu.m.

Example 10 (parallel distribution of double electrodes, silver-plated yarn)

The specific procedure of this example was the same as in example 7, except that two 50 μm diameter inner conductive layer silver-plated yarns were used in the electroluminescent fiber prepared, the thickness of the luminescent layer was 175 μm, the thickness of the outer transparent protective layer was 50 μm, and the overall filament diameter was 700. Mu.m.

Example 11 (three electrode distribution)

1. Two electroluminescent composites were prepared as in step 1 of example 1

The first is to prepare an electroluminescent composite material with a concentration of 50wt.% using 35g of polymethyl methacrylate (PMMA), 15g of fluororesin, 50g of electroluminescent material (luminescent material model D417B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 417 nm);

The second was to prepare an electroluminescent composite material having a concentration of 50wt.% using 35g of polymethyl methacrylate (PMMA), 15g of fluororesin, and 50g of electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 502 nm).

2. Preparation of a preform

(1) The two electroluminescent composites having a concentration of 50wt.% were used to prepare preforms, each having a semi-cylindrical shape (24 mm diameter and 100mm length) and labeled as preform 1 and preform 2, respectively, in the same manner as described in example 1, steps 3.1 (1) - (3)

(2) The preform was prepared using a transparent material (PMMA) in the same manner as in step 3.1 (5) of example 1, with a mold size of 100 mm. Times.32 mm (length. Times.width. Times.height), and the preform had a width of 32mm, designated as # 3 preform;

3. preparation of a preform with a porous Structure

And (4) processing the No. 3 preform by a lathe drill floor in the same way as in the step (4) of the example 1 to obtain the preform with the outer diameter of 30mm and the inner diameter of 24 mm. And combining the No. 1 prefabricated rod and the No.2 prefabricated rod with the processed No. 3 prefabricated rod to prepare a solid prefabricated rod with the outer diameter of 30mm (the No. 3 prefabricated rod is positioned on the cladding layer, and the No. 1 prefabricated rod and the No.2 prefabricated rod are juxtaposed as a core layer). And the drilling platform is used for processing to obtain a prefabricated rod with three parallel holes (one hole is positioned between the No. 1 prefabricated rod and the No.2 prefabricated rod, and the other two holes are respectively divided into the No. 1 prefabricated rod and the No.2 prefabricated rod), and the hole diameters are all 1.5mm.

4. Carrying out heat softening wire drawing on the preformed rod with the hole structure

The procedure of step 5 of example 1 was repeated except that the number of wire feeding coils (copper wires) was 3, the feeding speed was set to 0.1mm/min, and the stable wire collecting speed was set to 0.36m/min.

Thus, an electroluminescent fiber having a diameter of 500 μm was obtained, the diameter of the inner conductive layer was 50. Mu.m, the diameter of the light-emitting layer was 400. Mu.m, the thickness of the outer transparent protective layer was 50. Mu.m, and the overall filament diameter was 500. Mu.m (as shown in FIG. 4). Can realize double-color luminescence and realize multi-color luminescence by mixing and combining double colors.

Example 12 (four electrode square distribution)

1. Preparation of electroluminescent composite materials

An electroluminescent composite was prepared according to step 1 of example 1, three electroluminescent composites were prepared.

Of these, the first was an electroluminescent composite material prepared using 35g of polymethyl methacrylate (PMMA), 15g of fluororesin, 50g of electroluminescent material (luminescent material model D417B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 417 nm) at a concentration of 50 wt.%;

The second is to use 35g polymethyl methacrylate (PMMA), 15g fluororesin, 50g electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 502 nm) concentration of 50wt.% electroluminescent composite;

the third was to prepare an electroluminescent composite material having a concentration of 50wt.% using 35g of polymethyl methacrylate (PMMA), 15g of fluororesin, and 50g of electroluminescent material (luminescent material model D611B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 611 nm).

2. Preparation of a preform

(1) A preform was prepared using PMMA in the manner of step 3.1 (5) of example 1, with mold dimensions of 100mm by 32mm (length by width by height), labeled number 1;

(2) The above electroluminescent composite material at a concentration of 50wt.% was used to prepare preforms (respectively labeled No. 2, no. 3, no. 4, two of which No. 4 was prepared) respectively, using the method of example 1, steps 3.1 (1) - (3), and the mold was quarter-cylindrical (size 24mm in diameter and 100mm in length).

3. Preparation of preform with pore Structure

And (4) processing the No. 1 preform by a lathe drill floor in the same way as in the step (4) of the example 1 to obtain a preform with the outer diameter of 30mm and the inner diameter of 24 mm. And combining the No.2 prefabricated rod, the No. 3 prefabricated rod, the two No. 4 prefabricated rods and the processed No. 1 prefabricated rod (the No. 1 prefabricated rod is positioned on the cladding layer, the No.2 prefabricated rod, the No. 3 prefabricated rod and the two No. 4 prefabricated rods are positioned on the core layer, wherein the two No. 4 prefabricated rods are oppositely arranged), preparing a solid prefabricated rod with the outer diameter of 30mm, and processing the solid prefabricated rod through a drill floor to obtain prefabricated rods with four square holes (respectively contacted with interfaces of the No.2, 3 and 4 prefabricated rods), wherein the pore diameters are all 1.5mm.

4. Carrying out heat softening wire drawing on the preform rod with the hole structure,

The difference from step 5 of example 1 is that there are four wire feeding coils, the speed of feeding the rod is set to 0.1mm/min, and the stable wire receiving speed is 0.36m/min.

Thus, an electroluminescent fiber (as shown in FIG. 8) having a conductive layer diameter of 50 μm, a light-emitting layer diameter of 400 μm (thickness: 175 μm), a transparent protective layer thickness of 50 μm and an overall filament diameter of 500 μm was obtained. Can realize three-color luminescence and realize the combination of three colors into multicolor luminescence.

Example 13 (four electrode triangular distribution)

1. Preparation of electroluminescent composite materials

2. Preparation of a preform

(1) A preform was prepared using PMMA in the manner of step 3.1 (5) of example 1, with mold dimensions of 100 mm. Times.32 mm (length. Times.width. Times.height), labeled number 1;

(2) The above electroluminescent composite material at a concentration of 50wt.% was used to prepare preforms (respectively designated as No. 2 preform, no. 3 preform, no. 4 preform) respectively, the mold being one third cylindrical (24 mm in diameter and 100mm in length) in the same manner as in steps 3.1 (1) - (3) of example 1.

3. Preparation of preform with pore Structure

And (4) processing the No. 1 preform by a lathe drill floor in the same way as in the step (4) of the example 1 to obtain a preform with the outer diameter of 30mm and the inner diameter of 24 mm. The method comprises the steps of processing the fan-shaped symmetrically distributed prefabricated bars of the No. 2 prefabricated bar, the No. 3 prefabricated bar and the No. 4 prefabricated bar through a lathe drill floor, combining the fan-shaped symmetrically distributed prefabricated bars with the processed No. 1 prefabricated bar (the No. 1 prefabricated bar is located on a cladding layer, the No. 2 prefabricated bar, the No. 3 prefabricated bar and the No. 4 prefabricated bar are located on a core layer), preparing a solid prefabricated bar with the outer diameter of 30mm, and obtaining four prefabricated bars with parallel hole structures through drill floor processing (one hole is located at the two-to-two joint of the No. 2 prefabricated bar, the No. 3 prefabricated bar and the No. 4 prefabricated bar, and the other three holes are respectively divided into the No. 2 prefabricated bar, the No. 3 prefabricated bar and the No. 4 prefabricated bar), wherein the hole diameter is 1.5mm.

Thus, an electroluminescent fiber (as shown in FIG. 10) having a conductive layer diameter of 50 μm, a light-emitting layer diameter of 400 μm (thickness: 175 μm), a transparent protective layer thickness of 50 μm and an overall filament diameter of 500 μm was obtained. Can realize three-color luminescence and realize the combination of three colors into multicolor luminescence.

Example 14 (electroluminescent yarn)

Preparing multi-color electroluminescent yarn, twisting three electroluminescent fibers of different colors.

Three types of electrically conductive fibers were prepared according to the procedure of example 1, except,

The first (denoted as A) was an electroluminescent composite material prepared using 35g of polymethyl methacrylate (PMMA), 15g of a fluororesin, 50g of an electroluminescent material (luminescent material model D417B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 417 nm) at a concentration of 50 wt%,

The second (denoted as B) was an electroluminescent composite material prepared using 35g of polymethyl methacrylate (PMMA), 15g of fluororesin, 50g of electroluminescent material (luminescent material model D502B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 502 nm) at a concentration of 50 wt.%;

The third (denoted as C) was an electroluminescent composite material using 35g of polymethyl methacrylate (PMMA), 15g of fluororesin, 50g of electroluminescent material (luminescent material model D611B, luminescent component ZnS: cu, diameter 29 μm, luminescent band 611 nm) at a concentration of 50 wt.%.

Three electroluminescent fibers A, B and C with the wire diameter of 500 μm are prepared, wherein the diameter of an (inner) conductive layer (copper wire) is 50 μm, the diameter of a luminescent layer is 500 μm, the thickness of the luminescent layer is 225 μm, the thickness of an outer transparent conductive layer is 50 μm, and the overall wire diameter is 600 μm.

Twisting the electroluminescent fiber A, the electroluminescent fiber B and the electroluminescent fiber C to obtain the multicolor electroluminescent yarn.

Analysis of experimental results:

The prepared electroluminescent fiber examples 1-13 are subjected to optical performance test and mechanical performance test, specifically, the optical performance is tested by connecting an inner conductive layer and an outer conductive layer of the electroluminescent fiber to a positive electrode and a negative electrode of a high-voltage power supply, introducing 400v and 2khz high-voltage alternating current power supply, recording the luminescence brightness of the luminescent fiber in real time by adopting a brightness meter during the test, and the mechanical performance is tested by adopting an LC-202B universal material tester, selecting the length of the prepared electroluminescent fiber to be 10cm, fixing the two ends of the fiber on an upper chuck and a lower chuck of an instrument, fixing the lower chuck unchanged, adjusting the upward moving speed of the upper chuck to be 10mm/min, and recording the load condition of the fiber during the fiber breakage during the stretching process. The specific experimental results are shown in table 1.

TABLE 1 analysis of electroluminescent fiber properties of different examples

As can be seen from comparative examples 1 and 2, as the concentration of the electroluminescent material in the light-emitting layer increases, the light-emitting brightness of the light-emitting fiber is significantly improved, but the breaking strength thereof is reduced.

Comparative examples 1,2,3,4 show that the luminescent layer remains unchanged or gradually decreases or increases from inside to outside along the radial direction of the electroluminescent fiber. When the concentration distribution in the luminous layer is kept unchanged from inside to outside along the radial direction of the fiber, the excellent luminous performance of the electroluminescent fiber can be realized. When the concentration distribution in the luminous layer gradually increases along the radial direction of the fiber, the luminous performance of the electroluminescent fiber can be realized, and the mechanical performance of the electroluminescent fiber is simultaneously considered, compared with the concentration which is kept unchanged from inside to outside along the radial direction of the fiber (compared with the concentration of the outermost layer), the luminous performance is slightly weakened, but the mechanical performance is obviously improved. When the concentration distribution in the luminous layer gradually decreases along the radial direction of the fiber, the luminous performance of the electroluminescent fiber can be realized, and meanwhile, the mechanical performance is simultaneously considered, and compared with the concentration which is kept unchanged from inside to outside along the radial direction of the fiber (compared with the concentration of the outermost layer), the luminous performance is obviously improved, but the mechanical performance is weakened.

Comparative examples 2 and 5 show that the light-emitting effect and the mechanical properties are not greatly affected by the use of an electron-or ion-conductive layer.

Comparative examples 5,6 it was found that the electroluminescent fiber with the conductive layer of barium titanate coating added had significantly increased luminescent brightness and had little effect on mechanical properties.

Comparative examples 1,7 can find that the luminance of the dual electrode luminescence is significantly higher than that of the electroluminescent fiber of the on-axis structure, but that the luminance of the dual electrode luminescence is not uniform along the fiber circumference in the on-axis structure at the time of the test.

Comparative examples 7 and 8 show that the addition of functional materials to the cladding layer significantly improves the problem of circumferential luminous uniformity of the electroluminescent fiber, and also causes limitations such as reduced brightness and reduced mechanical properties.

Comparative examples 7,9,10 can be found that the conductive layer is mainly replaced by a different conductive material to affect the light emitting property and mechanical property thereof. It can be found that the luminous effect and the mechanical property are not greatly affected.

Examples 11 to 14 mainly introduce multicolor effects, and thus, no tests for luminescence properties and mechanical properties were carried out.

Examples 11-14 were subjected to luminescence performance testing, i.e., spectral broadening testing:

specifically, the center of three conductive layers (embodiment 11) of the electroluminescent fiber is a common end (one interface is omitted), and the three interfaces are connected to the positive and negative poles of two adjustable high-voltage power supplies to respectively regulate and control the output voltage and frequency of the high-voltage amplification power supplies. And (5) the electrified electroluminescent fiber is connected to a visible-ultraviolet optical fiber spectrometer to test the spectrum condition.

For example 12, two adjustable high voltage power sources were used.

For examples 13,14, three adjustable high voltage power supplies were used, with example 13 having a common center electrode (two interfaces omitted). Six interfaces are connected to the positive and negative poles of three adjustable high-voltage power supplies, respectively regulate and control the output voltage and frequency of the high-voltage amplifying power supplies, and the electrified electroluminescent fiber is connected to a visible-ultraviolet optical fiber spectrometer for testing the spectrum condition.

The results of example 12 are exemplified herein (e.g., fig. 13), and the results of other cases 11,13, and 14 can be used to achieve spectrum broadening, and the results are similar and will not be described in detail.

As can be seen from fig. 13, with the voltage change in the conductive layer in tuning example 12, it was found that the emission spectrum of the electroluminescent fiber was broadened, and a multicolor change was achieved.

In addition, through detection, the electroluminescent fibers prepared in the embodiments 1-14 can still keep stable display brightness after working at the extreme environment of-30 to +90 ℃ and the PH within the range of 0-14 and the like for 24 times, and can still keep stable luminescent brightness under the wear-resistant cycle of Martindale 5000 times. The electroluminescent fibers of examples 1 to 14 are not easily damaged (the bending radius is smaller than 1 mm) in the bending and folding state, and have the characteristics of excellent flame retardance (the burning rate is lower than 39mm/min and is far smaller than 100mm/min specified by automotive trim products), electromagnetic interference resistance, ultraviolet aging resistance, excellent wearability and the like.

Although the embodiments of the present application have been described above, the present application is not limited to the above-described specific embodiments and application fields, and the above-described specific embodiments are merely illustrative, and not restrictive. Those skilled in the art, having the benefit of this disclosure, may effect numerous forms of the application as described herein without departing from the scope of the application as claimed.

Claims

1. An electroluminescent fiber comprising:

More than two conductive layers, wherein the conductive layers are conductive wires, the conductive wires are metal wires, the outer surfaces of the conductive wires are distributed with rugged defects, and

A light-emitting layer containing a first polymer material and an electroluminescent material, the light-emitting layer including two or more kinds of light-emitting layer units arranged in an axial direction of an electroluminescent fiber, at least one of the light-emitting layer units having a different light-emitting wavelength band from the electroluminescent material between the other light-emitting layer units,

More than two conductive layers are arranged in the luminescent layer along the axial direction of the electroluminescent fiber, and the conductive layers are at least contacted with one luminescent layer unit so as to be capable of emitting light with different wave bands;

The outer surface of the conductive wire is coated with a dielectric insulating layer with a high dielectric constant, wherein the high dielectric constant is that the dielectric constant is larger than 10;

the outermost layer of the electroluminescent fiber is coated with a transparent protective layer, and the transparent protective layer is made of a polymer material;

functional materials are added into the transparent protective layer and are uniformly distributed in the transparent protective layer, wherein the functional materials comprise scattering agents;

the electroluminescent fiber is prepared by the following method:

Preparing an electroluminescent composite material into a preform, wherein a transparent material for forming the transparent protective layer is sleeved outside the preform, a hole structure is arranged in the preform along the axial direction of the preform, and the hole structure comprises more than two holes along the axial direction of the preform;

And respectively passing the conductive layers through more than two holes of the preform, and preparing the electroluminescent fiber by a heat softening wire drawing method.

2. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

The first polymer material is selected from one or more than two of polymethyl methacrylate, fluororesin, PMMA composite material doped with fluorinated polymer, styrene dimethyl methyl acrylate copolymer, cycloolefin polymer, polycarbonate, polyphenylene sulfone resin, polyether sulfone resin, polyethyleneimine, polystyrene, polyethylene, polypropylene, polyamide, polyimide, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, styrene-ethylene/butylene-styrene block copolymer, polyurethane, polyvinyl chloride, polypropylene terephthalate, polyvinylidene chloride resin, acrylonitrile-butadiene-styrene copolymer, polyethylene glycol, thermoplastic elastomer, polyoxymethylene, polyphenyl ether, polyester and sodium isophthalate sulfonate copolymer, acrylic ester copolymer, vinyl acetate resin and polyvinyl acetal.

3. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

The more than two conductive layers are arranged in parallel.

4. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

The dielectric insulating layer material with high dielectric constant is selected from one or more than two nano-paint of barium titanate, lead titanate, strontium titanate and titanium dioxide.

5. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

The transparent protective layer is made of a fourth polymer material, and the fourth polymer material is made of a transparent thermoplastic polymer material and is selected from one or more than two of polymethyl methacrylate, fluororesin modified polymethyl methacrylate, cycloolefin copolymer, polyvinylidene fluoride, polystyrene, polycarbonate, styrene dimethyl methyl acrylate copolymer, cycloolefin polymer and styrene-ethylene/butylene-styrene block copolymer.

6. The electroluminescent fiber according to claim 5, wherein the organic light emitting diode is formed of,

The functional material is uniformly distributed in the transparent protective layer.

7. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

The functional material also comprises a photoluminescent material and/or a fluorescent material, and/or,

The scattering agent is selected from one or more than two of TiO₂、BaSO₄、Al₂O₃、MgO、BeO、Y₂O₃、ZrO₂、GaAs、ZnS、ZnSe、MgF₂、CaF₂.

8. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

The electroluminescent material has a mass fraction in the luminescent layer of 0.1wt.% to 70wt.%, and/or,

9. The electroluminescent fiber according to claim 8, wherein the electroluminescent fiber is a fiber,

The electroluminescent material has a mass ratio in the luminescent layer of 20 wt to 50wt.%.

10. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

11. The electroluminescent fiber according to claim 10, wherein the electroluminescent fiber is a fiber,

The long afterglow material of the sulfide system comprises transition metal sulfide, wherein the transition metal sulfide is selected from one or more than two of ZnS: cu ²⁺、ZnS:Mn²⁺、ZnS:Cu²⁺,Co²⁺, and/or,

The alkaline earth metal sulfide is selected from one or more than two of CaS, cu ²⁺、CaS:Ba³⁺、 CaSrS:Ba³⁺, and/or,

The sulfide material of rare earth as activator is selected from one or more than two of Y₂O₂S:Eu³⁺, Mg²⁺, Ti⁴⁺、CaS:Eu²⁺, Pr³⁺、CaS:Eu²⁺, Tm³⁺, and/or,

The long afterglow material of aluminate system is one or more than two kinds of CaAl₂O₄:Eu²⁺, Nd³⁺、Sr₃Al₂O₄: Eu²⁺, Dy³⁺、Sr₄Al₁₄O₂₅: Eu²⁺, Dy³⁺、CaAl₄O₇:Ce³⁺、MAlO₃:Mn⁴⁺, Ge⁴⁺(M=La, Gd) and/or,

The long afterglow material of silicate system is one or more than two kinds selected from MgSiO₃:Mn²⁺, Eu²⁺, Dy³⁺、CdSiO₃:Mn²⁺、CdSiO₃:Sm²⁺、Ba₂ZrSi₃O₉:Eu²⁺, Pr³⁺ and/or,

The gallate system long afterglow material is selected from one or more than two of ZnGa₂O₄:Cr³⁺、Zn₃Ga₂Ge₂O₁₀:Cr³⁺、Zn₂Ga₂Ge₂O₁₀:Cr³⁺, Pr³⁺、Mg₄Ga₈Ge₂O₂₀:Cr³⁺ and/or,

The silicon-based oxynitride series includes LaSi ₃N₅: Ce³⁺, and/or,

The titanate system comprises CaTiO ₃:Pr³⁺, and/or,

The up-conversion luminescent material is selected from one or more than two of NaYF ₄、NaGdF₄、LiYF₄、YF₃、CaF₂ fluoride or Gd ₂O₃ oxide nanocrystals, and/or,

The luminous quantum dot is selected from one or more than two of cadmium sulfide, cadmium selenide and cadmium telluride.

12. The electroluminescent fiber according to claim 1 to 11, wherein the organic light emitting diode display device comprises,

13. The electroluminescent fiber according to claim 1, wherein the electroluminescent fiber is a fiber,

14. An electroluminescent yarn made from more than two electroluminescent fibers twisted;

The electroluminescent fiber is selected from any one or more than two electroluminescent fibers in claims 1-13.

15. An electroluminescent textile fabric, which comprises a base layer,

The electroluminescent fabric comprises electroluminescent fibers and/or electroluminescent yarns, or the electroluminescent fabric comprises transparent conductive fibers and electroluminescent fibers and/or electroluminescent yarns;

Wherein the electroluminescent fiber is selected from any one or more than two electroluminescent fibers in claims 1-13, and the electroluminescent yarn is the electroluminescent yarn in claim 14.