CN113462382A

CN113462382A - Rare earth color light conversion material, color converter containing the same and light-emitting device

Info

Publication number: CN113462382A
Application number: CN202110736364.6A
Authority: CN
Inventors: 史华红; 宋森川; 梁东
Original assignee: Foshan Huaeuropium Photoelectric Material Co ltd
Current assignee: Foshan Huaeuropium Photoelectric Material Co ltd
Priority date: 2021-06-30
Filing date: 2021-06-30
Publication date: 2021-10-01
Anticipated expiration: 2041-06-30
Also published as: CN113462382B

Abstract

The invention discloses a rare earth color light-conversion material. The rare-earth color light-conversion material is compounded by a red light-emitting organic rare-earth material and a green light-emitting organic rare-earth material to obtain a yellow light-emitting organic rare-earth material, a red-orange light-emitting organic rare-earth material, an orange light-emitting organic rare-earth material, and an orange light-emitting organic rare-earth material. The light-emitting organic rare-earth material and the yellow-green light-emitting organic rare-earth material also disclose a color converter and a light-emitting device using the rare-earth color light-converting material. The invention solves the two technical problems of high-energy blue light harming health and discontinuous spectrum loss of common white light LED light sources, improves the overall photophysical properties of common white light LED lighting devices, and shows the excellent characteristics of healthy lighting with high color rendering index and low blue light harm .

Description

Rare earth color light conversion material, color converter containing the same and light-emitting device

Technical Field

The invention relates to the technical field of illumination, in particular to a rare earth color light conversion material, a color converter containing the color light conversion material and a light-emitting device containing the color light conversion material.

Background

An LED (light emitting diode) is called a fourth generation illumination light source, and is a spontaneous emission semiconductor device that converts electric energy into light energy, and its light emitting device is gradually replacing conventional light sources such as incandescent lamps and fluorescent lamps. It has higher conversion efficiency, saves energy by 80%, has smaller volume and longer service life than the incandescent lamp, and has lower power than the conventional light source. LEDs may be used in a variety of lighting applications, such as indoor lighting, traffic signals, automotive lighting, or display backlighting systems.

The light emission of the LED is based on the fact that holes injected into an N region from a P region in a semiconductor PN junction and electrons injected into the P region from the N region are respectively recombined with electrons in the N region and holes in the P region in a micron-sized region near the PN junction to generate spontaneous-emission fluorescence. LEDs produce light in a narrow spectral wavelength range, with the wavelength of the central emission peak determined by the encapsulated luminescent material (also referred to as "fluorescent material" or "radiation converting luminophore" or "phosphor" or "fluorescent colorant" or "fluorescent dye"). For example, blue to green LEDs may be produced using nitride semiconductors such as InN (indium nitride), InGaN (indium gallium nitride), AlN (aluminum nitride), or GaN (gallium nitride); red LEDs may be produced using semiconductors such as GaP (gallium phosphide), GaAsP (gallium arsenide phosphide) or AlGaAs (aluminum gallium arsenide).

White light emitting LEDs are used as light sources in various applications or as backlights in full color displays, including flat panel display applications, due to their long lifetime, high reliability and low power consumption. Two methods are commonly used for LEDs to produce white light, the basis for emitting white light being the superposition (mixing) of various colors.

In the prior art, the emitted light of the white light LED generally cannot uniformly cover the visible spectrum range, cannot realize the simulation of the emission spectrum of natural light or incandescent light sources, has a low color rendering index, and has the problems of blue light hazard and photobiological safety of "rich blue", which are mainly reflected in the aspects of near ultraviolet radiation damage of eyes, photochemical damage of blue light of retina and the like.

In recent years, a new generation of white LED health lighting products with higher bio-safety and color rendering properties than the conventional white LEDs have become the mainstream of market development. The LED health lighting is a full-spectrum white light LED which is called by the industry, and the white light LED accords with the IEC 62471 light radiation safety standard, the blue light radiation hazard reaches the photoproduction biosafety risk-free grade (exemmpt Group-RG0), the spectrum coverage range is wide (380 plus 780nm), the spectrum is close to the solar visible light spectrum, the spectrum continuity is good, the spectrum distribution has no obvious wave crest and wave trough, the color rendering index is excellent, and the white light LED has strong color reduction capability to objects.

To obtain the LED health lighting product, the prior art still starts with the traditional inorganic rare earth luminescent material to realize the color coordinate of the white light LED at the LED chip packaging level to be close to (0.33 ): firstly, under the condition that the light effect of the YAG luminescent material is not influenced, the variety and the quantity of the rare earth doped luminescent material are changed to enable the emission spectrum to move to the long wave direction; and secondly, a red or orange-red luminescent material is properly added to make up the deficiency of the red light component of the spectrum. The methods can improve the color rendering index of the white light LED but cannot solve the problem of harm of high-energy blue light radiation, are limited by the problems of low luminous efficiency, poor stability and the like commonly existing in the prior rare earth materials, cannot be applied to the prior production line equipment, have complicated process and large investment, and develop a high-efficiency luminous material excited by blue light or purple light, which is a starting point and a terminal point of the prior LED healthy illumination technology.

Although the organic light-emitting material has excellent photophysical properties, its physical-chemical properties limit its use in LED light-emitting devices (directly applied to LED wafers without intervening space, such as encapsulated in a droplet or hemisphere shape on an LED chip or coated outside the chip), and it is subject to high thermal and radiation stress during its light source lifetime, and degradation and failure of light-emitting properties occur. The degradation may be due to low light stability, low thermal stability and/or high sensitivity to moisture and oxygen of the material. For these reasons, basf proposed the concept of "remote phosphor" that makes a color converter (also referred to as a "converter" or "light converter," which generally comprises a polymer layer and one or more radiation converting luminophores) of an organic luminescent material together with a plastic substrate spatially separated from the LED light source. Thus, the degree of influence of the heat and radiation generated from the light source on the organic fluorescent material is greatly reduced. Furthermore, LEDs according to the "remote phosphor" concept are more energy efficient than LEDs according to the "phosphor on wafer" concept. This is also known as hybrid LED technology, which uses a cold white LED or a blue LED as an excitation light source to excite a color converter made of organic luminescent material and plastic to achieve the desired spectral range, color temperature and color rendering index.

The prior application patent to basf (publication No. CN109803969A) relates to perylene bisimide compounds and their use in color converters. Such materials were first reported in 1989 to have excellent weatherability and high fluorescence quantum efficiency. The invention provides a novel organic fluorescent material, which has the following application properties: is suitable for converting a cold white LED with a correlated color temperature of 6000-; adapted to down-convert blue LED light into white light; high light stability; high thermal stability; high chemical stability to moisture and oxygen; high fluorescence quantum yield in a polymer matrix; high compatibility with LED manufacturing operations; good chemical resistance, especially resistance to bleaching with hypochlorite and solvent resistance (such as toluene, acetone or dichloromethane); good resistance to boiling water; high compatibility with a wide variety of formulations, in particular for light/heat curable thermoplastic polymer formulations.

Although the design of basf can meet the requirement of full-spectrum illumination, the perylene bisimide compound belongs to an organic fluorescent material, the half-peak width is between 80 and 100nm, and the STOKES displacement is less than 50nm, so that the color purity of light is low, and the emission peak and the absorption peak of different materials are seriously overlapped, thereby reducing the light efficiency.

Rare earth luminescent materials have narrow-band emission characteristics, which play a monopolistic role in the history of display and illumination. For example: in a cathode ray tube, Y₂O₂Tb is used as green powder and Y₂O₃:Eu/Y₂O₂S, Eu is used as red powder; in energy-saving fluorescent lamps, Tb³⁺:LaPO₄,Ce³⁺:LaPO₄And Eu³⁺:Y₂O₃Respectively used as green powder, blue powder and red powder; in the period of splendid attire, the annual output of these flours reaches thousands of tons. The demand for these fluorescent materials has greatly shrunk due to the rapid development of LED technology. In a white LED, a yellow-green powder YAG (Y)₃Al₅O₁₂Ce) and 465nm blue light chips are combined to emit white light. Red powder containing europium (Sr [ Li ])₂Al₂O₂N₂]:Eu²⁺) Provides a good way to improve color temperature and color rendering index. Although these fluorescent materials are stable to heat and do not readily decompose. However, since the fluorescent material is in direct contact with the chip, the light emitting performance of the fluorescent material is drastically reduced by the heat generated from the chip, thereby limiting the application of this technology. Considering that the inorganic rare earth luminescent material is not easy to be uniformly mixed with plastics, our attention is mainly focused on organic rare earth complexes, namely, organic rare earth complex luminescent materials generated by combining rare earth ions with organic ligands. Through molecular design and regulation synthesis, the organic rare earth complex luminescent material which is easy to be uniformly mixed with plastics can be obtained. Thus, the "rare earth color converter" according to the present invention can be obtained. The rare earth color converter is combined with a purple light/blue light LED or a white light LED, so that the spectrum is reduced blue, increased green and increased red, and an LED lamp for health illumination or a backlight plate light source system for ultra-high definition display is produced on the premise of not changing the existing materials and production processes. The successful development and industrialization of the LED rare earth color converter provides a perfect opportunity for the revival of rare earth luminescent materials in the fields of display and illumination.

The unique optical properties of rare earth materials are determined by their valence shell electron arrangement. The 4f sublayer of rare earth ions is filled with electrons and the 4f undergoes fragmentation under the combined influence of homolayer electron repulsion and spin-orbit coupling. The rare earth ion exists as a single 4f electron and an f-f electron transition within the 4f sub-layer. The 4f sub-layer is positioned in the inner layer of ions and is shielded by the 5d and 6s sub-layers, and f-f transition is slightly influenced by the surrounding environment and presents a sharp linear band. And the excited state has a relatively long lifetime, which is an advantage in that it emits light. However, rare earth ions have a small absorption coefficient in the near ultraviolet region, and thus have low luminous efficiency. When they form complexes with some organic ligands, such as beta-diketones, their luminous efficiency is greatly enhanced. Such complexes are commonly referred to as organic rare earth complex light emitting materials. The organic part of the complexes absorbs light and emits characteristic luminescence of rare earth ions through intermolecular energy transfer. This phenomenon is also referred to as "antenna effect".

Their emission spectra have the following characteristics: (1) luminescence covering the entire visible region, such as blue luminescence of cerium (III), orange-red luminescence of samarium (III), red luminescence of europium (III), green luminescence of terbium (III), yellow luminescence of dysprosium (III), blue luminescence of thulium (III) and europium (II). In addition, neodymium (III) and erbium (III) can emit infrared and near-infrared light. (2) Their luminescence is due to 4f inner layer electron transport, and therefore their spectra are determined by the central metal ion and do not change with ligand changes; (3) the emission spectrum of organic molecules is generally wide, and the half-peak width is about 80-100 nm. The rare earth complex has narrow-band emission with the spectral half-peak width less than 10nm and has the advantage of pure chromaticity; (4) their photoluminescence efficiency is high, for example, the reported optical quantum efficiency of solid europium complex reaches 85%.

The patent technology with Chinese patent publication No. CN103044466B describes a bipyridyl triazole rare earth complex; the patent technology with publication number CN103172649B describes o-phenanthroline triazole rare earth complexes; the patent technology with Chinese patent publication No. CN103242354B describes nitrogen-containing bidentate heterocycle substituted tetrazole rare earth complexes; the patent technology with the Chinese patent publication number of CN103265567B describes a1, 2, 3-triazole rare earth complex substituted by nitrogen-containing bidentate heterocycle; quinoline triazole rare earth complexes are described in chinese patent publication No. CN 108191827A. The complexes are prepared into the novel organic rare-earth complex luminescent materials in a coordination mode that a homogeneous ligand is combined with a rare-earth central ion. The triazole or tetrazole group in the ligand is used as an anion provider and is combined with the central rare earth metal cation to realize the electric neutrality of the complex, so that the bond energy of the ligand and the central metal ion exists in addition to the coordination bond and the interaction force of positive and negative charges between the ligand and the central metal ion, and the stability of the complex is improved as a whole. The organic rare earth complex has high light and heat stability, and is suitable for being made into devices by an evaporation film forming process, a solution film forming process and a physical blending process. The preparation method has the advantages of high yield, good product purity, short reaction time, simple operation and low comprehensive production cost.

Therefore, the organic rare earth complex luminescent material with high saturation chromaticity, low toxicity, high stability to light and heat and high chemical stability to moisture and oxygen is applied to the design and development of devices of the white light LED health lighting device, particularly a non-LED chip direct contact type photoluminescence (light conversion) device is developed, and the organic rare earth complex luminescent material is an innovative means for realizing the white light LED health lighting.

Disclosure of Invention

In order to solve the problems of the prior art, the invention provides a rare earth color light conversion material, a color converter containing the color light conversion material and a light-emitting device, high-energy blue light is converted into light by the light conversion function of the rare earth color light conversion material, and then the blue-green light and the red-orange light with lower (relatively missing) spectrum occupation ratio of a common white light LED are complemented, so that the problem of eyesight harm caused by the high-energy blue light is solved, and the color development problem of spectrum discontinuity is solved, thereby realizing the performance upgrade of the common white light LED by lower cost and simpler and more convenient process and meeting the basic index requirements of healthy illumination. The color converter (also called as a light conversion component or a light conversion device or a color conversion device) developed by using the rare earth color light conversion material and the light-emitting device applying the color converter are separated from a common white light LED light source on a physical space, are not directly influenced by thermal stress and radiation stress of an LED chip, and can meet different development requirements of the LED health illumination field on lamp design or transformation.

In order to achieve the purpose, the invention adopts the following technical scheme:

the rare earth color light conversion material is obtained by compounding a red light-emitting organic rare earth material and a green light-emitting organic rare earth material; the red luminescent organic rare earth material is tris [5- (2,2' -bipyridyl-6-yl) -1,2, 4-1H-triazole ] europium (III), tris [5- (1, 10-phenanthroline-2-yl) -1,2, 4-1H-triazole ] europium (III), tris [5- (4,4' -dimethyl-2, 2' -bipyridyl-6-yl-1, 2, 4-1H-triazole ] europium (III), tris [ 3-fluoromethyl-5- (2,2' -bipyridyl-6-yl) -1,2, 4-1H-triazole ] europium (III), tris [5- (2,2' -bipyridyl-6-yl) -1, at least one of 2,3, 4-1H-tetrazole ] europium (III) and tris [5- (1, 10-phenanthroline-2-yl) -1,2,3, 4-1H-tetrazole ] europium (III); the green luminescent organic rare earth material is tris [5- (2,2' -bipyridyl-6-yl) -1,2, 4-1H-triazole ] terbium (III), tris [ 3-phenyl-5- (2,2' -bipyridyl-6-yl) -1,2, 4-1H-triazole ] terbium (III), tris [5- (1, 10-phenanthroline-2-yl) -1,2,3, 4-1H-tetrazole ] terbium (III), tris [ 3-bromo-5- (2,2' -bipyridyl-6-yl) -1, at least one of 2, 4-1H-triazole terbium (III), tris [5- (2,2 '-bipyridin-6-yl) -1,2,3, 4-1H-tetrazole ] terbium (III), tris [ 3-fluoromethyl-5- (2,2' -bipyridin-6-yl) -1,2, 4-1H-triazole ] terbium (III); the rare earth color conversion material of the present invention is combined with a polymer matrix, and the amount of the rare earth color conversion material added in the polymer matrix depends on the correlated color temperature to be achieved.

Preferably, the red light-emitting organic rare earth material and the green light-emitting organic rare earth material are proportioned according to the following weight ratio range to obtain the yellow light-emitting organic rare earth material, wherein the ratio range is 1: 1-10.

Preferably, the red-orange luminescent organic rare earth material is obtained by proportioning the red-luminescent organic rare earth material and the green-luminescent organic rare earth material according to the following weight ratio ranges, wherein the ratio ranges are 1: 0.1-1.

Preferably, the red light-emitting organic rare earth material and the green light-emitting organic rare earth material are proportioned according to the following weight ratio range to obtain the orange light-emitting organic rare earth material, wherein the ratio range is 1: 0.1-4.

Preferably, the red light-emitting organic rare earth material and the green light-emitting organic rare earth material are proportioned according to the following weight ratio range to obtain a yellow-green light-emitting organic rare earth material, wherein the ratio range is 1: 0.01-1.

According to the spectrum difference of LED lamps with different color temperatures, the rare earth color light conversion materials for realizing color conversion have different types and proportions, the key of realizing the light conversion effect of higher color rendering index and lower blue component spectrum proportion is the accurate regulation and control of the proportions among the different rare earth color light conversion materials, and the developed orange light-emitting organic rare earth materials, yellow-green light-emitting organic rare earth materials, red-orange light-emitting organic rare earth materials and yellow-green light-emitting organic rare earth materials are key components for realizing the regulation and improvement of the spectrum of the LED lamps for better common use with red light-emitting organic rare earth materials. The rare earth color conversion material has high light stability when irradiated by light generated by a blue LED with a central emission wavelength of 380-480nm, particularly when irradiated by ultraviolet light.

The invention also provides another technical scheme, and the color converter comprises the rare earth color conversion material and a polymer matrix material, wherein the rare earth color conversion material is combined or blended with the surface of the polymer matrix material. In this example, the polymer matrix comprising the rare earth color converting material has a thickness of 25 μm to 600 μm.

For the purposes of the present invention, a color converter is understood to mean a device which is capable of absorbing light of a particular wavelength and converting it into light of other wavelengths.

Preferably, the polymeric matrix material is selected from the group consisting of Low Density Polyethylene (LDPE), polypropylene (PP), Polystyrene (PS), Polycarbonate (PC), Polymethylmethacrylate (PMMA), polyvinylpyrrolidone (PVP), polyvinyl acetate (PVAc), Polybutylene (PB), silicone, polyacrylate, epoxy, polyvinyl alcohol (PVA), poly (ethylene-vinyl alcohol) copolymer (EVA, EVOH), polyacrylonitrile, polyvinylidene chloride (PVDC), polystyrene acrylonitrile (SAN), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl butyrate (PVB), polyvinyl chloride (PVC), polyamide, Polyoxymethylene (POM), Polyimide (PI), Polyetherimide (PEI) and mixtures thereof.

Preferably, the color converter comprises at least one inorganic white pigment as a scattering body. Suitable scattering media are inorganic white pigments, for example titanium dioxide, lithopone, zinc sulfide, barium sulfate, calcium carbonate, zinc oxide, etc., whose mean particle diameter according to DIN 13320 standard is from 0.01 μm to 10 μm, preferably from 0.1 μm to 1 μm, further preferably from 0.15 μm to 0.5. mu.m, especially titanium dioxide being used as scattering media. The content of the scatterers is generally from 0.01 to 2.0% by weight, preferably from 0.05 to 1% by weight, further preferably from 0.1 to 0.5% by weight, based in each case on the polymer comprising the scatterer layer.

Preferably, the flame retardant further comprises an auxiliary agent, wherein the auxiliary agent is at least one of a flame retardant, an antioxidant, a light stabilizer, an ultraviolet absorber, a blue light absorber, a free radical scavenger and an antistatic agent.

The amount of rare earth color converting material added to the polymer matrix material depends on the correlated color temperature to be achieved. The light emitted from the LED can be tuned to longer wavelengths to obtain white light with a desired color temperature, for example by increasing the concentration of the yellow light converting material and the red light converting material. The concentration of the rare earth color converting material in the polymer matrix material is set according to the thickness of the color converter and the type of polymer. If a thin polymer layer is used, the concentration of the rare earth color converting material is typically higher than if a thick polymer layer is used. The particular concentration of rare earth color converting material required to convert a particular wavelength depends on the type of LED that is to generate light. Conversion of light produced by a blue LED typically requires higher concentrations of rare earth color converting material additions in order to achieve the same white color temperature as compared to a white LED.

The concentration of the red light-emitting organic rare earth material of the present invention is usually 0.0001 to 5% by weight, preferably 0.001 to 1% by weight, and more preferably 0.002 to 0.5% by weight, based on the amount of the polymer. If used in combination, the concentration of the other yellow-emitting organic rare earth material or yellow-green-emitting organic rare earth material is usually 0.002 to 5% by weight, preferably 0.003 to 0.4% by weight, based on the amount of the polymer. The ratio of the other yellow or yellow-green light-emitting organic rare earth material to the at least one red light-emitting organic rare earth material is generally in the range of 1:1 to 1:20, preferably 1:2 to 1:10, further preferably 1:2 to 1:5, for example 1:2.1 or 1:3 or 1: 4.

The proportion of rare earth color conversion material added depends on the base light source selected. For a desired set color temperature, the ratio of the yellow light-emitting organic rare earth material to the red light-emitting organic rare earth material is significantly larger when light is emitted from a blue LED having a central emission wavelength of 380-.

The color converter can be manufactured by different production processes, according to different combination modes of the rare earth color light conversion material and the polymer matrix material, the rare earth color light conversion material is combined with the polymer matrix material by at least one preparation process of casting molding, granulation tabletting molding, granulation film blowing molding, coating film scraping molding and printing molding, and the preferred combination curing mode is natural curing, heating curing, illumination curing and photo-thermal combination curing. The preparation process can be an independent manufacturing process of one-time processing and forming, and can also be a step-by-step manufacturing process of multiple processing and forming. As a specific example, in the coating scratch film formation preparation process, the color converter is produced by dissolving at least one of a polymer matrix material, a rare earth color conversion material and other auxiliary materials in a solvent, followed by coating a scratch film to remove the solvent; in the preparation process of granulating and film blowing, the color converter is prepared by extruding rare earth color conversion material, other auxiliary material and at least one polymer matrix, and cooling to obtain granules and film blowing.

In order to increase the high chemical stability towards water and oxygen, the color converter further comprises at least one barrier layer against oxygen and/or water, which is glass, quartz, a metal oxide, silicon dioxide, a multilayer system consisting of alternating layers of silicon dioxide and aluminium oxide, titanium nitride, a silicon dioxide/metal oxide multilayer material, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride (PVDC), a Liquid Crystal Polymer (LCP), polystyrene-acrylonitrile (SAN), polybutylene naphthalate (PBN), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyvinyl chloride (PVC), Polyvinyl Butyrate (PBT), polyamides, epoxies, polyoxymethylenes, polyetherimides, polyimides, polymers derived from ethylene-vinyl acetate (EVA) and polymers derived from ethylene-vinyl alcohol (EVOH) ) Any one of them.

The color converter of the present invention may optionally comprise other components, such as a backing layer. The backing layer may impart certain mechanical stability properties to the color converter. Common backing layer materials are glass or transparent rigid organic polymers such as polystyrene, polycarbonate, polymethacrylate or polymethylmethacrylate. The backing layer is generally 1mm to 10mm, preferably 0.1mm to 5mm, and more preferably 0.3mm to 2mm in thickness.

The color converter of the present invention can be manufactured in any desired geometric configuration depending on the lighting device, can be used in combination with LEDs in virtually any geometric form, can have essentially any geometric shape, and is independent of the configuration of the lighting device, preferably a film, plate, sheet, drop pattern, hemisphere pattern, cylinder, spherical surface lens or cover plate.

Regardless of the three-dimensional shape, the color converter of the present invention may be composed of a single layer or a multi-layer structure. When the color converter of the present invention comprises more than one rare earth color converting material, the rare earth color converting material and/or the diffuser therein may be present in the same/different layers. When the color converter of the present invention comprises a plurality of rare earth color converting materials, these rare earth color converting materials may be present adjacent to each other in the same layer. When the color converter has a layered structure, then the layers are continuous and do not have any holes or spaces.

The invention also provides another technical scheme, and the light-emitting device comprises at least one LED and at least one color converter, wherein a gap is formed between the LED and the color converter. The color converter is separated from a common white light LED light source in a physical space, is not directly influenced by thermal stress and radiation stress of an LED chip, and can meet different development requirements of the LED healthy illumination field on lamp design or transformation.

The color converter of the present invention is applied to a light emitting device in a remote photoluminescent setting. Under this premise, the color converter is physically separated from the LED light source in space. In general, the distance between the LED light source and the color converter is 0.05cm to 45cm, preferably 0.2cm to 9.5cm, and more preferably 0.4cm to 2.9 cm. Between the color converter and the LED there may be different media, such as dry air, noble gases, inert gases or other gases or mixtures thereof.

Preferably, the color converters can be concentrically arranged around the LEDs, and the specific application mode is not limited by commercial specifications of the illumination products, including but not limited to LED spot lights, LED bulb lights, LED fluorescent lights, LED down lights, LED ceiling lights, LED panel lights, LED street lights, LED tunnel lights, LED landscape lights, LED plant lights, LED trunk spot lights, and the like. Belongs to the upgrading optimization technology of the existing white light LED illuminating product and also belongs to the economic manufacturing technology of the white light LED in the novel health illuminating field.

Preferably, the light emitting device of the present invention comprises at least one LED having a central emission wavelength of 380nm to 480nm and at least one color converter as described above, the color converter and the LED being physically separated in space. Further preferably, the light emitting device comprises a plurality of LEDs selected from the group consisting of LEDs having a central emission wavelength of 380nm to 480nm and LEDs having a color temperature of 6000-.

In particular, the color converter is suitable for converting light generated by a cold white LED having a color temperature of 20000-. That is, the color converter of the present invention can shift the emission wavelength of the white light source toward a longer wavelength (red shift), thereby generating white light having a warm tone and improving the color rendering index of the light emitting device. Similarly, light generated by such an LED can be converted to light of a second, longer wavelength by passing light generated by an LED having a central emission wavelength of 380-480nm through a color converter comprising a light converting material. In the process, the color converter also realizes the function of absorbing and converting the high-energy surplus blue light of the LED light source, reduces the spectrum ratio of the high-energy blue light and protects the eyesight.

The invention has the beneficial effects that: the high-energy blue light is converted into light by the light conversion function of the rare earth color light conversion material, and then the blue-green light and the red-orange light with lower (relatively missing) spectrum occupation ratio of the common white light LED are complemented, so that the problem of eyesight harm caused by the high-energy blue light is solved, and the color development problem of spectrum discontinuity is solved, thereby realizing the performance upgrade of the common white light LED by lower cost and simpler and more convenient process, and meeting the basic index requirement of healthy illumination.

On the other hand, the color converter of the present invention can be manufactured by different production processes, and the rare earth color conversion material is combined with the polymer matrix material by at least one preparation process selected from casting molding, granulation sheet forming, granulation film blowing molding, coating film scraping molding and printing molding according to the combination manner of the light conversion material and the polymer matrix material. The color converter can be fabricated in any desired geometric configuration from light emitting device to light emitting device, can be used in combination with the LEDs in virtually any geometric form, can have substantially any geometric shape, and is product adaptable regardless of the configuration of the light emitting device.

In the present invention, the term "color converter" is also referred to as "light conversion device" or "light conversion assembly" or "light conversion device" or "color conversion device". These terms are used interchangeably and are understood to mean all physical devices capable of absorbing light of a particular wavelength and converting it to light of a second wavelength. The color converter is part of a light emitting device, in particular a light emitting device utilizing LEDs or OLEDs as light source, whereby blue light can be partly converted into visible light having a longer excitation wavelength.

LEDs with a central emission wavelength of 380-. The conventional LED light sources are commercial and mass-produced LED light sources.

In the present invention, "white light LED" refers to an LED capable of emitting light in the blue region of the electromagnetic spectrum, and the peak value of the light is between 380 and 480nm, preferably 440 and 470nm, and more preferably 440 and 460 nm. Standard indium gallium nitride (InGaN) based white LEDs are fabricated on sapphire substrates and have a main peak emission wavelength typically around 450 nm.

Drawings

Fig. 1 is a schematic structural diagram of an LED bulb device in embodiment 1 of the present invention;

FIG. 2 is a schematic structural diagram of a T8/T5 type LED fluorescent lamp device in embodiment 2 of the present invention;

fig. 3 is a schematic structural diagram of an LED row lamp apparatus in embodiment 3 of the present invention;

fig. 4 is a schematic structural diagram of an LED tube light device in embodiment 4 of the present invention;

fig. 5 is a schematic structural view of an LED panel lamp device in embodiment 5 of the present invention.

Description of reference numerals:

an LED lamp bead 101, an LED bulb lamp cover 102, a radiator 103, a driving power supply 104, an LED bulb lamp holder 105, a T8/T5 type LED fluorescent lamp substrate 201, a T8/T5 type LED fluorescent lamp cover 202, a T8/T5 type LED fluorescent lamp holder 203, a power supply, a lamp holder, a lamp base, a T8/T5 type LED fluorescent lamp substrate, a T8/T5 type LED fluorescent lamp holder, a T5/T5 type LED fluorescent lamp holder, a power supply, a lamp holder, a lamp base,

an LED row lamp substrate 301, an LED row lamp face cover 302, a serial connector 303,

An LED down lamp shell 401, a lamp bead belt 402, an LED down lamp light guide plate 403, a light conversion polymer plate 404, an LED down lamp face shield 405,

The LED display device comprises an outer cover 501, a light conversion material membrane 502, an LED panel light guide plate 503, an LED panel light strip 504, a reflector 505, a protective layer 506 and a frame base 507.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.

The invention relates to an organic rare earth material, in particular to five types of organic rare earth materials in the disclosed patent technology, the first type is a bipyridyl triazole rare earth complex, the structural formula and the preparation method thereof are referred to patent documents (patent name: bipyridyl triazole rare earth complex and the preparation method thereof, publication number: CN103044466B), and the bipyridyl triazole rare earth complex is selected from the group consisting of a formula A1-A4:

the second type is o-phenanthroline triazole rare earth complex, the structural formula and the preparation method thereof refer to patent documents (patent name: o-phenanthroline triazole rare earth complex and the preparation method thereof, publication number: CN103172649B), and the o-phenanthroline triazole rare earth complex is selected from formulas B1-B4:

the third category is nitrogen-containing bidentate heterocycle substituted tetrazole rare earth complexes, the structural formula and the preparation method thereof are referred to patent documents (patent name: nitrogen-containing bidentate heterocycle substituted tetrazole rare earth complexes and the preparation method thereof, publication number: CN103242354B), and the nitrogen-containing bidentate heterocycle substituted tetrazole rare earth complexes are selected from formulas C1-C2:

the fourth type is a1, 2, 3-triazole rare earth complex substituted by nitrogen-containing bidentate heterocycle, the structural formula and the preparation method thereof are referred to patent documents (the special name: 1,2, 3-triazole rare earth complex substituted by nitrogen-containing bidentate heterocycle and the synthesis method thereof, the publication number: CN103265567B), and the 1,2, 3-triazole rare earth complex substituted by nitrogen-containing bidentate heterocycle is selected from the formulas D1-D2:

the fifth type is quinoline triazole rare earth complex, the structural formula and the preparation method thereof refer to patent documents (the patent name is quinoline triazole rare earth complex, the preparation method and the application thereof, the publication number is CN108191827A), the structural formula of the quinoline triazole rare earth complex is as follows:

the structural formulas of five types of organic rare earth materials described in the above patent documents are shown in the specification, wherein R1, R2, R3, R4 and R5 represent organic substituents of each complex, and Ln represents a central rare earth ion of each complex. The selection range of the organic functional group of the substituent R1-R5 and the selection range of the rare earth ion at the center Ln are the same as those described in the above patent documents.

Based on the photoluminescence premise, suitable rare earth color conversion materials can be green light emitting organic rare earth materials, yellow light emitting organic rare earth materials, orange light emitting organic rare earth materials, red orange light emitting organic rare earth materials and red light emitting organic rare earth materials selected from the above five organic rare earth materials, and can be any rare earth color conversion materials which can absorb light with the wavelength within the range of 250-500nm and emit light with the wavelength longer than the absorbed light, especially emit light with the wavelength within the range of more than 450nm, such as within the wavelength range of 450-600nm or 450-650 nm. Preferably, the combined use of rare earth color conversion materials can provide a color converter to obtain a white LED light source with low color temperature (<6000K) and high color rendering (e.g., 90 or higher).

Example 1

As shown in fig. 1, in the application of the blue-light LED bulb light emitting device, a rare earth color light conversion material spray coating layer is formed in the LED bulb light face shield 102, so as to directly realize the healthy lighting application with high color rendering index and low blue light, and the preparation process comprises the following steps:

(1) dissolving 1.9g of red light-emitting organic rare earth material tris [5- (2,2' -bipyridine-6-yl) -1,2, 4-1H-triazole ] europium (III) and 2.0g of tris [5- (1, 10-phenanthroline-2-yl) -1,2, 3-1H-triazole ] terbium (III) green light-emitting organic rare earth material and 1.2g of orange light-emitting organic rare earth material A1 (A1) which is prepared by mixing tris [ 3-fluoromethyl-5- (2,2' -bipyridine-6-yl) -1,2, 4-1H-triazole ] europium (III) and tris [ 3-bromo-5- (2,2' -bipyridine-6-yl) -1,2, 4-1H-triazole ] terbium (III) in a weight ratio of 2.2: 1.5) together in 150g of 150g Obtaining a rare earth color light conversion material solution in DMF;

(2) 500g of a polyurethane resin, 1.2g of a defoaming agent (derived from

922) Mixing the obtained product with 150g of a mixture of ethyl acetate and toluene in equal proportion, and uniformly stirring and dispersing to obtain a coating mother solution;

(3) dropwise adding the rare earth color light conversion material solution prepared in the step (1) into the coating mother solution obtained in the step (2) under stirring, stirring and dispersing to uniformly disperse the rare earth color light conversion material solution, and filtering and defoaming to obtain the rare earth color light conversion coating;

(4) and (4) spraying the rare earth color light conversion coating obtained in the step (3) into the LED bulb lamp face mask 102 to obtain a first light conversion film, wherein the thickness of the film is less than 50 microns. The thermosetting temperature is 110 ℃, the curing time is 5min, and the prepared first light conversion film can be compounded with a blue light source to form white light under the excitation of a blue light LED light source.

Example 2

As shown in fig. 2, in the application of the light emitting device of a cool white T8/T5 type LED fluorescent lamp (designed based on a T8/T5 type fluorescent lamp filled with mercury-containing fluorescent powder by traditional inert gas) with a color temperature of 9100K, a film-shaped color converter is added in a T8/T5 type LED fluorescent lamp mask 202, i.e., the color converter is curled and shaped, and is attached inside the lamp mask to directly realize the health lighting application of high color rendering index and low blue light, and the preparation process steps are as follows:

(1) mixing 2.5g of red light-emitting organic rare earth material tris [5- (1, 10-phenanthroline-2-yl) -1,2, 4-1H-triazole ] europium (III) and 2g of yellow-green light-emitting organic rare earth material B1 (B1) which is formed by mixing tris [5- (4,4' -dimethyl-2, 2' -bipyridine-6-yl-1, 2, 4-1H-triazole ] europium (III) and tris [ 3-fluoromethyl-5- (2,2' -bipyridine-6-yl) -1,2, 4-1H-triazole ] terbium (III) in a weight ratio of 1.4: 2.3) with 1000g of low-density polyethylene (LDPE) base material particles and a certain auxiliary agent uniformly, and adding the mixture into a double-screw extruder charging barrel;

(2) setting the extrusion temperature to 145-165 ℃, performing melting, kneading, extruding, water-cooling, granulating and drying to obtain the light conversion material functional master batch;

(3) and then blending the light conversion material functional master batch and the same polymer base material particles according to a specific proportion, and adding the mixture into a co-extrusion film blowing machine for film blowing and cutting to obtain a second light conversion luminescent film, wherein the film thickness of the second light conversion luminescent film is 0.8 mm. The content of the light conversion material in the second light conversion luminescent film is about 0.4%.

(4) The second light conversion and luminous film is reasonably cut according to the standard length of a lampshade of the T8/T5 type LED fluorescent lamp and the circumference of a lamp tube, and finally is combined with the inside of the T8/T5 type LED fluorescent lamp mask 202 in a physical fixing mode. At this time, on the basis of the white light LED light source, the surplus blue light is absorbed and converted into red light and cyan light.

Example 3

As shown in fig. 3, the application of the color converter in the cold white LED row lamp lighting device with a color temperature of 9101K directly realizes the health lighting application of high color rendering index and low blue light by adding rare earth color light conversion material to the LED row lamp cover 302, and the preparation process comprises the following steps:

(1) uniformly mixing 2g of red light-emitting organic rare earth material tris [5- (1, 10-phenanthroline-2-yl) -1,2,3, 4-1H-tetrazole ] europium (III) and 1g of orange light-emitting organic rare earth material A2(A2 is formed by mixing tris [5- (1, 10-phenanthroline-2-yl) -1,2, 4-1H-triazole ] europium (III) and tris [ 3-bromo-5- (2,2' -bipyridine-6-yl) -1,2, 4-1H-triazole ] terbium (III) in a weight ratio of 4: 3) with a double-screw rod 1000g of low-density polyethylene (LDPE) base material particles and a certain auxiliary agent, and then adding the mixture into a charging barrel of an extruder;

(2) the extrusion temperature is 145-165 ℃, and the master batch with the light conversion material function is obtained after the fusion, kneading, extrusion, water cooling, grain cutting and drying;

(3) then blending the light conversion material functional master batch and the same polymer base material (LDPE) particles according to a standard proportion, and adding the mixture into a continuous tube blowing machine for high-temperature cast molding;

(4) the manufactured thick tube is reasonably cut according to the lengths of the LED row lamp bodies of different models, and the finally manufactured LED row lamp face cover 302 is combined with the lamp base part in a physical fixing mode. At this time, on the basis of the white LED light source, the LED row lamp cover 302 absorbs the surplus blue light and converts the surplus blue light into red light and orange light.

Example 4

As shown in fig. 4, the application of the color converter in the cold white LED down lamp lighting device with a color temperature of 8200K can directly realize the health lighting application of high color rendering index and low blue light by replacing the light diffusion plate in the LED down lamp mask 405 with a film-shaped color converter added with a rare earth color light conversion material, and the basic steps are as follows:

(1) 0.15g of red luminescent organic rare earth material tris [5- (4,4 '-dimethyl-2, 2' -bipyridyl-6-yl-1, 2, 4-1H-triazole]Europium (III) and 0.15g of red luminescent organic rare earth material tris [ 3-fluoromethyl-5- (2,2' -bipyridyl-6-yl) -1,2, 4-1H-triazole]Europium (III) incorporated, 100g of a transparent Polycarbonate (PC) based on a polycondensate of bisphenol A with phosgene (b), (c), (d) and (d) a)

2805 from Bayer Materials Science AG), 0.5g of titanium dioxide rutile pigment (

2233 from Kronos Titan) and appropriate amount of dichloromethane, and dissolving/dispersing;

(2) the obtained solution/dispersion was coated on the surface of a glass plate using an applicator frame (wet film thickness 900 μm). After the solvent has been dried off, the film is separated from the surface of the glass plate and dried. Obtaining a circular light converting polymer plate 404;

(3) the light conversion polymer plate 404 is reasonably cut according to the original size of the light diffusion plate of the white light LED down lamp, and finally is combined with the inside of the LED down lamp mask 405 in a physical fixing mode. At the moment, on the basis of a white light LED down lamp light source, the healthy illumination is realized by absorbing surplus blue light and converting the surplus blue light into red light.

Example 5

As shown in fig. 5, when the color converter is applied to the light emitting device of the cold white LED panel lamp with a color temperature of 7500K, the light diffusion plate in the mask is replaced by a film-shaped color converter added with a rare earth color light conversion material, or a layer of film-shaped color converter is added outside the mask, so that the health lighting application with high color rendering index and low blue light can be directly realized. The preparation process comprises the following steps:

(1) 800g of urethane acrylic resin, 10g of resin UV curing agent, 40g of monofunctional acrylate diluent (A)

SR423NS), 20g of hexafunctional acrylate diluent(s) ((R)

EM265) is stirred and dispersed evenly, and then 2.8g of red luminescent organic rare earth material tris [5- (2,2' -dipterodin-6-yl) -1,2, 4-1H-triazole is added]Europium (III) and 3.2g of tris [ 3-fluoromethyl-5- (2,2' -bipyridin-6-yl) -1,2, 4-1H-triazole]Terbium (III) -containing green light-emitting organic rare earth material and 2.3g orange light-emitting organic rare earth material A3(A3 is tris [5- (2,2' -bipyridine-6-yl) -1,2,3, 4-1H-tetrazole)]Europium (III) and tris [5- (1, 10-phenanthroline-2-yl) -1,2,3, 4-1H-tetrazole]Terbium (III) and tris [5- (2,2' -bipyridin-6-yl) -1,2,3, 4-1H-tetrazole]Terbium (III) is mixed according to the weight ratio of 4:2: 1) to be stirred so as to lead the light conversion material to be dispersed evenly, and then the rare earth color light conversion coating is obtained after filtration and deaeration;

(2) coating the rare earth color light conversion coating on the surface of the LED panel lamp light guide plate 503 with a PC (polycarbonate), PMMA (polymethyl methacrylate) or PET (polyethylene terephthalate) polymer matrix by using a coating machine, wherein the thickness of the light guide plate is 500 mu m;

(3) curing by irradiation with high-pressure mercury lamp at energy of 1200mJ/cm²Finally, a light conversion material film 502 with a thickness of 120 μm is formed on the surface of the light guide plate 503 of the LED panel lamp. At the moment, the white light LED tube lampOn the basis of the light source, the health illumination is realized by absorbing surplus blue light and converting the surplus blue light into red light and orange light.

Ra of the average Color Rendering Index (CRI), which is generally used to evaluate the color reproducibility of a light source, is obtained by averaging the values of the first eight special color rendering indices of CIE standard color samples (R1-R8), and it is necessary to increase the R9 index representing saturated red in addition to Ra to accurately represent red. Since the energy difference between the blue light of a higher energy level and the red light of a lower energy level is converted into heat during the color conversion process in the conventional blue light-excited white LED, the light emitting efficiency (LER) of the warm white LED is lower than that of the cool white LED. On the other hand, a cold white LED with high luminous efficiency generally has an insufficient color rendering index, and there is a trade-off constraint between luminous efficiency and color rendering index. The rare earth color light conversion material used in the invention can realize good compromise between the luminous efficiency and the color rendering index of the white light LED, and obtain the white light LED with high luminous efficiency and the average color rendering index close to 90 or higher.

Photophysical property test of the light-emitting devices of example 2 and example 4: the cold white LED of example 2 (noted as LED1) and the cold white LED of example 4 (noted as LED2) were each used as excitation light sources, and the light emitted from the surface of the color converter was photometrically detected and integrated using an ISP 500 integrating sphere spectrometer and a CAS 140CT detector to detect all the light emitted from the device. The measured spectra are used to obtain all relevant photometric data, such as CCT (correlated color temperature) values in kelvin [ K ], average color rendering index, CRI, values, and color rendering index (R9) values for reference color No. 9 (red). The results are summarized in table 1 below.

TABLE 1 Performance of devices made of organic rare earth complex light-converting materials in examples 2 and 4

Table 1 shows that the color converters made from the rare earth color conversion materials of the embodiments 2 and 4 of the present invention can improve the average color rendering index CRI and R9 values and reduce the blue light hazard of the LED light-emitting device. The rare earth color light conversion material improves the overall photophysical performance of a common cold white light LED lighting device and shows the excellent characteristics of high color rendering index and low blue light of healthy lighting.

The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. a rare earth color light conversion material, it is characterized in that: the rare earth color light conversion material of the present invention is compounded by red luminescent organic rare earth material and green luminescent organic rare earth material,

The red light-emitting organic rare earth material is selected from tris[5-(2,2'-bipyridin-6-yl)-1,2,4-1H-triazole] europium (III), tris[5-(1 ,10-O-phenanthrolin-2-yl)-1,2,4-1H-triazole]europium(III), tris[5-(4,4'-dimethyl-2,2'-bi Pyridin-6-yl-1,2,4-1H-triazole]europium(III), tris[3-fluoromethyl-5-(2,2'-bipyridin-6-yl)-1,2 ,4-1H-triazole]europium(III), tris[5-(2,2'-bipyridin-6-yl)-1,2,3,4-1H-tetrazole]europium(III) , at least one of three [5-(1,10-o-phenanthroline-2-yl)-1,2,3,4-1H-tetrazole] europium (III);

The green light-emitting organic rare earth material is selected from tris[5-(2,2'-bipyridin-6-yl)-1,2,4-1H-triazole]terbium (III), tris[3-phenyl -5-(2,2'-bipyridin-6-yl)-1,2,4-1H-triazole]terbium(III), tris[5-(1,10-o-phenanthroline-2- base)-1,2,3-1H-triazole]terbium(III), tris[5-(1,10-o-phenanthroline-2-yl)-1,2,3,4-1H-tetra azole]terbium(III), tris[3-bromo-5-(2,2'-bipyridin-6-yl)-1,2,4-1H-triazole]terbium(III), tris[5 -(2,2'-bipyridin-6-yl)-1,2,3,4-1H-tetrazole]terbium(III), tris[3-fluoromethyl-5-(2,2'- at least one of bipyridin-6-yl)-1,2,4-1H-triazole]terbium (III);

The rare earth color light conversion material of the present invention is combined with a polymer matrix, and the added amount of the rare earth color light conversion material in the polymer matrix depends on the correlated color temperature to be achieved.

2. The rare-earth color light-converting material according to claim 1, wherein the red light-emitting organic rare-earth material and the green light-emitting organic rare-earth material are proportioned in the following weight ratios to obtain a yellow light-emitting organic rare-earth material, and the The ratio range is 1:1-10.

3. The rare-earth color light-converting material according to claim 1, wherein the red-orange light-emitting organic rare-earth material is obtained by the red-orange light-emitting organic rare-earth material and the green light-emitting organic rare-earth material in the following weight ratios. The ratio range is 1:0.1-1.

4. The rare-earth color light-converting material according to claim 1, wherein the red-emitting organic rare-earth material and the green-emitting organic rare-earth material are proportioned in the following weight ratios to obtain an orange-emitting organic rare-earth material, and the The ratio range is 1:0.1-4.

5. The rare earth color light conversion material according to claim 1, wherein the red light-emitting organic rare-earth material and the green light-emitting organic rare-earth material are proportioned in the following weight ratios to obtain a yellow-green light-emitting organic rare-earth material, so The ratio range is 1:2-10.

6. A color converter, characterized in that: comprising the rare earth color light conversion material and a polymer matrix material as described in any one of claims 1-5, wherein the rare earth color light conversion material is combined with the surface of the polymer matrix material or blended.

7. The color converter of claim 6, wherein the color converter further comprises at least one barrier layer against oxygen and/or water.

8. The color converter of claim 6, further comprising an auxiliary agent, the auxiliary agent is a flame retardant, an antioxidant, a light stabilizer, an ultraviolet absorber, a blue light absorber, a free radical scavenger At least one of an antistatic agent and an antistatic agent.

9. The color converter according to claim 6, wherein the rare earth color light conversion material adopts at least one of casting molding, granulation and tablet molding, granulation blowing molding, coating scraping film molding, and printing molding. A preparation process is combined with a polymer matrix material.

10. A lighting device, characterized in that it comprises at least one LED and at least one color converter according to any one of claims 6-9, with a gap between the LED and the color converter.