TWI384051B - Liquid fluorescent composition and light emitting device - Google Patents

Description

Liquid phosphor composition and illuminating device

This invention relates to phosphors, and in particular to a liquid phosphor and its use.

There are two ways to fabricate white light-emitting diodes (LEDs): a blue light emitted by a blue LED chip (InGaN LED) to excite YAG: Ce3 ⁺ phosphor powder emits yellow light and unabsorbed blue light mixes white light, and One is an ultraviolet (UV) LED wafer (AlGaN) that excites red, green, and blue (RGB) phosphor mixed luminescence. However, regardless of the process, the phosphor powder needs to be dispersed and uniformly mixed in a highly transparent, high temperature resistant adhesive, and then hardened. However, because the phosphor powder is incompatible with the binder, it is often caused by fluorescence. Uneven dispersion of the powder leads to uneven illumination.

The patents of the fluorescent agents are mentioned in the prior art, such as the Republic of China Patent 459403, the Republic of China Patent 565956, the US Patent US 20040231554, the Japanese Patent JP2004-326910, and the like. However, all of the above patents are composed of a solid fluorescent agent, and it is necessary to mix the fluorescent material into the unsaturated transparent resin, add a hardener or other accelerator, and crosslink and harden to form a fluorescent layer for the LED.

The present invention provides a liquid phosphor composition comprising: (a) 0.001 to 2 parts by weight of a fluorescent material selected from a fluorescent polymer, a fluorescent dye, or a combination thereof; and (b) 100 parts by weight A cyclic molecular solvent having a boiling point greater than 100 ° C.

The present invention further provides a light-emitting device comprising: a substrate; an illumination unit disposed on the substrate; the liquid phosphor composition described above disposed on the illumination unit; and a package component, the liquid phosphor The composition is sealed in an accommodating area.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The present invention provides a liquid phosphor composition and an application thereof which are distinguished from the solid phosphors formed by the curing of a phosphor and a binder resin in the prior art. In the present invention, the soluble fluorescent material is dissolved in a cyclic molecular solvent to form a homogeneous liquid fluorescent agent, and the photoexcitation wavelength can be adjusted to the optimum light-emitting position by the conjugate ratio of the solvent molecules. In addition, a light color modifier can be selectively added to further finely adjust the color of the light and adjust the viscosity of the liquid phosphor to suit various liquid processing processes. The liquid phosphor composition is directly printed, screen printed, coated, poured or dispensed onto a light-emitting element (such as a blue LED wafer) to form a liquid phosphor layer (without a hardening process), and then sealed with a glass lens. A high-efficiency white light source or a composite LED light source of various light colors can be easily fabricated.

The composition of the liquid phosphor will be detailed below.

The liquid phosphor composition of the present invention mainly comprises:

(a) 0.001 to 2 parts by weight of the fluorescent material, particularly preferably 0.01 to 1 part by weight;

(b) 100 parts by weight of a cyclic molecular solvent. In addition, it can be selectively added:

(c) 1 to 50 parts by weight of the color control agent, particularly preferably 3 to 40 parts by weight;

(d) 0.02 to 5 parts by weight of the hindered amine light stabilizer, particularly preferably 0.5 to 2 parts by weight.

The aforementioned fluorescent material (a) may be a fluorescent polymer, a fluorescent dye, or a combination thereof. The fluorescent polymer may be a lanthanide-derived copolymer, for example, a 9,9-dialkyl-fluorene conjugated molecule as a core, and then introduced into other high-fluorescent aromatic molecules to adjust the fluorescing. The color of light increases the efficiency of fluorescence, and its structure is as shown in formula (I):

The oxime-derived copolymer of the formula (I) is composed of an anthracene derivative monomer unit and one or more phenyl, naphthyl, heterocyclic, polycyclic aromatic and polycyclic heterocyclic groups having at least one conjugate group.

The Ar ₁ , Ar ₂ , and Ar ₃ systems of the formula (I) are each independently, and may be selected from the group consisting of the following functional groups:

R in the above formula fluorescent polymer (I) and Formula (II) of lines ₁ ~ R ₁₂ are each independently hydrogen, an alcohol group, a linear or branched alkyl group of C _1-22, straight or branched C ₁ of _-22 alkoxy, an ortho, meta or para-alkylphenyl group, or an ortho, meta or para alkoxyphenyl group, and m, n, p, q of formula (I) is The number of repeating units. Wherein m of the formula (I) accounts for at least 10% or more, preferably 50% or more, of all repeating monomer ratios (m/(m+n+p+q)), but one or two of n, p, q may be 0 (indicating that this repeating unit is not included).

Further, the fluorescent polymer may be a poly(phenylene vinylene) (PPV) polymer represented by the following formula (III):

Formula (III)

Wherein R ₁₃ to R ₁₅ are each independently a linear or branched C _1-22 alkyl group, an ortho, meta or para-alkylphenyl group, an ortho, meta or para alkoxy group; Phenyl, and a, b are the number of repeating units. Based on the requirements of different illuminating colors, a may be 0 (for example: MEH-PPV for orange light) or b may be 0 (for example, DB-PPV for green light). In order to obtain a yellow excitation light source, two branched benzene molecules can be copolymerized to obtain a yellow fluorescent polymer, wherein a accounts for at least 50% of all repeating monomer ratios (a/(a+b)), preferably 80%. the above.

In addition to the fluorescent polymer, the fluorescent material (a) used in the present invention may also be a fluorescent dye such as Coumarin 6 , Fluorescein, Acridine, 4- Dimethylmethylene-2,6-dimethyl-4H-pyran (DCM; 4-(Dicyanomethylene)-2-methyl-6-[p-(dimethylamino)-styryl]-4H-pyran), nitro Nitrostilbene, Nitrobenzoxadiazole, Riboflavin, Rhodamine, or a combination of the foregoing.

In one embodiment, the ultraviolet-visible (UV-Vis) absorption spectrum of the phosphor material (a) is located at 440-470 nm to absorb the source of the blue LED. In other embodiments, the phosphor material (a) may have other absorption wavelengths for application to light sources of other colors.

The present invention utilizes the above-mentioned fluorescent material as a fluorescent luminescent material, and dissolves it in a solvent having a cyclic molecule, such as having a conjugated structure, which resonates with a conjugated molecule in the fluorescent substance, thereby reducing the fluorescing The energy gap of a light substance. Therefore, by controlling the amount of conjugate of the cyclic molecular solvent, the degree of displacement of the luminescent red color can be controlled to achieve the desired color.

The cyclic molecular solvent (b) used in the present invention is a high boiling point solvent having a boiling point of more than 100 ° C, and includes: a non-conjugated solvent such as methyl ethyl hexane, Decahydronaphthalene; a partially conjugated solvent; For example, Cyclohexylbenzene, 1,2,3,4-Tetrahydronaphthalene, Anisole, Phenetole, Ethylbenzene , Propylbenzene, Cumene; fully conjugated solvents such as toluene, Xylene, Tri-methylbenzene (TMB), Methylnaphthalene , dimethylnaphthalene or a combination of the foregoing. Table 1 lists the structure and characteristics of some cyclic molecular solvents.

In addition to the above components, the present invention may optionally add a photochromic modulator (c). The photochromic modifier (c) selected for use in the present invention is a non-conjugated molecule, a partially conjugated molecule, a fully conjugated molecule, or a combination thereof as described above, which is soluble in a cyclic molecular solvent. The non-conjugated photochromic modifier is, for example, a metallocene-catalyzed cyclic olefin copolymer (m-COC); a partially conjugated photochromic modulator such as polystyrene (PS); fully conjugated color control The agent is, for example, biphenylene, naphthalene or the like. Table 2 lists the structure and characteristics of some photochromic modifiers.

By the degree of conjugation of the light color modifier molecules, the luminescent color can be further fine-tuned to achieve a more precise luminescent color, such as 550 nm, to improve luminous efficiency. Furthermore, the light color modifier can also be used to adjust the viscosity, so that the liquid phosphor can be adapted to various liquid processing processes. The viscosity of the liquid phosphor composition can range from 1 to 50,000 cps (at 25 ° C). In general, when the photochromic modifier (c) is not added, the liquid phosphor has a low viscosity and is suitable for a low viscosity (25 ° C, 1-20 cps) printing or infusion process. After adding the color control agent (c), the liquid phosphor can be adjusted to a coating process suitable for medium viscosity (25 ° C, 10-1000 cps), or a high viscosity (25 ° C, 500-50,000 cps) screen printing or dot Glue process.

In one embodiment, the liquid phosphor composition of the present invention absorbs a blue LED (440-460 nm) source and is excited to a second light color (eg, 530-700 nm) of higher efficiency and longer wavelength, this second The light color can be mixed with the original blue light to emit white light, or completely converted to the second light color, and emit green light, yellow light and red light.

Further, the liquid phosphor composition of the present invention may further comprise a hindered amine light stabilizer (d) as needed to increase its stability. Useful hindered amine light stabilizers include: bis(2,2,6,6-tetramethyl-4-acridinyl)decane diester, N-methyl-1-butylamine, or a combination of the foregoing.

The application of the liquid phosphor composition of the present invention will be described below with reference to Fig. 1. Fig. 1 is a schematic view showing a light-emitting device 100 according to an embodiment of the present invention. As shown in the figure, the light-emitting device 100 includes a substrate 200, such as a ceramic cup, on which a light-emitting unit 210 is disposed. The light emitting unit 210 may be various types of light emitting elements including, but not limited to, inorganic light emitting diodes, laser diodes, organic light emitting diodes, and the like. In a particular embodiment, the light emitting unit 210 is a GaN or GaInN blue LED wafer.

The liquid phosphor composition 220 of the present invention can be disposed on the light emitting unit 210 by a process such as printing, screen printing, coating, pouring or dispensing, directly as a fluorescent color conversion layer (without curing), and then The liquid phosphor composition 220 is sealed in the accommodating region 240 by a package member 230 such as glass or plastic. The liquid phosphor composition 220 can absorb the first light source generated by the light emitting unit 210 and completely convert it into a second light source. Alternatively, the first light source generated by the light emitting unit 210 may be mixed with the second light source to generate white light. In this way, a high-efficiency white light source or a composite light source of various light colors can be easily produced.

In addition, before the liquid phosphor composition 220 is disposed, it is preferred to form a transparent protective layer 250 on the light emitting unit 210 to isolate the light emitting unit and the liquid phosphor composition, thereby preventing the light emitting unit from being directly exposed to the liquid fluorescent agent. The composition is under 220, which affects the luminous efficacy. The transparent protective layer 250 is, for example, an epoxy resin, an acrylic resin, or a polyvinyl alcohol (PVA) resin, and has a thickness of, for example, about 0.1 to 1.0 μm.

Although the substrate 200 shown in FIG. 1 is a cup-shaped substrate, and the liquid phosphor composition 220 is sealed in the accommodating region 240 between the package member 230 and the substrate 200, the illuminating device of the present invention is not For example, the substrate may be a substrate of other notch type or a planar substrate, and the package component is not limited to the lens shape shown in the drawing, for example, the package component may be a transparent plate, and this The liquid phosphor composition is poured into the accommodating area of the transparent flat plate, and then the edge is packaged, and the blue light source is used to form a planar light source.

In addition, different sizes of bubbles or transparent incompatible liquids can be poured into the accommodating area to form a circular floating light-transmitting bubble/liquid bubble, and an artistic totem light source is formed with blue light or other backlights. The transparent incompatible liquid may be a liquid having a different viscosity from the liquid phosphor composition or a liquid which is immiscible with the liquid phosphor composition. Furthermore, the transparent incompatible liquid may also be a liquid phosphor composition having different emission wavelengths.

In summary, the liquid phosphor composition of the present invention can illuminate the wavelength of the photoexcitation light to the optimal illuminating position by the ratio of the conjugated molecules of the cyclic molecular solvent to the photochromic modifier to improve the luminescence efficiency, and only needs a liquid state. The process does not require any hardening process, so the process is relatively simple. Since the liquid phosphor composition of the present invention is a homogeneous phase, there is no problem of uneven dispersion of the phosphor powder. In a preferred embodiment, an illuminating source of ultra-high efficiency white LEDs of 135 lm/W @ 4358 K CCT (warm color temperature) or 98 lm/W @6452 K CCT (pure white color) can be achieved. And the color rendering (CRI) can also be composed of organic fluorescent molecules of the same derivative, which can exceed the inorganic LED (YAG+Blue LED: CRI=70) to achieve high color rendering white light with CRI=84.

[Examples] [Monomer m1 synthesis] M1: 9,9-dioctyl-2,7-dibromofluorene (9,9-dioctyl-2,7-dibromofluorene)

10 g of 2,7-dibromofluorene (Aldrich, 97%) were placed in a round bottom flask, and 175 ml of dimethyl hydrazine (DMSO; ACROS) was added, followed by 8 g of t-butanol. Potassium t-butoxide (Aldrich) was slowly added dropwise to 19 g of 1-bromooctane (Aldrich) in an addition funnel and reacted at 45 ° C for 24 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed with EtOAc EtOAc EtOAc EtOAc EtOAc. The gram was a needle-like crystalline solid with a yield of 77%. 1H-NMR (CDCl3, 400MHz): δ (ppm) 7.51 (d, 2H), 7.45 (d, 2H), 7.44 (dd, 2H), 1.91 (t, 4H), 1.22-1.05 (m, 24H), 0.83 (t, 6H).

[monomer m2]

M2: 9,10-Dibromoanthracene (CAS No. 523-27-3) was purchased directly from Aldrich Co., dissolved in toluene (Acros) and recrystallized and purified.

[Monomer m3 synthesis] M3: 4,7-Dibromo-benzothiadiazole

13.6 g of benzothiadiazole (CAS: 273-13-2, Aldrich) was weighed and dissolved in 100 ml of dichloromethane (Dichloromethane, CH ₂ Cl ₂ , Merck), and 60 ml of acetic acid (HOAc; Merck) was further added. After stirring at room temperature, 50 ml of acetic acid and 40 ml of bromine water (Br ₂ , Merck) were added to the addition tube, and the mixture was slowly dropped into the stirring solution. The reaction was carried out at room temperature overnight. After completion of the reaction, the mixture was filtered, and the collected solid was washed with diethyl ether and evaporated to dryness, and the solid was recrystallized from isopropyl alcohol (IPA, ACROS) to give the monomer m3 as white needle crystals. ¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.724 (s, 2H).

[Monomer m4 synthesis]

M4: dibromophenothazothiazole (4,7-Bis-(5-bromo-thiophen-2-yl)-benzo[1,2,5]thiadiazole)

1 g (3.4 mmole) of 4,7-dibromo-2,1,3-benzothiadiazole; m3, 3.06 g (8.2 mmole) of tributyltin (2-(tributylstannyl)thiophene; Aldrich And 0.0477 g (0.068 mmole) of Pd(PPh ₃ ) ₂ Cl ₂ (STREM) was dissolved in 25 ml of tetrahydrofuran (THF) and heated to reflux for three hours. The reaction was stopped by cooling, and the THF was drained. Purification by column chromatography gave 0.71 g of the product, 4,7-dithien-2-yl-2, 1,3-benzothiadiazole, yield 69%. Weigh 3 g of 4,7-dithien-2-yl-2,1,3-benzothiadiazole and dissolve it with 30 ml of CH ₂ Cl ₂ (Aldrich), then add 30 ml of acetic acid (ACROS). Stir at room temperature. Further, a mixture of 20 ml of acetic acid and 4 ml of bromine water (Br ₂ ; Merck) was slowly added dropwise, and the mixture was reacted at room temperature for 18 hours, and the precipitate was washed with water and reprecipitated with dichloromethane to give a monomer m4 as a dark red solid. ¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.987 (d, 4H, 4.0 Hz), 7.140 (d, 2H, 4 Hz).

[Monomer m5 synthesis]

M5: 1,4-Bisbromomethyl-2,3-dibutoxy benzene

In a 1000 ml Erlangor, 118.5 g of Morpholine (Aldrich), 41 g of formaldehyde (Merck) and 500 ml of Isopropyl alcohol (ACROS) were added and heated to 95 °C. An additional 50 g of catechol (TCI) was added and the reaction was carried out at 95 ° C for 2.5 hours. After adding 100 ml of ethyl acetate (Ethyl acetate; ACROS), the mixture was stirred at room temperature for 30 minutes, and the obtained solid was added to ethyl acetate (300 ml), and then the mixture was stirred to warm to 60 ° C, and then filtered, and washed with ethyl acetate to give solid DB1 (82 g) The yield was 58.6%.

56.5 g of DB1, ethanol (99.5%, Merck) 1000 ml were added to a 2000 ml Erlangor, and then 100 g of K ₂ CO ₃ (Aldrich) and 113 g of n-butyl bromide (Aldrich) were added, followed by heating to reflux. The temperature was reacted for 69 hours. The filtered filtrate was drained with a reduced pressure concentrator. After adding 500 ml of ethyl acetate, it was extracted with water, and the residue was dried over MgSO ₄ , filtered, and concentrated to give a brown liquid of 66.36 g (DB 2 ).

66.36 g of DB2, 210 ml of CH ₃ COOH (ACROS), 91 g of CH ₃ COONa (Aldrich) and 105 ml of acetic anhydride (Acetic anhydride; Merck) were placed in a 1000 ml two-necked reaction flask and heated to a temperature of 130 ° C for 89 hours. Cuiqu with ethyl acetate and water, then anhydrified on MgSO _4, filtered, and concentrated to give a brown liquid 65.24g (DB3). Further, 200 ml of HBr (33% in glacial acetic acid, Aldrich) was added and reacted at room temperature for 2.5 hours. The reaction solution Cuiqu ethyl acetate and water, then anhydrified on MgSO _4, filtered, and concentrated to give a brown liquid may be 64.4g. Decolorization with activated carbon and recrystallization of methanol gave m5 as a white solid. _{^{1 H NMR (400MHz, CDCl 3}} ): δ (ppm) 7.082 (s, 2H), 4.519 (s, 4H), 4.086 (t, 4H, 6.7Hz), 1.798 (m, 4H), 1.534 (m, 4H ), 1.002 (t, 6H, 7.3 Hz).

The following shows the process for preparing monomer m5:

[Monomer m6]

Monomer m6: dimethyl bromide (1,5-Bis(bromomethyl)-1-methoxy-4-(2-ethylhexyloxy)benzene, CAS No. 2096255-56-2) was purchased directly from Aldrich Co. and purified by isocrystallization of isobutanol (IPA, ACROS).

【芴-ray fluorescent polymer copolymerization】

The m1 monomer is used as the main molecule in combination with the m2~m4 monomer, and is copolymerized by Yamamoto coupling reaction to obtain green, yellow and red fluorescent polymers. The following describes the polymerization method of the yellow light phenanthrene copolymer polymer, and other green light and red light polymers are also copolymerized by the same method:

2. In the deoxygenation and dehydration state, 2.91 g (10.59 mmole) of bis-(1,5-cyclooctadiene) nickel (Bis (1,5-cyclooctadiene) Nickle, Ni(COD) ₂ ; Stream), 1.65 g 2, 2 - bipyridine (2,2-Bipyridyl, BPY; Aldrich ) 1.3ml (10.59mmole) cis, cis-1,5-cyclooctadiene (cis, cis-1,5-cyclooctadiene , COD; Aldrich) After heating 5 ml of anhydrous THF (Merk) in a 50 ml reaction flask to 80 ° C and stirring for 30 minutes, the monomer previously dissolved in anhydrous THF was added under a nitrogen atmosphere. The monomer type and ratio are: m1: m2: m3: m4 = 50 (2.75 g, 5 mmole): 32.4 (0.96 g, 3.24 mmole): 17.5 (0.58 g, 1.75 mmole): 0.1 (0.04 g, 0.1 mole), After two days of reaction at 80 ° C, 0.15 g (0.7 mmole) of 4-tert-butylbenzyl bromide (Aldrich) and 10 ml of anhydrous THF were added, and the reaction was continued for 24 hours. After completion of the reaction, the sample was poured into 1000 ml of THF, and stirred for 1 hour by adding 1 cc of hydrochloric acid, and the filtrate was obtained by filtration, and the obtained filtrate was subjected to alumina column chromatography to remove the metal catalyst. Reprecipitation was carried out with methanol, the filtered solid was washed with methanol, and the solvent was evaporated in vacuo to give an orange solid of about 0.8 g. GPC: Mw = 42K dalton, PDI = 2.7. Soluble in toluene solvent (0.0005 M), the UV absorption peak (UV-Vis, solution) was measured to be 434 nm, and the 450 nm photoexcitation light (PL, solution) peak was 525 nm.

The monomer copolymerization ratio is changed, and the green light and the red light fluorinated fluorescent polymer can also be obtained in the same polymerization step, and the structural formula and monomer ratio are as follows:

Red light fluorene polymer m:n:p:q=50:17.5:30:2.5

Yellow light fluorescein polymer m:n:p:q=50:17.5:32.4:0.1

Green light fluorescein polymer m:n:p:q=50:17.5:32.5:0

[Polystyrene (PPV) fluorescent polymer polymerization]

The above m5, m6 monomer is passed through a Gilch dehydrohalogenation condensation polymerization, and is copolymerized into green light, yellow light and orange light fluorescent polymer in different proportions.

3 g (7.4 mmole) of m5 monomer and 0.158 g (0.39 mmole) of m6 monomer were placed in a four-necked flask, thoroughly baked and sealed with N ₂ , poured into 300 ml of anhydrous THF, and stirred until dissolved in a clear colorless liquid. 60 ml of potassium t-butoxide (t-BuOK; Aldrich, conc. 1M in THF) was taken and poured into a four-necked flask. At this time, the solution became a yellowish color and was subjected to N ₂ reaction at room temperature for 24 hours (Gilch dehydrohalogenation condensation polymerization). Get a viscous orange-colored viscous liquid. The high-viscosity liquid was poured into an addition funnel, and slowly dropped into a methanol beaker to obtain a filiform orange-yellow colloid, which was filtered and placed in a bottle and vacuum-dried to obtain an orange fiber flake solid. The orange fiber solid was dissolved again in THF, and slowly dropped into a methanol beaker to obtain a colloid, which was filtered and placed in a bottle and vacuum dried to obtain a DB-MEH-PPV copolymer, which was an orange fiber sheet solid. . The weight average molecular weight (Mw) is about 770 K dalton, PDI = 4.2. Dissolved in toluene solvent (0.0005 M), UV-Vis absorption spectrum 467, 497 nm, with 450 nm photoexcitation spectrum (PL) 556 nm. The structural formula of the PPV copolymer is as follows, where a, b are the number of repeating units:

DB-PPV and MEH-PPV were also synthesized according to the same polymerization procedure, and the chemical structure is as follows, where n represents the number of repeating units:

[Example 1: Yellow light ray polymer liquid fluorescent agent]

The copolymerized yellow fluorene-based fluorescent polymer was dissolved in 100 parts by weight of a non-conjugated solvent (Methyl-Cyclohexane/Aldrich; Decahydronaphthalene/Aldrich) at a concentration of 0.05 parts by weight; dissolved in 100 parts by weight of a partially conjugated solvent at a concentration of 0.05 parts by weight. (Cyclohexane benzene/Aldrich); dissolved in 100 parts by weight of a fully conjugated solvent (Trimethyl Benzene/Aldrich; 1-methyl Naphthalene/Aldrich) at a concentration of 0.05 parts by weight, and then added 10 parts by weight of non-conjugated light a color regulator (m-COC/Topas 6015, Ticona) in solution; and a 10 part by weight concentration of a portion of the conjugated photochromic modulator (Polystyrene/80G, Chi Mei) in solution; and the addition of 10 parts by weight The conjugated molecule (Naphthalene/Aldrich) is in solution.

Refer to Table 3. The solution absorption (UV-Vis) spectrum was measured by JAS CO. V-530 UV-Vis absorption spectrometer, and the photoexcitation spectrum was measured by excitation at 450 nm in a FL4500/Hitachi fluorometer. Photoluminescence (PL) was measured. ). The results are shown in Table 3. It can be seen from the table that the yellow light fluorescent polymer can adjust its absorption and luminescence wavelength by the ratio of the conjugated molecules of the solvent and the cosolvt molecule.

[Example 2: Other light color liquid fluorescent agent]

Copolymerized green light and red fluorene-based fluorescent polymer, poly-p-styrene (PPV) fluorescent polymer, and coumarin 6 (Coumarin-6) purchased from Aldrich were dissolved in 0.05 parts by weight. Conjugated solvent (Methyl-Cyclohexane/Aldrich or THF/Acros); additionally dissolved in a fully conjugated solvent (Toluene/Acros; 1-methyl Naphthalene/Aldrich) at a concentration of 0.05 parts by weight; green and red fluorescene A part of the photopolymer portion was added with a concentration of a part of a conjugated photochromic modulator (Polystyrene/80G, Chi Mei) in a solution, and referred to Table 4. The absorption spectrum of the solution was measured by JASCO. V-530 UV-Vis absorption spectrometer, and the photoexcitation spectrum was measured by excitation at 450 nm in a FL4500/Hitachi fluorometer. The results are shown in Table 4. It can be seen from the table that the organic fluorescent material can adjust the absorption and luminescence wavelength by the ratio of the conjugated molecules in the solvent.

[Example 3: Production of white light, green light and red light emitting diode]

The yellow, green and red fluorene-based fluorescent polymers are dissolved in 100 parts by weight of TMB in a concentration of 0.02 parts by weight (yellow light), 0.5 parts by weight (green light), and 0.5 parts by weight (red light), respectively. Add 10 parts by weight of polystyrene (PS/80G Chi Mei), drop it directly onto the Cree GaN blue LED chip with polyvinyl alcohol protective film, place it in the integrating sphere / SphereOptics measurement system, and illuminate at 20 mA. The photoelectric efficiency, color temperature and CIE color coordinates were measured, and the results are shown in Table 4. The liquid fluorescent agent was dropped into a glass lens, and then capped on a Cree GaN blue LED chip, placed in an integrating sphere/SphereOptics measuring system, and its photoelectric efficiency was measured. The results are shown in Table 5.

[Embodiment 4: White light emitting diodes of different color temperatures]

The yellow light fluorene fluorescent polymer is dissolved in 100 parts by weight of 1-methylnaphthalene (1-MeNa) at different concentrations by weight, and 10 parts by weight of naphthalene (Aldrich) is added, and the liquid fluorescent agent is dropped into the glass lens. Inside, it is capped on the Cree GaN blue LED chip, placed in the integrating sphere / SphereOptics measurement system, lit with 20mA current, measuring its photoelectric efficiency, color temperature, CIE color coordinates and excitation light peak, the results are shown in Table 6. .

Table 6

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

100. . . Illuminating device

200. . . Substrate

210. . . Light unit

220. . . Liquid phosphor composition

230. . . Package component

240. . . Included area

250. . . The protective layer

Fig. 1 is a view showing a light-emitting device according to an embodiment of the present invention.

100. . . Illuminating device

200. . . Substrate

210. . . Light unit

220. . . Liquid phosphor composition

230. . . Package component

240. . . Included area

250. . . The protective layer

Claims (21)

A liquid phosphor composition comprising: (a) 0.001 to 2 parts by weight of a fluorescent material selected from a fluorescent polymer, a fluorescent dye, or a combination thereof, wherein the fluorescent polymer has the formula (I) ) structure: Wherein the Ar ₁ , Ar ₂ , and Ar ₃ systems are each independently selected from the group consisting of functional groups of the following formula (II): Wherein R ₁ to R ₁₂ are each independently hydrogen, an alcohol group, a linear or branched C _1-22 alkyl group, a linear or branched C _1-22 alkoxy group, ortho, meta or pair Alkylphenyl, or ortho, meta or para alkoxyphenyl, and m, n, p, q of formula (I) are the number of repeating units, and m/(m+n+ p+q) at least 10%, and wherein the fluorescent dye comprises: Coumarin 6 (Fouorescein), Acridine (Acridine), 4-Dicyanomethylene-2, 6-Dimethyl-4H-pyran (DCM; 4-(Dicyanomethylene)-2-methyl-6-[p-(dimethylamino)-styryl]-4H-pyran), Nitrostilbene, Nitrate Nitrobenzoxadiazole, Riboflavin, Rhodamine, or a combination thereof; and (b) 100 parts by weight of a cyclic molecular solvent having a boiling point of greater than 100 ° C, wherein The cyclic molecular solvent includes: Toluene, Xylene, Anisole, Phenetole, Tri-methyl benzene (TMB), Ethylbenzene, Propylbenzene, Cumene, Methylnaphthalene , Dimethylnaphthalene, Cyclohexylbenzene, Methylcyclohexane, Decahydronaphthalene, 1,2,3,4-tetrahydronaphthalene (1,2,3, 4-Tetrahydronaphthalene), or a combination of the foregoing. The liquid fluorescent agent composition according to claim 1, wherein the fluorescent polymer is a poly(p-phenylene vinylene) polymer of the formula (III). Wherein R ₁₃ to R ₁₅ are each independently a linear or branched C _1-22 alkyl group, an ortho, meta or para alkylphenyl group, or an ortho, meta or para alkoxy group. A phenyl group, and a, b are the number of repeating units. The liquid phosphor composition of claim 1, wherein the phosphor material has an ultraviolet-visible (UV-Vis) absorption spectrum at 440-470 nm. The liquid phosphor composition as described in claim 1, further comprising: (c) 1 to 50 parts by weight of a color control agent. The liquid phosphor composition according to claim 4, wherein the photochromic modifier comprises: a cyclic olefin copolymer (m-COC), polystyrene, biphenylene, naphthalene. (naphthalene), or a combination of the foregoing. The liquid phosphor composition of claim 1, wherein the liquid phosphor composition has a viscosity of from 1 to 50,000 cps at 25 °C. The liquid phosphor composition of claim 1, wherein the liquid phosphor composition has an emission wavelength of 530-700 nm. The liquid phosphor composition according to claim 1, further comprising: (d) 0.02-5 parts by weight of a hindered amine light stabilizer. The liquid fluorescent agent composition according to claim 8, wherein the hindered amine light stabilizer comprises: bis(2,2,6,6-tetramethyl-4-acridinyl)decyl diester, N-methyl-1-butylamine, or a combination of the foregoing. A light-emitting device comprising: a substrate; a light-emitting unit disposed on the substrate; the liquid phosphor according to any one of claims 1-9 a composition disposed on the light emitting unit; and a package component sealing the liquid phosphor composition in an accommodating region. The illuminating device of claim 10, wherein the illuminating unit is an inorganic light emitting diode, a laser diode, or an organic light emitting diode. The illuminating device of claim 10, wherein the illuminating unit is a GaN or GaInN blue light emitting diode chip. The illuminating device of claim 10, wherein the liquid phosphor composition is disposed in the accommodating area by inkjet, dispensing, screen printing, or infusion. The illuminating device of claim 10, wherein the liquid phosphor composition absorbs the first light source generated by the illuminating unit and converts it into a second light source. The illuminating device of claim 14, wherein the first light source and the second light source are mixed to generate white light. The light-emitting device of claim 10, further comprising a protective layer disposed on the light-emitting unit to isolate the light-emitting unit from the liquid phosphor composition. The illuminating device of claim 10, wherein the packaging component is a glass or a plastic, and the accommodating region is located between the packaging component and the substrate. The light-emitting device of claim 10, wherein the package component is a transparent plate, and the receiving area is located in the transparent plate. The illuminating device of claim 10, further comprising a bubble in the accommodating area. The illuminating device of claim 10, further comprising a transparent liquid in the accommodating region, the transparent liquid and the liquid fluorescer composition being immiscible or having different viscosities. The illuminating device of claim 10, wherein the accommodating region has a plurality of liquid luminescent agent compositions having different illuminating wavelengths.