TW201038710A - Liquid fluorescent composition and light emitting device - Google Patents

Abstract

The invention provides a liquid fluorescent composition, including at least (a) 0.001-2 parts by weight of a fluorescent material; and (b) 100 parts by weight of a cyclic solvent having a boiling point above 100 DEG C. The invention also provides a light emitting device containing the above liquid fluorescent composition.

Description

201038710 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a fluorescent agent' and in particular to a liquid fluorescent agent and its use. [Prior Art] There are two methods for manufacturing white light emitting diodes (LEDs): a blue light emitted from a blue LED chip (InGaN LED) to excite YAG: Ce3+ fluorescent powder emits yellow light and unabsorbed blue light. The white light is mixed, and the other is an ultraviolet (UV) LED chip (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 agent are mentioned in the prior art, for example, the Republic of China Patent 459403, the Republic of China Patent 565956, the US Patent No. 20040231554, the Japanese Patent JP2004_32691(), and the like. However, all of the above patents are composed of solid-state phosphors. The fluorescent materials are mixed into an unsaturated transparent tree, and a hardener or other accelerator is added to crosslink and harden the LED layer. SUMMARY OF THE INVENTION The present invention provides a liquid phosphor composition comprising: (a) 0.001-2 parts by weight of a phosphor material selected from a fluorescent polymer, a glory dye, or a combination thereof, and b) 100 parts by weight of a cyclic molecular solvent having a boiling point of 3 201038710 at 100. . . The present invention further provides a light-emitting device comprising: a substrate; a light-emitting unit disposed on the substrate; the liquid phosphor composition described above disposed on the light-emitting unit 70; and, the package component, the liquid firefly The photoactive composition is sealed in an accommodating area. The above and other objects, features, and advantages of the present invention will become more apparent from the description of the preferred embodiments of the invention. The liquid phosphor composition and its use are different from the solid phosphors formed by the curing of the phosphor and the binder resin in the prior art. In the present invention, the soluble fluorescent material is dissolved in the cyclic molecular ionic agent to form a homogeneous liquid fluorescent agent that modulates the optical excitation wavelength to the optimum luminescent position through a common ratio of the solvent molecules. In addition, a light color control agent can be selectively added (〇pti〇nally) to further reduce the luminescent color 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. It can easily produce high-efficiency white light source or composite light source of various light colors. The composition of the liquid phosphor will be detailed below. The liquid phosphor composition of the present invention mainly comprises: (a) 0.001-2 parts by weight of a fluorescent material, particularly preferably 0 〇M by weight; ‘201038710 (b) 100 parts by weight of a cyclic molecular solvent. In addition, it may be optionally added: (c) 1-50 parts by weight of the color control agent, especially 3-40 parts by weight; (d) 0.02-5 parts by weight of the hindered amine light stabilizer, especially It is preferably 0.5 to 2 parts by weight. The aforementioned glare 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, a core molecule, and a high-fluorescence aromatic molecular copolymer thereof. Adjust the fluorescent color and increase the fluorescent efficiency. The 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 group, naphthyl group, heterocyclic group, polycyclic aromatic group and polycyclic heterocyclic group having at least one conjugate group. The Ar!, Ar2, and Ar3 systems of the formula (I) are each independently, and may be selected from the group consisting of the following formula (II): 201038710

Formula (π) The above-mentioned fluorescent polymer formula (I) and Ri to R12 of the formula (π) are each independently nitrogen, and the Ci_22 is a direct bond or a bond of a Ci_22 alkyl group or a bond Ci_22 An alkoxy group, an ortho, meta or para-alkylphenyl group, or an ortho, meta or para-alkoxyphenyl group, and m, n, p, q of the formula (1) are repeating units number. Wherein m of formula (I) accounts for at least 10% of all repeating monomer ratios (m/(m+n+p+q)), preferably 50% or more, but one or two of η, p, q may be 0 (indicating that this repeating unit is not included). Further, the fluorescent polymer may be a poly(phenylene vinylene) or PPV-based polymer represented by the following formula (ΠΙ):

6 201038710 Formula _ where Rl3~Rl5 are independent of the Ci-22, the ortho, meta or para-alkyl phenyl, ortho, meta or para-alkoxy A phenyl group, and a, b are the number of repeating units. Based on the demand for different luminescent colors, a can be 〇 (eg, MEH-PPV for orange) or b can be 〇 (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%. Take 0. In addition to glory polymer, the fluorescent material (a) used in the present invention may also be a fluorescent dye such as Coumarin 6 , Fluorescein, Acridine, 4-II. Cyanomethylene-2,6-dimethyl-4H-pyran (DCM; 4-(Dicyanomethylene)-2-methyl-6-[p-(dimethylamino)-styryl]-4H-pyran), nitro Styrene (Nitrostilbene), nitrobenzoxazole (Nitr〇benz〇xadiaz〇le), Riboflavin, Rh〇damine, or a combination of the foregoing. In one embodiment, the ultraviolet light-visible (uv_vis) absorption spectrum of the phosphor material (a) is located at 440-470 nm to absorb the light source of the blue LED. In other embodiments, the phosphor material (a) may have other absorption wavelengths for application to other sources of light. The present invention utilizes the above-mentioned glory material as a fluorescent luminescent material, which is dissolved in a spirulina with a cyclic molecule, and the cyclic molecular solvent, such as having a light-weight structure, resonates with the co-governing molecule in the fluorescent substance, thereby Reduce the energy gap of the phosphor material 201038710. Therefore, by controlling the conjugate of the % molecular solvent of the aid of the celestial system, 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, including: ## conjugated solvent, such as Methylcyclohexane, Decahydr〇naphthalene: part of the total Yoke solvent, such as cyclohexylbenzene ((:)^1〇116巧11^11form 1]^, 1,2,3,4_tetrahydronaphthalene (l,2,3,4-Tetrahydronaphthalene), anisole (Anisole), Phenetole, Ethylbenzene, Propylbenzene, Cumene; fully conjugated solvents, such as Toluene, Xylene, Tri-methyl benzene (TMB), Methylnaphthalene, Dimethylnaphthalene or a combination of the foregoing. Table 1 lists the structure and properties of a partially cyclic molecular solvent. Table 1 Conjugated chains Long solvent bp ( °C ) nd non-common solvent Methylcyclohexane 101 1.422 〇'~' Decahydronaphthalene 188 1.475 ❹ 8 201038710 Ο Partial conjugate solvent 239 1.526 \-/ Tetrahydronaphthalene 206 1.541 6 _ 153.7 1.5174 Fully conjugate solvent Toluene 111 1.4967 ( V o-Xylene 144 1.505 1 Tri-methyl Benzene 168 1.504 Q- 1 -Methylnaphthalene 242 1.615 In addition to the above components, the present invention may optionally add a photochromic modifier (C). The photochromic modulator (C) selected for use in the present invention is soluble in a cyclic molecular solvent. a conjugated molecule, a partial co-molecular molecule, a total of a total of molecules, or a combination thereof. A non-conjugated photochromic modulator is, for example, a metallocene-catalyzed cyclic olefin copolymer (m-COC); The agent is, for example, polystyrene (PS); the total color of the light color control agent is, for example, biphenylene, naphthalene, etc. Table 2 lists the structure and characteristics of the partial light color control 201038710 agent. .

Table 2 Total chain length light color modifier mp or Tg ( °C ) nd Non-common molecule m-COC Tg = 161.4 (Topas 6015 ) 1.52 (Topas 6015) Partially conjugated molecule Μ PS Tg = 94 ( 80G / CM ) 1.59 (80G / CM) Total molecular weight g Biphenylene mp = 70 — 8 Naphthalene mp = 81 1.582 By adjusting the conjugate degree of the light color modifier molecules, the luminescent color can be further fine-tuned to achieve more accurate luminescent color. For example, 550 nm to improve luminous efficiency. Furthermore, the color control agent can be used to adjust the viscosity at the same time, so that the liquid fluorescent agent can be adapted to various liquid processing processes. The liquid phosphor composition can have a viscosity of from 1 to 50,000 cps (at 25 ° C). In general, when the color control agent is not added (〇>, the viscosity of the liquid phosphor is low, suitable for low-viscosity (25 ° C, l-20 cps) printing or infusion process. Adding a color control agent ( c) After the liquid 10 201038710 state phosphor can be adjusted to a medium viscosity (25 ° C, 10-1000 cps) coating process, or a high viscosity (25 ° C, 500-50, 〇〇〇 CpS) network Printing or dispensing process. In one embodiment, the liquid phosphor composition of the present invention absorbs a blue LED (440-460 nm) source and is excited to emit a second light color of higher efficiency and longer wavelength (eg, 530- 700nm), the second 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 fluorescent agent composition of the present invention A hindered amine light stabilizer (d) may be further included as needed to increase its stability. The hindered amine light stabilizer may be used to include: bis(2,2,6,6-tetramethyl-4-anthracene) hydrazine. Diester, N-fluorenyl-I-butylamine, or a combination thereof. The application of the liquid phosphor composition of the present invention will be described below with reference to Fig. 1. Fig. 1 shows an embodiment of the present invention. A schematic diagram of a light-emitting device 1A. As shown in the figure, the light-emitting device 1A includes a substrate 2, for example, a ceramic cup bowl, on which a light-emitting unit 210 is disposed. The light-emitting unit 210 can be various types of light-emitting devices. The elements 'including but not limited to: inorganic light emitting diodes, laser diodes, organic light emitting diodes, etc. In a particular embodiment, the light emitting unit 210 is a GaN or GalnN blue LED chip. The liquid phosphor composition 220 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 package component 230, such as glass or plastic, seals the liquid phosphor composition 220 in the accommodating area 240. The liquid phosphor composition 220 can absorb the first light source generated by the light-emitting unit 21, and completely convert it into a The second light source, or *, can mix the first light source generated by the *201038710 light-emitting unit 210 with the second light source to generate white light. Thus, a high-efficiency white light source or a composite light source of various light colors can be simply fabricated. 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 from the liquid phosphor composition to prevent the light emitting unit from being directly exposed to the liquid fluorescent agent. The composition 220 is used to affect 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 (μηη). The substrate 200 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. However, the illuminating device of the present invention is not limited thereto. 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 匣, and at this time, The liquid phosphor composition is poured into the accommodating area of the transparent plate, and then the edge is packaged, and the blue light source is used to form a planar light source. ~ In addition, in the valley area, different sizes of bubbles or transparent liquids can be filled to form circular floating light bubbles/bubbles, which are combined with blue light or other backlights to form an artistic totem light source. The transparent incompatible liquid may be a liquid having a different viscosity from the liquid fluorescent agent composition or a liquid which is immiscible with the liquid fluorescent material. Furthermore, the transparent incompatible liquid may also have different illumination. The liquid crystal composition of the wavelength. 12 201038710 As described above, the liquid fluorescent ageing matter of the present invention can adjust the wavelength of the photoexcitation light to the beam by the ratio of the molecular weight of the ring-and-light-color S-control agent. Good light-emitting position to improve luminous efficiency, and only need one liquid process and no hardening process, so the process is relatively simple. Because the liquid core glory composition of the present invention is homogeneous-phase, there is no problem of fluorescent powder dispersion* In the 乂 乂 Λ Λ ' ' 135 135 135 135 lm / w @ 4κ [π (warm color temperature) or 98 lm / W @6452K CCT (pure white color) super high efficiency white LED light source. The color rendering property ((10)) can also be formulated by organic fluorescent molecules of the same derivative, and can exceed the inorganic LED (yag + Blue LED: CRI = 70) to achieve high color rendering white light of CRI = 84. [Examples] Ml synthesis] ml :9,9-dioctine -2,7-dibromofluorene (9,9-dioctyl-2,7-dibromofluorene) Ο ^8^17 〇8*^17 ml Take 10 g of 2,7-dibromoindole (2,7-dibr〇m 〇fluorene; Aldrich, 97%) was placed in a round bottom bottle, 175 ml of dimethyl hydrazine (DMSO; ACROS) was added, and 8 g of potassium t-butoxide (Aldrich) was added thereto. The addition funnel was slowly added dropwise to 19 g of 1-octyl bromide (octrybromide; Aldrich) for 24 hours at 45 ° C. After completion of the reaction, it was diluted with ethyl acetate, washed three times with 1 mL of water, dried and concentrated under reduced pressure. That is, 15 g of a white solid was obtained, which was purified by recrystallization from isopropanol (IPA, ACROS) 15 201038710 to give a total of 13.25 g of a monomeric solid, a needle-like crystalline solid, yield 77%. 1H-NMR (CDC13, 400 MHz) : 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 (9, i〇_Dibromoanthracene, CAS No. 523-27-3) was purchased directly from Aldrich Co., and dissolved in toluene (Acros). The freezer is recrystallized and purified.

M2 m3 / odorous nitrogen stagnation (4,7-Dibromo-benzothiadiazole) [monomer m3 synthesis]

M3 Weigh 13.6g of this and diazane nitrogen CAS: 273 13 2 Aldrich) and i〇〇mi dichloromethane (Dichl〇r〇methane, CHsCI2' M ck) search and dissolve and add 6〇mi acetic acid ( H〇ac; Merck) Add 50ml of acetic acid and 40ml of bromine water (Br2, Merck) to the feeding tube. The reaction was allowed to warm overnight. After the end of the reaction, the mixture was filtered. The collected solid was washed with diethyl ether and dried, and the solid was recrystallized from isopropyl 14 201038710 alcohol (IPA, ACROS) to give the original m3 ' as white needle crystals. ]H NMR (400 MHz, CDC13): δ (ppm) 7.724 (s, 2H). [monomer m4 synthesis] m4: dibromophene benzothiadiazolidine (4,7-Bis-(5-bromo-thiophen-2-yl)-benzo[l,2,5]thiadiazole)

1 g (3.4 111111〇16) Erqian benzodiazepine 11 sitting (4,7-£1丨1)1:〇111〇-2,1,3-benzothiadiazole;m3), 3.06 g (8.2 mmole) Tributyltin (2_(tributylstannyl)thiophene; Aldrich) and 0.0477 g (0.068 mmole) of Pd(PPh3)2Cl2 (STREM) were 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. The product was purified by column chromatography to give the desired product, bis benzothiadiazole (4,7-dithien.sup.-sup.-yl-2,1,3-benzothiadiazole), 0.71 g, yield 69%. ® Weigh 3 g of V-dithien-l-ylAU-benzothiadiazole and dissolve it with 30 ml of CH2C12 (Aldrich), and add 30 ml of acetic acid (ACROS) and stir at room temperature. Further, a mixture of 20 ml of acetic acid and 4 ml of bromine water (Br2; 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 obtain a monomer m4 as a dark red solid. 1H NMR (400 MHz, CDC13): δ (ppm) 7.787 (Mountain 4H, 4.0 Hz), 7.140 (d, 2H, 4 Hz). [Monomer m5 synthesis] 15 201038710 1115: dimethyl > odor 2,3-bisbutoxybenzene (1,4-3151) 1'〇111〇11161:11丫1-2,3-dibutoxy benzene) In a 1000 ml Erlangor, add 118.5 g of Morpholine (Aldrich), 41 g of decanoic acid (formaldehyde, Merck) and 500 ml.

50 g of catechol (TCI) was added and reacted at 95 ° C for 2.5 hours. Add l 〇〇ml ethyl acetate (Ethyl acetate; ACROS) and stir at room temperature for 3 〇 minutes. Add the solid and add 300 ml of ethyl acetate to 60 ° C to mix, cool down and filter with ethyl acetate. Rinse to give a solid DB1 (82 g). 56.5 g of DB1, ethanol (99.5%, Merck) 1000 ml was added to a 2000 ml Erlangor, and then 100 g of K2C03 (Aldrich) and 113 g of n-butyl bromide (Aldrich) were added, and then heated to reflux temperature. 69 hours. The filtrate was filtered, and the solvent was evaporated to dryness, and then evaporated to ethyl ether. EtOAc (EtOAc) 66.36g of DB2, 210 ml CH3COOH (ACROS), 91g of CH3COONa (Aldrich) and 105 ml of acetic acid gf (Acetic anhydride; Merck) were placed in a l〇〇〇ml two-necked reaction flask and heated to a temperature of i3〇°c. 89 hours. It was extracted with ethyl acetate and water, then dried over MgSO 4 , filtered and concentrated to give a brown liquid, 65.24 g (DB3). Further, 200 ml of HBr (33% m glacial acetic acid, Aldrich) was added and reacted at room temperature for 2.5 hours. Reaction 16 201038710 The liquid was quenched with water for acetic acid, and then dehydrated, transitioned and concentrated with MgS 4 to obtain 64.4 g of a brown liquid. Decolorization with activated carbon and recrystallization of methanol gave m5 as a white solid. NMR ( 400 MHz, CDC13) : δ (ppm ) 7.082 ( s, 2H ) , 4.519 ( s, 4H ) , 4.086 ( t, 4H, 6.7 Hz ), 1.798 (m, 4H), 1.534 ( m, 4H) , 1.002 ( t, 6H, 7.3 Hz). The following shows the process for preparing monomer m5:

Ch2o

Ο

QHgBr K2CO3, EtOH ΌΗ

DB1 DB2

^ΧΤί:: ί:^Χ·〇〇4Η9

^γί?ί^ν"〇〇4Η9

Br

HBr/AcOH Α〇2〇 ->

AcOH

AcNa

DB2 OAc

Br m5 DB3 [monomer m6] monomer m6: dimethyl bromide (1-methoxy-4-(2ethylhexyloxy))benzene (2,5-Bis(bromomethyl)-l-methoxy-4- (2-ethylhexyloxy) benzene, CAS No. 2096255-56-2) was purchased directly from Aldrich Co. and purified by recrystallization from 17 201038710 isobutanol (IPA, ACROS).

[芴-ray fluorescent polymer copolymerization] The m2 monomer is used as the main molecule in combination with m2~m4 monomer, and is copolymerized by 0 Yamamoto light reaction to obtain green, yellow and red fluorescent molecules. 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: in the oxygen removal and water removal state, 2.91 g (10.59 mmole) of double-(1,5- Bis (1,5-cyclooctadiene) Nickle, Ni(COD)2; Stream), 1.65g, 2,2-Bipyridyl, BPY; Aldrich 1.3 ml (10.59 mmole) , cis-1,5-cyclooctadiene (cis, cis-l, 5_cyclooctadiene, COD; Aldrich), 5 ml of anhydrous THF O (Merk) was heated to 80 ° C in a 50 ml reaction flask and stirred for 30 minutes. The monomer previously dissolved in anhydrous THF was added under a nitrogen atmosphere. The monomer type and ratio are: ml : 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 reacting at 80 ° C for two days, ruthenium 15 g (0.7 mm 〇le) 4-tert-butylbenzyl bromide (Aldrich) and 1 ml of anhydrous THF were added, and the reaction was continued for 24 hours. After the 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 gold. 18 201038710 is a catalyst. Reprecipitation was carried out with decyl alcohol, and the filtered solid was washed with decyl alcohol, and the residual solvent was removed by vacuum to give an orange solid of about 0.8 g, yield of about 40%. GPC: Mw = 42K dalton, PDI = 2.7. The UV absorption peak (UV_Vis, s〇luti〇n) was determined to be 434 nm in a toluene solvent (0.0005 M), and the wavelength of the 450 nm photoexcitation (PL, solution) was 525 nm. By changing the monomer copolymerization ratio, the same polymerization step can also obtain green light and red fluorene-based fluorescent polymer. The structural formula and monomer ratio are as follows:

Red fluorene-based fluorescent polymer m: n: p: q = 50 : 17.5 : 30 : 2.5 Yellow light fluorene polymer m : n : p : q = 50 : 17.5 : 32.4 : 0.1 Green fluorite fluorescence Polymer m : n : p : q = 50 : 17.5 : 32.5 : 0 [Polystyrene (PPV) fluorescent polymer polymerization] Dehydrohalogenation condensation by Gilch dehydrohalogenation condensation reaction from the above m5, m6 monomer Polymerization), which is copolymerized into green, yellow and orange fluorescent polymers in different proportions. 3 g (7.4 mmole) of m5 monomer and 〇.l58g (0.39 mmole) of m6 monomer were placed in a four-necked flask, thoroughly baked and sealed with n2, poured into 300 ml of anhydrous THF, and stirred until dissolved in a clear colorless liquid. 60 ml of tert-butanol unloading (t-BuOK; Aldrich, conc.lM in THF) was injected into the four-necked flask, and the solution was turned into a yellowish color at room temperature and charged with N2 for 24 hours at room temperature (Gilch dehydrohalogenation condensation polymerization). Get the belt 19 201038710 Fluorescent orange viscous liquid. The high-viscosity liquid was poured into an addition funnel, and slowly dropped into a methanol beaker to obtain a filamentous orange-yellow gel, which was filtered and placed in a bottle and vacuum-dried to obtain an orange fiber sheet-like solid. The orange fiber solid was dissolved again in THF, and slowly dropped into a decyl alcohol 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. Soluble in benzene solvent (〇·〇〇〇5Μ), UV-Vis absorption spectrum 467, 497 nm, 450 nm light excitation spectrum (PL) 556 nm.结构 The structural formula of PPV copolymer is as follows, where a and b are the number of repeating units:

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

DB-PPV

MEH-PPV [Example 1: Yellow light-based polymer liquid fluorescent agent] The copolymerized yellow light-based fluorescent polymer was dissolved in a concentration of 0.05 parts by weight * 20 201038710 in 100 parts by weight of a non-conjugated solvent (Methyl-Cyclohexane / Aldrich; In Decahydronaphthalene / Aldrich); dissolved in 100 parts by weight of a part of a total solvent (Cyclohexane benzene / Aldrich) at a concentration of 0.05 parts by weight; dissolved in 100 parts by weight of a fully conjugated solvent at a concentration of 0.05 parts by weight (Trimethyl Benzene / Aldrich; 1- In methyl naphthalene / Aldrich), 10 parts by weight of a non-conjugated color modifier (m-COC / Topas 6015, Ticona) is added to the solution; and 10 parts by weight of the total color of the unit is added. A regulator (Polystyrene/80G, ° Chi Mei) was added to the solution; and 10 parts by weight of a fully conjugated molecule (Naphthalene / Aldrich) was added to the 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. PL). 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 to the co-solvent molecule. 3 Table 3 Light color modifier (10 parts by weight) Fluorescent material (0.05 parts by weight) Cyclic molecular solvent (100 parts by weight) UV (nm) PL (nm) Ring-difficult copolymer 1-methylnaphthalene - 450nm Excitation does not detect the cyclic olefin copolymer yellow fluoranthene fluorescent polymer fluorenylcyclohexane 435 529.4 cyclic olefin copolymer yellow fluorene fluorescent polymer decahydronaphthalene 437 535.0 hydrazine olefin copolymer yellow fluorene fluorescent polymer cyclohexylbenzene 450 540.2 21 201038710 Ring-dilute copolymer yellow light fluorene-fluorescent south molecule 1-mercapto-naphthalene 451 543.0 polystyrene yellow light-based fluorescent polymer tridecylbenzene 449 542.8 polystyrene yellow light fluorene polymer cyclohexyl Stupid 449 541.3 polystyrene yellow light ray light polymer 1-methylnaphthalene 452 549.8 naphthalene-1-nonylnaphthalene - 450nm excitation can not detect naphthalene yellow light fluorescein southern molecular methylcyclohexane 446 537.6 naphthalene yellow light Miao fluorescent polymer decahydronaphthalene 450 537.6 naphthalene yellow light fluorene polymer cyclohexylbenzene 449 541.8 naphthalene yellow light fluorescens fluorescent polymer 1-mercapto naphthalene 456 552.8 — yellow light fluorene polymer 1-methyl 453 553.6 [Example 2: Other light color liquid fluorescent agent] Copolymerized green light and red light fluorene-based fluorescent polymer, poly-p-styrene (PPV) fluorescent polymer, and coumarin purchased from Aldrich 6 〇 (Coumarin-6), dissolved in a non-conjugated solvent (Methyl-Cyclohexane/Aldrich or THF /Acros) at a concentration of 5 parts by weight; additionally dissolved in a total solvent at a concentration of 0.05 parts by weight (Toluene/ Acros; 1-methyl Naphthalene / Aldrich); green light and red fluorene fluorescent polymer part of the sample added 10 parts by weight of a part of the conjugate color control agent (Polystyrene / 80G, Chi Mei) in solution, reference table 4. The absorption spectrum of the solution 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. The results are shown in Table 4. It can be seen from the table that there is a 201038710 machine fluorescent material that can adjust the absorption and luminescence wavelength by the ratio of conjugated molecules in the solvent. Table 4 Light color modifier (10wt%) Fluorescent material (0.05wt%) Cyclic molecular solvent UV (nm) PL (nm) - Green fluorene fluorescent polymer methylcyclohexane 433 524 polystyrene green Photoluminescence fluorescent polymer toluene 437 533.4 — Green fluorene fluorescent polymer 1-mercaptophthalene 455 543 — Red fluorene fluorescent polymer MeCHex 438 529 polystyrene red fluorene fluorescent polymer toluene 444 532.4, 625.4 — Red light fluorene fluorescent polymer 1-methylnaphthalene 455 625.4 DB-PPV methyl 445 524 — DB-PPV 1-methylnaphthalene 447 534.6 MEH-PPV Toluene 495 572 — MEH-PPV 1- Mercaptophthalene 500 585 - Coumarin 6 Tetrahydrofuran 460 490 - Coumarin 6 1-decylnaphthalene 465 536 [Example 3: Production of white, green and red light emitting diodes] Yellow light, green light and The red fluorene-based fluorescent polymer is 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), 0.5 parts by weight (red light), and 10 parts by weight of polystyrene is added. » - * · (PS/80G Chi Mei), drop it directly on the 23 with a protective film of polyvinyl alcohol 201038710

The Cree GaN blue LED chip was placed in the integrating sphere/SphereOptics measurement system to illuminate at 20 mA, and its photoelectric efficiency, color temperature and CIE color coordinates were measured. The results are shown in Table 4. The liquid phosphor was then dropped into a glass lens, and then capped on a Cree GaN blue LED chip, placed in an integrating sphere/SphereOptics measurement system, and its photoelectric efficiency was measured. The results are shown in Table 5. Table 5 ❹ 1(A) V CCT&CIE lm Test glass lens package directly on the wafer Clm/W) 0.02 2.716 4358 K (warm white) 6.806 125.3 135 0.02 2.714 CIE = 0.36, 0.59 (Green) 9.2931 172 184 0.02 2.716 CIE = 0.56, 0.32 (Red) 1.037 19.1 ·' - 20.6 〇 [Example 4: White light-emitting diodes of different color temperatures] The yellow light-emitting fluorescent polymer is dissolved in a weight of 1 part by weight in different weight fractions. In a portion of 1-nonylnaphthalene (l-MeNa), and adding 1 part by weight of naphthalene (Aldrich), the liquid fluorescent agent is dropped onto the broken glass (5) secret blue coffee wafer, placed in the integrating sphere / Sphere; In the cs measurement system, the current is illuminated at 20 mA, and the photoelectric efficiency, color temperature, CIE color coordinates and excitation light peak are measured. The results are shown in Table 6. 24 201038710 Fluorescent polymer concentration (parts by weight) Luminous flux (4) Luminous efficiency (lm/W) Color coordinates (C positive x, y) Color temperature (CCT) Excitation light peak (nm) 0.005 5.54 100.36 0.315, 0.41 9319 540 0.0063 6.19 112.14 0.312, 0.395 6201 540 0.0125 6.84 123.9 0.355, 0.48 5035 540 0.025 7.1 128.6 0.406, 0.564 4359 540 0.05 6.94 125.7 0.421, 0.563 4136 542 〇 Although the invention has been disclosed above in several preferred embodiments, it is not intended to be limiting In the present invention, any one of ordinary skill in the art can make any changes and modifications 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. Prevail. ❹ 25 201038710 [Simplified description of the drawings] Fig. 1 is a view showing a light-emitting device according to an embodiment of the present invention. [Description of main component symbols] 100 to light-emitting device 200 to substrate 210 to light-emitting unit 220 to liquid phosphor composition 230 to package member 240 to accommodation area 250 to protective layer 26

Claims (1)

201038710 VII. Patent Application Range: 1. A liquid phosphor composition comprising: (a) 0.001-2 parts by weight of a fluorescent material selected from a fluorescent polymer, a fluorescent dye, or a combination thereof; (b) 100 parts by weight of a cyclic molecular solvent having a boiling point greater than that of ruthenium (9). 2. The liquid phosphor composition according to claim 2, wherein the fluorescent polymer has the structure of the formula (1): Ri, R1 〇 where Ar, and the group of the formula (I), the group of t, Al" are independently selected from the following formula (Π) formula 27 (II) 201038710 The center ~1112 is independent of hydrogen, alcohol, linear or branched C] _22 unified base, direct bond or branch of the alkoxy 'ortho, meta or para An alkylphenyl group, or an ortho, meta or para alkoxyphenyl group, and m, n, p, q of the formula (I) are the number of repeating units, and m/(m+n+p+ q) At least 10% or more. 3. The liquid phosphor composition according to claim 1, wherein the fluorescent polymer is a poly(p-phenylenevinylene) polymer of the formula (III). Wherein R13 to Rl5 are each independently a linear or branched CU2 alkyl group, an ortho, meta or para-alkylphenyl group, or an ortho, meta or para-alkal alkoxy group; A phenyl group, and a, b are the number of repeating units. 4. The liquid phosphor composition of claim 1, wherein the fluorescent dye comprises: Coumarin 6 , Fluorescein, Acridine, 4 Dicyanomethylene-2,6-dimethyl-4H-indole (DCM; 4-(Dicyanomethylene)-2-methyl-6-[p-(dimethylamino)-styryl]-4H-pyran) Nitrostilbene, Nitrobenzoxadiazole, Riboflavin, Rhodamine, or a combination thereof. * · · 5. The liquid phosphor composition as described in claim 1, 28 201038710 wherein the ultraviolet-visible (UV-Vis) absorption spectrum of the phosphor material is at 440-470 nm. 6. The liquid phosphor composition of claim 1, wherein the cyclic molecular solvent comprises: a non-conjugated solvent, a partially conjugated solvent, a total co-solvent, or a combination thereof. 7. The liquid phosphor composition according to claim 1, wherein the cyclic molecular solvent comprises: 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-butyl 61^117 ( 1!*〇11&卩111:1^161^), or a combination thereof. 8. The liquid phosphor composition according to claim 1, ❹ further comprising: (c) 1-50 by weight The liquid coloring agent composition according to claim 8, wherein the light coloring agent comprises: a non-conjugated molecule, a partially conjugated molecule, a total of a total of molecules, or 10. The liquid phosphor composition of claim 8, wherein the color control agent package : a cyclic olefin copolymer (m-COC), polystyrene, biphenylene, naphthalene, or a combination thereof. 11. Liquid fluorinated as described in claim 1 The liquid composition, wherein the liquid phosphor composition has a viscosity of from 1 to 50,000 cps at 25 ° C. 12. The liquid phosphor composition of claim 1, wherein the liquid The phosphor composition has an emission wavelength of 530 to 700 nm. 13. The liquid phosphor composition according to claim 1, further comprising: (d) 0.02 to 5 parts by weight of a hindered amine light stabilizer. The liquid phosphor composition as claimed in claim 1, wherein the hindered amine light stabilizer comprises: bis(2,2,6,6-tetramethyl-4-base) bismuth An ester, N-methyl-1-butamine, or a combination thereof. 15. A light-emitting device comprising: a substrate; an illumination unit disposed on the substrate; The liquid phosphor composition according to any one of the preceding claims, wherein the liquid phosphor composition is disposed on the light emitting unit; and a package component The phosphor composition is sealed in a accommodating region. The illuminating device according to claim 15, wherein the early element is an inorganic light emitting diode, a laser diode, or an organic Luminescence 2. The illumination unit of the illumination device according to claim 15 is a GaN or GalnN blue light emitting diode chip. For example, the illuminating device described in claim 15 of the patent application, wherein the 兮=^ composition is inkjet, dispensed, screen printed, placed in the accommodating area. 々 ° ° 19 19 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯 鸯20. The illuminating device of claim 19, wherein the first light source and the second light source are mixed to produce white light. 21. The illuminating device of claim 15, further comprising a protective layer disposed on the illuminating unit to isolate the illuminating unit from the liquid luminescent agent composition. The illuminating device of claim 15, wherein the package component is a glass or a plastic, and the accommodating region is located between the package component 〇 and the substrate. 23. The illuminating device of claim 15, wherein the package component is a transparent plate and the receiving area is located in the transparent plate. 24. The illuminating device of claim 15, further comprising a bubble in the accommodating area. 25. The illuminating device of claim 15, further comprising a transparent liquid in the accommodating region, the transparent liquid being immiscible with the liquid fluorescer ® composition or having a different viscosity. 26. The illuminating device of claim 15, wherein the accommodating region has a plurality of liquid phosphor compositions of different illuminating wavelengths. 3Γ