Luminescent rare earth element compound and dichroic phosphor composition containing same

Abstract

The present invention relates to a luminescent rare earth compound and dichroism fluorescent composition thereof, and more particularly, the luminescent rare earth compound is a luminescent rare earth compound excited by shortwave UV (Ultra-Violet). The luminescent rare earth compound and/or products applied with the luminescent rare earth compound according to the present invention can emit strong red and green colors by being excited at 240-330 nm range of wavelengths, while not being excited at 360-380 nm range of wavelengths, and showing no colors under visible light. Furthermore, the compound may be variably utilized to printed materials and plastic mold products because of possessing high heat resistance, high light resistance and high dispersibility of medium light. In addition, compositions emitting respectively different colors at mutually different wavelength ranges can be provided by mixing the luminescent rare earth compound according to the present invention with other excited luminescent compounds.

Claims

1. A luminescent rare earth compound consisting of: Eu.sub.0.6Y.sub.0.4(Benzoic acid).sub.3, or Eu.sub.0.5Y.sub.0.5(1,2,4,5-Benzene-tetracarboxylic acid).sub.0.75.

2. The luminescent rare earth compound of claim 1, wherein the compound is not excited at a wavelength of 360-380 nm range and is excited at a wavelength of 240-330 nm range.

3. The luminescent rare earth compound of claim 1, wherein the compound emits red and green colors.

4. A dichroism fluorescent composition comprising: a luminescent rare earth compound comprising Eu.sub.0.6Y.sub.0.4(Benzoic acid).sub.3, Eu.sub.0.2Y.sub.0.8(1,3,5-Benzene-tricarboxylic acid).sub.1, Eu.sub.0.5Y.sub.0.5(1,2,4,5-Benzene-tetracarboxylic acid).sub.0.75, Eu(Pyridine-2-carboxylic acid).sub.3, or Eu(Pyridine-4-carboxylic acid).sub.3; and near ultraviolet excited rare earth compound having a structure of the following chemical formula II, ##STR00005## where, P and Q are rare earth metals independently selected from Ce, Nd, Sm, Eu, Gd, Tb, La and Y, and where R is alkaline earth metal selected from Ca (Calcium), Sr (strontium), and Ba (barium), and L 1, L 2, L 3, L 4 and L 5 are independently selected from hydrogen, C 1-8 aryl group, halogen group and C 1-8 alkoxy group, the a and b are respectively a real number greater than 0, and 0<a+b1.

5. The dichroism fluorescent composition of claim 4, wherein the composition emits a red color when excited with light at 360-380 nm range wavelength, and emits red and green colors when excited with light at 240-330 nm range wavelength.

6. The dichroism fluorescent composition of claim 4, wherein the composition further comprises at least one fluorescent substance selected from Red 620 (CAS No. 1417311-00-2), Yellow 565 (CAS No. 28683-92-3), Green 555 (CAS No. 1466444-84-7), Green 550 (CAS No. 1151-84-4), or Blue-green 510 (CAS No. 1461703-41-2).

Description

BEST MODES

(1) In order to more easily understand the present invention, certain terms will be defined herein for the benefit of convenience. Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Furthermore, as used herein, the terms a and an are open terms that may be used in conjunction with singular items or with plural items. The terms of manufacturing (manufactured) and producing (produced) may be interchangeably used.

(2) According to a general aspect, there is provided a luminescent rare earth compound having a structure of the following chemical formula I,

(3) ##STR00003##
where, A and B are rare earth metals independently selected from Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm, C is an amphoteric element selected from Al, Ga and In, each of R 1, R 2 and R 3 is independently carboxylate anion or H, and D is a nitrogen or carbon.

(4) In some exemplary embodiments, the R 1 and R 4 are H, the R 2 and R 3 are carboxylate anion, the D is carbon and the A and B may be selected from Eu and Tb. The number of repeating unit of ligands corresponding to aromaticity ring in the Chemical formula I may be defined as n, and at this time, the number of repeating unit may be defined as satisfying the stoichiometry of n: x+y+z=3/[the number of negative electric charge in above chemical formula I]: 1.

(5) In some exemplary embodiments, the compound may not be excited at a wavelength of 360-380 nm range and may be excited at a wavelength of 240-330 nm range. At this time, it is intended that the wavelength of 360-380 nm range may correspond to near ultraviolet area, and the wavelength of 240-330 nm range may correspond to ultraviolet area.

(6) The luminescent rare earth compound can emit strong red and green colors by being excited at 240-330 nm range of wavelengths, while not being excited at 360-380 nm range of wavelengths.

(7) Furthermore, although the compound may be a single compound having a same chemical formula, the compound may a mixture of a plural compound having mutually different chemical formulas, albeit having a structure of Chemical formula I.

(8) However, it should be understood that, even if the luminescent rare earth compound may be a plural compound, the characteristic of emitting strong red and green colors by being excited at 240-330 nm range of wavelengths is maintained.

(9) In another general aspect, there is provided a dichroism fluorescent composition comprising: the luminescent rare earth compound having a structure of the following chemical formula II, and including near ultraviolet excited rare earth compound,

(10) ##STR00004##
where, P and Q are rare earth metals independently selected from Ce, Nd, Sm, Eu, Gd, Tb, La and Y, and where R is alkaline earth metal selected from (Ca), strontium and barium, and L 1, L 2, L 3, L 4 and L 5 are independently selected from hydrogen, C 1-8 aryl group, halogen group and C 1-8 alkoxy group, the a and b are respectively a real number greater than 0, and 0<a+b1.

(11) Here, the luminescent rare earth compound can emit strong red and green colors of visible ray wavelengths by being excited at 240-330 nm range of wavelengths, while not being excited at 360-380 nm range of wavelengths.

(12) Meantime, the dichroism fluorescent composition can emit a strong red color of visible ray wavelength by not being excited at 240-330 nm range of wavelengths, while being excited at 360-380 nm range of wavelengths.

(13) That is, the dichroism fluorescent composition may be so configured as to emit mutually different colors at long wavelengths and short wavelengths.

(14) In some exemplary embodiments, the composition may further comprise at least one fluorescent substance selected from Red 620 (CAS No. 1417311-00-2),

(15) Yellow 565 (CAS No. 28683-92-3), Green 555 (CAS No. 1466444-84-7), Green 550 (CAS No. 1151-84-4) and Blue-green 510 (CAS No. 1461703-41-2).

(16) The luminescent rare earth compound and the near ultraviolet excited rare earth compound may be manufactured by respectively reacting in water at least one rare earth metallic salt and the repeating unit indicated by the Chemical formula I and II.

(17) The luminescent rare earth compound and the near ultraviolet excited rare earth compound may be generally product materials formed in sediments after the reaction, and may be used after being separated and dried by a method well known in the art.

(18) In still another aspect of the present invention, the luminescent rare earth compound and/or the dichroism fluorescent composition may be a mixture mixed with plastic or high polymer synthetic resin. This composition may be a coating-purpose resin composition that is used for coating a product.

(19) The coating-purpose resin composition may be manufactured by mixing the compound according to the present invention with at least one binder resin selected from acrylic polymer, polyurethane, polyester, polyethylene, polyethyleneterephthalate, polycarbonate and polypropylene, solvent and hardener.

(20) Here, the solvent may be selected from halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, trichloroethane, dichloroethane, tetrachloromethane and dichlorofluoro ethane, for example, ether such as ethyl ether, propyl ether, butyl ether and cyclohexyl, for example, alcohol such as methanol, ethanol, propanol, tetrafluoroborate and butanol, for example, ketone such as acetone, trifluoroacetone, hexafluoroacetone and cyclohexanone, and hydrocarbon such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, octane and cyclooctane, for example.

(21) The coating-purpose resin composition may be variably utilized by being coated on a surface of a product for red color luminescence by being irradiated with ultra violet. Although the compound according to the present invention in the coating-purpose resin composition may be contained in variable contents in response to usage, the compound may be preferable to be included with 110 part by weight relative to 100 part by weight of coating-purpose resin composition.

(22) When quantity of composition is less than 1 part by weight, the luminescence effect in response to excitation may be insignificant, and when quantity of composition is more than 10 part by weight, there may be generated a problem of degraded transmittance due to luminescence compound. Furthermore, the present invention may be a film containing the rare earth metallic complex compound.

(23) By way of example, the composition may be manufactured in a film type by laminating the composition included with the rare earth metallic complex compound on the polymer film under a high temperature. In addition, the film included with the compound according to the present invention may be variably manufactured by the well-known prior methods.

(24) By way of example, in the process of manufacturing a master batch by extrusion molding after fusion of resin, when the compound according to the present invention is mixed to the resin, the master batch is made by extrusion molding through fusion of resin thus mixed, and fused and formed using the conventional method, various shapes of products including the film can be manufactured.

(25) Hereinafter, the present invention will be described in more detail through exemplary embodiments. However, these exemplary embodiments are provided only for exemplification, and the scope of invention is not interpreted as limiting these exemplary embodiments.

First Exemplary Embodiment: Composition of Eu 0.6 Y 0.4 (Benzoic Acid) 3

(26) 13.7 g of benzoic acid (C 6 H 5 COOH Mw. 122.12, Samchun Chemical Co.) was suspended in a water of 150 ml within a 500 ml round bottom flask, and 4.5 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) was added and dissolved. A solution was obtained by dissolving 3.95 g of europium oxide (Eu 2 O 3 Mw. 351.926) and 1.69 g of yttrium oxide(Y 2 O 3 Mw. 225.81) in 12 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(27) Then, the sediment-removed europium-yttrium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Second Exemplary Embodiment: Composition of Eu 0.6 Y 0.4 (Isophthalic Acid) 1.5

(28) 10 g of isophthalic acid (C 6 H 4 (COOH) 2 Mw. 166.14, TCI) was suspended in a 150 ml-water within a 500 ml round bottom flask, and added with 4.8 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) and dissolved. A solution was obtained by dissolving 2.71 g of europium oxide (Eu 2 O 3 Mw. 351.926) and 2.71 g of yttrium oxide(Y 2 O 3 Mw. 225.81) in 12.5 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(29) Then, the sediment-removed europium-yttrium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Third Exemplary Embodiment: Composition of Eu 0.2 Y 0.8 (1,3,5-Benzene-Tricarboxylic Acid) 1

(30) 10.5 g of 1,3,5,-Benzenetricarboxylic acid (C 6 H 3 (COOH) 3 Mw. 210.14, TCI) was suspended in 150 ml water within a 500 ml round bottom flask, and added with 6 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) and dissolved.

(31) A solution was obtained by dissolving 1.76 g of europium oxide (Eu 2 O 3 Mw. 351.926) and 4.52 g of yttrium oxide(Y 2 O 3 Mw. 225.81) in 15.5 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(32) Then, the sediment-removed europium-yttrium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Fourth Exemplary Embodiment: Composition of Tb 0.2 Y 0.8 (1,3,5-Benzene-Tricarboxylic Acid) 1

(33) 14.2 g of 1,3,5,-Benzenetricarboxylic acid (C 6 H 3 (COOH) 3 Mw. 210.14, TCI) was suspended in 150 ml water within a 500 ml round bottom flask, and added with 8.2 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) and dissolved.

(34) A solution was obtained by dissolving 4.8 g of (TbCl.sub.36H.sub.2O Mw. 373.38) and 5.7 g of yttrium oxide (Y 2 O 3 Mw. 225.81) in 15.7 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(35) Then, the sediment-removed terbium-yttrium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Fifth Exemplary Embodiment: Composition of Eu 0.5 Y 0.5 (1,2,4,5-Benzene-Tetracarboxylic Acid) 0.75

(36) 9.5 g of 1,2,4,5-benzenetetracarboxylic acid (C 6 H 2 (COOH) 4 Mw. 254.15, TCI) was suspended in 150 ml water within a 500 ml round bottom flask, and added with 6 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) and dissolved.

(37) A solution was obtained by dissolving 4.4 g of europium oxide (Eu 2 O 3 Mw. 351.926) and 2.8 g of yttrium oxide (Y 2 O 3 Mw. 225.81) in 15.5 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(38) Then, the sediment-removed europium-yttrium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Sixth Exemplary Embodiment: Composition of Eu(Pyridine-2-Carboxylic Acid) 3

(39) 13.8 g of pyridine-2-carboxylic acid (C 6 H 5 NO 2 Mw. 123.11, Alfa aesar) was suspended in 150 ml water within a 500 ml round bottom flask, and added with 4.5 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) and dissolved.

(40) A solution was obtained by dissolving 6.6 g of europium oxide (Eu 2 O 3 Mw. 351.926) in 11.3 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(41) Then, the sediment-removed europium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Seventh Exemplary Embodiment: Composition of Eu(Pyridine-4-Carboxylic Acid) 3

(42) 13.8 g of pyridine-2-carboxylic acid (C 6 H 5 NO 2 Mw. 123.11, Alfa aesar) was suspended in 150 ml water within a 500 ml round bottom flask, and added with 4.5 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) and dissolved.

(43) A solution was obtained by dissolving 6.6 g of europium oxide (Eu 2 O 3 Mw. 351.926) in 11.3 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(44) Then, the sediment-removed europium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Eighth Exemplary Embodiment: Composition of Eu 0.6 Y 0.4 (2,5-Pyridinedicarboxylic Acid) 1.5

(45) 12.5 g of 2,5-pyridine dicarboxylic acid (C 7 H 5 NO 4 Mw. 167.12, TCI) 12.5 g was suspended in 150 ml water within a 500 ml round bottom flask, and added with 6 g of sodium hydroxide (NaOH Mw. 40, Samchun Chemical Co.) and dissolved.

(46) A solution was obtained by dissolving 5.25 g of europium oxide (Eu 2 O 3 Mw. 351.926) and 2.25 g of yttrium oxide (Y 2 O 3 Mw. 225.81) in 15.6 g of 35% hydrochloric acid and 80 ml of water, and the obtained solution was agitated for 30 minutes and dropped under 10-100 C.

(47) Then, the sediment-removed europium-yttrium complex compound was separated and dried, whereby no excitation was made at 360-380 nm range, and strong red fluorescence was shown at 240 nm to 330 nm wavelengths.

Ninth Exemplary Embodiment

(48) Offset ink of 20 weight % was manufactured by mixing the red shortwave fluorescent substance composed by the third exemplary embodiment of the present invention with yellow 565 of Nano CMS Company.

Tenth Exemplary Embodiment

(49) Offset ink of 20 weight % was manufactured by mixing the red shortwave fluorescent substance composed by the third exemplary embodiment of the present invention with green 550 of Nano CMS Company.

Eleventh Exemplary Embodiment

(50) Offset ink of 20 weight % was manufactured by mixing green shortwave fluorescent substance composed by the fourth exemplary embodiment of the present invention with red near ultraviolet complex compound of [structural formula 2] based on KR 10-12129.

(51) Excitation and luminescent brightness were measured from powder sample manufactured and obtained by the exemplary embodiments 1-8 using PL/PLE Measurement System (PSI 1100) and the measured result is shown in the following Table 1. The luminescent characteristic at 305 nm obtained by transferring the offset ink manufactured and obtained from the exemplary embodiments 9-11 on non-fluorescent paper is shown in Table 2, and the luminescent characteristic at 365 nm is shown in Table 3.

(52) TABLE-US-00001 TABLE 1 Maximum Maximum excitation color color luminescent wavelength coordinate coordinate wavelength Classification (nm) (CIEx) (CIEy) (nm) First exemplary 293 0.6725 0.3272 620 embodiment Second exemplary 299 0.6795 0.3203 622 embodiment Third exemplary 310 0.6690 0.3308 616 embodiment Fourth exemplary 310 0.3465 0.6144 554 embodiment Fifth exemplary 299 0.6746 0.3252 616 embodiment Sixth exemplary 285 0.6706 0.3292 622 embodiment Seventh exemplary 304 0.6743 0.3254 622 embodiment Eighth exemplary 301 0.6789 0.3209 618 embodiment

(53) TABLE-US-00002 TABLE 2 color Maximum coordinate color coordinate luminescent Classification (CIEx) (CIEy) wavelength (nm) Ninth exemplary 0.5059 0.4685 616 embodiment Tenth exemplary 0.4518 0.4874 616 embodiment Eleventh exemplary 0.4048 0.5630 554 embodiment

(54) TABLE-US-00003 TABLE 3 color Maximum coordinate color coordinate luminescent Classification (CIEx) (CIEy) wavelength (nm) Ninth exemplary 0.4229 0.5329 545.6 embodiment Tenth exemplary 0.3149 0.5823 515.6 embodiment Eleventh exemplary 0.4266 0.5396 544.6 embodiment

(55) Although the foregoing has explained the exemplary embodiment of the present invention, the present invention is not always limited to the given exemplary embodiments. The above disclosed subject matter is to be considered illustrative, and not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments which fall within the true spirit and scope of the present invention. Thus, to the maximum extent allowed by law, the scope of the present invention is to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description.

INDUSTRIAL APPLICABILITY

(56) The luminescent rare earth compound and/or products applied with the luminescent rare earth compound according to the present invention can emit strong red and green colors by being excited at 240-330 nm range of wavelengths, while not being excited at 360-380 nm range of wavelengths, and showing no colors under visible light.

(57) Furthermore, the compound may be variably utilized to printed materials and plastic mold products because of possessing high heat resistance, high light resistance and high dispersibility of medium light.