CN1062917A - A kind of rare-earth fluorescent composition and uses thereof - Google Patents
A kind of rare-earth fluorescent composition and uses thereof Download PDFInfo
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- CN1062917A CN1062917A CN 90110211 CN90110211A CN1062917A CN 1062917 A CN1062917 A CN 1062917A CN 90110211 CN90110211 CN 90110211 CN 90110211 A CN90110211 A CN 90110211A CN 1062917 A CN1062917 A CN 1062917A
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Abstract
The present invention relates to a kind of rare-earth fluorescent composition and uses thereof.This mixture comprises beta diketone complex compound, phosphorus compound and the superpolymer of europium at least.Under UV-light or sun exposure, can send red fluorescence, the luminous efficiency height is heat-resisting, moisture resistance properties good.Can be widely used on the various objects, purposes all be arranged in coating, paint, printing, plastics, building, fabric, luminous demonstration, distinctive mark material, fine arts field.Under rayed, can increase the vividness of object color or change original color.
Description
The present invention relates to fluorescent composition of a kind of beta diketone four ligand complexes that contain europium and uses thereof.
Some rare-earth complex has unique fluorescent characteristic, can be developed into to be transform light energy or luminescent material.For example can be used for making transform light energy device and coating etc., and in many fields such as optics demonstration, printing, distinctive mark, weaving, decoration, have a wide range of applications.
Research report and patent application to rare-earth luminescent material in the last few years increases gradually, but their common weak point is, light energy conversion efficiency is low, is difficult for homodisperse in macromolecule medium, and less stable is so difficulty finds suitable purposes.The beta diketone complex compound of some rare earth element has stronger absorption than its carboxylate complexes to the UV-light of 300-400nm by comparison, and the fluorescence transformation efficiency is also higher, relatively easily is dispersed into the fluorescent material of homogeneous transparent in macromolecule medium.
The beta diketone complex compound of rare earth elements europium is the material that can launch red fluorescence preferably, excite (the excitation spectrum highest peak is positioned at 360-380nm) that its ligand beta diketone is subjected to UV-light under the irradiation of UV-light so it has good emission red fluorescence characteristic to be, can give the Eu(III with transmission ofenergy) ion, be subjected to the Eu(III of part perturbation), promptly take place
5D
0-
7F
2Transition, and send the red fluorescence of the nearly 610nm of wavelength.The intensity of this fluorescent band depends on the ligand structure around the Eu atom.When different coordinating groups is incorporated into luminescence center Eu(III) around, changed the coordination environment of europium, and caused the symmetric variation of contiguous electric field, this variation directly influences fluorescence intensity.
The publication application of Mitsui and Kawasaki (day disclosure special permission communique (A), clear 63-150358,1988) discloses three ligand complexes of fluorine-containing beta diketone and europium or terbium formation and the fluorescent coating composition that phosphine oxide forms.Surprised rubbing opened the auxilliary publication application that waits (day disclosure special permission communique (A), clear 63-191884,1988) and disclosed with four ligand complexes of europium and the formation of fluorine-containing beta diketone and made the fluorescence resin composition.But the luminous efficiency of the two is neither enough strong.
But task of the present invention is the fluorescent material that overcomes above-mentioned deficiency and acquisition practical application.The present inventor finds, with europium (Eu
3+) be prepared into the ZEuL of beta diketone
4The type complex compound adds organo phosphorous compounds again, and they are distributed to suitable superpolymer or have in the multipolymer of coordination ability, can be made into the transparent fluorescent material that luminous efficiency is higher, heat-resisting, wet fastness is good.
Mixture of the present invention comprises at least:
1, europium four ligand complexes of logical formula I;
2, logical formula II, (III), (IV), (V), the organo phosphorous compounds of (VI) or (VII) or their mixture;
3, transparent high polymer;
Compound weight ratio in above-mentioned 3 and 2 and 1 is:
(100): (0.01-2): (0.02-20), this mixture day optical wavelength 200-400nm UV-light or the irradiation of Ultra-Violet Laser under, can produce red fluorescence.
The general formula of four ligand complexes of europium is as follows:
Z representative in the formula:
1. the following organic amine positively charged ion of general formula,
R in the formula
1, R
2, R
3, R
4Can be identical, also can be inequality, they can be C separately
1-C
12Alkyl or hydrogen atom, perhaps link to each other to form the monocycle amine between any two between them,
2. the positively charged ion that forms of aromatic amine or nitrogenous heterocyclic amine compound and hydrogen ion,
3. alkali metal cation such as sodium, potassium cationic,
L representative in the formula:
The beta diketone negative ion that general formula is following
R in the formula and R
1Can be identical, also can be inequality, they can be C separately
1-C
4Alkyl, the C that monobasic or polynary fluorine replace
1-C
4Alkyl, phenyl, the phenyl of monobasic or polynary replacement, furyl and thienyl, the perhaps furyl of monobasic or polynary replacement, the thienyl of monobasic or polynary replacement.
Above-mentioned Organophosphorous compounds comprise:
Phosphine oxide, as logical formula II, phosphonic acid ester, as logical formula III, (IV), phosphoric acid ester, as general formula (V), acidic phosphonate and acid phosphoric acid ester, respectively as logical formula VI and (VII):
R in the formula
1, R
2, R
3Can be identical, also can be inequality, they can be C separately
1-C
12Alkyl, phenyl or monobasic or the phenyl of polynary replacement.
Described transparent high polymer comprises: polystyrene, polyvinyl chloride, polyester, polymethyl acrylate, polyvinyl acetate (PVA), urethane, methyl methacrylate and methacrylic acid N, the multipolymer of N-dimethylaminoethyl, polyvinyl acetal or Resins, epoxy, petroleum resin, different third rubber, the superpolymer of modification by copolymerization and multipolymer with coordinative activity, derivatived cellulose.
Fluorescent composition of the present invention has higher luminous efficiency (seeing Fig. 1,2,3), and it is heat-resisting, wet fastness is all better, is transparence.Be preferably at 200-400nm under the UV-light or Ultra-Violet Laser or irradiation of 350-360nm, produce the red fluorescence of the nearly 610nm of wavelength at daylight.If this mixture is coated on the colored object, also can produce metachromatism, for example background color is white, then be bright red through UV-irradiation, green background color then is orange-yellow through UV-irradiation, can improve contrast gradient and resolving power,, under UV-irradiation, produce large red if be coated on the object of black.This metachromatism also makes fluorescent composition of the present invention that wider range of application is arranged.By the film that fluorescent composition of the present invention forms, when wherein containing europium amount 4ppm, promptly can show red fluorescence with the general ultraviolet light irradiation.
Compound in the mixture of the present invention can make with known synthetic method, perhaps use the suitable commercial goods of specification, then by above-mentioned suitable proportion preparation, the fluorescent composition that can obtain to share, it is dissolved in suitable solvent or its mixture, can carries out a series of application.Suitable organic solvent comprises: aromatic hydrocarbons, alkane, halogenated alkane, ester class, ketone, alcohol compound or tetrahydrofuran (THF).
Described fluorescent composition is dissolved into clear solution in organic solvent after, adopt any method and form to make it attached on any object, after the drying the film consistent that can suitably control of thickness with attached form.The object that is loaded with this film is preferably under the UV-light or Ultra-Violet Laser irradiation of 350-360nm at 200-400nm, shows red fluorescence or produces the fluorescence of other colors because of aforesaid metachromatism.This fluorescent composition solution can also mix with non-current animal matter; be used for coated, paint, printing, plastics, fabric or fine arts field; after perhaps it and pulverous solid or solia particle being mixed; remove and desolvate; get powdered solid or particulate composite fluorescent material; the indoor and outdoor that is used for construction industry is decorated, or in the plastics.Perhaps described fluorescent composition is made the pressed powder use or be added in solid or half free-flowing material and use, as be used for luminous demonstration or make distinctive mark material etc.Though how or what form use, under the UV-light or Ultra-Violet Laser irradiation of described wavelength, all can send fluorescence, therefore fluorescent composition of the present invention has very application prospects, be actually UV-light is converted into visible light, so can be widely used in transform light energy.
In order to be illustrated more clearly in the present invention, enumerate following examples, but this is not limited to them to scope of the present invention.
Embodiment 1
3 gram polymethylmethacrylates are dissolved in 100 milliliters of toluene, are referred to as solution A.With the Z in the logical formula I is the positively charged ion that pyridine and hydrogen ion form, and L is a trifluoromethyl, and the fluorescent chemicals of the basic beta diketone of thiophene-2 is dissolved in the solution that toluene is made into 0.001 mole, is referred to as solution B.Again 0.25 milligram of trioctyl-phosphine oxide is dissolved in 25 milliliters of toluene, is referred to as solution C.
Get 10 milliliters of solution A, 0.53 milliliter of solution B, 0.12 milliliter of solution C, mixing in a container, it is applied on the flint glass sheet, and promptly getting a thickness after the drying is the clear, colorless fluorescence membrane of 10-50 μ m, and it shows red under wavelength 300-400nm UV-irradiation.
Z in example 1 formula of (I) is replaced the positively charged ion that trioctylamine and hydrogen ion form, be made into toluene solution B,, mixes, formation fluorescent composition solution with its solution A and C with this solution such as example 1 as example 1.This solution is applied on the white fabric, does the UV-irradiation of back, show bright-coloured redness with wavelength 350-360nm.
Get 3 gram methyl methacrylate and methacrylic acid N, the multipolymer of N-dimethylaminoethyl is dissolved in 100 milliliters of toluene, get 10 milliliters of these solution and be dissolved in 25 milliliters of solution in the toluene in 3 milligrams of triphenylphosphine oxides of 2 milliliters of the solution B that wherein adds example 1 and 0.12 milliliter, remove behind the mixing desolvate the solid fluorescence mixture.
Embodiment 4
The fluorescent composition solution of embodiment 1 is applied on the colour picture, after the drying one under daylight with the picture that was as good as originally, with the UV-irradiation of wavelength 200-400nm, can see the picture of variable color, redness originally becomes scarlet, it is orange red etc. that yellow becomes.
Embodiment 5
Fluorescent composition solution with example 1 is drawn a width of cloth picture on blank sheet of paper or flint glass, dry back is as good as with blank sheet of paper and simple glass under daylight.Under the 200-400nm UV-irradiation, can see red picture.
If the europium complex concentration in the fluorescent composition is strengthened,, under daylight, also can see the incarnadine picture as 15% after this solution drying.
Description of drawings:
Fig. 1 EuL
3/ PMMA and PyEuL
4The comparison of/PMMA film intensity of emission spectra
Eu is the positively charged ion of trivalent europium,
L is trifluoromethyl thiophene-2 base, the beta diketone negative ion,
Py is the positively charged ion that pyridine and hydrogen ion form,
PMMA is a polymethylmethacrylate,
-be PyEuL
4,
Be EuL
3,
Ultraviolet wavelength 350nm, film contain europium amount 0.18%.
Fig. 2 PyEuL
4The emmission spectrum of/PMMA film,
Ultraviolet wavelength 350nm,
Top is the peak of the oxidation tri-n-octyl phosphine of adding 0.4%,
The bottom is the peak that does not add phosphine oxide.
Fig. 3 EuL
3The emmission spectrum of/PMMA film
Ultraviolet wavelength 350nm,
Top is the peak of adding 0.5% oxidation three positive hot phosphines,
The bottom is not for adding the peak of phosphine oxide.
Claims (5)
1, a kind of fluorescent composition that contains europium complex is characterized in that, this mixture comprises at least:
1, europium 4 ligand complexes of logical formula I;
2, logical formula II, (III), (IV), (V), (VI), the organo phosphorous compounds of (VII) or their mixture;
3, transparent high polymer;
Compound weight ratio in above-mentioned 3 and 2 and 1 is:
100: (0.01-2): (0.02-20), this mixture can produce red fluorescence under the irradiation of daylight, wavelength 200-400nm UV-light or Ultra-Violet Laser,
Z representative in the formula:
(1) the following organic amine positively charged ion of general formula:
R in the formula
1, R
2, R
3, R
4Can be identical, also can be inequality, they can be C separately
1-C
12Alkyl or hydrogen, perhaps link to each other to form the monocycle amine between any two between them;
(2) positively charged ion that forms of aromatic amine or nitrogenous heterocyclic amine compound and hydrogen ion;
(3) basic metal: sodium, potassium cationic;
L representative in the formula:
The beta diketone negative ion that general formula is following:
R in the formula and R
1Can be identical also can be inequality, they can be C separately
1-C
4Alkyl, the alkyl that monobasic or polynary fluorine replace, the phenyl of phenyl, monobasic or polynary replacement, the furyl of furyl or thienyl or monobasic or polynary replacement or thienyl,
R in the formula
1, R
2, R
3Can be identical also can be inequality, they can be C separately
1-C
12Alkyl, phenyl, monobasic or polynary substituted-phenyl.
2, according to the mixture of claim 1, it is characterized in that, described:
1, the Z in the logical formula I is the positively charged ion that pyridine and hydrogen ion form, and L is the basic beta diketone negative ion of trifluoromethyl thiophene-2;
2, organo phosphorous compounds is the oxidation tri-n-octyl phosphine as logical formula II;
3, transparent high polymer is a polymethylmethacrylate;
Compound weight ratio in 3 and 2 and 1 is:
（100）∶（0.1-1）∶（0.1-10），
Be preferably under the UV-light or Ultra-Violet Laser irradiation of wavelength 300-400nm, can produce strong red fluorescence.
According to the mixture of claim 1 or 2, it is characterized in that 3, the Z in the described logical formula I is the positively charged ion that tri-n-octyl amine and hydrogen ion form, described organo phosphorous compounds is a triphenylphosphine oxide.
4, according to claim 1,2 or 3 mixture, it is characterized in that, described transparent high polymer is: polystyrene, polyvinyl chloride, polyester, polymethyl acrylate, polyvinyl acetate (PVA), urethane, methyl methacrylate and methacrylic acid N, the multipolymer of N-dimethylaminoethyl, polyvinyl acetal or Resins, epoxy, petroleum resin, different third rubber, the superpolymer of modification by copolymerization and multipolymer with coordinative activity, derivatived cellulose.
5, the purposes of claim 1,2,3 and 4 described mixtures is characterized in that, described mixture is dissolved in the suitable organic solvent:
1, make this solution attached on any object with any method and mode, get the fluorescence membrane consistent that thickness can suitably be controlled after the drying with adhering mode, be preferably at wavelength 200-400nm under the UV-light or laser radiation of 300-400nm, show red fluorescence or coordinate the generation color changeable effect with red fluorescence because of the background color of object, form scarlet, green or fluorescent orange, perhaps
2, the non-water flow dynamic material of above-mentioned solution and other is mixed, be used for coated, paint, plastics, fabric, press or fine arts field, as show the fluorescence of redness or color changeable effect as described in 1 through UV-irradiation;
3, with above-mentioned solution and pulverulent solids or solia particle mixing, remove and desolvate, form Powdered or particulate composite fluorescent material, can be used in the indoor and outdoor decoration or plastics of construction industry;
4, described fluorescent composition is made pressed powder and used or be added in solid or half free-flowing material and use, as be used for luminous demonstration or distinctive mark material;
Described suitable organic solvent comprises: aromatic hydrocarbons, alkane, halogenated alkane, ester class, alcohol compound or tetrahydrofuran (THF) or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90110211 CN1030614C (en) | 1990-12-30 | 1990-12-30 | Rare-earth fluorescent composition and its usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90110211 CN1030614C (en) | 1990-12-30 | 1990-12-30 | Rare-earth fluorescent composition and its usage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062917A true CN1062917A (en) | 1992-07-22 |
| CN1030614C CN1030614C (en) | 1996-01-03 |
Family
ID=4881801
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90110211 Expired - Fee Related CN1030614C (en) | 1990-12-30 | 1990-12-30 | Rare-earth fluorescent composition and its usage |
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| US7205711B2 (en) | 2002-09-30 | 2007-04-17 | Futaba Corporation | Fluorescent display device and phosphor paste |
| GB2453953A (en) * | 2007-10-23 | 2009-04-29 | Univ Brunel | Protection of plastics using UV-absorbing phosphors |
| CN102656705A (en) * | 2009-09-29 | 2012-09-05 | 日立化成工业株式会社 | Fluorescent material for converting wavelengths, resin composition for converting wavelengths , solar cell module, process for producing resin composition for converting wavelengths, and process for producing solar cell module |
| CN102898971A (en) * | 2012-10-29 | 2013-01-30 | 常州大学 | Rare-earth light conversion agent and preparation method and application thereof |
| CN103172941A (en) * | 2011-12-26 | 2013-06-26 | 苏州新波生物技术有限公司 | Polystyrene fluorescent nanometer particle as well as preparation method and applications thereof |
| JP2014024767A (en) * | 2012-07-25 | 2014-02-06 | Kyushu Institute Of Technology | Europium diketone chelate compound, and fluorescence penetrant testing method of inorganic material or metal material |
| CN103806273A (en) * | 2014-02-13 | 2014-05-21 | 北京化工大学常州先进材料研究院 | Method for preparing fluorescent nanofibers based on photo-grafting surface modification |
| CN104045954A (en) * | 2014-07-04 | 2014-09-17 | 重庆理工大学 | Preparation method of rare earth red-light thin film with PMMA as substrate |
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1990
- 1990-12-30 CN CN 90110211 patent/CN1030614C/en not_active Expired - Fee Related
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| US7205711B2 (en) | 2002-09-30 | 2007-04-17 | Futaba Corporation | Fluorescent display device and phosphor paste |
| CN100339933C (en) * | 2002-09-30 | 2007-09-26 | 双叶电子工业株式会社 | Fluorescent display deivce and fluorescent sive |
| GB2453953A (en) * | 2007-10-23 | 2009-04-29 | Univ Brunel | Protection of plastics using UV-absorbing phosphors |
| CN102656705B (en) * | 2009-09-29 | 2015-06-17 | 日立化成株式会社 | Fluorescent material for converting wavelengths, resin composition for converting wavelengths , solar cell module, process for producing resin composition for converting wavelengths, and process for producing solar cell module |
| CN102656705A (en) * | 2009-09-29 | 2012-09-05 | 日立化成工业株式会社 | Fluorescent material for converting wavelengths, resin composition for converting wavelengths , solar cell module, process for producing resin composition for converting wavelengths, and process for producing solar cell module |
| CN103172941A (en) * | 2011-12-26 | 2013-06-26 | 苏州新波生物技术有限公司 | Polystyrene fluorescent nanometer particle as well as preparation method and applications thereof |
| JP2014024767A (en) * | 2012-07-25 | 2014-02-06 | Kyushu Institute Of Technology | Europium diketone chelate compound, and fluorescence penetrant testing method of inorganic material or metal material |
| CN102898971A (en) * | 2012-10-29 | 2013-01-30 | 常州大学 | Rare-earth light conversion agent and preparation method and application thereof |
| CN102898971B (en) * | 2012-10-29 | 2015-08-12 | 常州大学 | A kind of rare-earth light conversion agent and its preparation method and application |
| CN103806273A (en) * | 2014-02-13 | 2014-05-21 | 北京化工大学常州先进材料研究院 | Method for preparing fluorescent nanofibers based on photo-grafting surface modification |
| CN103806273B (en) * | 2014-02-13 | 2015-12-30 | 北京化工大学常州先进材料研究院 | A kind of method preparing fluorescent nano-fiber based on photo-grafting surface modification |
| CN104045954A (en) * | 2014-07-04 | 2014-09-17 | 重庆理工大学 | Preparation method of rare earth red-light thin film with PMMA as substrate |
| CN104045954B (en) * | 2014-07-04 | 2016-03-09 | 重庆理工大学 | A kind of PMMA is as the preparation method of the rare earth ruddiness film of matrix |
| CN106928774A (en) * | 2017-04-01 | 2017-07-07 | 北京金辰西维科安全印务有限公司 | A kind of ageing-resistant Antiforge fluorescent ink and preparation method thereof |
| CN107012527A (en) * | 2017-04-01 | 2017-08-04 | 北京金辰西维科安全印务有限公司 | A kind of ageing-resistant fluorescent composition of rare earth and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030614C (en) | 1996-01-03 |
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