CA2208568C - Triboluminescent lanthanide iii complexes - Google Patents
Triboluminescent lanthanide iii complexes Download PDFInfo
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- CA2208568C CA2208568C CA002208568A CA2208568A CA2208568C CA 2208568 C CA2208568 C CA 2208568C CA 002208568 A CA002208568 A CA 002208568A CA 2208568 A CA2208568 A CA 2208568A CA 2208568 C CA2208568 C CA 2208568C
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- 229910052747 lanthanoid Inorganic materials 0.000 title description 6
- 150000002602 lanthanoids Chemical class 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- BOFAIBPJCWFJFT-UHFFFAOYSA-N 4-methoxy-1-oxidopyridin-1-ium Chemical compound COC1=CC=[N+]([O-])C=C1 BOFAIBPJCWFJFT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- -1 aromatic nitriles Chemical class 0.000 claims description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 description 11
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005390 triboluminescence Methods 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000005923 long-lasting effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- DMGGLIWGZFZLIY-UHFFFAOYSA-N 3-methyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=C[N+]([O-])=C1 DMGGLIWGZFZLIY-UHFFFAOYSA-N 0.000 description 1
- IWYYIZOHWPCALJ-UHFFFAOYSA-N 4-methyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=[N+]([O-])C=C1 IWYYIZOHWPCALJ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical class C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CFZKDDTWZYUZKS-UHFFFAOYSA-N picoline N-oxide Chemical compound CC1=CC=CC=[N+]1[O-] CFZKDDTWZYUZKS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical group CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
In one of its aspects, the invention relates to compounds of formula (I), wherein M is En, Tb or Dy, Sm; R2 is hydrogen or C1-C6alkyl, and R1 and R3 are each independently of the other phenyl, hydrogen or C1-C6alkyl, and L is p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxypyridine-N-oxide. The invention also relates to the use of these compounds for optical sensors sensitive to impact, tension or pressure.
Description
2 PCTlEP96100005 Triboluminescent lanthanide~~~complexes The present invention relates to lanthanide~~~ complexes of 1,3-diketones, which complexes have a high luriinescence quantum yield as well as long-lasting luminescence, a narrowband emission spectrum and bright triboluminescence. The invention also relates to the use of said compounds for optical sensors sensitive to impact, tension or pressure.
The phenomenon of triboluminescence (emission of light under strong mechanical stress) has long been known and is described, inter alia, in Advances in Physics 1977, Vol. 26, No. 6, 887-948 or in Math. Naturwi ss. Unterricht 4514, 1992, 195-202. A great number of crystalline compounds display this phenomenon, but as yet only very few are known whose emission is so atrong as to be easily observable also in daylight. The brightest triboluminescent substance known so far is triethylammonium tetrakis(dibenzoylmethanato)-europate(III).
Although the p'~enomenon of triboluminescence is well known, its cause cannot be completely accounted for yet and hence no predictions can be made concerning the occurrence of particularly intense triboluminescent compounds.
Specific Eu(III) complexes with pyridine-N-oxide, 2-, 3-,or 4-picoline-N-oxide and bipyridine-N, N-dioxide as well as thenoyltrifluoroacetone as ligand are disclosed in CA 114(18):17'7114p as triboluminescent substances of intense brightness.
It has now been found that a specific group of predominantly colourless lanthanide complexes displays particularly bright triboluminescence, which complexes have very narrowband emission lines, pronounced Stokes' shift, as well as long-lasting luminescence and a high quantum yield of photochemically excited luminenscence.
By virtue of thE~ir long-lasting photochemically excited luminescence and high luminescence quantum yield, these compounds are also particularly suitable for use as pigments or dyes in the field of security printing. Bank notes and securities are typical examples requiring a high degree of security against unauthorised duplication. The high luminescence of the compounds is able to induce colour changes in the documents printed therewith when duplicated in conventional manner, so that the documents are identifiable as duplicates.
In one of its aspects, the invention relates to compounds of formula I
- L- MIII R~ w R3 O ~ 3 (1), wherein M is Eu, Tb or Dy, Sm;
R2 is hydrogen or C,-Csalkyl, and - R1 and Rg are each independently of the other phenyl, hydrogen or C,-Csalkyl, and L is p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxypyridine-N-oxide.
The Ci=Csalkyl groups can be straight-chain or branched and are typically methyl, ethyl, .
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or the different positional isomers of pentyl and hexyl. The alkyl groups preferably contain 3-5 carbon atoms.
M is preferably Eu , Tb or Dy.
R2 is preferably hydrogen.
Most preferably, R~ and R3 are each tert-butyl or phenyl.
The invention also relates to a process for the preparation of compounds of formula I, which comprises reacting compounds of formula II
Mlll R~~~R3 - S
(II) in an organic solvent with p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxy-pyridine-N-oxide, wherein R,, R?, R3 and M have the meaning given above.
The preparation of the compunds of formula II is known per se and is described in K. J.
Eisentraut, R. E. Sievers, Inorg. Syn. 11, 1968, 94.
The phenomenon of triboluminescence (emission of light under strong mechanical stress) has long been known and is described, inter alia, in Advances in Physics 1977, Vol. 26, No. 6, 887-948 or in Math. Naturwi ss. Unterricht 4514, 1992, 195-202. A great number of crystalline compounds display this phenomenon, but as yet only very few are known whose emission is so atrong as to be easily observable also in daylight. The brightest triboluminescent substance known so far is triethylammonium tetrakis(dibenzoylmethanato)-europate(III).
Although the p'~enomenon of triboluminescence is well known, its cause cannot be completely accounted for yet and hence no predictions can be made concerning the occurrence of particularly intense triboluminescent compounds.
Specific Eu(III) complexes with pyridine-N-oxide, 2-, 3-,or 4-picoline-N-oxide and bipyridine-N, N-dioxide as well as thenoyltrifluoroacetone as ligand are disclosed in CA 114(18):17'7114p as triboluminescent substances of intense brightness.
It has now been found that a specific group of predominantly colourless lanthanide complexes displays particularly bright triboluminescence, which complexes have very narrowband emission lines, pronounced Stokes' shift, as well as long-lasting luminescence and a high quantum yield of photochemically excited luminenscence.
By virtue of thE~ir long-lasting photochemically excited luminescence and high luminescence quantum yield, these compounds are also particularly suitable for use as pigments or dyes in the field of security printing. Bank notes and securities are typical examples requiring a high degree of security against unauthorised duplication. The high luminescence of the compounds is able to induce colour changes in the documents printed therewith when duplicated in conventional manner, so that the documents are identifiable as duplicates.
In one of its aspects, the invention relates to compounds of formula I
- L- MIII R~ w R3 O ~ 3 (1), wherein M is Eu, Tb or Dy, Sm;
R2 is hydrogen or C,-Csalkyl, and - R1 and Rg are each independently of the other phenyl, hydrogen or C,-Csalkyl, and L is p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxypyridine-N-oxide.
The Ci=Csalkyl groups can be straight-chain or branched and are typically methyl, ethyl, .
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or the different positional isomers of pentyl and hexyl. The alkyl groups preferably contain 3-5 carbon atoms.
M is preferably Eu , Tb or Dy.
R2 is preferably hydrogen.
Most preferably, R~ and R3 are each tert-butyl or phenyl.
The invention also relates to a process for the preparation of compounds of formula I, which comprises reacting compounds of formula II
Mlll R~~~R3 - S
(II) in an organic solvent with p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxy-pyridine-N-oxide, wherein R,, R?, R3 and M have the meaning given above.
The preparation of the compunds of formula II is known per se and is described in K. J.
Eisentraut, R. E. Sievers, Inorg. Syn. 11, 1968, 94.
Organic solvent's are preferably alcohols, ethers, ketones, acid amides, aliphatic or aromatic nitrites, saturated or unsaturated hydrocarbons, chlorinated hydrocarbons or aromatic compounds, or Emixtures thereof.
Particularly preferred solvents are C,-Csalcohol, benzonitrile or acetonitrile.
The reaction is ;preferably carried out in the temperature range from 20° C to 150° C.
Reaction time and printing conditions are per se non-critical, and the reaction is preferably carried out under conditions of nom~al pressure. The reaction time may be in the range from minutes to 24 hours and is preferably from 1 to 5 hours.
By virtue of their luminescent properties, the compounds can be used as optical sensors for detecting oxygE~~n, as is disclosed in the case of some lanthanide complexes, inter alia, in EP-A-0 259 95'i .
Another potential field of use for triboluminescent lanthanide complexes is also, for example, that of surface analysis in grinding processes in spiral jet mills, as described by H. Kurten and (a. Rumpf in Chem. Ing. Technik 38, 3 (1966) 331-342.
Their tribolumirescent properties make the compounds of formula I admirably suited for use as optical sensors sensitive to impact, tension or pressure, which sensors can, for example, be attached as warning elements to cargo which has to be protected from too great a mechanical strE~ss.
Accordingly, th~:~ invention also relates to a coated material sensitive to impact, tension or pressure, whersin a crystalline layer a) consisting of the compounds of formula I is coated onto at least ore side of a substratE~.
The form of thEsubstrate is intrinsically non-critical and will depend on the requirements of .
r , the user. Possible embodiments are, for example, spherical, cylindrical, u-shaped or planar.
The substrate is preferably substantially planar.
The substrate i:an be coated with the crystalline layer a) on one side or on both sides, but preferably on cane side only.
Particularly preferred solvents are C,-Csalcohol, benzonitrile or acetonitrile.
The reaction is ;preferably carried out in the temperature range from 20° C to 150° C.
Reaction time and printing conditions are per se non-critical, and the reaction is preferably carried out under conditions of nom~al pressure. The reaction time may be in the range from minutes to 24 hours and is preferably from 1 to 5 hours.
By virtue of their luminescent properties, the compounds can be used as optical sensors for detecting oxygE~~n, as is disclosed in the case of some lanthanide complexes, inter alia, in EP-A-0 259 95'i .
Another potential field of use for triboluminescent lanthanide complexes is also, for example, that of surface analysis in grinding processes in spiral jet mills, as described by H. Kurten and (a. Rumpf in Chem. Ing. Technik 38, 3 (1966) 331-342.
Their tribolumirescent properties make the compounds of formula I admirably suited for use as optical sensors sensitive to impact, tension or pressure, which sensors can, for example, be attached as warning elements to cargo which has to be protected from too great a mechanical strE~ss.
Accordingly, th~:~ invention also relates to a coated material sensitive to impact, tension or pressure, whersin a crystalline layer a) consisting of the compounds of formula I is coated onto at least ore side of a substratE~.
The form of thEsubstrate is intrinsically non-critical and will depend on the requirements of .
r , the user. Possible embodiments are, for example, spherical, cylindrical, u-shaped or planar.
The substrate is preferably substantially planar.
The substrate i:an be coated with the crystalline layer a) on one side or on both sides, but preferably on cane side only.
The compounds of formula I can also be homogeneously dispersed in crystalline form in polymers in which they do not dissolve.
Suitable polymers are, for example, thermoplastic polymers, typically polyolefins, polyesters orpolyamides. However, it is also possible to use crosslinked polymers, typically heat-curable melamine resins, as well as acrylates and polyesters which are crosslinked with melamine resins; epoxy resins or polyurethanes. Radiation-curable polymers, typically unsaturated polyesters or acrylate-functional prepolymers, can also be used.
A preferred embodiment of the invention is that wherein the compounds of formula I are .. homogeneously dispersed in a polymeric material and the substrate is coated with said polymeric material.
If the crystalline layer a) is first applied to the substrate, then in a preferred embodiment of the invention a polymeric protective layer is additionally coated onto said crystalline layer a).
Another preferred embodiment of the invention conisists of a substrate coated on at least one side with an adhesive layer to which the crystalline layer a) is applied.
In this case, too, a polymeric protective layer can, if required, be additionally applied.
The substrate can consist of any material. It may consist of metal, plastic, a mineral or a semi-conductor.
The substrate is preferably a plastic material.
The substrate is preferably flexible.
The invention also relates to the use of compounds of formula 1 in optical sensors which are sensitive to impact, tension or pressure.
Suitable polymers are, for example, thermoplastic polymers, typically polyolefins, polyesters orpolyamides. However, it is also possible to use crosslinked polymers, typically heat-curable melamine resins, as well as acrylates and polyesters which are crosslinked with melamine resins; epoxy resins or polyurethanes. Radiation-curable polymers, typically unsaturated polyesters or acrylate-functional prepolymers, can also be used.
A preferred embodiment of the invention is that wherein the compounds of formula I are .. homogeneously dispersed in a polymeric material and the substrate is coated with said polymeric material.
If the crystalline layer a) is first applied to the substrate, then in a preferred embodiment of the invention a polymeric protective layer is additionally coated onto said crystalline layer a).
Another preferred embodiment of the invention conisists of a substrate coated on at least one side with an adhesive layer to which the crystalline layer a) is applied.
In this case, too, a polymeric protective layer can, if required, be additionally applied.
The substrate can consist of any material. It may consist of metal, plastic, a mineral or a semi-conductor.
The substrate is preferably a plastic material.
The substrate is preferably flexible.
The invention also relates to the use of compounds of formula 1 in optical sensors which are sensitive to impact, tension or pressure.
The following Examples illustrate the invention.
Working Examples Example A1: Preparation of a tris(1,3 di-tert-butyl-fi-propanedione)europate-p-dimethyl-aminopyridine complex ml of a 5 mmolar ethanolic solution of p-dimethylaminopyridine are slowly added to 50 ml of a 5 mmolar solution of tris(1,3 di-tert-butyl=~i-propanedione)europate in ethanol. The turbid solution is refluxed for 2.5 hours. After cooling, the solution is filtered over Kieselgur*
and the filtrate is fully concentrated by evaporation to dryness. The crude product is recrystallised from acetonitrile (only the-complex containing p-methoxypyridine-N-oxide is recrystallised from petroleum ether).
The tris(1,3 di-tert-butyl-a-propanedione)europate-p-dimethylaminopyridine complex is obtained in good yield.
The compounds A2=A6 characterised in Table 1 are 'prepared in analogous manner.
*Trade-mark WO 96/20942 PCT/EP96/0000~
Working Examples Example A1: Preparation of a tris(1,3 di-tert-butyl-fi-propanedione)europate-p-dimethyl-aminopyridine complex ml of a 5 mmolar ethanolic solution of p-dimethylaminopyridine are slowly added to 50 ml of a 5 mmolar solution of tris(1,3 di-tert-butyl=~i-propanedione)europate in ethanol. The turbid solution is refluxed for 2.5 hours. After cooling, the solution is filtered over Kieselgur*
and the filtrate is fully concentrated by evaporation to dryness. The crude product is recrystallised from acetonitrile (only the-complex containing p-methoxypyridine-N-oxide is recrystallised from petroleum ether).
The tris(1,3 di-tert-butyl-a-propanedione)europate-p-dimethylaminopyridine complex is obtained in good yield.
The compounds A2=A6 characterised in Table 1 are 'prepared in analogous manner.
*Trade-mark WO 96/20942 PCT/EP96/0000~
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z° Q a a Q a Q
~°
_7_ Use Examples Example B1 0. 6 g of the compound of Example A1 is stirred into a mixture consisting of 4.43 g of polyisocyanate (Desmodur~ N 75, supplied by Bayer AG) and 5.54 g of polyol (Desmophen~ 650, supplied by Bayer AG) until the mixture is homogeneous. A 2 mm metal plate is coated with this mixture over a surface area of c. 50 cm2. The layer is dried for 30 minutes at 80° C to form a hard polyurethane layer: The thickness of the dry layer is c.
500 N.m. Irradiation of this layer with light having a wavelength of 365 nm results in bright green luminescence.
Bright green luminescence .is also visible when the surface is subjected to pressure, impact or friction.
Example 82 0.6 g of the compound of Example A1 is stirred into 10 g of a commercial adhesive ( Kohstruvit,~supplied by Geistlich AG ) until the mixture is homogeneous. The mixture is then coated onto a plastic card over a surface area of c. 20 cm2 and allowed to dry.
Irradiation of this adhesive layer with light having a wavelength of 365 nm results in bright green luminescence.
-- Bright green luminescence is also visible when the surface is subjected to pressure, impact.
or friction.
Example B3 0.7 g of the compound of Example A1 are stirred into 7.4 g of a rubber adhesive (Sanford-rubber cement) until the mixture is homogeneous. The mixture is then coated onto a plastic card over a surface~area of c. 20 cm2 and allowed to dry. Bright green luminescence is visible when the surface is subjected to pressure, impact or friction.
Irradiation of this adhesive layer with tight having a wavelength of 365 nm results in bright green luminescence.
*Trade-mark
'- ~3 o ~? ~ ~ ~ ~ o . U 3 ~ ~ 3 ~ >. o O T T
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T T T T T T
.: Z X r Cm ('09 ~ ~ N
~ C~ CO C~ T M M
.. = X ~ O
o ~ ~ O O
1~ CD N CD 00 CO
tn tn N T ~ O
o ~ t0 a ~ ~ ~ CD
Z ~ C~ C~ ~t Cfl tn ~
o " c~ CO C9 T C~ N
_ ~ O Or r CD O IOC
' .y o ""' CO 00 GO P~ 00 d' ~ C~O N ~ N
- o ~ ~ ~ tOI~ ~ i~ COO
z z z a z ! a~
J ".", a pC .~, .., ... » r .:. sz a~ o ~, = a c ~ u> > :~ c r ~ .n .c ~ ~ t ~ c 'o CC »r .;. .~. .~. .~. Q. ~ a~ Q
E r c N O O -- ~ _ _ _ _ _ _ O O- O
N E
~ H D W E~-. ~ Uj 11 II !I
T
_. , Q Q
z° Q a a Q a Q
~°
_7_ Use Examples Example B1 0. 6 g of the compound of Example A1 is stirred into a mixture consisting of 4.43 g of polyisocyanate (Desmodur~ N 75, supplied by Bayer AG) and 5.54 g of polyol (Desmophen~ 650, supplied by Bayer AG) until the mixture is homogeneous. A 2 mm metal plate is coated with this mixture over a surface area of c. 50 cm2. The layer is dried for 30 minutes at 80° C to form a hard polyurethane layer: The thickness of the dry layer is c.
500 N.m. Irradiation of this layer with light having a wavelength of 365 nm results in bright green luminescence.
Bright green luminescence .is also visible when the surface is subjected to pressure, impact or friction.
Example 82 0.6 g of the compound of Example A1 is stirred into 10 g of a commercial adhesive ( Kohstruvit,~supplied by Geistlich AG ) until the mixture is homogeneous. The mixture is then coated onto a plastic card over a surface area of c. 20 cm2 and allowed to dry.
Irradiation of this adhesive layer with light having a wavelength of 365 nm results in bright green luminescence.
-- Bright green luminescence is also visible when the surface is subjected to pressure, impact.
or friction.
Example B3 0.7 g of the compound of Example A1 are stirred into 7.4 g of a rubber adhesive (Sanford-rubber cement) until the mixture is homogeneous. The mixture is then coated onto a plastic card over a surface~area of c. 20 cm2 and allowed to dry. Bright green luminescence is visible when the surface is subjected to pressure, impact or friction.
Irradiation of this adhesive layer with tight having a wavelength of 365 nm results in bright green luminescence.
*Trade-mark
Claims (16)
1. A compound of formula I
wherein M is Eu, Tb, Dy or Sm;
R2, is hydrogen or C1-C6alkyl, and R1 and R3 are each independently of the other phenyl, hydrogen or C,-C6alkyl, and L is p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxypyridine-N-oxide.
wherein M is Eu, Tb, Dy or Sm;
R2, is hydrogen or C1-C6alkyl, and R1 and R3 are each independently of the other phenyl, hydrogen or C,-C6alkyl, and L is p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxypyridine-N-oxide.
2. A compound according to claim 1, wherein M is Eu, Tb or Dy.
3. A compound according to claim 1 or 2, wherein R2 is hydrogen.
4. A compound according to any one of claims 1 to 3, wherein R1 and R3 are each phenyl or tert-butyl.
5. A process for the preparation of a compound of formula I, which comprises reacting a compound of formula II
in an organic solvent with p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxy-pyridine-N-oxide, wherein the compound of formula I, R1, R2, R3 and M are as defined in claim 1.
in an organic solvent with p-N,N-dimethylaminopyridine, N-methylimidazole or p-methoxy-pyridine-N-oxide, wherein the compound of formula I, R1, R2, R3 and M are as defined in claim 1.
6. A process according to claim 5, wherein the organic solvent is selected from the group consisting of alcohols, ethers, ketones, acid amides, aliphatic and aromatic nitriles, saturated and unsaturated hydrocarbons, chlorinated hydrocarbons and aromatic compounds, and mixtures thereof.
7. A process according to claim 6, wherein the organic solvent is a C1-C6 alcohol, benzonitrile or acetonitrile.
8. A process according to any one of claims 5 to 7, which comprises carrying out the reaction in the temperature range from 20°C to 150°C.
9. A coated material, wherein a crystalline layer a) consisting of one or more compounds of formula I as defined in claim 1, is coated onto at least one side of a substrate.
10. A coated material according to claim 9, wherein the substrate is planar.
11. A coated material according to claim 9 or 10, wherein a polymeric protective layer is coated onto the crystalline layer a).
12. A coated material according to any one of claims 9 to 11, wherein the substrate is coated with a polymeric dispersion material, said polymeric dispersion material comprising the one or more compounds of formula I
homogeneously dispersed in a polymeric material.
homogeneously dispersed in a polymeric material.
13. A coated material according to any one of claims 9 to 11, wherein the substrate is coated on at least one side with an adhesive layer to which the crystalline layer a) is applied.
14. A coated material according to any one of claims 9 to 13, wherein the substrate is a plastic material.
15. A coated material according to claim 14, wherein the substrate is flexible.
16. Use of the material as claimed in any one of claims 9 to 15 as an optical sensor which is sensitive to impact, tension or pressure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4095 | 1995-01-06 | ||
| CH40/95 | 1995-01-06 | ||
| PCT/EP1996/000005 WO1996020942A2 (en) | 1995-01-06 | 1996-01-03 | Triboluminescent lanthanideiii complexes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2208568A1 CA2208568A1 (en) | 1996-07-11 |
| CA2208568C true CA2208568C (en) | 2006-10-24 |
Family
ID=37309465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002208568A Expired - Fee Related CA2208568C (en) | 1995-01-06 | 1996-01-03 | Triboluminescent lanthanide iii complexes |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2208568C (en) |
-
1996
- 1996-01-03 CA CA002208568A patent/CA2208568C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2208568A1 (en) | 1996-07-11 |
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