DE102010011564A1 - New modified polyvinyl alcohol exhibiting vinyl alcohol repeating units and substituted (1,3)dioxane repeating units, useful as colorant for dyeing purposes, printing and writing inks and as fluorescent dyes - Google Patents

Abstract

Modified polyvinyl alcohol exhibiting vinyl alcohol repeating units (I) and substituted [1,3]dioxane repeating units (II), is new. Modified polyvinyl alcohol exhibiting vinyl alcohol repeating units of formula (-(CH 2-CH(OH))-) (I) and substituted [1,3]dioxane repeating units of formula (II), is new. Y1 : chromophoric structural unit, which absorbs light in a wavelength region of 350-3500 nm. Independent claims are also included for: (1) nanoparticles comprising at least one above mentioned modified polyvinyl alcohol; (2) nanodistribution of the nanoparticles in a polymeric solid or a liquid; and (3) preparing the modified polyvinyl alcohol. [Image].

Description

State of the art

Ink is widely used in printing techniques, such as today's popular inkjet printers, and as writing ink. Here, mainly hydrophilized chromophores are used to obtain the dyeings. However, chromophores homogeneously dissolved in water have two disadvantages, in particular for such applications. Thus, on the one hand, in the case of inkjet printing products, the dyeing can be washed out of the material relatively easily, so that such printed products are not water-resistant and in general are also non-documentary. On the other hand, the relatively small amount of dye applied adversely affects the light fastness of such products. A much higher concentration of chromophores results in the use of pigments, which not only can be expected to be more light-fast, but also, as insoluble materials, are much more difficult to remove from the paper surface. The Chinese ink, which is a finely divided carbon pigment, is the most prominent example of such colloidal dispersions used for writing and painting purposes. Ink drawings are characterized by their water resistance and high light fastness and are known for their durability over thousands of years. However, such a colloid is disadvantageous to the ink-carrying structures required for writing, painting, and printing because it easily clogs thin fluid channels. A middle ground between ink and ink would bring considerable progress. Moreover, if such a material still fluoresces, then print products can easily be made machine readable.

task

The object of the present invention was to develop improved inky writing and printing fluids.

description

A middle ground between the homogeneous, molecularly disperse solution and colloids with macroscopic particles offers the nanotechnology. Nanoparticles are much larger than molecular structures and therefore have many of the advantages that are appreciated for pigment particles. On the other hand, they have many properties of homogeneously dissolved material. However, the use of nanoparticles often faces health and environmental concerns, especially with long-lived inorganic nanoparticles. This can be problematic in their use in outspoken mass-produced articles.

A compromise would be purely organic nanoparticles, from which one can expect a sufficiently rapid biodegradation. However, purely organic functional nanoparticles have been little investigated in relation to the inorganic particles.

For the preparation of strongly polar, water-compatible nanoparticles, we have started from a suitable macromolecular material. Here is polyvinyl alcohol because of the large number of polar OH groups a promising candidate. At a molecular weight of about 15,000 nanoparticles of 70 nm diameter are found in aqueous solution. We have tried to combine these nanoparticles with suitable chromophores to obtain colored nanoparticles. For lightfast nanoinks correspondingly stable chromophores are needed. Here, the perylene dyes 1 are particularly attractive, since they are characterized by their high light fastness, high fluorescence quantum yields and chemical resistance; however, they are usually sparingly soluble and are used as pigments.

[1]

a) H. Langhals, Molecular devices. Chiral, bichromophoric silicones: Ordering principles in complex molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51–63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4 . b) H. Langhals, Helv. Chim. Acta. 2005, 88, 1309–1343. c) H. Langhals, Heterocycles 1995, 40, 477–500 .

. Die Verbindung 1a erhält durch ihre langkettigen sec-Alkylreste eine hohe Löslichkeit in lipophilen Medien, so dass die Verbindung problemlos für Fluoreszenzanwendungen zugänglich wird und hier z. B. für das Kalibrieren von Fluoreszenzspektrometern eingesetzt worden ist [2]

[2]

a) S. Kalinin, M. Speckbacher, H. Langhals, L. B.-A. Johansson, Phys. Chem. Chem. Phys. 2001, 3, 172–174 . b) H. Langhals, J. Karolin, L. B.-A. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919–2922 .

. Solche Farbstoffe haben insbesondere auch bei modernen technologischen Entwicklungen eine zunehmende Bedeutung erlangt, wie z. B. photovoltaische Zellen [3]

[3]

a) C. J. Brabec, N. S. Sariciftci, J. C. Hummelen, Adv. Funct. Mater. 2001, 11, 15–26 ; b) S. Günes, H. Neugebauer, N. S. Sariciftci, Chem. Rev. 2007, 107, 1324–1338 .

, photoelektrochemische Zellen [4]

[4]

a) M. Grätzel, Nature 2001, 414, 338–344 ; b) H. Choi, S. Kim, S. O. Kang, J. Ko. M, -S. Kang, J. N. Clifford, A. Forneli, E. Palomares, M. K. Nazeeruddin, M. Grätzel, Angew. Chem. 2008, 120, 8383–8387; Angew. Chem. Int. Ed. 2008, 47, 8259–8263 ; c) F. Gao, Y. Wang, D. Shi, J. Zhang, M. Wang, X. Jing, R. Humphry-Baker, P. Wang, S. M. Zakeeruddin, M. Grätzel, J. Am. Chem. Soc. 2008, 130, 10720–10728 .

und bei der künstlichen Photosynthese [5]

[5]

a) D. Gust, T. A. Moore, A. L. Moore, Acc. Chem. Res. 2001, 34, 40–48 ; b) M. R. Wasielewski, J. Org. Chem. 2006, 71, 5051–5066 . c) F. Gärtner, B. Sundararaju, A.-E. Surkus, A. Boddien, B. Loges, H. Junge, P. H. Dixneuf, M. Beller, Angew. Chem. 2009, 121, 10147–10150; Angew. Chem. Int. Ed. 2009, 48, 9962–9965 .

. Sie wären wegen ihrer ungewöhnlich guten Eigenschaften ideale Chromophore für fluoreszierende Nanopartikel.Easily soluble derivatives of 1 are obtained by the substitution of the nitrogen atoms with sec-alkyl radicals, such as. With the 1-hexylheptyl radical in 1a, so that they can be handled in homogeneous solution [1]

[1]

a) H. Langhals, Molecular Devices. Chiral, bichromophoric silicones: Ordering principles in complex molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51-63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4 , b) H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343. c) H. Langhals, Heterocycles 1995, 40, 477-500 ,

, The compound 1a obtained by their long-chain sec-alkyl radicals a high solubility in lipophilic media, so that the compound is easily accessible for fluorescence applications and here z. B. has been used for calibrating fluorescence spectrometers [2]

[2]

a) S. Kalinin, M. Speckbacher, H. Langhals, LB-A. Johansson, Phys. Chem. Chem. Phys. 2001, 3, 172-174 , b) H. Langhals, J. Karolin, LB-A. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922 ,

, Such dyes have in particular in modern technological developments acquired an increasing importance, such. B. photovoltaic cells [3]

[3]

a) CJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct. Mater. 2001, 11, 15-26 ; b) Günes, H. Neugebauer, NS Sariciftci, Chem. Rev. 2007, 107, 1324-1338 ,

, photoelectrochemical cells [4]

[4]

a) M. Grätzel, Nature 2001, 414, 338-344 ; b) H. Choi, S. Kim, SO Kang, J. Ko. M, -S. Kang, JN Clifford, A. Forneli, E. Palomares, MK Nazeeruddin, M. Graetzel, Angew. Chem. 2008, 120, 8383-8387; Angew. Chem. Int. Ed. 2008, 47, 8259-8263 ; c) F. Gao, Y. Wang, D. Shi, J. Zhang, M. Wang, X. Jing, R. Humphry-Baker, P. Wang, SM Zakeeruddin, M. Grätzel, J. Am. Chem. Soc. 2008, 130, 10720-10728 ,

and in artificial photosynthesis [5]

[5]

a) D. Gust, TA Moore, AL Moore, Acc. Chem. Res. 2001, 34, 40-48 ; b) MR Wasielewski, J. Org. Chem. 2006, 71, 5051-5066 , c) F. Gärtner, B. Sundararaju, A.-E. Surkus, A. Boddien, B. Loges, H. Junge, PH Dixneuf, M. Beller, Angew. Chem. 2009, 121, 10147-10150; Angew. Chem. Int. Ed. 2009, 48, 9962-9965 ,

, They would be ideal chromophores for fluorescent nanoparticles because of their unusually good properties.

[6]

H.-G. Elias, Makromoleküle, Bd. 2, Technologie, 5. Aufl., S. 158–159, Hüthig und Wepf, Basel, 1992, ISBN 3-85739-102-2 .

. Wir haben untersucht, ob derartige Reaktionen mit Perylenaldehyden möglich sind. Hier ist als Komplikation eine Unverträglichkeit der beiden sehr unterschiedlich polaren Materialien zu erwarten, denn Polyvinylalkohol löst sich als ausgesprochen polares Polymer bevorzugt in polaren Medien, während die Perylenfarbstoffe ausgeprägt lipophile Eigenschaften aufweisen.In order to make the said polyvinyl alcohol to an optical functional material, one has to ask whether it can be linked to chromophores. Such a reaction should proceed with high efficiency in order to achieve a correspondingly high loading with the chromophores functioning as optical components. The reaction of polyvinyl alcohol with butyraldehyde is carried out to polyvinyl butyral, which is characterized as mechanically tough plastic, z. B. is used as splinter protection for silicate glass [6]

[6]

H.-G. Elias, macromolecules, Vol. 2, Technology, 5th ed., Pp. 158-159, Hüthig and Wepf, Basel, 1992, ISBN 3-85739-102-2 ,

, We have investigated whether such reactions with perylene aldehydes are possible. Here is to be expected as a complication of an incompatibility of the two very different polar materials, because polyvinyl alcohol dissolves as pronounced polar polymer preferably in polar media, while the perylene dyes have pronounced lipophilic properties.

[7]

H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328–4336 .

synthetisiert und diesen mit Polyvinylalkohol im Lösungsmittel DMSO als Reaktionsmedium unter Zusatz von 4-Toluolsulfonsäure als Katalysator umgesetzt und damit eine erstaunlich leicht ablaufende Reaktion zum betreffenden Acetal 2 erzielen können [8]

[8]

H. Langhals, T. Pust, Ger. Offen. DE 10 2010 006 182.4 (29.1.2010).

; siehe 2. Das auf diese Weise erhaltene Material ist überraschenderweise komplett in Wasser löslich und bildet stark fluoreszierende Lösungen mit zwei Typen von Nanopartikeln mit Häufigkeitsmaxima bei Durchmessern von 70 und 350 nm, siehe 1, während der Ausgangs-Aldehyd in Wasser komplett unlöslich ist.As starting material for polymer-analogous reactions of polyvinyl alcohol, we have a perylene aldehyde [7]

[7]

H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328-4336 ,

synthesized and this reacted with polyvinyl alcohol in the solvent DMSO as the reaction medium with the addition of 4-toluenesulfonic acid as a catalyst and thus can achieve a surprisingly easy-going reaction to the respective acetal 2 [8th]

[8th]

H. Langhals, T. Pust, Ger. Open. DE 10 2010 006 182.4 (29.1.2010).

; please refer 2 , The material obtained in this way is surprisingly completely soluble in water and forms strongly fluorescent solutions with two types of nanoparticles with abundance maxima at diameters of 70 and 350 nm, see 1 while the starting aldehyde is completely insoluble in water.

However, the absorption of these nanoparticles in water is still relatively short-waved, so that they are less suitable as a dark ink, because significantly deeper-colored materials are expected here. We have therefore searched for alternatives to the chromophores 1.

The dye 1a can be converted with sodium amide and benzonitrile into the longer-wavelength absorbing imidazole derivative 3, whose NH group we have alkylated as a nucleophile with a Benzylbromid, which was substituted in the 4-position with a protected as ethylene acetal aldehyde. Its deprotection in the course of work-up gave the aldehyde 4 as a synthetic building block for the fluorescent labeling of the polyvinyl alcohol to 5; please refer 3 , As an alternative, we synthesized a benzonitrile that was 4-positioned with an aldehyde function protected as an ethylene acal. This resulted in the reaction with sodium amide and 1a and deprotection in the course of work-up in an analogous manner, the aldehyde 6; please refer 4 ,

The two aldehydes 4 and 6 were each condensed with polyvinyl alcohol under acid catalysis in DMSO. There were surprisingly strong colored solids 5 and 7, in which the dyeing with no solvents, such as. As the highly lipophilic chloroform, was removed, so that a covalent linkage with the polyvinyl alcohol is occupied.

When the fluorescence-labeled dye 7 is introduced into water, it surprisingly spontaneously forms nanoparticles, which also pass smoothly through a D5 glass frit without leaving any residue, so that the Nanodimensions of the particles distributed in water are occupied. The size distribution of the nanoparticles has been determined by the DLS method; please refer 5 , One finds for 7 a maximum at 25 nm and a second at about 100 nm; this corresponds to the behavior of 2. At 5 we even find three maxima: at 25 nm, at 90 nm and at 300 nm. According to the results so far, these are associates that exchange dynamically. If little material is introduced into water, then a "royal blue" aqueous phase is formed, which turns blue black at a higher level; please refer 6 , There is a faint red fluorescence, which is noticeable only in strong light sources. Large parts of the fluorescence spectrum extend into the NIR region. Fluorescence is thus less noticeable under normal illumination, but the NIR fluorescence can be used for a machine reading of the substance. The labeled polyvinyl alcohol 5 absorbs much shorter wavelength than the labeled alcohol 7, so that blue water phases are obtained with a purple shade. At higher concentration these are black-purple. But you can already clearly see a red fluorescence with usual lighting. The substance is therefore suitable as a dark fluorescent ink, in which the fluorescence should be seen under normal lighting. The UV / Vis absorption and fluorescence spectra are in 6 shown. The spectra differ significantly from the spectra of the chromophores in homogeneous solution. In particular, the fluorescence spectra are long-wavelength shifted, while the absorption spectra are hypsochromic shifted. This is an indication that an aggregation of chromophores occurs, with their skewed arrangement is likely.

The colored nanoparticles 5 and 7 can be applied to surfaces such as paper or alumina. 7 applied from aqueous phase on paper, then results in a strong blue color, which could be removed after drying, surprisingly, neither with water, nor with ethanol, or with DMF or DMF / water, and it was not possible, the dye by concentrated sodium hypochlorite Bleach solution (25%). In the material applied to paper, a barely visible red fluorescence of the blue color appears. The solid fluorescence excitation spectrum is bathochromic with respect to that of the nanoparticles displaced in solution, while the fluorescence spectrum is almost congruent with the spectrum of the particles in water; please refer 7 , It can be seen that a large part of the fluorescence extends into the NIR region. This makes it easy to read out with machines. The dye 5 also draws on paper, and it did not succeed after drying to remove a stain with water, ethanol or DMF or bleach with concentrated hypochlorite solution. The staining with 5 has a clear red nuance with respect to 7, and there is a visually striking red fluorescence.

Both the aqueous phases of Dyes 5 and 7 and the dyeings on paper are extremely stable. No changes are observed neither in the storage (more than half a year) nor in the colorings. Solutions and colorings survive months of direct sunlight. The sum of these unusually good properties makes the substances interesting as a document-fast ink. This applies to pen and writing instruments (ink fountain pen, glass pen or fountain pens in question), ballpoint pen writing and drawing instruments (ballpoint pens), felt-writing and drawing equipment (felt pens) as well as for machine printing processes, especially inkjet printing devices - here is the great durability of the ink really important. Finally, the ink, possibly with the addition of thickeners in high pressure, gravure and in planographic printing use; In this case, the planographic printing of particular interest because the dyes have highly hydrophilic properties and are tailored to special interactions with surfaces, as they are needed in planographic printing.

conclusion

From perylenetetracarboxylic bisimides such as 1a, lateral expansion and functionalization give long-wave absorbing aldehydes, which in a polymer-analogous reaction with polyvinyl alcohol lead to deep-colored materials. These spontaneously disperse into nanoparticles in the aqueous phase. Such a phase can be used depending on the substitution pattern of the dye to pure blue or red-blue inks. While the former fluoresce in the NIR so that prints printed with them are also machine readable via fluorescence, the fluorescence of the latter can also be visually detected. Paper inks are resistant to water and various organic solvents, including bleach sodium hypochlorite. Such inks can also be used for writing as well as printing purposes.

Experimental part

General.

• IR spectra: FT 1000; UV / Vis spectra: Varian Cary 5000; Fluorescence spectra: Varian Eclispe; NMR spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95.

4-(1,3-Dioxolan-2-yl)benzonitril ^[7]H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328–4336 (8):

4- (1,3-dioxolan-2-yl) benzonitrile ^[7] H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328-4336 (8):

2,11-Bis(1-hexylheptyl)-5-(4-formylphenyl)imidazolo[4',5':3,4]anthra[2,1,9-def:6,5,10-d'e'f']diisochinolin-1,3,10,12(2H,11H)-tetraon (6): Cyanobenzaldehyde (15.6 g, 0.119 mol) in toluene (150 mL) was treated with ethylene glycol (47.2 mL, 0.476 mmol) and a spatula tip of 4-toluenesulfonic acid monohydrate, stirred for 20 h under reflux on a water separator, allowed to cool to room temperature, with aqueous NaHCO ₃ (5%, 50 mL) and then extracted twice with distilled water (30 mL), dried with magnesium sulfate, evaporated (colorless oil) and allowed to crystallize: yield. 19.7 g (94.7%) of colorless, hygroscopic solid, mp. 41-42 ° C. ¹ H-NMR (300 MHz, CDCl ₃ , 25 ° C): δ = 3.98-4.12 (m, 4H, OCH ₂ CH ₂ ), 5.82 (s, 1H, OCH), 7.53-7.59 (m, 2H, CH _aryl ), 7.61-7.68 (m, 2H, CH _aryl ). ¹³ C-NMR (75 MHz, CDCl _3, 25 ° C): δ = 65.6, 102.6, 113.1, 118.8, 127.4, 132.4, 143.3. MS (DEI ⁺ , 70 eV): m / z (%): 176.1 (3.2), 175.1 (28.7), 174.1 (100) [M ⁺ -H], 131.1 (4.0), 130.1 (34.8) [M ⁺ - C ₂ H ₄ O], 103.2 (16.3), 102.1 (15.1) [M ⁺ -C ₃ H ₄ O ₂ ]. HRMS (C ₁₀ H ₉ O ₂ N): Ber. m / z: 175.0633, Gef. m / z: 175.0612, Δ = -0.0021

2,11-bis (1-hexylheptyl) -5- (4-formylphenyl) imidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d'e ' f '] diisoquinoline-1,3,10,12 (2H, 11H) -tetraone (6):

N, N'-bis (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid 3,4: 9,10-bisimide (1a, 200 mg, 0.265 mmol) and sodium amide (0.200 g, 5.13 mmol) were in 4 [1,3] dioxolan-2-yl-benzonitrile (8.5 g) for 5 h at 165 ° C heated (blue color), allowed to cool, evaporated to dryness and washed with a 1: 1 mixture of 2 N aqueous HCl and chloroform (300 mL). The organic phase was filtered and freed from chloroform, evaporated, taken up in a little chloroform, purified by column chromatography (silica gel, chloroform), dissolved in THF (100 ml) for deprotection, with a mixture of 2N aqueous HCl and glacial acetic acid (1: 1, 100 mL), boiled under reflux for 8 h, separated from the aqueous phase after cooling, dried with magnesium sulfate, evaporated, dissolved in a little chloroform and precipitated with methanol. Y. 57 mg (23.7%) black-violet dye, mp> 250 ° C. R _f (silica gel, chloroform) = 0.15. IR (ATR): v ~ = 3291.4 br, 2952.7 m, 2920.2 s, 2853.1 s, 1699.9 s, 1681.1 vs, 1649.8 s, 1637.0 s, 1611.5 m, 1592.2 vs, 1575.7 m, 1537.8 w, 1495.4 w, 1465.8 w, 1436.5 w, 1414.0 w, 1388.0 w, 1340.6 vs, 1305.4 m, 1259.1 m, 1213.4 m, 1172.8 w, 1122.8 w, 1060.1 w, 1015.9 w, 967.4 w, 871.2 vw, 845.7 w, 813.9 m, 753.8 m, 729.6 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.76-0.89 (m, 12H, CH _3), 1:15 to 1:42 (m, 32H, CH _2), 1.84-1.96 (m, 4H, β-CH ₂ ), 2.21-2.36 (m, 4H, β-CH ₂ ), 5.16-5.31 (m, 2H, α-CH), 8.17 (d, ³ J = 8.3 Hz, 2H, CH _aryl ), 8.50 -8.58 (m, 2H, CH _aryl ), 8.61-8.87 (m, 5H, CH _perylene ), 10.18 (s, 1H, CHO), 10.78 (d, ³ J = 8.0 Hz, 1H, CH _perylene ), 11.68 ppm (s, 1H, NH). ¹³ C-NMR (100 MHz, CDCl _3, 25 ° C): δ = 14.3, 14.3, 22.8,122.8, 25.4, 27.2, 27.3, 29.5, 32.0, 32.0, 32.7, 54.9, 121.7, 123.2, 124.0, 127.0, 127.2, 128.5, 129.4, 130.7, 130.7, 131.1, 133.6, 134.9, 138.6, 138.6, 143.8, 191.5 ppm. UV / Vis (CHCl _3): λ _max (ε) = 393.0 (15240), 440.0 (12800), 464.0 (12800), 508.0 (14100), 546.4 (42850), 591.6 nm (813,450). Fluorescence (CHCl _3, λ _exc = 546.4 nm): λ _max (I _rel) = 599.6 (1.00) 653.7 (00:41), 715.8 nm (12:09). Fluoreszenzquantenausb. λ _exc = 546.4 nm, E _{546.4 nm / 1 cm} = 0.0156, CHCl ₃ , reference 1a with Φ = 1.00): Φ = 1.00. MS (DEI ⁺ , 70 eV): m / z (%): 901.2 (21.3), 900.2 (61.7), 899.2 (93.1) [M ⁺ ], 718.7 (11.6), 717.7 (29.2), 716.7 (32.1) [ M ⁺ -C ₁₃ H ₂₇ ], 536.2 (22.8), 535.3 (69.3), 534.1 (100) [M ⁺ -2C ₁₃ H ₂₇ ]. HRMS (C ₅₈ H ₆₆ N ₄ O ₅ ): Ber. m / z: 898.5033; Gef. M / z: 898.5029, Δ = -0.0004. C ₅₈ H ₆₆ N ₄ O ₅ (899.2): Ber. C 76.10, H 7.58, N 6.02; Gef. C 75.66, H 7.38, N 5.90.

2-(4-Bromomethyl-phenyl)-[1,3]dioxolan ^[7]H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328–4336 (9):

2- (4-Bromomethylphenyl) - [1,3] dioxolane ^[7] H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328-4336 (9 ):

4-Bromomethylbenzaldehyde (4.00 g, 20.1 mmol), ethylene glycol (4.99 g, 80.4 mmol) and a spatula tip of 4-toluenesulfonic acid in toluene (50 mL) were heated to 130 ° C using a water trap for 12 h, allowed to cool, with aqueous sodium bicarbonate solution (5 percent, 50 mL) and then extracted twice with distilled water (100 mL), dried over magnesium sulfate and evaporated. Y. 3.51 g (71.8%) of yellowish oil. ¹ H-NMR (200 MHz, CDCl ₃ , 25 ° C): δ = 3.98-4.14 (m, 4H, O-CH ₂ -CH ₂ -O), 4.48 (s, 2H, CH ₂ Br), 5.79 (s, 1H, O-CH-O), 7.33-7.50 ppm (m, 4H, CH _aryl ). ¹³ C-NMR (100 MHz, DMSO-d ₆ , 25 ° C): δ = 34.1, 64.8, 64.9, 102.4, 126.9, 129.2, 138.2, 138.9 ppm. MS (DEI, 70 eV): m / z (%): 244.1 (2.0), 243.1 (14.7), 242.1 (1.8), 241.1 (14.7) [M ⁺ ], 165.2 (1.5), 164.2 (12.0), 163.2 (100.0) [M ⁺ -Br]. HRMS (C ₁₀ H ₁₀ ⁷⁹ BrO ₂ ): Ber. m / z: 240.9859, Gef. m / z: 240.9859, Δ = -0.0000.

4-(4-Formylbenzyl)-2,11-bis(1-hexylheptyl)-5-phenylimidazolo[4',5':3,4]anthra[2,1,9-def:6,5,10-d'e'f']diisochinolin-1,3,10,12(2H,11H)-tetraon(4):

4- (4-formylbenzyl) -2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d 'e'f'] diisoquinoline-1,3,10,12 (2H, 11H) -tetraon (4):

2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def.6,5,10-d'e'f '] diisochinolin- 1,3,10,12 (2H, 11H) -tetraone (3.45 mg, 0.517 mmol) and potassium carbonate (700 mg, 5.07 mmol) in DMPU (20 mL) were heated to 110 ° C (blue coloration), dropwise with 2- (4-bromomethylphenyl) - [1,3] dioxolane (9, 627 mg, 2.58 mmol) (violet color), stirred at 110 ° C for 20 h, allowed to cool, terminated by addition of 2 N aqueous HCl, filtered off with suction, Dried at 110 ° C for 16 h, dissolved in chloroform (50 mL) for deprotection, treated with a mixture of glacial acetic acid and 2 N aqueous HCl (1: 1) for 30 min, freed from the aqueous phase, dried with magnesium sulfate, evaporated, chromatographed (Silica gel, dichloromethane), dissolved in a little chloroform and precipitated with methanol. Y. 354 mg (69.3%) of black-purple solid, mp 198-201 ° C. R _f (silica gel / dichloromethane): 0.13. IR (ATR): v ~ = 2953.6 m, 2923.6 s, 2854.9 m, 1687.8 vs, 1641.9 vs, 1591.3 s, 1530.0 w, 1485.8 w, 1465.3 w, 1424.3 w, 1406.1 vw, 1377.7 vw, 1358.1 vw, 1331.8 vs, 1253.0 m, 1209.3 w, 1181.7 w, 1107.2 w, 1027.8 vw, 931.4 vw, 872.1 w, 843.5 w, 809.2 m, 772.3 w, 749.5 m, 724.0 vw, 702.1 vw cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.81 (t, ³ J = 7.0 Hz, 12H, CH _3), 1:03 to 1:40 (m, 32H, CH _2), 1.79-1.94 ( m, 4H, β-CH _2), 2:04 to 2:18 (m, 2H, β-CH _2), 2:21 to 2:31 (m, 2H, β-CH _2), 4.98-5.25 (m, 2 H, α-CH ), 6.27 (s, 1H, N-CH ₂ ), 6.32 (s, 1H, N-CH ₂ ), 6.67-6.79 (br, 2H, CH _benzyl ), 7.52 (d, ³ J = 8.5 Hz, 2H, CH _{, benzyl} ), 7.61-7.71 (br, 3H, CH _phenyl ), 7.94-8.07 (br, 2H, CH _phenyl ), 8.55-8.80 (m, 5H, CH _perylene ), 9.76 (s, 1H, CHO), 10.79 ppm (d, 1H, ³ J = 8.0 Hz, CH _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.3, 22.8, 22.9, 27.2, 27.3, 29.5, 29.5, 32.0, 32.7, 52.6, 54.9, 65.4, 121.7, 123.0, 124.1, 126.0, 126.5, 127.0, 129.3, 129.5, 129.6, 130.2, 130.5, 131.7, 131.7, 132.6, 134.8, 134.9, 135.0, 135.8, 139.6, 144.7, 163.7, 164.0, 165.1, 191.2 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 376.0 (7320), 395.4 (8250), 436.0 (8760), 499.6 (14500), 536.4 (44810), 580.8 nm (85160). Fluorescence (CHCl ₃ , λ _exc = 536.4 nm): λ _max (I _rel ) = 591.7 (1.00), 643.6 nm (0.45). Fluoreszenzquantenausb. (λ _exc 536.4 nm, E _{536.4 nm / 1 cm} = 0.0134, CHCl ₃ , reference 1a with Φ = 1.00): Φ = 1.00 MS (DEI ⁺ , 70 eV): m / z (%): 991.3 (28.1) 990.3 (72.1), 989.3 (100.0) [M ⁺ + H], 962.3 (4.1), 961.3 (5.7) [M ⁺ -CHO], 808.8 (7.2), 807.8 (17.8), 806.8 (22.0) [M ⁺ - C ₁₃ H ₂₆ ], 625.3 (22.8), 624.3 (41.2) [M ⁺ -2C ₁₃ H ₂₆ ], 507.1 (28.9), 506.1 (39.4, [M ⁺ -2C ₁₃ H ₂₆ -C ₈ H ₇ O]. HRMS (C ₆₅ H ₇₂ N ₄ O ₅ ): m.r./m .: 988.5503, m / z: 988.5491, Δ = -0.0012, C ₆₅ H ₇₂ N ₄ O ₅ (989.3): Ber. C 78.91, H 7.34, N 5.66, Gef C 78.75, H 7.37, N 5.63.

Polymer analogue reaction for the representation of 7:

2,11-bis (1-hexylheptyl) -5- (4-formylphenyl) imidazolo [4 ', 5': 3,4] anthra [2,1,9-def.6,5,10-d'e 'f'] diisoquinoline-1,3,10,12 (2H, 11H) -tetraone (6, 15 mg) was heated to 80 ° C with DMSO (5 mL) and stirred until a homogeneous solution was obtained, dropwise with a homogeneous mixture of DMSO (35 ml) heated to 140 ° C., polyvinyl alcohol (2.5 g, fully hydrolyzed, Merck, M _n = 16,000, degree of hydrolysis 96%, Ester value 30-50) and 4-toluenesulfonic acid (20 mg) added dropwise within 5 min, stirred for 2 h at 100 ° C, allowed to cool, precipitated to stop the reaction with acetone, filtered with suction through a D4 glass frit, with acetone until washed colorless, dried 1 d in vacuo over calcium chloride and phosphorus pentoxide. Dark powder UV / Vis (water): λ _max (E _rel ) 389.0 (0.41), 448.2 (0.57), 470.8 (0.59), 556.4 (1.00), 602.2 nm (0.70). Fluorescence (CHCl ₃ , λ _exc = 556 nm): λ _max (I _rel ) = 726.1 nm (1.00).

Polymer-analogous reaction for the representation of 5:

4- (4-formylbenzyl) -2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d 'e'f'] diisoquinoline-1,3,10,12 (2H, 11H) -tetraone (4, 15 mg) was reacted analogously to 7 and worked up. Dark powder. UV / Vis (CHCl _3): λ _max (E _rel) = 399.0 (0.31), 442.0 (12:31), 542.8 (1.00), 591.0 nm (0.70). Fluorescence (CHCl ₃ , λ _exc = 542 nm): λ _max (I _rel ) = 701.9 nm (1.00).

Subject of the invention

• a. Imidazoloperylenebisimidodioxanpolyvinylakoholderivate of general formula 10,
  
  in which the radicals R 1 to R 10 can be identical or different and independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by in each case carbonyl groups, oxygen atoms , Sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5 - or 3,4-disubstituted thiophene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2 , 6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups by Nitrogen atoms can be replaced, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9, 10 disubs substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10-od he 9,10-disubstituted Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I. The indices m and n in each case independently of one another denote integers in the range from 1 to 1000, preferably 10 to 350.
• b. Imidazoloperylenebisimidodioxanpolyvinylacro derivatives of general formula 11,
  
  in which the radicals R 1 to R 10 have the meaning mentioned under a and R 11 to R 14 have the meaning of R 1 to R 4 mentioned under a.
• c. Nanoparticles of the compounds according to a and b, preferably in the liquid or polymeric phase, more preferably in the liquid phase, most preferably in water.
• d. Use of the substances according to a and b as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as. For example, for glues and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints, as pigments in paints, preferred paints are synthetic resin paints such as acrylic - or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as zapon lacquer, shellac or Qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for bulk dyeing of polymers, examples are materials of polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers , Polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzyl chloride, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples being paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. As for coloring painting and decorating paints, varnishes and other paints, paper colors, printing inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, are particularly luminous hues.
• e. Use of the substances according to a and b for marking, security and display purposes, in particular taking into account their fluorescence, such. B. as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of logotypes and drawings or other graphic products, for marking signs and other objects and in display elements for many display, reference and marking purposes, in which a particular optical color impression can be achieved is for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, the great chemical and photochemical stability and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents , Identification papers and the like, in which a special, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via the fluorescence, preferably the machine detection of objects for sorting, z. B. also for the recycling of plastics, as fluorescent dyes for machine-readable markings, alphanumeric prints or barcodes are preferred as dyes in ink-jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, lighting or image converter systems, in which the excitation by electrons, ions or UV radiation takes place, for. As in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, eg. As in biochemistry, medicine, technology and science, here, the dyes may be covalently linked to substrates or on Nebenvalenzen such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent systems, eg. As in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method and as a material for leak testing of closed systems.
• f. Use of the dyes according to a and b as functional materials, such. As in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"), the frequency conversion of light, z. B. to make short-wave light of longer wavelength, visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collection systems, such as. As the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, eg. As in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. Example, in the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, z. B. for the frequency doubling and frequency tripling of laser light.

figure description

1 , Size distribution of polyvinyl alcohol-based nanoparticles in water. Dashed line: polyvinyl alcohol with a molecular weight of 15,000 (PVA 15,000). Thick, solid line: nanoparticles from the reaction of 5 g of PVA 15000 and 50 mg of a perylene aldehyde. Thin, solid line: nanoparticles from the reaction of 5 g of PVA 15000 and 5 mg of a perylene aldehyde.

2 , Condensation product of a perylene aldehyde and polyvinyl alcohol (2) - schematic structure.

3 , Synthesis of fluorescently labeled polyvinyl alcohol 5.

4 , Synthesis of fluorescence-labeled polyvinyl alcohol 7.

5 , Size distribution of nanoparticles in water determined by the DLS method (dynamic light scattering). 7: thick, solid line, 5: thin, dashed line.

6 , UV / Vis absorption (left) and fluorescence spectra (right) of 7 as nanoparticles in water (thick lines) compared to 5 as nanoparticles (thin dashed lines).

7 , Solids UV / Vis absorption (left) and fluorescence spectra (right) of 7 plotted on paper (thick lines) compared to 5 on paper (thin dashed lines).

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102010006182 [0008]

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• H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343. c) H. Langhals, Heterocycles 1995, 40, 477-500 [0006]
• S. Kalinin, M. Speckbacher, H. Langhals, LB-A. Johansson, Phys. Chem. Chem. Phys. 2001, 3, 172-174 [0006]
• H. Langhals, J. Karolin, LB-A. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922 [0006]
• CJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct. Mater. 2001, 11, 15-26 [0006]
• S. Günes, H. Neugebauer, NS Sariciftci, Chem. Rev. 2007, 107, 1324-1338 [0006]
• M. Grätzel, Nature 2001, 414, 338-344 [0006]
• H. Choi, S. Kim, SO Kang, J. Ko. M, -S. Kang, JN Clifford, A. Forneli, E. Palomares, MK Nazeeruddin, M. Graetzel, Angew. Chem. 2008, 120, 8383-8387; Angew. Chem. Int. Ed. 2008, 47, 8259-8263 [0006]
• F. Gao, Y. Wang, D. Shi, J. Zhang, M. Wang, X. Jing, R. Humphry-Baker, P. Wang, SM Zakeeruddin, M. Grätzel, J. Am. Chem. Soc. 2008, 130, 10720-10728 [0006]
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Claims (6)

Imidazoloperylenebisimidodioxanpolyvinylakoholderivate of general formula 10,

in which the radicals R 1 to R 10 can be identical or different and independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by in each case carbonyl groups, oxygen atoms , Sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5 - or 3,4-disubstituted thiophene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2 , 6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups can be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted Anthracene residues in which one or two CH groups can be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9, 10 disubs substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10-od he 9,10-disubstituted Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary C Atoms are linked in pairs, so that rings arise, such. B. cyclohexane rings. The radicals R ¹ to R ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I. The indices m and n in each case independently of one another denote integers in the range from 1 to 1000, preferably 10 to 350. Imidazoloperylenebisimidodioxanpolyvinylakoholderivate of general formula 10,

in which the radicals R 1 to R 10 have the meaning mentioned under 1 and R 11 to R 14 have the meaning of R 1 to R 4 mentioned under 1. Nanoparticles of the compounds according to 1 and 2, preferably in the liquid or polymeric phase, more preferably in the liquid phase, most preferably in water. Use of the substances according to 1 and 2 as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as. For example, for glues and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints, as pigments in paints, preferred paints are synthetic resin paints such as acrylic or vinyl resins, polyester lacquers, novolaks, nitrocellulose lacquers (nitro lacquers) or also natural substances such as zapol lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for mass coloration of polymers, examples are materials of polyvinyl chloride, Polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, polyethylene, polypropylene, polyvinylacetate, Polyacrylnit ril, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples being paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, Flax or its transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. B. for Coloring of painting and decorating paints, varnishes and other paints, paper inks, printing inks, inks and other colors for painting and writing purposes, in addition to other colors in which a particular shade is to be achieved, preferred are particularly bright shades. Use of the substances according to 1 and 2 for marking, security and display purposes, in particular taking into account their fluorescence, such. B. as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of logotypes and drawings or other graphic products, for marking signs and other objects and in display elements for many display, reference and marking purposes, in which a particular optical color impression can be achieved is for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, the great chemical and photochemical stability and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents , Identification papers and the like, in which a special, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via the fluorescence, preferably the machine detection of objects for sorting, z. B. also for the recycling of plastics, as fluorescent dyes for machine-readable markings, alphanumeric prints or barcodes are preferred as dyes in ink-jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, lighting or image converter systems, in which the excitation by electrons, ions or UV radiation takes place, for. As in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, eg. As in biochemistry, medicine, technology and science, here, the dyes may be covalently linked to substrates or on Nebenvalenzen such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent systems, eg. As in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method and as a material for leak testing of closed systems. Use of the dyes according to 1 and 2 as functional materials, such. As in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"), the frequency conversion of light, z. B. to make short-wave light of longer wavelength, visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collection systems, such as. As the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, eg. As in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. Example, in the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, z. B. for the frequency doubling and frequency tripling of laser light.

Images