WO2011092028A1 - Nanoparticles and nanoink - Google Patents

Abstract

The invention relates to a modified polyvinyl alcohol that is covalently linked to chromophore structural units and that can form nanoparticles, in particular a modified polyvinyl alcohol in the form of a compound comprising repeating units of the following formula (I) and repeating units of the following formula (II): Formula (I) and formula (II), where Y in formula (II) denotes a chromophore structural unit.

Description

 Nanoparticles and nanoinks

The present invention relates to polymers which contain organic chromophores and are suitable for the formation of nanoparticles.

Nanoparticles are gaining increasing interest in science and technology and are used in numerous technical products. In this case, water-dispersible nanoparticles are of particular importance. The introduction of chromophores as light-absorbing structures turns these nanoparticles into functional optical materials. When fluorescent structures are used, the absorbed light energy is not converted into heat, but is available for further processes. Organic materials are of particular interest as chromophores because they are characterized by a strong light absorption capacity, a broad and effective variation possibility and a special environmental compatibility.

An interesting application of nanoparticles is the production of inks. 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 brings the use of pigments. They are not only characterized by a high light fastness, but they are also as insoluble materials also much more difficult to remove from the paper surface again. 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 colloid is disadvantageous to the ink-bearing structures required for writing, painting, and printing because it easily clogs thin fluid channels. A material that combines the advantages of the ink in terms of handling and the benefits of the ink in terms of durability through the use of nanoparticles containing chromophores would bring a significant advance here. In addition, if such a material fluoresces in addition, then printed products can be easily made machine readable.

Nanoparticles occupy an intermediate position between homogeneous, molecularly disperse solutions and colloids with macroscopic particles, e.g. Pigments. Nanoparticles are much larger than molecular structures and therefore offer 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 fast biodegradation. However, purely organic functional nanoparticles have so far been little investigated in relation to the inorganic particles.

In the context of the present invention, organic polymers which have hydroxyl groups as polar groups and thus are hydrophilic have proved to be ideal starting materials for nanoparticles. Flexible organic polymers can form random coils that are present in the aqueous phase as nanoparticles. In particular, polyvinyl alcohol (hereinafter also referred to as PVA) is a technically readily available, water-soluble organic polymer which is produced as a mass product and is of interest for such applications. At a molecular weight of M _n = 15000 of the PVA, nanoparticles with a particle size of 70 nm form in water. To make polyvinyl alcohol an optical functional material, one must link the polymer with chromophores. Such a reaction would have to be carried out with high efficiency in order to achieve a correspondingly high loading with the chromophores acting as optical components.

The reaction of polyvinyl alcohol with butyraldehyde to form polyvinyl butyral, a mechanically tough plastic used, for example, as splinter protection for silicate glass, is known (H.G. Elias, Makromoleküle, Vol. 2, Technologie, 5th ed., P. 159, Hüthig and Wepf, Basel, 1992, ISBN 3-85739-102-2). In the context of the present invention, attempts have been made to use such reactions of PVA with chromophores for the production of organic nanoparticles.

Particularly lightfast nanoinks require correspondingly stable chromophores. Here, perylene dyes are particularly attractive because they are characterized by their high light fastness, high fluorescence quantum yields and chemical resistance.

Actin 2005, 88, 1309-1343, H. Langhals, Heterocycles 1995, 40, 477-500, H. Langhals, Molecular Devices, Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (Editor), Silicon Based Polymers, pp. 51-63, Springer, 2008, ISBN 978-1 -4020-8527-7, e-ISBN 978-1-4020- 8528-4), such as perylene-3,4: 9,10-tetracarboxylic bisimides of the following structure (structure 1) in which the radicals R independently represent an alkyl radical, are high photostability, high absorption coefficient and strong fluorescence because of their remarkable properties interesting fluorescent dyes for

 Structure 1

They have also become increasingly important in modern technological developments, such as photovoltaic cells (CJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct Mater., 2001, 11, 15-26, S. Günes, H. Neugebauer, NS Sariciftci, Chem. Rev. 107, 107, 1324-1338), photoelectrochemical cells (Grätzel M., Nature 2001, 414, 338-344, H. Choi, S. Kim, SO Kang, J. Ko. M, -S Kang, JN Clifford, A. Forneli, E. Palomares, MK Nazeeruddin, M. Grätzel, Angew Chem., 2008, 120, 8383-8387; Angew Chem. Int. Ed., 2008, 47, 8259-8263; 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 (Gust D.G., TA Moore, AL Moore, Acc. Chem. Res. 2001, 34, 40-48; MR Wasielewski, J. Org. Chem. 2006, 71, 5051 Gärtner, B.Sundararaju, A.E. Surkus, A. Boddien, B. Loges, H. Junge, PH Dixneuf, M. Beller, Angew Chem Chem 2009, 121, 10147-10150; Angew , Chem. Int. Ed. 2009, 48, 9962-9965). Because of their unusually good properties, perylene dyes have been considered to be particularly suitable chromophores for fluorescent nanoparticles within the scope of the invention.

However, perylene dyes are usually sparingly soluble and are used as pigments. Perylene dyes of the above structure 1 which are soluble in lipophilic media are, for example, those in which the two radicals R are secondary alkyl radicals, e.g. a hexylheptyl radical (compound 1a). When using such substituted compounds would still be expected in combination with PVA complications, since polyvinyl alcohol dissolves as pronounced polar polymer preferably in polar media, while the perylene have pronounced lipophilic properties. Surprisingly, however, polymers with polyvinyl alcohol and perylene dyes as chromophores can be prepared simply and in good yields using the techniques of the present invention.

The present invention accordingly provides a modified polyvinyl alcohol covalently linked to chromophoric moieties and which can form the nanoparticles described above.

In particular, the invention relates to a modified polyvinyl alcohol in the form of a compound which comprises repeating units of the formula I below and repeating units of the formula II below:

 Where Y in formula II represents a chromophoric structural unit which absorbs light in the wavelength range from 350 to 3500 nm.

In addition, the invention provides nanoparticles formed from the modified polyvinyl alcohol according to the invention, as well as their colloidal solutions or nanoparticles in a liquid. Finally, the invention also relates to inks in which the modified polyvinyl alcohol is used as a colorant.

Fig. 1 shows schematically the synthesis of the modified polyvinyl alcohol 3 from 1b and polyvinyl alcohol 2 (PVA, molecular weight of 15,000) under acid catalysis as polymer-analogous reaction. The polymer chain in polymer 3 also contains unreacted OH groups of the polyvinyl alcohol. 3a: 50 mg 1b to 5 g 2, 3b: 5 mg 1b to 5 g 2.

Fig. 2 shows the size distribution of the modified polyvinyl alcohol-based nanoparticles, as according to the reaction. Fig. 1 emerge, in water. Dashed line: Polyvinyl alcohol (2) with a molecular weight of 15,000 (PVA 15,000). Thick, solid line: nanoparticles from the reaction of 5g PVA 15000 and 50 mg 1 b. Thin, solid line: nanoparticles from the reaction of 5g PVA 15000 and 5 mg 1 b.

Figure 3 shows UV / Vis absorption (left) and fluorescence spectra (right) of nanoparticles formed by the modified polyvinyl alcohol 3a in water (thick lines) compared to perylene dye 1a in chloroform (thin dashed lines) and compound 4 in chloroform ( thin, solid lines).

Fig. 4 shows UV / Vis absorption (left) and fluorescence spectra (right) of nanoparticles in water: 3a at various concentrations c.

FIG. 5. Synthesis of the Modified Polyvinyl Alcohol 1 1 According to the Invention

FIG. 6. Synthesis of the Modified Polyvinyl Alcohol 10 According to the Invention

Fig. 7. Size distribution of the nanoparticles in water, determined by the DLS method (dynamic light scattering), modified polyvinyl alcohol 10: thick, solid line; modified polyvinyl alcohol 11: thin, dashed line.

8. UV / Vis absorption (left) and fluorescence spectra (right) of the modified polyvinyl alcohol 10 in the form of nanoparticles in water (thick lines) compared to the modified polyvinyl alcohol 11 as nanoparticles (thin dashed lines). Figure 9. Solid UV / Vis absorption (left) and fluorescence spectra (right) of the modified polyvinyl alcohol 10 as drawn on paper (thick lines) compared to the modified polyvinyl alcohol 11 on paper (thin, dashed lines).

As stated above, the invention relates to a modified polyvinyl alcohol in the form of a compound which comprises repeating units of the above formula I and repeating units of the above formula II. The square brackets indicate in this and the following formulas according to general practice in the field of polymer chemistry repeating units that are present within a polymer. The bonds that are broken by the bracket are those with which the repeating units are bound to adjacent units.

Y in formula II, independently at each occurrence within the compound of the invention, is a chromophoric moiety which absorbs light in the wavelength range of 350 to 3500 nm, preferably in the wavelength range of 400 to 1000 nm and most preferably in the range of 400 to 750 nm , Preferably, an absorption maximum is present within the specified wavelength range. The absorption spectrum of the modified polyvinyl alcohol according to the invention and the covalently bound chromophore residues is determined with a commercial UV / Vis spectrometer.

Suitable chromophoric structural units Y form e.g. covalently bonded moieties formed from a nitro dye, nitrosyl dye, diphenylmethane dye, triphenylmethane dye, acridine dye, indigoid dye, quinoidal vat dye, indigosol, sulfur dye, stilbene dye, xanthene dye, azine dye, methine dye, quinoneimine, anthraquinone dye, thiazole dye, azo dye, phthalocyanine, porphyrins, squarylium dye or a dye comprising a perylene skeleton. A structural unit Y comprising a perylene skeleton is preferred.

The sum of the number of units of the formula I and of the formula II in the compound according to the invention is generally in the range from 5 to 10,000, preferably in the range from 100 to 5000, in particular in the range from 100 to 2000. The ratio of the total number of units of the formula I to those of the formula II, ie mol (I) / mol (II) is typically in the range of 1 to 200, in particular from 10 to 100. The modified polyvinyl alcohol of this embodiment of the invention may comprise, in addition to the units of formulas I and II, other polymerized units. However, it is preferred that the units of formulas I and II provide at least 80 mol%, more preferably at least 90 mol% and especially at least 95 mol%, based on the total number of polymerized units of the modified polyvinyl alcohol. Units that may still be present in addition to the units of the formulas I and II are not particularly limited, provided that they can form a copolymer with the units of the formulas I and II. These may be, for example, units in which the OH group shown in formula I is esterified. Examples of suitable ester-forming acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic, caprylic, capric, lauric, palmitic and stearic acids, their unsaturated variants such as oleic, linoleic and linolenic acid, lactic acid, the natural amino acids, benzoic acid, 1-naphthoic acid and 2-naphthoic acid, nicotinic acid and isonicotinic acid, with units containing acetic acid, due to the production of the polyvinyl alcohol, most frequently occurring in the modified polyvinyl alcohol of the present invention. The modified polyvinyl alcohol of the present invention very particularly preferably consists of units of the formulas I and II or consists essentially of units of the formulas I and II. The term "consists essentially of" is understood to mean that apart from the units of the formulas I and II, only a small amount of units may be present in which the OH group of formula I is esterified by an acetyl group Such groups may be present in a commercially available polyvinyl alcohol, preferably as starting material for the modified polyvinyl alcohol of the present invention A "small amount" here typically means a maximum of 5 mol%, based on the total number of polymerized units.

Therefore, a preferred embodiment of the invention is a modified polyvinyl alcohol of the formula III

in der Y wie vorstehend definiert ist. Die Indices m und n stellen unabhängig voneinander ganze Zahlen im Bereich von 1 bis 1000, bevorzugt 10 bis 350 dar. Die Summe m + n liegt bevorzugt im Bereich von 5 bis 2000, besonders bevorzugt von 100 bis 1000. Das Verhältnis m/n liegt bevorzugt im Bereich von 1 bis 200, insbesondere von 10 bis 100. Dabei sollte klar sein, dass es sich bei der vorstehenden Schreibweise der Formel III um eine auf dem Gebiet der Polymerchemie gängige schematische Darstellung handelt, die auch alternierende Folgen der enthaltenen Wiederholungseinheiten beschreibt.

wherein Y is as defined above. The indices m and n independently represent integers in the range of 1 to 1000, preferably 10 to 350. The sum m + n is preferably in the range from 5 to 2000, particularly preferably from 100 to 1000. The ratio m / n is preferably in the range from 1 to 200, in particular from 10 to 100. It should be understood that in the above notation of formula III is a common schematic in the field of polymer chemistry, which also describes alternating consequences of the repeating units contained.

According to a further preferred embodiment, a modified polyvinyl alcohol is provided in the form of a compound which comprises repeating units of the following formula I and repeating units of the following formula IIa, IIb and / or IIc:

IIa Mb

IIc

The radicals R ^1a , R ^1b , R ^1c , R ^2b and R ^2c , the radicals R ^3a , R ^4a , R ⁵³ , R ^6a , R ^3b , R ^4b , R ^5b , R ^3c , R ^4c and R ⁵⁰ , which Radicals R ^7b and R ^2c are identical or different in the formulas IIa, IIb and Ilc and independently of one another in each occurrence represent hydrogen or a linear alkyl radical having at least one and at most 37 C atoms or one of the halogen atoms F, Cl, Br or I. In the alkyl group, one to 10 CH ₂ units may be independently replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an ic or frans CH = CH group in which a CH May also be replaced by a nitrogen atom, an acetylenic C ^ C group, a divalent phenyl radical (eg, 1, 2, 1, 3 or 1, 4-phenyl), divalent pyridine (eg 2,3-, 2 , 4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine), divalent thiophene (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene ), divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms, and a divalent anthracene radical (eg, 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 anthracene radical) in which one or two CH groups are replaced by nitrogen atoms could be. Up to 12 individual hydrogen atoms of the CH ₂ groups can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a to 6 CH ₂ units can be replaced independently by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis- or frans-CH =CH group in which a CH unit may be replaced by a nitrogen atom, an acetylenic C =C group, a divalent phenyl radical ( eg 1, 2-, 1, 3- or 1, 4-phenyl), a divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3, 5-pyridine), a divalent thiophene (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene), a divalent naphthalene (eg 1, 2-, 1, 3, 1, 4 -, 1, 5, 1, 6, 1, 7, 1, 8-,

2,3-, 2,6- or 2,7-naphthalene radical) in which one or two CH groups can be replaced by nitrogen atoms, and a divalent anthracene radical (for example 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 anthracene radical) in which one or two CH groups can be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups in an alkyl radical can each be independently replaced by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, even at the same carbon atoms, wherein one to 6 CH ₂ units can be independently replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis or frans CH = CH group in which a CH unit is replaced by a nitrogen atom may be an acetylenic CsC group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine), a divalent thiophene (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene), a divalent naphthalene (eg 1 , 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical) in which one or two CH groups can be replaced by nitrogen atoms, un d is a divalent anthracene radical (eg 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-anthracene) in which one or two CH groups may be replaced by nitrogen atoms. CH ₂ groups, in which a hydrogen atom is replaced as described above, may also be linked together to form a ring, ie instead of carrying substituents, the free valencies of the methine groups or the quaternary C atoms may be linked in pairs, so that Rings are formed, such as cyclohexane rings. The radical R ^12c may furthermore have the formula Vc:

Vc in which the radicals R ^13c , R ^14c , R ^5c , R ^16c and R ^7c satisfy the definition of the radicals R ^3c to R ^5c given above. X ^a , X ^b and X ^c are bivalent linker units.

Unless otherwise stated, in the context of this description, a CH ₂ unit which can be replaced by definition can also be a terminal unit in an alkyl group / an alkyl chain, ie a corresponding unit within a -CH ₃ group. Thus, for example, the reference to a divalent ring or a divalent ring system which can replace a CH ₂ unit (for example, divalent phenyl radicals or 1, 2, 1, 3 or 1, 4-phenyl) here and hereinafter so too understand that one of the two valences can also be saturated with an H atom. This also includes the situation where, starting from a methyl group, by replacing a formal CH ₂ unit contained therein, a phenyl group, pyridine group, thiophene group, etc. are present at the corresponding position. Therefore, the radicals R ^1a , R ^1b , R ^1c , R ^2b and R ^2c , the radicals R ^3a , R ^4a , R ^5a , R ^6a , R ^3b , R, R ^5b , R ^3c , R ^4c and R ^5c , the radical R ^7b and the radical R ^12c in the above definition, for example, aryl radicals, in particular phenyl or Naphtylreste, Heterorarylreste, in particular pyridyl or thiophenyl, aralkyl radicals and Heteroaralkylreste represent.

In a preferred embodiment, the radicals R ^1a , R ^1b , R ^c , R ^2b and R ^2c , the radicals R ^3a , R ^4a , R ^5a , R ^6a , R ^3b , R ^4b , R ⁵ , R ^3c , R ^4c and R ^5c and R ⁷ , the same or different and independently at each occurrence, are hydrogen or a linear alkyl group having at least one and at most 37 C atoms. In the alkyl radical, one to 10 CH ₂ units can be replaced independently of one another by a c / ^' s or irans-CH =CH group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4). Phenyl radical), divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene). Up to 12 individual hydrogen atoms of the CH ₂ groups can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a up to 6 CH ₂ units can be replaced independently of one another by an cis- or trans-CH = CH group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent thiophene radical ( eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6-, 1-, 7-, 1-, 8-, 2,3-, 2,6- or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene residue). Particularly preferably, the radicals R ^1a , R ^1b , R ^1c , R ^2b and R ^{2c is} an alkyl radical which may be branched and which contains 1 to 20 carbon atoms, particularly preferably 6 to 20.

Particularly preferably, the radicals R ^3a , R ⁴³ , R ⁵³ , R ^6a , R ^3b , R ^4b , R ^5b , R ^3c , R ⁴⁰ and R ⁵⁰ and the radical R ^{7b are} hydrogen or an alkyl radical which may be branched, and containing from 1 to 20 carbon atoms, most preferably hydrogen.

In a preferred embodiment, the radical R ^{12c is} a radical of the formula Vc, where the radicals R ^3c , R ^14c , R ^5c , R ^16c and R ^{7c are} as defined above:

Vc

In a more preferred embodiment, the radicals R ^13c , R ^14c , R ^15c , R ^16c and R ^17c , the same or different and independently at each occurrence, are hydrogen or a linear alkyl radical having at least one and at most 37 C atoms. In the alkyl group, one to 10 CH ₂ units may be independently replaced by an eis or frans-CH = CH group, a divalent phenyl group (eg

1.2, 1, 3 or 1, 4-phenyl radical), divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1 , 8-, 2,3-, 2,6- or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene residue). Up to 12 individual hydrogen atoms of the CH ₂ groups can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a to 6 CH ₂ units can be replaced independently of each other by an eis or irans-CH = CH group, a divalent phenyl radical (eg 1, 2, 1, 3 or

1,4-phenyl radical), a divalent thiophene radical (for example 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (for example 1, 2, 1, 3, 1, 4 -, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene residue). Particularly preferably, the radicals R ^{1 c} , R ^14c , R ^15c , R ^16c and R ^{17c are} hydrogen or an alkyl radical which may be branched and which contains 1 to 20 carbon atoms, most preferably hydrogen.

The linker unit X ^a preferably represents one to 12 CH ₂ units in which independently one or more may be replaced by in each case a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis- or iran-CH = CH group in which a CH unit can also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine), a divalent thiophene (eg 2,3-, 2,4-, 2,5 - or 3,4-thiophene), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2 , 3, 2, 6 or 2,7-naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms and one divalent anthracene radical (eg 1, 2, 1, 3, 1, 4 or 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-anthracene residue) 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 be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a to 6 CH ₂ - units can be independently replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, a cis - or CHR-CH = CH group in which a CH unit may be replaced by a nitrogen atom , an acetylenic C 1 -C 4 group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine), divalent thiophene (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene), divalent naphthalene (eg 1, 2 -, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene) at one or two CH groups can be replaced by nitrogen atoms, and a divalent Anthracenres t (eg 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-anthracene) in which one or two CH groups 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, a cyano group or a linear alkyl chain with up to 18 carbon atoms, at wherein one to 6 CH ₂ units may independently be replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis- or iran-CH = CH- group in which a CH unit may be replaced by a nitrogen atom , one acetylenic OC group, a divalent phenyl radical (eg, 1,2-, 1,3- or 1,4-phenyl radicals), divalent pyridine radical (eg, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine radical), divalent thiophene radical (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), divalent naphthalene radical (eg 1,2-, 1,3- , 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-naphthalene radical) in which one or two CH-, Groups may be replaced by nitrogen atoms, and a divalent anthracene radical (eg 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-anthracene) in which one or two CH groups are represented by nitrogen atoms can be replaced. CH ₂ groups in which a hydrogen atom has been replaced as described above may also be linked together to form a ring, ie instead of carrying substituents, the free valences of the methine groups or of the quaternary C atoms may be linked in pairs, so that rings arise, such as cyclohexane rings.

Particularly preferably, the linker unit X ^{a is} one to 12 CH ₂ units in which one or more can be replaced independently of one another by a cis or iran-CH = CH group, a divalent phenyl radical (eg 1,2-, 1,3- or 1,4-phenyl), a divalent naphthalene radical (eg 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8- , 2,3-, 2,6- or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene), 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 be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a to 6 CH ₂ - units can be replaced independently of one another by an eis or frans-CH = CH group, a divalent phenyl radical (eg, 1,2-, 1,3- or 1,4-phenyl), divalent naphthalene (zB1 , 2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-naphthalene radical) , and a divalent anthracene radical (eg 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-anthracene).

The unit X ^a most preferably represents one to 12 CH ₂ units in which one or more may be replaced independently of one another by a divalent phenyl radical (eg 1,2-, 1,3- or 1,4-phenyl radical).

wobei die Reste R^8b, R^9b, R^10b und R^11b gleich oder verschieden sind und unabhängig voneinander bei jedem Auftreten für Wasserstoff stehen oder einen linearen Aikylrest mit mindestens einem und höchstens 37 C-Atomen oder für eines der Halogenatome F, Cl, Br oder I. In dem Aikylrest können eine bis 10 CH2-Einheiten unabhängig voneinander ersetzt sein durch eine Carbonylgruppe, ein Sauerstoff atom, Schwefelatom, Selenatom, Telluratom, eine eis- oder frans-CH=CH-Gruppe, bei der eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, eine acetylenische C^C-Gruppe, einen divalenten Phenylrest (z.B. 1 ,2-, 1 ,3- oder 1 ,4- Phenylrest), divalenten Pyridinrest (z.B. 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5- Pyridinrest), divalenten Thiophenrest (z.B. 2,3-, 2,4-, 2,5- oder 3,4- Thiophenrest), divalenten Naphthalinrest (z.B. 1 ,2-, 1 ,3-, 1 ,4-, 1 ,5-, 1 ,6-, 1 ,7-, 1 ,8-, 2,3-, 2,6- oder 2,7- Naphthalinrest), bei dem eine oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können, und einen divalenten Anthracenrest (z.B. 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- oder 9,10- Anthracenrest), bei dem eine oder zwei CH- Gruppen durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH₂-Gruppen können jeweils unabhängig voneinander auch an gleichen C-Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder lod, eine Cyanogruppe oder eine lineare Alkylkette mit bis zu 18 C-Atomen, bei der eine bis 6 CH₂-Einheiten unabhängig voneinander ersetzt sein können durch eine Carbonylgruppe, ein Sauerstoffatom, Schwefelatom, Selenatom, Telluratom, eine eis- oder irans-CH=CH-Gruppe, bei der eine CH-Einheit durch ein Stickstoffatom ersetzt sein kann, eine acetylenische C=C-Gruppe, einen divalenten Phenylrest (z.B. 1 ,2-, 1 ,3- oder 1 ,4- Phenylrest), einen divalenten Pyridinrest (z.B. 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5- Pyridinrest), einen divalenten Thiophenrest (z.B. 2,3-, 2,4-, 2,5- oder 3,4- Thiophenrest), einen divalenten Naphthalinrest (z.B. 1 ,2-, 1 ,3-, 1 ,4-, 1 ,5-, 1 ,6-, 1 ,7-, 1 ,8-, 2,3-, 2,6- oder 2,7- Naphthalinrest), bei dem eine oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können, und einen divalenten Anthracenrest (z.B. 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- oder 9,10- Anthracenrest), bei denen eine oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH₂- Gruppen in einem Aikylrest können jeweils unabhängig voneinander auch an gleichen C- Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder lod, eine Cyanogruppe oder eine lineare Alkylkette mit bis zu 18 C-Atomen, bei der eine bis 6 CH₂-Einheiten unabhängig voneinander ersetzt sein können durch eine Carbonylgruppe, ein Sauerstoffatom, Schwefelatom, Selenatom, Telluratom, eine eis- oder frans-CH=CH- Gruppe, bei der eine CH-Einheit durch ein Stickstoffatom ersetzt sein kann, eine acetylenische C^C-Gruppe, einen divalenten Phenylrest (z.B. 1 ,2-, 1 ,3- oder 1 ,4- Phenylrest), einen divalenten Pyridinrest (z.B. 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5- Pyridinrest), einen divalente Thiophenrest (z.B. 2,3-, 2,4-, 2,5- oder 3,4- Thiophenrest), einen divalenten Naphthalinrest (z.B. 1 ,2-, 1 ,3-, 1 ,4-, 1 ,5-, 1 ,6-, 1 ,7-, 1 ,8-, 2,3-, 2,6- oder 2,7- Naphthalinrest), bei dem ein oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können, und einen divalenten Anthracenrest (z.B. 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- oder 9,10- Anthracenrest), bei dem eine oder zwei CH- Gruppen durch Stickstoffatome ersetzt sein können. CH₂-Gruppen, an denen wie vorstehend beschrieben ein Wasserstoffatom ersetzt ist, können auch unter Bildung eines Rings miteinander verknüpft sein, d.h. statt Substituenten zu tragen, können die freien Valenzen der Methingruppen bzw. der quartären C-Atome paarweise verknüpft werden, so dass Ringe entstehen, wie z.B. Cyclohexanringe. The linker unit X ^b is preferably a divalent radical of the formula IVb,

wherein the radicals R ^8b , R ^9b , R ^10b and R ^{11b are the} same or different and independently at each occurrence represent hydrogen or a linear Aikylrest having at least one and at most 37 C-atoms or one of the halogen atoms F, Cl, Br or I. In the Aikylrest one to 10 CH 2 units can be replaced independently of one another by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an eis or frans-CH = CH group in which a CH unit also may be replaced by a nitrogen atom, an acetylenic C ^ C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), divalent pyridine radical (eg 2,3-, 2,4- , 2,5-, 2,6-, 3,4- or 3,5-pyridine), divalent thiophene (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene), divalent Naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2, 7-naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms , and a divalent anthracene residue (eg 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-anthracene), 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 be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a to 6 CH ₂ units may be independently replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, a cis or irans CH = CH group in which a CH unit may be replaced by a nitrogen atom, a acetylenic C = C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2 , 6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), in which one or two CH groups can be replaced by nitrogen atoms, and a divalent one n anthracene residue (eg 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 anthracene radical) in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups in an Aikylrest can each be independently replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain with up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently of one another by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis- or frans-CH = CH group in which a CH unit may be replaced by a nitrogen atom, an acetylenic C 1 -C 4 group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg 2 , 3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg 2,3-, 2,4-, 2,5-) or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2, 3-, 2,6- or 2,7-naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms, and a divalent anthracene radical (eg 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-anthracene residue) in which one or two CH groups are substituted by nitrogen atoms e can be replaces. CH ₂ groups, in which a hydrogen atom is replaced as described above, may also be linked together to form a ring, ie instead of carrying substituents, the free valencies of the methine groups or the quaternary C atoms may be linked in pairs, so that Rings are formed, such as cyclohexane rings.

In a preferred embodiment, the radicals R ^8b , R ^9b , R ^0b and R ^11b , identical or different and independently of one another at each occurrence, are hydrogen or a linear alkyl radical having at least one and at most 37 C atoms. In the alkyl radical, one to 10 CH ₂ units can be replaced independently of one another by a cis or frans-CH =CH group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2 , 7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene). Up to 12 individual hydrogen atoms of the CH ₂ groups can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a up to 6 CH ₂ units can be replaced independently of one another by an cis- or trans-CH = CH group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent thiophene radical ( eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6-, 1-, 7-, 1-, 8-, 2,3-, 2,6- or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene). Particularly preferably, the radicals R ^8b , R ^9b , R ^10b and R ^{11b are} hydrogen or an alkyl radical which may be branched and which contains 1 to 20 carbon atoms, most preferably hydrogen.

The linker unit Xc preferably represents a divalent radical of the formula IVc

IVc wherein the radicals R ^8c , R ⁹ °, R ^10c and R ^{11c are} identical or different and independently of one another in each occurrence represent hydrogen or a linear alkyl radical having at least one and at most 37 C atoms or one of the halogen atoms F, Cl , Br or I. In the alkyl radical, one to 10 CH ₂ units may independently be replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis- or iran-CH = CH group in which a CH- Unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl), divalent pyridine (eg 2,3-, 2, 4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine), divalent thiophene (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene) , divalent naphthalene (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical) in which one or two CH groups are replaced by nitrogen atoms k and a divalent anthracene radical (eg 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-anthracene) 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 be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a to 6 CH ₂ units may be replaced independently of each other by a Carbonyigruppe, an oxygen atom, sulfur atom, selenium atom, tellurium atom, a cis or iran-CH = CH-group, wherein a CH-unit may be replaced by a nitrogen atom, acetylenic C = C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2 , 6-, 3,4- or 3,5-pyridine radical), a divalent one Thiophene radical (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms, and a divalent anthracene radical (eg 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-anthracene), in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups in an alkyl radical can each independently of one another also be replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, wherein one to 6 CH ₂ units can be independently replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis- or iran-CH = CH- group in which a CH unit is replaced by a nitrogen atom can, an acetylenic C = C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl), a divalent pyridine radical (eg 2,3-, 2,4-, 2.5 , 2,6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical ( eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7 Naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms, and a divalent anthracene residue (eg 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-anthracene) in which one or two CH groups may be replaced by nitrogen atoms. CH ₂ groups, in which a hydrogen atom is replaced as described above, may also be linked together to form a ring, ie instead of carrying substituents, the free valencies of the methine groups or the quaternary C atoms may be linked in pairs, so that Rings are formed, such as cyclohexane rings.

In a preferred embodiment, the radicals R ^8c , R ^9c , R ^0c and R ^11c , the same or different and independently each occurrence, are hydrogen or a linear alkyl radical having at least one and at most 37 C atoms. In the alkyl radical, one to 10 CH ₂ units may independently be replaced by a c / ^' s or frans-CH = CH group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4). Phenyl radical), divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene). Up to 12 individual hydrogen atoms of the CH ₂ groups can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a until 6 CH ₂ units can be replaced independently of one another by an e- or trans-CH = CH group, a divalent phenyl radical (for example 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent thiophene radical (for example 2 , 3, 2,4, 2,5 or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6 , 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), and a divalent anthracene radical (eg 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-anthracene).

Particularly preferably, the radicals R ^8c , R ^9c , R ^10c and R ^{11c are} hydrogen or an alkyl radical which may be branched and which contains 1 to 20 carbon atoms, most preferably hydrogen.

In the polyvinyl alcohol modified according to the invention, the units I may occur together with a single type of units IIa, IIb or Ilc, or several types of units IIa, IIb and Ilc may be combined in the modified polyvinyl alcohol with the units I. Preference is given to compounds which have units I together with units IIb and those which have units I together with units Ilc.

The sum of the number of units of the formula I and of the formulas IIa, IIb and IIc in the compounds according to the invention is generally in the range from 5 to 10,000, preferably in the range from 100 to 5000, in particular in the range from 100 to 2000. The ratio the total number of units of formula I to those of formula IIa, IIb and Ilc, ie mol (I) / (mol (IIa) + mol (IIb) + mol (Ilc)) is preferably in the range of 1 to 200, especially 10 to 100.

The modified polyvinyl alcohol of this embodiment of the invention may comprise, in addition to the units of the formulas I and IIa, IIb or IIc, other polymerized units. However, it is preferred that the units of the formulas I and IIa, IIb or IIc provide at least 80 mol%, more preferably at least 90 mol% and in particular at least 95 mol%, based on the total number of polymerized units of the modified polyvinyl alcohol. Units which may still be present in addition to the units of the formulas I and II are not particularly limited, provided that they can form a copolymer with the units of the formulas I and IIa, IIb or IIc. These may be, for example, units in which the OH group shown in formula I is esterified. Examples of suitable ester-forming acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic, caprylic, capric, lauric, palmitic and stearic acids, their unsaturated variants such as oleic, linoleic and linolenic acid, lactic acid, the natural amino acids, benzoic acid, 1-naphthoic acid and 2- Naphthoic acid, nicotinic acid and isonicotinic acid, wherein acetyl group-containing units, due to the production of the polyvinyl alcohol, most frequently occur in the modified polyvinyl alcohol of the present invention. Most preferably, the modified polyvinyl alcohol of the present invention consists of units of the formulas I and IIa, of units of the formulas I and IIb or of units of the formulas I and IIc or consists essentially of these units. The term "consists essentially of" is understood to mean that apart from the units mentioned, only a small amount of units may be present in which the OH group of the formula I is esterified by an acetyl group In this case, a "small amount" typically means a maximum of 5 mol%, based on the total number of polymerized units.

Therefore, further preferred embodiments of the invention are modified polyvinyl alcohols of the formulas IIIa, IIIb and IIIc:

purple illb

nie in denen alle Definitionen für Variablen gelten, die für die Formeln IIa, IIb und llc bereits angegeben wurden, einschließlich der bevorzugten Definitionen. Die Indices m und n stellen unabhängig voneinander ganze Zahlen im Bereich von 1 bis 1000, bevorzugt 10 bis 350 dar. Die Summe m + n liegt bevorzugt im Bereich von 5 bis 2000 besonders bevorzugt im Bereich von 100 bis 1000. Das Verhältnis m/n liegt bevorzugt im Bereich von 1 bis 200, insbesondere von 10 bis 100. Dabei sollte klar sein, dass es sich bei der vorstehenden Schreibweise der Formeln lila, lllb bzw. Illc um eine auf dem Gebiet der Polymerchemie gängige schematische Darstellung handelt, die auch alternierende Folgen der enthaltenen Wiederholungseinheiten beschreibt.

never in which all definitions apply to variables already specified for Formulas IIa, IIb and llc, including the preferred definitions. The indices m and n independently represent integers in the range from 1 to 1000, preferably 10 to 350. The sum m + n is preferably in the range from 5 to 2000, more preferably in the range from 100 to 1000. The ratio m / n is preferably in the range from 1 to 200, in particular from 10 to 100. It should be clear that the preceding notation of the formulas IIIa, IIIb or IIIc is a schematic representation common in the field of polymer chemistry, which also includes alternating Describes consequences of the repeating units contained.

The modified polyvinyl alcohol in any of the foregoing embodiments of the present invention may be a linear polymer or, in the presence of suitable higher functional units, may have one or more branches in the polymer chain. However, linear polymers are preferred.

The modified polyvinyl alcohol according to the invention is capable of forming nanoparticles in polar solvents and solvent mixtures. Colloidal solutions or nanoparticles of such nanoparticles form spontaneously after introduction of the modified polyvinyl alcohol in the solvent. Particularly suitable solvents for the formation of the nanoparticles are water or aqueous solvents. Water is particularly preferred. As aqueous solvents here are referred solvent mixtures containing a volume fraction (Vol./Vol.) Of water of at least 50%, preferably at least 70%, in particular at least 90%, based on the total volume of the solvent.

In this case, nanoparticles are particles whose diameter is in the range from 1 to 1000 nm. In particular, in the context of the present invention, nanoparticles typically have size distributions determined by means of dynamic laser scattering (DLS) on a nanodivision of the nanoparticles in water, with a maximum in the range from 10 to 1000 nm, preferably from 10 to 500 nm As described below, bimodal or multimodal size distributions may occur, in which case it is preferable that all maxima of the size distribution are within the above ranges.

The nanoparticles can be colloidally dissolved in liquids, preferably water or aqueous solutions, but also in polymeric solids. As noted above, liquids and solids-soluble nanoparticles, due to their size, occupy an intermediate position between solid dispersions on one side and molecularly disperse solutions on the other side. Such systems, in which nanoparticles are dispersed in a liquid or solid, are referred to herein as colloidal solutions or equivalently as nanodivisions.

The preparative accessibility of the modified polyvinyl alcohols of this invention may be considered a particular advantage over other colorants, such as the cyclophan of structure 4. Another advantage is, for example, in the case of compounds according to the invention having chromophoric structural units of perylene dyes in the readily achievable water solubility or water dispersibility of the substance. As a result, the aqueous phase is easily accessible to the usually highly lipophilic perylene dyes. Since the link between polymer and chromophore is covalent, there is also no risk of segregation or separation. The aqueous phase offers many advantages for the modified polyvinyl alcohols according to the invention, because it is not only characterized by its low cost and easy accessibility, but is also incombustible and has a very large heat capacity. The chromophene-modified polyvinyl alcohols of the present invention can be used, for example, as colorants for dyeing purposes, also for decorative and artistic purposes. Specific examples are glue colors and related colors such as watercolor paints, water colors, ink jet printer colors, paper colors, printing inks, inks and inks, and other colors for painting and writing. Furthermore, they can be used as colorants in paints, as colorants in paints, preferably 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 varnish or East Asian varnish), for bulk dyeing of polymers such as 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 copolymers of said monomers. The modified polyvinyl alcohols of the present invention may also be used for coloring natural products such as paper, wood, straw or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their transformation products such as the viscose fiber , Nitrate silk or copper rayon (rayon), as mordant dyes, eg for coloring natural products, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their transformation products such as For example, the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts.

Further exemplary uses for the modified polyvinyl alcohols of the present invention are marking, safety and display purposes, especially taking into account their fluorescence, such as colorants or fluorescent colorants for signal colors, preferably for highlighting logos and drawings or other graphic products, for characterizing Signs and other objects and in display elements for a variety of display, reference and marking purposes, where a particular visual color impression is to be achieved, for passive display elements, traffic signs, such as traffic lights for security marking purposes, the large chemical and photochemical Resistance and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents, identity documents and the like, in which a special, unmistakable color impression is to be achieved. The modified polyvinyl alcohols of the present invention are furthermore suitable for marking articles in order to enable machine recognition of these objects via fluorescence; preferred is the automatic recognition of objects for sorting, eg also for the recycling of plastics, as fluorescent dyes for machine-readable markings; preferred are alphanumeric imprints or barcodes, as colorants or fluorescence colorants in display, illumination or image converter systems, in which the excitation by electrons, ions or UV radiation takes place, for example in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, eg in biochemistry, medicine, technology and natural sciences, as dyes or fluorescent dyes in chemiluminescent systems, eg in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection methods and as a material for leak testing our systems.

Furthermore, the modified polyvinyl alcohols of the present invention can be used 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 colorants in electrophotography eg for dry copying systems (Xerox process) and laser printers ("non-impact printing"), for the frequency conversion of light, eg to make longer-wave visible light from short-wave light, as starting material for superconducting organic materials, as fluorescent colorant in scintillators, as dyes or fluorescence colorants in optical Lichtsammeisystemen, such as the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as a colorant or fluorescent colorant in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent color Materials for testing materials, eg in the production and testing of semiconductor circuits and semiconductor components, as colorants or fluorescent colorants in photoconductors, as colorants or fluorescent colorants in photographic processes, as colorants or fluorescent colorants as part of a semiconductor integrated circuit, the colorants as such or in combination with other semiconductors eg in the form of an epitaxy, as a colorant or fluorescence colorant in dye lasers, preferably as a fluorescence colorant for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, eg for frequency doubling and frequency tripling of laser light.

A particularly advantageous use of the modified polyvinyl alcohols of the present invention is that of a colorant for inks. Accordingly, an article of the present invention is also an ink comprising one or more modified polyvinyl alcohols as defined above. The term ink herein includes compositions in which the modified polyvinyl alcohol is present alone or as a mixture of different compounds in a liquid solvent. It preferably comprises compositions in which the modified polyvinyl alcohol forms nanoparticles in the solvent. Such compositions are also referred to herein as "nanoinks." These nanoparticles are generally in the form of a nano-distribution in the solvent.

For use as colorants for inks, e.g. the chromophene-modified polyvinyl alcohols which have a perylene unit have advantageous properties, and in particular the modified polyvinyl alcohols having units of the formula IIa, IIb or IIc or the modified polyvinyl alcohols of the formulas IIIa, IIIb or Never. Because of their light absorption properties, the modified polyvinyl alcohols having units of the formula IIb or IIc or the modified polyvinyl alcohols of the formulas IIIb or IIIc are particularly suitable as colorants for inks, since they produce dark shades.

Suitable solvents for these inks are, in particular, substances or mixtures of substances which, at standard application temperatures, e.g. over a range of 5 ° C to 40 ° C, preferably from 5 ° C to 80 ° C, in liquid form. Particularly advantageous solvents are water or aqueous solvents, in particular water. In such solvents, the modified polyvinyl alcohols of the present invention typically spontaneously form nanoparticles. As aqueous solvents here are referred solvent mixtures containing a volume fraction (Vol./Vol.) Of water of at least 50%, preferably at least 70%, in particular at least 90%, based on the total volume of the solvent.

The ink of the invention is suitable for both printing and writing purposes. It can be advantageously used in devices in which the ink is passed through narrow fluid channels. The modified polyvinyl alcohols of the invention tend Unlike pigment particles, including in the form of nanoparticles, they do not clog these fluid channels. A preferred application is machine printing, especially ink jet printers. However, the inks according to the invention can also be used in spring writing instruments and drawing instruments (ink fountain pen, glass pen or corresponding fountain pen), ballpoint pen writing and drawing instruments (ballpoint pens), or felt-writing and drawing instruments (felt-tip pens). Finally, the ink, optionally with the addition of thickeners, can be used in high pressure, intaglio and in planographic printing; In this case, the planographic printing is of particular interest because the modified polyvinyl alcohols generally have hydrophilic properties and are therefore suitable for special interactions with surfaces, as required in planographic printing. Further interesting fields of application result from the fluorescence properties of the inks or the resulting colorations. Thus, with a modified polyvinyl alcohol which fluoresces in the near infrared range (NIR) and absorbs light in the visible range, machine-readable documents can advantageously be produced. A modified polyvinyl alcohol in which both the light absorption and the fluorescence wavelength are in the visible range can be used, for example, for visual security markings.

The concentration of the modified polyvinyl alcohols in the ink of the present invention is not particularly limited. Typical amounts are in the range of 0.01 g / l to 10 g / l, preferably 0.03 to 5 g / l. In the ink of the invention, a single type of modified polyvinyl alcohol may be used which may be modified with one or more different chromophores. It is also possible to use mixtures of different types of modified polyvinyl alcohols. However, the ink according to the invention preferably contains exclusively as the colorant the modified polyvinyl alcohols, and very particularly preferably only the modified polyvinyl alcohols having units of the formula IIb or IIc or the modified polyvinyl alcohols of the formulas IIIb or IIIc. In particular, preferably no pigments, i. in the solvent used insoluble colorant with particle sizes in the range above 1 μιτι included. If necessary, conventional inks may also be added to the ink, e.g. Viscosity modifier (thickener), preservative or flow or wetting property improver.

Both the inks containing the modified polyvinyl alcohols and the colorations of the modified polyvinyl alcohols on substrates such as paper extraordinarily stable. No changes are observed either in storage (over several months) or in colorings. Solutions and colorings survive months of direct sunlight. The sum of these unusually good properties makes the use as a document-proof ink interesting.

The colored nanoparticles according to the invention, e.g. from compounds 10 and 11, can be applied to surfaces such as paper or alumina. For example, if 10 is applied from aqueous phase on paper, then results in a strong blue color. After drying the ink according to the invention, the resulting color on the substrate can surprisingly be removed neither with water nor with ethanol nor with DMF or DMF / water, nor is it possible to bleach the dye by concentrated sodium hypochlorite solution (25%). In the case of the material applied to paper, a barely visible red fluorescence of blue color appears at 10. The solid fluorescence excitation spectrum is bathochromically shifted in relation to that of the nanoparticles in solution, while the fluorescence spectrum is almost congruent with the spectrum of the particles in water; See Figure 9. It can be seen that much of the fluorescence extends into the NIR region. This makes it easy to read out with machines. The dye 11 also draws on paper, and it does not succeed after drying here to remove a stain with water, ethanol or DMF or bleach with concentrated hypochlorite solution. The staining with 11 has a clear red nuance with respect to 10, and there is a visually striking red fluorescence.

As a starting material for the preparation of the modified polyvinyl alcohols according to the invention chromophoric compounds (also referred to as

"Aldehydes" are used in aldehyde form and react with polyvinyl alcohol .. Corresponding aldehydes have the general formula VI, wherein Y is as defined above:

 VI

Perylene dyes which are used in a preferred embodiment of the invention have as aldehydes the formula via, all variables, including their preferred embodiments, being as defined above (see formula IIa):

Via

The preparation of a perylene aldehyde of the formula VIA, such as compound 1b shown in FIG. 1, is described by way of example in H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328- 4336th

Perylene dyes which are used in further preferred embodiments of the invention can react as aldehydes of the formula VIb or VIc, wherein here too all variables, including their preferred embodiments, are as defined above (see formulas IIb and IIc, respectively).

For the preparation of perylene-aldehydes of formula VIb, e.g. from a compound having a perylene-3,4: 9,10-tetracarboxylic bisimide skeleton of the above-mentioned structure 1 as a chromophore. Thus, for example, as shown schematically in FIG. 5, the compound 1a can be converted into the imidazole derivative 8 with sodium amide and benzonitrile. Its NH group can be alkylated with a nucleophile, such as benzyl bromide, which is substituted with an aldehyde protected as an ethylene acetal. Its deprotection in the course of workup gives the aldehyde 9 as a synthetic building block for the reaction with polyvinyl alcohol to 11. Alternatively, as shown by way of example in Fig. 6, a benzonitrile 5 is used, which is provided with a protected as ethylene acetal aldehyde function. This results in the reaction with sodium amide and 1a and subsequent deprotection in an analogous manner, the aldehyde 6, which can also react with polyvinyl alcohol.

The aldehyde-form chromophores can react with polyvinyl alcohol (schematically as compound 2 in FIG. 1). As polyvinyl alcohol, a commercially available polyvinyl alcohol can be used. The number average molecular weight of the PVA may, for example, be between 200 and 500,000, preferably between 10,000 and 200,000. It is preferred to use a fully hydrolyzed PVA whose acetyl groups have been removed as far as possible. The reaction between the aldehydes and the polyvinyl alcohol preferably takes place in a suitable solvent, such as DMSO, as reaction medium and under acid catalysis, for example by addition of 4-toluenesulfonic acid as catalyst. The reaction with the corresponding acetal of the polyvinyl alcohol (compare Formulas II including IIa-c and III including IIa-c above, by way of example compounds 3, 10 and 11 in Fig. 1, Fig. 5 and Fig. 6) is surprisingly smooth. The material obtained in this way shows good water solubility and usually forms strongly fluorescent solutions, even if the starting aldehyde is insoluble in water. Two types of nanoparticles with frequency maxima at two different diameters may form in this reaction, for example in the case of the reaction shown at 70 and 350 nm in FIG. 1, see FIG. 2.

A strong staining of the aqueous phase by the polymer clearly shows the linkage of the polyvinyl alcohol with the chromophore; The colored components of the polymer can not be washed out by lipophilic media such as chloroform - this demonstrates the covalent linkage of the hydrophilic polymer chain with the chromophoric compound. The chromophore-polymer combination results in particles in water with a diameter that is typically in the scale range of nanoparticles, but greater than that of pure polyvinyl alcohol in water; See Figure 2. Further evidence for the nanometer dimension of the particles is the fact that they can not be filtered off with a D5 glass frit. By way of example, the size distribution of the nanoparticles according to FIG. 2 shows two maxima, of which the maximum at approx. 70 nm is presumably due to unreacted polyvinyl alcohol particles, since this size distribution is also found in pure polyvinyl alcohol in water, while the second, newly added maximum at 350 nm the polyacetal 3 (Figure 1) is assigned. This is also shown by the fact that the second maximum increases at the expense of the first, if the proportion of perylenaldehyde used for the acetalization is increased, as can also be seen from FIG. 2. FIG. 7 shows the size distribution for nanoparticles obtained according to the reactions in FIGS. 5 and 6 and containing the polymeric compounds 10 and 11. One finds for 10 a maximum at 25 nm and a second at about 100 nm; this corresponds to the behavior of 3. At 11 you can even find three maxima: at 25 nm, at 90 nm and at 300 nm. These are probably associates that exchange dynamically. If a small amount of material is introduced into water, a "royal blue" aqueous phase is formed, which turns blue-black at a higher level, see Figure 8. There is a faint red fluorescence that is conspicuous only in strong light sources, and large portions of the fluorescence spectrum extend into the NIR range (near infrared), so fluorescence is not very noticeable under normal However, fluorescence can be used for a machine reading of the substance. The polyvinyl alcohol 11 provided with chromophores absorbs significantly shorter than the marked alcohol 10, so that blue water phases with a purple shade are obtained. At higher concentration these are black-purple. But you can already clearly see a red fluorescence with usual lighting. The substance is therefore particularly suitable as a dark fluorescent ink, in which the fluorescence should be seen under normal lighting. The UV / Vis absorption and fluorescence spectra are shown in FIG.

The spectra differ significantly from the spectra of the chromophores in homogeneous organic 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. Thus, the UVA / is absorption spectrum of the nanoparticles of compound 3 of Figure 1 in water does not correspond to the spectrum of perylene dyes, e.g. 1a in lipophilic media, but rather the perylene cylophane 4; see FIG. 3.

 4

On dilution of the nanoparticles distributed in water, the structure of the spectra hardly changes, as can be seen, for example, from the spectra of FIG. 4. This suggests a preferred intramolecular interaction of the chromophores in the nanoparticle, for example the formation of dimeric chromophore units as shown in FIG. The similarity of the spectra of the nanoparticles to the spectrum of a solution of compound 4 indicates that the chromophores are preferably in direct proximity to each other. Also, a reaction of the polyvinyl alcohol even with only very small proportionate amounts of the dye to completely analogous spectra. From this it can be concluded that already in the condensation of the aldehyde with polyvinyl alcohol can lead to an aggregation of the chromophore component, so that the chromophore is preferably incorporated in pairs or in higher aggregates.

The fluorescence quantum yield of 3a at 37% is comparable to the fluorescence quantum yield of 4 at 40%. The strong bathochromic shift of the fluorescence spectrum compared to monochromophoric perylene dyes and the resulting increase in the Stokes shift are extremely interesting for practical applications of the nanoparticles, since this reduces the reabsorption of the fluorescence light. This is important for laser applications as well as for analytical applications or for applications in fluorescence solar collectors.

Examples

Unless otherwise stated, spectroscopic data were obtained to characterize the following exemplary compounds as with the following devices: IR spectra: FT 1000; UV / Vis spectra: Varian Cary 5000; Fluorescence spectra: Varian Eclipse; NMR spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95.

4- [9- (1-hexylheptyl) -1,3,8,10-tetraoxoanthra [2,1,9-def; 6,5,10-dibenzoquinolin-2-yl] benzaldehyde (1b):

9- (1-Hexylheptyl) -2-benzopyrano [6 ', 5', 4 ': 10.5.6] anthra [2.1, 9-cfe] isoquinoline-1, 3,8,10-tetrazone (1.00 g, 1.74 mmol), 4- [1,3] dioxolan-2-yl-benzylamine (500 mg, 2.79 mmol), imidazole (15 g) and a spatula tip of zinc acetate dihydrate were added 4 hours under air and moisture exclusion (Ar shielding gas) Stirred at 140 ° C, allowed to cool and while warm with so much ethanol, that the solidifying imidazole was dissolved, by addition of 2 N aqueous HCl precipitated, filtered off with suction (D4 glass frit), with 2 N HCl and distilled water washed, dried in a drying oven at 110 ° C for 16 h, dissolved in chloroform, shaken three times with 100 ml_ of a 1: 1 mixture of glacial acetic acid and 2 N HCl and purified by column chromatography (silica gel, chloroform / ethanol 80: 1, fourth band). Y. 817 mg (68%) of red solid, mp> 250 ° C. R <(silica gel, chloroform / ethanol 30: 1): 0.46. IR (ATR): v = 2954w, 2923m, 2856w, 1699s, 1658s, 1645s, 1610w, 1594s, 1578m, 1507w, 1482w, 1467w, 1436m, 1404m, 1378 w, 1338s, 1301m, 1250m, 1213m, 1200w, 1168m, 1125w, 1106w, 1078m, 1003w, 987w, 932w, 903w, 859w, 849m, 823w, 809s, 791w, 774m, 743s, 723w, 641w, 632w, 616w, 606cm ^-1 w. ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.81 (t, ³ J _H .H = 7.0 Hz, 6 H, 2 CH ₃ ), 1.17-1.38 (m, 16 H, 8 CH _2), 1.83 - 1.93 (m, 2H, _.beta.-CH2), 2:19 to 2:29 (m, 2H, _.beta.-CH2), 5:13 to 5:22 (m, 1H, a-CH), 5:42 (s , 2 H, CH), 7.68 (d, ³ J _H .H = 8.2 Hz, CH _arom ), 7.83 (d, ³ J _{H. H} = 8.2 Hz, CH _arom ) '8.56 - 8.71 ppm (m, 8 H , CH _aroma ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): ö ^"= 14.0, 22.6, 26.9, 29.2, 31.7, 32.4, 43.5, 54.9, 122.6, 122.8, 123.1, 123.5, 126.1, 126.3, 129.3, 129.4 , 130.0, 130.9, 131.5, 131.7, 133.9, 134.8, 135.7, 143.7, 163.2, 191.8 ppm UV / Vis (CHCl _3):. Um _ax (ε) = 459 (19110), 490 (52890), 527 nm (86770 Fluorescence (CHCl ₃ ): ηη ₃ , ( _β /) = 535 (1.00), 577 (0.50), 627 nm (0.12), fluorescence quantum yield (CHCl ₃ , λ ^ _χ = 490 nm, E ₄ 90 nm). 0.01358 cm ^"1 , reference: 1a with Φ = 1.00): 1.00. HRMS (C45H42N2O5): Ber. m / r. 617.3094, Gef. M / z. 690.3079, Δ = 1.5 mmu. C ₃ 9H4oN ₂ 0 ₅ (617.3): Ber. C 78.24, H 6.13, N 4.06; Gef. C 77.72, H 6.17, N 4.01.

Polymer-analogous reaction for the preparation of 3a and 3b (see Fig. 1):

4- [9- (1-Hexylheptyl) -1,3,8,10-tetraoxoanthra [2,1,9-ce1 / 6,5,10 c'-diisoquinolin-2-yl] benzaldehyde (1b, 50 mg for 3a and 5 mg for 3b) was heated to 80 ° C. with DMSO (25 ml) and stirred until a homogeneous solution was obtained, dropwise with a mixture of DMSO (75 ml) heated to 60 ° C., polyvinyl alcohol (5 g, fully hydrolyzed, Merck, M _n = 15000, degree of hydrolysis 96%, ester value 30-50) and a spatula tip of 4-toluenesulfonic added dropwise within 5 min, stirred for 1 h at 80 ° C, allowed to cool, to stop the reaction with acetone precipitated, filtered off with suction through a D4 glass frit, washed with acetone until colorless and dried for 1 day in vacuo over calcium chloride and phosphorus pentoxide. Pink powder. UV / Vis (3a, water): _* ( _β /) = 470 (2.38), 495 (3.19), 539 nm (1.86). UV / Vis (3b, water): / * (£ _e /) = 469 (1.19), 494 (1.50), 537 nm (1.07). Fluorescence (3a, water): = 549 (88),

663 nm (400). Fluorescence (3b, water): λ ", _3Χ (/ _« =,) = 548 (56). 658 nm (288). Fluoreszenzquantenausb. (3a, water, Äa _nr, = 497 nm) = 37%. Dynamic light scattering DLS (3a, comparison polyvinyl alcohol: 97 nm, peak 79 nm, polydispersity 0.39 at M _n = 15000): particle size (maxima, polydispersity PDI) = 244 nm (78, 378 nm, 0.68). Dynamic light scattering DLS (3b, comparison polyvinyl alcohol: 97 nm, peak 79 nm, polydispersity 0.39 at M _n = 15000): particle size (maxima, polydispersity PDI) = 235 nm (69, 239 nm, 0.73).

4- (1,3-dioxolan-2-yl) benzonitrile (5):

 5

Synthesis according to H. Langhals et al., Eur. J. Org. Chem. 2007, 4328-4336. 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, stirred 20 h under reflux on a water separator, allowed to cool to room temperature, washed with aqueous NaHC0 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. 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 _ary1 ), 7.61-7.68 (m, 2H, CH _ary ,). 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) [AT -H], 131.1 (4.0), 130.1 (34.8) [M ^* -C 2 H 4 O ], 103.2 (16.3), 102.1 (15.1) [M ^* -C3H4O2]. 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):

O-bisimid (1a, 200 mg, 0.265 mmol) und Natriumamid (0.200 g, 5.13 mmol) wurden in 4-[1 ,3]Dioxolan-2-yl- benzonitril (5, 5 g) 5 h auf 165°C erhitzt (Blaufärbung), abkühlen lassen, bis zur Trockene eingedampft und mit einem 1 :1-Gemisch aus 2 N wässriger HCl und Chloroform (300 mL) aufgenommen. Die organische Phase wurde filtriert und vom Chloroform befreit, eingedampft, in wenig Chloroform aufgenommen, säulenchromatographisch (Kieselgel, Chloroform) gereinigt, zur Entschützung in THF (100 mL) gelöst, mit einem Gemisch aus 2 N wässriger HCl und Eisessig (1 :1 , 100 mL) versetzt, 8 h unter Rückfluss gekocht, nach dem Erkalten von der wässrigen Phase abgetrennt, mit Magnesiumsulfat getrocknet, eingedampft, in wenig Chloroform gelöst und mit Methanol gefällt. Ausb. 57 mg (23.7 %) schwarz-violetter Farbstoff, Schmp. >250°C. R_f (Kieselgel, 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, 161 1.5 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, 1 172.8 w, 1 122.8 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. ¹H-NMR (600 MHz, CDCI₃, 25°C): δ = 0.76-0.89 (m, 12 H, CH₃), 1.15-1.42 (m, 32 H, CH₂), 1.84-1.96 (m, 4 H, ß-CH₂), 2.21 -2.36 (m, 4 H, 3-CH₂), 5.16-5.31 (m, 2 H, a-CH), 8.17 (d, ³J =8.3 Hz, 2 H, CH_aryl), 8.50-8.58 (m, 2 H, CH_{ar l}), 8.61-8.87 (m, 5 H, CH_pery1en), 10.18 (s, 1 H. CHO), 10.78 (d, ³J =8.0 Hz, 1 H, CH_pe(yten), 1 1 -68 ppm (s, 1 H, N-H). ¹³C-NMR (100 MHz, CDCI₃, 25°C): δ = 14.3, 14.3, 22.8, 22.8, 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 (CHCI₃) :Lax (ε) = 393.0 (15240), 440.0 (12800), 464.0 (12800), 508.0 (14100), 546.4 (42850), 591.6 nm (813450). Fluoreszenz (CHCI₃₎ A_exc = 546.4 nm) :

(/_rei) = 599.6 (1.00), 653.7 (0.41 ), 715.8 nm (0.09). Fluoreszenzquantenausb. λ_ΘΚ = 546.4 nm, E546.4 _nm/i cm ⁼ 0.0156, CHCI₃, Referenz 1a mit Φ = 1.00) : Φ = 1.00. MS (DEI⁺, 70 eV) : m/z (%) : 901.2 (21.3), 900.2 (61.7), 899.2 (93.1 ) [AT], 718.7 (11.6), 717.7 (29.2), 716.7 (32.1 ) [M^* -C₁₃H₂₇], 536.2 (22.8), 535.3 (69.3), 534.1 (100) [M^* -2 C₁₃H₂₇]. HRMS

: Ber. m/z : 898.5033 ; Gef. m/z : 898.5029, Δ = -0.0004. C₅₈H₆₆N40₅ (899.2) : Ber. C 76.10, H 7.58, N 6.02 ; Gef. C 75.66, H 7.38, N 5.90.

O-bisimide (1a, 200 mg, 0.265 mmol) and sodium amide (0.200 g, 5.13 mmol) were heated in 4- [1,3] dioxolan-2-yl-benzonitrile (5.5 g) at 165 ° C for 5 h (Blue color), allowed to cool, evaporated to dryness and taken up with a 1: 1 mixture of 2N 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, 161 1.5 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, 1 172.8 w, 1 122.8 w, 1060.1 w, 1015.9 w, 967.4 w, 871.2 vw, 845.7 w, 813.9 m, 753.8 m, 729.6 wcm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.76-0.89 (m, 12 H, CH ₃ ), 1.15-1.42 (m, 32 H, CH ₂ ), 1.84-1.96 (m, 4H, _.beta.-CH2), 2:21 to 2:36 (m, 4 H, 3-CH _2), 5:16 to 5:31 (m, 2 H, a-CH), 8.17 (d, ³ J = 8.3 Hz, 2 H, CH _aryl ), 8.50-8.58 (m, 2 H, CH _{ar I} ), 8.61-8.87 (m, 5 H, CH _perylene ), 10.18 (s, 1 H. CHO), 10.78 ( d, ³ J = 8.0 Hz, 1 H, CH _{pe (yt} in), 1 1 -68 ppm (s, 1 H, NH) ¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C): δ = 14.3, 14.3, 22.8, 22.8, 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 ): Lax (ε) = 393.0 (15240), 440.0 (12800), 464.0 (12800), 508.0 (14100), 546.4 (42850), 591.6 nm (813,450). Fluorescence (CHCl ₃₎ A _exc = 546.4 nm):

(/ _re i) = 599.6 (1.00), 653.7 (0.41), 715.8 nm (0.09). Fluoreszenzquantenausb. λ _ΘΚ = 546.4 nm, E546.4 _n m / i 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) [AT], 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 ^* -2 C ₁₃ H ₂₇ ]. HRMS

: Ber. m / z: 898.5033; Gef. M / z: 898.5029, Δ = -0.0004. C ₅₈ H ₆₆ N40 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-bromomethylphenyl) - [1,3] dioxolane (7)

 7

Synthesis according to H. Langhals et al., Eur. J. Org. Chem. 2007, 4328-4336. 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 _ar ). 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) [Af], 165.2 (1 -5), 164.2 (12.0), 163.2 (100.0) [M ^* -Br]. HRMS (C ₁₀ H ₁₀ ⁷⁹ BrO ₂ ): Ber. m / r. 240.9859, Gef. M / r. 240.9859, Δ = -0.0000.

,9- o^,e :6₍5₎10-d'e'ndiisochinolin-1₍3_I10,12(2H,11H)-tetraon (9): 4- (4-Formylbenzyl) -2,11-bis (1-hexylheptyl) -5-phenylimidazolo

, 9- ^o, e: 6 ₍₅₎ 10-d'e'ndiisochinolin-1 _{(3 I} 10.12 (2H, 11H) -tetraon (9):

 9

2,11 -bis (1-hexylheptyl) -5-phenylimidazolo [4 \ 5 ^ 3,4] anthra [2,1, 9-Gief.6,5,10-d'e'-diisoquinoline-1, 3,10 , 12 (2 / -, 11 -) -tetraone (8, 450 mg, 0.517 mmol) and potassium carbonate (700 mg, 5.07 mmol) in DMPU (20 mL) were heated to 1 10 ° C (blue coloration), dropwise with 2 - (4-bromomethylphenyl) - [1, 3] dioxolane (7, 627 mg, 2.58 mmol) (violet dyeing), stirred for 20 h at 1 10 ° C, allowed to cool, terminated by addition of 2 N aqueous HCl, filtered 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 2N aqueous HCl (1: 1) for 30 minutes, freed of 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, 1 181.7 w, 1 107.2 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): <5 = 0.81 (t, ³ J = 7.0 Hz, 12 H, _CH3), 1:03 to 1:40 (m, 32 H, CH _2), 1.79-1.94 (m, 4 H , β-C ₂ ), 2.04-2.18 (m, 2H, β-C ₂ ), 2.21-2.31 (m, 2H, 3-CH ₂ ), 4.98-5.25 (m, 2H, a-CH) , 6.27 (s, 1 H, _W-CH2), 6:32 (s, 1 H, A / CH _2), 6.67-6.79 (br, 2 H, CH _b e _{n z} yl), 7:52 (d, ³ J = 8.5 Hz, 2 H, CH, _b s _Z yi), 7.61-7.71 (br, 3 H, CH nyi _Phe), 7.94-8.07 (br, 2 H, CHP _heny i), 8.55-8.80 (m, 5 H, CH _{pe [ylene),} 9.76 (s, 1 H, CHO), 10.79 ppm (d, 1 H, ³ J = 8.0 Hz, CH _{Pery, e} n). ¹³ C-NMR (150 MHz, CDCl ₃ , 25 ° C): <5 = 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 ): / W _* (ε) = 376.0 (7320), 395.4 (8250), 436.0 (8760), 499.6 (14500), 536.4 (44810), 580.8 nm (85160). Fluorescence (CHCl ₃ , λ _βκ = 536.4 nm): A _max (= 591.7 (1 .00), 643.6 nm (0.45).) Fluorescence quantum yield ( _exc = 536.4 nm, E536.4 nm / cm = 0.0134, CHCl ₃ , reference 1 a 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) [Af-C ₁₃ H ₂₆ ], 625.3 (22.8) , 624.3 (41.2) [M * - 2C ₁₃ H ₂ 6], 507.1 (28.9), 506.1 (39.4, [h / - 2Ci ₃ H ₂₆ - C ₈ H ₇ 0]. HRMS (C ₆₅ H72N ₄ 05 988.5491, Δ = - 0.0012, C65H72N4O5 (989.3): C 78.91, H 7.34, N 5.66, C 78.75, H 7.37, N 5.63.

(l_rel) = 726.1 nm (1 .00). Polymer-analogous reaction to give 10: 2, 11-bis (1-hexylheptyl) -5- (4-formylphenyl) imidazolo [4 \ 5 ^ 3,4] anthra [2, 1, 9-des: 6,5, 10 -cf'-diisoquinoline-1, 3, 10, 12 (2 / - /, 11 H) -tetraone (6, 15 mg) was heated to 80 ° C with DMSO (5 mL) and stirred until a homogeneous solution, dropwise with a heated to 140 ° C, homogeneous mixture of DMSO (35 mL), polyvinyl alcohol (2.5 g, fully hydrolyzed, Merck, M _n = 16000, degree of hydrolysis 96%, ester value 30-50) and 4- Toluene sulfonic acid (20 mg) added dropwise within 5 min, stirred at 100 ° C for 2 h, allowed to cool, precipitated to stop the reaction with acetone, filtered with suction through a D4 glass frit, washed with acetone until colorless, 1 d in vacuo dried over calcium chloride and phosphorus pentoxide. Dark powder UV / Vis (water): _max (l _re i) 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):

(l _rel ) = 726.1 nm (1 .00).

(l_ret) = 701 .9 nm (1.00). Polymer analogous reaction to prepare 11: 4- (4-formylbenzyl) -2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2, 1, 9-def: 6,5,10-N'-diisoquinoline-1,3,10,12 (2 - /, 11/-) -tetraone (9,15 mg) was reacted and worked up analogously to 6. Dark powder. UV / Vis (CHCI ₃ ): _max (E _re! ) = 399.0 (0.31), 442.0 (0.31), 542.8 (1 .00), 591 .0 nm (0.70). Fluorescence (CHCl ₃ , _c = 542 nm):

(l _ret ) = 701 .9 nm (1.00).

Claims

claims A modified polyvinyl alcohol having repeating units of the following formula (I) and repeating units represented by the following formula (II):

 I II wherein Y in formula (II) represents a chromophore structural unit which absorbs light in the wavelength range of 350 to 3500 nm. 2. The modified polyvinyl alcohol according to claim 1, wherein the light-absorbing structure Y is a structure comprising a perylene unit. 3. Modified polyvinyl alcohol having repeating units of the following formula (I) and repeating units of the following formula (IIa), (IIb) and / or (IIc):

I -40-

where the radicals R ^1a , R ^1b , R ^1c , R ^2b and R ^2c , the radicals R ^3a , R ⁴ *, R ⁵³ , R ^6a , R ^3b , R ^b , R ^5b , R ^3c , R ⁴ and R ^5c in which the radicals R ^7b and R ^12c in the formulas IIa, IIb and Ilc are identical or different and independently of one another in each occurrence represent hydrogen or a linear alkyl radical having at least one and at most 37 C atoms or one of the halogen atoms F, Cl, Br or I; in the alkyl radical, one to 10 CH ₂ units may independently be replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis- or iran-CH = CH- group in which a CH unit is also represented by a nitrogen atom may be replaced, an acetylenic C ^ C group, a divalent phenyl radical (eg, 1, 2, 1, 3 or 1, 4-phenyl), divalent pyridine (eg 2,3-, 2,4-, 2, 5, 2,6, 3,4 or 3,5-pyridine), divalent thiophene (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene), divalent naphthalene (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical ), in which one or two CH groups may be replaced by nitrogen atoms, and a divalent anthracene residue (eg 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-anthracene), at one or two CH groups may be replaced by nitrogen atoms; Up to 12 individual hydrogen atoms of the CH ₂ - groups can each be replaced independently of the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain with up to 18 carbon atoms, in which a to 6 CH ₂ units may independently be replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, a cis or frans-CH = CH group in which a CH unit may be replaced by a nitrogen atom, a acetylenic C = C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2 , 6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), wherein one or two CH groups may be replaced by nitrogen atoms, and one divalent en anthracene residue (eg 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 anthracene radical) in which one or two CH groups may be replaced by nitrogen atoms; Up to 12 individual hydrogen atoms of the CH ₂ groups in an alkyl radical may each be independently replaced by the halogens fluorine, chlorine, bromine or iodine, a cyano group or a linear alkyl chain having up to 18 carbon atoms, wherein one to 6 CH ₂ units can be independently replaced by a carbonyl group, an oxygen atom, sulfur atom, selenium atom, tellurium atom, an cis or frans-CH = CH group in which a CH unit is replaced by a nitrogen atom can a acetylenic C = C group, a divalent phenyl radical (eg 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg 2,3-, 2,4-, 2,5-, 2 , 6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), in which one or two CH groups may be replaced by nitrogen atoms, and one divalent anthracene radical (eg 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 anthracene radical) in which a or two CH groups may be replaced by nitrogen atoms; CH ₂ groups on which, as described above, a hydrogen atom is replaced, may also be linked together to form a ring, ie instead of carrying substituents, the free valences of the methine groups or the quaternary carbon atoms can be linked in pairs, so that Rings are formed, such as cyclohexane rings; the radical R ^12c may furthermore have the formula Vc:

 Vc in which the radicals R ^13c , R ^14c , R ^15c , R ^16c and R ^17c satisfy the definition given above of the radicals R ^3c to R ^5c and X ^a , X ^b and X ^{c are} bivalent linker units. 4. Modified polyvinyl alcohol according to claim 3, represented by the formula IIIa

wherein the radicals R ^1a , R ^3a , R ^4a , R ^5a , R ^6a and X ^{a are} as defined in claim 3, and the indices m and n independently represent integers in the range from 1 to 1000. 5. A modified polyvinyl alcohol according to claim 3, represented by the formula IIIb

wherein the radicals R ^1b , R ^2b , R ^3b , R ^b , R ^5b , R ^7b and X ^{b are} as defined in claim 3, indices m and n independently represent integers in the range of 1 to 1000. 6. A modified polyvinyl alcohol according to claim 3, represented by the formula IIIc

IIIc wherein the radicals R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , R ^12c and X ° are as defined in claim 3, and the indices m and n independently represent integers in the range of 1 to 1000. 7. nanoparticles consisting of one or more compounds according to any one of claims 1 to 6. 8. nanoparticles nanoparticles according to claim 7 in a polymeric solid or a liquid. 9. A process for the preparation of a compound according to any one of claims 1 to 6, which comprises the reaction of an aldehyde with polyvinyl alcohol with acetal formation. 10. Use of one or more compounds according to any one of claims 1 to 6, the nanoparticles according to claim 7 or the nanodistribution according to claim 8 as colorants for dyeing purposes. 11. Use of one or more compounds according to any one of claims 1 to 6 or the nanoparticles according to claim 7 as colorants for printing or writing inks. 12. Use of one or more compounds according to any one of claims 1 to 6 or the nanoparticles according to claim 7 as fluorescence colorant.