DE19835730A1 - New liquid crystalline carbonic acid ester(s) - Google Patents

Abstract

Liquid crystalline carbonic acid esters of formula (Ia) are new P<1>-Y<1>-A<1>-O-M-O-C(=O)-O-A<2>-Y<2>-P<2> (Ia), where P<1>, P<2> = H, 1-4C alkyl or reactive radicals by means of which polymerisation can be performed; Y<1>, Y<2> = a single bond, -O-, -S-, -O-CO-, -CO-O-, -O-CO-O-, -CO-NR-, -NR-CO-, -O-CO-NR-, -NR-CO-O- or -NR-CO-NR-; R = H or 1-4C alkyl; A<1>, A<2> = 1-30C spacer chains optionally interrupted by O, S or non-adjacent imino or 1-4C alkylimino; and M = a mesogenic group. Also claimed are (1) mixtures of (Ia) with (Ib) and/or (Ic) P<1>-Y<1>-A<1>-O-M-O-A<2>-Y<2>-P<2> (Ib), P<1>-Y<1>-A<1>-O-C(=O)-O-M-O-C(=O)-O-A<2>-Y<2>-P<2> (Ic); and (2) mixtures of (Ia) with (Ib') and (Ic') P<1>-Y<1>-A<1>-O-M-O-A<1>-Y<1>-P<1> (Ib'), P<2>-Y<2>-A<2>-O-C(=O)-O-M-O-C(=O)-O-A<2>-Y<2>-P<2> (Ic'), obtainable by reacting (II) HO-M-OH (II) with (IIIa) and/or (IIIb) P<2>-Y<2>-A<2>-O-C(=O)-Cl (IIIa), P<1>-Y<1>-A<1>-Y<3> (IIIb), where Y<3> is a leaving group.

Description

The present invention relates to liquid-crystalline compounds of the formula Ia

in which the variables have the following meaning
P ¹ , P ² each independently of one another are hydrogen, C ₁ -C ₄ alkyl or reactive radicals, via which a polymerization can be brought about,
Y ¹ , Y ² each independently of one another are a single chemical bond, oxygen, sulfur, -O-CO-, -CO-O-, -O-CO-O-, -CO-NR-, -NR-CO-, - O-CO-NR-, -NR-CO-O- or -NR-CO-NR-,
R is hydrogen or C ₁ -C ₄ alkyl,
A ¹ , A ² spacers with one to 30 C atoms, in which the carbon chain can be interrupted by oxygen in ether function, sulfur thioether function or by non-adjacent imino or C ₁ -C ₄ alkylimino groups, and
M a mesogenic group.

The invention further relates to mixtures, which compounds of formula Ia, and compositions which Compounds of the formula Ia and, if appropriate, further additives contain a process for the preparation of compounds of Formula Ia, process for producing coatings from the Compounds, mixtures or compositions according to the invention and articles coated by this method.

The invention further relates to the use of the invention compounds, mixtures or compositions for the Manufacture of optical components and liquid crystalline color medium, liquid crystalline colorants and aqueous emulsions or dispersions containing the compounds according to the invention, Contain mixtures or compositions, and pigments, which by polymerization of the compounds according to the invention, Mixtures or compositions are available, the later pigment size and shape either before the polymerization  by suitable methods or by polymerization subsequent comminution is set.

Numerous liquid crystalline compounds are from the literature known which have reactive (polymerizable) end groups. These end groups are from the mesogenic group M by spacers separated, the connection of the spacer to M mostly via an ether bond such as e.g. B. in the documents EP-A 0648 827, EP-A 0611 981, EP-A 0739 403, WO 95/24454, WO 95/24455 or 86/24647. Examples for connecting the Spacers on M via an ether bond as well as via a direct chemical bonding can be found in WO 95/22586. Liquid crystalline Compounds in which the spacer groups have carbonate units the mesogenic group M are bound in the scriptures 97/00600 listed.

As a rule, comparable liquid crystalline ver bindings with ether bound spacers (liquid crystalline "Ether") compared to such compounds with carbonate-bound Spacers (liquid crystalline "carbonates") lower viscosities, which is mostly desirable, as well as a higher tendency to go out formation of defect-free, smooth films, what with regard to the manufacture position of platelet-shaped particles of defined thickness or the Application in paints is of great importance. In addition is the ether linkage of the spacer to the mesogenic group M in Ver chemically more stable compared to the carbonate bond for example basic substances such as u. a. Amines. A application-related disadvantage of liquid-crystalline "ethers" compared to the "carbonates", however, is, as a rule, low gere liquid-crystalline phase width, which is its scope constricts.

The object of the present invention was therefore liquid-crystalline Provide compounds that have the positive properties the liquid crystalline "ether" and "carbonate" ver one without having its negative qualities. Further these new liquid crystalline compounds should be easier Be wise and therefore cost-effective and time-saving.

It has now been found that the Ver bonds of formula Ia the desired property profile in correspond in an excellent way and moreover in a simpler way Way can be made.

Mixtures which contain are further claimed according to the invention
(A ₁ ) one or more liquid-crystalline compounds of the formula Ia,
(A ₂ ) optionally one or more liquid-crystalline compounds of the formula Ib

P ¹ -Y ¹ -A ¹ -OMOA ² -Y ² -P ² (Ib)

and or
(A ₃ ) optionally one or more liquid-crystalline compounds of the formula Ic

where the variables P ¹ , P ² , Y ¹ , Y ² , A ¹ , A ² and M in formulas Ib and Ic each have the same general meaning as in formula Ia and in the specific individual case the selection of these variables for the compounds Ia, Ib and Ic do not have to be the same.

Such mixtures can therefore contain component A ₁ alone, a mixture of component A ₁ and A ₂ or of component A ₁ and A ₃ or a mixture of components A ₁ , A ₂ and A ₃ . Compounds and mixtures of compounds which can be used according to the invention as component A ₂ and which also correspond to the formula Ib in their structure are in the preparation examples of the documents WO 95/24454 and WO 95/24455 and in the preparation examples of the earlier German patent registration 197 16 822.1. These compounds and their mixtures as preferred component A ₂ are expressly referred to here. Furthermore, WO 97/00600 in the preparation examples lists compounds and mixtures of compounds which can be used according to the invention as component A ₃ and which correspond to the formula Ic in their structure. Express reference is therefore made to these compounds and their mixtures as preferred component A ₃ .

Mixtures which contain are further claimed according to the invention
(A ₁ ') one or more liquid-crystalline compounds of the formula Ia,
(A ₂ ') one or more liquid-crystalline compounds of the formula Ib',

P ¹ -Y ¹ -A ¹ -OMOA ¹ -Y ¹ -P ¹ (Ib ')

and
(A ₃ ') one or more liquid-crystalline compounds of the formula Ic'

obtainable by one or more compounds of the formula II

HO-M-OH (II)

with one or more compounds of the formulas IIIa and IIIb

P ¹ -Y ¹ -A ¹ -Y ³ (IIIb),

implemented, the variables P ¹ , P ² , Y ¹ , Y ² , A ¹ , A ² and M have the meaning given above and Y ^{3 is} a leaving group.

In contrast to the previously mentioned mixtures, which contain component A ₁ and, if appropriate, component A ₂ and / or A ₃ , these mixtures result from the fact that the variables of the compounds of the formulas Ia, Ib 'and Ic' are dependent on one another.

Within the scope of the present invention, compositions are also claimed which contain

• (A) Compounds of the formula Ia or mixtures containing component A _1, if appropriate in a mixture with components A ₂ and / or A ₃ , or mixtures containing components A ₁ ', A ₂ ' and A ₃ ', and
• (B) other additives.

All of the radicals familiar to the person skilled in the art can be used as reactive radicals P ¹ and P ² , via which a polymerization can be brought about, in the compounds of the formula Ia according to the invention and in the mixtures and compositions according to the invention.

Preferred reactive radicals P ¹ and P ² are

where the radicals R here are hydrogen or C ₁ -C ₄ alkyl and can be the same or different.

Particularly preferred polymerizable groups P ¹ and P ² are those which are accessible to radical polymerization, that is to say especially the olefinically unsaturated groups, and among these in combination with Y ¹ and Y ^{2 have} the groups

special meaning.

Hydrogen or C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or t-butyl can be used as unreactive radicals P ¹ and P ² . These alkyl radicals are also suitable both for the radicals R mentioned above for the preferred reactive radicals P ¹ and P ² and for the radicals R mentioned in the definition of the groups Y ¹ and Y ² .

All groups known for this purpose can be considered as spacers A ¹ and A ² . The spacers contain 1 to 30, preferably 3 to 12 carbon atoms and consist of predominantly linear aliphatic groups. You can in the chain, e.g. B. by not neigh disclosed oxygen or sulfur atoms or imino or alkylimino groups, such as methylimino groups, may be interrupted. Fluorine, chlorine, bromine, cyano, methyl and ethyl can also be used as substituents for the spacer chain.

Representative spacers are for example:

in which
m stands for 1 to 3 and p stands for 1 to 12.

All known mesogenic groups can be used as residues M. In particular come groups of formula Iaa

(-TY ⁵ ) _r -T- (Iaa)

in which the variables have the following meaning:
T divalent saturated or unsaturated iso- or heterocyclic radicals,
Y ⁵ groups of the definition for Y ¹ and Y ² or -CH ₂ -O-, -O-CH ₂ -, -CH = N-, -N = CH- or -N = N- and
r 0, 1, 2 or 3,
where in the case r <O both the radicals T and the groups Y ⁵ can each be the same or different from one another.

R is preferably 1 or 2.

The radicals T can also carry up to three identical or different substituents from the following group:
Hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ monoalkylaminocarbonyl, C ₁ -C ₂₀ alkylcarbonyl, C ₁ -C ₂₀ alkyl carbonyloxy , C ₁ -C ₂₀ alkylcarbonylamino, formyl, carboxyl, halogen, cyan, hydroxy or nitro.

Preferred substituents for the radicals T are, in addition to fluorine, chlorine, Bromine, cyan, formyl, carboxyl, nitro and hydroxy especially briefly chain aliphatic radicals such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl and alkoxy-, alkoxy carbonyl, alkylcarbonyl, alkylcarbonyloxy, alkylcarbonyl amino and monoalkylaminocarbonyl residues containing these alkyl groups contain.  

Examples of such radicals T are:

Preferred as mesogenic groups M are z. B .:

Mesogenic groups M of the following formulas are particularly preferred

where each ring Z can carry up to three identical or different substituents from the following group:
Hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ monoalkylaminocarbonyl, C ₁ -C ₂₀ alkylcarbonyl, C ₁ -C ₂₀ alkyl carbonyloxy , C ₁ -C ₂₀ alkylcarbonylamino, formyl, carboxyl, halogen, cyan, hydroxy or nitro.

Preferred substituents for the aromatic rings are besides Fluorine, chlorine, bromine, cyan, formyl, carboxyl, nitro and hydroxy all short-chain aliphatic radicals such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl and alkoxy, Alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, alkyl carbonylamino and monoalkylaminocarbonyl residues that this alkyl groups included.  

The outer benzene rings or, if there are only two benzene rings, have a benzene ring of the particularly preferred groups M or preferably have the following substitution patterns:

or they are or it is analogously substituted with F, Cl, Br, CH ₃ , OCH ₃ , CHO, COOH, COCH ₃ , OCOCH ₃ or CN instead of Cl, where the substituents can also be mixed. Furthermore, the structures

to be mentioned in which s is 2 to 20, preferably 8 to 15.

The preferred substitution patterns of the middle benzene ring in mesogenic groups M with three residues T of the particularly preferred groups M are

For technical applications, for example in the printing area often setting a desired viscosity is important.

It can therefore in the mixtures and together according to the invention Settlements also mixtures of compounds of the formulas Ia, Ib, Ic or Ia, Ib ', Ic' with different mesogenic groups M u. a. for this purpose. Such mixtures have in usually a changed viscosity compared to such mixtures, which in all connections only one and the same mesogenic Group M is present.  

If, for example, mixtures are to be produced which contain the components A ₁ ', A ₂ ' and A ₃ ', not only z. B. "tetranuclear", optionally substituted on the rings Z, mesogenic groups M of the formula

according to a connection to be used

or the corresponding mono- or dianion, where Ia, Ib 'and Ic' are to be used for

a chemical single bond or

r: equal to 3,
but z. B. also "trinuclear", optionally substituted on the rings Z, mesogenic groups M of the formula

according to a connection to be used

or the corresponding mono- or dianion, where Ia, Ib 'and Ic' are to be used for

r: equal to 2,
or z. B. also "dinuclear" groups M of the formulas

according to a connection to be used

or the corresponding mono- or dianion, in which formulas Ia, Ib 'and Ic' are to be used for
Y ⁵ : a chemical single bond,

r: equal to 1,
or z. B.

according to a connection to be used

or the corresponding mono- or dianion, where is to be set in the formulas Ia, Ib 'and Ic for
Y ⁵ : a chemical single bond,

r: equal to 1.

Particularly preferred "binuclear" mesogenic groups M are the fragments

according to the connection to be used

or the corresponding mono- or dianion, which additionally still on the aromatic rings Z, as described above, can be substituted.

All groups known to the person skilled in the art can function as leaving groups Y ³² , Y ⁴² . Halogens are preferably used here, particularly preferably Cl and Br. Also preferred are aliphatic or aromatic sulfonic acid derivatives and the partially or completely fluorine-substituted aliphatic sulfonic acid derivatives. examples for this are

For the preparation of a mixture containing the components A ₁ ', A ₂ ' and A ₃ ', mesogen diols are used in an advantageous manner, the mesogenic group M of which corresponds to the formula Ia and in which Y ^{5 is} -COO- or -OOC-. These mesogen diols are usually prepared by azeotropic esterification. For example, as is also known from the literature, p-hydroxybenzoic acid and (substituted) hydroquinone with the addition of xylene as entrainer and p-toluenesulfonic acid as catalyst can be used to produce either a mixture of "dinuclear" mesogen diols (depending on the molar ratio used) ( Equation 1):
Equation 1:

or a "trinuclear" mesogen diol (Equation 2):
Equation 2:

produce. The radicals R correspond in meaning to Substituents of the rings Z mentioned above of the preferred mesogenic groups M. Is R in equation 1 synonymous with hydrogen, so the two result the "binuclear" mesogen diols are of course chemically identical.

In addition to xylene, toluene and others can also be used as entrainer higher-boiling aromatics or mixtures of such hydrocarbons fabrics that are sold under the names Solvesso® or Aromatic® are commercially available, are used.

In addition to p-toluenesulfonic acid, the acids on which the preferred leaving groups Y ³ described above are based, preferably in pure form or as a concentrated aqueous solution, can also be used. Concentrated sulfuric acid, boric acid or a mixture of these two acids can also be used advantageously.

The ratio of starting materials to entrainer is not critical. Usually, however, about 100 g of the starting materials are used 200 to 350 µg of the entrainer.

The amount of catalyst used is approximately 1 to 10 g based on 100 g of the starting materials used.

Additions of 1.5 to 4.5 g per 100 g of educt are preferred.

The reaction mixture, consisting of starting materials, entrainer and Catalyst, is rendered inert with nitrogen and under reflux heated, the water as an azeotropic mixture with the tow medium is completely removed. Here are the implementation usually last from 4 to 12 hours. These times are hanging however, on the amounts and chemical nature of those used Educts and the entrainer used as well as the amounts and the nature of the acid catalyst and can therefore in detail fall below or be exceeded. After esterification has ended the batch is cooled to room temperature and the crystalline Raw product after suction with further entrainer or, if higher purities are desired, with solvents such as e.g. B. methanol or ethanol or their mixtures with water washed. Alternatively, the excess towing can medium also by steam distillation, optionally under Add a commercially available defoamer, separate and add the fe Isolate the product from water by filtration. Similar syn theses of such mesogen diols have already been described elsewhere (e.g. Kongas et al., Polym. Prep. (Ani. Chem. Soc., Div. Polym. Chem.) 30, pp. 462-463 (1989) and Müller et al., DE-A 36 22 611).

If sulfonate groups are used as the leaving groups Y ^{3 of} the compounds IIIb, which are derived from optionally partially or perfluorinated aliphatic or aromatic sulfonic acid derivatives, preference is given to starting from hydroxy compounds and the acid chlorides of the sulfonic acid derivatives for the preparation of the compounds IIIb. The following implementation is intended to explain this example of hydroxyalkyl acrylates (equation 3), which many representatives are readily available commercially.
Equation 3:

R 'here denotes a radical which is derived, for example, from preferred sulfonate radicals already mentioned above. A ¹ has the meaning as defined in formula IIIb, -Y ¹ -P ¹ corresponds to the grouping

The solvent toluene can also by other solvents, such as e.g. As methylene chloride or ether, are replaced. In addition to pyridine come as auxiliary bases tertiary amines, such as. B. N, N-Dimethylcyclo hexylamine, trimethyl or triethylamine, but also alkali or Alkaline earth carbonate or hydrogen carbonate in question, here the potassium salts are preferred. Mixtures of such organic and inorganic bases can be used.

An elegant way to convert the OH group chloride to the leaving group Y ³ in hydroxyalkyl acrylates is to convert the hydroxy compounds with phosgene to the intermediate chloroformates, which combine with the addition of catalytic amounts of dimethylformamide with elimination of CO ₂ Decompose chloroalkyl acrylates (Equation 4):
Equation 4:

This usually forms as by-products in one Proportion of less than 40 mol% also the corresponding compounds, which is an addition of the HCl to the vinyl group of the acrylate the rest was done. However, this is not a further problem since in In the course of the further implementation, hydrogen chloride under back again formation of the vinyl group is eliminated.

For the conversion of the mesogen diols II to the compounds Ia according to the invention or to the mixtures according to the invention, containing the compounds Ia, Ib 'and Ic' as components A ₁ ', A ₂ ' and A ₃ ', compounds IIIa and IIIb are particularly preferably used in which the reactive radicals P ¹ or P ² together with groups Y ¹ or Y ^{2 form} the following groupings:

The etherification of the mesogen diols II with the compounds IIIb usually takes place under the conditions of William son's ether synthesis. Alkali or alkaline earth carbonates are preferably used as bases, sodium carbonate and potassium carbonate and calcium carbonate being used with particular preference. In the case of the preferred mesogen diols and the particularly preferred reactants in which the groups Y ⁵ and Y ¹ and Y ^{2 are} each correspondingly -COO- or -OOC-, the benzoic and acrylic acid ester groups present surprisingly remain intact, while these groups are in use partial or complete splitting of bases such as sodium hydroxide or potassium hydroxide, depending, among other things, on the amount of water and lye.

Alkali bromides or can be used to catalyze the etherification reaction iodides and tetraalkylammonium bromides or iodides are added be, in the former case potassium bromide or potassium iodide, in the latter case tetrabutylammonium bromide or tetrabutylammonium iodide is preferably used.

Examples of solvents are dimethylformamide and dimethyl acetamide, N-methyl-pyrrolidone or dimethyl sulfoxide net, with dimethylformamide preferably used.  

The temperatures during the etherification reaction are in usually at 70 to 110 ° C, the reaction times are usually for 4 to 24 hours, with the specified Temperature ranges and time intervals in individual cases also below or can be exceeded.

Advantageously, the etherification can also be carried out using chloroformates of the formula IIIa, since in the presence of dimethylformamide, be it as a solvent or in catalytic amounts in one of the other solvents mentioned above, a spontaneous temperature under the reaction listed for the etherification Decarboxylation of these chloroformates takes place (see also the second partial equation of equation 4). ultimately, the reactants are compounds of the formula IIIb in which the leaving group Y ^{3 is} chlorine (or chloride). Therefore, what is said in the etherification with respect to the bases, catalysts, solvents, reaction temperatures and durations applies without restriction.

If you want to react mesogen diols of the formula II with compounds IIIa to obtain the carbonate group, you generally have to proceed at lower temperatures than in the etherification. Usually one works at temperatures from 0 to 60 ° C, mostly in the range from 40 to 50 ° C. Depending on the reactivity of the reaction partners, the reaction times are usually between 3 and 24 hours. The solvents mentioned in the etherification are again suitable as solvents, dimethylformamide is preferably used again. Although the latter also favors the decarboxylation reaction at the lower temperatures, here the reaction with the mesogen diol or with the compound HO-MOA ² -Y ² -P ² obtained by the previous etherification step to the target compound is kinetically favored. The etherification in the first step and the reaction with the chloroformates, at lower temperatures, in the subsequent step are also advantageous. When the reaction sequence is reversed, the cleavage and / or decarboxylation of the carbonate unit under the conditions of ether formation must generally be expected, but in individual cases this procedure can also lead to desired products.

To trap the ent during the reaction with the chloroformate standing hydrogen chloride is advantageous in front of the chlorfor miat addition of an auxiliary base at least equimolar to the chlorine Formate amounts added. Tertiary amines come into question such as B. trimethyl, triethyl or N, N-dimethylcyclohexyl amine, pyridine or inorganic bases such as alkali or earth  alkali carbonates or alkali or alkaline earth hydrogen carbonates as well as mixtures of organic and inorganic bases.

Alkali or alkaline earth acetates can also be used as further bases be set. N, N-Dimethylcyclohexylamine and Potassium carbonate added alone as well as in a mixture.

If, in a first etherification step, equimolar amounts of mesogendiol II and compound IIIb are used, then, in addition to the desired intermediate HO-MOA ¹ -Y ¹ -P ¹ , portions of the double-etherified product PY ¹ -A ¹ -OMOA ^{1 are also} expected -Y ¹ -P ¹ and on unreacted mesogen diol. In order to shift these shares in favor of the intermediate product, the procedure can advantageously be such that, in deviation from the stoichiometric mole ratio of 1: 1, the diol in a molar excess of 2.5 for the ratio mesogendiol P ¹ -Y ¹ -A ¹ -Y ³ : 1 to 10: 1, preferably 5: 1, in a solvent. The compound IIIb is added and the excess, unreacted mesogen diol is precipitated with a precipitant. After filtering off the solid, the filtrate, which contains the intermediate P ¹ -Y ¹ -A ¹ -OM-OH, which is readily soluble in both the solvent and the precipitant, is added in a second step with the chloroformate P ² -Y ² - A ² -O-CO-Cl too. After the usual work-up, the pure target compound of the formula Ia or, in the case of an asymmetrical mesogenic group M or when using a plurality of mesogen diols, a corresponding isomer mixture or a mixture of asymmetrical compounds Ia is obtained.

As a rule, they can already be used as solvents above compounds such. B. Dimethylacetamide, N-methyl pyrrolidone or dimethylformamide, methanol, vinegar as precipitant use ethyl acetate, dichloromethane or butyl acetate, where the effect as a solvent or precipitant from the Solution properties of the mesogen diol depends and the intermediate product in the resulting mixture of solution and precipitant must be readily soluble. In individual cases, however, easily determine the suitable solvents and precipitants by hand.

If particularly pure products are desired, it is advantageous to the etherification reaction and the reaction with the chlorine formats under an inert atmosphere, for example nitrogen atmosphere to perform. This can be oxidative addition Prevent reactions, especially on the mesogen diols.

An addition of radical scavengers, such as. B. commercially available Nitroxyl compounds or phenol derivatives prevents Use of compounds of the formulas IIIa containing acrylate groups  and / or IIIb, especially when working up, the premature Polymerization of the target compounds.

While the activity of phenol derivatives in the presence of Oxygen is usually increased, are nitroxyl compounds also effective under an inert atmosphere, which is why they are used in this Case also preferably used.

Of course, you can, if desired, also in the manufacture of Mesogen diols are already working under inert conditions. Of the The use of radical scavengers is then not necessary, can however, take place when the etherification reaction and the Implementation with the chloroformates in the sense of a one-pot reaction connect. As already mentioned above, one is considered inert Conditions then preferably add nitroxyl compounds.

In the case of relatively unreactive starting compounds of the formulas II and IIIb, it can be useful to work with two immiscible liquids, such as water and methylene chloride. In this case, compound IIIb preferably has a halogen as the leaving group Y ³ , particularly preferably Cl or Br, and is practically exclusively in the organic phase. If inorganic or strongly ionic, organic bases are used, examples of which are potassium carbonate or tetraalkylammonium hydroxides such as tetramethyl or tetraethylammonium hydroxide, on the contrary these are almost exclusively in the aqueous phase. When the mesogen diol is added, it is converted into its mono- or dianion, which is only slightly soluble in the organic phase, but because of its lower solvation it has a higher nucleophilicity and therefore with the halogen compound dissolved in it, without the base anion having to compete can react from.

The reaction mixture is usually worked up with Water and a little or immiscible with water organic extractant diluted, the organic phase several times with water and finally with aqueous mineral acid washed.

The organic extractant is removed using vacuum distillation at temperatures from 20 ° C to 40 ° C. To prevent premature polymerization of the product / the Products become common before they are worked up by distillation Inhibitors such as methoxyphenol, Kerobit® BHT or phenothiazine, mostly in a mixture, in quantities of 0.01 to 1% by weight on the product (s) added. The mix of the below  different volatile inhibitors ensures one sufficient stabilization of the product (s) both in the Liquid as well as vapor phase.

The compounds of the formula Ia according to the invention can either have two radicals P ¹ and P ² , both of which are unreactive, that is to say hydrogen or the C ₁ -C ₄ alkyl groups already mentioned, one of the radicals P ¹ or P can be present in these compounds ^{2 are} unreactive and the other is reactive, or both residues and P ² are reactive. Furthermore, mixtures of different compounds Ia are also possible, in which two unreactive (P ¹ and P ² are unreactive), one unreactive or one reactive (P ¹ is unreactive and P ² reactive or vice versa) and / or two reactive ( P ¹ and P ² are reactive) Compounds Ia are included. Compounds Ia and mixtures of compounds Ia in which at least one of the radicals P ¹ or P ^{2 is} reactive or at least one compound Ia in the mixture of these compounds contains at least one reactive radical P ¹ or P ^{2 are} preferred. Also preferred are mixtures according to the invention (components A ₁ , A ₂ and A ₃ and components A ₁ ', A ₂ ' and A ₃ 'and compositions according to the invention in which at least one of the radicals P ¹ or P ^{2 is present} in at least one compound Ia is reactive.

By proportions of compounds Ia which terminates once or twice with unreactive radicals P ¹ , P ² , that is to say hydrogen or C ₁ -C ₄ -alkyl, and the properties of the mixtures or compositions according to the invention, such as, for. B. adjust the liquid-crystalline phase width or viscosity, the respective requirements. It also affects the properties of the polymers obtained from such mixtures or compositions. So z. B. their hardness, elasticity, glass transition temperature and liquid and gas permeability vary due to the changed degree of crosslinking. Examples of simply unreactive (or equivalently simply reactive) compounds Ia are

Examples of double unreactive compounds of the formula Ia are

If you put the mesogen diol

corresponding to a compound of formula II, with the compounds

corresponding to compounds of the formulas IIIb or IIIa, a mixture is obtained which contains compounds of the formulas a ₁ , a ₂ , a ₃ and a ₄ shown below. The compounds shown below of the formulas a ₁ and a ₂ correspond to compounds Ia according to the invention with two reactive radicals P ¹ and P ² .

The compounds of the formulas a ₁ and a ₂ are also to be mentioned as component A ₁ ', the compounds of the formulas a ₃ and a ₄ accordingly as components A ₂ ' and A ₃ 'of mixtures obtainable according to the invention.

More details on the implementation of the mesogen diols of formula II with compounds of the formulas IIIb and IIIa have already been described above addressed.

For example, if you put a mixture of the mesogen diols

with the connections

um, a mixture is obtained which contains compounds of the formulas b ₁ to b ₇ shown below.

Here again, the compounds b ₁ , b ₂ and b _{3 are to be seen} both as examples of compounds of the formula Ia according to the invention with two reactive radicals P ¹ and P ² and as constituents of component A ₁ 'of mixtures obtainable according to the invention. The compounds b ₄ and b ₅ or b ₆ and b ₇ are to be addressed analogously as components A ₂ 'or A ₃ ' of such mixtures. It should be noted here that the compounds b ₂ and b ₃ , due to the asymmetrical mesogenic unit, represent different chemical species. In the case of compound b ₁ , two different compounds of the formulas b ₁ 'and b ₁ ''would also be obtained if the symmetry of the mesogenic unit was removed, for example by methyl substitution on the middle benzene ring of the mesogenic unit.

Aspects of symmetry of mesogenic are detailed Groups as well as identity and non-identity from them conducted liquid crystalline compounds in the older German patent application 197 16 822.1 received.

The compounds of components A ₁ ', A ₂ ' and A ₃ 'mentioned in the two examples can of course be regarded as a special selection of compounds of components A ₁ , A ₂ and A _{3 of} the mixtures according to the invention which are linked to one another via the preparation.

If further compounds B are added to the compounds of the formula Ia or mixtures according to the invention containing components A ₁ , optionally A ₂ and / or optionally A ₃ or components A ₁ ', A ₂ ' and A ₃ ', this results compositions according to the invention.

Such additives B can be one or more chiral compounds to serve.

In this way, cholesteric, liquid-crystalline form Phases that above all have interesting optical properties and, for example, depending on the viewing angle of light reflect different wavelength. Such liquid crystal compositions are found especially as cholesteric liquid crystalline colorants use.

Particularly suitable chiral components are those which on the one hand have a great ability to twist and on the other hand easily miscible with the liquid crystalline Ver Bonds are without the liquid crystalline phase structure to disturb.  

Preferred chiral compounds are e.g. B. those of the general formulas Id, Ie, If, Ig

(P ¹ -Y ⁵ ) _n X (Id),

(P ¹ -Y ¹ -A ¹ -Y ⁵ ) _n X (Ie),

(P ¹ -Y ⁵ ) _n X (If),

(P ¹ -Y ¹ -A ¹ -Y ³ -MY ⁴ ) _n X (Ig),

in which the variables P ¹ , Y ¹ , A ¹ , Y ⁵ , M have the meaning given for the formulas Ia and Iaa, n stands for an integer from 1 to 6, X is an n-valent chiral radical and Y ³ and Y ^{4 have} the meaning given for Y ¹ and Y ² .

Residues X are for example:

in which
Is LC ₁ to C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, COOR, OCOR, CONHR or NHCOR and means RC ₁ -C ₄ alkyl.

(Enter the end lines in the formulas listed the free valences).

Are particularly preferred

These and other chiral components are, for example, in the Writings WO 95/16007, DE-A 195 20 660 and DE-A 195 20 704 called.

Liquid crystalline compounds can also be used as further additives B. or mixtures thereof are added, which are in the script ten WO 95/22586, WO 95/24454, WO 95/24455, WO 96/30352 and 97/00600 are listed, or liquid crystalline mixtures those corresponding to that described in the document WO 96/04351 Processes were made.

If the compounds, mixtures or compositions according to the invention are polymerized, which is of course only possible if at least one of the radicals P ¹ or P ^{2 is} reactive, the liquid-crystalline order state can be fixed. The polymerization can, depending on the polymerizable group, for. B. thermally or photo chemically. Other monomers can also be copolymerized together with the liquid-crystalline compounds or mixtures. These monomers, which are also to be addressed as additives B of the compositions according to the invention, either alone or as a mixture with other additives, also include conventional crosslinking agents. Possible monomers include. B .:
vinyl aromatic compounds, such as styrene or styrene derivatives of the general formula

in which S ¹ and S ^{2 represent} hydrogen or C ₁ - to C ₆ -alkyl;
Acrylonitrile, methacrylonitrile, cyanoacrylonitrile;
C ₁ - to C ₄ -alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate and the corresponding esters of methacrylic acid and cyanoacrylic acid ; also the glycidyl esters, glycidyl acrylate and methacrylate.

Crosslinking agents (crosslinking monomers) can be used bi- or polyfunctional compounds with at least 2 ole finical double bonds, for example divinyl esters of Dicarboxylic acids such as succinic acid and adipic acid, diallyl and Divinyl ethers of bifunctional alcohols such as ethylene glycol and butane-1,4-diol, methacrylic acid ester or acrylic acid ester polyfunctional alcohols, especially those that Hydroxyl groups no further functional groups or al if necessary contain ether groups. Examples of such alcohols are e.g. B. bifunctional alcohols, such as ethylene glycol, propylene glycol, and their more highly condensed representatives, e.g. B. like diethylene glycol, Triethylene glycol, dipropylene glycol, tripropylene glycol etc., Butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds, such as ethoxylated or propoxylated Bisphenols, cyclohexanedimethanol, trifunctional and higher functional alcohols, such as glycerin, trimethylolpropane, butane triol, trimethylolethane, pentaerythritol, ditrimethylolpropane, Dipentaerythritol, sorbitol, mannitol and the corresponding alkoxy lated, especially ethoxy and propoxylated alcohols.

Also suitable are polyester (meth) acrylates, which are the (meth) acrylic acid ester is about polyesterols.

As polyesterols such. B. consider such as by Esterification of polycarboxylic acids, preferably dicarboxylic acids, can be produced with polyols, preferably diols. The Starting materials for such hydroxyl-containing polyesters are Known specialist. Succinic acid, Glutaric acid, adipic acid, sebacic acid, o-phthalic acid, their iso mers and hydrogenation products and esterifiable derivatives, such as Anhydrides or dialkyl esters of the acids mentioned are used become. The above-mentioned alcohols are preferred as polyols as ethylene glycol, propylene glycol 1,2 and 1,3, butanediol 1,4, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol and Polyglycols of the ethylene glycol and propylene glycol type in Consideration.

It may also be the case with the crosslinking agents (crosslinking Monomers) e.g. B. are epoxy or urethane (meth) acrylates.  Epoxy (meth) acrylates are e.g. B. such as those by the expert known implementation of epoxidized olefins or poly or di glycidyl ethers, such as bisphenol A diglycidyl ether, with (meth) acrylic acid are available.

Urethane (meth) acrylates are, in particular, the Reaction products of hydroxy also known to those skilled in the art alkyl (meth) acrylates with poly- or diisocyanates.

Other suitable crosslinking agents (crosslinking monomers) are 1,4-divinylbenzene, triallyl cyanurate, acrylic acid esters of tricyclodecenyl alcohol of the formula below

known under the name dihydrodicyclopentadienyl acrylate, as well the allyl esters of acrylic acid, methacrylic acid and cyana crylic acid.

If monomers and / or crosslinking agents (crosslinking mono mer), these must be sent to the Polymerisa in their quantity tion ratios are adjusted that on the one hand a satisfied desired effect is achieved, but on the other hand the liquid-crystalline phase behavior was not impaired too much is done. The amount of monomers that may be used and / or crosslinking agent usually depends on the use the polymers. A pigment can be used to produce pigments large amount of monomers / crosslinking agents, for the production of thermo plastic layers a lower amount of monomers / crosslinking medium advantageous. The amount of monomers / crosslinking agents can usually be determined by a few preliminary tests. Usually, however, one will try to determine the proportion of monomers / ver to keep wetting agents (crosslinking monomers) small or to do without it entirely.

Other additives (B) can be polymeric auxiliaries, such as. B. Ver walking aids, defoamers, deaerators, rheology aids or be an adhesion promoter. Such excipients should be considered preferably either be soluble in the starting mixtures or but in an organi compatible with the original mixtures solvent. Typical representatives of such polymeric auxiliaries fabrics are e.g. B. polyester, cellulose esters, polyurethanes and polyether or polyester modified or unmodified Silicones. If necessary, add to the desired purpose giving amount of polymeric adjuvant, its chemical nature  and possibly the amount and type of solvent are generally familiar to the expert or can be if determined experimentally by a few preliminary tests.

Are the compositions of the invention a photo subjected to chemical polymerization, so you can as another Add additives to photoinitiators. Examples of this are the under the brand names Lucirin®, Irgacure® and Darocure® kommer currently available substances, such as Lucirin® TPO, Irgacure® 184, Irgacure® 369, Irgacure® 907 and Darocure® 1173. Die Initiators are used in usual amounts, what a share of about 0.5 to 5.0 wt .-% in the polymeri corresponding mixture or composition.

The compositions according to the invention can be used as further Additions B also compounds are added, which are not covalently built into the polymer network. You can for example, also commercially available nematic liquid be crystals.

Other additives B can also include pigments, dyes and fillers be fabrics.

In the case of the pigments, these can be inorganic compounds, such as for example iron oxides, titanium oxide and soot. In the organic Connections come into question e.g. B. pigments or dyes the class of monoazo pigments, monoazo dyes and their Metal salts, disazo pigments, condensed disazo pigments, iso indoline derivatives, derivatives of naphthalene or perylene tetra carboxylic acid, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridones, dioxazines, pyrazoloquinazolones, phthalo cyanine pigments or basic dyes such as triarylmethane dyes and their salts.

Other pigments that can be used are effect agents such as aluminum or Mica flakes or pigments such as B. the among Names Iriodin® and Paliocrom® commercially available pearlescent and Effect pigments.

Common fillers such as chalk, talc, plaster, barite can also be used etc. are added.

Are the compositions of the invention as additives B the Crosslinking agents and / or monomers and / or described above one or more of those also described above chiral compounds added, the latter are in one proportion 0.001 to 50, preferably 0.01 to 20, particularly preferably 0.1  up to 10% by weight. The proportion of crosslinking agents and / or Monomers is 5 to 50% by weight, preferably 10 to 20% by weight, the sum of the proportions of the liquid crystalline Ver bonds, the crosslinking agent and / or monomers and the chiral compounds must of course add 100% by weight and the proportions relate to the total amount of so obtained Obtain compositions.

For the claimed objects described below, compounds, mixtures or compositions according to the invention are used in which at least one of the radicals P ¹ or P ^{2 is} a reactive radical in at least one compound of the formula Ia. For the sake of simplicity, these compounds, mixtures or compositions are referred to as "polymerizable (inventive) compounds, mixtures or compositions".

According to the invention, a method for printing on Objects or to create coatings with liquid claims crystalline order on objects that is characterized in that polymerizable, fiction appropriate compounds, mixtures or compositions on the Brings up objects, if necessary an orientation leads and then the Ver applied to the objects polymerized bonds, mixtures or compositions.

Other suitable methods for coating counter stands or of substrates can also z. B. Scripture Take 96/02597.

The liquid crystalline orientation is either spontaneous during application or it is known by physical Methods such as B. squeegee or applying an electrical or magnetic field.

Is about the use of the polymerizable, according to the invention Compounds, mixtures or compositions in the range of Screen printing or flexographic printing, so you can visi Reduce activity by adding diluents. Except the use of rheology aids and the like the additives, there is another possibility, the viscosities the liquid crystalline compounds, mixtures or together to influence settlements, in mixtures of such Ver create bonds that differ in the number of cores of their distinguish mesogenic groups M.  

For example, mixtures of liquid crystalline ver bonds with "trinuclear" and "binuclear" mesogenic Groups M, depending on their mixing ratio, one more or less reduced viscosity compared to the pure "three robust "compound or a mixture of" trinuclear " Compounds (regarding the "nuclei" of the mesogenic groups M explanations have already been given at the beginning). In reverse Consideration of course gives the possibility of viscose activity of, for example, "dinuclear" compounds or their Mixtures by the presence of appropriate amounts three or higher-"core" liquid-crystalline compounds more or increase less. Higher viscosities are around of offset printing and letterpress printing.

Objects that are caused by Printing or coating by means of the aforementioned, The inventive method are available.

The use of the polymerizable, Compounds, mixtures or compositions according to the invention for the production of optical components, such as. B. polar Color filters, especially notch filters, d. H. narrow banded Interference filters, or polarizers for LCD displays, as well as the Use for the production of liquid crystalline colorants, the z. B. in the printing or automotive painting technology applications find.

According to the invention, liquid-crystalline colors are also used means claimed which polymerizable, inventive Contain compounds, mixtures or compositions.

With regard to low solvent and thus u. a. also environmental and More user-friendly formulations are increasingly emulsions and dispersions used. These usually have clear lower viscosities than conventional formulations and are therefore especially with regard to spray painting techniques interesting.

Therefore, aqueous emulsions or dispersions will continue to be used speaks, the polymerizable compounds of the invention, Mixtures or compositions and others, for the Her usually use emulsions or dispersions Contained auxiliaries. The production of dispersions, which u. a. contain liquid crystalline compounds for example in WO 96/02597 and leaves analogously also to the dispersions and Transfer emulsions.  

The aqueous emulsions and dispersions according to the invention can besides the liquid crystalline compounds and given if further additions B, such as those already mentioned chiral compounds, monomers (crosslinking agents), pigments, Dyes, fillers, processing aids or photoinitiators if desired contain additional aids such. B. Sunscreens and preservatives. The content of poly Merizable compounds, mixtures or according to the invention Compositions in the aqueous emulsions according to the invention or dispersions, which can also be used as colors for interior and Exterior paints are generally between 20 and 95% by weight.

The addition of emulsifying and / or is of particular importance Dispersants as further auxiliaries.

As such, water-soluble high molecular weight is preferred organic compounds with polar groups, such as polyvinyl pyrrolidone, copolymers of vinyl propionate or acetate and Vinyl pyrrolidone, partially saponified copolymers from an acrylic esters and acrylonitrile, polyvinyl alcohols with different Residual acetate content, cellulose ether, gelatin or mixtures of these substances used. Particularly preferred emulsifying and / or Dispersant with the function of a protective colloid are polyvinyl alcohol with a residual acetate content of less than 35, in particular 5 to 30 mole percent and / or a vinyl pyrrolidone / vinyl propionate copolymer with a vinyl ester content of below 35, especially 5 to 30 percent by weight.

It can be both non-ionic and, in special cases, too ionic emulsifiers / dispersants can be used. Preferred Dispersants are long-chain alcohols or phenols different degrees of ethoxy and / or propoxylation (adducts of 4 to 50 mol ethylene oxide and / or propylene oxide). Especially before Combinations of the protective colloids mentioned above are advantageous with such emulsifiers / dispersants, because they are very fine Partial emulsions / dispersions are obtained.

Other suitable emulsifiers / dispersants are, for example, dihexylsulfosuccinate, sulfosuccinate half-esters, the sodium salts of dodecylbenzenesulfonic acid and pentadecanesulfonic acid, potassium oleate, sodium lauryl sulfate, alkyl polyglycosides, isooctyl phenol, isononylphenol, C ₁₂ -C ₁₈ fatty alcohol alcohols.

Emulsifying / dispersing aids are also particularly suitable based on polysiloxane.

The emulsifying / dispersing aids described are suitable for Production of oil-in-water emulsions. However, it is also possible , emulsions or dispersions based on To produce water-in-oil emulsions. For such emulsions or Dispersions are particularly suitable for emulsifiers and emulsifiers mixtures such as B. are described in EP-A 0 623 630. Suitable emulsifiers / dispersants are also Sorbitan monostearate, sorbitan monopalmitate, sorbitan tristearate, Sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene sorbitol ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and Polyoxyethylene oleyl ether.

The emulsions according to the invention can also be mini-emulsions. Mini emulsions have the advantage of particularly stable emulsions train and are therefore particularly stable in storage. For the production the mini emulsions are, for example, those previously described Emulsions that typically have droplet diameters in the micro have meter range, with the help of a high-pressure homogenizer homogenized. In this way, droplet emulsions are obtained diameter in the range of a few hundred nm, in which over No phase separation is observed for weeks.

For the preparation of the emulsions or dispersions according to the invention ions, the compounds, mixtures or Compositions, if desired, in a small amount a solvent such as tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, the propanols, the butanols, ethyl acetate, butyl acetate, methylene chloride, the xylenes or toluene or water mixed to reduce the viscosity. Preferably be however the polymerizable compounds according to the invention, Mixtures or compositions directly with the emulsifying / dispersing agent auxiliary, which is also added as an aqueous solution can be moved. The resulting mixture is e.g. B. by Intensely homogenized stirring. Then water is added and again thoroughly homogenized. The amount of water depends on the desired use. Preferably be 20 to 80 wt .-%, particularly preferably 40 to 60 wt .-% water added, based on the total amount of the finished emulsion or Dispersion. The emulsions / dispersions can be used for processing with water, which in turn is an emulsifying / dispersing aid can be added to the desired viscosity and color medium concentration can be diluted.  

To harden the films formed from the emulsion / dispersion such as for thermal processes or radiation mixtures procedures such as light or electron beam curing, possible, each by type of polymerizable groups. Even for the hardenable Dispersion films is the addition of polymerization initiators advantageous, as they are described for the paint mixtures.

The advantage of dispersion coatings is their light weight Processability. The dispersions have low viscosities on, can be manufactured without solvent and require therefore no ventilation devices and can be known by everyone simple application techniques such as brushing, rolling, spraying, Printing, dipping or applied through a casting nip. The dispersion according to the invention also emerges from the dispersion Coating process a spontaneous orientation so that, in the presence of suitable additives, such as. B. chiral ver bindings, a desired one depending on the viewing angle Color impression can arise.

Pigments are furthermore used, which are obtainable by that the polymerizable compounds of the invention, Mixtures or compositions as a thin film on one Polymerizes substrate, detaches the polymer mass from the substrate and crushed to pigment particle size.

The film thicknesses are chosen during production so that the finished pigment particles thicknesses of 0.5 to 50 microns, preferred 1 to 25 µm, particularly preferably 2 to 10 µm. The average diameter of the pigment particles are values that correspond to 3 to 100 times the thickness of the pigment particles, d. H. the ratio of average diameter to the thickness of the pigment Particle corresponds to 3: 1 to 100: 1. A ratio is preferred 4: 1 to 25: 1, particularly preferably from 5: 1 to 15: 1 Film application can z. B. by using a squeegee respectively. Typical gap widths are 7.5 to 400 µm.

Through casting techniques, for example in the manufacture of Magnetic tapes are common, film thicknesses of a few microns to adjust. Depending on which volatile additives in which Amounts present during film production are then Thickness in the finished pigment particle more or less large break share this "wet film thickness".

It is advantageous if the by appropriate procedures Dimension and shape of the one present after the polymerization Specifies products before the polymerization. By a subsequent comminution and classification of the polymer  Losses occurring primarily due to the incidence of fine material can be largely avoided.

Pigments which are thereby particularly preferred are available that polymerizable, according to the invention Compounds, mixtures or compositions by means of pressure process applied to a substrate whereby by the pressure the later pigment shape and pigment dimensions are pre-selected will give said compounds, mixtures or together Subjects to polymerization and the polymers Then detaches products from the substrate. Regarding the pigment dimensions also applies here.

Procedures to produce appropriately trained pigments to deliver, z. B. in the older German applications 196 02 795.0 and 196 02 848.5.

The pigments obtainable according to the invention are not only in conventional but can also be used in water-based paints. Examples of such formulations in which the Invention appropriate pigments can be used as effects the publications WO 95/29961 and WO 95/29962.

Manufacturing examples example 1

49.4 g (0.133 mol) bis-1,4- (p-hydroxybenzoic acid) methylphenylene diester, 22.2 g (0.133 mol) chlorobutyl acrylate, 20.2 g (0.15 mol) potassium carbonate (ground), 0. 2 g of potassium iodide, 0.05% Kerrobit® BHT and 0.01% 4-hydroxytempo (commercially available from Hüls) were stirred in 250 ml of DMF for 5 hours at 80 ° C. under nitrogen. The mixture was cooled to room temperature. Then 38.3 ml (0.255 mol) of N, N-dimethylcyclohexylamine and 38.5 g (0.186 mol) of acrylic butyl chloroformate were added dropwise. Finally, the reaction mixture was stirred at 40 ° C. for a further 3 h. After 500 ml of ethyl acetate had been added, inorganic residues were filtered off with suction and the organic phase was extracted with dilute hydrochloric acid and then with water. The organic phase was dried with sodium sulfate, filtered and concentrated. 83 g of product were obtained, corresponding to a yield of 94.5%.

in a molar ratio of about 1: 1: 1: 1.

The phase behavior of the mixture is n 117-125 i, i.e. H. the mixture is nematic-liquid up to 117 ° C crystalline (n) and goes into an isotropic phase (i) in the range from 117 to 125 ° C (two-phase area) about. From 125 ° C only the isotropic phase remains.  

Example 2

The procedure was analogous to Example 1. Instead of the chlorobutyl acrylate, the corresponding number of moles of bromhexane was used. The resulting mixture contains the compounds

in a molar ratio of about 1: 1: 1: 1.

The phase behavior of the mixture is n 131-138 i.  

Example 3

The procedure was analogous to Example 1. The corresponding number of moles of butyl chloroformate was used instead of the acrylic butyl chloroformate. The resulting mixture contains the compounds

in a molar ratio of about 1: 1: 1: 1.

The phase behavior is n 131-141 i.

Claims (15)

1. Liquid crystalline compounds of the formula Ia
in which the variables have the following meaning
P ¹ , P ² each independently of one another are hydrogen, C ₁ -C ₄ alkyl or reactive radicals, via which a polymerization can be brought about,
Y ¹ , Y ² each independently of one another a chemical bond, oxygen, sulfur, -O-CO-, -CO-O-, -O-CO-O-, -CO-NR-, -NR-CO-, - O-CO-NR-, -NR-CO-O- or -NR-CO-NR-,
R is hydrogen or C ₁ -C ₄ alkyl,
A ¹ , A ² spacers with one to 30 C atoms, in which the carbon chain can be interrupted by oxygen in ether function, sulfur in thioether function or by non-adjacent imino or C ₁ -C ₄ alkylimino groups, and
M a mesogenic group. 2. Mixtures containing
(A ₁ ) one or more liquid-crystalline compounds of the formula Ia according to Claim 1,
(A ₂ ) optionally one or more liquid-crystalline compounds of the formula Ib
P ¹ -Y ¹ -A ¹ -OMOA ² -Y ² -P ² (Ib)
and or
(A ₃ ) optionally one or more liquid-crystalline compounds of the formula Ic
where the variables P ¹ , P ² , Y ¹ , Y ² , A ¹ , A ² and M in the formulas Ib and Ic each have the same general meaning as formula Ia and in the specific individual case the selection of these variables for the compounds Ia, Ib and Ic doesn't have to be the same. 3. Mixtures containing
(A ₁ ') one or more liquid-crystalline compounds of the formula Ia according to Claim 1,
(A ₂ ') one or more liquid-crystalline compounds of the formula Ib'
P ¹ -Y ¹ -A ¹ -OMOA ¹ -Y ¹ -P ¹ (Ib ')
and
(A ₃ ') one or more liquid-crystalline compounds of the formula Ic'
obtainable by one or more compounds of the formula II
HO-M-OH (II)
with one or more compounds of the formulas IIIa and IIIb
implements, wherein the variables P ¹ , P ² , Y ¹ , Y ² , A ¹ , A ² and M have the meaning given in claim 1 and Y ^{3 is} an outgoing group. 4. Compositions containing

• (A) compounds or mixtures according to claims 1, 2 or 3 and
• (B) other additives.

5. Compounds, mixtures or compositions according to claims 1 to 4, in which M is a mesogenic group of the formula Iaa
(-TY ⁵ ) _r -T- (Iaa)
means, where the variables have the following meaning:
T divalent saturated or unsaturated iso- or heterocyclic radicals,
Y ⁵ groups of the definition of Y ¹ and Y ² or -O-CH ₂ -, -CH ₂ -O-, -CH = N-, -N = CH- or -N = N- and
r 0, 1, 2 or 3,
where in the case of r <0 both the radicals T and the groups Y ⁵ can each be the same or different from one another. 6. Compounds, mixtures or compositions according to claims 1 to 4, in which M is a mesogenic group of the following formulas
means, each ring Z can carry up to three identical or different substituents from the following group:
Hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkoxy carbonyl, C ₁ -C ₂₀ monoalkylaminocarbonyl, C ₁ -C ₂₀ alkylcarbonyl, C ₁ -C ₂₀ alkylcarbonyloxy , C ₁ -C ₂₀ alkylcarbonylamino, formyl, carboxyl, halogen, cyan, hydroxy and nitro. 7. Compounds, mixtures or compositions according to claims 1 to 6, in which in at least one compound of the formula Ia at least one of the radicals P ¹ or P ^{2 is} a reactive radical. 8. Process for printing objects or for producing Coatings with a liquid crystalline order on objects, characterized in that Ver Bonds, mixtures or compositions according to claim 7 applies an orien to the objects brought about and then onto the objects brought compounds, mixtures or compositions polymerized. 9. Printed or coated items, available after A method according to claim 8. 10. Use of compounds, mixtures or together settlements according to claim 7 for the production of optical Components. 11. Use of compounds, mixtures or together settlements according to claim 7 for the production liquid crystalline colorant. 12. Liquid-crystalline colorants containing compounds Mixtures or compositions according to claim 7. 13. Aqueous emulsions or dispersions containing Ver Bonds, mixtures or compositions according to claim 7 as well as others, for the production of emulsions or Dispersions commonly used auxiliaries. 14. Pigments, obtainable by making compounds Mixtures or compositions according to claim 7 as thin Film on a substrate subject to polymerization polymer mass detaches from the substrate and on pigment particles size crushed.   15. Pigments obtainable by liquid crystalline Compounds, mixtures or compositions according to Claim 7 applied to a substrate by means of printing processes, whereby the later pigment form and Pigment size is specified, said compounds, Mixtures or compositions of the polymerization under throws and then detaches the polymeric products from the substrate.