HK1011042B - Photo-curable liquid crystals - Google Patents

Description

The present invention relates to photorelatable liquid crystals, liquid crystalline mixtures containing such compounds, and their use in the lattice state for optical components.

The resulting orientation is maintained even at high temperatures, even when the orientation layer consists of photo-oriented polymer network layers (PPNLO) which induce high-resolution orientation patterns on liquid crystal layers by selective irradiation with polarized UV light. Solotovoltaic layers allow the optical composite to be inscribed into a high-voltage or low-density polymer orientation structure. Such optical components are used in optical systems (such as optical filters) and optical filters (such as liquid crystals) and are used in optical systems (such as optical filters) and optical filters.

Err1:Expecting ',' delimiter: line 1 column 62 (char 61)

Other properties, such as double refraction, refractive indices, transparency, etc., need to meet different requirements depending on the application area.

In addition to the general interest in photorelatable liquid crystals for optical components, such liquid crystalline materials are suitable as a cladding of glass fibres for optical data transmission, as is known, for example, from EP-A 0 501 563.

The photoresist liquid crystals shall have good chemical and thermal stability, good solubility in common solvents and good stability to electric fields and electromagnetic radiation, and an appropriate mesophase of approximately 25°C to approximately 80°C, preferably between approximately 25°C and approximately 100°C, such as a broad smectic or nematic mesophase or a chiral smectic and cholesteric mesophase for the above applications.

Since liquid crystals are generally used as mixtures of several components, it is important that the components are well mixed with each other.

The present invention now provides compounds which are excellent as individual components or as components of liquid crystal mixtures for such optical components. "Technology" according to the General Technology Note for the "development" or "production" of equipment specified in 1C002.a.

The mesogenic residue A means In which R1 means acrylate, methacrylate, 2-chlor acrylate, 2-phenylacrylate, vinyloxy or epoxy;Z33- ((CH2) m'-, -(CH2) m'O-, -(CH2) m'COO- or -(CH2) m'OOC- means;m'is an integer from 4 to 12;Ring C1 means 1,4-phenylene, or trans-1,4-cyclohexylene, where applicable, substituted with halogens; andZ1-CH2CH2, -CH2O-, -COO-, -OOC-, -CH2- or -CH4-

The compounds of the general formula I are characterized by their relatively low viscosity, which makes them easy to apply to a suitable surface, usually by spin coating.

The most preferred are the mesogenic residues, where rings C and D independently represent unsubstituted or fluorine-substituted 1,4-phenylenes, pyridine-2,5-diyl, pyrimidine-2,5-diyl or trans-1,4-cyclohexyls; Z1 represents -CH2O, -COO or -OOC; and Z2 represents a single bond, -CH2CH2, -CH2O, -OCH2, -COO or -OOC.

Err1:Expecting ',' delimiter: line 1 column 56 (char 55)

Err1:Expecting ',' delimiter: line 1 column 43 (char 42)

R-residue preferred are acrylate, methacrylate, 2-chloracrylate, 2-phenylacrylate, acryloylphenylenes, acrylamide, methacrylamide, 2-phenylacrylamide, vinyl ethers, vinyl esters, styrene derivatives, maleic acid derivatives, fumaric acid derivatives and the like, which can be photochemically cross-linked with formula I compounds after coating the appropriate carrier.

The R-residue is particularly preferred for acrylate, methacrylate, acryloxy, methacryloxy, vinyloxy and epoxy.

Preferably, X in compounds of formula I means a -COO, -CONH or -CH2O group. These groups are readily available from the corresponding aldehyde and can then be readily translated with a suitable derivative of the Q group, preferably -(CH2)p-, where p is an integer between 2 and 12, or 1,4-phenylene.

The mesophase type of the compounds of the invention can be affected by variation of the rings in the mesogenic side chains A. Thus, heterocyclic rings tend to produce smectic phases, while cyclohexyl rings promote nematic tendencies.

In particular, compounds of formula I are preferred. where m' is an integer from 4 to 12 and p is an integer from 2 to 12.

The compounds of the invention are extremely easy to access and can be manufactured in a familiar way as shown in Figures 1-6.

In diagrams 1 to 6, m means an integer from 1 to 16 and p means an integer from 2 to 12.

Err1:Expecting ',' delimiter: line 1 column 102 (char 101)

The compounds of formulae I can be used as pure compounds, or in the form of mixtures with each other and/or with other liquid crystal components.

The liquid crystal mixtures of the invention contain at least 2 components, at least one of which is a compound of formula I. A second and, where appropriate, additional component may be further compounds of formula I or other known liquid crystal compounds with or without photoreceptable groups. The mixture may also contain one or more chiral components.

Due to the good solubility of the compounds of formula I and their good miscibility with each other, the proportion of various compounds of formula I in the mixtures of the invention may be high and may be up to 100% by weight.

Preferably, the mixtures of the invention contain, in addition to one or more compounds of formula I, one or more compounds from the group of compounds of the general formulae where R1 and R2 are alkyl or alkenyl with 2 to 12 carbon atoms, independently of each other; X is hydrogen, niederalkyl, fluorine, bromine, chlorine or cyano; and m is an integer from 1 to 16.

The invention is further illustrated by the following examples: C is a crystalline phase, N is a nematic phase, S is a smectic phase and I is an isotropic phase.

Example 1

The reaction mixture was heated overnight at 80°C, poured on 100 ml of water and then extracted three times with 50 ml of ethyl acetate each. The combined organic phases were washed twice with 100 ml of water, rubbed with a magnesium magnet, filtered and then sealed. Chromatic cleaning of the residue with hexazoxyethyl ether (N/E) (N/E) (C.I.N.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.C.I.I.C.I.C.I.I.C.I.C.I.I.C.I.I.C.I.I.C.I.I.I.C.I.I.I.C.I.I.C.I.I.C.I.I.I.C.I.I.I.C.I.I.I.I.C.I.I.I.C.I.I.I.C.I.I.I.I.I.C.I.I.I.I.I.C.I.I.I.I.I.I.C.I.I.I.I.I.I.C.I.I.I.I.I.I.I.I.C.I.I.I.I.I.I.I.I.I.I.C.I.I.I.I.I.I.I.I.I.I.I.C.I.I.I.I.I.I.I.I.I.I.I.I.I.I.I

The 2,5-bis ((4-[6-Acryloyloxyhexyloxy) ]phenylcarbonyloxy) benzoic acid used as starting material was obtained as follows: (a) A solution of 8.3 g of 2,5-dihydroxybenzaldehyde, 35.1 g of 4-[6-acryloyloxyhexyloxy]benzoic acid and 0.1 g of 4-dimethylamino) pyridine (DMAP) was agitated at 0°C for 15 minutes to 600 ml of dichloromethane, 29.7 g N,N'-dihydroxyhexylcarbodiimide (DCC). The reaction mixture was stirred overnight at room temperature, then filtered and then administered. Chromatographic cleaning of the back of the pebble with hexane/ethylmethacrylate (vol. 1:1) and double organic oxidation of the thinly coated copolymer resulted in a heating of the back of the pebble with 7,8 g of ethylmethacrylate (vol. 2,8-dihydroxyhexylmethacrylate) for up to 100 ml of Pebble. 2,5-dihydroxyhexylmethacrylate (vol. 2,5-dihydroxyloxy) at room temperature, and then agitated at 50 °C. The two components were combined at 122°C. The two phases were obtained by heating the back of the pebrile with ethylmethacrylate (vol. 2,5-dihydroxy) and 2,5-dihydroxyloxymethacrylate (vol. 2,5-dihydroxy) at room temperature.

The following compounds can be produced by analogy: The following is a list of the most commonly used chemical compounds: bisphenol-alpha-methyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl

Example 2

(a) A solution of 4.0 g hydroquinone, 35.1 g 2.5-bis ((4-[6-Acryloyloxyhexyloxy) ]phenylcarbonyloxy) benzoic acid and 0.1 g 4- ((Dimethylamino) pyridine is added to 600 ml of dichloromethane by stirring at 0 °C for 15 minutes to 29.7 g N,N 'dicyclohexy-carbodiimide. The reaction mixture is stirred overnight at room temperature, then filtered and then iced. Chromatographic cleaning of the residue of gel with hexane/ethylloxy acetate (vol. 1:1) and double recycling of the rectangular crystallisation of the thin layer of dichloromethane from fractions of ethyl alcohols yields 7,8 g (1,4-bis (2,2-[4-acryloxyloxy) ether) to 1,4-[5-phenylloxyloxy) ether).

The following compounds can be produced by analogy: 1,4-Phenylphenyl bis[2,5-bis ((4-[7-acryloxyheptyloxy) ]phenylbenzoic acid[1,4-Phenylphenyl bis[2,5-bis[4,4-[4,5-[4,5-[4,5-[4,5-[4,5-[4,5-[4,5-],5-[4,5-],6-[4,5-],6-[4,5-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],6-[4,6-],7-[4,6-],7-[4,6-],7-[4,7-],7-[4,7-],8-[4,7-],8-[4,7-],8-[4,7-],8-[4,7-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],8-[4,8-],-9,8-[9,8-],-9,8-[9,8-],-9,8-[9,8-,[9] and also known as the other names of these names include: [the names of these names],[the names of these names],[the names of these names],[the names of these names], and the names of these names, the names of these names, the names, the names of these names, the names, the names of these names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names, names

Example 3

The reaction mixture is stirred overnight at room temperature, poured on 100 ml of water, and then extracted three times with 50 ml of ethyl acetate each. The combined organic phases are washed twice with 100 ml of water, dried over magnesium sulphate, filtered and finally solidified. Chatographic reaction of the residue of glycerol with hexyxyxyxyxyxyxyxyxyxyxyxyxyxy (ethyl acetate) and two-chromatographic reactions yields 0.2-[1,2-,2-]-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy.

The 2,5-bis ((4-[6-Acryloyloxyhexyloxy) ]phenylcarbonyloxy) benzyl alcohol used as starting material is obtained as follows:

(a) A mixture of 32 g sodium borohydride and 180 ml ethanol is added at 0 °C with 165 ml water, stirred for 10 minutes, then dripped at 0-5 °C with a solution of 50 g 2.5-bis ((4-[6-acryloxyhexyloxy]phenylcarbonyloxy) benzaldehyde in 100 ml ethanol and 10 ml chloromethane. The reaction mixture is stirred for another 30 minutes at 0 °C, then poured on 100 ml dichloromethane and extracted twice with 50 ml dichloromethane. The combined organic phases are then washed twice with 100 ml of water, dried over magnesia sulphate, filtered and the filtrate is added. The residue is then tertily-butyl-therystriated. This gives 35 g g (2,4 to 2,5-acryloxyloxyloxyloxy) ethanol.

The following compounds can be produced by analogy: 1,5-Pentylenesyl bis[2,5-bis ((4-[6-acryloxycryxy) bis]phenylbis[2,5-bis[2,5-bis[2,4-bis]phenylbis[2,5-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,4-bis]phenylbis[2,5-bis]phenylbis[2,5-bis]phenylbis[2,5-bis]phenylbis[2,5-bis]phenylbis[2,5-bis]phenylbis[2,5-bis]phenylbis[2,5-bis,[5-bis]phenyl[2,5-bis]bis[5-bis,[6-bis] bisphenyloxy[2,5-bis] bispheny[2,5-bisyl[2,5-bis], bispheny[6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl], bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl], bisyl[6,6-bisyl[6,6-bisyl[6,6-bisyl[6,6-bis], bisyl[6,6-bisyl[6,6-bisyl[6,6-bis], bisyl[6,6-bisyl[6,6-bisyl[6,6-bis], bisyl[6,6-bisyl[6,6-bis,[6-bis], bisyl[6,6-bis,[6-bisyl[6,6-bis,[6-bis], bisyl[6,6-bis,[6-bis,[6-bis], bis2,6-bisyl[6-bis,[6-bis,[6-bis,[6-bis], bis2,6-

Example 4

The reaction mixture is stirred overnight at room temperature, poured on 100 ml of water and then extracted three times with 50 ml of ethyl acetate each. The combined organic phases are washed twice with 100 ml of water each, dried by magnetic magnetic sulphate, tri-filtrated and then pressed together. Chromatic cleaning of the back of the gel with hexane/ethyl acetate (vol. volume) and two other crystals results in a fine-grained solution of 1,4-acetyl acetate (F-acetyl acetate) obtained from 2,4-acetyl acetate.

The 2,5-bis ((4-[6-Acryloyloxyhexyloxy) ]phenylcarbonyloxy) benzoic acid chloride used as starting material is obtained as follows:

(a) 1,5 g of 2,5-bis ((4-[6-Acryloyloxyhexyloxy) ]phenylcarbonyloxy) benzoic acid is heated at 80 °C for 2 hours in 100 ml of toluene with 25 ml of thionyl chloride. The resulting solution is immersed in a reducing pressure vessel, the residue is added to 20 ml of absolute toluene and the solution is again immersed in a reducing pressure vessel. The residue is introduced into the next step without further purification.

The following compounds can be produced by analogy: 1,5-Pentylenes bis[2,5-bis ((4-[6-acryloxyloxy) benzamines] 1,6-Pentylenes bis[2,5-bis[4-[6-acryloxyloxy) benzamines].1,6-Pentylenes bis[2,5-bis[4-[6-acryloxyloxyloxy] benzamines.1,7-Pentylenes bis[2,5-bis][4-[6-acryloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxylo

Example 5

(a) A solution of 4,0 g 1,5-bis ((hydrochinoyl) pentane, 35,1 g 4-[6-Acryloyloxyhexyloxy]benzoic acid and 0,1 g 4- ((Dimethylamino) pyridine is added to 600 ml of dichloromethane by stirring at 0 °C for 15 minutes to 29,7 g N,N'-Dicyclohexycarbodiimide. The reaction mixture is stirred overnight at room temperature, then filtered and then compressed. Chromatographic cleaning of the silica gel residue with hexane/ethyl acetate (vol. 1:1) and bi-dimensional reclassification of the thin-layer chromatographic reactions results in 7,8 g (1,5-bis[4-[acryloxyloxyloxyphen]phenyl) ethyl alcohol.

The following compounds can be produced by analogy: The following entry is inserted after the last column of row No. 1 of Annex I to Regulation (EC) No 1907/2006 of the European Parliament and of the Council: 'Act No. 1 of the Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 16 December 2006 on the approximation of the laws of the Member States relating to the making available on the market of certain types of motor vehicles and their trailers (OJ L 176, 20.12.2006, p.

Example 6

After 10 minutes, the reaction mixture is compressed. Chromatographic cleaning of the silica gel residue with hexane/ethylacetate (vol.2:1) and double recrystallization of the grass layer chromatography of pure acetone fractions yields 0.3 g of 1,5-bis[2,5-bis[6-acryloxyhexyloxyloxy]phenyldihydroxybenzyl]pentamine.

The following compounds can be produced by analogy: The following substances are to be classified in the same heading as the active substance:

Example 7

1,6-hexylene to [2,5-bis(4-[6-acryloyloxyhexyloxy) ]phenylcarbonyloxy (benzoic acid ester] was submitted, mixed with 1 wt.% of a photoinitiator (IRGACURE, Ciba Geigy) and 1 wt.% of BHT, dissolved in anisol (2 wt.%) and then thrown at 3500 revolutions per minute onto a PVA-coated (PVA = polyvinyl alcohol) and rubbed glass plate. The layer was dried at 90°C on a heat bank, then exposed to Xenon light (e.g. 3 minutes) in a vacuum tank at 90°C. A parallel oriented nematic layer with a thickness of 200μm and a Doppler refraction of 0.15 μn (Δn) was produced by this layer.

Example 8

1,6-hexylene to[2,5-bis(4-[6-acryloyloxyhexyloxy) ]phenylcarbonyloxy (benzoic acid ester] was submitted, 1 g/g IRGACURE and 1 g/g BHT were added, anisol was dissolved (2 g/g) and then a glass plate was thrown on at 3500 revolutions per minute. The glass plate was previously coated with methaloyloxyethyl-3-ΔE) [4-cyano-4'-biphenyl]acrylate and then retracted with linear polarized light. A given structure was photolithographically inscribed into the original (PPN) layer by means of a mask. The new layer (on the PPN) was inscribed at 90°C on a dry layer, then exposed to a vacuum at 90°C. This structure was preserved as a transparent layer and was inscribed in a vacuum-clear X-ray.

Claims (6)

1. Compounds of the general formula wherein

   X   signifies a single bond, -COO-, -CH₂O-, -CONH- or -C=N-;

   Q   represents n-alkylene, c-alkylene, 1,4-phenylene, 4,4'-biphenylene or 2,6-naphthylene; and

   A   represents a residue of the formula

   wherein

   R¹   signifies acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, vinyloxy or epoxy;

   Z³³   signifies -(CH₂)_m'-, -(CH₂)_m'O-, -(CH₂)_m'COO- or -(CH₂)_m'OOC-;

   m'   is a whole number of 4 to 12;

   ring C   signifies 1,4-phenylene, which is optionally substituted with halogen, or trans-1,4-cyclohexylene; and

   Z¹   signifies -CH₂CH₂-, -CH₂O-, -COO-, -OOC-, -(CH₂)₄- or -(CH)₃O-.
2. Compounds according to claim 1, of the formulae    wherein m' signifies a whole number of 4 to 12 and p signifies a whole number of 2 to 12.
3. Cross-linkable, liquid crystalline mixtures consisting of at least 2 components, of which at least one component is a compound of formula I defined in claim 1.
4. Cross-linkable, liquid crystalline mixtures according to claim 3, characterized in that they contain, in addition to one or more compounds of formula I, one or more compounds from the group of the formulae    wherein R¹ and R² each independently represent alkyl or alkenyl with 2 to 12 carbon atoms; X represents hydrogen, lower alkyl, fluorine, bromine, chlorine or cyano; and m signifies a whole number of 1 to 16.
5. The use of compounds according to any one of claims 1 to 2 in their cross-linked state for optical building elements.
6. The use of cross-linkable liquid crystalline mixtures according to claim 3 or 4 in their cross-linked state for optical building elements.