DE102009039801A1 - Polymerizable chiral compounds - Google Patents

Abstract

[Object] to provide polymerizable chiral compounds with strong HTP and low melting point. [Means for Solving the Problem] To provide polymerizable chiral compounds of the general formula (I). [Compound 1] $ F1 The compounds of the present invention have a strong HTP and a low melting point, and because of this low melting point, are excellent in solubility in the other liquid crystal compounds, so that they are useful as structural members for liquid crystal components. Further, the content of the structural parts and the polymerizable liquid crystal components on the polymerizable chiral compounds according to the present invention can be increased very much so that optically anisotropic materials having excellent optical properties can be produced. The optically anisotropic materials according to the present invention are useful for use in deflector plates, phase contrast plates and the like.

Description

[Technical Application]

The The present invention relates to polymerizable chiral compounds, and these polymerizable chiral compounds containing polymerizable liquid crystal components and further for curing these polymerizable liquid crystal components serving optically anisotropic materials.

[Technical background]

In recent years is in the context of the development of the information society the meaning of in for liquid crystal displays indispensable deflector plates, phase contrast plates and the like used, optically anisotropic materials. The required optical properties of the optically anisotropic Materials vary depending on the purpose, making connections with properties suitable for the respective purposes required are. Further, not only the optical properties, but also the rate of polymerization of the compounds, solubility, Melting point, the glass transition point, the transparency the polymers, the mechanical strength of the polymers and the like are other important factors.

In In recent years, the polymerizable cholesterol Liquid crystals using functional elements for Separation of circularly polarized light used to in the form of films to increase the light intensity. Cholesteric liquid crystals can normally by adding nematic liquid crystals forming, optically active compounds (called chiral compounds below) become. To as optical compensation films for liquid crystal devices functional elements for the separation of circularly polarized Light from the ultraviolet range to the visible Obtaining light is a spiral structure with extreme short periodicity (p) required. The molecular periodicity p of the spur gears is reversed according to the formula (a) proportional to the concentration c of the chiral compounds in the liquid crystal components. The proportion constant of the chiral compounds is the chiral Induction (Helical Twisting Power = HTP). A short periodicity can be achieved by either the concentration of the chiral Compounds increased or the chiral induction increased becomes.

[Formula 1]

• P = 1 HTP · 1 C  (A)

Indeed this is associated with the disadvantage that by admixing large quantities of chiral compounds the liquid crystallinity, Solubility, transparency of the polymers and the like optical Properties deteriorate while at the same time the Costly chiral connections increase costs. In this context, the use of chiral compounds with strong chiral induction (HTP) for the liquid crystal components desirable. As compounds with a corresponding strong HTP chiral compounds have been proposed, whose optically active portions have a cyclic structure (see Patent Documents 1 and 2). In these documents are based on optically active Compounds such as 1,4: 3,6-dianhydro-D-mannitol (isomannide), dianhydro-D-glucitol (Isosorbitol) and the like polymerizable chiral compounds shown with strong HTP. However, these have optically active Compounds have the disadvantage that all have a high melting point, a poor solubility and in part only a low compatibility having the liquid crystal compounds (Patent Document 1). Further, while the solubility with compounds could be improved to some extent, for the purpose of improvement the solubility of an asymmetric structure, their manufacture was complicated and had these compounds the disadvantage that the relevant optically anisotropic materials were very expensive (Patent Document 2).

[Prior art documents]

[Patent Documents]

• [Patent Document 1] JP 09-506088 W
• [Patent Document 2] JP 2003-137887 A

Summary of the Invention

[To be solved by the invention Tasks]

The The present invention has the object of polymerizable chiral To offer compounds with strong HTP and low melting point.

[Means to solve the problem]

The Inventors of the present application have based on the results of investigations of the most diverse substitution groups for the polymerizable chiral compounds are the present invention elaborated, wherein the polymerizable compounds more specific Structure can provide the solution of the above task.

(in der Formel sind R¹ und R² voneinander unabhängige polymerisierbare Gruppen, S¹ und S² sind voneinander unabhängige Spacer-Gruppen, Y¹ und Y² repräsentieren voneinander unabhängige CH₂CH₂COO-, -OCOCH₂CH₂-, -OCOOS³O-, -OS³OCOO-, -CH=CH-COO- und -OCO-CH=CH-, S³ ist eine Alkylgruppe mit 2 bis 6 Kohlenstoffatomen sowie Alkoxygruppen, A¹ und A⁴ sind voneinander unabhängige 1,4-Phenylengruppen und Naphthalen-2,6-diylgruppen, A² und A³ sind voneinander unabhängige 1,4-Cyclohexylengruppen, 1,4-Phenylengruppen, Pyridin-2,5-diylgruppen, Pyrimidin-2,5-diylgruppen, Naphthalen-2,6-diylgruppen, Tetrahydronaphthalen-2,6-diylgruppen, 1,3-Dioxan-2,5-diylgruppen, aber A¹, A², A³ und A⁴ können auch durch voneinander unabhängige Alkylgruppen, halogenierte Alkylgruppen, Alkoxygruppen, Halogene, Cyanogruppen oder Nitrogruppen substituiert werden, während B¹ und B² voneinander unabhängige -O-, -S-, -OCH₂-, -CH₂O-, -CO-, -COO-, -OCO-, -OCOO-, CO-NR¹¹-, -NR¹¹-CO-, -SCH₂-, -CH₂S-, -CH=CH-COO-, -OCO-CH=CH-, -CH₂CH₂-COO-, -OOC-CH₂CH₂-, -NR¹¹-CO-, -CO-NR¹¹-, -CO-CH=CH-, -CH₂-, -C₂H₄-, -CF₂-, -CF₂O-, -OCF₂-, -CF₂CH₂-, -CH₂CF₂-, -CF₂CF₂-, -CH=N-, -N=OH-, -N=N-, -CH=CH-, -CF=CH-, -CH=CF-, CF=CF-, -C≡C-, oder einfache kovalente Bindungen darstellen, X¹ repräsentiert -CO-, -CH=CH-CO-, -CH₂CH₂-CO-, -CH₂-, -C₂H₄-, -CF₂-, -NR¹¹-CO- oder einfache kovalente Bindungen, X² repräsentiert -OC-, -OC-CH=CH-, -OC-CH₂CH₂-, -CH₂-, -C₂H₄-, -CF₂-, -CO-NR¹¹- oder einfache kovalente Bindungen (hinsichtlich B¹, B², X¹ und X² repräsentiert R¹¹ voneinander unabhängige Wasserstoffatome oder Alkylgruppen mit 1 bis 4 Kohlenstoffatomen), m und n repräsentieren 0, 1 oder 2) stellt polymerisierbare chirale Verbindungen zur Verfügung, wobei die betreffenden Verbindungen für Strukturteile von Flüssigkristallbestandteilen, sowie ferner optisch anisotrope Materialien aus der besagten Flüssigkristallbestandteile angeboten werden.The present invention of the general formula (I) [Compound 1]

(in the formula, R ¹ and R ² are mutually independent polymerizable groups, S ¹ and S ² are independent spacer groups, Y ¹ and Y ² represent mutually independent CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ - OCOOS ³ O-, -OS ³ OCOO-, -CH = CH-COO- and -OCO-CH = CH-, S ³ is an alkyl group having 2 to 6 carbon atoms and alkoxy groups, A ¹ and A ⁴ are independent 1, 4-phenylene groups and naphthalene-2,6-diyl groups, A ² and A ³ are independent 1,4-cyclohexylene groups, 1,4-phenylene groups, pyridine-2,5-diyl groups, pyrimidine-2,5-diyl groups, naphthalene groups. 2,6-diyl groups, tetrahydronaphthalene-2,6-diyl groups, 1,3-dioxane-2,5-diyl groups, but A ¹ , A ² , A ³ and A ⁴ may also be substituted by independent alkyl groups, halogenated alkyl groups, alkoxy groups, Halogens, cyano groups or nitro groups, while B ¹ and B ² are mutually independent -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -OCO- , CO-NR ¹¹ -, NR ¹¹ -CO-, -SCH ₂ -, -CH ₂ S-, -CH = CH-COO-, -OCO-CH = CH-, -CH ₂ CH ₂ -COO-, -OOC-CH ₂ CH ₂ -, - NR ¹¹ -CO-, -CO-NR ¹¹ -, -CO-CH = CH-, -CH ₂ -, -C ₂ H ₄ -, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, - CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH = N-, -N = OH-, -N = N-, -CH = CH-, -CF = CH-, -CH = CF-, CF = CF-, -C≡C-, or represent simple covalent bonds, X ¹ represents -CO-, -CH = CH-CO-, -CH ₂ CH ₂ -CO-, -CH ₂ -, -C ₂ H ₄ -, -CF ₂ -, -NR ¹¹ -CO- or simple covalent bonds, X ² represents -OC-, -OC-CH = CH-, -OC-CH ₂ CH ₂ -, - CH ₂ -, -C ₂ H ₄ -, -CF ₂ -, -CO-NR ¹¹ - or simple covalent bonds (with respect to B ¹ , B ² , X ¹ and X ² R ¹¹ represents independent hydrogen atoms or alkyl groups with 1 to 4 carbon atoms), m and n represent 0, 1 or 2) provides polymerizable chiral compounds, wherein the compounds in question for structural parts of liquid crystal components, as well as further optically anisotropic materials of the said Flüssigk crystal components are offered.

[Effects of the Invention]

The polymerizable chiral compounds of the present invention have a strong HTP and a low melting point and reason This low melting point, they are characterized by a excellent solubility in the other liquid crystal compounds out, making them as structural parts for polymerizable Liquid crystal components are useful. These Compounds also have the advantage that their production is simple is and they can be produced inexpensively. The salary the structural parts and the polymerizable liquid crystal components on the polymerizable chiral compounds according to the present invention can be very high, so that optically anisotropic Materials produced with excellent optical properties can be. The optically anisotropic materials after of the present invention are for use in deflector plates, Phase contrast plates, selective reflector plates and the like useful.

Embodiment of the Invention

In the general formula (I), R ¹ and R ² represent polymerizable groups independent of each other, which polymerizable groups may have, for example, the structures listed below. [Compound 2]

These polymerizable groups can be obtained by free-radical polymerization, free radical addition polymerization, cationic polymerization and anionic polymerization are cured. Especially at Carrying out a UV polymerization as a polymerization process are formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), Formula (R-11), Formula (R-13), and Formula (R-15), respectively desirable, and below, in turn, formula (R-1), formula (R-2), Formula (R-7), Formula (R-11), and Formula (R-13), respectively particularly preferred.

S ¹ and S ² are independent spacer groups or simple covalent bonds, which are preferably used for these spacer groups alkylene groups having 2 to 6 carbon atoms and thus the said alkylene groups are not directly connected via the oxygen atoms, so that the carbon atoms through the oxygen atoms may be substituted, and in view of the liquid crystallinity and compatibility with the other liquid crystal compounds, alkylene groups having 2 to 4 carbon atoms are desirable.

Y ¹ and Y ² preferably represent independently -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -OCOOS ³ O-, -OS ³ OCOO-, -CH = CH-COO-, -OCO-CH = CH -, S ³ further preferably represents alkyl groups having 2 to 6 carbon atoms and alkoxy groups, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH = CH-COO-, -OCO-CH = CH-. To increase HTP and from the standpoint of using unsaturated compounds, -CH = CH-COO-, -OCO-CH = CH- are particularly desirable.

A ¹ to A ⁴ are 2-valent groups having a cyclic structure, with A ¹ and A ⁴ being preferably 1,4-phenylene group and naphthalene-2,6-diyl group, while A ² and A ^{3 are} 1,4-cyclohexylene groups , 1,4-phenylene groups, naphthalene-2,6-diyl groups or tetrahydronaphthalene-2,6-diyl groups are preferred. R ¹ and R ² are preferably -O-, -S-, OCH ₂ -, -CH ₂ O-, - COO, -OCO, -C ₂ H ₄ COO or -COOC ₂ H ₄ -, -OC ₂ H ₄ O-, or -OC ₃ H ₆ -, -C ₃ H ₆ O-, wherein from the standpoint of cost-effective preparation and alignment of liquid crystals -COO-, -OCO-, or -OCH ₂ -, -CH ₂ O- are particularly preferred.

X ¹ represents a covalently bonded group, preferably -CO-, -CH = CH-CO-, -CH ₂ CH ₂ -CO-, -CH ₂ -, while for X ² -OC-, -OC-CH = CH- , -OC-CH ₂ CH ₂ -, -CH ₂ - are preferred. For X ¹ are in particular -CO- and for X ² -OC- desirable because of their high chiral induction. The letters m and n each represent the values 0, 1 or 2, where m and n should preferably stand for 0 or 1.

[Verbindung 4]

[Verbindung 5]

[Verbindung 6]

(In der Formel repräsentieren p und q voneinander unabhängige ganze Zahlen von 2 bis 8.)As concrete examples of the compounds represented by the general formula (I), preferred are the compounds represented by the general formulas (I-1) to (I-15) below. [Compound 3]

[Compound 4]

[Compound 5]

[Compound 6]

(In the formula, p and q represent independent integers from 2 to 8.)

The Compounds according to the present invention can be prepared according to the methods described below.

(Production Method 1)

Preparation of the compounds with the in of the general formula (I-1) shown structure

p-Bromobenzoic acid and isosorbitol are esterified by using dicyclohexylcarbodiimide and the like dehydrating and condensing agents, and further from the resulting products via a Heck reaction with hydroxyethyl acrylate and a palladium catalyst, the isosorbitol derivatives (S-2) are obtained. [Compound 7]

Subsequently, the isosorbitol derivatives (S-2) and acrylic acid chloride are esterified in the presence of triethylamine, and thus the target compound having p = 2 (I-1) can be obtained. [Compound 8]

(Production method 2)

Preparation of the compounds with the in of the general formula (I-7) shown structure

6-hydroxy-2-naphthoic acid is reacted with trifluoromethanesulfonyl chloride, and then the isosorbitol with dicyclohexylcarbodiimide and the like dehydrating and condensing agents is understood so as to obtain the isosorbitol derivative (S-3). [Compound 9]

Further, the isosorbitol derivatives (S-3) and hydroxyethyl acrylate are reacted in a Heck reaction in the presence of a palladium catalyst so as to obtain the isosorbitol derivative (S-4) and then the isosorbitol derivative with palladium on carbon in a hydrogenation reaction (S-5). [Compound 10]

Subsequently, the isosorbitol derivative (S-5) and acrylic acid chloride are esterified in the presence of triethylamine, and thus the target compound having p = 2 (I-7) can be obtained. [Compound 11]

(Production method 3)

Preparation of the compounds with the in of general formula (I-9)

p-hydroxybenzoic acid and benzyl chloride are etherified in the presence of suitable alkaline bases such as sodium hydroxide and the like, and used after combining with phenol protecting groups dicyclohexylcarbodiimide and the like dehydrating and condensing agents to conduct esterification, and further from the formed products using a palladium catalyst by hydrogenation in a reduction reaction, the phenol protecting groups again separated, so that in this way the isosorbitol derivative (S-7) can be obtained. [Compound 12]

Further, the isosorbitol derivative (S-7) and the diethylene glycol monotertiary butyl ether are etherified by using triphenylphosphine and diisopropyl azodicarboxylate through a Mitsunobu reaction and further deprotected with trifluoroacetic acid tertiary butyl groups to give the hydroxyl group-containing isosorbitol derivative (S-8) becomes. [Compound 13]

Subsequently are the hydroxyl group-containing isosorbitol derivative (S-8) and Acryloylethyl chloroformated in the presence of pyridine, thus obtaining the target compound with p = 2 (I-9) can be.

(Production Method 4)

Preparation of the compounds with the in of general formula (I-16)

p-nitrobenzoic acid and isosorbitol are esterified using dicyclohexylcarbodiimide and the like dehydrating and condensing agents, and then the nitro group is reduced with palladium on carbon to obtain the amino group-containing isosorbitol derivative (S-9). [Compound 14]

In addition, the isosorbitol derivative (S-9) and bromobenzoic acid chloride are esterified in the presence of triethylamine to obtain the amide compound (S-10), and then the reaction product and hydroxybutyl acrylate are reacted by using a palladium catalyst in a Heck reaction, and further Acrylic acid esterified in the presence of triethylamine, so that in this way the target compound with p = 4 (I-16) can be obtained. [Compound 15]

(Production method 5)

Preparation of the compounds with the in of general formula (I-17)

One mole of the isosorbitol derivative (S-7) synthesized in the production process (3) is esterified with 1 mole of 6-bromo-2-naphthoic acid and dicyclohexylcarbodiimide and the like dehydrating and condensing agents to obtain an isosorbitol derivative and further reacted with trifluoromethanesulfonic anhydride brought to obtain in this way the asymmetric isosorbitol derivative (S-12). [Compound 16]

Subsequently, the isosorbitol derivative (S-12) and hydroxyethyl acrylate are reacted using a palladium catalyst in the course of a Heck reaction and further esterified acrylic acid chloride in the presence of triethylamine, so that in this way the target compound with p = 2 (I-17) are obtained can. [Compound 17]

For the compounds according to the present invention, chirally nematic, chiral smectic and cholesteric liquid crystal constituents are particularly suitable. The compounds of the present invention according to the present application are preferably added to the structural parts and liquid crystal components in a proportion of 0.1 to 40% by weight, but more preferably in one Ratio of 3 to 25 wt .-% of the polymerizable chiral compounds.

The as constituents of liquid crystals serving polymerizable chiral compounds of the invention according to the present invention Registration are not limited, apart from that on the in the general formula (I) dargestelten compounds but in terms of being used in combination Polymerizable liquid crystal compounds should preferably in the compounds acryloyloxy groups (R-1) and metacryloyloxy groups (R-2), and preferably should not be less than two functional polymerizable groups in the molecule in question be included.

(in der Formel repräsentieren W¹ und W² voneinander unabhängige, einfache kovalente Bindungen, -O-, -COO- oder -OCO-, während Y³ und Y⁴ voneinander unabhängige -COO- oder -OCO- darstellen, und r und s sind voneinander unabhängige ganze Zahlen zwischen 2 und 18, die in der Formel enthaltene 1,4-Phenylengruppe kann jedoch auch durch nicht weniger als eine Alkylgrupp mit 1 bis 7 Kohlenstoffatomen, Alkoxygruppe mit 1 bis 7 Kohlenstoffatomen, Alkanoylgruppe mit 1 bis 7 Kohlenstoffatomen, Cyanogruppe oder ein Halogenatom ersetzt werden) die dargestellten Verbindungen wünschenswert sind.Concrete examples of the liquid crystal compounds containing two functional polymerizable groups used in combination are shown in the general formula (II), wherein [Compound 18]

(In the formula, W ¹ and W ^{2 represent} mutually independent, single covalent bonds, -O-, -COO- or -OCO-, while Y ³ and Y ^{4 represent} independent -COO- or -OCO-, and r and s are independent integers between 2 and 18, but the 1,4-phenylene group included in the formula can also be represented by not less than one alkyl group of 1 to 7 carbon atoms, alkoxy group of 1 to 7 carbon atoms, alkanoyl group of 1 to 7 carbon atoms, cyano group or a halogen atom is replaced) the compounds shown are desirable.

(In der Formel haben r und s die gleichen Bedeutungen wie in der allgemeinen Formel (II).)The compounds represented by the general formulas (II-1) to (II-8) are desirable as concrete examples of the compounds represented by the general formula (II). [Compound 19]

(In the formula, r and s have the same meanings as in the general formula (II).)

In The general formulas of (II-1) to (II-8) should preferably be r and s be independent integers between 3 and 6.

(in der Formel repräsentieren W³ und W⁴ voneinander unabhängige, einfache kovalente Bindungen, -O-, -COO- oder -OCO-, Y⁵ repräsentiert -COO- oder -OCO-, p und q sind voneinander unabhängige ganze Zahlen zwischen 2 und 18 und die Wasserstoffatome der drei in der Formel enthaltenen 1,4-Phenylengruppen können auch durch voneinander unabhängige, nicht weniger als eine Alkylgruppe mit 1 bis 7 Kohlenstoffatomen, Alkoxygruppe, Alkanoylgruppe, Cyanogruppe oder Halogenatom ersetzt werden) die dargestellten Verbindungen wünschenswert sind.Concrete examples of the liquid crystal compounds containing two functional polymerizable groups used in combination are shown in the general formula (III), wherein

(In the formula, W ³ and W ^{4 represent} independent, single covalent bonds, -O-, -COO- or -OCO-, Y ⁵ represents -COO- or -OCO-, p and q are independent integers between 2 and 18 and the hydrogen atoms of the three 1,4-phenylene groups contained in the formula can also be replaced by independent, not less than an alkyl group having 1 to 7 carbon atoms, alkoxy group, alkanoyl group, cyano group or halogen atom) the compounds shown are desirable.

(In der Formel haben p und q die gleichen Bedeutungen wie in der allgemeinen Formel (III).)As concrete examples of the compounds represented by the general formula (III), the compounds represented by the general formulas (III-1) to (III-8) are desirable. [Compound 21]

(In the formula, p and q have the same meanings as in the general formula (III).)

Under These types of compounds are the compounds with the general Formula (III-2), general formula (III-5), general Formula (III-6), general formula (III-9), general Formula (III-10) from the standpoint of heat resistance and Durability ago preferred, wherein the compound of the general Of which formula (III-2) is particularly desirable.

(In der Formel sind u und v voneinander unabhängige ganze Zahlen zwischen 2 und 18.)The compounds having not less than two polymerizable functional groups in the molecule which later serve as host liquid crystals may be compounded with the compounds represented by the general formulas (a-1) to (a-10). [Compound 22]

(In the formula, u and v are independent integers between 2 and 18.)

Under these in turn should preferably the compounds of the general Formula (a-2) or the general formula (a-3) are added. u and v should preferably be values between 3 and 18, where a value between 4 and 16 better and a value between 6 and 12 especially good.

(in der Formel repräsentiert e eine ganze Zahl zwischen 0 und 18, und wenn e entweder 0 oder 1 ist, dann repräsentiert f 0, wenn ein Wert zwischen 2 und 18 ist, repräsentiert f eine ganze Zahl von entweder 0 oder 1, wenn i eine ganze Zahl zwischen 0 und 2 repräsentiert, dann sind C, D und E voneinander unabhängige, 1,4-Phenylengruppen, 1,4-Cyclohexylengruppen, 1,4-Cyclohexenylgruppen, Tetrahydropyran-2,5-diylgruppen, 1,3-Dioxan-2,5-diylgruppen, Tetrahydrothiopyran-2,5-diylgruppen, 1,4-Bicyclo(2,2,2)octylengruppen, Decahydronaphthalen-2,6- diylgruppen, Pyridin-2,5-diylgruppen, Pyrimidin-2,5-diylgruppen, Piradin-2,5-diylgruppen, 1,2,3,4-Tetrahydronaphthalen-2,6-diylgruppen, 2,6-Naphthylengruppen, Phenanthren-2,7-diylgruppen, 9,10-Dihydrophenanthren-2,7-diylgruppen, 1,2,3,4,4a,9,10a-Octahydrophenanthren-2,7-diylgruppen oder Fluoren-2,7-diylgruppen repräsentieren, wobei die besagten 1,4-Phenylengruppe, 1,2,3,4-Tetrahydronaphthalen-2,6-diylgruppe, 2,6-Naphthylengruppe, Phenanthren-2,7-diylgruppe, 9,10-Dihydrophenanthren-2,7-diylgruppe, 1,2,3,4,4a,9,10a-Octahydrophenanthren-2,7-diylgruppe oder Fluoren-2,7-diylgruppe nicht substituiert ist, oder als substituierte Reste jeweils eine oder nicht weniger als zwei F, Cl, CF_{3 ,} OCF₃ oder CH₃ Reste tragen können, Y⁶ und Y⁷ stellen voneinander unabhängige, einfache kovalente Bindungen -COO-, -OCO-, -CH=N-, -N=CH-, -C≡C-, -CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂O-, -OCH₂CH₂CH₂-, -CH₂O-, -OCH₂-, -CF₂O-, -OCF₂-, -CH=N-N=CH-, -CF=CF-, -CH=CH-, -CH₂CH₂CH=CH-, -CH=CHCH₂-, -CH=CHCOO-, -OCOCH=CH-, -CH₂CH₂OCO- oder stellen -COOCH₂CH₂- dar, während Y⁸ einfache kovalente Bindungen wie -O-, -CO-, -COO-, -OCO-, -CH₂-, -OCH₂-, -CH₂O-, -CONH-, -NHCO-, -CH₂COO- oder -CH₂OCO- darstellt, Z steht für Alkylgruppen mit 1 bis 18 Kohlenstoffatomen, für Alkenylgruppen mit 2 bis 18 Kohlenstoffatomen, Halogenatome, Cyanogruppen oder NCS, die genannten Alkylgruppen oder Alkenylgruppen können unsubstituiert sein, oder aber können als Substituenten jeweils einen oder nicht weniger als zwei F, Cl, Cyano-, CH₃ oder CF₃ Reste haben, wobei in den genannten Alkylgruppen oder Alkenylgruppen entweder 1 oder nicht weniger als zwei CH₂-Gruppen vorhanden sind, die gegenseitig nicht direkt mit den Sauerstoffatomen verbunden sind und durch O, CO oder COO substituiert sein können) mit einzelnen funktionellen Gruppen den polymerisierbaren Flüssigkristallverbindungen hinzugesetzt werden.As the polymerizable liquid crystal compounds for the liquid crystal components of the invention of the present application, compounds represented by the general formula (IV) may be used for the purpose of adjusting the liquid crystal temperature range and birefringence, and reducing the viscosity [Compound 23]

(In the formula, e represents an integer between 0 and 18, and if e is either 0 or 1, then f represents 0, if a value is between 2 and 18, f represents an integer of either 0 or 1 if i represents an integer between 0 and 2, then C, D and E are independent 1,4-phenylene groups, 1,4-cyclohexylene groups, 1,4-cyclohexenyl groups, tetrahydropyran-2,5-diyl group pen, 1,3-dioxane-2,5-diyl groups, tetrahydrothiopyran-2,5-diyl groups, 1,4-bicyclo (2,2,2) octylene groups, decahydronaphthalene-2,6-diyl groups, pyridine-2,5- diyl groups, pyrimidine-2,5-diyl groups, piradine-2,5-diyl groups, 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups, 2,6-naphthylene groups, phenanthrene-2,7-diyl groups, 9, Represent 10-dihydrophenanthrene-2,7-diyl groups, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl groups or fluorene-2,7-diyl groups, said 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4, 4a, 9,10a-octahydrophenanthrene-2,7-diyl group or fluorene-2,7-diyl group is unsubstituted, or substituted radicals each carry one or not less than two F, Cl, CF _{3 ,} OCF ₃ or CH ₃ radicals For example, Y ⁶ and Y ^{7 may} represent independent, single covalent bonds -COO-, -OCO-, -CH = N-, -N = CH-, -C≡C-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ O-, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH = NN = CH-, -CF = CF-, -CH = CH-, -CH ₂ CH ₂ CH = CH-, -CH = CHCH ₂ -, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ OCO- or represent -COOCH ₂ CH ₂ -, while Y ⁸ simple covalent bonds such as -O-, -CO-, -COO-, -OCO-, -CH ₂ -, -OCH ₂ -, -CH ₂ O- Z is -CONH-, -NHCO-, -CH ₂ COO- or -CH ₂ OCO-, Z is alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, halogen atoms, cyano groups or NCS, said alkyl groups or Alkenyl groups may be unsubstituted, or may each have as substituents one or not less than two F, Cl, cyano, CH ₃ or CF ₃ radicals, wherein in said alkyl groups or alkenyl groups either 1 or not less than two CH ₂ groups are present, which are mutually not directly connected to the oxygen atoms and may be substituted by O, CO or COO) with individual functional Groups are added to the polymerizable liquid crystal compounds.

(In der Formel haben e und f die gleichen Bedeutungen wie in der allgemeinen Formen (IV) und R repräsentiert Alkylgruppen mit 1 bis 12 Kohlenstoffatomen, oder Alkenylgruppen mit 2 bis 12 Kohlenstoffatomen).The amount of the compounds represented by the general formula (IV) should preferably be not more than 50% by weight, with a ratio of not more than 30% by weight being more suitable and a ratio of not more than 15% by weight. -% is particularly desirable. As concrete examples of the compounds represented by the general formula (IV), the compounds represented by the general formulas (IV-1) to (IV-11) are desired. [Compound 24]

(In the formula, e and f have the same meanings as in the general forms (IV) and R represents alkyl groups having 1 to 12 carbon atoms, or alkenyl groups having 2 to 12 carbon atoms).

Further, the polymerizable liquid crystal components according to the present invention are compounds having polymerizable functional groups and can be added with compounds showing no liquid crystallinity. As such compounds, macromolecule-forming monomers or macromolecule-forming oligomers are normally used in this technical field of application and if these can be identified, these compounds are not limited in their use, but the addition amount must be adjusted so that the ingredients have liquid crystallinity properties.

The Concentration of in the polymerizable liquid crystal components according to the present invention contained photoinitiators The present invention should preferably be 0.1 to 10% by weight, better yet 0.2 to 5 wt .-% but best 0.4 to 3 wt .-% amount. Further, as photoinitiators in the present Invention, other photoinitiators are added. As photoinitiators can Benzoin ethers, benzophenones, acetophenones, benzyl ketals, Acylphosphine oxides and the like may be mentioned.

Further, in the polymerizable liquid crystal components according to the present invention can be used for improvement storability and stability also stabilizers be added. As stabilizers, for example Hydroquinones, hydroquinone monoalkyl ethers, tert-butyl catechols, Pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, Nitroso compounds and the like may be mentioned. Using of stabilizers, the amount added should preferably be 0.005 to 1% by weight of the liquid crystal components, However, a ratio of 0.02 to 0.5 wt .-% even better and 0.03 to 0.1 wt% is particularly desirable.

If the polymerizable liquid crystal components accordingly of the present invention as a starting material for polarizing films or oriented membranes, or as a printing ink or paint, for protective films and the like can be used depending on the purpose Metals, metal complexes, colorants, pigments, dyes, fluorescent materials, phosphorizing materials, wetting agents, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbing Agents, infrared absorbing agents, antioxidants, ion exchange resins, Titanium oxide and the like metal oxides and the like become.

In the following, the optically anisotropic materials of the present invention are explained in more detail. The optically anisotropic materials prepared by polymerizing the polymerizable liquid crystal components of the present invention can be used for a variety of purposes. For example, the polymerizable liquid crystal components of the present invention can be used as non-aligned state as scattering plates, depolarization plates, moire protection plates when polymerized. When the polymerizable liquid crystal components of the present invention are polymerized in an aligned state, the optically anisotropic materials thus prepared are useful because of their physical, optically anisotropic properties. With this kind of optically anisotropic materials, for example, on the surface of the polymerizable liquid crystal components of the present invention, by abrasive treatment with cloth or like substrate plates, or by abrasive treatment with cloth or the like, substrate plates on which organic thin films have been applied or may be prepared Aligned films of SiO ₂ applied to substrate plates and produced after pinching by polymerization of the liquid crystals of the present invention.

With regard to the methods of applying the polymerizable liquid crystal components of the present invention to substrate plates, there may be mentioned spin coating, dye coating, flow coating, roll cladding, wire bar coating, gravure coating, spray coating, dipping, printing and the like. In addition, organic solvents may also be added to the polymerizable liquid crystal components of the present invention in the coating. As organic solvents, there may be mentioned ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, dichloromethane, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone, 7-butyl lactone, acetoxy-2-ethoxyethane, propylene glycol monomethylacetate and the like. These agents may be used singly but also combined with each other, and should be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal components. Further, the amount added should preferably be 90% by weight. As a method for volatilizing the added organic solvents, natural drying, drying by heating, vacuum drying and vacuum heat drying can be used. For improving the coating properties of the polymerizable liquid crystal materials, a thin intermediate layer of polyimide may be applied to the substrate plate, but the addition of leveling agents to the polymerizable liquid crystal materials is also useful. The formation of a polyimide thin film on the substrate plate or like intermediate layers is an effective means for improving the adhesion when the contact of the optically anisotropic ones obtained by polymerization of the polymerizable liquid crystal materials pen materials and the slab plate is not good.

When Method of clamping the polymerizable liquid crystal materials on the substrate plate can be called the injection method, which uses the capillary phenomenon. The injection of the polymerizable liquid crystal components in between the substrate plates formed space in which generates a negative pressure is also an effective remedy.

Besides the grinding treatment or the oblique evaporation of SiO ₂ for orientation treatment, it is possible to use a flow treatment of the liquid crystal materials or to use electric or magnetic fields for this purpose. These orienting agents may be used singly or in combination. Moreover, instead of the grinding treatment as the orientation treatment, photo-alignment may also be used. In this method, for example, organic thin films in which macromolecules contain photodimerizing functional groups in polyvinyl cinnamate or the like, or organic thin films with light-induced optically isomerizing functional groups or organic thin films of polyimides are irradiated with polarized light, preferably polarized ultraviolet radiation aligned membranes are formed. By employing suitable optical masks for this photo-alignment process, patterns in alignment can be easily obtained so that it is possible to precisely control the molecular orientation within the optically anisotropic materials.

The Shape of the substrate plates can also curved in addition to flat plates comprise molded sections. As building materials can organic materials and inorganic materials alike be used. As organic materials for the substrate plates For example, polyethylene terephthalate, Polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, Polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, Polyarylate, polysulfone, triacetylcellulose, cellulose, polyether ether ketone and to be called the like. In addition, you can as inorganic materials, for example silicon, glass, calcite and the like.

These Type of substrate plates are then polished with cloth or the like and if this does not give adequate guidance can be substrate plates made of organic thin films with according to known methods applied polyimide thin films or polyvinyl alcohol thin films are formed and These are then polished with cloth or the like. Further is the use of polyimide thin films, the ordinary Twisted nematic (TN) element or super twisted nematic (STN) element give a pretilt angle, so that the molecular Alignment structure within the optically anisotropic materials can be controlled in more detail, particularly desirable.

substrate plates with electrode layers are used when the alignment controlled by an electric field. In this Case, the organic thin films in the form of aforementioned polyimide thin films preferably on the Electrodes are formed.

Out the ingredients to which the polymerizable chiral compounds may be added according to the present invention orient them and by polymerization in a crystalline state Phase contrast plates made with spiral structure become. If the periodicity of the spiral gears half or the same of the wavelength of the Light is, then light of this wavelength can after be selectively reflected Bragg's law. This can be for Example in functional elements for the separation of circular be exploited polarized light.

As for the method of polymerizing the polymerizable liquid crystal components according to the present invention, a method in which the polymerization proceeds rapidly is desirable, so that a method in which the polymerization is carried out by irradiation with ultraviolet rays, electron beams or the like, the rays providing activation energy becomes. When using UV rays, a light source for polarized light can be used, or even a light source for unpolarized light. Further, if the polarization is performed while the liquid crystal components are sandwiched between two substrate plates, then at least the substrate side irradiation plates must be given adequate transparency for the rays providing the activation energy. In addition, it is possible to polymerize by using masks on exposure only certain areas and then by changing the conditions of the electric or magnetic field or temperature to change the orientation of the not yet polymerized areas, to finally by re-irradiation with the activation energy-providing radiation to polymerize the not yet polymerized areas. The temperature in the irradiation should preferably be in a range in which the polymerizable liquid crystal components according to the present invention remain in the liquid crystal state. In particular, when optically anisotropic materials are to be prepared by photopolymerization, it is preferable to conduct the polymerization as much as possible at a temperature near room temperature in order to avoid unintentional heat polymerization, that is, the polymerization should typically be at a temperature of 25 ° C be performed. The intensity of the rays providing the activation energy should preferably be 0.1 mW / cm ² to 2 W / cm ² . At an intensity of not more than 0.1 mW / cm ² , a very long time is required until photopolymerization is completed, which later affects productivity, and at not less than 2 W / cm ^{2 there} is a risk that the polymerizable liquid crystal compounds and the polymerizable liquid crystal components, respectively decompose.

The by the polymerization obtained optically anisotropic materials according to the present invention are then heat treated, to reduce variations in the initial properties and to produce stable properties. The temperature for the heat treatment should be in the range of 50 ° C to 250 ° C and whose duration should preferably between 30 seconds and 12 hours.

The correspondingly prepared in this way optically anisotropic materials of the present invention may be either from the substrate plate detached and independent or not from the Substrate plate are used detached. The thus obtained Optically anisotropic materials can also be layered and by sticking to another substrate plate.

[Embodiments]

in the The invention is based on the listed embodiments explained in more detail, but the invention is not limited to the described embodiments. Further, in the embodiments described below and comparative examples of the components respectively means "% by weight".

(Embodiment 1)

In a reaction vessel equipped with stirrer, condenser and thermometer, 33.2 g (240 mmol) of 3- (p-hydroxyphenyl) benzoic acid, 4 g of potassium iodide, 1 g of tetrabutylammonium bromide and 400 ml of ethanol were prepared and stirred at room temperature. This was done by titrating slowly a 25% aqueous reading of 24 g sodium hydroxide. After completion of the titration, the reaction vessel was kept at 50 ° C and 50 g (288 mmol) of benzyl bromide slowly titrated. After completion of the titration, the reaction vessel was then heated to 70 ° C and the reaction allowed to proceed for a further 3 hours. After completion of the reaction, neutralization was made with 10% aqueous hydrochloric acid solution and ethyl acetate was extracted and, after drying over sodium sulfate, synthesized by concentration of the solvent 38 g of the compound shown in the formula (1). [Compound 25]

Next, in a reaction vessel equipped with a stirrer, condenser and thermometer, 28 g (123 mmol) of the compound synthesized as described above in formula (1), 7.7 g (55 mmol) of isosorbitol, 1.8 g of dimethylaminopyridine and 500 ml of dichloromethane were prepared and the reaction vessel kept cooled to not more than 5 ° C on an ice bath. Under a nitrogen atmosphere, 19 g (150 mmol) of diisopropylcarbodiimide was then slowly added dropwise. After completion of the titration, the reaction vessel was then returned to room temperature, and the reaction was allowed to proceed for 5 hours. After filtration of the reaction liquid, 200 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, and further washed with a saturated saline solution, and then the organic phase was dried with sodium sulfate anhydride. After distilling off the solvent, the product was refined in a column of five times the amount (weight ratio) of silica gel to obtain 23 g of the compound shown in formula (2). [Compound 26]

Subsequently, in an autoclave equipped with a stirrer, 11 g (17.7 mmol) of the compound synthesized as described above and shown in formula (2), 1 g of palladium on carbon and 150 ml of ethanol and then at 0.1 MPa, a reduction reaction of hydrogen (reaction temperature 50 ° C, duration 3 hours). After filtration of the reaction liquid and distilling-off of the solvent, 7.5 g of the compound shown in formula (3) was obtained. [Compound 27]

Next, in a reaction vessel equipped with a stirrer, condenser and thermometer was 4.5 g (38 mmol) of ethylene glycol monotertiary butyl ether, 6.2 g (16 mmol) of the compound shown in the formula (3) above, 9.6 g (37 mmol) of triphenylphosphine and 200 ml THF set and the reaction vessel under a nitrogen atmosphere to equal or below 5 ° C cooled. Subsequently, 7 g (35 mmol) of diisopropyldiazocarboxylic acid were slowly added dropwise. After completion of the titration, the reaction is allowed to proceed at room temperature for 4 hours. After completion of the reaction, 100 ml of THF was distilled off and the thus concentrated reaction liquid was cooled to equal to or below 5 ° C and then methanol / purified water = 300/60 ml was added dropwise, thus reprecipitation. After filtration of the precipitate and drying, 8 g of the compound shown in formula (4) was synthesized. [Compound 28]

Subsequently was in a equipped with a stirrer reaction vessel 40th ml of trifluoroacetic acid and then the reaction vessel under nitrogen atmosphere until equal to or below 5 ° C cooled. Further, 8 g was synthesized as described above Compound of formula (4) added in small amounts. To Upon completion of the addition, the mixture was allowed to set at this temperature Stirred for 30 minutes to react. To Completion of the reaction was extracted with dichloromethane / pure water, again with pure water, saturated sodium bicarbonate solution washed, the organic phase concentrated and dried and after substitution of the tertiary butoxy group by a Hydroxy group obtained 6 g of alcohol.

Next, in a reaction vessel equipped with a stirrer, condenser and thermometer, the entire 6 g of the above-mentioned alcohol, 6 g (77 mmol) of pyridine and 150 ml of THF were prepared and the reaction cooled under nitrogen atmosphere to equal or below 5 ° C. Then, 5.5 g (31 mmol) of acryloyloxyethyl chloroformate was slowly added. After completion of the titration, the reaction was allowed to proceed at room temperature for 4 hours. After completion of the reaction, ethyl acetate was added and then the organic phase was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, the product was refined in a column of five times the amount (weight ratio) of silica gel, to obtain 6 g of the oily target compound shown in the formula (5).

[Compound 29]

(Physical Properties)

• H NMR (solvent: deuterated chloroform): δ: 4.26-4.10 (m, 4H), 4.40 (m, 2H), 4.42 (s, 8H), 4.54 (m, 4H), 4.66 (m, 1H), 5.03 (m, 1H), 5.45 (m, 2H), 5.84 (d, 2H), 5.86 (m, 2H), 6.14 (m, 2H), 6.45 (d, 2H), 6.93 (m, 4H), 7.98 ( d, 2H), 8.04 (d, 2H) ¹³ C-NMR (solvent: deuterated chloroform): δ: 62.0, 65.7, 66.0, 70.7, 74.3, 78.3, 81.1, 86.1, 114.1, 122.3, 127.7, 131.4, 131.7, 154.6, 162.1, 165.5 Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809

The Compound shown in formula (5) is a viscous liquid and by excellent solubility in the other liquid crystal compounds characterized.

1.0% was added to the nematic liquid crystal components shown below, and the result of calculation of HTP by light microscopic studies of the aimed periodicity revealed a high value of HTP = 30. [Compound 30]

(Embodiment 2)

In a reaction vessel equipped with stirrer, condenser and thermometer, 25 g (124 mmol) of benzoic acid bromide, 9 g (62 mmol) of isosorbitol, 1.8 g of dimethylaminopyridine and 200 ml of dichloromethane were set and the reaction vessel was kept at or below 5 ° C. on an ice bath and 18.8 g (149 mmol) of diisopropylcarbodiimide are slowly added dropwise under a nitrogen atmosphere. After completion of the titration, the reaction vessel was returned to room temperature, and the reaction was allowed to proceed for 5 hours. After filtration of the reaction liquid 200 ml of dichloromethane was added to the filtrate, with Washed 10% aqueous hydrochloric acid solution and moreover washed with a saturated saline solution and then the organic phase dried with sodium sulfate anhydride. After distilling off the solvent and washing the desired product with methanol, recrystallization in dichloromethane / methanol to obtain 25 g of the compound shown in formula (6). [Compound 31]

Then, in a reaction vessel equipped with stirrer, condenser and thermometer, 25 g (48.8 mmol) of the compound synthesized as described above and shown in formula (6), 18 g (126 mmol) of hydroxybutyl acrylate, 14 g (146 mmol) of triethylamine, 31 g (97 mmol) tetrabutylammonium bromide, 1 g of palladium acetate and 300 ml of dimethylformamide and the reaction vessel heated under a nitrogen atmosphere at 90 ° C and the mixture was reacted. After completion of the reaction, ethyl acetate and THF were added and the organic phase was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, the product was refined in a column of five times the amount (weight ratio) of silica gel to obtain 20 g of the compound shown in formula (7). [Compound 32]

Next, in a reaction vessel equipped with a stirrer, condenser and thermometer, 10 g (15.6 mmol) of the compound shown in formula (7), 3 g (33.8 mmol) of acryloyl chloride and 200 ml of dichloromethane were added and the reaction vessel was made equal to or under a nitrogen atmosphere cooled below 5 ° C. Subsequently, 3.4 g (33.8 mmol) of triethylamine was slowly added dropwise. After completion of the titration, the reaction was allowed to proceed at not more than 10 ° C for 1 hour. After completion of the reaction, dichloromethane was added and the organic phase was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, the product was refined in a column of five times the amount (weight ratio) of silica gel, to obtain 5 g of the target compound shown in formula (8). [Compound 33]

(Physical Properties)

• ¹ H-NMR (solvent: deuterated chloroform): δ: 1.83 (s, 8H), 4.08 (m, 4H), 4.27 (m, 8H), 4.71 (d, 1H), 5.09 (m, 1H), 5.44 ( m, 2H), 5.84 (d, 2H), 6.17 (m, 2H), 6.43 (d, 2H), 6.55 (dd, 2H), 7.60 (m, 4H), 7.72 (m, 2H), 8.04 (d, 2H), 8.10 (d, 2H)
• ¹³ C-NMR (solvent: deuterated chloroform): δ: 25.2, 63.7, 64.0, 70.5, 73.1, 74.5, 78.4, 80.9, 85.8, 120.3, 120.4, 127.6, 128.0, 129.8, 130.2, 130.3, 138.5, 138.6, 142.7 , 142.8, 162.7, 164.4, 164.7, 165.6, 165.8
• Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
• (Melting point) 82 ° C

The in the formula (8) shown compound has 82 ° C a low melting point and is characterized by excellent Solubility in the other liquid crystal compounds out.

The As in the embodiment 1 obtained calculation result for the HTP showed a high value of HTP = 41.

(Embodiment 3)

In a reaction vessel equipped with a stirrer, condenser and thermometer, 26.5 g (48.8 mmol) of the synthesized compound represented by Formula (6), 14.6 g (126 mmol) of hydroxybutyl acrylate, 14 g (146 mmol) of triethylamine, 31 g (97 mmol) of tetrabutylammonium bromide, 1 g of palladium acetate and 300 ml of dimethylformamide and the reaction vessel heated under a nitrogen atmosphere to 90 ° C and the mixture was reacted. After completion of the reaction, ethyl acetate and THF were added and the organic phase was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, the product was refined in a column of five times the amount (weight ratio) of silica gel to obtain 16 g of the compound shown in formula (9). [Compound 34]

Subsequently, in an autoclave equipped with a stirrer, 10 g (16.3 mmol) of the compound synthesized as described above and represented in formula (9), 1 g of palladium on carbon and 100 ml of ethyl acetate and 100 ml of ethanol were added and then at 0.1 MPa a reduction reaction of Hydrogen (reaction temperature 50 ° C, duration 3 hours) performed. After filtration of the reaction liquid and distilling-off of the solvent, 8.0 g of the compound shown in formula (10) was obtained. [Compound 35]

When Next was in a with stirrer, condenser and thermometer equipped reaction vessel 8 g (13 mmol) of the compound shown in formula (10), 2.8 g (31 mmol) Acrylic acid chloride and 200 ml of dichloromethane and set the reaction vessel under a nitrogen atmosphere cooled to equal or below 5 ° C. Subsequently 3.1 g (31 mmol) of triethylamine were slowly added dropwise. Upon completion of the titration, the reaction was not more than 10 ° C for 1 hour. After graduation the reaction was added dichloromethane and the organic phase with 10% aqueous hydrochloric acid solution, washed with pure water and brine. After distilling off the solvent, the product became in a column with five times the amount (weight ratio) refined on silica gel to give 6 g of that shown in formula (11) Target compound received.

[Compound 36]

(Physical Properties)

• ¹ H-NMR (solvent: deuterated chloroform): δ: 2.67 (m, 4H), 3.02 (m, 4H), 4.04 (m, 4H), 4.34 (s, 8H), 4.66 (m, 1H), 5.04 ( m, 1H), 5.40 (m, 2H), 5.84 (d, 2H), 6.15 (m, 2H), 6.44 (dd, 2H), 7.28 (m, 4H), 7.94 (d, 2H), 7.99 (i.e. , 2H)
• ¹³ C-NMR (solvent: deuterated chloroform): δ: 25.2, 63.7, 64.0, 70.5, 73.1, 74.5, 78.4, 80.9, 85.8, 120.3, 120.4, 127.6, 128.0, 129.8, 130.2, 130.3, 138.5, 138.6, 142.7 , 142.8, 162.7, 164.4, 164.7, 165.6, 165.8
• Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809

The Compound shown in formula (11) is a viscous liquid and by excellent solubility in the other liquid crystal compounds characterized.

The as in Embodiment 1 obtained calculation result the HTP showed a high value of HTP = 34.

(Embodiment 4)

In a reaction vessel equipped with stirrer, condenser and thermometer was added to 30 g (120 mmol) of 4-bromo-2-fluorobiphenyl 120 ml of dichloromethane and the mixture was cooled to 0 ° C. Then, after addition of 17.6 g of aluminum chloride, 16.7 g of oxalyl chloride were carefully added dropwise, paying close attention to the development of heat and after completion of the titration the reaction was allowed to proceed at 20 ° C. for 1 hour. After completion of the reaction and decomposition of the oxalyl chloride with water, the organic phase was washed with saturated brine, and by distilling off the solvent, the compound shown in formula (12) was obtained. [Compound 37]

Subsequently was in a with stirrer, condenser and thermometer equipped reaction vessel 35 g (111 mmol) which was synthesized as described above, shown in formula (12) Compound, 8.1 g isosorbitol (56 mmol) and 200 ml dichloromethane and do not put the reaction vessel on an ice bath more attached and the reaction vessel on a Ice bath kept at not more than 5 ° C cooled and 13.4 g (133 mmol) of triethylamine are slowly added dropwise. After completion of the titration, the reaction vessel was then brought back to room temperature and the reaction for Expire for 5 hours. After filtration of the reaction liquid was 200 ml of dichloromethane added to the filtrate, with 10% aqueous Washed hydrochloric acid solution and above washed out with a saturated saline solution and then the organic phase with sodium sulfate Dried anhydride. After distilling off the solvent and washing the title compound with methanol was done in dichloromethane / methanol recrystallized to give 34 g of the compound shown in formula (13) receive.

[Compound 38]

Subsequently was in a with stirrer, condenser and thermometer equipped reaction vessel 34 g (47.5 mmol) which was synthesized as described above and shown in formula (13) Compound, 16.5 g (115 mmol) hydroxybutyl acrylate, 14 g (146 mmol) Triethylamine, 31 g (97 mmol) tetrabutylammonium bromide, 1 g of palladium acetate and 300 ml of dimethylformamide and the Reaction vessel under a nitrogen atmosphere heated to 90 ° C and the mixture was reacted. After completion of the reaction, ethyl acetate and THF were added and the organic phase with 10% aqueous hydrochloric acid solution, washed with pure water and brine. After distilling off the solvent, the product became in a column with five times the amount (weight ratio) refined on silica gel to give 30.5 g of that shown in formula (14) Received connection.

[Compound 39]

Thereafter, in an autoclave equipped with a stirrer, 30.5 g (40.5 mmol) of the compound synthesized as described above and shown in formula (14), 1 g of palladium on carbon, 300 ml of ethyl acetate and 100 ml of ethanol were added and then a reduction reaction of 0.1 MPa Hydrogen (reaction temperature 50 ° C, duration 3 hours) performed. After filtration of the reaction liquid and distilling off the solvent, 30 g of the compound shown in formula (15) was obtained. [Compound 40]

In addition, in a reaction vessel equipped with a stirrer, condenser and thermometer, 30 g (40 mmol) of the compound shown in formula (15), 7.9 g (88 mmol) of acryloyl chloride and 200 ml of dichloromethane were added and the reaction vessel was equal to or under a nitrogen atmosphere cooled below 5 ° C. Subsequently, 8.8 g (88 mmol) of triethylamine was slowly added dropwise. After completion of the titration, the reaction is allowed to proceed at not more than 10 ° C for 1 hour. After completion of the reaction, dichloromethane was added and the organic phase was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, the product was refined in a column of five times the amount (weight ratio) of silica gel to obtain 28 g of the objective compound shown in formula (16). [Compound 41]

(Physical Properties)

• ¹ H-NMR (solvent: deuterated chloroform): δ: 1.71 (m, 8H) 2.68 (m, 4H), 2.99 (m, 4H), 4.09-4.18 (m, 12H), 4.70 (d, 1H), 5.09 (t, 1H), 5.46 (t, 1H), 5.52 (m, 1H), 5.84 (dd, 2H), 6.11 (m, 2H), 6.37 (dd, 2H), 7.01-7.10 (m, 4H), 7.35-7.41 (m, 2H), 7.59-7.64 (m, 4H) 8.078.15 (d, 2 ¹³ C NMR (solvent: deuterated chloroform): δ: 25.2, 30.3, 35.2, 63.9, 64.1, 70.7, 74.5 , 78.5, 81.2, 115.9, 116.2, 124.5, 128.4, 128.9, 129.8, 129.9, 130.5, 130.8, 166.1, 172.5
• Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
• (Melting point) 64 ° C

The in the formula (16) shown compound has 64 ° C a low melting point and is characterized by excellent Solubility in the other liquid crystal compounds out.

The As in the embodiment 1 obtained calculation result for the HTP showed a high value of HTP = 51.

Comparative Example 1

A reaction vessel equipped with stirrer, condenser and thermometer was charged with 21.4 g (100 mmol) of 4- (4-hydroxyphenyl) benzoic acid, 2.5 g of potassium iodide, 0.7 g of tetrabutylammonium bromide and 400 ml of ethanol and stirred at room temperature. Here, a 25% aqueous solution of 12 g of sodium hydroxide was slowly titrated. After completion of the titration, the reaction vessel was kept at 50 ° C and 20 g (150 mmol) of 6-chloropropanol slowly titrated. After completion of the titration, the reaction vessel was then heated to 70 ° C and the reaction allowed to proceed for a further 3 hours. After completion of the reaction, it was neutralized with 10% aqueous hydrochloric acid solution and extracted with ethyl acetate, and after drying over sodium sulfate, by concentration of the solvent, synthesized 22 g of the compound shown in the formula (17). [Compound 42]

Then, in a reaction vessel equipped with stirrer, condenser and water separator, 22 g (71 mmol) of the compound synthesized as described above and shown in formula (17), 10 g (140 mmol) of acrylic acid, 1 g of p-toluenesulfonic acid and 100 ml of toluene were added , Thereafter, the reaction vessel was heated and the reaction allowed to reflux for 4 hours while refluxing with toluene. After completion of the reaction, the reaction liquid was washed with a saturated sodium bicarbonate solution, then neutralized with 10% aqueous hydrochloric acid solution and further washed with a saturated saline solution, and then the organic phase was dried with sodium sulfate anhydride. By distilling off the solvent, 19 g of the compound shown in formula (18) was obtained. [Compound 43]

Next, in a reaction vessel 19 equipped with a stirrer, condenser and thermometer g (51 mmol) of the compound synthesized as described above and shown in formula (18), 3.8 g (27 mmol) of isosorbitol, 0.9 g of dimethylaminopyridine and 200 ml of dichloromethane and the reaction vessel then cooled to equal or below 5 ° C on an ice bath held. Under a nitrogen atmosphere, 9 g (71 mmol) of diisopropylcarbodiimide was then slowly added dropwise. After completion of the titration, the reaction vessel was then returned to room temperature, and the reaction was allowed to proceed for 5 hours. After filtration of the reaction liquid, 100 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, and further washed with a saturated saline solution, and then the organic phase was dried with sodium sulfate anhydride. After distilling off the solvent, the product was refined in a silica gel column and recrystallized to obtain 14 g of the objective compound shown in formula (19). The melting point of this compound was equal to or above 150 ° C and was not measurable. [Compound 44]

(Physical Properties)

• ¹ H-NMR (solvent: deuterated chloroform): δ: 1.55-1.45 (m, 8H), 1.71 (m, 4H), 1.83 (m, 4H), 2.66 (m, 4H), 2.96 (m, 4H), 3.93 (m, 2H), 3.98 (m, 2H), 4.03 (s, 4H), 4.30 (t, 4H), 4.50 (t, 4H), 5.35 (s, 2H), 5.65 (dd, 2H), 5.85 (d, 2H), 5.85 (d, 2H), 6.15 (q, 2H), 6.55 (d, 2H), 7.10 (d, 4H), 7.50 (m, 4H), 8.12 (d, 4H), 8.13 ( d, 4H)
• Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
• (Melting point)> 150 ° C

The in Comparative Example 1 under the formula (19) shown compound has none for the compounds of the present invention characteristic spacer with ester bonds. That is why the Melting point high and in terms of solubility in others There were also problems with connections. The same way As in the embodiment 1 obtained calculation result for the HTP showed a high value of HTP = 33, but due to poor solubility, only 0.5% could be added become.

Comparative Example 1

20 g (120 mmol) of 3- (p-hydroxyphenyl) propionic acid, 2 g of potassium iodide, 0.5 g of tetrabutylammonium bromide and 400 ml of ethanol were prepared in a reaction vessel equipped with stirrer, condenser and thermometer and stirred at room temperature. Here, a 25% aqueous solution of 12 g of sodium hydroxide was slowly titrated. After completion of the titration, the reaction vessel was kept at 50 ° C and 25 g (144 mmol) of benzyl bromide slowly titrated. After completion of the titration, the reaction vessel was then heated to 70 ° C and the reaction allowed to proceed for a further 3 hours. After completion of the reaction, it was neutralized with 10% aqueous hydrochloric acid solution, extracted with ethyl acetate, and synthesized after drying over sodium sulfate by concentration of the solvent 44 g of the compound shown in the formula (20). [Compound 45]

Next, in a reaction vessel equipped with a stirrer, condenser and thermometer, 32 g (123 mmol) of the compound synthesized as described above and shown in formula (20), 7.7 g (55 mmol) of isosorbitol, 1.8 g of dimethylaminopyridine and 500 ml of dichloromethane were prepared and the reaction vessel kept cooled to not more than 5 ° C on an ice bath. Under a nitrogen atmosphere, 19 g (150 mmol) of isopropylcarboimide was then slowly added dropwise. After completion of the titration, the reaction vessel was then returned to room temperature, and the reaction was allowed to proceed for 5 hours. After filtration of the Reaction liquid was added to the filtrate 200 ml of dichloromethane, washed with 10% aqueous hydrochloric acid solution and further washed with a saturated saline solution, and then the organic phase was dried with sodium sulfate anhydride. After distilling off the solvent, the product was refined in a column of five times the amount (weight ratio) of silica gel to obtain 27 g of the compound shown in formula (21). [Compound 46]

Subsequently, in an autoclave equipped with a stirrer, 11 g (17.7 mmol) of the compound synthesized as described above and represented in formula (21), 1 g of palladium on carbon and 150 ml of ethanol were added and then at 0.1 MPa a reduction reaction of the hydrogen (reaction temperature 50 ° C, duration 3 hours). After filtration of the reaction liquid and distilling-off of the solvent, 7.8 g of the compound shown in formula (22) was obtained. [Compound 47]

Next, in a reaction vessel equipped with a stirrer, condenser and thermometer were added 13.8 g (100 mmol) of 4-hydroxybenzoic acid, 2.5 g of potassium iodide, 0.7 g of tetrabutylammonium bromide and 400 ml of ethanol, and stirred at room temperature. Here, a 25% aqueous solution of 12 g of sodium hydroxide was slowly titrated. After completion of the titration, the reaction vessel was kept at 50 ° C and 20 g (150 mmol) of 6-chlorohexanol slowly titrated. After completion of the titration, the reaction vessel was then heated to 70 ° C and the reaction allowed to proceed for a further 3 hours. After completion of the reaction, it was neutralized with 10% aqueous hydrochloric acid solution, extracted with ethyl acetate, and synthesized after drying over sodium sulfate by concentration of the solvent 17 g of the compound shown in the formula (23). [Compound 48]

Then, in a reaction vessel equipped with stirrer, condenser and water separator, 17 g (71 mmol) of the compound synthesized as described above and shown in formula (23), 10 g (140 mmol) of acrylic acid, 1 g of p-toluenesulfonic acid and 100 ml of toluene were added , Thereafter, the reaction vessel was heated and the reaction allowed to reflux for 4 hours while refluxing with toluene. After completion of the reaction, the reaction liquid was washed with a saturated sodium bicarbonate solution, then neutralized with 10% aqueous hydrochloric acid solution and further washed with a saturated saline solution, and then the organic phase was dried with sodium sulfate anhydride. By distilling off the solvent, 22 g of the compound shown in formula (24) was obtained. [Compound 49]

Next, in a reaction vessel equipped with stirrer, condenser and thermometer, 7 g (16 mmol) of the compound synthesized as described above and shown in formula (24), 9.2 g (32 mmol) of the compound shown in formula (22), 0.43 g Dimethylaminopyridin and 100 ml of dichloromethane and the reaction vessel kept on an ice bath cooled to equal to or below 5 ° C. Under a nitrogen atmosphere then 4.7 g (38 mmol) of isopropylcarboimide was slowly added dropwise. After completion of the titration, the reaction vessel was then returned to room temperature, and the reaction was allowed to proceed for 5 hours. After filtration of the reaction liquid, 100 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, and further washed with a saturated saline solution, and then the organic phase was dried with sodium sulfate anhydride. After distilling off the solvent, the product was refined in a silica gel column and recrystallized to obtain 13 g of the compound shown in formula (25). [Compound 50]

(Physical Properties)

• ¹ H-NMR (solvent: deuterated chloroform): δ: 1.55-1.45 (m, 8H), 1.71 (m, 4H), 1.83 (m, 4H), 2.66 (m, 4H), 2.96 (m, 4H), 3.76 (m, 2H), 3.90 (s, 4H), 4.03 (t, 4H), 4.17 (t, 4H), 4.29 (t, 1H), 4.76 (t, 1H), 5.18 (d, 2H), 5.78 (d, 2H), 6.15 (q, 2H), 6.37 (d, 2H), 6.96 (d, 4H) 7.23 (d, 4H), 7.25 (m, 4H), 8.12 (d, 4H)
• ¹³ C-NMR (solvent: deuterated chloroform): δ: 25.6, 28.4, 28.8, 30.1, 30.2, 35.3, 35.5, 64.3, 67.9, 73.0, 73.8, 80.6, 85.7, 114.0, 121.3, 121.5, 128.3, 129.0, 130.2 , 131.9, 137.1, 137.4, 149.2, 163.0, 164.5, 165.9, 171.3, 171.6
• Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
• (Melting point) 79 ° C

The in formula (25) shown at 79 ° C a low melting point and also excellent solubility in the other liquid crystal compounds, but that up the same manner as obtained in Embodiment 1 Calculation result of HTP showed a low value of HTP = 12.

(Embodiment 5)

Preparation of the polymerizable liquid crystal components

Polymerizable liquid crystal components (ingredient 1) having the composition shown below were prepared. [Compound 51]

The polymerizable liquid crystal components had a good compatibility stability and had a cholesteric liquid crystal phase. As a photoinitiator for these ingredients, 1% of benzyldimethylketal (commercial name: IrgaCure 651, product of Chiba Specialty Chemicals) was added to prepare polymerizable liquid crystal components (component 2). This component 2 was injected by vacuum injection into 5 cm long and 5 cm wide polyimide cells with a gap width of 5 microns. When these were then irradiated with a high-pressure mercury vapor lamp for 120 seconds with 4 mW / cm ^{2 of} ultraviolet rays, the component 2 was polymerized while maintaining a uniform orientation, thus obtaining the optically anisotropic materials. These optically anisotropic materials had good circular polarization properties.

(Embodiment 6)

Preparation of the polymerizable liquid crystal components

Polymerizable liquid crystal components (component 3) having the composition shown below were prepared. [Compound 52]

The polymerizable liquid crystal components had a good compatibility stability and had a cholesteric liquid crystal phase. As a photoinitiator for this ingredient, 1% benzyldimethyl ketal (commercial name: IrgaCure 651, product of Chiba Specialty Chemicals) was added to prepare the polymerizable liquid crystal components (Ingredient 4). Ingredient 4 was injected by vacuum injection into 5 cm long and 5 cm wide polyimide cells with a gap width of 5 μm. When these were then irradiated with a high-pressure mercury vapor lamp with 4 mW / cm ² UV rays for 120 seconds, the component 4 was polymerized while maintaining a uniform orientation and thus the optically anisotropic materials were obtained. These optically anisotropic materials had good circular polarization properties.

(Comparative Example 3)

Preparation of polymerizable liquid crystal components

Polymerizable liquid crystal components (ingredient 5) having the composition shown below were prepared. [Compound 53]

The polymerizable liquid crystal components had a cholesteric liquid crystal phase on, but the alignment was uneven. As the photoinitiator for this ingredient, 1% of benzyldimethyl ketal (commercial name: IrgaCure 651, product of Chiba Specialty Chemicals) was added to prepare the polymerizable liquid crystal component (Ingredient 6). This component 6 was injected by vacuum injection into 5 cm long and 5 cm wide polyimide cells with a gap width of 5 microns. When irradiated with 4 mW / cm ² UV rays for 120 seconds with a high pressure mercury vapor lamp, the optically anisotropic material exhibited circular polarization properties, but was whitish clouded and uneven.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• JP 09-506088 W [0004]
• JP 2003-137887 A [0004]

Claims (5)

Polymerizable Chiral Liquid Crystal Compounds Represented by General Formula (I) [Compound 1]

(in the formula, R ¹ and R ² are independent polymerizable groups, S ¹ and S ² are independent spacer groups, Y ¹ and Y ² represent mutually independent -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -OCOOS ³ O-, -OS ³ OCOO-, -CH = CH-COO- and -OCO-CH = CH-, S ³ is an alkyl group having 2 to 6 carbon atoms and alkoxy groups, A ¹ and A ⁴ are independent 1 , 4-phenylene groups and naphthalene-2,6-diyl groups, A ² and A ³ are independent 1,4-cyclohexylene groups, 1,4-phenylene groups, pyridine-2,5-diyl groups, pyrimidine-2,5-diyl groups, naphthalene 2,6-diyl groups, tetrahydronaphthalene-2,6-diyl groups, 1,3-dioxane-2,5-diyl groups, but A ¹ , A ² , A ³ and A ⁴ may also be represented by independent alkyl groups, halogenated alkyl groups, alkoxy groups Halogens, cyano groups or nitro groups, while B ¹ and B ² are mutually independent -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -OCOO -, -CO-NR ¹¹ -, NR ^{1 1} -CO-, -SCH ₂ -, -CH ₂ S-, -CH = CH-COO-, -OCO-CH = CH-, -CH ₂ CH ₂ -COO-, -OOC-CH ₂ CH ₂ -, -NR ¹¹ -CO-, -CO-NR ¹¹ -, -CO-CH = CH-, -CH ₂ -, -C ₂ H ₄ -, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH = N-, -N = CH-, -N = N-, -CH = CH-, -CF = CH- , -CH = CF-, -CF = CF-, -C≡C-, or represent simple covalent bonds, X ¹ represents -CO-, -CH = CH-CO-, -CH ₂ CH ₂ -CO-, - CH ₂ -, -C ₂ H ₄ -, -CF ₂ -, -NR ¹¹ -CO- or simple covalent bonds, X ² represents -OC-, -OC-CH = CH-, -OC-CH ₂ CH ₂ - , -CH ₂ -, -C ₂ H ₄ -, -CF ₂ -, -CO-NR ¹¹ - or simple covalent bonds (with respect to B ¹ , B ² , X ¹ and X ² R ¹¹ represents independent hydrogen atoms or alkyl groups with 1 to 4 carbon atoms), m and n represent 0, 1 or 2). Polymerizable chiral compounds according to claim 1, wherein A ² and A ³ are independent 1,4-cyclohexylene groups, 1,4-phenylene groups, naphthalene-2,6-diyl groups, tetrahydronaphthalene-2,6-diyl groups (A ² and A ³⁾ are also substituted by independent alkyl groups, halogenated alkyl groups, alkoxy groups, halogens, cyano groups or nitro groups), B ¹ and B ² are mutually independent -O-, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -C ₂ H ₄ -, -C≡C-, or represent simple covalent bonds, X ¹ represents -CO-, -CH = CH-CO-, -OC-CH ₂ CH ₂ -, X ² represents -OC-, -OC-CH = CH-, -OC-CH ₂ CH ₂ - where m and n represent 0 or 1 or 2. Polymerizable chiral compounds according to claim 1 or 2, wherein at least one of m and n is 0. Liquid crystal components, the polymerizable chiral Compounds according to one of claims 1 to 3 included. Optically anisotropic materials as defined in claim 4 Use liquid crystal components.