JPS5884858A - Azo-based multicolor dyestuff and liquid crystal composition and display containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI{X is -OCOR<1> or -COOR<1>[R<1> is (cyclo)alkyl cyclohexyl, (3-18C alkyl, aryl, halogen-substituted) phenyl, etc.]; Y is H, (cyclo) alkyl, nitro, cyano, aryl, halogen, group of formula II (R<2> and R<3> are each H, alkyl, etc.), etc.; Z<1>-Z<3> are each H, halogen, methyl, OH, cyano, etc.; n is 0-2}. EXAMPLE:A compound of formula III. USE:Liquid crystal display elements. PROCESS:A reaction between a compound of formula IV and a second compound of formula R<1>X<2> (X<1> and X<2> are each OH, or carboxylic acid halide; being not same at the same time) is carried out to yield the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an azo pleochroic dye, a liquid crystal composition containing the dye, and a display.

A pleochroic dye is a dye that exhibits the property that the light absorption intensity differs depending on the direction of the dye molecule. In other words, for this dye, the absorption intensity is highest when the direction of the absorption transition moment is parallel to the electric vector of light, and it becomes perpendicular! The absorption intensity is the smallest at .

In the liquid crystal display element described above, the orientation of the dye molecules can be changed by utilizing the fact that the alignment direction of the liquid crystal molecules changes when an electric field is applied. This allows the color of the liquid crystal display element to be changed by applying a voltage. Considering the liquid crystal compound as the host and the dye as the guest, this color change is called the guest-host effect.

Among the pleochroic dyes, 5% of them have parallel dichroism, and the direction of the absorption transition moment of visible light is almost parallel to the long axis direction of the molecule, and when dissolved as a guest molecule in the host liquid crystal. It has a property that the long axis of the dye molecules is aligned in the same direction as the alignment direction of the liquid crystal molecule axes.

For example, in a liquid crystal display element in which the liquid crystal composition consists of a pleochroic dye with parallel dichroism and a nematic liquid crystal compound with positive dielectric anisotropy, and which is subjected to homogeneous alignment treatment, the long axis of the dye molecules is aligned with the liquid crystal molecules. Similarly, a homogeneous orientation is formed parallel to the electrode surface and arranged in a constant direction. When white light propagates in the direction perpendicular to the electrode plane and polarized in the same direction as the alignment direction of the liquid crystal molecules through the liquid crystal layer in this aligned state, its electric vector becomes parallel to the dye molecules, A specific wavelength range is particularly strongly absorbed, and as a result, the liquid crystal layer assumes a strongly colored state. Next, when an electric field is applied to the liquid crystal layer, the long axes of the dye molecules form a homeotropic alignment because the dielectric anisotropy of the host liquid crystal is positive.

The long axis of the dye molecules is then perpendicular to the electric vector of the incident white light, so that the incident light is hardly absorbed by the dye molecules, resulting in the liquid crystal layer being in a weakly colored state.

The guest-host effect is naturally obtained not only by using a nematic liquid crystal compound as described above, but also by using, for example, a smectic liquid crystal compound or a cholesteric-nematic phase transition. In the case of utilizing the phase transition, each molecule of the cholesteric liquid crystal assumes a helical molecular arrangement in an element subjected to homogeneous alignment treatment. When white light propagates through the liquid crystal layer perpendicular to the electrode plane, the dye molecules are oriented in various directions, so that a specific wavelength range of all side light components is particularly strongly absorbed by the dye molecules. As a result, the liquid crystal layer becomes strongly colored. Next, when a voltage is applied to the liquid crystal layer, if the dielectric anisotropy of the cholesteric liquid crystal is positive, the helical molecular alignment is dissolved and the long axes of the dye molecules form a homeotropic alignment like the liquid crystal molecules. As a result, the liquid crystal layer becomes weakly colored.

The above pleochroic dyes have (1) high order parameters in the host liquid crystal (represented by the symbol S), (2) sufficient solubility in the host liquid crystal, and (3) high stability against light, heat, and electricity. (4) Any hue depending on the purpose is required. In particular, in order to enhance the contrast of the element, at least (1) and (2) above are required.

The order parameter S is defined by equation (1) and experimentally determined by equation (II). In the formula, the cos2θ term is time averaged, θ is the angle between the absorption axis of the dye molecule and the alignment direction of the liquid crystal molecules, and A/ and A┷ are parallel and parallel to the alignment direction of the liquid crystal molecules, respectively. It is the absorbance of a dye molecule for vertically polarized light.

S=(3cos2θ-1)/2...(1)S=(A/
-A┴)/(-2A┴+A/)...(II) For parallel dichroic pleochroic dyes, the closer the S value is to the theoretical maximum value of 1, the weaker the residual color in the colored state. This results in a bright and clear display with high contrast.

The object of the present invention is to provide a novel parallel dichroic pleochroic dye that satisfies the requirements (1), (2), and (3) above, a liquid crystal composition that can provide clear display with high contrast, and a display body. is to provide.

The relationship between the molecular structure and various properties of pleochroic dyes has not yet been fully investigated, and it is a difficult task to select a pleochroic dye that satisfies all of the above required performances in the desired hue. It is not easy to make an analogy and select from known materials.

As a result of extensive studies, the present inventors have found that by introducing a saturated or unsaturated ring, that is, a benzene ring or a cyclohexane ring, into an azo dye matrix through an ester bond, order parameters and solubility can be improved. We have discovered that this is the case and have completed the present invention.

That is, the gist of the present invention is the general formula (1) (wherein, ~18 alkyl groups, cycloalkyl groups, aryl groups, cyano groups.

Indicates a phenyl group substituted with a substituent selected from a halogen atom, an acyloxy group, a carboxylic acid ester group, and an arylazo group. Y represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a nitro group, a cyano group, a carboxylic acid ester group, an acyloxy group, an alkylsulfonyl group, an aryl group, a halogen atom, and R1 and R2 are hydrogen. Atoms, alkyl groups, or R1 and R2 may be linked to each other to form a nitrogen-containing ring. Z1, Z2, and Z3 are hydrogen atoms and halogen atoms.

It may be linked with a methyl group, hydroxy group, methoxy group, cyano group, or R2, R3 to form a nitrogen-containing ring, and Z1
, Z2 may be connected to each other to form an aromatic ring. n
indicates 0, 1, 2. ), a liquid crystal composition containing the dye, and a display.

To explain the present invention below, the azo pleochroic dye represented by the general formula (1) of the present invention is a novel dye with excellent order parameters and solubility in liquid crystal materials, and good stability. .

Specific examples of R1 in the general formula (1) include 1, a linear or branched propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, dodecyl group, octadecyl group; an alkylcyclohexyl group substituted with an alkyl group such as a cyclohexyl group; a cycloalkylcyclohexyl group substituted with a cycloalkyl group such as a cyclohexyl group, a propylcyclohexyl group, a butylcyclohexyl group, a heptylcyclohexyl group; a propoxy group;
Alkoxycyclohexyl group substituted with an alkoxy group such as butoxy group or octoxy group; carbon number 3 to 18
Phenyl group substituted with a linear or branched alkyl group; cyclohexyl group, propylcyclohexyl group,
Phenyl group substituted with cycloalkyl group such as butylcyclohexyl group, octylcyclohexyl group; Phenyl group substituted with aryl group such as phenyl group, butylphenyl group, octylphenyl group, butoxyphenyl group, heptyloxyphenyl group; cyano Phenyl group; phenyl group substituted with a halogen atom such as fluorine atom, chlorine atom, bromine atom; acetoxy group, pentanoyloxy group, octanoyloxy group, benzoyloxy group, butylbenzoyloxy group, octylbenzoyloxy group,
Phenyl group substituted with acyloxy group such as butoxybenzoyloxy group, pentylcyclohexylcarbonyloxy group, (wherein Y, Z1, Z2, Z3 and n have the same meanings as in formula [I]); methoxycarbonyl group, butoxycarbonyl group, octoxycarbonyl group, propylcyclohexyloxycarbonyl group, heptylcyclohexyloxycarbonyl group, phenoxycarbonyl group, butylphenoxycarbonyl group, nonylphenoxycarbonyl group, butoxyphenoxycarbonyl group, octoxyphenoxycarbonyl group, A phenyl group substituted with a carboxylic acid ester group such as a pentylcyclohexylphenoxycarbonyl group (wherein Y, Z1, Z2, Z3 and n have the same meanings as in formula [1]) ;(
In the formula, Y, Z1, Z2, Z3 and n have the same meanings as in formula [I].

Specific examples of Y in general formula [1] include a hydrogen atom; a methyl group, an ethyl group, a linear or branched propyl group,
Alkyl groups such as butyl group, heptyl group, octyl group, dodecyl group, octadecyl group; cycloalkyl groups such as cyclohexyl group, propylcyclohexyl group, butylcyclohexyl group, heptylcyclohexyl group; methoxy group, propoxy group, pentoxy group, octoxy group , alkoxy groups such as octadecyloxy groups; nitro groups; cyano groups; methoxycarbonyl groups, butoxycarbonyl groups, octoxycarbonyl groups, propylcyclohexyloxycarbonyl groups, heptylcyclohexyloxycarbonyl groups, butylphenoxycarbonyl groups, butoxyphenoxycarbonyl groups groups, carboxylic acid ester groups such as pentylcyclohexylphenoxycarbonyl groups; acyloxy groups such as acetoxy groups, pentanoyloxy groups, octanoyloxy groups, butylbenzoyloxy groups, butoxybenzoyloxy groups, and pentylcyclohexylcarbonyloxy groups; Alkylsulfonyl groups such as ethylsulfonyl, butylsulfonyl, and octylsulfonyl; aryl groups such as phenyl, butylphenyl, octylphenyl, butoxyphenyl, and heptyloxyphenyl; fluorine, chlorine, bromine, etc. Examples include the halogen atom;

When Y is the formula %, R2 and R3 are hydrogen atoms; methyl group,
Specific examples of Z1, Z2, and Z3 in which R3 and R4 may be linked to each other to form a nitrogen-containing ring such as a lower aruno group such as an ethyl group or a propyl group, or a piperazino group include a hydrogen atom or a fluorine atom. , halogen atoms such as chlorine atoms and bromine atoms, methyl groups,
A hydroxy group, a methoxy group, a cyano group, or one of Z1, Z2, and Z3 is R2, R3 as in the case where % formula % is % formula %
may be linked to form a nitrogen-containing ring, or Z1 and Z2 may be linked to each other to form a part of a benzene ring.

The azo pleochroic dye represented by the general formula (1) is, for example, a compound represented by the following formula [R1x2] R1x2...[II] (Formula x1 and x2 in [blank] and [seal] represent a hydroxy group or a carboxylic acid halide group; when x1 is a hydroxy group, x2 represents a carboxylic acid halide group,
When x1 is a carboxylic acid halide, x2 represents a hydroxy group. R1, Y, Z1, Z2, Z3 and n have the same meanings as in formula (1). ) is produced by reacting the compound represented by the formula by a known method.

The nematic liquid crystal used in the present invention can be selected from a wide range as long as it exhibits a nematic state within the operating temperature range.

Furthermore, by adding an optically active substance to such a nematic liquid crystal, it can be made to take a cholesteric state. Examples of nematic liquid crystals include the substances shown in Table 1.
Alternatively, these derivatives can be mentioned.

Table 1 In the above formula, R' represents an alkyl group or an alkoxy group,
represents a nitro group, a cyano group, or a halogen atom.

The liquid crystals listed in Table 1 all have positive dielectric anisotropy, but the known ester-based, azoxy-based, azo-based,
A Schiff-based, pyrimidine-based, diester-based, or biphenyl ester-based liquid crystal can also be mixed with a liquid crystal having positive dielectric anisotropy to form a positive liquid crystal as a whole.

Furthermore, it goes without saying that even a liquid crystal with negative dielectric anisotropy can be used as is if an appropriate element configuration and driving method are used.

The host liquid crystal substance used in the present invention may be any of the liquid crystal compounds shown in Table 1 or a mixture thereof, but the following four
Liquid crystal compounds sold by Merck under the trade name ZLI-1132 as a mixture of 38.4% by weight, 34.2% by weight, 18.1% by weight, 9.3% by weight, and the following: The liquid crystal substance sold under the trade name E-7 by British Drug House as a mixture of four types of liquid crystal compounds (W51% by weight, 25% by weight, 16% by weight, 8% by weight) is particularly useful in the present invention. I understand.

As the optically active substance added to the liquid crystal composition of the present invention, chiral nematic compounds such as 2-methylbudel group, 3-methylbutoxy group, 3-methylpentyl group, 3-
There are compounds in which optically active groups such as methylpentoxy, 4-methylhexyl, and Hiro-methylhexyl groups are introduced into nematic liquid crystal compounds. Also, JP-A-51-4554
Alcohol derivatives such as l-menthol and d-borneol shown in Publication No. 6, ketone derivatives such as d-camphor and 3-methylcyclohexane, carboxylic acid derivatives such as d-citronellaic acid and l-camphoric acid, and d-citronellal. Of course, optically active substances such as aldehyde derivatives, alkene derivatives such as d-linonene, other amines, amides, and nitrile derivatives can be used.

As the element used in the present invention, a known liquid crystal display element can be used. That is, generally, transparent electrodes in an arbitrary pattern are provided on two glass substrates, at least one of which is transparent, and a suitable spacer is interposed so that the electrode surfaces face each other.
An element is used in which a single glass substrate is arranged in parallel. In this case, the spacer determines the gap between the elements. The element gap is 3 to 100
μm, particularly 5 to 50 μm is preferred from a practical standpoint.

Examples of parallel dichroic pleochroic dyes used in the liquid crystal composition of the present invention and liquid crystal compositions using these dyes will be specifically explained below using Examples.

Example-1 A synthesis example of the pleochroic dye of the present invention is shown, and Table 2 shows the order parameter (S) and maximum absorption wavelength (λma
x).

Synthesis Example-1; 51.5 g of P-n-octylbenzoic acid was added to 50 g of dioxane.
ml thionyl chloride 4.89, dimethylformamide 0.
2 ml, reacted at 90 to 100°C for 2 hours, and
After cooling to 0°C, it is represented by the following structural formula. Azo compound 7 synthesized by a known method
．． 5g, dioxane 30ml, triethylamine 10m
1 was added, reacted at 80°C for 3 hours, cooled to room temperature, and then discharged into 500ml of water.
．． 3 dyes were obtained.

The dye exhibited a melting point of 127.1-127.5°C.

Synthesis Example-2 Trans-4-n-pentylcyclohexanecarboxylic acid 4369 was used instead of p-n-octylbenzoic acid in Synthesis Example-1, and the following structural formula was used instead of the azo compound represented by the structural formula -. Using the azo compound synthesized by the known method shown in Table 2, No. Sixteen dyes were obtained. The dye exhibited a melting point of 137.0-138.7°C.

Synthesis Example-3 Azo compound 3 synthesized by a known method represented by the following structural formula.
73g, dioxane 30ml, dimethylformamide 0
．． 1 ml and 2.4 g of thionyl chloride were reacted at 80°C for 2 hours, and after cooling to 50°C, 1.6 g of P-n-butylphenol and 5 ml of triethylamine were added and the mixture was heated to 80°C.
After reacting at ℃ for 2 hours, it was cooled to room temperature and discharged into 300 ml of water, and the resulting precipitate was purified by column chromatography to obtain No. 2 in Table 2. A dye of No. 23 was obtained, which exhibited a melting point of 185.8-186.8°C.

Synthesis Example 4 Instead of 3.77 g of the azo compound represented by the following structural formula in Synthesis Example 3, an azo compound 4 synthesized by a known method shown by the following structural formula was used.
23g, and the other conditions were the same as in Synthesis Example-3, using Table 2 No.
．． 25 dyes were obtained. This pigment is 196.8-197.5
The melting point was shown in °C.

Table 2 shows azo pleochroic dyes of the present invention synthesized according to Synthesis Examples 1 to 4 above.

The characteristics of each dye listed in Table 2 were investigated as follows. That is, to the above-mentioned phenylcyclohexane-based mixed liquid crystal ZLI-1132, one of the dyes shown in Table 2 was added as a pleochroic dye, and the mixture was heated to 70° C. or higher, so that the liquid crystal became an isotropic liquid. After stirring well, the process of leaving to cool was repeated to dissolve the dye.

The above-mentioned liquid crystal composition prepared in this manner was applied to an intersubstrate gap 10 consisting of two glass substrates having transparent electrodes and a homogeneous alignment treatment performed by applying and curing a polyamide resin on the surface in contact with the liquid crystal and then rubbing the same. It was encapsulated in an element of ~100 μm.

In the device subjected to the above alignment treatment, when a voltage is applied, the liquid crystal composition assumes a homogeneous alignment state as shown in FIG. 1, and the dye molecules also assume a similar alignment according to the host liquid crystal.

The structure of the liquid crystal display element shown in FIG. 1 is a common one except that the liquid crystal composition of this example is sealed.

In other words, the device is comprised of upper and lower transparent glass substrates 1, transparent electrodes 2 formed inside each substrate, and liquid crystal molecules 3 and pleochroic dye molecules 4 sandwiched between the substrates. and a liquid crystal composition. Incident natural light 5 passes through a polarizing plate 6 and is polarized in an incident light polarization direction 7, reaching the element as incident white polarized light 8. In addition, 9 is an observer.

The absorption spectrum of the liquid crystal composition of this example was measured using light polarized parallel to and perpendicular to the alignment direction of the liquid crystal molecules, and the absorbance A/ of the dye for each of these polarized lights was A and the maximum absorption wavelength were determined. In determining the absorbance of the dye, corrections were made for absorption by the host liquid crystal and glass substrate and reflection loss of the element. The S value was calculated from the above-mentioned formula (1) using the value A/ of the absorbance of the dye for each of the above-mentioned polarized lights and the value on A obtained in this way.

Accelerated aging tests were conducted to gain insight into the practical stability of the dyes listed in Table 2. That is, the above-mentioned liquid crystal composition in which each dye shown in Table 2 was dissolved was sealed in the above-mentioned device and left in a sunshine weather meter for about 100 hours, and the rate of decrease in absorbance and rate of increase in current consumption value were monitored.

The light source of the sunshine weather meter used in this example was a carbon arc lamp, and the conditions in the sample chamber were such that the temperature was approximately 50 DEG C. and no humidification or water sprinkling was performed.

As a result, when the above test was performed while protecting the above element with an ultraviolet cut filter, the accelerated deterioration test was 100%.
For each dye in Table 2, the absorbance decrease rate is 1 over time.
The increase in current consumption value when applying an AC of 0% or less, 32 Hz, and 5 V was within 2 times. Especially No. 2 in Table 2. 1.No
．． 2.No. 3.No. 6, No. 8, No. 9.No
．． 10, No. 11, No. 16 No. Dye No. 17 had a low fading property, and even when the above test was conducted without protecting the device with an ultraviolet cut filter, the rate of decrease in absorbance after 100 hours of accelerated deterioration was less than 10%.

Such excellent light resistance is comparable to the type of anthraquinone dye with high photostability shown below as a pleochroic dye known so far for guest-host display.

OOH Such high light resistance has not been known for conventional azo pleochroic dyes. It is no exaggeration to say that, for the first time, through the present invention, an azo pleochroic dye having the same level of light resistance as a highly light-fast anthraquinone pleochroic dye has been realized, at least in practical terms.

The dye according to the present invention has excellent thermal stability, and the decrease rate of the absorbance of the dye in the device after 100 hours at 90°C in the dark is less than 10%, and the increase rate of current consumption when applying 5V AC at 32Hs is It was less than twice that.

Example 2 The same liquid crystal as used in Example 1 was coated with No. 2 in Table 2. 3
Example-1 A liquid crystal composition to which 1.11 weight of the dye was added was prepared.
It was sealed in the element used in Example 1, and the absorption spectrum was measured in the same manner as in Example-1. However, the gap between the substrates was approximately 10 μm. FIG. 2 shows the absorption spectrum of the liquid crystal composition of this example. In the figure, curve i shows A/, and curve ii shows A soil. The maximum absorption wavelength in the visible region is 426n
m, and the S value of the dye of this example at the maximum absorption wavelength is 0.73.

Example-3 The same liquid crystal as that used in Example-1 was coated with No. 2 in Table 2. 2
A liquid crystal composition containing 0.19% by weight of the dye No. 3 was encapsulated in the same device as in Example-2 (however, the device gap was 50 μm), and the absorption spectrum was measured in the same manner as in Examples-1 and 2. FIG. 3 shows the absorption spectrum of the liquid crystal composition of this example. The maximum absorption wavelength in the visible region is 508n
m, and the S value of the dye of this example at the maximum absorption wavelength is 0.76.

[Brief explanation of drawings]

1 and 4 are schematic cross-sectional views of an example device of the present invention in a state where no voltage is applied, FIGS. 2 and 3 are spectral characteristic diagrams of the example device of the present invention, and FIG. FIG. 2 is a schematic cross-sectional view of an example element of the invention in a voltage applied state. 3...Liquid crystal molecule, 4...Pleochroic dye molecule Applicant: Mitsubishi Chemical Industries, Ltd. and one other person Figure 1, Figure 2, JL length 'nyyy') Figure 3, back and front (nm') Figure 4 ++t-6 75, lff1 11 Shiro Page 1 continued 0 Inventor Akio Mukao 3-1-1 Saiwai-cho, Hitachi-shi Stocks 3-1-1 Saiwai-cho, Hitachi City Hitachi, Ltd. Hitachi Research Institute @ Applicant Hitachi, Ltd., No. 1, Marunouchi-5-chome, Chiyoda-ku, Tokyo, Procedural Amendment (voluntary), Showa J7 Sunset Sun, JPO Director-General Shimada Harumari, 1 Indication of the case, 1960 Patent Application No. 113346, 2 Title of the invention Person responsible for correction of azo pleochroic dyes, liquid crystal compositions containing the dyes, and displays 3 Mitsubishi Kazuki Industries Co., Ltd. (#1 person) 4 agents 〒100 ( (1 person) 6 Contents of amendment (1) "Special Wfi 111! Scope of request" - Attachment 1:S
(2) "Detailed Description of the Invention" - ■ Correct the statement in line 1, o, 7, and J of the specification. ■Edit 1/11 - Correct line KrZ', Z"aZ"u" to ai to "zI~z9wa"・ノfrZ'-Z"t
Good #iZ'eZ'i &HZ'-Z'd' is corrected. - Correct the statement in the first line of Xie/J Makoto. 01'J 1st j) ji-2 rows KrY, z', Z", z"
> ``Yobi nke'' is corrected to ``ry, zr~211 and nke'' ・■ In the same 73rd negative line 73, it is corrected to ``Toarame wobi nwa''. ■ On the first page of the same page, in line J, correct the text ``n, J'' to ``Y, Zl~spear and n''. 0 Same No./j' @ bottom line - page 16, first line, "low-protection alkyl group such as propyl group" was corrected to "alkyl group such as propyl group, butyl group, hexyl group, octyl group" do. ■ In the striped line of the 6th page of the same page, the text ``rZl, Zfuzs'' is corrected to ``z'~z0''. ■No. 76 Negative V~! The line that says ``atom'' is changed to ``fluorine atom.'' [Stocks] Same! /d Put "Zl, 7.2" on the negative line; 2rZ', Z"-4 FiZ', Z'l;&UZ', Z
Correct it as "Ka J. [Share] 4 to 4/4 true to the bottom line. Q')krk'', ``.z1#-spear and n'' is corrected. ■The entries for compounds AJ/, AjJ, and JJ in Table #I of the same No. Jjx are corrected as follows. 137 The numbers in Figure 81 and Figure 1 are corrected as in the attached sheet. Separate Paper/Claims [(1) General formula (, I] (wherein, X represents 1000RI or -000RI) group 1
,, R1 is an alkylcyclohexyl group, a cycloalkylcyclohexyl group, an alkoxycyclohexyl group, or an alkyl fi having 13 to 1 carbon atoms, a dichlorofurkyl group, an aryl group, a cyano island, a halogen atom, an acyloxy group, or a carphone ester jlk and a phenyl group substituted with a substituent selected from arylazo groups. YFi hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, nitro group, cyano group, carbonyl ester group, acyloxy group, alkylsulfonyl group, aryl group, halogen atom, alkyl group, Rt, Rs are connected to each other may be used to form a nitrogen-containing ring.
L may be linked with a halogen atom, a methyl group, a hydroxyl group, a methoxy group, a cyano group, or R1, R1 to form a nitrogen-containing ring. An azo thread pleochroic dye represented by .ntiO.l, -. (2) General formula [110 alkylcyclohexyl group, alkoxycyclohexyl group, spanning, number of carbon atoms 3~/J' (7) alkyl group, cycloalkyl group, aryl group, cyano group, halogen atom, sodium atom group, M of the carboxylic acid ester, 1 and arylazo group are substituted with h6 substituents to show a phenyl group. Y is a hydrogen atom, an apalkyl group, a cycloalkyl group, an alkoxy group, C1, IE, a cyano group, a carboxylic acid diXfyb(7)g, an acylmexy group, an alkylsulfonyl group, an aryl group, an atom atom, and group, or 1. (x1 criminals are connected to each other, including
child, methyl group, hydroxy group, methoxy group, cyano group,
Alternatively, it may be connected to R2 and Rj to form a nitrogen-containing fJiI (, Zl. Z2-straddle Z4.Zl or zt and za may be connected to each other to form an aromatic ring. A liquid crystal set containing an azo pleochroic dye shown in . (3+ General formula [1) In the C formula, Xld-00OR' or u-00OR'noitx
t is an alkylcyclohexyl group, a cycloalkylcyclohexyl group, an alkoxycyclohexyl group, or an alkyl group or cycloalkyl group having 3 to 1 carbon atoms. Aryl groups, cyano groups, halogen atoms, acyloxy groups, and carboxylic acid esters. and a phenyl group substituted with a tIIL substituent carried from an arylazo group. Y is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a nitro group, a cyano group,
Carboxylic acid ester group, acyloxy group, alkylsulfonyl aryl group, halogen alkyl group, or R
2, R3 may be connected to each other (to form a nitrogen-containing ring). It may form an aromatic number region, and zl. z2 may be connected to Z4. Display material using a liquid crystal composite material, which refers to azo thread pleochroic dye with 4-4-

Claims (2)

[Claims] (1) General formula [1] (wherein 2 represents a group of -OCOR1 or -COOR,
R1 is an alkylcyclohexyl group, a cycloalkylcyclohexyl group, an alkoxycyclohexyl group, or
an alkyl group having 3 to 18 carbon atoms, a cycloalkyl group,
Aryl group, cyano group, halogen atom, acyloxy group. It shows a phenyl group substituted with a substituent selected from a carboxylic acid ester group and an arylazo group. Y represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a nitro group, a cyano group, a carboxylic acid ester group, an acyloxy group, an alkylsulfonyl group, an aryl group, a halogen atom, -N, :R group, R1 and R2 may be a hydrogen atom, an alkyl group, or R1 and R2 may be linked to each other to form a nitrogen-containing ring. Z1, Z2, Z3 may be connected to a hydrogen atom, a halogen atom, a methyl group, a hydroxy group, a methoxy group, a cyano group, or R1, R2 to form a nitrogen-containing ring, and Z1, Z2 may be connected to each other to form a nitrogen-containing ring. An aromatic ring may also be formed. n represents 0, 1, or 2. ) is an azo pleochroic dye. (2) General formula [■] (wherein, , a cycloalkyl group, an aryl group, a cyano group, a halogen atom, an acyloxy group, a carboxylic acid ester group, and an arylazo group. Y represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a nitro group, a cyano group, a carboxylic acid ester group, an acyloxy group, an alkylsulfonyl group, an aryl group, or a halogen atom, and R2 and R3 are hydrogen atoms. , an alkyl group, or R2 and R3 may be linked to each other to form a nitrogen-containing ring. Z1, Z2, Z3 may be linked to a hydrogen atom, halogen atom, methyl group, hydroxy group, methoxy group, cyano group, or R8, R9 to form a nitrogen-containing ring, and Z1, Z2 may be linked to each other to form a nitrogen-containing ring. An aromatic ring may also be formed. n represents 0, 1, or 2. ) A liquid crystal composition containing an azo pleochroic dye. (wherein,
an alkyl group having 3 to 18 carbon atoms, a cycloalkyl group,
Indicates a phenyl group substituted with a substituent selected from an aryl group, a cyano group, a halogen atom, an acyloxy group, a carboxylic acid ester group, and an arylazo group. Y is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group,
It represents a nitro group, a cyano group, a carboxylic acid ester group, an acyloxy group, an alkylsulfonyl group, an aryl group, a halogen atom, and R2 and R3 are hydrogen atoms, alkyl groups, or R2 and R3 are connected to each other. A nitrogen ring may be formed. Z1, Z2, and Z3 may be linked to a hydrogen atom, a halogen atom, a methyl group, a hydroxy group, a methoxy group, a cyano group, or R2 and R3 to form a nitrogen-containing ring, and Z
1 and Z2 may be linked to each other to form an aromatic ring. n represents 0, 1, or 2. ) A display using a liquid crystal composition containing an azo pleochroic dye.