ANTHRAQUINONE COMPOUNDS AND LIQUID-CRYSTAL COMPOSITION CONTAINING THEM

Abstract: Anthraquinone compounds represented by general for­ mula (I) and having a hue of yellow to yellowish orange, and compositions for liquid-crystal display elements obtained by dissolving said compounds in a liquid crystal, wherein X¹ and X² each represents a sulfur atom or a selenium atom, and R¹ and R² each represents a substituted or unsub­ stituted phenyl group, a substituted or unsubstituted naph­ thyl group, a substituted or unsubstituted pyridil group, or a substituted or unsubstituted pyrimidyl or tetrahydronaphthyl group, provided that the following cases are excluded: (1) X¹ = X² = S and R¹ = R² = substituted or unsubstituted phenyl group; (2) X¹ and X² = S, R¹ = substituted or unsub­ stituted naphtyl group and R² = a phenyl or naphtyl group; and (3) X¹ = X² = Se and R¹ = R² = tetrahydronaphthyl group.

Description: This invention relates to a novel anthraquinone type compound and a liquid crystal composition containing such compound. There has so far been known to effect color display in utilization of the guest-host effect between a pigment compound and liquid crystal by interposing between a pair of mutually opposing electrodes a liquid crystal composition prepared by dissolving a pigment compound into liquid crystal. The pigment compound to be used for such liquid crystal composition is required to have, among other things, high dichroic ratio, high solubility to the liquid crystal, and other properties. Thus, use of anthraquinone type compounds exhibiting yellow to orange-colored hue in the liquid crystal composition has been known Japanese Unexamined Patent Publication No. 73067/1982 and Japanese Unexamined Patent Publication No. 158262/1982). However, these conventionally known anthraquinone type compounds did not always satisfy the properties which are required of the pigment compound to be used in the liquid crystal composition as mentioned above. EP-A-0 059 095, discloses a compound wherein 1-, 5-positions of the anthraquinone structure are substituted with an aryl-thio group. However, the reference discloses nothing about a compound having a pyridyl or pyrimidyl subsituent. GB-A- 2 043 097 discloses a compound wherein 1-, 5-positions of the anthraquinone structure are substituted with a substituted or unsubstituted phenyl-thio group or a substituted or unsubstituted benzothiazinylthio group. There is nothing disclosed in the reference about a compound having a pyridyl or pyrimidyl substituent. JP-A-57-92080 discloses a compound wherein 1-, 5-positions of the anthraquinone structure are substituted with a substituted or unsubstituted heterocyclicthio group. However, the reference discloses nothing about a compound having a pyridyl group or a pyrimidyl group. DE-A-33 14 467 discloses a dye having a substituent represented by -SAr at the 1-, 5-positions of the anthraquinone structure. Examples of "Ar" include monocyclic or polycyclic groups such as phenyl, pyridyl, substituted phenyl and the like. However, all the -SAr substituents are composed of a combination of the same type of substituents and the reference discloses nothing about specific combinations of different types of substituents. The present invention aims at providing anthraquinone compounds which exhibit high dichroic ratio and good solubility to the liquid crystal, as well as liquid crystal compositions which are capable of exhibiting good color display. With a view to attaining such objective, the present inventors conducted repeated studies and researches, as the result of which they have come to a finding that, by introduction of the thio group into the first or fifth position of the anthraquinone nucleus of the anthraquinone type pigment compounds, the compounds exhibit high dichroic ratio and good solubility to liquid crystal, and that liquid crystal compositions containing such pigment compounds perform satisfactory color display. Based on this finding, they have arrived at the present invention. The present invention has its gist in providing anthraquinone type compounds and liquid crystal compositions containing such compounds, which are represented by the following general formula (I): wherein R¹ represents a pyridyl group which may optionally be substituted with a C₁-C₁₈ alkyl group or a pyrimidyl group which may optionally be substituted with a C₁-C₁₈ alkyl group; and R² represents a phenyl group which may optionally be substituted with a C₁-C₁₈ alkyl group, a C₁-C₁₈ alkoxy group, (wherein R³ denotes a C₁-C₁₈ alkyl group and m is an integer of from 1 to 5), (wherein R⁴ denotes hydrogen, a C₁-C₁₃ alkyl group or a cyclohexyl group), {wherein R⁵ denotes (R⁶ is hydrogen or a C₁-C₁₈ alkyl group), (R⁷ is hydrogen or a C₁-C₁₈ alkyl group) or (R⁸ is a C₁-C₁₈ alkyl group, ℓ being an integer of 1 to 5), and n is 0 or 1}, (R⁹ is hydrogen or a C₁-C₁₃ alkyl group) or halogen. In the following, detailed explanations will be given as to the structure of the anthraquinone type compounds according to the present invention, which is represented by the above-indicated general formula (I). The substituents for the phenyl group, the pyridyl group and the pyrimidyl group represented by R¹ and R² in the general formula (I) may be an alkyl group or an alkoxy group. The substituents for the phenyl group represented by R² may further be a halogen; those groups represented by (wherein m is an integer of 1 to 5; R³ denotes a alkyl group); those groups represented by (wherein n is an integer of 0 or 1; R⁵ denotes those groups represented by an aryl group, a cyclohexyl group, or a trans-4-alkylcyclohexyl group); or a trans-4-alkylcyclohexyl group. As the alkyl group in these substituents, there may be exemplified those alkyl groups having the carbon content of from 1 to 18. Such alkyl groups may further contain therein other substituents, for example, carboxylic acid ester. Also, as the above-mentioned alkoxy group, there may be exemplified those alkoxy groups having the carbon content of from 1 to 18. As the halogens, there may be exemplified fluorine, chlorine, and bromine. As the trans-4-alkylcyclohexyl group, there may be exemplified a trans-4-alkyl (e.g. alkyl having the carbon content of from 1 to 13) cyclohexyl group. The above-mentioned alkyl group or alkoxy group having the carbon content of 3 or more may be in the form of either the straight chain or the branched chain. In the following, explanations will be given in further detail as to the compound of the present invention as shown by the general formula (I). The invention includes an anthraquinone type compound represented by the general formula (IV): (where: R¹⁻³ denotes a pyridyl or pyrimidyl group optionally substituted by alkyl C₁₋₁₈; R²⁻³ denotes a phenyl group which may contain a substituent as given in connection with formula (I). Compounds of the above formula (IV), wherein R¹⁻³ is a pyridyl group or a lower alkyl-substituted pyrimidyl group; and R²⁻³ is a phenyl group or a phenyl group substituted by an alkoxy group, an alkyl group, a halogen, a 4-alkyl-phenyl group, a 4-alkylphenyloxycarbonyl-substituted alkenyl group, a trans-4-alkylcyclohexyloxycarbonyl group or an alkoxyalkoxycarbonyl-substituted alkenyl group, are particularly effective. The anthraquinone type compound represented by the above-indicated general formula (I) may be synthesized by a method represented, for example, by the following reaction formula: R¹ and R² in the general formulae (a), (b) and (c) of the above reaction formula have the same meaning as those in the above-indicated general formula (I). The synthesizing method represented by the above reaction formula can be carried out by use of an amide type solvent such as N,N-dimethylformamide, acetamide, N-methylpyrrolidone; or a solvent such as dimethylsulfoxide, sulforan, at a temperature condition ranging from 50 o C to 200 o C, preferably from 80 o C to 150 o C, in the presence of an acid binding agent, for example, an alkali metal carbonate such as potassium carbonate or sodium carbonate; alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; acetate such as potassium acetate or sodium acetate; or an organic acid binding agent such as triethylamine. The nematic liquid crystal to be used for the liquid crystal composition according to the present invention may be selected from fairly broad varieties, provided that they are able to exhibit the nematic state within a range of their operating temperatures. It may also be possible that such a nematic liquid crystal is caused to assume the cholesteric state by addition thereto of an optically active substance to be described later. As the nematic liquid crystal, there may be exemplified those substances as shown in No. 1 to No. 3 of the following Table 1 or their derivatives. In the above Table 1, R a denotes an alkyl group or an alkoxy group; and X represents an alkyl group, an alkoxy group, a nitro group, a cyano group, or a hologen. All the liquid crystals shown in Table 1 above have the positive dielectric anisotropy. However, even those known liquid crystals of ester type, azoxy type, azo type, Schiff type, pyrimidine type, diester type, or biphenyl ester type, the dielectric anisotropy of which is negative, can be used by mixing them with those liquid crystals having the positive dielectric anisotropy so that the mixture has the positive dielectric anisotropy. Further, even those liquid crystals having the negative dielectric anisotropy cna be used as they are, when they are adapted into an appropriate element construction and operated under an appropriate driving mode. While the host liquid crystal substance to be used for the liquid crystal composition according to the present invention may be selected from any of those liquid crystals shown in Table 1 above or their mixtures, the liquid crystal produced and marketed by Merck & Co. under a tradename of "ZLI-1132"; the liquid crystal produced and marketed by Merck & Co. under a tradename of "ZLI-1565"; and the liquid crystal produced and marketed by British Drug House & Co. under a tradename of "E-7", are recommended as useful. As the optically active substances to be used in the liquid crystal composition according to the present invention, there may be exemplified, chiral nematic compounds, for example, those compounds having optically active groups such as a 2-methylbutyl group, a 3-methylbutoxy group, a 3-methylpentyl group, a 3-methylpentoxy group, a 4-methylhexyl group, a 4-methylhexoxy group, etc. introduced into the nematic liquid crystals; alcohol derivatives disclosed in Japanese Unexamined Patent Publication No. 45546/1976 such as ℓ-menthol and d-borneol; ketone derivatives such as d-camphor and 3-methyl cyclohexane; carboxylic acid derivatives such as d-citronellic acid and ℓ-camphoric acid; aldehyde derivatives such as d-citronellal; alkene derivatives such as d-linonene; or other optically active substances such as amines, amides and nitrile derivatives. As the elements for performing the liquid crystal display by use of the liquid crystal composition according to the present invention, there may be used known liquid crystal display elements. In more detail, transparent electrodes of any arbitrary patterns are formed on each of two sheets of glass substrates, at least one of which is transparent, and then these two sheets of glass substrates are arranged in parallel relationship such that the surface sides of the glass substrates, on which the electrodes have been formed, may be mutually opposed with appropriate spacers being interposed between them to construct the liquid crystal display element to be used. In this case, a space gap for the element is determined by the spacers. A preferred range of the space gap for the liquid crystal display element may be from 3 to 100 µm, or more preferably from 5 to 50 µm from the practical standpoint. EXAMPLES In the following, the present invention will be explained more concretely in reference to practical examples, although the present invention is not restricted by these examples. Here, explaining briefly about the order parameter S for indicating the dichroism, it can be empirically found on any pigment compound from the following equation. In the above equation, A// and A⊥ respectively denote light absorbances of the pigment with respect to light beams which have been polarized in parallel with and perpendicular to, respectively, the direction of orientation of the liquid crystal. Specifically, the order parameter S is a value which indicates a display contrast of the guest-host type liquid crystal element, according to which the nearer this value comes theoretically to 1, the less becomes the degree of color remnant in the whitened portion, whereby a clear display of high brightness and contrast can be obtained. Example 1 (Reference) To 20 ml of N-methylpyrrolidone solution (hereinafter abbreviated as "NMP"), into which 90 mg of potassium hydroxide had been dissolved, there were added 270 mg of p-t-butylthiophenol and 600 mg of a compound represented by the following structural formula: and the batch was agitated for three hours at a temperature ranging from 120 o C to 130 o C. After lowering the temperature, the reaction liquid was released into a 30% aqueous solution of sodium chloride. Then, the deposited crystals were filtered and dried, after which they were refined in a column chromatography with silica gel (a product of Wako Junyaku Kogyo Kabushiki Kaisha, under a tradename of "C-200") as a carrier, and chloroform as a separating solvent, by which impurities were removed. As the result, there was obtained 400 mg of a compound represented by the follwing structural formula: This compound indicated its melting point in a range of from 249.0 o C to 249.5 o C . The anthraquinone type compound (pigment) according to the present invention which had been obtained in the above-described process steps was added to the afore-mentioned mixed liquid crystal ZLI-1565 (the tradename of the product of Merck & Co.), and the batch was heated to a temperature of 70 o C or higher, followed by agitating the same when it assumed a state of isotropic liquid, after which the mixture was left to cool. These process steps were repeated to well dissolve the above-mentioned compound (pigment) into the liquid crystal. The thus prepared liquid crystal composition according to the present invention was sealed into a space gap of 10 µm of an element composed of a pair of upper and lower glass substrates, each having a transparent electrode and been subjected to treatment, wherein the surface side of the glass substrate in contact with the liquid crystal was coated with a polyamide type resin, and cured, after which the resin was rubbed to have the homogeneous orientation. The above-mentioned liquid crystal within the element as treated for the above-mentioned homogeneous orientation took that homogeneous orientation when no electric voltage was applied to it, and the molecules of the pigment also took the same orientation in accordance with the host liquid crystal. The thus fabricated guest-host element was measured for its absorption spectrum by use of light polarized in parallel with the direction of orientation of the liquid crystal molecules, and light polarized vertically thereto, from which the maximum absorbing wavelength of the pigment to each of these polarized lights were found. In finding out the absorbance of the pigment, there was made corrections on the absorption by the host liquid crystal and the glass substrates as well as the reflection loss of the element. Also, using the absorbances A// and A⊥ with respect to each of the polarized lights, the values of the order parameter S were calculated based on the afore-mentioned equation of: Example 2 To 20 ml of N-methylpyrrolidone solution (hereinafter abbreviated as "NMP"), into which 180 mg of potassium hydroxide had been dissolved, there were added 520 mg of p-t-butylthiophenol and 1.0 g of a compound represented by the following structural formula: and the batch was agitated for three hours at a temperature ranging from 120 o C to 130 o C. After lowering the temperature, the reaction liquid was released into a 30% aqueous solution of sodium chloride. Then, the deposited crystals were filtered and dried, after which they were refined in a column chromatography with silica gel (a product of Wako Junyaku Kogyo Kabushiki Kaisha, under a tradename of "C-200") as a carrier, and chloroform as a separating solvent, by which impurities were removed. As the result, there was obtained 450 mg of a compound represented by the following structural formula: This compound indicated its melting point in a range of from 206.0 o C to 207.0 o C. The anthraquinone type compound (pigment) according to the present invention which had been obtained in the above-described process steps was added to the afore-mentioned mixed liquid crystal ZLI-1565 (the tradename of the product of Merck & Co.), and the batch was heated to a temperature of 70 o C or higher, followed by agitating the same when it assumed a state of isotropic liquid, after which the mixture was left to cool. These process steps were repeated to sufficiently dissolve the above-mentioned compound (pigment) into the liquid crystal. The maximum absorbing wavelength ( λ max) and the order parameter S of the thus prepared liquid crystal composition according to the present invention were measured and calculated in the same manner as in Example 1 above. The results from the above calculation are shown in No. 3-1 of Table 1 below. Example 3 To 20 ml of NMP solution, into which 120 mg of potassium hydroxide had been dissolved, there were added 360 mg of p-t-butylthiophenol and 700 mg of a compound represented by the following structural formula: and the batch was agitated for three hours at a temperature ranging from 120 o C to 130 o C. After lowering the temperature, the reaction liquid was released into a 30% aqueous solution of sodium chloride. Then, the deposited crystals were filtered and dried, after which they were refined in a column chromatography with silica gel (a product of Wako Junyaku Kogyo Kabushiki Kaisha, under a tradename of "C-200") as a carrier, and chloroform as a separating solvent, by which impurities were removed. As the result, there was obtained 360 mg of compound represented by the following structural formula: This compound indicated its melting point in a range of from 229.5 o C to 230.0 o C. The anthraquinone type compound (pigment) according to the present invention which had been obtained in the above-described process stops was added to the afore-mentioned mixed liquid crystal ZLI-1565 (the tradename of the product of Merck & Co.), and the pigment compound was dissolved into the liquid crystal in the same manner as in Example 1 above. Using the thus prepared liquid crystal composition according to the present invention, the maximum absorbing wavelength ( λ max) and the order parameter S thereof were measured and calculated in the same manner as in Example 1 above. The results from the above calculation are shown in No. 3-2 of Table 1 below. Example 4 To 20 ml of the NMP solution, into which 180 mg of potassium hydroxide had been dissolved, there were added 540 mg of p-t-butylthiophenol and 1.0 g of a compound represented by the following structural formula: and the batch was agitated for three hours at a temperature ranging from 120 o C to 130 o C. After lowering the temperature, the reaction liquid was released into a 30% aqueous solution of sodium chloride. Then, the deposited crystals were filtered and dried, after which they were refined in a column chromatography with silica gel (a product of Wako Junyaku Kogyo Kabushiki Kaisha, under a tradename of "C-200") as a carrier, and chloroform as a separating solvent, by which impurities were removed. As the result, there was obtained 380 mg of a compound represented by the following structural formula: This compound indicated its melting point in a range of from 208.0 o C to 209.0 o C. The anthraquinone type compound (pigment) according to the present invention which had been obtained in the above-described process steps was added to the afore-mentioned mixed liquid crystal ZLI-1565 (the tradename of the product of Merck & Co.), and the pigment compound was dissolved into the liquid crystal in the same manner as in Example 1 above. Using the thus prepared liquid crystal composition according to the present invention, the maximum absorbing wavelength ( λ max) and the order parameter S thereof were measured and calculated in the same manner as in Example 1 above. The results from the above calculation are shown in No. 3-3 of Table 1 below. Example 5 By the method as described in Example 2 above, there were produced and isolated the anthraquinone type compounds (pigments) according to the present invention, each having the structural formula as shown in No. 3-4 to No. 3-15 of Table 1 below. Using the thus obtained 19 pigment compounds, the maximum absorbing wavelengths ( λ max) and the order parameters S thereof were measured and calculated in the same manner as in Example 1 above. The results from the above calculations are shown in No. 3-4 through No. 3-15 of Table 1 below. INDUSTRIAL APPLICABILITY The novel anthraquinone type compound according to the present invention which forms yellow to orange-colored hue exhibits good solubility to liquid crystal, and the liquid crystal composition according to the present invention, which is obtained by dissolving the compound into the liquid crystal, has high dichroic ratio and has its value of the order parameter S of being closer to 1, hence it is capable of providing clear color display of bright and high contrast of the displayed image.

Claims: An anthraquinone type compound which is represented by the following general formula (I): wherein R¹ represents a pyridyl group which may optionally be substituted with a C₁-C₁₈ alkyl group or a pyrimidyl group which may optionally be substituted with a C₁-C₁₈ alkyl group; and R² represents a phenyl group which may optionally be substituted with a C₁-C₁₈ alkyl group, a C₁-C₁₈ alkoxy group, (wherein R³ denotes a C₁-C₁₈ alkyl group and m is an integer of from 1 to 5), (wherein R⁴ denotes hydrogen, a C₁-C₁₃ alkyl group or a cyclohexyl group), {wherein R⁵ denotes (R⁶ is hydrogen or a C₁-C₁₈ alkyl group), (R⁷ is hydrogen or a C₁-C₁₈ alkyl group) or (R⁸ is a C₁-C₁₈ alkyl group, ℓ being an integer of 1 to 5), and n is 0 or 1}, (R⁹ is hydrogen or a C₁-C₁₃ alkyl group) or halogen. The anthraquinone type compound according to Claim 1, wherein R² is a 4-substituted phenyl group. The anthraquinone type compound according to Claim 1, wherein R² is a phenyl group, the 4-position of which is substituted with a C₁-C₁₈ alkyl group, a C₁-C₁₈ alkoxy group, a cyclohexyl group, or a trans-cyclohexyl group having a C₁-C₁₃ alkyl substituent at the para-position. The anthraquinone type compound according to Claim 1, wherein R¹ is a pyridyl group. A composition for liquid crystal display element, which contains therein an anthraquinone type compound represented by the following general formula (I): wherein R¹ represents a pyridyl group which may optionally be substituted with a C₁-C₁₈ alkyl group or a pyrimidyl group which may optionally be substituted with a C₁-C₁₈ alkyl group; and R² represents a phenyl group which may optionally be substituted with a C₁-C₁₈ alkyl group, a C₁-C₁₈ alkoxy group, (wherein R³ denotes a C₁-C₁₈ alkyl group and m is an integer of from 1 to 5), (wherein R⁴ denotes hydrogen, a C₁-C₁₃ alkyl group or a cyclohexyl group), {wherein R⁵ denotes (R⁶ is hydrogen or a C₁-C₁₈ alkyl group), (R⁷ is hydrogen or a C₁-C₁₈ alkyl group) or (R⁸ is a C₁-C₁₈ alkyl group, ℓ being an integer of 1 to 5), and n is 0 or 1}, ( R⁹ is hydrogen or a C₁₋C₁₃ alkyl group) or halogen. The liquid crystal composition according to Claim 5, wherein R² is a 4-substituted phenyl group. The liquid crystal composition according to Claim 5, wherein R² is a phenyl group, the 4-position of which is substituted with a C₁-C₁₈ alkyl group, a C₁-C₁₈ alkoxy group, a cyclohexyl group, or a trans-cyclohexyl group having a C₁-C₁₃ alkyl substituent at the para-position. The liquid crystal composition according to Claim 5, wherein R¹ is a pyridyl group.

Inventors: IWANAMI, JUNKO, MIURA, KONOE, OZAWA, TETSUO
Applicants: MITSUBISHI KASEI CORPORATION
Application year: 1986
Main classification: C09B1
IPC codes: C09K19, C09B1