Polyimide-based liquid crystal aligning agent

Abstract: A liquid crystal aligning agent is provided which contains a polyimide comprising repeating units of general formula (VII) and optionally general formula (V): where A³ represents a tetravalent organic group of constituting a tetracarboxylic acid, A⁴ represents a divalent organic group of constituting a diamine, B represents a divalent organic group, R¹ and R⁵ may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, m represents an integer of 1 or more, and n represents an integer of from 1 to 6; provided that n, m, A³, A⁴, B, R¹ and R² may optionally be different ones in every repeating unit, and the combination of the repeating units are: a) a unit of formulae (V) and (VII), or b) a unit of formulae (VII) and the polyimide having a weight-average molecular weight of 10,000 or more and having a siloxane group in the side chain thereof.

Description: The present invention relates to a polyimide having a siloxane chain in its side chain, which is produced from a diaminobenzene starting material and has excellent heat-resistance and solvent-resistance and also excellent surface characteristics. It concerns a liquid crystal-aligning agent, which contains a polyimide having a siloxane chain in its side chain. The polyimide is produced from a diaminobenzene starting material having a siloxane chain and having excellent heat-resistance, solvent-resistance and surface characteristics. Where a substrate for a liquid crystal is treated with the liquid crystal-aligning agent, liquid crystal molecules provided on the substrate are aligned to the substrate, with an elevated tilt angle. In particular, the polyimide of the present invention, may be formed into a film which displays excellent heat-resistance, permeability and separatability when used in separation of a gaseous mixture or a liquid mixture. It may be thinned with ease to give a thin film having a sufficient film strength and a high separating capacity. The film is therefore useful as a separation film. Background of the Invention Hitherto, aromatic polyimides have widely been used as protecting materials, insulating materials and adhesives in the filed of electronic appliances and also as films or construction materials in other various fields, because of their high mechanical strength, heat-resistance and solvent-resistance. However, conventional polyimides have various drawbacks that the shaping workability is poor, the flexibility is poor, the wet stability is poor and the adhesiveness to inorganic materials such as silicone wafer or glass is insufficient. In order to overcome the drawbacks, modified polyimides having various chemical structures have been produced and studied in these days. Above all, a technique of producing a polyimide/polysiloxane block copolymer from a polyimide precursor to be obtained by substituting a part of the diamine component of a starting material of a polyimide by a polysiloxane having a diamino group at the both terminals thereof has been proposed, for the purpose of improving the flexibility and adhesiveness to inorganic materials among the necessary properties of polyimides. (For instance, refer to JP-A-57-143328, 58-7473, 58-13631, 61-83228 and 61-118424. The term "JP-A" as used herein means an "unexamined published Japanese patent application".) However, such block copolymers may have improved flexibility and adhesiveness but, on the other hand, have a problem that the filming capacity is lowered with increase of the siloxane content in the copolymer. There is another proposal of using an aromatic polyimide as a gas-separating film material. (Refer to JP-A-57-15819.) As the film of the kind made of such an aromatic polyimide has an excellent selective permeability especially to hydrogen gas, it has already been put to practical use. Since the gas permeability coefficient of such an aromatic polymide film is generally small, the film may well be applied to a gas having a relatively small molecular size and having a high diffusibility through the film, such as hydrogen gas. However, the film is unsuitable to separation of any other gas, such as oxygen or carbon dioxide because of such a small gas permeability coefficient. Additionally, there are few examples of using a polyimide film as a liquid-separating film. As one example, there is a report relating to separation of a water/ethanol mixture with a polyamic acid film which has been controlled with respect to its imidation percentage (refer to Polymer Preprints, Japan, Vol. 36, 1987, page 2021). However, also in the case, as the permeability coefficient of the reported film is relatively small, the film could not be said to be practically usable. In order to elevate the gas and liquid permeability of a polyimide film, copolymerization with a maerial having a high substance permeability like the above-mentioned polyimide/polysiloxane copolymer could be proposed. In fact, however, there is no report relating to gas or liquid separation with such a copolymer up to this date because of the problem on the filming property of the copolymer. On the other hand, the present inventors previously investigated various matters for the purpose of obtaining new film materials of aromatic polyimides which have excellent mechanical strength, heat-resistance and solvent-resistance of aromatic polyimides of themselves and have sufficient liquid permeability and separatability of a practical level. As a result, they have found that production of a polysiloxane macromonomer having a diaminophenyl group at one terminal thereof and having an organosiloxane repeating unit is possible, that polycondensation of the macromonomer gives a siloxane-containing polyimide via a siloxane-containing polyimide precursor, and that the film to be obtained from the resulting siloxane-containing polyimide has excellent mechanical strength, heat-resistance, solvent-resistance and flexibility and also has an excellent gas or liquid selective permeability (refer to JP-A-1-204931). On the other hand, in the field of a liquid crystal-aligning agent, an organic resin film such as a polyimide resin film or the like has heretofore been used most popularly as a substrate-treating agent, which is applied to a transparent substrate such as a transparent glass or plastic film as combined with a transparent electrode so as to orient nematic liquid crystal molecules almost in parallel to the treated substrate. In the case, it is known that the organic resin film as formed on the substrate is rubbed with a cloth in a determined direction, whereby the liquid crystal molecules as provided on the substrate are oriented to the rubbed direction to simultaneously yield a liquid crystal tilt angle of generally from 1 to 3 degrees to the surface of the substrate. As a method of greatly tilting and orienting liquid crystal molecules to the substrate, a method of depositing an inorganic film such as a silicon oxide film on a substrate by vapor deposition has heretofore been known. The present inventors earnestly investigated various polyimides so as to further improve the poor wet stability of polyimides as well as the surface and separation characteristics of siloxane-containing polyimide films. As a result, they have found a technique for producing a polyimide having a siloxane chain in its side chain, by polycondensation of a diaminobenzene derivative followed by imidation of the resulting polycondensate, and they have further found that the polyimides thus obtained have a high water-repellancy. In the field of liquid crystal-aligning agents, a method of rubbing an organic resin film as formed on a substrate has heretofore been carried out. In the method, however, it is difficult to sufficiently largely tilt and orient the liquid crystal molecules as provided on the rubbed film. On the other hand, a method of depositing an inorganic film on a substrate by vapor deposition is more complicated than the rubbing method and therefore it is not always a suitable method in practical industrial production of liquid crystal devices. Accordingly, it has been found that a satisfactory liquid crystal-aligning agent for liquid crystal cells can be produced from the polyimides of the present invention. Specifically the liquid crystal-aligning agent containing the polyimide used in the present invention yields a sufficiently large tilt angle when applied to a substrate of liquid crystal cell. On the basis of the findings, the present inventors have achieved the present invention. JP-A-62-142099 has proposed a liquid crystal-aligning agent, which comprises a reaction product of a long-chain alkylamine and a polyimide resin precursor. JP-A-64-25126 has proposed a liquid crystal-aligning agent, which comprises a polyimide derived from an alkyl group-containing diamine. However, a liquid crystal-aligning agent, which comprises a polyimide having a siloxane chain in its side chain, the polyimide being obtained from a siloxane-containing diaminobenzene derivative, as in the present invention, was not known to yield liquid crystal molecules having an extremely large tilt angle. (Detailed Explanation of the Invention) (Summary of the Invention) The object of the present invention is to provide a liquid crystal-aligning agent with an elevated tilt angle, which contains a polyimide having a siloxane chain. The present invention relates to a liquid crystal aligning agent which contains a polyimide comprising repeating units of general formula (VII) and optionally general formula (V): and where A 3 represents a tetravalent organic group constituting a tetracarboxylic acid, A 4 represents a divalent organic group constituting a diamine, B represents a divalent organic group, R 1 to R 5 may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 1 or more; provided that m, A 3 , A 4 , B, R 1 and R 2 may optionally be different in every repeating unit, and the combinations of the repeating units are: a) a unit of formulae (V) and (VII), or b) a unit of formulae (VII), the polyimide having a weight-average molecular weight of 10,000 or more and having a siloxane group in its side chain. The tetravalent organic group constituting a tetracarboxylic acid, which is represented by A 3 in formulae (V), and (VII), may include the following: Additionally, the group A 3 may further include a tetravalent alicyclic group, for example, those of the following formulae as well as a tetravalent aliphatic group. The divalent organic group constituting a diamine, which is represented by A 4 in the above-mentioned formula (V), may include the following formulae and may further include an alicyclic or aliphatic divalent organic group: As examples of the divalent organic group of B in the above-mentioned formula (VII), there are mentioned a substituted or unsubstituted methylene group as well as a polymethylene group, a silylene-polymethylene group, a phenylene-polymethylene group, an oxy-polymethylene group and a phenyleneoxy-polymethylene group each having 2 or more carbon atoms. The polyimides used in the present invention, which have a siloxane chain in their side chains and have repeating units of the above-mentioned formulae (V), and (VII), are produced from a diamine of the below-mentioned formula (XXI) and/or a diaminobenzene derivative of the below-mentioned formula (XIII) by the method of condensation followed by imidation, which will be mentioned below. A tetracarboxylic acid formula (XX) and its derivative, e.g. a tetracarboxylic acid dianhydride where A 3 represents a tetravalent organic group constituting a tetracarboxylic acid, and the four carbonyl groups bonded to A 3 are directly bonded to different carbon atoms, and derivatives thereof, is reacted and polymerized with a mixture comprising a siloxane chain-containing diaminobenzene derivative of formula (XIII) : where B represents a divalent organic group, R 1 to R 5 may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 1 or more, provided that R 1 and R 2 may be different in every repeating unit, and/or a diamine of formula (XXI): H 2 N - A 4 - NH 2 where A 4 represents a divalent organic group constituting a diamine, and/or a polyorganosiloxane of the above-mentioned formula (XIII) having a diaminophenyl group at one terminal thereof, in an organic polar solvent to give a polyamide acid which is polyimide intermediate. The concrete combinations of repeating units are as follows: a) a unit of formulae (V) and (VII) or b) a unit of formulae (VII). Specific examples of tetracarboxylic acids of the above-mentioned formula (XX) and derivatives thereof include aromatic tetracarboxylic acids, such as pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6naphthalenetetracarboxylic acid, 1,4,5,8naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3',4,4'diphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2bis(3,4-dicarboxyphenyl) propane, bis(3,4dicarboxyphenyl)dimethylsilane, bis(3,4dicarboxyphenyl)diphenylsilane, 2,3,5,6-pyridinetetracarboxylic acid, and 2,6-bis(3,4-dicarboxyphenoxy)pyridine, and dianhydrides and dicarboxylic acid di-acid halides thereof; alicyclic tetracarboxylic acids, such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, and dianhydrides and dicarboxylic acid di-acid halides thereof; and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and dianhydrides and dicarboxylic acid di-acid halides thereof. Tetracarboxylic acids of formula (XX) and derivatives thereof may be used singly or as a mixture of two or more of them. Specific examples of diamine compounds of the above-mentioned formula (XXI) include aromatic diamines, such as m-diaminobenzene, p-diaminobenzene, 2,7-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminoanthracene, 2,6-diaminoanthracene, 1,8diaminoanthracene, 3,3'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'diaminobenzophenone, 4,4,-diaminobenzophenone, 3,3'diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,3'diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3aminophenyl)propane, 1,3-bis-(4-aminophenoxy)benzene, 1,4-his(4aminophenoxy)benzene, 4,4'-di(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro2,2-bis(4-aminophenyl)propane, and 1,1,1,3,3,3-hexafluoro-2,2bis [4-(4-aminophenoxy)phenyl]propane; as well as diaminosiloxanes, for example, as follows: Additionally, other alicyclic diamines or aliphatic diamines may also be used. These diamines can be used singly or as a mixture of two or more. Polyorganosiloxanes of the above-mentioned formula (XIII), which have a diaminophenyl group at one terminal thereof, may be produced, for example, as follows: Specifically, a hydrogen-monoterminated polyorganosiloxane of general formula (XIV): where R 1 to R 5 may be same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 1 or more, provided that R 1 and R 2 may be different ones in every repeating unit, is reacted with a dinitro compound of a general formula (XV): where Y represents a group having a carbon-carbon double bond, by hydrosilylation in the presence of a catalyst to give an intermediate polyorganosiloxane having a dinitrophenyl group at one terminal thereof and represented by a general formula (XVI): where B represents a divalent organic group, R 1 to R 5 may be same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 1 or more, provided that R 1 and R 2 may be different in every repeating unit; and thereafter the dinitro group of the resulting intermediate compound is reduced by an ordinary method to a diamino group to thereby obtain the intended polyorganosiloxane of the above-mentioned formula (XIII). Some of hydrogen-monoterminated polyorganosiloxanes of the above-mentioned formula (XIV) where the polymerization degree m is 1 are commercially sold. (For example, Pentamethyldisiloxane as produced by Shin-etsu Chemical Industrial Co. is referred to.) Others of formula (XIV) where m is 2 or more may be produced, for example, in accordance with the reaction process mentioned below. Briefly, an equimolar amount of an alkyl lithium compound (RLi) is added to a tri-substituted silanol to give a silanolate anion, and using the resulting anion as an initiator, a cyclosiloxane compound is polymerized by living ring-opening polymerization, whereupon the reaction is terminated with a diorganohalogenosilane compound having one Si-H bond to give the intended compound of formula (XIV). In the case, by varying the proportion of the tri-substituted silanol to the cyclosiloxane compound to be fed into the reactor, the mean polymerization degree (m) of polyorganosiloxanes of the above-mentioned formulae (XIII), (XIV) and (XVI) may be controlled. (Referential Examples 2 to 4 mentioned hereinafter are referred to.) In these formulae, R 1 to R 5 , R 1' and R 2' may be same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, R represents an alkyl group or a phenyl group, X represents a halogen atom, provided that R 1 and R 2 may be different ones in every repeating unit, q represents an integer of from 3 to 6, r represents an integer of 1 or more, and (r q + 1) is equal to m in the above-mentioned formulae (XIV) and (XVI). Examples of alkyl lithium compounds to be used in the reaction (RLi in the above-mentioned reaction formula) include methyl lithium, ethyl lithium, n-butyl lithium, secbutyl lithium, t-butyl lithium, n-hexyl lithium and phenyl lithium. As examples of tri-substituted silanols of a general formula (XVII): where R 3 to R 5 may be same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, which are used for production of the above-mentioned hydrogen-monoterminated polyorganosiloxanes, there are mentioned trimethylsilanol, triethylsilanol, dimethyloctylsilenol, dimethyloctadecylsilanol, 3-chloropropylmethylsilanol, 3,3,3trifluoropropyldimethylsilanol, tridecafluoro-1,1,2,2tetrahydrooctyldimethylsilanol, diphenylmethylsilanol, triphenylsilanol and pentfluorophenyldimethyisilanol. Some or these silanol compounds are commercially sold. Anyway, these silanol compounds may easily be produced from the corresponding chlorosilanes. As examples of cyclosiloxane compounds of a general formula (XVIII): where R 1 and R 2 may be same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and q represents an integer of from 3 to 6, the following compounds are referred to. A mixture comprising two or more of these cyclosiloxane compounds may also be used in the present invention. As examples of diorganohalogenosilane compounds of a general formula (XIX): where R 1' and R 2' may be same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and X represents a halogen atom, which are used as a stopper in the above-mentioned reaction, there are mentioned dimethylchlorosilane, diethylchlorosilane, methyloctylchlorosilane, 3,3,3-trifluoropropylmethylchlorosilane, phenylmethylchlorosilane, diphenylchlorosilane, and pentafluorophenylmethylchlorosilane. The reaction of producing hydrogen-monoterminated polyorganosiloxanes of the above-mentioned formula (XIV) in accordance with the procedure mentioned above is Preferably effected in a solvent. As examples of usable solvents, organic solvents such as tetrahydrofuran, diethylether, hexane, cyclohexane and benzene are mentioned. The reaction is generally effected at a temperature near room temperature desirably in an inert atmosphere such as argon or nitrogen. It is indispensable that the dinitro compound of the above-mentioned formula (XV), which is used in production of the polyorganosiloxane of the above-mentioned formula (XVI) having a dinitrophenyl group at one terminal thereof from the hydrogenmonoterminated polyorganosiloxane of the above-mentioned formula (XIV), has a carbon-carbon double bond. As examples of the dinitro compound, the following compounds are referred to, where the nitro groups are bonded to any two carbon atoms of 2-positioned to 6positioned carbons of the benzene ring. Though not available as commercial products, these compounds can easily be produced, for example, by the method of Referential Example 1 which will be mentioned hereinafter. As the catalyst to be used for hydrosilylation of the dinitro compound of the above-mentioned formula (XV) with the hydrogenmonoterminated polyorganosiloxane of the above-mentioned formula (XIV), a platinum catalyst such as platinum metal, chloroplatinic acid or dicyclopentadienyl platinum dichloride is most popularly used. In addition, any other metal complexes such as palladium or rhodium complexes may also be used as the catalyst. For instance, usable catalysts include (Ph 3 P) 4 Pd, (Ph 3 ) 2 PdCl 2 , (PhCN) 2 PdCl 2 , (Ph 3 P) 3 RhCl, (Ph 2 PH) 2 PhCl, (Ph 3 P) 2 (CO)PhCl, and [(C 2 H 5 ) 3 P] 2 (CO)PhCl. In general, the amount of the catalyst to be used for the reaction may well be approximately from 1/100 to 1/1000 equivalent to the carbon-carbon double bond-having group. The reaction is desirably effected in a solvent. As the solvent usable for the reaction, there are mentioned, for example,hexane, benzene, toluene, acetone, trichloroethylene, carbon tetrachloride and tetrahydrofuran (THF). The reaction temperature is generally within the range of from 40°C to 100°C, and the reaction is preferably effected in an inert gas atmosphere such as argon or nitrogen. The liquid crystal-aligning agent of the present invention is coated on a transparent substrate, such as a transparent glass or plastic film substrate, and combined with a transparent electrode to form a polyimide resin film thereon, and thereafter the thus coated resin film is rubbed in a predetermined direction. In this way, it is used as an aligning agent for liquid crystal cells. In using the liquid crystal-aligning agent of the present invention, the tilt angle of liquid crystal molecules may freely be controlled or adjusted by varying the molar ratio of the repeating unit of formula (VII) in the polyimide. One object of the present invention is to use a certain class of polyimides as a liquid crystal-aligning agent so as to control the tilt angle of liquid crystal molecules on a substrate. The polyimides of the present invention are produced from starting materials of a diaminobenzene derivatives of formula (I) and/or formula (XIII), so that they may elevate the tilt angle of liquid crystal molecules on a substrate when they are applied to the substrate. In general, the ratio of the number of total mols of the diamine mixture to the number of total mols of the tetracarboxylic acid dianhydride to be used in the polymerization falls within the range of from 0.5 to 1.5, more preferably from 0.8 to 1.2. In general, where the ratio is nearer to 1 (one), the molecular weight of the polymer to be obtained is larger, like an ordinary polycondensation reaction. Where the polyimides of the present invention are used as a liquid crystal-aligning agent, the films to be formed therefrom are necessary to have a higher film strength than a determined one. In order to satisfy the requirement, the molecular weight of the polyimides of the present invention must substantially be 10,000 or more as a weight average molecular weight. The intermediate polyamic acid is dehydrated under heat at 100 to 400°C or is subjected to chemical imidation with a conventional imidating agent such as triethylamine/acetic anhydride to thereby give the intended siloxane-containing polyimide of the present invention, which has repeating units of the above-mentioned formulae (V), and (VII). Where the polyimides of the present invention thus produced are used as a liquid crystal-aligning agent, it is necessary to form a polyimide film having a thickenss of from 200 to 3000 Å on a substrate as combined with a transparent electrode. The method of forming such a polyimide film is not specifically defined. In general, for example, a solution of a polyamic acid intermediate is directly coated on a substrate and heated thereon for imidation to form a polyimide film on the substrate. As the solution of a polyamic acid intermediate to be used in the case, the above-mentioned polymer solution may directly be used; or alternatively, a polyamic acid intermediate as produced by the process mentioned above is put in a large amount of a poor solvent such as water or methanol, this is precipitated and recovered from the solvent and thus recovered precipitate may be re-dissolved in a solvent. The solvent to be used form forming the above-mentioned polymer solution of a polyamic acid intermediate and/or for redissolving the precipitated and recovered polyamic acid intermediate is not specifically defined, provided that it may dissolve the intended polyamic acid intermediate. As specific examples of such solvents, there are mentioned N,Ndimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, Nmethylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, and ϒ -butyrolactone. These solvents may be used either singly or as a combination of two or more of them. Other solvents than the above-mentioned ones, which could not form a uniform solution when used singly, may also be used in combination of the above-mentioned solvent(s) only within such an amount that may form a uniform solution. The temperature in the heating step for imidation of the polymer film as coated on a substrate may be selected from the range between 100°C and 400°C, and especially preferably it is selected from the range between 150°C and 350°C. If the temperature for imidation is lower than 150°C, the imidation percentage would lower so that alignment of liquid crystal molecules as provided on the coated substrate would be unstable. On the other hand, if it is higher than 350°C, the coated film would color to yield a problem on display of liquid crystal cells. Where the polyimides of the present invention are soluble in solvents, the polyamic acid intermediate to be obtained in accordance with the process mentioned above may directly be imitated in the form of its solution to give a solution of the resulting polyimide. In the case, the thus formed polyimide may be isolated from the solution and is again dissolved in any other pertinent solvent to give an intended polyimide solution. Accordingly, the resulting polyimide solution may be coated on a substrate, whereupon the solvent is evaporated out to finally form an intended polyimide film on the substrate. As mentioned above, a polyimide film having a thickness of from 200 to 3000 Å is formed on a transparent substrate, such as a transparent glass or plastic film substrate, as combined with a transparent electrode, and thereafter the film is rubbed. In this way, the polyimides of the present invention can be used as an aligning agent for liquid crystal cells. Since the polyimides of the present invention having a polysiloxane chain are novel polyimides which have high mechanical strength, heat-resistance and solvent-resistance, as characteristics of aromatic polyimides, and also have a high water-repelling property they can be applied to various fields where conventional polyimides have been used and also to other broader fields where conventional polyimides have not been used up to these days. Precisely, the novel polyimides of the present invention can be applied widely to protecting materials, insulating materials, adhesives, films, resist materials and construction materials in the field of electronic appliances and also to gas or liquid separation film materials in the other field. In particular, the polyimides of the present invention having a polysiloxane chain are useful as novel gas or liquid separation film materials having high film strength, heat-resistance, solvent resistance and water-repelling property and also having high permeability and separation capacity. Accordingly, using films formed from the polyimides of the present invention having a polysiloxane chain, separation of various gaseous mixtures or concentration of the separated gases, for example separation and concentration of oxygen from air or separation of hydrogen or carbon dioxide from air, as well as separation and concentration of an organic liquid from a water-containing organic liquid mixture may be effected extremely efficiently. The polyimides of the present invention is useful as a liquid crystal-aligning agent capable of giving a large liquid crystal tilting angle. Additionally, where the polyimides of the present invention is used as a liquid crystal-aligning agent, the liquid crystal tilting angle may be controlled by varying the amounts of the repeating units having a siloxane chain in the polyimides. Next, the present invention will be explained in more detail by way of the following Referential Examples, Working Examples, Experimental Examples and Use Examples. Referential Example 1: Production of 3,5-Dinitrobenzyl Allyl Ether: 20.0 g (101 mmol) of 3,5-dinitrobenzyl alcohol, 22 ml (254 mmol) of allyl bromide and 2.0 g (5.89 g) of tetrabuytlamonium hydrogensulfate were dissolved in 100 ml of tetrahydrofuran, and a solution of 8.0 g (200 mmol) of sodium hydroxide as dissolved in 16 ml of water was added thereto and stirred overnight at room temperature. The reaction solution was extracted with diethyl ether and the organic phase was taken out and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain a crude product, which was then purified by column chromatography with silica gel (using a developer of chroroform/hexane = 1/1). As a result, 19.1 g of 3,5-dinitrobenzyl allyl ether having a structural formula of: was obtained as a yellow oil. Yield: 80 %. The product was identified to have the above-mentioned structure by the following IR spectrum, 1 H-NMR spectrum and elementary analysis. IR Spectrum (cm -1 ): 3110(s), 2880(s), 1630(m), 1600(m), 1540(s, characteristic absorption by nitro group), 1470(m), 1345(s), characteristic absorption by nitro group), 1265(w), 1225(w), 1120(s, characteristic absorption by ether bond), 1075(s), 990(m), 910(m), 810(m), 758(m), 725(s). 1 H-NMR Spectrum, δ (CDCl 3 , ppm): 4.17(d, 2H, -OCH 2 CH=CH 2 ), 4.71 (s, 2H, PhCH 2 O-), 5.35(m, 2H, -OCH 2 CH=CH 2 ), 6.00(m, 1H, -OCH 2 CH=CH 2 ), 8.54(d, 2H, peak of benzene ring), 8.94(t, 1H, peak of benzene ring). Elementary Analysis (%): C: 50.40, H: 4.05, N: 11.47 (calculated values: C: 50.42, H: 4.24, N: 11.75) Referential Examples 2 to 4: Production of Hydrogen-monoterminated Polydimethylsiloxanes: Trimethylsilanol of the amount as indicated in Table 1 below was dissolved in 200 ml of dry tetrahydrofuran, and a hexane solution of an equimolar amount of n-butyl lithium was added thereto in an argon stream atmosphere. After stirred for 10 minutes, a solution of hexamethylcyclotrisiloxane of the amount also indicated in Table 1, as dissolved in 200 ml of dry tetrahydrofuran, was added thereto and stirred for 21 hours at room temperature. An excessive amount of dimethylchlorosilane was added to the reaction solution as a stopper to thereby stop the polymerization reaction. Next, the solvent was removed by distillation under reduced pressure, the salt as precipitated out was removed by filtration, and the resulting reaction mixture was heated at 120°C for 3 hours in vacuum of 0.1 mmHg or less to remove the non-reacted cyclosiloxane and the excessive stopper therefrom. As a result, a hydrogenmonoterminated polydimethylsiloxane having a structural formula of: was obtained as a colorless transparent viscous liquid. The thus obtained hydrogen-monoterminated polydimethylsiloxane and the 3,5-dinitrobenzyl allyl ether (about 1.2 molar times) as obtained in Referential Example 1 were dissovled in 50 ml of toluene and heated at 80°C in an argon stream atmosphere, and thereafter 100 µl of isopropanol solution (0.1 mol/liter) of chloroplatinic acid (H 2 PtCl 6 .6H 2 O) was added thereto and stirred for about 4 hours. The solvent was removed by distillation under reduced pressure to obtain a crude product, which was then purified by column chromatography with silica gel (using a developer of diethyl ether/hexane = 1/8). As a result, a polydimethylsiloxane having a dinitrophenyl group at one terminal thereof and having a structural formula of: was obtained as a pale yellow oil. Next, 5.0 g of 5 % palladium-carbon powder (product by Japan Engelhard Co.) was dissolved in 50 ml of ethanol and hydrogen was introduced thereinto for 15 minutes so as to activate the catalyst. Afterwards, a solution of the hydropolydimethylsiloxane having a dinitrophenyl group at one terminal thereof, which had been obtained by the above-mentioned reaction, as dissolved in 50 ml of ethanol was added to the thus activated catalyst solution, and the polymer was reduced for about 2 hours with introducing hydrogen into the reaction solution. After the catalyst was removed from the reaction solution by filtration, the solvent was concentrated under reduced pressure to obtain a crude product. This was then purified by column chromatography with silica gel (using a developer of ethyl acetate/hexane = 1/1). As a result, a hydropolydimethylsiloxane having a diaminophenyl group at one terminal thereof and having a structural formula of: was obtained as colorless transparent viscous liquid. The product was identified to have the above-mentioned structure by the following IR spectrum, 1 H-NMR spectrum and elementary analysis data. The yield of the polysiloxane thus obtained as well as the value of the average degree of polymerization (m) as obtained from the ratio of the peak areas of the 1 H-NMR spectrum are shown in Table 1 below. IR Spectrum (cm -1 ): 3370(s, characteristic absorption by amino group), 2950(m), 2860(m), 1600(s), 1530(s), 1470(m), 1350(s, characteristic absorption by diaminophenyl group), 1250(s, characteristic absorption by Si-C bond), 1190(s), 1000 to 1100 (s, characteristic absorption by Si-O-Si bond), 840(m). 1 H-NMR Spectrum, δ (CDCl 3 , ppm): 0.10(s, Si-CH 3 ), 0.89(t, -OCH 2 CH 2 CH 2 Si-), 1.63(m, -OCH 2 CH 2 CH 2 Si-), 3.43 (t, -OCH 2 CH 2 CH 2 Si-), 3.58(bs, Ph-NH 2 ), 4.35(s, PhCHCO 2 O-), 5.98 ( t ,peak of benzene ring), 6.13 (d, peak of benzene ring). No. of Referential Example Amount (g) of Trimethylsilanol Amount (g) of hexamethylcyclotrisiloxane Yield(g) Average Degree of Polymerisation (m) 2 2.00 9.86 9.22 7.7 3 1.00 7.40 6.54 10.3 4 1.00 9.86 8.89 13.5 Referential Example 5: Production of Polyimide Homopolymer : 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride and 4,4'-diaminodiphenyl ether were weighed each in an equimolar amount and dissolved in 15 ml of anhydrous N,N dimethylacetamide and stirred for one hour at 60°C in an argon gas atmosphere for polycondensation. The reaction solution was then cooled to room temperature and 3.32 ml (23.8 mmol) of triethylamine and 2.25 ml (23.8 mmol) of acetic anhydride were added and the mixture was heated to 100°C for 30 minutes to effect imidation. The reaction solution was then poured into 800 ml of methanol to precipitate the polymer formed. As a result, a polyimide homopolymer having a repeating unit of: was obtained. Preparation Reference Example 1: 0.058 g (0.1 mmol) of the following compound: as a fluorine-containing diaminobenzene derivative, 0.779 g (1.9 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter referred to as BAPB) as a diamine, and 0.39 g (2.00 mmol) of 1,2,3,4cyclobutanetetracarboxylic acid dianhydride (hereinafter referred to as CBDA) were dissolved in 7.5 g of N-methylphyrrolidone (hereinafter referred to as NMP) and stirred for 4 hours at 20°C for polycondensation to prepare a solution of a polyamic acid intermediate. The molecular weight of the polymer thus obtained was measured by gel permeation chromatography. As a result, the polymer had a weight average molecular weight of 1.1 x 10 5 in polyethylene glycol conversion. The solution was diluted with NMP to a concentration of 4 % by weight, and the diluted solution was then coated over a transparent electrode-having glass substrate by spin-coating at 3500 rpm and heat-treated at 180°C for 60 minutes to form a uniform polyimide film on the substrate. The coated film was rubbed with a cloth, and two substrates thus coated and rubbed were combined via a 50 µm-spacer therebetween with the rubbing direction of the two substrates being in parallel to each other. Then, a liquid crystal (ZLI-2293, product by Merk Co.) was introduced into the combined substrates to form a cell as homogeneously aligned. The cell was rotated in cross nicol, whereupon distinct light and darkness was admitted. Accordingly, it was ascertained that the liquid crystal being between the two rubbed substrates was well aligned to the rubbing direction. The tilt angle of the cell was measured by a crystal rotation mehtod to be 4.3 degrees. Working Example 1: A solution of a different polyamic acid intermediate was prepared in the same manner as in Preparation Reference Example 1 except that 0.082 g (0.1 mmol) of a silicone chain-containing diaminobenzene derivative of the following formula: was used in place of the fluorine-containing diaminobenzene derivative of Preparation Reference Example 1, that 0.779 g (0.1 mmol) of BAPB was used as a diamine, that 0.39 g (2.0 mmol) of CBDA was used as an acid anhydride, and that 7.1 g of NMP was used as a solvent. The molecular weight of the polymer thus obtained was measured by gel permeation chromatography. As a result, the polymer had a weight average molecular weight of 1.0 x 10 5 in polyethylene glycol conversion. Next, a cell was prepared in the same manner as in Preparation Reference Example 1 except that the polyamic acid intermediate solution prepared above was used. After this was rotated in a Cross Nicol, distinct light and darkness was admitted. Accordingly, it was ascertained that the liquid crystal being between the two rubbed substrates was well aligned to the rubbing direction. The tilt angle of the cell was measured by a crystal rotation method to be 8.2 degrees. Preparation Reference Example 2: 0.87 g (2.28 mmol) of a fluorine-containing diaminobenzene derivative of the following formula: 2.31 g (2.27 mmol) of a silicone chain-containing diaminobenzene derivative of the following formula: 0.46 g (2.27 mmol) of diaminodiphenyl ether (hereinafter referred to as DDE) as a diamine, and 3.03 g (6.82 mmol) of 1,1,1,3,3,3hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride (hereinafter referred to as 6FDA) as an acid anhydride were dissolved in 43.3 g of N,N-dimethylacetamide and stirred for 1 hour at 60°C for polycondensation to obtain a solution of a polyamic acid intermediate. Next, after the solution was cooled to room temperature, 3.32 ml (23.8 mmol) of triethylamine and 2.25 ml (23.8 mmol) of acetic anhydride were added thereto for effecting imidation at 100°C for 30 minutes. The reaction solution was then put in 800 ml of methanol, and the white precipitate thus formed was taken out by filtration and dried to obtain a white polyimide powder. The molecular weight of the polymer thus obtained was measured by gel permeation chromatography. As a result, the polymer had a weight average molecular weight of 8.03 x 10 4 in polystyrene conversion. 1.0 g of the powder was dissolved in 24 g of NMP to form a solution having a concentration of the total solid content of being 4 % by weight. The resulting solution was coated over a transparent electrode-having glass substrate by spin-coating at 3500 rpm and heat-treated at 180°C for 60 minutes to form a uniform polyimide coat on the substrate. Next, a cell was prepared in the same manner as in Preparation Reference Example 1, using the thus coated substrates, and the tilt angle of the cell was measured by a crystal rotation method. In the case, however, the tilt angle was found to be higher than the critical limitation of 15 degrees measurable by the crystal rotation method. The cell was observed with a polarizing microscope, whereupon a distinct isogyre was seen in the vicinity of the center of the visual field. Accordingly, the tilt angle was found to be almost 90 degrees. Preparation Reference Example 3: A solution of a different polyamic acid intermediate was prepared in the same manner as in Preparation Reference Example 1, except that 0.12 g (0.2 mmol) of a fluorine-containing diaminobenzene derivative of the following formula: 0.74 g (1.8 mmol) of BAPB as a diamine, and 0.60 g (2.0 mmol) of 3,4dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid anhydride (hereinafter referred to as TDA) as an acid anhydride were used. 0.9 ml (12 mmol) of pyridine and 0.9 ml (20 mmol) of acetic anhydride were added to the solution, which was then subjected to imidation at 50°C for 3 hours. The reaction solution was put in 500 ml of methanol, and the white precipitate formed was taken out by filtration and dried to obtain a white polyimide powder. The molecular weight of the polymer thus obtained was measured by gel permeation chromatography. As a result, the polymer had a weight average molecular weight of 5.0 x 10 4 in polyethylene glycol conversion. 1.0 g of the powder was dissolved in 24 g of γ-butyrolactone to form a solution having a concentration of the total solid content of being 4 % by weight, and the resulting solution was coated on a transparent electrode-having glass substrate by spin-coating at 3500 rpm and heat-treated at 180°C for 60 minutes to form a uniform polyimide film on the substrate. Next, using the thus coated substrates, a cell was prepared in the same manner as in Working Example 11, and this was rotated in a cross nicol, whereupon distinct light and darkness was admitted. Accordingly, it was ascertained that the liquid crystal being between the two rubbed substrates was well aligned to the rubbing direction. The tilt angle of the cell was measured by a crystal rotation method to be 1.5 degrees. Comparative Example 1: A solution of a comparative polyamic acid intermediate was prepared in the same manner as in Preparation Reference Example 1 except that the fluorine-containing diaminobenzene derivative was not used but 2.05 g (5.0 mmol) of BAPB, 0.97 g (4.93 mmol) of CBDA and 17.1 g of NMP were used. The molecular weight of the polymer thus obtained was measured by gel permeation chromatography. As a result, the polymer had a weight average molecular weight of 9.4 x 10 4 in polyethylene glycol conversion. Next a cell was prepared also in the same manner as in Preparation Reference Example 1, except that the polymer prepared above was used. The tilt angle of the cell was measured by a crystal rotation method to be 2.5 degrees. Comparative Example 2: A comparative white polyimide powder was prepared in the same manner as in Preparation Reference Example 2, except that the fluorine-containing diaminobenzene derivative was not used but 1.00 g (5.0 mmol) of DDE and 2.20 g (4.95 mmol) of 6FDA were dissolved in 18.1 g of N,N-dimethylacetamide. The molecular weight of the polymer thus obtained was measured by gel permeation chromatography. As a result, the polymer had a weight average molecular weight of 1.1 x 10 5 in polystyrene conversion. 1.0 g of the powder was dissolved in 24 g of NMP to form a solution having a concentration of the total sold content of 4 % by weight, and the solution was coated on a transparent electrode-having glass substrate by spin-coating at 3500 rpm and heat-treated at 180°C for 60 minutes to form a uniform polyimide coat on the substrate. Next, a cell was prepared in the same manner as in Preparation Reference Example 1, using the substrate as coated above. The tilt angle of the cell was measured by a crystal rotation method to be 2.9 degrees. Comparative Example 4: A comparative white polyimide powder was prepared in the same manner as in Preparation Reference Example 3, except that the fluorine-containing diaminobenzene derivative was not used but 2.05 g (5.0 mmol) of BAPB and 1.50 g (5.0 mmol) of TDA were used The molecular weight of the polymer thus obtained was measured by gel permeation chromatography. As a result, the polymer had a weight average molecular weight of 7.5 x 10 4 in polyethylene glycol conversion. Next a cell was prepared also in the same manner as in Preparation Reference Example 3, and the tilt angle of the cell was measured by a crystal rotation method to be 0.6 degree.

Claims: A liquid crystal aligning agent which contains a polyimide comprising repeating units of general formula (VII) and optionally general formula (V): and where A 3 represents a tetravalent organic group constituting a tetracarboxylic acid, A 4 represents a divalent organic group constituting a diamine, B represents a divalent organic group, R 1 to R 5 may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 1 or more; provided that m, A 3 , A 4 , B, R 1 and R 2 may optionally be different in every repeating unit, and the combinations of the repeating units are: a) a unit of formulae (V) and (VII), or b) a unit of formulae (VII), the polyimide having a weight-average molecular weight of 10,000 or more and having a siloxane group in its side chain.

Inventors: ABE TOYOHIKO, FUKURO HIROYOSHI, KOHTOH NORIAKI, NAGASE YU, TAKAMURA YURIKO, ABE, TOYOHIKO, FUKURO, HIROYOSHI, KOHTOH, NORIAKI, NAGASE, YU, TAKAMURA, YURIKO, ABE, TOYOHIKO, C/O NISSAN CHEM. IND., LTD., FUKURO, HIROYOSHI, C/O NISSAN CHEM. IND., LTD., KOHTOH, NORIAKI, C/O NISSAN CHEM. IND., LTD.
Applicants: NISSAN CHEMICAL IND LTD, SAGAMI CHEM RES, NISSAN CHEMICAL INDUSTRIES LTD., SAGAMI CHEMICAL RESEARCH CENTER
Application year: 1991
Main classification: C08G73
IPC codes: C07C217, C08G73, G02F1