Alignment film for liquid crystal and method for production thereof, as well as liquid crystal display device utilizing said alignment film and method for production thereof

Abstract: An alignment film for liquid crystal formed by monomolecular film comprising silane-type compounds with a linear hydrocarbon chain and method for production of said film, as well as liquid crystal display units utilizing said film and method for production of said display unit are disclosed.

Description: BACKGROUND OF THE INVENTION FIELD OF THE INVENTION This invention relates to the alignment film for liquid crystals usable for planar display panels which display television picture images and computer picture images and method for production thereof, as well as liquid crystal display devices (sometimes referred to as units) utilizing said film and method for production thereof. RELATED ART STATEMENT Liquid crystal display units such as color liquid crystal display panels have conventionally been produced by sealing liquid crystal between two substrates formed of a matrix of counter electrodes through an alignment film for liquid crystal formed by coating polyvinyl alcohol or polyimide using a spinner. These units, as shown in Figure 8, are produced by precoating poly(vinyl alcohol) or polyimide using a spinner in an insulating manner onto the respective electrodes of the first glass substrate (31) with a thin-film transistor (hereinafter abbreviated as TFT) array (33) with a picture element electrode (32), and the second glass substrate (34) formed of multiple red, blue, and green color filters (35) and a common transparent electrode (36) on top of the aforementioned color filters, forming an alignment film for liquid crystal (37) by rubbing, then assembling them facing each other by electrode side on either side of the spacer (38) using the adhesive (39); the twist nematic (hereinafter abbreviated as TN) liquid crystal (40), etc., is then inserted, forming a panel structure; polarizing plates (41, 42) are then installed on the front and back sides of the panel, and the TFT is operated while irradiating with the back light (43) so that the color picture image is displayed in the arrow direction A. However, the conventional production of an alignment films for liquid crystal involves dissolving polyvinyl alcohol or polyimide in an organic solvent, then forming a film using rotating coating methods, then finally rubbing it with a felt cloth; therefore, it was difficult to achieve uniform coating of the alignment film for liquid crystal panels with large surface areas, e.g., 14-inch display; further, rotating coating methods resulted in films up to several 5 µm thick, causing a large defect in performance of display panels such as ferroelectric liquid crystal requiring alignment films for liquid crystal with a thickness of approximately 1,000 Angstroms. Alignment films providing the desired properties of low thickness and a high degree of uniformity are disclosed in US-A-3,854,793. The films disclosed in said document are composed of silane-type surfactants with a linear hydrocarbon chain. However, it has been shown that the alignment properties of like films are not sufficient. An alignment film which provides the desired properties of low thickness and a high degree of uniformity and which additionally is at least principally suited to provide acceptable alignment properties is disclosed in EP-A-0 286 539, from which document the precharacterizing portion of appended Claim 1 departs. However, reliable formation of an alignment film described in said document is hardly achieved or only proceeds at a temperature of 100°C or more. In case that such high temperatures have to be applied, the alignment properties of the resulting film are strongly deteriorated. OBJECT AND SUMMARY OF THE INVENTION The purpose of this invention is to provide a highly efficient, uniform, yet thin alignment film for liquid crystal as defined in claims 1 and 3 and method for production thereof according to claims 7 and 10, as well as liquid crystal display devices utilizing said film and a method for production thereof as defined in claims 15 and 16, respectively. In conducting various tests to achieve the above-mentioned purpose, the inventors found that a film with superior uniformity in coating and a thickness of approximately 10 - 30 Angstroms could be achieved by mixing more than two types of chlorosilane-type compounds (also referred to as silane-type surfactants) in proportions of 10:1 to 1:10, and adsorbing the mixture onto the substrate to form a monomolecular film, and completed this invention. Liquid crystal display units using alignment films for liquid crystal formed related with this invention have characteristics well suited to the production of large scale display panels. BRIEF EXPLANATION OF THE DRAWINGS Figures 1, 3, and 5 show cross sectional views of the alignment film for liquid crystal of Examples of this invention magnified to the molecular level; Figures 2, 4, and 6 show conceptional cross sectional views of the alignment film for liquid crystal of Examples of this invention to which liquid crystal has been inserted; Figure 7 shows a cross sectional view of a liquid crystal display unit using the alignment film for liquid crystal of this invention; Figure 8 shows a cross sectional view of a liquid crystal display unit using the conventional alignment film for liquid crystal; Figure 9 shows the FTIR spectrum of an alignment film formed by adsorption method and an alignment film formed by conventional spin-coat method. The numbers and codes used in the figures are described below: 1 ... substrate; 2 ... monomolecular film; 3, 3a ... long hydrocarbon chain; 4, 4a ... short hydrocarbon chain; 5 ... liquid crystal; 6, 6a ... nematic liquid crystal portion; 7 ... nematic liquid crystal; 8, 8a ... ferroelectric liquid crystal portion; 9 ... ferroelectric liquid crystal; 11 ... first electrode group; 13 ... first substrate; 15 ... second electrode group; 16 ... second substrate; 17 ... alignment film for liquid crystal; 20 ... liquid crystal; 21 ... polarizer; 22 ... polarizer; 23 ... back light; A ... direction of picture image; 31 ... first glass substrate; 32 ... picture element electrode; 33 ... TET array; 34 ... second glass substrate; 35 ... color filter; 36 ... common transparent electrode; 37 ... alignment liquid crystal film for liquid crystal; 38 ... spacer; 39 ... adhesive; 40 ... twist nematic liquid crystal; 41 ... polarizer; 42 ... polarizer; 43 ... back light; G ... Green filter; B ... Blue filter; R ... Red filter. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS This invention solves the above-mentioned problem areas; one aspect of the invention is related with the alignment film for liquid crystal containing monomolecular film formed by adsorbing a mixture in 10:1 to 1:10 proportions of a chlorosilane-type compound with a long linear hydrocarbon chain and a chlorosilane-type compound with a hydrocarbon chain shorter than the aforementioned hydrocarbon chain onto the substrate. An even better alignment film for liquid crystal is produced by a monomolecular film formed by adsorbing a mixture in 10:1 to 1:10 proportions of a chlorosilane-type compound bonded to a liquid crystal molecule instead of a chlorosilane compound with a long linear hydrocarbon chain and a chlorosilane-type surfactant with a short hydrocarbon chain onto a substrate. Moreover, the aforementioned method for production of alignment film for liquid crystal is derived from the process of directly forming a single layer of monomolecular film onto the substrate by submerging the substrate into a nonaqueous organic solution into which two or more types chlorosilane-type compounds with varying lengths of linear hydrocarbon chain have been dissolved in proportions of 10:1 to 1:10, and causing the aforementioned chlorosilane-type compounds to be chemisorbed onto the substrate through chemical bonding between the silicon in the molecules of the aforementioned chlorosilane-type compound and the natural oxidization film on the surface of the aforementioned substrate. Further, the liquid crystal display unit of this invention achieves better characteristics in case of placing two alignment films for liquid crystal facing each other consisting of monomolecular films formed by adsorbing a mixture in 10:1 to 1:10 proportions of a chlorosilane-type compound with a long linear hydrocarbon chain and a chlorosilane-type compound with a hydrocarbon chain shorter than the aforementioned hydrocarbon chain facing each other onto a substrate, and inserting the liquid crystal between them, or placing two alignment films for liquid crystal facing each other consisting of monomolecular films formed by adsorbing a mixture in 10:1 to 1:10 proportions of a chlorosilane-type compound bonded to a liquid crystal molecule instead of a chlorosilane compound with a long linear hydrocarbon chain and a chlorosilane-type surfactant with a short hydrocarbon chain onto a substrate and inserting the liquid crystal between them. Moreover, the method for production of the liquid crystal display unit of this invention consists of a process chemisorbing chlorosilane-type compounds dissolved in 10:1 to 1:10 proportions in a nonaqueous organic solvent onto a first substrate on which a first electrode group have been installed and a second substrate with second electrode group facing each other by electrode side, then directly forming a single layer of monomolecular film as the alignment film for liquid crystal on each aforementioned substrate by chemically bonding the silicon in the aforementioned silane-type compound with the natural oxidization layer on the surface of the aforementioned substrate; a process affixing the aforementioned first substrate and second substrate facing each other with adhesive; and a process inserting the specified liquid crystal between the aforementioned first and second substrates. Examples of chlorosilane-type compounds with long linear hydrocarbon chains are: CH 3 -(CH 2 -) n -SiCl 3 (n = an integer 10 to 25); and CF 3 -(CH 2 -) n -SiCl 3 (n = an integer 10 to 25); Examples of chlorosilane-type compounds with short linear hydrocarbon chains are: CH 3 -(CH 2 -) m -SiCl 3 (m = an integer 1 to 5); and CF 3 -(CH 2 -) m -SiCl 3 (m = an integer 1 to 5). Further, compounds represented by: CF 3 -(CF 2 -)x-(CH 2 -)y-SiCl 3 (x and y are both integers, and the sum of X and Y is 10 to 25) may also be used as chlorosilane-type compounds with long linear hydrocarbon chains. Further, chlorosilane-type compounds bonded with ferroelectric liquid crystal such as azomethyne-type, azoxy-type, or ester-type liquid crystal, can be used instead of silane-type compounds with long linear hydrocarbon chains. Further, it is possible to alter the orientation characteristics by adsorbing a mixture in specified proportions of a chlorosilane-type surfactant with an optional substituent (R 1 ) other than trichlorosilyl group in a section of the long linear hydrocarbon chain and a trichlorosilyl terminal group, and a chlorosilane-type surfactant with an optional substituent (R 2 ) other than trichlorosilyl group in a section of the short linear hydrocarbon chain and a trichlorosilyl terminal group. Needless to say, any compound with a group can be used. To be used, the above-mentioned compounds are mixed in proportions of 10:1 to 1:10, then dissolved in a nonaqueous organic solvent, e.g., n-paraffin types such as n-hexadecane and n-cetane, CCl 4 , chloroform, or a mixture of these. Preferable substrates have a hydrophilic surface and forms a bond when reacting with the Si in the above-mentioned compounds. Because the structure of the alignment film for liquid crystal of this invention is that of direct monomolecular chemisorption of chlorosilane-type surfactants onto the surface of a substrate, it is uniform and thin. Further, through adsorbing a chlorosilane-type surfactant consisting of a mixture of a compound with long linear hydrocarbon chains and one with shorter carbon chains than the aforementioned compound in proportions of 10:1 to 1:10, the liquid crystal molecules can insert themselves into the gaps in the aforementioned long hydrocarbon chains; thus, controllability of alignment of the liquid crystal molecules can be improved. Moreover, by using chlorosilane-type surfactant whose molecules are bonded to the liquid crystal molecules, controllability of orientation is further improved. Examples Examples will be explained below using Figures 1 through 7. For example, as shown in Figure 1, after drying a hydrophilic substrate 1 (e.g., glass or quartz), a chlorosilane-type surfactant is adsorbed by chemisorption directly onto the entire surface, forming a monomolecular film (2) consisting of a chlorosilane-type surfactant (R 1 and R 2 in Figure 1 indicate substituents, but may also be hydrogen). For example, the compound of the formula: CH 3 -(CH 2 -) n -SiCl 3 (n = an integer, optimally 10 to 25) is used as a chlorosilane-type compound with a long linear hydrocarbon chain (3), and mixed in a 1:2 proportion with the compound of the formula: CH 3 -(CH 2 -) m -SiCl 3 (m = an integer 1 to 5) which has a shorter hydrocarbon chain (4) than aforementioned (3), then the resultant mixture is dissolved at an approximately 2 x 10 -3 to 5 x 10 -2 mol/L concentration in a mixed solution of n-hexadecune (80 v/v%), carbon tetrachloride (12 v/v%), and chloroform (8 v/v%); the aforementioned substrate (1) is immersed in this solution. At this time, the aforementioned substrate (1) has a hydrophilic surface, containing -OH groups in the surface. Thus, the -SiCl 3 group in the chlorosilane-type surfactant and the -OH group in the surface of the substrate (1) react, generating a bond of forming a single layer (10 to 30 Angstroms) of monomolecular film (2) comprising chlorosilane-type surfactants on the surface of the substrate (1). That is, conventional films are several hundred microns thick and require rubbing; by using the process of this invention, a hydrohobic monomolecular film (2) of 10 to 30 Angstroms, consisting of long linear hydrocarbon chains (3) and short hydrocarbon chains (4) in specific proportions in side-by-side can be formed on the substrate (1). Thus, as shown in Figure 2, when liquid crystal comes in contact with a substrate on which this type of monomolecular film has been formed, the molecules of the liquid crystal (5) insert themselves into the gaps in the monomolecular film of long hydrocarbon chains (3a), controlling the overall alignment of liquid crystals, forming an alignment film for liquid crystal. Further, (3a) and (4a) in Figure 2 are conceptional indications of the long hydrocarbon chain (3) and the short hydrocarbon chain (4) in Figure 1. Further, any compound may be used instead of the above-mentioned compounds, as far as such a compound has in its molecule groups capable of bonding with -OH groups. Moreover, as shown in Figure 3, by mixing a chlorosilane-type surfactant bonded with the same liquid crystal molecules as those of the sealed liquid crystal (e.g., nematic liquid crystal portion (6)) and a chlorosilane-type surfactant with a short hydrocarbon chain (4) in specified proportions, forming an alignment film for liquid crystal through adsorption, an alignment film for liquid crystal with especially superior characteristics of orientation to the sealed specific liquid crystal can be produced (R 3 in Figure 3 normally indicates substituents of hydrocarbon chains, but may be hydrogen atom). Thus, as shown in Figure 4, when the nematic liquid crystal (7) comes in contact with this type of substrate formed of a monomolecular film with a nematic crystal portion (6a), the molecules of the nematic liquid crystal (7) insert themselves into the space in the nematic crystal portion (6a), resulting in an excellent control of the overall liquid crystal orientation. Further, (4a) and (6a) shown in Figure 4 are conceptional indications of the short carbon chain (4) and the nematic liquid crystal portion (6) shown in Figure 3. Moreover, as shown in Figure 5, when the liquid crystal molecules to be sealed are ferroelectric liquid crystal, if the chlorosilane-type surfactant bonded to the ferroelectric liquid crystal portion (8) and the chlorosilane-type surfactant with a short hydrocarbon chain (4) are adsorbed in specified proportions, an alignment film for liquid crystal consisting of monomolecular film can be produced. Also, as shown in Figure 6, when the ferroelectric liquid crystal (9) comes in contact with a substrate with a monomolecular film containing this type of ferroelectric liquid crystal portion (8a), the ferroelectric liquid crystal molecules (9) insert themselves into the gaps in the ferroelectric liquid crystal portion (8a) of the monomolecular film, resulting in excellent control of the overall liquid crystal orientation. Further, (4a) and (8a) shown in Figure 6 are conceptional indications of the short carbon chain (4) and the nematic liquid crystal portion (8) shown in Figure 5. The examples described above are the most representative cases of alignment film for liquid crystal in which multiple chlorosilane-type surfactants mixed in specified proportions are concurrently chemisorbed, and of an alignment film for liquid crystal consisting of monomolecular film formed of a chlorosilane-type surfactant bonded to liquid crystal molecules and a chlorosilane-type surfactant with a short hydrocarbon chain which are adsorbed in specified proportions; however, in cases where an alignment film for liquid crystal is formed, through adsorption of only a chlorosilane-type surfactant with long linear hydrocarbon chains, an alignment film for liquid crystal able to orient the aforementioned liquid crystal almost perpendicularly is produced. As an example, Figure 9 shows the spectrum data measured by FTIR spectroscopy of an alignment film produced through adsorption compared to that of an alignment film produced by the conventional spin-coating method. The test compound used here was CH 2 =CH-(CH 2 -) 17 -SiCl 3 ; in the alignment film produced by adsorption (A), the absorptions of 2930 cm -1 and 2860 cm -1 were clearly split, but in the spin-coated oriented film (B), two absorption peaks overlapped; thus it was determined that the hydrocarbon chain is oriented almost perpendicularly to the substrate in the adsorbed monomolecular film, but the orientation in the spin-coated film was irregular at the molecular level. As shown in Figure 7, when producing a liquid crystal display unit using an alignment film for liquid crystal comprising monomolecular film of two types of chlorosilane-type compounds with different linear hydrocarbon chain lengths, chlorosilane-type surfactants which can efficiently control the orientation of long molecules dissolved in n-cetane are chemisorbed onto the second substrate (16), on which an electrode matrix has been formed in advance; thereby single layers of monomolecular film for alignment film for liquid crystal (17) areformed onto the surface of the aforementioned substrate through the chemical bonding between the silicone in the afore-mentioned chlorosilane-type surfactants and the -OH group in the natural oxidization film on the surface of the aforementioned substrate. Next, the aforementioned first substrate (13) is installed facing the second substrate (16) across the spacer (18), and then fixed using adhesive (19). Next, the specified liquid crystal (20) is inserted between the aforementioned first substrate (13) and the second substrate (16). It is then completed by assembling the polarizers (21) and (22). With this type of liquid crystal display unit, a picture image can be displayed in the direction of the arrow (A) by driving various transistors using video signals while irradiating the entire surface with the back light (23). As described above, because the alignment film for liquid crystal of this invention is structured by the direct monomolecular chemisorption of chlorosilane-type surfactants onto the surface of the substrate, it is efficient, uniform, and thin; further, it has the ability to improve the controlling characteristics of the liquid crystal molecule orientation. Moreover, by using chlorosilane-type surfactants with molecules bonded to the liquid crystal molecules, the controlling characteristics of the orientation is further improved. Also, in liquid crystal display units using the oriented film for liquid crystal of this invention, the insulating film between the liquid crystal and the electrode is extremely thin; therefore, the energy requirements to drive the liquid crystal display unit can be reduced. Additionally, more than two chlorosilane type surfactants may be mixed to produce an alignment film. Further, because the alignment film produced by the process of this invention, as well as liquid crystal cells using this alignment film, have the ability to line up the molecules with large intramolecular dipoles in a specific direction, extremely large secondary nonlinear optical effects can be generated.

Claims: An alignment film for liquid crystal which comprises a film (2, 17) of silane-type surfactants with a linear hydrocarbon chain (3, 3a, 4, 4a) which is formed by chemisorption wherein said chemisorption is effected by using a mixture in specified proportions of a silane-type surfactant with a first linear hydrocarbon chain (3, 3a) and a silane-type surfactant with a second linear hydrocarbon chain (4, 4a) characterized in that said silane-type surfactants are chlorosilane-type surfactants, said first linear hydrocarbon chain comprises 11 to 26 carbon atoms, said second linear hydrocarbon chain comprises 2 to 6 carbon atoms, and said film is a monomolecular film of said chlorosilane-type surfactants. An alignment film for liquid crystal according to Claim 1, wherein said monomolecular film (2, 17) is formed by adsorption in specified proportions of a chlorosilane-type surfactant with said first linear hydrocarbon chain (3, 3a) in which one terminal is a substituent other than trichlorosilyl group and another terminal is a trichlorosilyl group, and a chlorosilane-type surfactant with said second hydrocarbon chain (4, 4a) in which one terminal has a substituent other than trichlorosilyl group and another terminal is a trichlorosilyl group. An alignment film for liquid crystal which comprises a monomolecular film (2, 17) being formed by mixed adsorption in specified proportions of a chlorosilane-type surfactant bonded with liquid crystal molecules (6, 6a, 8, 8a) and a chlorosilane-type surfactant with a hydrocarbon chain (4, 4a) comprising 2 to 6 carbon atoms. An alignment film for liquid crystal according to Claim 3, wherein nematic liquid crystal (6, 6a) is utilized as a liquid crystal molecule. An alignment film for liquid crystal according to Claim 3, wherein ferroelectric liquid crystal (8, 8a) is utilized as a liquid crystal molecule. An alignment film for liquid crystal according to claim 5, wherein an azomethyne-type, an azoxy-type, or an ester-type liquid crystal is utilized as the ferroelectric liquid crystal (8, 8a). A method for production of an alignment film for liquid crystal which comprises forming a single layer of monomolecular film formed through chemisorption of two or more types of chlorosilane-type surfactants with different lengths of linear hydrocarbon chains mixed in specified proportions in a non-aqueous solvent onto the surface of a specified substrate on which electrodes are formed, causing the chemical bonding directly on the surface between the aforementioned surfactant and the surface of the aforementioned substrate, wherein a chlorosilane-type surfactant with a first linear hydrocarbon chain comprising 11 to 26 carbon atoms and a second chlorosilane-type surfactant comprising 2 to 6 carbon atoms are mixed and wherein the mixing proportions of the chlorosilane-type surfactants with said first linear hydrocarbon chain and those with said second hydrocarbon chain are 10:1 to 1:10. A method for production of an alignment film for liquid crystal according to claim 7, wherein a chlorosilane-type surfactant with said first linear hydrocarbon chain in which one terminal is a substituent other than a trichlorosilyl group and another terminal is a trichlorosilyl group, and a chlorosilane-type surfactant with said second hydrocarbon chain in which one terminal is a substituent other than a trichlorosilyl group and another end is a trichlorosilyl group are utilized. A method for production of an alignment film for liquid crystal according to claim 7, wherein a chemical substance in which one terminal is an group or a chemical substance represented by CH 3 -(CH 2 -) n -SiCl 3 (n = integer) is utilized as a chlorosilane-type surfactant. A method for production of an alignment film for liquid crystal which comprises forming a single layer of monomolecular film formed through chemisorption of two or more types of chlorosilane-type surfactants mixed in specified proportions in a non-aqueous solvent onto the surface of a specified substrate on which electrodes are formed, causing the chemical bonding directly on the surface between the aforementioned surfactants and the surface of the aforementioned substrate, wherein said "two types of chlorosilane-type surfactants" is a combination of a chlorosilane-type surfactant bonded with a liquid crystal molecule and a chlorosilane-type surfactant with a linear carbon chain comprising 2 to 6 carbon atoms. A method for production of an alignment film for liquid crystal according to claim 10, wherein a chlorosilane-type surfactant in which one terminal is bonded with a trichlorosilyl group, and a chlorosilane-type surfactant with a linear hydrocarbon chain comprising 2 to 6 carbon atoms in which one terminal of the linear hydrocarbon chain is a substituent other than trichlorosilyl group and another terminal is a trichlorosilyl group are utilized. A method for production of an alignment film for liquid crystal according to claim 10, wherein nematic liquid crystal is utilized as the liquid crystal molecules. A method for production of an alignment film for liquid crystal according to claim 10 which comprises the formation of a monomolecular film through the adsorption of a chlorosilane-type surfactant bonded with a ferroelectric liquid crystal as a liquid crystal molecule and a chlorosilane-type surfactant with a linear hydrocarbon chain comprising 2 to 6 carbon atoms in specified proportions. A method for production an alignment film for liquid crystal according to claim 13, wherein an azomethyne-type, an azoxy-type, or an ester-type liquid crystal is utilized as a ferroelectric liquid crystal. A liquid crystal display unit in which liquid crystal (20) is inserted between two alignment films (17) for liquid crystal according to any of claims 1 to 6 facing each other. A method for production of a liquid crystal display device in which a first substrate (13), with a first electrode group (11) fixed in a matrix in advance, and a second substrate (16), with a second electrode group (15) fixed so that they face the first electrode group, are processed according to any of claims 7 to 14, so as to form single layers of monomolecular film as the alignment film (17) for liquid crystal (20) on the surface of said substrate, respectively, by the chemical bonding between the silicon in the surfactant and the surface of said substrate; next said substrates are fixed by adhesive facing each other; and finally, the specified liquid crystal is inserted between said substrates. A method for production of a liquid crystal display unit according to claim 16, wherein n-paraffin is used as the non-aqueous solvent. A method for production of a liquid crystal display unit according to claim 17, wherein the n-paraffin is n-cetane.

Inventors: MINO NORIHISA, OGAWA KAZUFUMO, TAMURA HIDEHARU, MINO, NORIHISA, OGAWA, KAZUFUMI, TAMURA, HIDEHARU, OGAWA, KAZUFUMO
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1990
Main classification: G02F1
IPC codes: G02F1