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    • 专利摘要:
    The present invention relates to polyamic acid B (a radical derived from tetracarboxylic acids and a radical derived from a diamine, each of which does not have a side chain group, a radical having a side chain alkyl group of less than 3 carbon atoms, or a radical having a mixed composition thereof), a polyamide A polymer component and a solvent containing an acid A (at least one of a radical derived from tetracarboxylic acids and a radical derived from a diamine is a radical having a C3 or more branched alkyl group or a radical having a composition containing the radical) and a soluble polyimide It contains, the ratio of polyamic acid A and soluble polyimide is 1/99-99/1 by weight ratio, the total amount of polyamic acid A and soluble polyimide is 1 to 80 weight% in a polymer component, polyamic acid B Is 99 to 20% by weight in the polymer component, the proportion of the polymer component in the varnish composition total amount is 0 A liquid crystal display device having a varnish composition of .1 to 40% by weight and an alignment film formed by using the varnish composition.
    公开号:KR20020026477A
    申请号:KR1020017016735
    申请日:2000-06-21
    公开日:2002-04-10
    发明作者:다니오카사토시；후쿠이구미코；무라타시즈오；오노히로시；시미즈이츠오
    申请人:고토 기치；칫소가부시키가이샤；
    IPC主号:
    专利说明:

    Varnish composition and liquid-crystal display element
    [2] In liquid crystal display elements, display elements using nematic liquid crystals are mainstream. 90 ° Twisted matrix TN element, STN element, typically twisted by 180 ° or more, TFT liquid crystal display element using thin film transistor, IPS (In electric field oriented parallel to the circuit board plane) type with improved visual characteristics Display elements by various methods such as Plane Switching) liquid crystal display elements have been put into practical use. However, the progress of the liquid crystal display device is not only seen in the development of the display system. Improvement of the peripheral material is also actively performed for the purpose of the improvement of the characteristic of a liquid crystal display element. In addition, the liquid crystal aligning film is one of important factors related to the display quality of the liquid crystal display element, and its role is further increased as the quality of the display element is required.
    [3] Currently, the liquid crystal aligning film material mainly used is polyamic-acid resin and soluble polyimide-type resin which use imidize polyamic acid. However, in these conventional liquid crystal aligning film materials, it is still found that the liquid crystal display element has sufficient properties in general in terms of electrical properties, coating property of the alignment agent, pretilt angle (preferably large), alignment property of liquid crystal molecules, and the like. It is not becoming.
    [4] In order to improve the electrical properties (especially small residual charge and large voltage retention) of the liquid crystal display device, a method of mixing soluble polyimide with polyamic acid, etc. has been studied. In this case, however, the side chain group is contained in the soluble polyimide. Even if it is used, the pretilt angle does not increase very much (see Comparative Example). Therefore, when the pretilt angle of the magnitude | size which is about TFT element, STN element, etc. is needed, there exists a problem that a domain becomes easy to generate | occur | produce. Soluble polyimide has poor solubility compared to polyamic acid, and thus the selection range of its solvent is limited. However, even if a polyimide having solubility as good as polyamic acid is obtained, the polyimide alignment film using the same tends to invade into the liquid crystal due to its good solubility, and thus there is a risk that the orientation of the liquid crystal molecules is disturbed.
    [5] In addition, most of the good solvents for polyimide are aprotic polar solvents, and generally have problems such as large surface tension and apt to cause cissing during application. In the case of using polyamic acid, a solvent having a small surface tension such as cellosolve or carbitol is usually mixed in these solvents for the purpose of further improving the coatability. However, when many of these solvents are used as a solvent of a polyimide varnish to the extent that the applicability | paintability improves, the problem that polyimide becomes easy to precipitate will arise. In addition, the applicability of the polyimide varnish may be worse than that of the polyamic acid varnish, as well as the problem that the selection range of the aforementioned solvent is limited, and the polyimide may not have a carboxyl group.
    [6] In addition, there is a problem regarding the voltage retention with respect to the electrical characteristics of the liquid crystal display element. That is, the liquid crystal display element is not capable of applying the intervoltage displaying the image, and continuing the operation. The voltage is applied as shown in Fig. 2, and then the voltage is turned off in a short time. Image display is performed by the method which applies the voltage for a short time and turns off again. When the image is displayed in this manner, it is preferable that the applied voltage is kept as it is when the voltage is turned OFF. However, in practice, the applied voltage is not maintained as it is and a voltage drop occurs. If this voltage drop is large, the contrast of the display image is lowered. Therefore, the larger the voltage retention, the more preferable.
    [7] On the other hand, in the case where a polyamic acid having a long side chain group is mixed with a polyamic acid having no side chain group, a liquid crystal display device having a small residual charge may be obtained as a combination thereof, but even in this case, the improvement of the residual image is insufficient. Do.
    [8] If it is left for a while with voltage applied to the liquid crystal display element, charges accumulate, and even when the voltage is turned OFF, the accumulated charges remain and may be as if a voltage was applied. In such a state, even when the voltage is turned OFF or the image is switched, a phenomenon occurs in which the previous image is displayed or the traces of the image dimly remain. Such a phenomenon is usually called "afterimage."
    [9] It is commonly said that such residual afterimage is improved when the residual charge is small, and generally considered to be correct, but the mechanism by which the afterimage occurs is complicated, and the residual image cannot be sufficiently evaluated by simply measuring the residual charge. (It is true that the mechanism of afterimages is not sufficiently explained.)
    [10] In the present invention, the residual image of the cell is judged visually without actually measuring the residual charge in the evaluation of the residual image.
    [11] This phenomenon is particularly a problem in TN type TFTs and IPS devices.
    [12] An object of the present invention is to provide an aligning agent which overcomes and improves the above-mentioned drawbacks when mixing polyamic acid and soluble polyimide in a varnish for aligning agent having a great influence on the display characteristics of a liquid crystal display element.
    [13] That is, the pretilt angle can be arbitrarily adjusted (hence, it is difficult for domains to be generated), and there are few afterimages or no afterimages, and the varnish composition for the alignment agent having excellent applicability (no aggregation and a uniform film thickness is obtained). The task is to provide.
    [1] The present invention, when used as a liquid crystal alignment film, provides excellent properties in terms of electrical properties (voltage retention, residual charge or image sticking), proper pretilt angle, applicability or orientation of liquid crystal molecules, and the like. It relates to a varnish composition. Since the varnish composition of this invention is excellent in electrical characteristics, it can be used also for insulating films, protective films, etc. of the field of other electronic materials of a liquid crystal aligning film.
    [278] 1 is a circuit diagram used for measuring the voltage retention.
    [279] In FIG. 2, V s is a square wave having a gate pulse width of 69 Hz, a frequency of 60 Hz and a wave height of ± 4.5 V, and a period of polarity conversion is 16.7 ms. In addition, V D is a waveform read by an oscilloscope by applying V s to the source of the circuit shown in FIG. 1.
    [14] The present inventors have made an effort to improve the above problems in the prior art, and as a result, have found that the varnish composition according to a specific combination is useful as an alignment film material used in a liquid crystal display device, and has completed the present invention. That is, this invention is (1)-(20) described below.
    [15] (1) a polymer component containing polyamic acid B of formula (1), polyamic acid (A) of formula (2) and soluble polyimide of formula (3), and a solvent for dissolving such polymer component; And the ratio of soluble polyimide is 1/99 to 99/1 by weight, the total amount of polyamic acid A and soluble polyimide is 1 to 80% by weight in the polymer component, and polyamic acid B is 99 to 20 in the polymer component. A varnish composition, wherein the varnish composition is by weight and the proportion of the polymer component in the whole varnish composition is 0.1 to 40% by weight.
    [16]
    [17]
    [18]
    [19] In the above formula,
    [20] R 1 is a tetravalent organic radical derived from tetracarboxylic acids,
    [21] R 2 is a divalent organic radical derived from a diamine, each a radical having no side chain group, a radical having a side chain alkyl group having less than 3 carbon atoms, or a radical having a mixed composition thereof,
    [22] m is a positive integer,
    [23] R 3 is a tetravalent organic radical derived from tetracarboxylic acids,
    [24] R 4 is a divalent organic radical derived from a diamine,
    [25] At least one of R 3 and R 4 is a radical having a side chain group having 3 or more carbon atoms, or a radical having a composition containing the radical,
    [26] n is a positive integer,
    [27] R 5 is a tetravalent organic radical derived from tetracarboxylic acids,
    [28] R 6 is a divalent organic radical derived from a diamine,
    [29] p is a positive integer.
    [30] (2) The soluble polyimide of the formula (3) in the polymer component contains a radical having a branched group of 3 or more carbon atoms in at least one of the tetravalent organic radical R 5 derived from tetracarboxylic acids and the divalent organic radical R 6 derived from diamine. To (1), wherein the ratio of polyamic acid A and soluble polyimide is 10/90 to 90/10 by weight, and the total amount of polyamic acid A and soluble polyimide is 2 to 50% by weight in the polymer component. The varnish composition described.
    [31] (3) Of the tetravalent organic radicals R 1 derived from tetracarboxylic acids in the polyamic acid B of the general formula (1), 10 to 100 mol% thereof are tetravalent organic radicals derived from alicyclic tetracarboxylic acids, and divalent organic radicals R derived from diamines. A group consisting of a divalent organic radical derived from a divalent aromatic diamine, a divalent organic radical derived from an alicyclic diamine, and a divalent organic radical derived from a diamine containing two or more groups of an aromatic group, an alicyclic group and an aliphatic group. The varnish composition according to the above (1) or (2), which is a radical having a composition containing at least one divalent organic radical selected from.
    [32] (4) Of the tetravalent organic radicals R 1 derived from tetracarboxylic acids in the polyamic acid B of the general formula (1), 10 to 100 mol% thereof are tetravalent organic radicals derived from alicyclic tetracarboxylic acids, and divalent organic radicals R derived from diamines. The varnish composition according to any one of (1) to (3), wherein 1 to 100 mol% of 2 is at least one radical selected from the group consisting of radicals of the formula (4).
    [33]
    [34] In the above formula,
    [35] X is a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 or C (CH 3 ) 2 ,
    [36] R 9 and R 10 are each independently hydrogen, methyl group or ethyl group,
    [37] a and b are each 1 or 2,
    [38] q is an integer from 0 to 3, and when q is 2 or 3, each X may be different from each other.
    [39] (5) Of the tetravalent organic radicals R 1 derived from tetracarboxylic acids in the polyamic acid B of the general formula (1), 10 to 100 mol% thereof are tetravalent organic radicals derived from cyclobutane tetracarboxylic acids, and divalent organic radicals R derived from diamine. 2 is 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl ethane, 1,4-bis [2- (4-aminophenyl) ethyl] benzene, 1,4-bis (4- Derived from at least one compound selected from the group consisting of aminophenylmethyl) benzene, 1,3-bis [4- (4-aminophenylmethyl) phenyl] propane and bis [4- (4-aminophenylmethyl) phenyl] methane The varnish composition as described in any one of said (1)-(4) which is a radical of the composition containing the bivalent organic radical of the above.
    [40] (6) In polyamic acid A of formula (2), R 3 is a tetravalent organic radical derived from aromatic tetracarboxylic acids, a tetravalent organic radical derived from aliphatic tetracarboxylic acids and a tetravalent organic radical derived from alicyclic tetracarboxylic acids. A divalent organic radical derived from R 4 valent aromatic diamine, a divalent organic radical derived from alicyclic diamine, a divalent organic radical derived from aliphatic diamine, and aromatic Any one of the above items (1) to (5) consisting of at least one divalent organic radical selected from the group consisting of divalent organic radicals derived from diamine containing at least two groups from among groups, alicyclic groups and aliphatic groups. Varnish composition according to claim.
    [41] (7) In the polyamic acid A of formula (2), (1) to (6), wherein in divalent organic radical R 4 derived from diamine, 1 to 100 mol% thereof is a divalent organic radical derived from diamine having a side chain group having 3 or more carbon atoms. The varnish composition as described in any one of Claims).
    [42] (8) The tetravalent organic radical R 3 derived from tetracarboxylic acids in the polyamic acid A of the general formula (2) is a pyromellitic acid radical, a cyclobutane tetracarboxylic acid radical or a pyromellitic acid radical and a cyclobutane tetracarboxylic acid as essential components thereof. Containing both radicals, 1 to 100 mol% of the divalent organic radicals R 4 derived from diamines consisting of the radicals of the formulas 5-1, 5-2, 5-3, 5-4, 6, 7 and 8 The varnish composition according to any one of (1) to (7), wherein at least one radical selected from the group, 99 to 0 mol% thereof is at least one radical selected from the group consisting of radicals of the formula (4).
    [43]
    [44]
    [45]
    [46]
    [47]
    [48]
    [49]
    [50] In the above formula,
    [51] R 13 , R 25 and R 26 are each independently hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms,
    [52] Ring A is a benzene ring or a cyclohexane ring,
    [53] Z is a single bond, CH 2 , CH 2 CH 2 or oxygen,
    [54] r is an integer from 0 to 3,
    [55] s is an integer from 0 to 5,
    [56] t is an integer from 0 to 3, and when t is 2 or 3, each Z may be the same or different from each other,
    [57] In Formulas 5-1 to 5-4, any hydrogen on the benzene ring or the cyclohexane ring may be substituted with an alkyl group having 1 to 4 carbon atoms,
    [58] However, in the formulas 5-2 and 5-3, the steroid skeleton may contain any ring reduced, enlarged, cleaved or three-membered ring, unsaturated bond at any position may be increased or decreased, and any position Hydrogen atom or alkyl group of may be substituted with any monovalent organic group,
    [59] X 1 is a single bond, CH 2 , CH 2 CH 2 or oxygen,
    [60] R 14 and R 15 are each independently hydrogen or a linear or branched alkyl group or perfluoroalkyl group having 1 to 12 carbon atoms, and at least one of R 14 and R 15 is a linear or branched alkyl group or purple having 3 or more carbon atoms Is a fluoroalkyl group,
    [61] u is an integer from 0 to 3, and when u is 2 or 3, each X 1 may be the same or different from each other,
    [62] In formula (6), any hydrogen on the benzene ring may be substituted with an alkyl group having 1 to 4 carbon atoms,
    [63] X 3 and X 4 are each independently a single bond, O, COO, OCO, NH, CONH or (CH 2 ) n ,
    [64] R 22 and R 23 are each independently a group of 1 to 3 rings having a single bond, an aromatic ring and / or an alicyclic ring [If R 22 and / or R 23 has 2 or 3 rings, these rings are single bonds; , O, COO, OCO, NH, CONH or (CH 2 ) n ], or a steroidal group,
    [65] R 24 is hydrogen, fluorine, hydrocarbon group, fluorohydrocarbon group, alkoxy group, cyano group or OH group,
    [66] n is an integer from 1 to 5,
    [67] A 1 is a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms, wherein any non-adjacent methylene group in the group may be substituted with an oxygen atom,
    [68] A 2 is a single bond or an alkylene group having 1 to 5 carbon atoms, wherein any non-adjacent methylene group in the group may be substituted with an oxygen atom,
    [69] m is an integer from 0 to 3,
    [70] n is an integer of 1-5.
    [71] (9) soluble polyimide tetracarboxylic acids tetravalent organic radical R 5 is an aromatic tetracarboxylic acids tetravalent organic radical and a cycloaliphatic sikgye organic radical, 4 of aliphatic tetracarboxylic acids derived from the origin of derived from a solution of the formula 3-carboxylic acid acids and organic radicals at least one selected 4 from group 4 of the origin consisting of organic radicals, divalent organic radical of a diamine derived from R 6 is an aromatic diamine divalent organic radical, a cycloaliphatic sikgye diamine derived from a divalent organic radical derived from At least one divalent organic radical selected from the group consisting of divalent organic radicals derived from aliphatic diamines and divalent organic radicals derived from diamines containing at least two groups of aromatic groups, alicyclic groups and aliphatic groups, The varnish composition of any one of said (1)-(8).
    [72] (10) The above (1) to (9), wherein in a soluble polyimide of formula (3), 1 to 100 mol% of divalent organic radicals R 6 derived from diamine are divalent organic radicals derived from diamine having a C 3 or more side chain group. The varnish composition according to any one of claims.
    [73] (11) A tetravalent organic radical R 5 valent tricarboxycyclopentyl acetic acid, 3,3,4-tricarboxy-1,2,3,4-tetrahydronaphthalene succinic acid derived from tetracarboxylic acids in a soluble polyimide of formula (3) , At least one radical selected from the group consisting of respective acid radicals of cyclobutane tetracarboxylic acid and butane tetracarboxylic acid, 1 to 100 mol% of the divalent organic radical R 6 derived from diamine is represented by the formulas 5-1, 5-2, At least one radical selected from the group consisting of 5-3, 5-4, 6, 7 and 8 radicals, 99 to 0 mol% thereof is at least one radical selected from the group consisting of radicals of the formula (4) The varnish composition of any one of Claims 1-10.
    [74] (12) The varnish composition as described in any one of said (1)-(11) is used, The liquid crystal aligning agent characterized by the above-mentioned.
    [75] (13) It has an alignment film formed using the liquid crystal aligning agent of said (12), The liquid crystal display element characterized by the above-mentioned.
    [76] (14) Using the liquid crystal composition comprising two or more compounds containing at least one compound selected from the group consisting of compounds of the formulas (9), (10) and (11) and at least one optically active compound as an optional component, (13) The liquid crystal display element of Claim.
    [77]
    [78]
    [79]
    [80] In the above formula,
    [81] R 1 is a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group which is not adjacent to each other in the group may be substituted with —O— or —CH═CH—, and any hydrogen atom is May be substituted with a fluorine atom;
    [82] X 1 is a fluorine atom, a chlorine atom, -OCF 3 , -OCF 2 H, -CF 3 , -CF 2 H, -CFH 2 , -OCF 2 CF 2 H or -OCF 2 CFHCF 3 ,
    [83] L 1 and L 2 are each independently a hydrogen atom or a fluorine atom,
    [84] Z 1 and Z 2 are each independently 1,2-ethylene, 1,4-butylene, -COO-, -CF 2 O-, -OCF 2- , -CH = CH- or a single bond,
    [85] Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom;
    [86] Ring C is trans-1,4-cyclohexylene or 1,4-phenylene in which the hydrogen atom may be substituted with a fluorine atom.
    [87] (15) To the above (13), which uses a liquid crystal composition composed of two or more compounds containing at least one compound selected from the group consisting of the compounds of the formulas (12) and (13) and at least one optically active compound which is an optional component. The liquid crystal display element described.
    [88]
    [89]
    [90] In the above formula,
    [91] R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- Any hydrogen atom may be substituted with a fluorine atom;
    [92] X 2 is -CN or -C≡C-CN;
    [93] Ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;
    [94] Ring E is trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom;
    [95] Ring F is trans-1,4-cyclohexylene or 1,4-phenylene;
    [96] Z 3 is 1,2-ethylene, -COO- or a single bond;
    [97] L 3 , L 4 and L 5 are each independently hydrogen or fluorine;
    [98] e, f and g are each independently 0 or 1.
    [99] (16) Using a liquid crystal composition comprising two or more compounds containing at least one compound selected from the group consisting of compounds of the formulas (14), (15) and (16) and at least one optically active compound as an optional component, (13) The liquid crystal display element of Claim.
    [100]
    [101]
    [102]
    [103] In the above formula,
    [104] R 4 and R 5 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    [105] Ring G and ring I are each independently trans-1,4-cyclohexylene or 1,4-phenylene,
    [106] L 6 and L 7 are each independently a hydrogen atom or a fluorine atom, but at the same time are not a hydrogen atom,
    [107] Z 4 and Z 5 are each independently 1,2-ethylene, -COO- or a single bond.
    [108] (17) at least one compound selected from the group consisting of compounds of the formulas (9), (10) and (11) as the first component, and at least one compound selected from the group consisting of the compounds (17), (18) and (19) as the second component The liquid crystal display element as described in said (14) containing and using the liquid crystal composition containing 1 or more types of optically active compounds as arbitrary 3rd components.
    [109]
    [110]
    [111]
    [112] In the above formula,
    [113] R 6 and R 7 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- Any hydrogen atom may be substituted with a fluorine atom;
    [114] Ring J, ring K and ring M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    [115] Z 6 and Z 7 are each independently 1,2-ethylene, —C≡C—, —COO—, —CH═CH— or a single bond.
    [116] (18) contains as a first component at least one compound selected from the group consisting of compounds of the formulas (12) and (13), and contains as at least one compound selected from the group consisting of the compounds of the formulas (17), (18) and (19) The liquid crystal display element as described in said (15) which uses the liquid crystal composition containing 1 or more types of optically active compound as arbitrary 3rd components.
    [117] (19) At least one compound containing at least one compound selected from the group consisting of compounds of formulas (14), (15) and (16) as a first component, and at least one compound selected from the group consisting of compounds of formulas (17), (18) and (19) as a second component. The liquid crystal display element as described in said (16) containing and using the liquid crystal composition containing 1 or more types of optically active compounds as arbitrary 3rd components.
    [118] (20) contains as a first component at least one compound selected from the group consisting of compounds of formulas (9), (10) and (11), and as a second component contains at least one compound selected from the group consisting of compounds of formula (12) or (13) Using a liquid crystal composition containing at least one compound selected from the group consisting of compounds of the formulas (17), (18) and (19) as a third component, and containing at least one optically active compound as an optional fourth component (14). The liquid crystal display element of Claim.
    [119] The varnish composition of the present invention is mainly composed of a polymer component containing polyamic acid B of formula (1), polyamic acid (A) of formula (2) and a soluble polyimide of formula (3), and a solvent for dissolving such a polymer component. Varnish composition containing 0.1 to 40% by weight. By setting it as such a polymer composition, especially when it is set as a liquid crystal aligning film, it can be set as the liquid crystal aligning film more balanced by electrical characteristics (especially excellent in afterimage prevention), applicability | paintability, orientation, etc.
    [120] The present invention is described in more detail below.
    [121] Polyamic acid B of general formula (1) is a component which does not have a C3 or more side chain group among the polymer components used for the varnish composition of this invention. If such a polyamic acid B has a side chain group having 3 or more carbon atoms in the same manner as other polymer components, the effect of the present invention on the electrical properties is hardly obtained.
    [122] In general formula (1), R <1> is tetravalent organic radical derived from tetracarboxylic acid, tetracarboxylic dianhydride, or tetracarboxylic-acid diacid halide (in this invention, "tetracarboxylic acid" is a general term for these compounds), Radicals which do not have, radicals having branched alkyl groups having less than 3 carbon atoms, or mixtures thereof. Such R 1 can be widely selected from tetravalent organic radicals of known tetracarboxylic acids. However, it is preferable that tetravalent organic radicals derived from alicyclic tetracarboxylic acids are contained in R <1> , and it is preferable that such radicals are 10 mol% or more in R <1> .
    [123] In the case of the aligning agent for TFT elements, it is especially preferable to use together the polymer which has tetravalent organic radicals derived from alicyclic tetracarboxylic acids, and the polymer which has tetravalent organic radicals derived from aromatic tetracarboxylic acids, It is effective in further improving display characteristics (particularly, it is effective in preventing afterimages and has a large voltage retention). In this case, the ratio of alicyclic system and aromatic system is preferably in the molar ratio of 10/90 to 90/10, and also in the range of 70/30 to 10/90.
    [124] Moreover, in the case of the orientation agent for STN elements, it is especially preferable to make the polymer which has tetravalent organic radicals derived from alicyclic tetracarboxylic acids, and the polymer which has tetravalent organic radicals derived from aliphatic tetracarboxylic acids coexist, and the current value of an element It is possible to achieve the effect of decreasing the reliability and improving the reliability. In this case, the ratio of alicyclic system and aliphatic system is preferably in the range of 10/90 to 90/10, and 70/30 to 30/70 in molar ratio.
    [125] As a raw material component which comprises the organic radical derived from the tetracarboxylic acids of polyamic acid B, the following tetracarboxylic dianhydride normally known can be used.
    [126] Examples of alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, bicycloheptane tetracarboxylic dianhydride, bicyclo (2,2,2) -oct (7) -ene-2,3 , 5,6-tetracarboxylic dianhydride, cyclohexane-1,2,5,6-tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid 2 Anhydride, 3,3'-bicyclohexyl-1,1 ', 2,2'-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetra Hydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2, -c] -furan-1,3-dione, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5- tetrahydrofuran tetracarboxylic dianhydride, tetracyclo [6.2.1 1,3 .0 2,7] dodecane -4,5,9,10- Tet Although partial substitution of lower alkyl groups, such as methyl and / or ethyl group, is mentioned to carboxylic dianhydride and these compounds, Especially cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and cyclohexane tetracarboxylic dianhydride This is preferred.
    [127] Examples of aromatic tetracarboxylic acids include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, naphthalene dianhydride (2,3,6,7-naphthalene anhydride, etc.). ), 3,3'-4,4'-diphenylmethane tetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane tetracarboxylic dianhydride, 3,3'-4,4'-diphenyl Propanetetracarboxylic dianhydride, 3,3'-4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4 '-Dimethyldiphenylsilanetetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) di Phenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenylmethyl) diphenylmethane dianhydride, 4,4'-bis (3,4-dicarboxyphenylmethyl) diphenylethane dianhydride, 4 , 4'-bis (3,4-dicarboxyphenylmethyl) diphenylpropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylmethane dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylethane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4 '-Perfluoropropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylsulphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) Dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride and bis (triphenylphthalic acid) -4,4'-diphenylmethane Dianhydrides; and the like, and particularly, are acid dianhydrides composed of phenyl groups such as pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, and terphenyl tetracarboxylic dianhydride, and 2,2-diphenylpropane tetracarboxylic acid 2 Preference is given to tetracarboxylic dianhydrides consisting solely of phenyl groups and aliphatic groups (which may include alicyclic), such as anhydrides, and the like. The electrical properties and easy oxygen atom or a sulfur atom is adversely affected to a structure which does not contain in its backbone of the radical are preferred.
    [128] Moreover, an ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, etc. are mentioned as an example of aliphatic tetracarboxylic acids used in combination with alicyclic tetracarboxylic acids. Further, one hydrogen at the 2,3-position of the butane tetracarboxylic dianhydride may be substituted with another organic radical.
    [129] By combining pyromellitic dianhydride, which is a suitable example of aromatics, and cyclobutane tetracarboxylic dianhydride, which is a suitable example of alicyclic tetracarboxylic dianhydrides, tetravalent organic radicals derived from tetracarboxylic acids of the most representative configuration in the present invention can be obtained. In particular, the polyamic acid B component suitable for the alignment agent for TFT can be constituted. Furthermore, by combining butane tetracarboxylic dianhydride and cyclobutane tetracarboxylic dianhydride, which are one of the aliphatic suitable examples, a polyamic acid B component particularly suitable for the alignment agent for STN can be constituted.
    [130] Next, R 2 in the general formula (1) is a divalent organic radical derived from a diamine, a radical having no side chain group, a radical having a branched alkyl group having less than 3 carbon atoms, or a mixture thereof, among the diamine compounds providing such radicals. The following compound is mentioned as an example of a compound which does not have a side chain group.
    [131] For example, 4,4'- diamino diphenyl ether, 4,4'- diamino diphenyl sulfide, 4,4'- diamino diphenyl sulfone, 4,4'- diamino biphenyl, 3,3 '-Dimethoxybenzidine, 4,4'-diaminobenzanilide, 1,5-diaminonaphthalene, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'- Diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenoxy) propane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] methane, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 9,10-bis (4-aminophenyl) anthracene, 4,4 '-(1,4-phenylenediisopropylidene) bisaniline, 4,4'-(1,3-phenylenediisopropylidene) bisaniline, p-xylylenediamine, m-xylylenediamine, etc. Aromatic diamines, ethylenediamines, Aliphatic diamines such as propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, heptamethylenediamine, 1,4-diaminocyclohexane, 1,3-diamino Cyclobutane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylethane, isophoronediamine, norbornanediamine, tetrahydro Alicyclic diamines such as dicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 2,7 ] -undecylenedimethyldiamine, 2,3-diaminopyridine, Heterocyclic diamines such as 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyridine, diaminopyrimidine and diaminopiperazine.
    [132] Such diamine-derived divalent organic radicals can be constituted by using a wide range of known diamine compounds, but divalent organic radicals derived from aromatic diamines, divalent organic radicals derived from alicyclic diamines, and aromatic groups and alicyclic groups And at least one divalent organic radical selected from the group consisting of divalent organic radicals derived from diamine containing two or more kinds of aliphatic groups, and containing oxygen, which is liable to cause deterioration of electrical properties of the liquid crystal display device. It is preferable that it is a divalent organic radical of the structure which does not contain an ester group, an ether group, etc.
    [133] As representative diamines that provide such divalent organic radicals, compounds of formula 20 may be described, some of which may be mentioned among the compounds exemplified above.
    [134]
    [135] In the above formula,
    [136] X is a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 or C (CH 3 ) 2 ,
    [137] R 9 and R 10 are each independently hydrogen or an alkyl group having less than 3 carbon atoms (preferably a methyl group),
    [138] a and b are each 1 or 2,
    [139] q is an integer from 0 to 3, and when q is 2 or 3, each X may be different from each other.
    [140] Examples of such diamines of the general formula (20) are described in more detail below, but are not limited thereto.
    [141] Examples of the case where q is 0 include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine and the like. As an example where q is 1, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 3,3'-dimethylbenzidine, 1 , 3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-2-methylphenyl) methane, 1 , 2-bis (4-amino-3-methylphenyl) ethane, 1,3-bis (4-amino-3-methylphenyl) propane, 1,2-bis (4-amino-2-methylphenyl) ethane, 1,3 -Bis (4-amino-2-methylphenyl) propane and the like. As an example where q is 2, 1,4-bis (4-aminophenyl) benzene, 1,4-bis [(4-aminophenyl) methyl] benzene, 1,4-bis [(3-aminophenyl) Methyl] benzene, 1,4-bis [(4-aminophenyl) ethyl] benzene, 1,4-bis [(3-aminophenyl) ethyl] benzene, 1,4-bis [(4-amino-3-methyl -Phenyl) methyl] benzene, 1,4-bis [(4-amino-3-methyl-phenyl) ethyl] benzene, etc. are mentioned. As an example when q is 3, 4,4 '-(4-aminophenyl) biphenyl, bis-[(4- (4-aminophenylmethyl) phenyl] methane, bis-[(4- (4-amino Phenylmethyl) phenyl] ethane, bis [(4- (3-aminophenylmethyl) phenyl] methane, bis [(4- (3-aminophenylmethyl) phenyl] ethane, 2,2-bis [(4- (4 -Aminophenylmethyl) phenyl] propane, 2,2-bis [(4- (3-aminophenylmethyl) phenyl] propane, and the like.
    [142] The polyamic acid B of the general formula (1) is obtained by reacting tetracarboxylic acids with diamine as starting materials, but in this reaction, dicarboxylic anhydrides and / or monoamines for forming terminal groups of the polyamic acid in addition to the starting materials described above. An aminosilicon compound, a diaminosilicon compound, a diaminosiloxane compound, etc. which are effective for improving the adhesiveness of a compound, the obtained liquid crystal aligning film, and a board | substrate can be used together.
    [143] Specific examples of such aminosilicon compounds include paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane and aminopropyltri. Ethoxysilane etc. are mentioned. Further, specific examples of the diaminosilicon compound include 1,3-bis (3-aminopropyl) -1,1,3,3-tetraphenyldisiloxane and 1,3-bis (3-aminopropyl) -1,1 , 3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, and the like. These compounds can also be used for the following polyamic acid A or soluble polyimide.
    [144] It is preferable that the tetravalent organic radical derived from the tetracarboxylic acids of the polyamic acid A of General formula (2) consists of an aromatic type and / or an alicyclic type radical as an essential component. Radicals derived from aliphatic (chain) tetracarboxylic acids can be co-existed here. However, since an aliphatic component (chain system) may harm the orientation of a liquid crystal, it should be used in the range which does not interfere with the orientation of a liquid crystal in the combined use thereof.
    [145] Regarding the radicals of these carboxylic acids, a structure containing no oxygen atom or sulfur atom in the skeleton is preferable. However, when the compounding amount of polyamic acid A is not large, these effects are small, and such atoms may be contained. Therefore, in this respect, although tetracarboxylic acids which can be used for polyamic acid A manufacture can be selected from the wider range than tetracarboxylic acids used for polyamic acid B manufacture, the example which can be used for polyamic acid B manufacture specifically, The tetracarboxylic acids mentioned above can be described.
    [146] Moreover, since polyamic acid A needs to have a function which gives a pretilt angle to a liquid crystal, R <3> (tetravalent organic radical derived from tetracarboxylic acids) and R <4> (divalent organic radical derived from diamine) are represented by General formula (2). Or one of them contains a composition containing a radical having a branched group having 3 or more carbon atoms.
    [147] Examples of the group having 3 or more carbon atoms include an aliphatic hydrocarbon, a hydrocarbon containing an alicyclic structure, an aromatic hydrocarbon, a group having a siloxane group, a group having a steroid skeleton or a complex group thereof. Specifically, the side chain group of general formula (21) is mentioned.
    [148] -X 3 -R 22 -X 4 -R 23 -R 24
    [149] In the above formula,
    [150] X 3 and X 4 are each independently a single bond, O, COO, OCO, NH, CONH or (CH 2 ) n ,
    [151] R 22 and R 23 are each independently a group of 1 to 3 rings having a single bond, an aromatic ring and / or an alicyclic ring (if R 22 and / or R 23 has 2 or 3 rings, these rings are single bonds; , O, COO, OCO, NH, CONH or (CH 2 ) n can be combined) or a steroid group,
    [152] R 24 is hydrogen, fluorine, hydrocarbon group, fluorohydrocarbon group, alkoxy group, cyano group or OH group,
    [153] n is an integer of 1-5.
    [154] Although some of the hydrocarbon groups may be substituted with other atoms such as oxygen, it is preferable not to contain groups having oxygen atoms or sulfur atoms such as O, CO, COO, S, SOO, and the like. The alicyclic hydrocarbon group or the aromatic hydrocarbon group may have a substituent such as an alkyl group, an alkoxy group, a halogen or an OH group. Steroids of the steroid group include cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estryl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanoster Reel, melatolanyl, methyltestosterolyl, noresterosteryl, pregnnonyl, β-sitosteryl, stigmasterilyl, testosteryl, cholesterol acetate, and the like.
    [155] As a diamine used for manufacture of polyamic acid A, when the tetracarboxylic acid has a C3 or more side chain group, the diamine compound for polyamic acid B manufacture mentioned above can also be used, The diamine which has a C3 or more side chain group can be used together. Can be. In addition, when tetracarboxylic acids do not have a C3 or more side chain group, it is necessary to use the diamine which has such C3 or more side chain groups.
    [156] As a diamine compound which provides the radical which has such a side chain group, the diamine compound of following formula 22-1-25 can be mentioned.
    [157]
    [158]
    [159]
    [160]
    [161] In the above formula,
    [162] R 13 , R 25 and R 26 are each independently hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms,
    [163] Ring A is a benzene ring or a cyclohexane ring,
    [164] Z is a single bond, CH 2 , CH 2 CH 2 or oxygen,
    [165] r is an integer from 0 to 3,
    [166] s is an integer from 0 to 5,
    [167] t is an integer of 0 to 3, and when t is 2 to 3, each Z may be the same or different from each other.
    [168] In addition, any hydrogen on the benzene ring or cyclohexane ring may be substituted with an alkyl group having 1 to 4 carbon atoms. Provided that, in Formula 22-2 and Formula 22-3, the steroid backbone may be that any ring is reduced, enlarged or cleaved or may contain a three-membered ring, and the unsaturated bond at any position may be increased or decreased, or The hydrogen atom or alkyl group at any position may be substituted with any monovalent organic group.
    [169]
    [170] In the above formula,
    [171] X 1 is a single bond, CH 2 , CH 2 CH 2 or oxygen,
    [172] R 14 and R 15 are each independently hydrogen or a linear or branched alkyl group or perfluoroalkyl group having 1 to 12 carbon atoms, and at least one of R 14 and R 15 is a linear or branched alkyl group or purple having 3 or more carbon atoms Is a fluoroalkyl group,
    [173] u is 0 to 3, and when u is 2 to 3, each X 1 may be the same or different from each other.
    [174] In addition, hydrogen on any benzene ring may be substituted with lower alkyl groups.
    [175]
    [176] In the above formula,
    [177] X 3 and X 4 are each independently a single bond, O, COO, OCO, NH, CONH or (CH 2 ) n ,
    [178] R 22 and R 23 are each independently a group of 1 to 3 rings having a single bond, an aromatic ring and / or an alicyclic ring (when R 22 and / or R 23 has 2 to 3 rings, these rings are single A bond, O, COO, OCO, NH, CONH or (CH 2 ) n ) or a steroidal group,
    [179] R 24 is hydrogen, fluorine, hydrocarbon group, fluorohydrocarbon group, alkoxy group, cyano group or OH group,
    [180] n is an integer of 1-5.
    [181] In addition, about the steroid type group in Formula 5-2, 5-3, 7, 22-2, 22-3, and 24, the thing similar to the example described in description about Formula 21 which is an example of a C3 or more side chain group is mentioned. Can be.
    [182]
    [183] In the above formula,
    [184] A 1 is a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms, wherein any non-adjacent methylene group in the group may be substituted with an oxygen atom,
    [185] A 2 is a single bond or an alkylene group having 1 to 5 carbon atoms, wherein any non-adjacent methylene group in the group may be substituted with an oxygen atom,
    [186] m is an integer from 0 to 3,
    [187] n is an integer of 1-5.
    [188] As a specific example of such a diamine compound, the following can be mentioned first about the thing of General formula 22-1.
    [189] As an example when Z = oxygen, r = 0, t = 1, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy Phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-ethylcyclohexane, 1,1-bis [4- (4-aminophenoxy) Phenyl] -4-n-propylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-butylcyclohexane, 1,1-bis [4- (4-aminophenoxy Phenyl] -4-n-pentylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-hexylcyclohexane, 1,1-bis [4- (4- Aminophenoxy) phenyl] -4-n-heptylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-octylcyclohexane, 1,1-bis [4- ( 4-aminophenoxy) phenyl] -4-n-nonylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-decylcyclohexane, 1,1-bis [4 -(4-aminophenoxy) phenyl] -4-n-undecylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-dodecylcyclohexane, 1,1 -ratio [4- (4-aminophenoxy) phenyl] -4-n-tridecylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-tetradecylcyclohexane, 1 , 1-bis [4- (4-aminophenoxy) phenyl] -4-n-pentadecylcyclohexane, etc. are mentioned.
    [190] As an example when r = 0, t = 0, 1,1-bis (4-aminophenyl) cyclohexane, 1,1-bis (4-aminophenyl) -4-methylcyclohexane, 1,1-bis (4-aminophenyl) -4-ethylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-propylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-butyl Cyclohexane, 1,1-bis (4-aminophenyl) -4-n-pentylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-hexylcyclohexane, 1,1-bis (4 -Aminophenyl) -4-n-heptylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-octylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-nonyl Cyclohexane, 1,1-bis (4-aminophenyl) -4-n-decylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-undecylcyclohexane, 1,1-bis ( 4-aminophenyl) -4-n-dodecylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-tridecylcyclohexane, 1,1-bis (4-aminophenyl) -4- n-tetradecylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-pentadecyl In hexane, and the like.
    [191] As an example when ring A = cyclohexyl group, r = 1, s = 0, t = O, 1,1-bis (4-aminophenyl) -4-cyclohexylcyclohexane, 1,1-bis (4 -Aminophenyl) -4- (4-methyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-ethyl-trans-cyclohexyl) cyclohexane, 1,1 -Bis (4-aminophenyl) -4- (4-n-propyl-1-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-butyl-trans -Cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-pentyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-hexyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-heptyl-trans-cyclohexyl) cyclohexane, 1,1-bis ( 4-aminophenyl) -4- (4-n-octyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-nonyl-trans-cyclohexyl) cyclo Hexane, 1,1-bis (4- Aminophenyl) -4- (4-n-decyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-undecyl-trans-cyclohexyl) cyclohexane , 1,1-bis (4-aminophenyl) -4- (4-n-dodecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n- Tridecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-tetradecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-amino Phenyl) -4- (4-n-pentadecyl-trans-cyclohexyl) cyclohexane and the like.
    [192] As an example when ring A = cyclohexyl group, Z = oxygen, r = 1, s = 0, t = 1, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (cyclo Hexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-methylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) Phenyl] -4- (4-ethylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-propylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-butylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-pentylcyclo Hexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-hexylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) Phenyl] -4- (4-heptylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-octylcyclohexyl) cyclohexane, etc. are mentioned.
    [193] As an example when ring A = cyclohexyl group, r = 1, s = 1, t = 0, 1,1-bis (4-aminophenyl) -4- (cyclohexylmethyl) cyclohexane, 1,1- Bis (4-aminophenyl) -4-[(4-methylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-ethylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-propylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-butylcyclohexyl) methyl ] Cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-pentylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-hexyl Cyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-heptylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4- [ (4-octylcyclohexyl) methyl] cyclohexane etc. are mentioned.
    [194] As an example when ring A = phenyl group, Z = oxygen, r = 1, s = 1, t = 1, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (phenylmethyl ) Cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-methylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) Phenyl] -4-[(4-ethylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-propylphenyl) methyl] cyclohexane, 1 , 1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-butylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4 -[(4-pentylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-hexylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-heptylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4 -Octylphenyl) methyl] cyclohexane, etc. are mentioned.
    [195] As an example when ring A = phenyl group, r = 1, s = 1, t = O, 1,1-bis (4-aminophenyl) -4- (phenylmethyl) cyclohexane, 1,1-bis ( 4-aminophenyl) -4-[(4-methylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-ethylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-propylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-butylphenyl) methyl] cyclohexane, 1,1 -Bis (4-aminophenyl) -4-[(4-pentylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-hexylphenyl) methyl] cyclohexane, 1 , 1-bis (4-aminophenyl) -4-[(4-heptylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-octylphenyl) methyl] cyclohexane Etc. can be mentioned.
    [196] As an example when ring A = phenyl group, Z = CH 2 , r = 1, s = 1, t = 1, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- (Phenylmethyl) cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-methylphenyl) methyl] cyclohexane, 1,1-bis {4-[( 4-aminophenyl) methyl] phenyl} -4-[(4-ethylphenyl) methyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4- Propylphenyl) methyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-butylphenyl) methyl] cyclohexane, 1,1-bis {4- [(4-aminophenyl) methyl] phenyl} -4-[(4-pentylphenyl) methyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyll-4-[( 4-hexylphenyl) methyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-heptylphenyl) methyl] cyclohexane, 1,1-bis { 4-[(4-aminophenyl) methyl] phenyl} -4-[(4-octylphenyl) methyl] cyclohexane and the like.
    [197] As an example when Z = CH 2 , r = O, t = 1, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} cyclohexane, 1,1-bis {4-[( 4-aminophenyl) methyl] phenyl} -4-methylcyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-ethylcyclohexane, 1,1-bis {4- [(4-aminophenyl) methyl] phenyl} -4-propylcyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-butylcyclohexane, 1,1-bis { 4-[(4-aminophenyl) methyl] phenyl} -4-pentylcyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4-hexylcyclohexane, 1,1- Bis {4-[(4-aminophenyl) methyl] phenyl} -4-heptylcyclohexane, 1,1-bis (4-((4-aminophenyl) methyl) phenyl) -4-octylcyclohexane, etc. are mentioned. Can be.
    [198] As an example of ring A = cyclohexyl group, Z = CH 2 , r = 1, t = 1, s = 2, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [ 2- (cyclohexyl) ethyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-methyl-trans-cyclohexyl) ethyl] cyclohexane , 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-ethyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis {4- [ (4-aminophenyl) methyl] phenyl} -4- [2- (4-propyl-1-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] Phenyl} -4- [2- (4-butyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4 -Pentyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-amyl-trans-cyclohexyl) ethyl] Cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-hexyl-trans-cyclohexyl) ethyl] Ichlorohexane, 1,1-bis (4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-heptyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis { 4-[(4-aminophenyl) methyl] phenyl} -4- [2- (4-octyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl ] Phenyl} -4- [2- (4-nonyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} -4- [2- ( 4-dodecyl-trans-cyclohexyl) ethyl] cyclohexane, etc. are mentioned.
    [199] Next, a specific example is given about the diamine compound of General formula (23).
    [200] As an example when X 1 = O (oxygen), u = 1, 2,2-bis [4- (4-aminophenoxy) phenyl] pentane, 2,2-bis [4- (4-aminophenoxy ) Phenyl] hexane, 2,2-bis [4- (4-aminophenoxy) phenyl] heptane, 2,2-bis [4- (4-aminophenoxy) phenyl] octane, 2,2-bis [4 -(4-aminophenoxy) phenyl] nonane, 2,2-bis [4- (4-aminophenoxy) phenyl] decane, 2,2-bis [4- (4-aminophenoxy) phenyl] undecane , 2,2-bis [4- (4-aminophenoxy) phenyl] dodecane, 2,2-bis [4- (4-aminophenoxy) phenyl] tridecane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] tedecane, 2,2-bis [4- (4-aminophenoxy) phenyl] pentadecane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexadecane , 2,2-bis [4- (4-aminophenoxy) phenyl] heptadecane, 2,2-bis [4- (4-aminophenoxy) phenyl] octadecane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] nonadecane, etc. are mentioned.
    [201] As an example when X 1 = CH 2 , u = 1, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} pentane, 2,2-bis {4-[(4-aminophenyl ) Methyl] phenyl} hexane, 2,2-bis (4-[(4-aminophenyl) methyl] phenyl} heptane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} octane, 2 , 2-bis {4-[(4-aminophenyl) methyl] phenyl} nonane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} decane, 2,2-bis {4- [ (4-aminophenyl) methyl] phenyl} undecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} dodecane, 2,2-bis {4-[(4-aminophenyl) Methyl] phenyl} tridecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} tetradecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} pentadecane , 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} hexadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} heptadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} octadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} nonadecan, 2,2-bis {4-[(4 -Aminophenyl) methyl] phenyl} perfluoropentane, 2,2-bis { 4-[(4-aminophenyl) methyl] phenyl} perfluorohexane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoroheptane, 2,2-bis {4- [(4-aminophenyl) methyl] phenyl} perfluorooctane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorononane, 2,2-bis {4-[( 4-aminophenyl) methyl] phenyl} perfluorodecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorodecane, 2,2-bis {4-[(4- Aminophenyl) methyl] phenyl} perfluorododecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluorotridecane, 2,2-bis {4-[(4-aminophenyl ) Methyl] phenyl} perfluorotetedecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoropentatecan, 2,2-bis {4-[(4-aminophenyl ) Methyl] phenyl} perfluorohexadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoroheptadecane, 2,2-bis {4-[(4-aminophenyl ) Methyl] phenyl} perfluorooctadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perflu Oronona decan etc. are mentioned.
    [202] In addition, although the above was described about the example of a 2, 2-bis system compound, 1, 1-bis system, 3, 3-bis system, 4, 4-bis system, or 5, according to carbon number of R <14> and R <15> , Needless to say, the same can be said about the 5-bis compound.
    [203] Next, regarding the diamine compound of the formula (24), 4- [8- (4-biphenyloxy) octyloxy] -1,3-diaminobenzene, 4- [3- (4-cyanobiphenyl-4 ' -Oxy) propoxy] -1,3-diaminobenzene, 4- [12- (4-cyanobiphenyl-4'-oxy) dodecyloxy] -1,3-diaminobenzene, 4- [6- (4-methoxybiphenyl-4'-oxy) hexyloxy] -1,3-diaminobenzene, 4- [3- (4-fluorobiphenyl-4'-oxy) propoxy] -1,3- Diaminobenzene, 1,4-diamino-3- [4- (4-alkylcyclohexyl) cyclohexyloxy] benzene, 1,4-diamino-3- [4- (4-alkylphenyl) cyclohex Siloxy] benzene, 1,4-diamino-3-((4-alkylterphenyl) oxy) benzene, 1,4-diamino- (2-alkyl) benzene, 1,4-diamino- (2, 5-dialkyl) benzene and 2-alkyloxy-1,4-diaminobenzene, 2,4-diaminobenzoic acid dodecyl, 2,4-diaminobenzoic acid octyl, 1,5-diamino-2-octyloxy Carbonyl amino benzene, etc. are mentioned.
    [204] Moreover, the diamine compound etc. which have various steroid substituents described in description of General formula 21 are mentioned.
    [205] Next, as a specific example of the diamine compound of Formula 25, 1-cyclohexyl-4- [4- (4-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-methylcyclohexyl) -4- [4- (4-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-propylcyclohexyl) -4- [4- (4-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-pentylcyclohexyl) -4- [4- (4-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-octylcyclohexyl) -4- [4- (4-aminobenzyl)- 2-aminophenyl] cyclohexane, 1- (4-decylcyclohexyl) -4- [4- (4-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-dodecylcyclohexyl) -4 -[4- (4-aminobenzyl) -2-aminophenyl] cyclohexane, 1-cyclohexyl-4- [4- (3-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-methyl Cyclohexyl) -4- [4- (3-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-propylcyclohexyl) -4- [4- (3-aminobenzyl) -2-aminophenyl ] Cyclohex , 1- (4-pentylcyclohexyl) -4- [4- (3-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-octylcyclohexyl) -4- [4- (3-amino Benzyl) -2-aminophenyl] cyclohexane, 1- (4-decylcyclohexyl) -4- [4- (3-aminobenzyl) -2-aminophenyl] cyclohexane, 1- (4-dodecylcyclohexyl ) -4- [4- (3-aminobenzyl) -2-aminophenyl] cyclohexane, etc. are mentioned.
    [206] As mentioned above, only the specific examples of the diamine compounds of the formulas 22-1 to 22-4, 23, 24 or 25 are described, and the diamine compounds having a C 3 or more side chain group used in the present invention are limited thereto. It doesn't happen.
    [207] When the side chain of these diamine compounds is short or when the usage-amount of the said diamine compound is small, a pretilt angle becomes small, but when a pretilt angle is small, it is suitable for an IPS element, and a pretilt angle is 3-8 degrees. In the case of precision, it is suitable for a TN type TFT element. In addition, larger pretilt angles may be required in STN devices and ferroelectric liquid crystal display devices, and larger pretilt angles are required in OCB (0ptically compensated Birefringence) devices and vertical alignment devices. In such a case, it is preferable to use a component having a long side chain group or to use a large component of polyamic acid A.
    [208] In addition, the diamine compound which has a C3 or more side chain group (henceforth a 1st diamine compound), and the diamine compound which does not have a C3 or more side chain group (henceforth a 2nd diamine compound) may be called. You can use together. The first diamine compound is a compound as mentioned in the description of the above formulas 22-1 to 22-4, 23, 24 or 25. Further, as the second diamine compound, a diamine compound composed of only the same aromatic system as the compound of the above formula (20), an aromatic diamine compound, an alicyclic diamine compound, an aliphatic diamine compound or an aromatic group, and an alicyclic group as listed below And at least one of diamine compounds and the like containing at least two kinds of aliphatic groups are preferably used in view of electrical characteristics and display characteristics of the liquid crystal display device.
    [209] Examples of the aromatic diamine compound include 2,2-bis (4-aminophenyl) propane, 2,6-diaminopyridine, bis (4-aminophenyl) diethylsilane and bis (4-aminophenyl) diphenylsilane , Bis (4-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) -N-butylamine, N, N-bis (4-aminophenyl) -N-methylamine, N- (3-aminophenyl ) -4-aminobenzamide, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 2,2-bis (3-amino Phenyl) propane, 1,3-bis (3-aminophenyl) propane, 3,3'-diaminodiphenylsulfide, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl -p-phenylenediamine, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, p-xylylenediamine, m-xylylenediamine, 2,4-diaminotoluene , 2,6-diaminotoluene, 1,2-bis (3-diaminophenyl) ethane, 1,1-bis (3-diaminophenyl) ethane, 4,4'-diaminodiphenylhex Fluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenyl Sulfone, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, bis [4- (4-aminophenoxy ) Phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4 -(4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 4,4'-bis (4-aminophenoxy) diphenylketone, bisL4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfide, 1,3- Bis [4- (4-aminophenoxy) phenyl] benzene, 1,4-bis [4- (4-aminophenoxy) phenyl] benzene, 4,4'-bis [4- (4-aminophenoxy) Phenyl] biphenyl, 1,2-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,3-bis [4 -(4-aminophenoxy) phenyl] cyclohexane, 1,4-bis [4- (4-aminophenoxy) phenyl] cyclohexane, bis [4- (4-aminophenoxy) phenyl] hexafluoropropane , 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-carbamoyl-4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (3-sulfamoyl-4-aminophenyl) hexafluoropropane, 2,2-bis (3 -Carboxy-4-aminophenyl) hexafluoropropane, 2,2-bis [4- (3-sulfamoyl-4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3 -Carboxy-4-aminophenoxy) phenyl] hexafluoropropane, 1,3-bis [2,2- {4- (4-aminophenoxy) phenyl} hexafluoroisopropyl] benzene, 2,4- Bis (β-amino-t-butyl) toluene, bis (p-β-methyl-γ-aminopentyl) benzene, bis-p- (1,1-dimethyl-5-aminopentyl) benzene, bis (p-β -Amino-t-butylphenyl) ether, ratio S (4-aminobenzyloxy) methane, bis (4-aminobenzyloxy) ethane, bis (4-aminobenzyloxy) propane, bis (4-aminobenzyloxy) cyclohexane and the like.
    [210] Examples of the alicyclic diamine compound include 1,4-diaminodicyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diaminodi Cyclohexyl methane, bis (2-methyl-4-aminocyclohexyl) methane, isophoronediamine, 2,5-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,6-bisaminomethyl-ratio Cyclo [2.2.1] heptane, 2,3-diaminobicyclo [2.2.1] heptane, 2,5-diaminobicyclo [2.2.1] heptane, 2,6-diaminobicyclo [2.2.1 ] Heptane, 2,7-diaminobicyclo [2.2.1] heptane, 2,3-diamino-7-azabicyclo [2.2.1] heptane, 2,5-diamino-7-azabicyclo [2.2. 1] heptane, 2,6-diamino-7-azabicyclo [2.2.1] heptane, 2,3-diamino-7-thiabicyclo [2.2.1] heptane, 2,5-diamino-7- Thiabicyclo [2.2.1] heptane, 2,6-diamino-7-thiabicyclo [2.2.1] heptane, 2,3-diaminobicyclo [2.2.2] octane, 2,5-diamino anecdote Chloro [2.2.2] octane, 2,6-diaminobicyclo [2.2.2] octane, 2,5-diaminobicyclo [2.2.2] octane-7-ene, 2,5-diamino-7 Azabicyclo [2.2.2] octane, 2,5-diamino-7-oxabicyclo [2.2.2] octane, 2,5-diamino-7-thiabicyclo [2.2.2] octane, 2, 6-diaminobicyclo [3.2.1] octane, 2,6-diaminoazabicyclo [3.2.1] octane, 2,6-diaminooxabicyclo [3.2.1] octane, 2,6-diamino Thiabicyclo [3.2.1] octane, 2,6-diaminobicyclo [3.2.2] nonane, 2,6-diaminobicyclo [3.2.2] nonan-8-ene, 2,6-diamino -8-azabicyclo [3.2.2] nonane, 2,6-diamino-8-oxabicyclo [3.2.2] nonane, 2,6-diamino-8-thiabicyclo [3.2.2] nonane and the like Can be mentioned.
    [211] Examples of aliphatic diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like, and diamines such as alkylenediamine having an oxygen atom in the alkylene group.
    [212] When a large amount of aliphatic diamine is used in these second diamine compounds, the orientation of liquid crystal molecules may be adversely affected, so the amount of the aliphatic diamine should be within a range in which such adverse effects can be avoided. Moreover, in order to avoid the fall of the electrical property of a liquid crystal element, these 2nd diamine compounds have the thing of the structure which does not contain oxygen and sulfur, such as ester group and an ether group, in a skeleton.
    [213] The ratio of the first diamine compound and the second diamine compound in the diamine used to prepare the polyamic acid A is determined by the type of electron and the required pretilt angle, and cannot be specified uniformly, but is generally the first diamine compound. When represented by / 2nd diamine compound (molar ratio), it is 100/0-1/99, Preferably it is 100/0-10/90, More preferably, it is 100/0-20/80.
    [214] Next, it is preferable that the composition of any one of soluble poly tetracarboxylic imide acids radical R 5, R 6 diamine radical or a formula (3) containing a radical having a carbon number of 3 or more side groups.
    [215] As such tetracarboxylic acids, aliphatic, aromatic, and alicyclic tetracarboxylic acids commonly used for soluble polyimides are used. Specific examples of such aliphatic systems include ethane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. And dianhydrides of butane tetracarboxylic acid wherein hydrogen at the position of 3 is substituted with another organic group (methyl, ethyl, phenyl, benzyl group, etc.). In addition, examples of the alicyclic system include tricarboxycyclopentyl acetic acid dianhydride, 1,4-hexylylenedicarboxylic acid, 3,3,4-dicarboxy-1,2,3,4-tetrahydronaphthalenesuccinic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-norbornane-2-acetic acid dianhydride, Tetracarboxylic acid furanyl dianhydride, bicyclo [2.2.2] -oct-7-enderacarboxylic dianhydride, tetracyclo [6.2.1.0 2,7 ] dodeca-4,5,9,10-tetracarboxylic dianhydride And bicycloheptane tetracarboxylic dianhydride. Moreover, as an example of an aromatic system, 2,3,3 ', 4'- benzophenone tetracarboxylic dianhydride, 3,4,3', 4'- benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-Biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 3,4,3 ', 4'-diphenylethertetracarboxylic dianhydride, 3,4,3' , 4'-dicarboxydiphenylmethane tetracarboxylic dianhydride, 3,4,3 ', 4'-dicarboxydiphenylethane tetracarboxylic dianhydride, 3,4,3', 4'-dicarboxydiphenylpropanetetra Carboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylmethane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylethane dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4'-bis (3,4-dicarboxyphenylmethyl) diphenylmethane dianhydride, 4,4'-bis (3 , 4-dicarboxyphenylmethyl) diphenylethane dianhydride, 4,4'-bis (3,4-dicarboxyphenylmethyl) diphenylpropane dianhydride, 3,4,3 ', 4'-dimethyldiphenylsilane Tetracarboxylic acid 2, anhydride, 3, 4'-bis (3, 4- dicarboxy) diphenyl sulfide dianhydride, 2, 2-bis (3, 4- dicarboxy phenyl) hexafluoro propane dianhydride, etc. are mentioned. Moreover, the siloxane tetracarboxylic dianhydride can be mentioned, These can be used together with other alicyclic type and aromatic tetracarboxylic acid in the range in which a polyimide shows solubility.
    [216] Tetracarboxylic acids used in the production of soluble polyimide are preferably alicyclic or aliphatic, but aliphatic may adversely affect the orientation of the liquid crystal. Therefore, in the use thereof, it is preferable to use the alicyclic or combined with the aromatic. . In addition, when using an aromatic system, it is preferable to use only an aromatic type, or to combine aromatic type and aliphatic type, or aromatic type and alicyclic type, as described in the description about polyamic acid A. Moreover, as long as it is soluble, three components of an aromatic type, an alicyclic type, and an aliphatic type can be used together.
    [217] In addition, regarding the diamine used for manufacture of soluble polyimide, the description demonstrated about the diamine used for manufacture of polyamic acid A can be applied as it is. Similarly, it is preferable to use diamine which has a C3 or more side chain, and the use ratio of such diamine can be 1-100 mol% in all the diamine components.
    [218] By reacting such tetracarboxylic acids with diamine according to a conventional method, a soluble polyimide of formula (3) can be obtained.
    [219] It is preferable that the imidation ratio of the polyimide of this invention is 50% or more, Preferably it is 70% or more, More preferably, it is 90% or more.
    [220] The polymer component of the present invention contains polyamic acid B of formula (1), polyamic acid (A) of formula (2) and soluble polyimide of formula (3) as essential components, and the ratio of polyamic acid A to soluble polyimide is 1 by weight. / 99 to 99/1, preferably 10/90 to 90/10, the total amount of which is 1 to 80% by weight, preferably 2 to 50% by weight, more preferably 4 to 30% by weight of the total polymer components. %to be. Therefore, the proportion of polyamic acid B in the total polymer component is calculated as 99 to 20% by weight, the preferred ratio is 98 to 50% by weight, and the more preferable ratio is 96 to 70% by weight.
    [221] In the ratio of the polyamic acid A and the soluble polyimide, the pretilt angle is hardly increased at 1% by weight or less of the total amount of the polyamic acid A, and the effect of preventing afterimages is small at 99% by weight or more. Moreover, since applicability | paintability tends to worsen when the ratio of the soluble polyimide which occupies in a polymer component increases, it is preferable that this ratio is 25 weight% or less. In addition, it is preferable that the ratio is 1 weight% or more from the surface of an afterimage prevention. Moreover, as long as the effect of this invention is not impaired, other polymers, such as polyamide or polyamideimide, which substituted H of polyamide, polyamideimide, or amide group (CONH) with another monovalent organic group, may be contained. .
    [222] The varnish composition of the present invention has such a polymer component and a solvent for dissolving it as an essential component, and the preferred proportion of the polymer component in the varnish composition is 0.1 to 40% by weight.
    [223] When apply | coating a varnish composition to a board | substrate, the operation of diluting the polymer component concentration in a composition with a solvent in advance and lowering for the film thickness adjustment may be needed. However, when the concentration of the polymer component exceeds 40% by weight, the viscosity of the composition becomes too high, so that even if a solvent is added, it does not mix well with the composition, and may cause adverse effects such as undiluted as expected. . In the case of a spinner method and a printing method, in order to maintain film thickness favorably, it is usually made into 10 weight% or less in many cases. In other coating methods, for example, immersion, the concentration may be lower than 10% by weight.
    [224] On the other hand, when the density | concentration of a polymer component is less than 0.1 weight%, the problem that the film thickness of the liquid crystal aligning film obtained becomes too thin tends to arise.
    [225] Therefore, the concentration of the polymer component is suitably 0.1% by weight or more, and preferably about 0.5 to 10% by weight in the usual spinner method, printing method and the like. However, depending on the application method of the varnish, it can be used at a thinner concentration.
    [226] The solvent used with the polymer component described above in the varnish composition of the present invention can be applied without limitation as long as it is a solvent having the ability to dissolve the polymer component.
    [227] As such a solvent, the solvent normally used in the manufacturing process and use aspect of a polyamic acid or soluble polyimide is suitable, It is good to select suitably according to a use purpose.
    [228] As an example of these solvents, aprotic polar organic solvents which are aprotic to polyamic acid and polyimide, for example, N-methyl-2-pyrrolidone, dimethylimidazolidinone, and N-methylcaprolactam , N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide or γ-butyrolactone can be used. In addition, other solvents for the purpose of improving the coating properties, for example, ethylene glycol monoalkyl such as alkyl lactate, 3-methyl-3-methoxy butanol, tetralin, isophorone, ethylene glycol monobutyl ether Diethylene glycol monoalkyl ether such as ether, diethylene glycol monoethyl ether, propylene glycol such as ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monobutyl ether Ester compound systems, such as dipropylene glycol monoalkyl ethers, such as dialkyl malonate, such as a recall monoalkyl ether and diethyl malonate, and a dipropylene glycol monomethyl ether, or these acetates, are mentioned.
    [229] The varnish composition of the present invention thus obtained is mainly suitable for the formation of the liquid crystal alignment film for TFT, but is usually 90 ° from the point that appropriate pretilt can be provided as necessary. It is useful for forming liquid crystal alignment films for TN devices, STN devices, OCB devices, ferroelectric liquid crystal display devices, or anti-ferroelectric liquid crystal display devices, and as a liquid crystal display device, a protective film and It can be used for an insulating film and the like.
    [230] When forming a liquid crystal aligning film, it is performed by the process of apply | coating a varnish composition on a board | substrate, the following drying process, and the process of performing the heat processing required for dehydration and ring-closure reaction.
    [231] Although a spinner method, a printing method, an immersion method, a dropping method, etc. are generally known as a method of an application | coating process, these methods can also be applied similarly to this invention. Moreover, as a process method of performing the heat processing required for a drying process and dehydration and a ring-closure reaction, the method of heat-processing in an oven or an infrared furnace, the method of heat-processing on a heating plate, etc. are generally known, These methods are also this invention. The same applies in.
    [232] It is preferable to perform a drying process at the comparatively low temperature within the range which can evaporate a solvent, and it is preferable to perform a heat processing process generally at the temperature of about 150-30 degreeC.
    [233] The varnish composition of this invention can contain various additives as needed. For example, in order to promote imidization, a catalyst according to this purpose, an antistatic agent in the case of requiring an antistatic improvement, or a silane coupling agent or a titanium type in the case of improving the adhesiveness with a substrate. Coupling agents, such as epoxy type, can be mix | blended. In addition, the varnish composition of the present invention has improved applicability, but does not prevent the addition of a surfactant for the purpose of further improving applicability.
    [234] As a liquid crystal composition used for the liquid crystal display element of this invention, it is obtained by mixing the compound selected from the compound groups in any one of Formulas 9-19 according to the objective of a liquid crystal composition. Moreover, a well-known compound can be mixed for the purpose of preparing a threshold voltage, a liquid crystal phase temperature range, refractive index anisotropy, dielectric anisotropy, a viscosity, etc. In addition, the atoms constituting these compounds can be substituted with their isotopes.
    [235] The following compound is mentioned as a preferable example of the compound of General formula (9), 10, or 11 used for the liquid crystal composition for constructing the liquid crystal display element of this invention.
    [236]
    [237]
    [238]
    [239]
    [240]
    [241]
    [242]
    [243]
    [244]
    [245] In the above formula,
    [246] R 1 and X 1 have the same meanings as in the description in the formulas (9) to (11).
    [247] The compound of the formula (9), (10) or (11) is a compound having a positive dielectric anisotropy value and is excellent in thermal stability or chemical stability, and particularly when preparing a liquid crystal composition for TFT requiring high reliability of high voltage retention or high specific resistance. Very useful compound.
    [248] When preparing the liquid crystal composition for TFT, the amount of the compound represented by the formula (9), (10) or (11) is in the range of 0.1 to 99.9 wt% with respect to the total weight of the liquid crystal composition, preferably 10 to 97 wt%, more preferably. Preferably in the range 40 to 95% by weight. In addition, the compound of formula 17, 18 or 19 may be further contained for the purpose of viscosity adjustment.
    [249] When preparing the liquid crystal composition for STN or TN, although the compound of Formula 9, 10 or 11 can be used, it is preferable to use it at 50 weight% or less.
    [250] The following compound is mentioned as a preferable example of the compound of General formula (12) or 13 used for the liquid crystal composition for configuring the liquid crystal display element of this invention.
    [251]
    [252]
    [253]
    [254]
    [255] In the above formula,
    [256] R 2 , R 3 and X 2 have the same meanings as the description in the descriptions of the formulas (12) and (13).
    [257] The compound of the formula (12) or (13) has a positive dielectric anisotropy value, a large value thereof, and is particularly suitable for use for the purpose of reducing the threshold voltage of the liquid crystal composition. Moreover, it is used for the purpose of broadening the nematic range, such as adjusting refractive index anisotropy value and making transparent point high. Moreover, it is used for the purpose of improving the steepness of the voltage-transmittance of the liquid crystal composition for STN or TN.
    [258] The compound of the formula (12) or (13) is a particularly useful compound when preparing a liquid crystal composition for STN or TN.
    [259] When the amount of the compound of the formula 12 or 13 in the liquid crystal composition is increased, the threshold voltage of the liquid crystal composition is small but the viscosity is increased. Therefore, as long as the viscosity of a liquid crystal composition satisfies a required value, it is advantageous to use it in large quantities because it can drive low voltage. When preparing a liquid crystal composition for STN or TN, the amount of the compound represented by Formula 12 or 13 is in the range of 0.1 to 99.9% by weight based on the total amount of the liquid crystal composition, but preferably 10 to 97% by weight, more preferably. Preferably from 40 to 95% by weight.
    [260] The following compound is mentioned as a preferable example of the compound of General formula (14), 15, or 16 used for the liquid crystal composition which comprises the liquid crystal display element of this invention.
    [261]
    [262] In the above formula,
    [263] R 4 and R 5 have the same meaning as the description in the description of the formulas (14) to (16).
    [264] Compounds of formula (14), (15) or (16) are compounds having negative dielectric anisotropy. Since the compound of the formula (14) is a bicyclic compound, it is mainly used for the purpose of adjusting the threshold voltage, adjusting the viscosity or adjusting the refractive index anisotropy. The compound of the formula (15) is used for the purpose of expanding the nematic range, such as increasing the clearing point, or for adjusting the refractive index anisotropy. In addition to the purpose of expanding the nematic range, the compound of the formula (16) is used for the purpose of decreasing the threshold voltage and for increasing the refractive anisotropy.
    [265] Compounds of formula (14), (15) or (16) are mainly used in liquid crystal compositions with negative dielectric anisotropy. Increasing its amount of use decreases the threshold voltage of the composition and increases the viscosity. Therefore, it is preferable to use less as long as the value required for the threshold voltage is satisfied. However, since the absolute value of dielectric anisotropy is 5 or less, when it becomes less than 40 weight% with respect to liquid crystal composition whole quantity, voltage driving may become impossible. The amount of the compound of the formula (14), (15) or (16) is preferably at least 40% by weight when preparing a composition for TFT having a negative dielectric anisotropy value, but is preferably 50 to 95% by weight. In addition, in order to control the elastic constant and control the voltage-transmittance curve of the composition, the compound of the formula (14), (15) or (16) may be mixed in the composition having a positive dielectric anisotropy. In this case, the amount of the compound of Formula 14, 15 or 16 is preferably 30% by weight or less.
    [266] The following compound is mentioned as a preferable example of the compound of General formula (17), 18 or 19 used for the liquid crystal composition used for the liquid crystal display element of this invention.
    [267]
    [268]
    [269]
    [270] In the above formula,
    [271] R <6> and R <7> has the same meaning as the description in description regarding General formula 17-19.
    [272] Compounds of the formula (17), (18) or (19) have a low absolute value of dielectric anisotropy and are close to neutral compounds. The compound of the formula (17) is mainly used for the purpose of adjusting the viscosity and adjusting the refractive index anisotropy. In addition, the compounds of the formulas (18) and (19) are used for the purpose of expanding the nematic range such as increasing the clearing point or for adjusting the refractive index anisotropy.
    [273] Increasing the amount of the compound of the formula (17), (18) or (19) increases the threshold voltage of the liquid crystal composition and decreases the viscosity. Therefore, it is preferable to use these compounds in large quantities, so long as the requirement value of the threshold voltage of a liquid crystal composition is satisfied. In the case of preparing the composition for TFT, the amount of the compound represented by the formula (17), (18) or (19) is preferably 40% by weight or less, more preferably 35% by weight or less based on the total amount of the liquid crystal composition. In addition, when preparing the liquid crystal composition for STN or TN, the usage-amount of the compound of Formula 17, 18, or 19 becomes like this. Preferably it is 70 weight% or less, More preferably, it is 60 weight% or less with respect to liquid crystal composition whole quantity.
    [274] Moreover, in the liquid crystal display element of this invention, except for special cases, such as a liquid crystal composition for OCB modes, by inducing the spiral structure of a liquid crystal composition, it is normally optical for the purpose of adjusting to the spiral pitch according to a twist angle, or preventing reverse twist. Add active compound. Although any optically active compound known for this purpose can be used, the following optically active compound is mentioned as a preferable example.
    [275]
    [276] The liquid crystal composition used for the liquid crystal display element of this invention normally adds these optically active compounds, and adjusts the pitch of a twist. It is preferable to adjust the pitch of a twist in the range of 40-200 micrometers as it is a liquid crystal composition for TFT and TN. It is preferable to adjust to the range of 6-20 micrometers as it is a liquid crystal composition for STN. Moreover, in the case of bistable TN mode, it is preferable to adjust to the range of 1.5-4 micrometers. Moreover, 2 or more types of optically active compound can be added for the purpose of adjusting the temperature dependence of pitch.
    [277] The liquid crystal composition used for the liquid crystal display element of this invention can be generally prepared according to the method used normally, for example, the method of melt | dissolving various components mutually under high temperature degree. In addition, the liquid crystal display element of the present invention is optimized by adding an appropriate additive as necessary in the liquid crystal composition to be used. Such additives are well known to those skilled in the art and are described in detail in the literature and the like. The liquid crystal display device of the present invention contains a dichroic dye such as a melocyanine series, a styryl series, an azo series, an azomethine series, a subfamily clock, a quinophthalone series, an anthraquinone series, or a tetrazine series in the liquid crystal composition used. Guest host (GH) mode liquid crystal display device, NCAP produced by microencapsulating nematic liquid crystal, polymer dispersed liquid crystal display device produced by forming 3D network polymer in liquid crystal [PDLCD, a representative example thereof is a polymer network liquid crystal display Element (PNLCD)], and a liquid crystal display element of birefringence control (ECB) mode or dynamic scattering (DS) mode.
    [280] 1. Description of the abbreviation of the raw material component and the polymer used in each Example
    [281] 1) tetracarboxylic dianhydride component
    [282] PMDA: pyromellitic dianhydride
    [283] CBDA: cyclobutane tetracarboxylic dianhydride
    [284] BTDA: butane tetracarboxylic dianhydride
    [285] 2) diamine compound component
    [286] DPM: 4,4'-diaminodiphenylmethane
    [287] DPEt: 4,4'-diaminodiphenylethane
    [288] 4Ch: 1,1-bis [4- (4-aminophenylmethyl) phenyl] -4-n-butylcyclohexane
    [289] 5ChCh: 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-pentylcyclohexyl) cyclohexane
    [290] 3) Solvent Ingredients
    [291] NMP: N-methyl-2-pyrrolidone
    [292] BC: Butyl Cellosolve
    [293] 4) polymer
    [294] PA acid A: polyamic acid A
    [295] PA acid B: polyamic acid B
    [296] PI: Soluble Polyimide
    [297] 2. Synthesis method of polymer used in the present invention
    [298] 1) Synthesis of Polyamic Acid
    [299] 4.89 g of DPM and 120.0 g of dehydrated NMP were added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, and stirred and dissolved under a dry nitrogen stream. While maintaining the temperature of the reaction system in the range of 5 to 70 ° C, the reaction was performed by adding 2.69 g of PMDA and 2.42 g of CBDA, and then reacting for 24 hours by adding 70.0 g of butyl cellosolve, resulting in a polymer concentration of 5%. 20 g of a polyamic acid (PA acid B1) varnish are obtained by weight. The weight average molecular weight of the polymer at this time is 75000.
    [300] Also about polyamic acid A1, the varnish with a polymer concentration of 5 weight% is synthesize | combined by the method similar to the above-mentioned method except having changed the raw material. The molecular weight at this time is shown in Table 1.
    [301] 2) Synthesis of Soluble Polyimide
    [302] In a 200 ml four-necked flask equipped with a thermometer, agitator, raw material inlet and nitrogen gas inlet, 4.23 g of 4Ch and 4.02 g of 5ChCh were added together with 54.37 ml of dehydrated NMP, and stirred and dissolved in a dry nitrogen stream.
    [303] While maintaining the temperature of the reaction system in the range of 5 to 70 ° C., 1.87 g of CBDA and 1.89 g of tetracarboxylic acids were added and reacted for 24 hours to obtain about 70 g of a polyamic acid solution having a concentration of 20% by weight. To this solution, 70 ml of NMP, 12.6 ml of acetic anhydride and 7.75 ml of pyridine are added, and the side chain group-containing PI (PI1) is synthesized by reacting for 2 hours while maintaining the temperature of the reaction system in the range of 100 to 140 ° C.
    [304] This PI1 is purified via reprecipitation and isolation by methanol addition, dissolution by NMP and reprecipitation by pure addition, and is 73,00 as a weight average molecular weight.
    [305] Raw material composition (molar ratio) of polyamic acid and soluble polyimide polymerTetracarboxylic dianhydrideDiamine compoundsMolecular Weight PMDACBDABTDADPADPEt4Ch5ChCh PA acid B12525 50 75000 PA acid A1 3515 32.517.5 83000 PI1 2525 32.517.573000
    [306] 3. Combination of varnish for formation of alignment film
    [307] Each polyamic acid uses a 5% by weight solution at the time of synthesis, and the soluble polyimide is also dissolved in NMP, followed by adding BC to finally 75% by weight NMP, 20% by weight BC and 5% by weight polymer. Solution.
    [308] These varnishes are mixed so as to have the ratios described in Examples and Comparative Examples, and then diluted to 3% again to form a coating liquid for forming an alignment film.
    [309] 4. Preparation of Cell for Alignment Film Evaluation
    [310] 1) Fabrication of cell for evaluation of voltage retention
    [311] Each coating varnish was applied on a glass substrate with a transparent electrode ITO with a spinner, prebaked at 80 ° C. for about 5 minutes, and then heated at 200 ° C. for 30 minutes. Next, the surface of the above-mentioned substrate on which the alignment film is formed is rubbed with a rubbing device to perform an alignment treatment. Subsequently, the gap material for 7 micrometers is spread | spreaded on the said board | substrate, the liquid crystal injection hole is left to the periphery with the surface in which the oriented film was formed, and it sealed with an epoxy hardening | curing agent, and the antiparallel cell of a gap 7 micrometers is produced.
    [312] The following liquid crystal composition is injected into these cells as a liquid crystal material, the injection hole is sealed with a photocuring agent, and UV irradiation is performed to cure the liquid crystal injection hole. Next, heat processing is performed at 110 degreeC for 30 minutes, and it is set as the cell for voltage retention evaluation. The composition of the liquid crystal composition used is described below (% is% by weight).
    [313]
    [314] The NI point of this composition is 81.3 ° C, and the birefringence is 0.39.
    [315] 2) Preparation of Afterimage Evaluation Cell
    [316] Transparent electrode ITO attachment (matrix electrode) Each application varnish was applied on a glass substrate with a spinner, prebaked at 80 ° C. for about 5 minutes, and then heated at 200 ° C. for 30 minutes. Next, the surface of the above-described substrate on which the alignment film is formed is rubbed with a rubbing device, an alignment treatment is performed, and then a gap material for 9 µm is sprayed on the substrate, and the surface on which the alignment film is formed is placed inside, and the liquid crystal is surrounded by the liquid crystal. Residue of injection hole is sealed with epoxy curing agent, 90 ° of gap 9㎛ Create a twist cell.
    [317] The liquid crystal composition is injected into the cell as a liquid crystal material, the injection hole is sealed with a photocuring agent, and the liquid crystal injection hole is cured by UV irradiation to seal the liquid crystal. Next, heat processing is performed at 110 degreeC for 30 minutes, and it is set as the afterimage evaluation cell. The liquid crystal material for afterimage evaluation is used by mixing 0.25 wt% of cholesteryl nonanoate with respect to the liquid crystal composition as the chiral agent in the liquid crystal composition.
    [318] 3) Fabrication of pretilt measuring cell
    [319] In preparation of the cell for voltage retention evaluation, the cell for pretilt measurement is produced by the same method except having produced the antiparallel cell which has a cell thickness of 20 micrometers using the gap material for 20 micrometers. In the pretilt measurement, the liquid crystal material also uses the same liquid crystal material (excluding chiral agent) at the time of voltage retention evaluation.
    [320] 5. Evaluation method of liquid crystal cell
    [321] Below, the evaluation method is demonstrated as an orientation film material of the varnish evaluated by this invention.
    [322] 1) How to measure the voltage retention
    [323] As for the method of measuring the voltage retention, as shown in Figs. 1 and 2, a square wave (V s ) having a gate width of 69 Hz, a frequency of 60 Hz and a wave height of ± 4.5 V is applied to the source, and the changing drain V D is applied. By reading with an oscilloscope. If the voltage retention is 100%, V D shown in Fig. 2 is in the shape of a rectangle indicated by a dotted line, but usually becomes a solid line gradually approaching zero. As a calculation method of a maintenance rate, it shows with the percentage of the area of a diagonal part from the area of a diagonal line and the area of a broken line. Therefore, 100% is the maximum value as the voltage retention. The measurement of voltage retention is measured at 60 ° C.
    [324] 2) Evaluation method of afterimage
    [325] DC voltage 5V is applied to the afterimage evaluation cell which filled the liquid crystal at 60 degreeC for 3 hours. Subsequently, an alternating voltage of 4 V (frequency 0.01 HZ) is applied at room temperature to visually evaluate the occurrence of afterimages under orthogonal nicotine. Evaluation of an afterimage is determined as follows.
    [326] ○: no afterimage ×: afterimage
    [327] 3) How to measure the pretilt angle
    [328] The measurement of the pretilt angle of a liquid crystal is measured by the crystal rotation method currently performed.
    [329] 4) Evaluation method of applicability
    [330] Regarding applicability, the agglomeration property is evaluated when applying the varnish by the spinner when producing the above-described cell. The judgment criteria are as follows.
    [331] ○: no aggregation
    [332] △: aggregation occurs around the substrate
    [333] X: There is a tendency to concentrate in the center part of a board | substrate
    [334] 6. Comparative Examples 1 to 14 and Examples 1 to 14
    [335] Table 2 shows the results when only polysoluble acid (pI1) or polyamic acid A component (PA acid A1) is mixed with polyamic acid B1 (PA acid B1). In addition, the result is shown in Table 3 and 4 when mixing three characters. In addition, in Tables 2-4, abbreviation VHR is voltage retention (%), and the number of a polymer component column is a mixing ratio by weight.
    [336] From this result, it is judged that the pretilt angle becomes larger in the case of using PA acid A1 in combination with PA acid B1 and in the case of a three-component system in which PI1 is used in combination, compared with the case where only soluble polyimide is mixed in PA acid B1. . Moreover, as can be seen when comparing the diamine component used as a raw material of PI1 and PA acid A1, the component which has a longer side chain group of PI1 is used together. In addition, since the amount of the component having a long side chain group is higher in the PI1 side than in the case of PA acid A1, this is the reason why the PI1 side can contribute to making the pretilt angle larger than that of PA acid A1. This point indicates that the mechanism is not clear, but it is difficult to increase the pretilt angle in polyimide. From this result, it can be predicted that the generation of a domain that is likely to occur when the pretilt angle is small can be easily prevented. Therefore, since it is no longer necessary to mix a large amount of polyimide for the purpose of increasing the pretilt angle, it is possible to prevent deterioration of applicability caused when mixing a large amount of polyimide.
    [337] In addition, the residual image problem in the mixing system of the polyamic acid B component and the polyamic acid A component is also considered to be improved by the three-component mixing system, and in the system without the polyamic acid B, the voltage retention is small. Afterimage is bad. In addition, in these Examples, the film thickness is also uniform (judged from the point where the interference color of the film is uniform), and there is no problem at all in the orientation of the liquid crystal.
    [338] Comparative Examples 1 to 10One2345678910 PA acid B1949290800949290800 PI168102010000000 PA acid A100000681020100 Pretilt angle0.81.21.42.6-6.68.710.210.910.7 Applicability○○○△×○○○○○ VHR98.698.598.498.2-98.898.698.698.496.8 afterimage○○○○-×××××
    [339] Examples 1-8 and Comparative Examples 11-12ExampleComparative exampleExampleComparative example One23411567812 PA acid B194.092.090.080.0094.092.090.080.00 PI11.21.62.04.0204.86.48.016.080 PA acid A14.86.48.016.0801.21.62.04.020 Pretilt acid5.67.37.36.85.22.73.03.44.34.0 Applicability○○○○△○○○○× VHR98.698.798.798.696.898.698.798.798.596.5 afterimage○○○○×○○○○× In Examples 1 to 4 and Comparative Example 11, PI1 / PA acid A1 = 20/80, and in Examples 5 to 8 and Comparative Example 12, PI1 / PA acid A1 = 80/20.
    [340] Examples 9-14 and Comparative Examples 13-14ExampleComparative exampleExampleComparative example 910111213131414 PA acid B194.092.090.080.0090.080.00 PI13.64.86.012.0601.02.010 PA acid A12.43.24.08.0409.018.090 Pretilt angle3.54.14.64.94.58.88.98.0 Applicability○○○○×○○△ VHR98.898.798.798.696.598.698.498.0 afterimage○○○○×○○× In Examples 9 to 12 and Comparative Example 13, PI1 / PA acid A1 = 60/40, and in Examples 13 to 14 and Comparative Example 14, PI1 / PA acid A1 = 10/90.
    [341] By using the varnish composition of the present invention in a liquid crystal aligning agent, it is possible to obtain an excellent liquid crystal display device having good orientation and coatability, arbitrarily adjusting the pretilt angle, no or less afterimages, and large voltage retention.
    [342] The varnish composition of the present invention is particularly preferably used in TFT devices (TN-type TFT, IPS devices), STN devices, or OCB devices, but the ferroelectric liquid crystal and the semi-ferroelectric liquid crystal display device are excellent because they are excellent in electrical properties and can be arbitrarily adjusted in pretilt angle. It can also be used as an aligning agent. In addition, the thin film which concerns on the varnish composition of this invention can be used as a protective film and an insulating film from the point which is excellent in an electrical characteristic.
    权利要求:
    Claims (20)
    [1" claim-type="Currently amended] A polymer component containing polyamic acid B of formula (1), polyamic acid (A) of formula (2) and soluble polyimide of formula (3) and a solvent for dissolving the polymer component, wherein the polyamic acid A and soluble poly The ratio of the mead is 1/99 to 99/1 by weight, the total amount of polyamic acid A and soluble polyimide is 1 to 80% by weight in the polymer component, and the polyamic acid B is 99 to 20% by weight in the polymer component. The varnish composition whose ratio of the polymer component to a varnish composition whole quantity is 0.1 to 40 weight%.
    Formula 1

    Formula 2

    Formula 3

    In the above formula,
    R 1 is a tetravalent organic radical derived from tetracarboxylic acids,
    R 2 is a divalent organic radical derived from a diamine, each a radical having no side chain group, a radical having a side chain alkyl group having less than 3 carbon atoms, or a radical having a mixed composition thereof,
    m is a positive integer,
    R 3 is a tetravalent organic radical derived from tetracarboxylic acids,
    R 4 is a divalent organic radical derived from a diamine,
    At least one of R 3 and R 4 is a radical having a side chain group of 3 or more carbon atoms or a radical of a composition containing the radical,
    n is a positive integer,
    R 5 is a tetravalent organic radical derived from tetracarboxylic acids,
    R 6 is a divalent organic radical derived from a diamine,
    p is a positive integer.
    [2" claim-type="Currently amended] The radical according to claim 1, wherein the soluble polyimide of formula (3) in the polymer component has a radical having at least one branched group having at least one of a tetravalent organic radical R 5 derived from tetracarboxylic acids and a divalent organic radical R 6 derived from a diamine. A varnish composition, wherein the ratio of polyamic acid A and soluble polyimide is 10/90 to 90/10 by weight, and the total amount of polyamic acid A and soluble polyimide is 2 to 50% by weight in the polymer component.
    [3" claim-type="Currently amended] The diamine according to claim 1 or 2, wherein in the polyamic acid B of the general formula (1), 10 to 100 mol% of the tetravalent organic radicals R 1 derived from tetracarboxylic acids are tetravalent organic radicals derived from alicyclic tetracarboxylic acids, and diamines. Derived from diamine containing a divalent organic radical derived from divalent organic radical R 2 divalent aromatic diamine, a divalent organic radical derived from alicyclic diamine, and two or more kinds of aromatic groups, alicyclic groups and aliphatic groups A varnish composition which is a radical of a composition containing at least one divalent organic radical selected from the group consisting of divalent organic radicals.
    [4" claim-type="Currently amended] The tetravalent organic according to any one of claims 1 to 3, wherein from 10 to 100 mol% of the tetravalent organic radicals R 1 derived from tetracarboxylic acids in the polyamic acid B of the general formula (1) are derived from alicyclic tetracarboxylic acids. A varnish composition, which is a radical and from 1 to 100 mol% of the divalent organic radical R 2 derived from diamine is at least one radical selected from the group consisting of radicals of the formula (4).
    Formula 4

    In the above formula,
    X is a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 or C (CH 3 ) 2 ,
    R 9 and R 10 are each independently hydrogen, methyl group or ethyl group,
    a and b are each 1 or 2,
    q is an integer from 0 to 3, and when q is 2 or 3, each X may be different from each other.
    [5" claim-type="Currently amended] The tetravalent organic derived from cyclobutane tetracarboxylic acids according to any one of claims 1 to 4, wherein in the polyamic acid B of formula (1), 10 to 100 mol% of tetravalent organic radicals R 1 derived from tetracarboxylic acids are derived from cyclobutane tetracarboxylic acids. A divalent organic radical R 2 derived from a diamine, which is a radical, is 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 1,4-bis [2- (4-aminophenyl) ethyl ] Benzene, 1,4-bis (4-aminophenylmethyl) benzene, 1,3-bis [4- (4-aminophenylmethyl) phenyl] propane and bis [4- (4-aminophenylmethyl) phenyl] methane A varnish composition which is a radical having a composition containing a divalent organic radical derived from at least one compound selected from the group consisting of compounds.
    [6" claim-type="Currently amended] The polyamic acid A of the formula (2) according to any one of claims 1 to 5, wherein R 3 is a tetravalent organic radical derived from an aromatic tetracarboxylic acid, a tetravalent organic radical derived from an aliphatic tetracarboxylic acid, and an alicyclic ring. sikgye tetrahydro are four of acids derived composed of the organic radical at least one selected four from the group consisting of an organic radical, R 4 is an aromatic diamine divalent organic radical, a divalent organic radical of the aliphatic sikgye diamine derived from a pedigree aliphatic Varnish composition consisting of at least one divalent organic radical selected from the group consisting of divalent organic radicals derived from diamines and divalent organic radicals derived from diamines containing at least two groups of aromatic groups, alicyclic groups and aliphatic groups. .
    [7" claim-type="Currently amended] The divalent derived from diamine according to any one of claims 1 to 6, wherein 1 to 100 mol% of divalent organic radicals R 4 derived from diamine in polyamic acid A of formula (2) have side chain groups having 3 or more carbon atoms. Varnish composition, which is an organic radical.
    [8" claim-type="Currently amended] The tetravalent organic radical R 3 derived from tetracarboxylic acids in the polyamic acid A of the formula (2) is a pyromellitic acid radical, a cyclobutane tetracarboxylic acid radical according to any one of claims 1 to 7. Or a pyromellitic acid radical and a cyclobutane tetracarboxylic acid radical, wherein 1 to 100 mol% of the divalent organic radical R 4 derived from diamine is represented by the formulas 5-1, 5-2, 5-3, 5- A varnish composition, wherein the varnish composition is at least one radical selected from the group consisting of 4, 6, 7, and 8 radicals, and 99 to 0 mol% thereof is at least one radical selected from the group consisting of radicals of the formula (4).
    Formula 5-1

    Formula 5-2

    Formula 5-3

    Formula 5-4

    Formula 6

    Formula 7

    Formula 8

    In the above formula,
    R 13 , R 25 and R 26 are each independently hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms,
    Ring A is a benzene ring or a cyclohexane ring,
    Z is a single bond, CH 2 , CH 2 CH 2 or oxygen,
    r is an integer from 0 to 3,
    s is an integer from 0 to 5,
    t is an integer from 0 to 3, and when t is 2 or 3, each Z may be the same or different from each other,
    In Formulas 5-1 to 5-4, any hydrogen on the benzene ring or the cyclohexane ring may be substituted with an alkyl group having 1 to 4 carbon atoms,
    However, in the formulas 5-2 and 5-3, the steroid skeleton may contain any ring reduced, enlarged, cleaved or three-membered ring, unsaturated bond at any position may be increased or decreased, and any position Hydrogen atom or alkyl group of may be substituted with any monovalent organic group,
    X 1 is a single bond, CH 2 , CH 2 CH 2 or oxygen,
    R 14 and R 15 are each independently hydrogen or a linear or branched alkyl group or perfluoroalkyl group having 1 to 12 carbon atoms, and at least one of R 14 and R 15 is a linear or branched alkyl group or purple having 3 or more carbon atoms Is a fluoroalkyl group,
    u is an integer from 0 to 3, and when u is 2 or 3, each X 1 may be the same or different from each other,
    In formula (6), any hydrogen on the benzene ring may be substituted with an alkyl group having 1 to 4 carbon atoms,
    X 3 and X 4 are each independently a single bond, O, COO, OCO, NH, CONH or (CH 2 ) n ,
    R 22 and R 23 are each independently a group of 1 to 3 rings having a single bond, an aromatic ring and / or an alicyclic ring [If R 22 and / or R 23 has 2 or 3 rings, these rings are single bonds; , O, COO, OCO, NH, CONH or (CH 2 ) n ], or a steroidal group,
    R 24 is hydrogen, fluorine, hydrocarbon group, fluorohydrocarbon group, alkoxy group, cyano group or OH group,
    n is an integer from 1 to 5,
    A 1 is a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms, wherein any non-adjacent methylene group in the group may be substituted with an oxygen atom,
    A 2 is a single bond or an alkylene group having 1 to 5 carbon atoms, wherein any non-adjacent methylene group in the group may be substituted with an oxygen atom,
    m is an integer from 0 to 3,
    n is an integer of 1-5.
    [9" claim-type="Currently amended] The tetravalent organic radical R 5 derived from tetracarboxylic acids in the soluble polyimide of the formula (3), the tetravalent organic radical derived from an aromatic tetracarboxylic acid, and an aliphatic tetracarboxylic acid according to any one of claims 1 to 8. At least one tetravalent organic radical selected from the group consisting of tetravalent organic radicals derived from and tetravalent organic radicals derived from alicyclic tetracarboxylic acids, and divalent organic radicals R 6 derived from diamine are divalent organics derived from aromatic diamines. A group consisting of a radical, a divalent organic radical derived from an alicyclic diamine, a divalent organic radical derived from an aliphatic diamine, and a divalent organic radical derived from a diamine containing two or more groups of an aromatic group, an alicyclic group and an aliphatic group. A varnish composition, wherein the varnish composition is at least one divalent organic radical selected from.
    [10" claim-type="Currently amended] The divalent organic derived from a diamine according to any one of claims 1 to 9, wherein 1 to 100 mol% of divalent organic radicals R 6 derived from diamine in the soluble polyimide of formula (3) have side chain groups having 3 or more carbon atoms. Varnish composition that is a radical.
    [11" claim-type="Currently amended] The tetravalent organic radical R 5 derived from tetracarboxylic acids in the soluble polyimide of the formula (3) is tricarboxycyclopentyl acetic acid, 3,3,4-tricarboxy-1, At least one radical selected from the group consisting of respective acid radicals of 2,3,4-tetrahydronaphthalene succinic acid, cyclobutane tetracarboxylic acid and butane tetracarboxylic acid, 1 to 100 mol thereof in a divalent organic radical R 6 derived from diamine % Is at least one radical selected from the group consisting of the radicals of the formulas 5-1, 5-2, 5-3, 5-4, 6, 7 and 8, 99 to 0 mol% of which is a group consisting of the radicals of formula 4 Varnish composition, which is at least one radical selected from.
    [12" claim-type="Currently amended] The varnish composition of any one of Claims 1-11 is used, The liquid crystal aligning agent characterized by the above-mentioned.
    [13" claim-type="Currently amended] It has an alignment film formed using the liquid crystal aligning agent of Claim 12, The liquid crystal display element characterized by the above-mentioned.
    [14" claim-type="Currently amended] The liquid crystal display according to claim 13, wherein the liquid crystal composition comprising two or more compounds containing at least one compound selected from the group consisting of the compounds of the formulas (9), (10) and (11) and at least one optically active compound as an optional component. device.
    Formula 9

    Formula 10

    Formula 11

    In the above formula,
    R 1 is a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group which is not adjacent to each other in the group may be substituted with —O— or —CH═CH—, and any hydrogen atom is Can be substituted with a fluorine atom,
    X 1 is a fluorine atom, a chlorine atom, -OCF 3 , -OCF 2 H, -CF 3 , -CF 2 H, -CFH 2 , -OCF 2 CF 2 H or -OCF 2 CFHCF 3 ,
    L 1 and L 2 are each independently a hydrogen atom or a fluorine atom,
    Z 1 and Z 2 are each independently 1,2-ethylene, 1,4-butylene, -COO-, -CF 2 O-, -OCF 2- , -CH = CH- or a single bond,
    Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    Ring C is trans-1,4-cyclohexylene or 1,4-phenylene in which the hydrogen atom may be substituted with a fluorine atom.
    [15" claim-type="Currently amended] The liquid crystal display device using a liquid crystal composition according to claim 13, which contains at least one compound selected from the group consisting of compounds of the formulas (12) and (13) and at least one optically active compound which is an optional component.
    Formula 12

    Formula 13

    In the above formula,
    R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    X 2 is -CN or -C≡C-CN,
    Ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl,
    Ring E is trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    Ring F is trans-1,4-cyclohexylene or 1,4-phenylene,
    Z 3 is 1,2-ethylene, -COO- or a single bond,
    L 3 , L 4 and L 5 are each independently a hydrogen atom or a fluorine atom,
    e, f and g are each independently 0 or 1.
    [16" claim-type="Currently amended] A liquid crystal display using a liquid crystal composition according to claim 13, which contains at least one compound selected from the group consisting of compounds of the formulas (14), (15) and (16) and at least one optically active compound which is an optional component. device.
    Formula 14

    Formula 15

    Formula 16

    In the above formula,
    R 4 and R 5 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    Ring G and ring I are each independently trans-1,4-cyclohexylene or 1,4-phenylene,
    L 6 and L 7 are each independently a hydrogen atom or a fluorine atom, but at the same time are not a hydrogen atom,
    Z 4 and Z 5 are each independently 1,2-ethylene, -COO- or a single bond.
    [17" claim-type="Currently amended] 15. The compound according to claim 14, which contains at least one compound selected from the group consisting of compounds of the formulas 9, 10 and 11 as the first component, and at least one compound selected from the group consisting of the compounds of the formulas 17, 18 and 19 as the second component. The liquid crystal display element containing the above compound and using the liquid crystal composition containing 1 or more types of optically active compounds as arbitrary 3rd components.
    Formula 17

    Formula 18

    Formula 19

    In the above formula,
    R 6 and R 7 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    Ring J, ring K and ring M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    Z 6 and Z 7 are each independently 1,2-ethylene, —C≡C—, —COO—, —CH═CH— or a single bond.
    [18" claim-type="Currently amended] 16. The compound according to claim 15, which contains at least one compound selected from the group consisting of compounds of formulas 12 and 13 as a first component, and at least one compound selected from the group consisting of compounds of formulas 17, 18 and 19 as a second component And a liquid crystal composition containing at least one optically active compound as an optional third component.
    Formula 17

    Formula 18

    Formula 19

    In the above formula,
    R 6 and R 7 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    Ring J, ring K and ring M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    Z 6 and Z 7 are each independently 1,2-ethylene, —C≡C—, —COO—, —CH═CH— or a single bond.
    [19" claim-type="Currently amended] 17. The compound according to claim 16, which contains at least one compound selected from the group consisting of compounds of the formulas 14, 15 and 16 as the first component and at least one compound selected from the group consisting of the compounds of the formulas 17, 18 and 19 as the second component. The liquid crystal display element containing the above compound and using the liquid crystal composition containing 1 or more types of optically active compounds as arbitrary 3rd components.
    Formula 17

    Formula 18

    Formula 19

    In the above formula,
    R 6 and R 7 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    Ring J, ring K and ring M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    Z 6 and Z 7 are each independently 1,2-ethylene, —C≡C—, —COO—, —CH═CH— or a single bond.
    [20" claim-type="Currently amended] 15. The compound according to claim 14, which contains at least one compound selected from the group consisting of the compounds of the formulas 9, 10 and 11 as the first component and at least one compound selected from the group consisting of the compounds of the formulas 12 and 13 as the second component. Liquid crystal containing at least one compound selected from the group consisting of compounds of the formulas (17), (18) and (19) as a third component, and containing at least one optically active compound as an optional fourth component. Display elements.
    Formula 12

    Formula 13

    Formula 17

    Formula 18

    Formula 19

    In the above formula,
    R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    X 2 is -CN or -C≡C-CN,
    Ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl,
    Ring E is trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    Ring F is trans-1,4-cyclohexylene or 1,4-phenylene,
    Z 3 is 1,2-ethylene, -COO- or a single bond,
    L 3 , L 4 and L 5 are each independently a hydrogen atom or a fluorine atom,
    e, f and g are each independently 0 or 1,
    R 6 and R 7 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein any methylene group that is not adjacent to each other in the group may be substituted with -O- or -CH = CH- , Any hydrogen atom may be substituted with fluorine atom,
    Ring J, ring K and ring M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom,
    Z 6 and Z 7 are each independently 1,2-ethylene, —C≡C—, —COO—, —CH═CH— or a single bond.
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    同族专利:
    公开号 | 公开日
    JP4686954B2|2011-05-25|
    US6746730B1|2004-06-08|
    WO2001000732A1|2001-01-04|
    KR100637013B1|2006-10-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-06-28|Priority to JP18255299
    1999-06-28|Priority to JPJP-P-1999-00182552
    2000-06-21|Application filed by 고토 기치, 칫소가부시키가이샤
    2002-04-10|Publication of KR20020026477A
    2006-10-23|Application granted
    2006-10-23|Publication of KR100637013B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP18255299|1999-06-28|
    JPJP-P-1999-00182552|1999-06-28|
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