TW200530712A - Composition for liquid crystal alignment film, liquid crystal alignment film, liquid crystal holding substrate and liquid crystal display device - Google Patents

Abstract

The present invention provides a composition for liquid crystal orientation film of polyimide group, which has high uniaxial alignment, an alignment film using this composition and liquid crystal holding substrate containing this alignment film, and an IPS liquid crystal display device which contains this liquid crystal holding substrate, has superior contrast, and less residual accumulated charges. More specifically, the present invention provides a composition for liquid crystal alignment film of polyimide group, containing polyimide of specific diamine and tetracarboxylic acid dianhydride or soulable polyimide, a liquid crystal alignment film formed by the composition, a liquid crystal holding substrate with this alignment film and a liquid crystal display device with this liquid crystal holding substrate.

Description

20053iQ3plf.2c IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a lateral electric field method for displaying by dominantly parallel to the surface of a substrate, meaning g " ps (inpi: two lateral electric field drive) Polyimide alignment for liquid crystal display elements = and alignment products formed using this composition and containing this alignment

Liquid crystal substrates and substrates with slit crystals are based on the electric field method. The display element is called a IPS display [prior art] liquid. Crystal display elements were originally used in notebook computers or desktop computers. Various types of liquid crystal display devices, such as viewfinders, (viewfin and projection type) of portable camcorders, have also recently been used as nozzles for optical display systems for television display elements, optical Fourier transform elements, and 7C components. In the past, liquid crystal display elements were mainly using nematic (say, display 7C), and now TN (Twi⑽ e_lc twisted nematic) type liquid crystal display elements that twist 9 () degrees are usually twisted more than ⑽ ° STN (Super Twisted Nematic liquid crystal display elements using 4 film transistors are known as TFT (Thin Film Qi Shenxin thin film) type liquid crystal display elements are gradually put into practical use. However, such liquid crystal display elements can be Correctly identify the viewing angle of the image. When viewed from an oblique direction, there are disadvantages such as decreased brightness or contrast, and half-color: brightness inversion in half (halfQne). It is expected that this viewing angle is in use. TN-type liquid crystal display element compensating film school, and the protrusion and the vertical alignment structures MVA technology (Multi_d〇main 6 20053iQ ^ plf.2 > c

Technology such as VerticalAhgnment 'multi-quadrant vertical alignment method) type element display element or IPS type liquid crystal display element of the direction-of-direction method has been improved and put into practical use. 2. Japanese Patent Laying-Open No. 6-1680878 and Japanese Patent Laying-Open No. 9-16565. Among them, the method of using an optical compensation film in a conventional TN-type liquid crystal display element, although the burden of equipment investment and the like is small, can be easily realized, but the effect of improving the viewing angle in half tone display is not good. • On the other hand, the vertical alignment type liquid crystal display device represented by the MVA type liquid crystal display device aligns the η-shaped nematic liquid crystal with negative dielectric anisotropy with respect to the normal direction of the substrate surface. Slanted and made invisible. Since the liquid crystal is vertically aligned when no electric field is applied, and no birefringence is generated at all, the polarized surface of human light passes through the liquid crystal with little change. Therefore, a black display can be easily realized under the positive polarization (CrOssedNicolstate), so the liquid crystal display element can obtain high contrast. This type of MVA type liquid crystal display element is a vertical alignment type liquid crystal display element which is very advantageous in terms of contrast. However, the MVA type liquid crystal display element is the same as the above-mentioned optical compensation film synchronization method, especially in the halftone tone display, and the liquid crystal is inclined with respect to the substrate surface, and the viewing angle characteristics are deteriorated. MVA 3! | Liquid crystal display elements reduce the viewing angle dependence or defect occurrence by forming a protruding structure on the substrate and controlling the tilt direction of the liquid crystal. There is still room for further improvement in this viewing angle characteristic. IPS, liquid crystal display elements are aligned with the liquid crystal substantially parallel to the substrate surface. At the same time, the electric field generated by the comb-shaped electrodes formed on the substrate is substantially parallel to the substrate surface of the 200520053P12O substrate, and the liquid crystal is rotated within the substrate surface for display. . Even if an electric field is applied to the ips-type liquid crystal display element itself, the liquid crystal does not tilt with respect to the substrate surface. Therefore, the birefringence basically does not change greatly with the change of the viewing angle. Therefore, the IPS-type liquid crystal display element can obtain very desirable viewing angle characteristics including halftone display. ~ But, IPS-type liquid crystal display elements are sensitive to the alignment state of liquid crystals because they are obtained in black display at the cross-polarization extinction position, and the contrast will decrease due to the occurrence of phosgene. This contrast problem is particularly serious when compared with an MVA type display element that uses vertical alignment to completely generate birefringence. As mentioned above, the IPS liquid crystal display element has superior quality in terms of viewing angle compared with other methods, but is inferior in contrast to the MVA type liquid crystal display element, which is famous for crystal display elements. For example, it can be used for makeup Nikkei Micro Devices (Nipponbori 7th and 8th), May 2003, p71 〇 The contrast ratio of the white display brightness to the black display brightness ratio is used to express the φ liquid display element One of the indicators of performance. Generally speaking, the brightness of a white display does not change much, so the contrast depends largely on the black ... indicator'U degree as the denominator. Therefore, it is important to reduce the brightness of the black display in order to improve the South contrast. IPS-type liquid crystal display elements generally use a single polarizing plate to align with the alignment direction of the liquid crystal under orthogonal polarized light, and are used as normal black display without black display when no electric field is applied. When such a device is constituted, the uniaxial alignment of the right alignment film is insufficient, and the distribution of the alignment direction of the liquid crystal represented by the molecular arrangement rank 8 2005301¾ ^ orderness is caused by deterioration in display characteristics and decrease in contrast. Into the well: "'It can also cause black display ^ PS-type liquid crystal display element right side rubbing friction to give the alignment m uniaxial alignment. However, the area next to the step equipped with comb electrodes is difficult to ... The exposure of this area == 向 = leads to the deterioration of the contrast. The orientation produced by the alignment as described above is important for the uniaxial alignment of the naming IPS-type liquid-one system alignment film.

Said display: 彳 t; r is a 1ps type liquid crystal display element and any liquid is displayed for a long time after the same screen is displayed, go = to: when the previous image is left as a residual image is called residual In particular, in order to obtain a high-quality liquid crystal display element, it is necessary to cover this problem. The reason for the remaining is thought to be: the accumulation of charges such as impure ions contained in the membrane surface, the second liquid phase, or the voltage applied to the remaining% liquid phase can not be eliminated. Day-to-day knife Because the electric field directions of the TN and IPS methods are different, the voltage elimination process of the liquid crystal accumulation is also different. In summary, in the D-N method, the applied electric field is perpendicular to the substrate direction, and the ship crystal layer is in line with the alignment film or the insulation film. At the same time, it is conceivable that in the IPS method, the liquid crystal layer is aligned in parallel with the alignment film, the insulating film, and the components of the substrate. This can be achieved by applying an electric field in the horizontal direction of the substrate. Therefore, since the electrical connection between the liquid crystal layer and other cell components is different, and the IPS method and the TN method have different electrical actions, the IPS liquid crystal display element must take a unique countermeasure to reduce the accumulated charge. 9 200530¾¾ For example, refer to the non-patent literature, LCD, 1998, r Le 2 Vol. At present, there have been proposals to disclose polyimide containing sulfur bonds in a TN-type liquid crystal display element, which can form a liquid crystal alignment agent with less accumulated charge, but the liquid crystal layer and other box structures are not described. In the connected IPS-type liquid crystal display element, "j", "', for example, refer to Japanese Patent Application Laid-Open No. Hei 5-263263. ~ Furthermore, polyimide containing sulfur bonds in the IPS method has been disclosed. However, the effect of sulfur bonds on the contrast or reducing the accumulated charge in the IPS method has not been disclosed. For example, refer to Japanese Patent Laid-Open No. Hei 5 -2630i and Japanese Patent Laying-Open No. 10 ~ 10535. [Non-Patent Document 2] Liquid Crystal '1998 Vol. 2 P311 [Summary of the Invention] The object of the present invention is to provide a composition for forming a polyfluorene-based liquid crystal alignment film having a high uniaxial alignment film, and use the composition An alignment film formed from a substrate, a liquid crystal holding substrate containing the alignment film, and an IPS-type liquid crystal display element containing the liquid crystal holding substrate, which has excellent contrast and does not cause a reduction in residual accumulated charges. The present inventors made intensive research to solve the above-mentioned problems, and found that a composition for a polyimide / liquid crystal liquid crystal alignment film containing a polyimide acid or a soluble polyimide, which is a reaction product of a specific diamine and a tetracarboxylic dianhydride, is composed of The liquid crystal alignment film formed by the composition, the liquid crystal holding substrate containing the alignment film, and the liquid crystal display element containing the liquid crystal holding substrate are very effective for solving the problems, and thus completed the present invention. 10 200530¾¾.¾ The structure of the present invention is as follows. (1) A polyimide-based liquid crystal alignment film composition suitable for a transverse electric field type liquid crystal display element, comprising polyamidic acid or polyimide, which is a reaction product of a tetracarboxylic dianhydride and a diamine. The diamine contains the compound of the formula [1] as an essential component, and further contains at least one of the compounds of the formula [2] and the formula [3]. H2N one x "Nh2 [1] H2N-χ — χ2 one X one base [2]

[3] In the formula, & is a divalent organic group contained, each X is an intrinsic bad or cyclohexane, and χ2 is a divalent organic group containing-(CH2) n- or. 1 is an integer of 2 to 7, and Ri and R2 are each a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 5 stone groups or an alkoxy group having 1 to 5 carbon atoms. (2) The composition for a liquid crystal alignment film according to item 1, wherein '' in Formula [1] is a divalent group represented by Formula [4].仏 Ma—Y "— [4] is single C 3 is or Yang Shi, respectively, Y is 0 or _〇 ... u is 0 or 1, u is 0 when q is 0, u is 1" ,, 1 or 2, r is an integer from 2 to 10. (3) The composition for a liquid crystal alignment film according to item 2, wherein the divalent group not included in the formula [4] is a group represented by the formula [5] or the formula [6]. [5] 20053 < 〇7 ^ pild2:

S- (CH2) —s

In the formula, t is 1, 2 or 3, and rl is an integer of 2 to 7. (4) The composition for a liquid crystal alignment film according to item 2, wherein the group represented by the formula [4] is a divalent group represented by the formula [7].

[7] (5) The composition for a liquid crystal alignment film according to any one of items 1 to 4, wherein X2 in the formula [2] is a divalent group represented by the formula [8]. —Y — (Z — Y) m— [8]

Y is -0-, a benzene ring, a cyclohexane ring, a single bond, a divalent group represented by formula [9] or formula [10], Z is an alkylene group having 2 to 7 carbon atoms, and m is 0 or l, p is 1 or 2. However, when m is 0, Y is -0-, a group represented by formula [7] or formula [8]. (6) The composition for a liquid crystal alignment film according to item 5, wherein in formula [8], Υ is a single bond. (7) The composition for a liquid crystal alignment film according to item 5, wherein in formula [8], Υ is a divalent group represented by formula [9]. 12 200530 ^ pJf2c (8) The composition for a liquid crystal alignment film according to item 5, wherein in the formula [8], Y is a divalent group represented by the formula [10]. (9) The liquid crystal alignment film composition according to any one of items 1 to 8, in the formula [3], R! And I are each a fluorene atom or an alkyl group or an alkoxy group having a number of ∼3, respectively. . (10) The liquid crystal alignment film composition according to any one of items 1 to 9, wherein the position of the two amine groups in the formula [3] is a para position. (11) The liquid crystal alignment film composition according to any one of 1 to 10, wherein in the diamine, a compound of the formula π] and a formula m, a compound of the formula π] and a formula [3], or a formula Π] In the combination with the compound of the formula [2] and the formula [3], the content of the compound of the formula [丨] is 30 to 99 mol%, and the total content of the compound of the formula [2] and the formula [3] is 1 to 70 mol Er%. (12) The liquid crystal alignment film composition according to any one of items 1 to 11, wherein the tetra-acid dianhydride is composed of 20 to 80 moles of 0 / 〇 pyromellitic dianhydride and 80 to 20 moles. % Cyclobutane tetraacid dianhydride. (13) A liquid crystal alignment film formed from the liquid crystal alignment film composition according to any one of 1 to 12. (14) A liquid crystal holding substrate comprising the liquid crystal alignment film according to item 13. (15) A liquid crystal display element including a liquid crystal alignment film according to item 13 on a liquid crystal holding substrate having electrodes disposed on a liquid crystal surface. ^ (16) A composition for a liquid crystal alignment film suitable for a transverse electric field type liquid crystal display element, comprising a polyamic acid or a polyimide, which is a reaction product of a tetracarboxylic dianhydride and a diamine, characterized in that the liquid crystal alignment The composition for a film contains at least 13 20053Θ? ΡI & The following reaction product A and reaction product B are included. The reaction product A ·· tetracarboxylic dianhydride and a diamine containing a compound of the formula [1] as an essential component, polyamidic acid or polyimide. Reaction product B: a polyamic acid or a polyimide that is a reaction product of a tetracarboxylic acid dianhydride and a diamine containing a compound of the formula [2] as an essential component. H2N-X-X2-X-NH2 [2] where X is a divalent organic group containing -S-, X is a stupid ring or cyclohexane, respectively. X2 is a group containing-(CHJn- or -〇- Divalent organic group, η is an integer of 2 to 7. (17) The composition for a liquid crystal alignment film according to item 16, wherein in formula [η, Xi is a divalent group represented by formula [4] -[4] where A is " ^ ~ or-((:: 112) ", γ is a single bond, -S- or -〇-, u is 0 or 1, and u is 0 When q is 0, when u is 1, q is 0, 1, or 2'r is an integer from 2 to 10.

(18) The composition for a liquid crystal alignment film according to item 17, wherein the divalent group represented by the formula [4] is a divalent group represented by the formula [5] or the formula [6].

S— (CH2) 7TS

[5]

[6] In the formula, t is 1, 2 or 3, and rl is an integer of 2 to 7. (19) The composition for a liquid crystal alignment film according to item 17, wherein the group represented by the formula [4] 14 20053305 »42 is a divalent group represented by the formula [7]. m-y ~ (z-Y) m- (20) The composition for a liquid crystal alignment film according to any one of items 16 to 19, wherein & in the formula [2] is 2 shown in the formula [8] Valence group. [8]

σ [9] 々 (c%-[10] Y is -0-, benzene ring, cyclohexane ring, single bond, divalent group of formula [9] or formula [10], respectively, z is An alkylene group having 2 to 7 carbon atoms, m is 0 or 'P is 1 or 2. However, when m is 0, γ is a group not represented by Formula [7] or Formula [8]. (21) The composition for a liquid crystal alignment film according to item 2 (), wherein Y is a single bond in formula [8].

Y (22) The composition for a liquid crystal alignment film according to item 20, wherein (23) the liquid crystal alignment according to item 20 in the formula [8] is a divalent group represented by formula [9] The composition for a film has a divalent group represented by the formula [10] in Formula [8] 'Y. (^ 4) The liquid crystal alignment film composition according to any one of items 16 to 23, ': The content of the reaction product A in the polydonimide-based liquid crystal alignment film composition A c · 50 ～ 95 Moore. / 〇, the content of the reaction product B is 5 mol% to 50 mol 0 / 〇. (25) The liquid crystal alignment film composition according to any one of items 16 to 24, 15 20050 ^ pt2c, wherein the tetracarboxylic dianhydride used in the reaction product A is composed of 20 to 80 moles. / 〇 pyromellitic dianhydride with 80 ~ 20 Moore. / 〇 cyclobutane tetraacid dianhydride. (26) The liquid crystal alignment film composition according to any one of items 16 to 25, wherein the tetracarboxylic dianhydride used in the reaction product B is composed of 20 to 80 mol% pyromellitic dianhydride It is composed of 80 to 20 mol% of cyclobutane tetraacid dianhydride. (27) A liquid crystal alignment film formed of the liquid crystal alignment film composition according to any one of items 16 to 26. (28) A liquid crystal holding panel containing the liquid crystal alignment film according to item 27. (29) A liquid crystal display element including a liquid crystal alignment film as described in Item 27 on a liquid crystal holding substrate having an electrode facing a liquid crystal surface. The present invention may lengthen the IPS-type liquid crystal display element having particularly excellent contrast and reducing residual DC without causing residual accumulated charge reduction, an alignment film capable of achieving this purpose, and a composition for a liquid crystal alignment film capable of forming the alignment film. > In order to make the above and other objects, features, and advantages of the present invention more comprehensible, preferred embodiments are described below in detail with the accompanying drawings, as follows. [Embodiment] A preferred form of the composition for a liquid crystal alignment film of the present invention is a polyfluorenic acid or a polyimide having a reaction product of a tetracarboxylic acid monoanhydride and a diamine. A composition for a liquid crystal alignment film, wherein the polyamidic acid or polyimide & imine contains a compound of formula [II] as an essential component, and further contains at least one diamine of the compounds of formula [2] and formula [3] Copolymerization reaction with tetracarboxylic dianhydride 16 20053〇77p12 It is a composition of polyimide / liquid crystal alignment film which is characterized by a soil product and is suitable for a transverse electric field type liquid crystal display element. In the present invention, the diamine represented by the formula [1] includes the following compounds.

o〇cr

R, R '= H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH

R, R, = H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH

17 2 11200530¾¾ 9 10

H2N

12

13 14 15

SH N " ^ N

16 17

z / S—R N ^ N -NH 2

H2N R = CH3, C2H5, C3H7, C4H9, C5H11, C6H13, C7H15

H2N

2

R = H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH 18

R two H, CH3, C2H5, C3H7, C4H9, C5Hll OCH3, OC2H5, OC3H7, Cl, Br, I, OH

R = H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH 21

R

R = H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH

R = H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH 18 23 20053i0 ^ p1f.2c 22

R = H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH

R = H, CH35C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH

R = H, CH35C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH 26

S- (CH2) -S n

25

n = 2 ~ 10 19 200530 ^ 1 ^ 28 29

20 37 20053 Hidden 36 Heart Oaas Mine 38 Η9Ν 弋 / -S- aaa 39 w Η2Ν〇-σΆ · σ n = 2 ~ 10 h2nU ^ s- (ch4U n (CH2)-S +

NH2 41 〇 / = \ H2N〇-〇r ^ -Cr

, NH X2 n = 2 ~ 10 42

2

NH 43 H2N〇-CT, ‘v〇r: n〇_s0s ~ ^ s-〇 "

NH 44 45 n = 2 ~ 10 h2n〇 ^ s-㈣; 0 ~ 〇-〇- (CH2) n-sHQNH2 46 n = 2 ~ 10 Η2Ν0 ^-(, η-δ " 〇 ~ δ-(CH2) rTS_0NH2 n = 2 ~ 10 21 20053〇77p1c2p 47

48

49

50

51

S " S ^ nh2

H2N Preferred diamines represented by formula [1] include the following compounds. 22 200530¾¾

Examples of the more preferable diamine represented by the formula [1] include the following compounds.

Particularly preferred diamines represented by formula [1] include the following compounds. Μ 1-2

One kind of diamine represented by formula [1] can be used, or two or more kinds can be mixed and used. 0 23 20053〇77pild2

Examples of the diamine represented by the formula [2] include the following compounds.

24 2005307¾¾ 72

n = 2 to 7 73

H2N

H2N 74

(C%-

n = 2 to 7 p = l to 2 NH〇 75 76

H2N

(CH2) n

nh2 h2n

^ (ch2) -QT n〇 ^ N n = 2 to 7 n = 2 to 7, P 2 1 to 2 77

78

_ (CH2) ten H2N'n_ / p

NH〇 p = l ~ 2 79 Η2Νοσ (,

nh2 h2n CHm n = 2 to 7 11 = 2 to 7, P = 1 to 2 81

H2N

(〇h2)

82

nh2 n = 2 to 7 n = 2 to 7 83

H〇N

(CH2) (CH slightly

• (CH2)

NH〇 η-2 ~ 7, P-1 ~ 2 25 20053Θ ^ ρ12〇 Preferred diamines represented by formula [2] include the following compounds 84

85 H2N 87 H2N 89 H2N 91 H2N JOr (ch2) 2 < y (ch2) 4 J ^ r (CH2) 6

86 H2N 88 H2N 90 H2N < y (ch2) 3 -o- (CH2) 5 o -Or (ch2) 7 points 92 92 ^^ (ch2) 2-〇 一 η2ν-^^ > -〇 一 ( ch2) 3-〇 ^^-nh2 93 94 h2n— ~ ^ ―〇 一 (ch2) 4-〇 一 nh2 h2n — (^ ~ ^ —〇 一 (ch2) 5-o-- ~ >-Bu 95 96 h2n -^ ~ ^)-O- (CH2) e-〇- ^ ~ -nh2 h2n- ~ > -〇 一 (ch2) 7-〇 一 ^ ~ > ^ nh2 97 98 H2N ^^ _ 0 ^^ _ ( CH2) 3〇Nh2 26 100200530¾¾ 99 h2N— (ch2) 4—h2n— ^ ~ ^ o— (ch2) 5- ^ ~ ^ —nh2 101 102 H2N — ^ ^ ^ ~ (CH2) 6— ^ ~ ^ --NH2 H2N — (~ y) —O— ^ — (CH2) 7 ~ ^ ~~ --nh2 103 h2n104 h2n105 h2n106 < y (ch2) 2 (ch2) 2 contention 2 〇-〇 乂 (ch2) 2 h2n-^^ -cd ~ ^ >-( ch2) 4 ^^-c ^^-nh2 107 h2n108 h2n109 h2n

Χ ^ 〇 ~ 〇-((: η2) 6 ^ Ό " · 〇η〇- I 110 h2n ^^ ch2 < ^ (ch2) 3 < ^ ch2 " < ^ Knh2 27 2005310¾ ^ 111 h2n 〇 * (ch2) 2 -o- (ch2) 6 (ch2) 2 112 h2n (ch2) 2 (ch2) 7 (ch2) 2 ~ Qr ^ 113 h2n 114! (CH2) 3 (ch2) 2 (CH2) 3 is called h2n115 h2n < y (CH2) 3 (CH2) 3 (CH2) 3 (CH2) 3 Or (ch2) 4 (CH2) 3 JOr 2

NH 丨 2

116 H2N) _ _ _ _ (CH2) 3 < y (CH2) 5 (CH2) 3 117

H2N (CH2) 3 o (ch2) 6 (CH2) 3 o

NH '2 118 h2n (CH2) 3 < y (ch2) 7 < y (CH2) 3 A more preferable diamine represented by formula [2] includes the following compounds 28 120 119 120h2n ^ D ^ 〇 ^) ^ nh2 (ch2) 2 121 122 H2N < y (CH2) 3 hQ ^ nh2 h2n < y (CH2) 4 124 123 H2N (CH2) 5 nh2 h2n ~ Qr (ch2) 2 < y (ch2) 2 2

NH

126 H2N

NH 2

127 H2N 2

128 H2N 2

129 H2N-^) kch2 < ^ (ch2) 3 ^^-ch2 < ^-nh2 One kind of diamine represented by formula [2] may be used, or two or more kinds of diamine represented by formula [3] may be used in combination. The following compounds are listed. 29 20053 ^^ 1 ^ 130

131

132

133

134

R = CH3, C2H5, C3H7, C4H9, C5Hl 1 R '= CH3, C2H5, C3H7, C4H9, C5Hl 1 R = CH3, C2H5, C3H7, C4H9, C5Hl 1 R, = CH3, C2H5, C3H7, C4H9, C4H9 Preferred diamines represented by formula [3] include the following compounds. 135 136 ch3 137 H2N H2N h2n l " ^ νη2 1 nh2 138 139 c2h5 140 H2N Λ H2N h2n 1 " ^ nh2 ^^ ch3 1 Li nh2

ch3

c2h5

30 2005307T5fdoc

146 147

OC2H5

〇C2H5

〇C2H5

〇c3H7

OC3H7

OC3H7 154 155 〇CH?

159 OH λ 160 h2n r ^ r -fV0H h2n / OH u 1! ^ NH !, OH 31 200530¾¾

OCH, 166

Examples of the more preferable diamine 'represented by the formula [3] include the following compounds

? CH〇

0CH3 H2N 172

use. The following formulas can be used: amines, or two or more types of ^, which are used to improve the black display characteristics when no voltage is applied, and the two amine groups are positioned adjacent to each other or in between. The person is better, and the m-type clothing just shown is suitable for private use, or used in combination with the diamines shown in formulas [2] and [3]. At this time, in the combination of the amines of the formulas ⑴ and ⑵, ⑴ and ⑶, or ⑴ and ⑺ t, the diamine content of the formula 为 is 30 mol%, which is better. If the content is 30% by mole or more, the liquid crystal display element using the obtained composition for a polyδimine-based liquid crystal alignment film obviously exhibits a significant effect of accumulated charge or residual DC reduction. Among the diamines represented by the formula, a diamine represented by the formula [2] and / or the formula [3] is used in combination, and a liquid crystal display element using a composition of a polyfluorene-based liquid crystal alignment film is used, and a black display is performed when no voltage is applied. The effect of improving the characteristics is obvious. The diamine content of the formula [2] and / or the formula [3] can increase the black display characteristics, and at the same time consider the effect of reducing the residual DC. The total content of the content is preferably in the range of imol% to 70mol%. Inside. Furthermore, the present invention may further include diamines other than the above formula [1], [2], and formula # (hereinafter referred to as "other diamines"). The ratio of other diamines in this case is preferably The total amount of diamine is less than 30%, and if it exceeds 30%, the liquid crystal display element using the composition for the sub-moon-type liquid crystal alignment film provided does not have the effect of reducing DC or improving contrast. Examples of compounds that can be used as the diamines other than the above formula [1], [2], and [3] are as follows. 4,4, -diaminodiphenylphosphorane, 3,3, -diaminodiphenylphosphorane, 3,3, difluorenyl-4,4, -diaminodiphenylphosphonium, 2,2 · di [4- (4-aminophenoxy) phenyl] propane, 2,2bis [4- (4-aminobenzyloxy) phenyl] hexafluoropropane, m-phenyl Diamine, p-phenyldiamine, m-diphenylphenyldiamine, p-diphenylphenyldiamine, 2,2, -diaminodiphenylpropane, p-diaminobiphenyl, 1, 1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, bis [4- (4-aminophenoxy) phenyl] -4-fluorenylcyclohexane, bis [4- (4-Aminophenylfluorenyl) phenyl] methane, 1,1-bis [4- (4-aminophenylfluorenyl) phenyl] cyclohexane, hydrazone, fluorene · di [4_ (4_aminophenylbenzene Fluorenyl) phenyl H-fluorenylcyclohexane, 1,1-di [4_ (4-aminophenylbenzyl) benzyl] hexane, 1,1-^-[4_ (4-aminobenzyl Group) phenyl] -4-fluorenylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] fluorene. 33 20053® W2 You can use one or more of the above-mentioned other diamines, or you can use a mixture of these two or more other diamines. In addition, the present invention is not limited to the above-mentioned diamine as long as the object of the present invention can be achieved. As the tetra-acid-anhydride, pyromellitic dianhydride is preferably used in a proportion of 20 mol% or more of the total amount of tetra-acid dianhydride used, and more preferably used in a ratio of ~ ⑽ mol 0 / 〇 Benzotetracarboxylic dianhydride. As the tetracarboxylic dianhydride other than stuply tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, H4,% cyclohexanetetracarboxylic dianhydride, 4_ (2,5_dioxotetrahydrofuran_3_yl ", ^ , Hydronaphthyl- 丨 succinic anhydride, 5- (2,5_dioxotetraol) _3_fluorenyl-3_cyclohexyl dianhydride ^ = good. The amount of pyromellitic dianhydride used is Below 80 mole%, the solubility of the polymer is improved. Above 20 mole%, in the liquid crystal display device using the obtained polyimide-based liquid crystal alignment film composition, it is easy to reduce the accumulated charge and the so-called residual DC. '° To the extent that the characteristics of the present invention are not impaired, other aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides may be used in combination. Examples of dianhydrides other than tetraacid dianhydride are listed below. 34 20053iQ ^ plf2 -17Q r \ ΛΊΑ

179

180 〇

35 2ΟΟ53ι03ρ12〇 185 186

191 192

193

195 194

Ο Ο

36 2OO53i03p12c

199 201

200 202

203 204 205

207 209

206 210 208

〇 37 213 212 20053iQXJf.2c

211

219

The above-mentioned tetracarboxylic acid dianhydrides may be used singly or in combination of two or more kinds. Further, as the applicable formula [丨], formula [2], and formula [3] used in the present invention

The amines used in combination with other diamines include non-limiting examples of the sulfonium dioxin-containing diamine containing sulfonium oxo, and those shown in formula [11] are suitable. Used in the present invention. H2N — ^ R5 ^ Si—〇) —s | ^ R5 ^ _NH2 In the formula [n], I and R4 are alkyl or phenyl groups of carbon number 丨 ~ 3, and R5 is fluorenyl, phenylene or Alkyl substituted phenylene. X is an integer of 1 to 6, and y is an integer of 1 to 10. 38 2 Ο Ο 5 3iQ ΑΙΑ Another suitable form of the composition for a liquid crystal alignment film of the present invention is a polyimide-based liquid crystal containing polyfluoric acid or a polyimide of the reaction product of a tetracarboxylic dianhydride and a diamine. A composition for an alignment film. This composition for a liquid crystal alignment film includes at least the following reaction product A and reaction product b, and is a liquid crystal alignment film composition suitable for a lateral electric field type liquid crystal display element. Reaction product A ... As a reaction product of tetracarboxylic dianhydride and a diamine containing a compound of the formula [丨] as an essential component, polyamidic acid or polyimide. H2N-X "NH2 tl] • Reaction product B: Polyamic acid or polyimide as a reaction product of tetracarboxylic dianhydride and a diamine containing a compound of the formula [2] as an essential component. H2N-X- X2-X-NH2 [2] In formula [1] and formula [2], X! Is a divalent organic group containing -S-, X is a benzene ring or cyclohexane, and X2 is containing _ (CH2) A divalent organic group of n- or -0, η is an integer of 2 to 7. In addition, the composition for a liquid crystal alignment film may contain only a reaction product A and a reaction product B, or may be necessary and may To the extent that the present invention is impaired, polyamines or polyimines other than the reaction product A and the reaction product B are further contained. The diamine used in the reaction product A is a compound of the formula [丨] The "essential component" may further be used in combination with formula [2], formula [3], the "other diamine", or a diamine represented by formula [11]. In addition, one type of various diamines may be used in combination, or may be used in combination. Two or more types are mixed and used. At this time, the content of the diamine of the formula [丨] in the combination of the above diamines varies with the reaction product A and the reaction product in the composition for a liquid crystal alignment film. The content of the substance B is different, and it is preferably 30 mol% to 100 mol ° / °, and more preferably 51 mol% to 100 mol%. The diamine of the formula [丨] The larger the content, the more effective it is to reduce the accumulated charge and so-called residual DC. Therefore, if the content is 30 mol% or more, it can be suitably used as a composition for a polyimide-based liquid crystal alignment film of the present invention. Examples of the tetracarboxylic dianhydride used in the reaction product A include the same examples as the tetracarboxylic acid dianhydride described in the description of the tetracarboxylic acid dianhydride. The acid dianhydride is preferably a proportion of 20 mol% or more of the total amount of tetracarboxylic dianhydride, and more preferably a pyromellitic dianhydride in a proportion of 20 to 80 mol%. Other than pyromellitic dianhydride The tetracarboxylic dianhydride is cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4- (2,5_dioxotetrahydrofuran-3-yl) _1,2, 3,4-tetrahydronaphthyl-1,2-diacid anhydride, 5- (2,5_dioxotetraol) -3-fluorenyl-3-cyclohexyl-1,2-diacid anhydride, etc. are preferred The tetracarboxylic dianhydride used in the reaction product A is preferably from 20 to 80%. The pyromellitic dianhydride is composed of 80 to 20% cyclobutanetetracarboxylic dianhydride. The diamine used in the reaction product B contains a compound of the formula [2] as an essential component, and can further use formulas [1] and [3], the "other diamine", or a diamine represented by the formula [11]. In addition, various diamines that can be used in combination may be used singly or in combination of two or more kinds. At this time, the content of the diamine of the formula [2] in the combination of the above diamines varies with the content of the reaction product A and the reaction product B in the composition for a liquid crystal alignment film, and is 30 mol% to 100 mol%. Preferably, it is preferably in the range of 51 mol% to 100 mol%. The larger the diamine content of the formula [2], the better the black display characteristics of the liquid crystal display element, so it is suitable. If the content is 30 mol% or more, it is suitable for use as the polyimide-based liquid crystal alignment surface composition of the present invention. Examples of the tetracarboxylic acid dianhydride used in the reaction product B include the same examples as the tetracarboxylic acid dianhydride described in the description of the tetracarboxylic acid-anhydride. That is, among the tetracarboxylic dianhydrides, it is preferable to use stuply tetratetracarboxylic dianhydride in a proportion of more than 20 mol% of the total amount of tetrasic dianhydride, and more preferably to use benzene in a proportion of 20 to 80 mol% Mesamic acid dianhydride. Tetrahexyl dianhydride other than pyromellitic dianhydride is% butane tetracarboxylic dianhydride, 1,2,4,5_cyclohexanetetracarboxylic dianhydride, 4_ (2,5_dioxolite Pyran-3-yl) -1,2,3,4-tetranaphthyl diacid anhydride, ^ (2, ^ dioxotetrafluoromethylcarbamoylcyclohexyl-1,2-diacid anhydride, etc. are preferred. It is preferable that the tetracarboxylic dianhydride used in the reaction product A is composed of 20 to 80% pyromellitic dianhydride and 80 to 20% cyclobutanetetracarboxylic dianhydride. Furthermore, the reaction produces The raw material composition of the product B is different from that of the reaction product A. The reaction raw materials of the reaction product A and the reaction product B of the tetracarboxylic dianhydride and the diamine may have the same raw material composition, but the reaction product at this time must be The above-mentioned copolymerization reaction product. The composition for a liquid crystal alignment film containing the reaction product A and the reaction product B is obtained by combining the reaction product A, the reaction product B, and the reaction product A added as necessary. It is prepared by mixing polyamidic acid or polyimide other than reaction product B. The content of mixed reaction product A is preferably 50 to 95 mol% of all polyamidic acid or polyimide. . If the content is 50 mol% or more, a liquid crystal display element using the obtained polyimide-based liquid crystal alignment film composition exhibits an effect of significantly reducing the accumulated charge and the residual DC. 20053〇77pi1 & The content of the reaction product b is preferably 5 to 50 mol% of the total polyamidic acid or polyimide. If the content is 5 mol% or more, the obtained polyimide-based liquid crystal alignment is used. The black display characteristics of the liquid crystal display element of the film composition are improved. Furthermore, in order to improve the adhesion between the liquid crystal alignment film material and the substrate of the present invention, amino silicon can be added to the liquid crystal alignment film composition. Compounds.

Examples of the aminosilane compound include p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenyltriethoxy Silane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, etc. The molecular weight of the polyamidic acid or soluble polyimide used in the present invention is, for example, a gel permeation chromatography (GPC), and the weight average molecular weight (] \ ^) in terms of polystyrene is 10,000 to 500,000, more It is preferably 20,000 to 200,000 ′. The concentration of the polymer component polyisocyanate or soluble sulfonium imine in the composition for the polyimide-based liquid crystal alignment film of the present Sanming is not limited, but it is preferably 0.1 to 40% by weight. When this composition is applied to a substrate, it is necessary to perform an operation of diluting the polymer components contained in the solvent in advance in order to adjust the film. When the high concentration is 40% by weight or less, the viscosity of the amine m2 composition of the liquid crystal alignment film is used, and it is necessary to dilute the liquid crystal alignment in order to adjust the film thickness. Hiroshima 2 has a film that maintains a good film when the spin coating method or printing method is used, and U is 1% by weight or less. Other coating methods, such as the wetting method or the 42 inkjet method, require lower concentrations. On the other hand, if the concentration of the polymer component is at least 0.1 wt%, it is easy to obtain an optimal alignment film thickness. For this reason, the concentration by the usual rotation method or printing method is more than or equal to 0. wt%, and preferably from 0.5 to 1 wt%. However, with this varnish coating method, thinner concentrations can also be used. In the polyimide-based liquid crystal alignment film composition of the present invention, the solvent used together with the polymer component is not particularly limited as long as it has a solvent-dissolving ability. This solvent covers solvents commonly used in the production process or application of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected for the purpose of use. Examples of these solvents are shown below. The soluble solvent of polyfluorene, acid or soluble polyfluorene imine is an aprotic organic solvent. Examples are N-ψ-based _2-succinofluorenone, bis-fluorated strontium, N 2 caprolactam, N_f-methylamidoamine, N, N_dimethylamidoamine, dimethyl-dimethylamidoamine, Ν, Ν • diethylmethylamidoamine, dimethyldiJ-existence: Neiyi, etc. Nesi said. Examples of other composites for the purpose of improving coating properties include alkyl lactate, naphthalene, isophorone, ethylene glycol monobutyl methyl dongmei butanol, tetrahydrodiol monoethyl _Etc.-Ethyl 1⑽ = trans-ethylene glycol monoethyl ether, diethyl acetate, triethyl ethylene glycol mono- or phenyl axyl, malonic acid :: =, propylene glycol monobutyl ether, etc. Dipropylene glycol mono ", dipropylene glycol monofilament, etc. Among the dipropylene glycol monolayers, it is preferred to use some acetic acid, vinegar and other brewing compounds. Its butyrin, ethylene glycol monobutyrate, Dimethyl ketone ketone, γ-butyl alcohol and dipropylene glycol mono; using ethylene glycol monoethyl bond, propylene glycol mono 43 200530 ^ 13 ^ The composition for the polyfluorene imide liquid crystal alignment film of the present invention, as necessary Various additives can be included. For example, 'Interactive agents that can achieve this can be mixed when the coating performance is desired, antistatic agents can be mixed when the antistatic property needs to be improved, or Ishiba can be mixed when the adhesiveness with the substrate is desired. A sintering coupling agent or a coupling agent. In the IPS type liquid crystal display device according to the present invention, the thin film converter is formed by The first transparent substrate is composed of a second transparent substrate opposite to the first transparent substrate and the liquid crystal sandwiched between the substrates. The first transparent substrate has a day electrode and a common electrode formed by the extension of the interactive comb teeth. The second transparent substrate It has a black matrix that shields light outside the pixel area, ochre moon, *. Used on transparent substrates such as comb electrodes, glass, etc. == Second == After metal: Etching with a photoresist pattern in a predetermined shape as a mask After that, a process of coating the composition for liquid crystal alignment f on the two obtained transparent substrates is performed, followed by a drying process, and a heat treatment process necessary for dehydration and closed-loop. Among the coating methods in the coating process, the conventional methods are spin-coating method, printing method, wetting method, dripping method, tincture method, etc. These methods can also be applied to the force necessary for the second reaction and coffee reaction of the present invention. Treatment process: = 3 Heat treatment method. These m treatment methods and m method on the heating table are also applicable to the present invention. The temperature of the solvent at a lower temperature within the allowable range of the base = Heat treatment process-generally preferably at ™ right 44 205053 077ρ12 〇 After the implementation of the alignment process of the obtained liquid crystal alignment film, the process of holding the crystal holding substrate through the spacer, the process of sealing the liquid crystal two-flying process, and sticking the polarizing film Process to manufacture liquid crystal display elements. Among the alignment processing methods in the process of alignment two, the conventional methods include friction method, 弁 " processing and transliteration method, etc. In the scope of achieving the purpose of the present invention, this method is applicable to the present invention. Invention. The method can also be used in the present invention. The alignment processing method that is particularly suitable for use in the present invention is realistic. Any friction place within the scope of the purpose: 5 ~ 25mm / SeC, roller rotation speed 500 ~ 2, _pm 〇 The cleaning liquid of the IPS liquid crystal display element of the invention is subjected to a cleaning treatment. The cleaning method can be used after cleaning, or can be cleaned by ultrasonic or ultrasonic cleaning. ,, steam You can use pure water or methanol, ethanol, = alone, or can be used together. T Ben et al. No hydrocarbons, chloro r methyl ethyl, etc. As cleaning liquid liniments, these same cleaning liquids are fully invented. Of course, the IPS-type liquid crystal display of the present invention is dizabel. ,of. There is no particular limitation, and the liquid crystal composition and product used for the towel can be made into a product. Examples of suitable liquid crystal compositions ^ Various anisotropic liquid crystal panels, Japanese Patent No. 263M35, Japanese Patent No. 3086228, Japanese Gazette No. 5-5, Japanese Patent No. 5-5 Japanese Patent Publication, Japanese Patent Publication No. Hei 8-157828, Japanese Patent Publication No. Hei 8-8231960, Japanese Patent Publication No. Hei 9 ~ 241644 45 20053® ^ plf2c (EP885272A1 specification), Japanese Patent Early Publication Japanese Patent Application Publication No. 302346 (Ep8060466A1 specification), Japanese Patent Early Publication Japanese Patent Application Publication No. 8-199168 (EP722998A1 specification), Japanese Patent Early Publication Japanese Patent Application Publication No. 9-235552, Japanese Patent Early Publication Patent Publication Japanese Patent Application Laid-Open No. 9-255956, Japanese Patent Early Publication No. 9: 241643 (EP concept 71A1 specification), Japanese Patent Early Temple = Japanese Patent Application Laid-open No. 10-204016 (EP844229A1 description * Bu = this patent Early Publication of Heihei 1G_Tsunami Bulletin, Japan = Publication of Heihei 10-231482, Early Publication of Japanese Patent Laid-Open No. 2_-087_ Second Detail-Move 2 Publication No. _. Material 1 Kai Di Kai can also use a heavy liquid crystal composition with a negative dielectric anisotropy, such as the test date, and the finished product. Better report, early Japanese patent = —Early Publication of Japanese Patent Publication No. JP-A ^^, Japanese Patent Publication No. 8-69, Lu 953, Japanese Patent Early Publication No. 10-168076, Ergen, Japanese Patent Publication No. Japanese Patent Publication No. 168453, Japanese Patent Publication No. Hei 10 ~, Early Japanese Patent 'Early Publication Japanese Patent No. 10-23_ Early Japanese Patent Publication No. ^ Japanese Patent Publication No. 1G-23699G, Early Japanese Patent Laid-Open No. 10 ~ 2, 236992, Japanese Patent Laid-Open No. 10-236994, Hashiba A, Japanese Patent Early Publication No. 10-237000, m, Japanese Patent Laid-Open No. 1-1994 Early Public Gong Heping 10 ～ 46 20053 &7; 7P.mk Mod, Japanese Patent Early Publication No. Gazette, Japanese Patent Early Thousands ω ~ 237024 Japanese Patent Early Publication No. Khan, -237035, Early Eight Hadite No. 237075, Sincere sincerity, a Japanese Patent Application Publication No. 10-237〇76 f ^ Hei 10-23 Patent Publication No. 1A1 Early Public Patent Publication No. 1G-2878 74, Japan / Straight, said this publication No. Kaiping omega-assisted with the patent No. 75 early Kaiping

-〇29581 The early publication of this patent, Japanese Unexamined Patent Publication No. U 29581, the Japanese Patent Early Publication, the Japanese patent_public_open 2i == 〇r The early publication of this patent, Japanese Patent Publication No. 2001 ~ 019965, and the first publication of Japanese Patent Publication No. 2001 ~ 019965. Japanese Patent Publication No. 2001-072626, Japanese Patent Publication No. 192-192657, etc. disclosed earlier in this patent that more than one optical activity is added to a liquid crystal composition with a dielectric anisotropy of positive or positive. There is no difference in the use of the compounds. In the above, the polyfluorene-based liquid crystal alignment film composition 3 is within the range of the characteristics of the present invention (preferably within 2G Moire%), and ^ 5 is used in combination with polyamino acids and soluble polyisocyanates containing other compositions. Polymer components such as acrylic polymers, acrylate polymers, etc. Furthermore, in the composition for a polyfluorene-based liquid crystal alignment film of the present invention, a polymer component such as a dicarboxylic acid or a derivative thereof is added to the composition for the liquid crystal alignment film within a range that is harmful to the purpose of the present invention. Polymer components such as polyamidoamine or tetralin dianhydride, a reaction product of diamine, or diamine or a derivative thereof with polyamine, such as polyamidoimine. In addition to the diamines shown in Formulas [1], [2], and [3] of the present invention, the diamines at this time include the above-mentioned diamines that can be used in combination with this diamine, and the like. A mixture of diamines. [Examples] Hereinafter, the present invention will be described by examples and comparative examples, but the present invention is not limited to these examples. The names of the tetracarboxylic dianhydrides, diamines, and solvents used in the examples and comparative examples are indicated by abbreviations. This abbreviation may be used in the following description.

Tetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride CBDA pyromellitic dianhydride PMDA 1,2,3,4-tetracarboxylic dianhydride diamine BBDA 4,4, diamine Diphenylphosphorane DDM 4,4'-diaminodiphenylsulfide ASD 4,4'-diamino-1,2-diphenylethenyl DDET 2-benzyl-1,4- Dibenyldiamine P1PDA 1,3-bis (4- (4-aminophenylphenyl) phenyl) propane BZ3 4,4'-diamino-1,3-diphenylpropane DDPP 4,4 ' -Diamino-1,4-diphenylbutane DDPB 1,4-bis (4-aminophenylthio) butane DDSB 1,3-bis (4-aminophenylthio) propane DDSP 1,2-bis (4-amine basic thio) ethyl DDSE 1,4-bis (4-aminophenyloxy) butane DDOB 1,3-bis (4-aminophenyloxy) DDOP 48 20053〇7? Ρ1Α

·· DDOE •• APE: APDS NMP GBL BC 1,2-bis (4-aminophenyloxy) ethane 4,4'-diaminodiphenyl ether 1,3'-bis (3-amine (Propyl) tetramethyldilithium scorch N-methyl-2-pyrrolidone γ-butyrolactone butyl cellulose solvent Example 1

1) Preparation of Polyimide-based liquid crystal alignment film composition A1 (varnish A1) A 200-ml four-necked flask with a meter / meter, agitator, raw material inlet, and nitrogen inlet was charged with i28gASD, 1.26gDDET, and 55.0g Dehydrated NMP 'lion dissolves under dry degassing. The temperature of the reaction system was maintained at 5 ° C, and U6g CBDA and 1.29g PMDA were added, and after stirring for 30 minutes, 25.0gBC and 15.0gGBL were added to prepare a varnish having a polymer concentration of 5% by weight. When the temperature rises due to the reaction during the reaction of the raw materials, the reaction is controlled by controlling the reaction temperature to 70 C or lower. In addition, in the examples of the present invention, the viscosity of the reactants was checked during the reaction, and the viscosity of the varnish after adding BC and GB1 reached 30 to 35 mPa.s (using an E-type viscometer, the reaction was terminated at 25.0, and the temperature was low. The weight average molecular weight of the obtained polyamic acid was 63,000. The weight average molecular weight was measured at a column temperature of 50 ° C using a GPC measuring device (ChromatoPack C-R7A, product name) manufactured by Shimadzu Corporation (company name). The varnish A1 obtained as described above was diluted with a mixed solvent of NMP / BC / GBL (= 60/25/15 'weight ratio) to adjust the concentration of all polymer components. 49 20053 The pI # was called 3% by weight. Varnish for cloth 2) Production of contrast and residual DC measurement celi Two glass substrates, such as a glass substrate with a comb electrode for IPS and a glass substrate without electrodes, as shown in FIG. 1 were used. The obtained coating varnish was applied as a spin coating film on the glass substrate with a comb-shaped electrode for IPS described above under a coating condition of 2300 melons for 15 seconds. After coating (8 minutes after TC 5 minutes, sintering was performed at 21 ot for 30 minutes to form a liquid crystal alignment film with a film thickness of about 8 Gnm. The obtained polyimide film was prepared using rice > 3 standard ruler. The friction treatment device manufactured by the company is used to perform friction treatment under the conditions of the fiber pushing amount of the friction cloth (fiber length 19mm: acetate fiber) H0mm, the specimen table moving speed 60mm / sec, and the roller rotation speed 1000rpm. The paid liquid crystal holding substrate was ultrasonically cleaned in ethanol for 5 minutes, and the film was washed with pure water in an oven for 12 minutes (TC drying for 30 minutes. The above IPS :: 4 μηι spacers were spread on a glass substrate with k-shaped electrodes After the surface with the alignment film formed as the inner side is opposed to the non-electrode glass substrate, it is sealed with Wang Ai milk curing agent to make a parallel assembly with an interval of 4 mm. The liquid crystal material is injected. The injection is made by light curing. After the C 2 was heat-treated for 30 minutes, a polarizing film was affixed to the outside of the opposite Lang substrate to form a contrast and residual DC measurement assembly. In addition, the glass substrate of the shape electrode and the glass substrate without the electrode were ° Feng Tong Orientation. The polarization transmission axis of the polarizing film on one side and the rubbing rod are two liquids, and the other side is arranged perpendicularly to this. As a liquid crystal material, the composition of the product A is shown below. The Nom point of this composition is 50 20053iQ3pt2c

100.0 ° C, the birefringence is 0.093. Liquid crystal composition A

F

17wt.% 17wt.%

C3H7 16wt.% I Owt.%

5wt.% LOwt.% C5H11

6wt.% 6wt.% 13wt.% • (1) Measurement of Contrast Thereafter, a liquid crystal panel evaluation device (LCD-5100, product name) manufactured by Otsuka Electronics Co., Ltd. was used for the contrast measurement assembly manufactured as described above. A transmittance-applied voltage curve was obtained, and the contrast ratio was calculated from the ratio of the luminance of the white display to the luminance of the black display to be 195. Furthermore, alignment spots such as friction marks or alignment defects were not found at all, and a very uniform display was obtained. The conditions for the contrast measurement are a driving voltage of 0 to 10 Vp_p, a driving frequency of 70 Hz, and a rectangular wave. 51 2OO53i03p12c (2) Residual DC measurement A 30Hz, 3V rectangular wave was superimposed with a DC voltage of IV for 30 minutes. The flicker elimination voltage was measured immediately. The absolute value of this value was used as the residual DC. The smaller the residual DC, the smaller the residual DC, which is considered good. The residual DC was 45 mV when measured using the method for measuring the residual DC prepared as described above. Examples 2 to 36 and Comparative Examples 1 to 6 were prepared with varnishes A2 to A36 and varnishes B1 to B6, respectively, as shown in Table 1 below. Instead of varnish A1 in Example 1, the contrast was the same as in Example 1. And evaluation of residual DC voltage. Fabrication of a TN assembly shown in Comparative Example 5 A pair of glass substrates with ITO (indium tin oxide) transparent electrodes were formed using a spacer of 4 µm, and 90 ° in the rubbing direction. In combination, a liquid crystal composition A to which an optically active compound was added was used, except that a polarizing film was applied in a normal black mode, and a TN assembly was produced by the same method as in the case for contrast and residual DC voltage measurement. 1 The evaluation of the residual DC voltage was performed similarly. Preparation of various varnishes Varnishes A2 to A36 and Varnishes B1 to B6 are prepared in the same manner as Varnish A1. When the temperature rises due to the heat of reaction during the reaction, the reaction temperature is controlled to about 70 ° C or lower. In addition, when preparing a polyamic acid varnish, check the viscosity of the reactants during the reaction. When the viscosity of the varnish after adding BC and GBL reaches 30 to 35 mPa.s (using an E-type viscometer, 25 ° C), the reaction is terminated. , Store at low temperature. 52 200530% 2 < It means that the initial polyamic acid was synthesized only in NMP, after which BC and GBL were added, and finally the polyamic acid concentration of the varnish was adjusted to 5% by weight. Molar ratio and weight average molecular weight of raw materials in Examples and Comparative Examples

The results are shown in Tables 1 to 4. 【Table 1】

Varic acid dianhydride " Diamine molecular weight 21 Assembly PMDA CBDA ASD DDET P1PDA BZ3 APE DDM Example 1 A1 25 25 25 25 63,000 IPS Example 2 A2 25 25 25 25 54,000 IPS Example 3 A3 25 25 25 25 65,000 IPS Implementation Example 4 A4 25 25 25 15 10 58,000 IPS Example 5 A5 25 25 25 25 68,000 IPS Example 6 A6 25 25 25 15 10 65,000 IPS Comparative Example 1 B1 25 25 25 25 25 55,000 IPS Comparative Example 2 B2 25 25 50 57,000 IPS Comparative Example 3 B3 25 25 50 70,000 IPS Comparative Example 4 B4 25 25 50 51,000 IPS Comparative Example 5 B5 25 25 25 25 48,000 IPS Comparative Example 6 B6 25 25 25 25 63,000 TN Note: 1) Tetracarboxylic dianhydride 2) Weight Average molecular weight [Table 2]

Varic acid dianhydride n diamine molecular weight 2) Assembly PMDA CBD A ASD DDSB DDSP DDSE DDET DDPB Example 7 A7 25 25 10 15 25 65,000 IPS Example 8 A8 25 25 10 15 25 61,000 IPS Example 9 A9 25 25 10 15 25 60,000 IPS Example 10 A10 25 25 25 25 6 63,000 IPS Example Π All 25 25 25 25 58,000 IPS Example 12 A12 25 25 25 25 57,000 IPS Example Π A13 25 25 10 15 25 63,000 IPS Example 14 A14 25 25 10 15 25 58,000 IPS Example 15 A15 25 25 10 15 25 57,000 IPS Example 16 A16 25 25 30 20 70,000 IPS Example 17 A17 25 25 30 20 68,000 IPS Example 18 A18 25 25 30 20 67,000 IPS Note: 1) Tetracarboxylic dianhydride 2) Weight average molecular weight [Table 3]

1 Example 19 Example 20 Varic acid dianhydride M diamine molecular weight 2> Assembly PMDA CBDA ASD DDOB DDOP DDOE DDET DDPB A19 25 25 20 10 20 71,000 IPS A2025 25 20 10 20 68,000 IPS ~ ~ f Example 21 Implementation Example 22 A21 25 25 20 10 20 69,000 IPS A22 25 25 20 10 20 68,000 IPS Example 23 Example 24 A23 25 25 20 10 20 64,000 IPS --- A24 25 25 20 10 10 20 65,000 IPS 53 20053QMf2 > c Note: 1 ) Tetracarboxylic dianhydride 2) Weight average molecular weight [Table 4] Varnish-Needle

BBD A

ASD

DDSB diamine

DDSP

DDSE

DDET

DDPB molecular weight 2) Assembly Example 25 Example 26 Example 27 Example 28 ~ Example 29 Example 30 1 Example 3T ~ Example 33 Example 34 Α25 Α26 Α27 Α28 Α29 Α30 Α31 —Α32 Α33 Α34 Α35 Α36 25 25 25 25 25 25 25 ~ ΊΓ 25 ~ 15 ~ ~ 25 ~ ~ Ϊ 25 25 25 25 25 25 25 ΤΓ 25 25 25 25 15 15 15 25 25 25 58,000 56,000

IPS

IPS 25 25 55,000

IPS 25 25 65,000 25 25 63,000

IPS 10 Τό ~ 10 15 15 15 62,000

IPS 30 25 ΤΓ 54,000 51,000

IPS IPS

IPS 20 30 20 65,000

IPS 30 20 62,000 61,000

IPS

IPS% Note: 1) Tetracarboxylic dianhydride 2) Weight-average molecular weight Contrast of varnishes A1 to A36 and varnishes B1 to B5 and the remaining DC value. Table 5 shows the remaining DC evaluation results. In the test method of the value of atr ', the preferred contrast ratio is 150 or more, and the preferred residual DC is 70 mV or less.

54 20053 ^ ¾¾ [Table 5]

Varnish contrast residual DC / mV Example 1 A1 195 45 Example 2 A2 175 62 Example 3 A3 205 58 Example 4 A4 185 60 Example 5 A5 175 65 Example 6 A6 202 55 Example 7 A7 230 55 Example 8 A8 205 57 Example 9 A9 220 57 Example 10 A10 250 60 Example 11 A12 210 63 Example 12 A13 235 64 Example 13 A13 240 55 Example 14 A14 220 57 Example 15 A15 235 57 Example 16 A16 250 50 Example 17 A17 210 52 Example 18 A18 230 52 Example 19 A19 190 60 Example 20 A20 185 60 Example 21 A21 200 60 Example 22 A22 195 63 Example 23 A23 180 63 Example 24 A24 200 63 Example 25 A25 230 55 Example 26 A26 205 57 Example 27 A27 215 58 Example 28 A28 250 61 Example 29 A29 205 63 Example 30 A30 230 63 Example 31 A31 240 57 Example 32 A32 220 59 Example 33 A33 230 59 Example 34 A34 250 53 Example 35 A35 210 55 Example 36 A36 225 55 Comparative Example 1 B1 110 85 Comparative Example 2 B2 115 35 Comparative Example 3 B3 210 110 Comparative Example 4 B4 180 120 Comparative Example 5 B5 106 100 Comparative Example 6 B6-130 55 2OO530 ^ p12c Preparation of various varnishes Varnishes A37 to A41 and Varnish B7 are prepared in the same way as Varnish A1. When the temperature rises due to the heat of reaction during the reaction, the reaction temperature is controlled to about 70 ° C or lower. In addition, when preparing a polyamic acid varnish, check the viscosity of the reactants during the reaction. After adding BC and GBL, the viscosity of the varnish reaches 30 to 35 mPa.s (using an E-type viscometer, the reaction ends at 25.0, Stored at low temperature. I thought, "Dare to make polyamines in NMP only in NMP", then add BC and GBL, and finally adjust the polyamic acid concentration of the varnish to 5% by weight. Raw materials of each example and comparative example Mole ratio and weight average molecular weight are shown in Table 6. [Table 6]

Varnish dianhydride n diamine molecular weight 2) Box PMDA CBD A APDS DDM BZ3 DDET DDPB DDBU Synthesis Example 1 A37 25 25 10 40 46,000 IPS Synthesis Example 2 A38 25 25 10 40 45,000 IPS Synthesis Example 3 A39 25 25 10 40 40. 〇〇〇IPS Synthesis Example 4 A40 25 25 10 40 43,000 IPS Synthesis Example 5 A41 25 25 15 35 38,000 IPS Synthesis Example 6 B7 25 25 Pl 10 40 40,000 IPS Note: 1) Tetracarboxylic dianhydride 2) Weight average molecular weight implementation Examples 37 to 42 and Comparative Example 7 Varnishes A37 to 42 and Varnish B7 and Varnish B2 were each formulated with the polymer composition shown in Table 7 below, and evaluations of contrast and residual DC voltage were performed in the same manner as in Examples. Among them, in the test method of the examples of the present invention, the preferred contrast is a value of 150 or more, and the preferred residual DC is a value of 70 mV or less. 56 2ΟΟ53ι03ρ1A [Table 7] Reaction product A Reaction product B Mixing ratio contrast i Residual DC / mV Example 3 7 B2 A37 A37 / B2 = 1/9 200 '~ 50 Example 38 B2 A38 A38 / B2 = 1 / 9 190 ~ ^ 5 'Example 3 9 B2 A39 A39 / B2 = l / 9 210 " 78 ~ Example 40 B2 A40 A40 / B2 = l / 9 220 ~ 60 " Example 41 B2 A41 A41 / B2 = l / 9 210 Example 42 B2 A37 A37 / B2 = 2/8 220 ~ 60 ~~ Comparative Example 7 B2 B7 B7 / B2 = l / 9 120 ~ 40 '~~ κ Examples 1 to 42 and Comparative Example 1 The results of ~ 7 show that a good IPS-type display element can be obtained by using a varnish having a contrast of 150 or more and a residual DC of 70 mV or less. In addition, the results of Example 1 and Comparative Example $ show that the cumulative charge reduction effect of ASD containing sulfur groups is not obvious in the TN-type liquid crystal display element and is unique to the IPS-type liquid crystal display element. Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of the protection can shall be determined by the scope of the attached patent application. [Brief description of the drawings] FIG. 1 illustrates a comb electrode structure for IPS. [Description of main component symbols] 〇 57

Claims (1)

20053i @ Wf2c 10. Scope of patent application: 1. A composition for liquid crystal alignment film 'Polyimine' is suitable for horizontal electric field mode liquid crystal display elements, which contains the reaction product of a tetracarboxylic dianhydride and a diamine A polyimide-based polyimide-based liquid crystal alignment film composition for polyimide, characterized in that the diamine includes a compound of formula [1] as an essential component, and further includes formula [2] and formula At least one of the compounds of [3], Η2Ν-Χ 「ΝΗ2 [1] Η2Ν — χ-Χ2-Χ-ΝΗ2 [21 Η〇Ν [3] In the formula, “χι is a divalent organic group contained, each χ is 2 and has been”, respectively, & is a divalent organic group containing _ (CH2) n- or -〇-, n 1L5 is an integer of ^, and R2 is a hydrogen atom, a hydroxyl group, an alkyl group having a carbon number or an alkoxy group having a carbon number of 1 to 5. The composition for the liquid crystal alignment film described in item 1 of the scope of patent application for it—X in formula [1] is a divalent group represented by formula [4], * [4] and U'A are respectively Bond, beijing uu or _ (CH2) r, Y is single 0, 1 嵝 0 ... u is 0 or l'u is 0 when q is 0, and u is 1 ^ 2 is an integer from 2 to 10. 1 is a substance, in which the liquid crystal alignment composition described in the second item of the patent application " The divalent group represented by the formula [4] is a group represented by the formula [5] or the formula [6], 58 20053 Secret 2. (CH2) 7rS_ ^ [6] where 't is 1, 2 or 3, and " is an integer from 2 to 7. = The composition for a liquid crystal alignment film according to item 2 of the scope of the patent application, and the group represented by the formula [4] in the formula is a divalent group represented by the formula [7]. [7] (Z-Υ), 1 Υ [8] 5. The composition for a liquid crystal alignment film according to any one of claims 1 to 4 in the scope of the patent application, wherein in the formula [2], χ2 is a divalent group represented by the formula [8], [10] Υ is -0-benzene ring, cyclohexane ring, single bond, formula [9] or formula [10] For divalent groups, ζ is an alkylene group having 2 to 7 carbon atoms, m is 0 or P is 1 or 2, where “1 is 0, γ is _〇_, formula [7] Or the group represented by formula [8]. 6. The composition for a liquid crystal alignment film as described in item 5 of the scope of patent application, in [8], γ is a single bond. In the above-mentioned composition for a liquid crystal alignment film ', in the formula [8], γ is a divalent group represented by the formula [9]. 8. The composition for a liquid crystal alignment film according to item 5 of the scope of patent application 59 2OO53i0SJr .2c. In the formula [8], Y is a divalent group represented by the formula [1〇]. Specialty: The composition for a liquid crystal alignment film described in the range item 1 and R2 are a hydrogen atom, Alkyl group or alkoxy group having 1 to 3 carbon atoms. The composition for a liquid crystal alignment film described in the first item of the patent scope has a position of two amine groups in formula [3] as a para position. 11. The composition for a liquid crystal alignment film as described in item 丨 of the patent application, wherein in the diamine, a compound of formula (2) and formula [2], a compound of formula [1] disc formula [3], or The content of the compound of the formula (1) in the combination of the formula [1] and the compound of the formula [2] and the formula [3] is 3G to 99 Mo, and the total content of the compounds represented by the formulas [2] and [3] is 1 to 70 mol%. 12. The composition for a liquid crystal alignment film according to item i in the scope of application for a patent, wherein the tetracarboxylic dianhydride is composed of 20 to 80 mole% of stearic dianhydride and 80 to 20 mole% of cyclobutane. Consisting of tetraacid dianhydride. 13. A liquid crystal alignment film formed of the liquid crystal alignment film composition described in item 丨 of the patent application scope. 14. A liquid sa holding substrate 'characterized by comprising a liquid crystal alignment film as described in item 13 of the patent application range. 15. A liquid crystal display element, characterized in that a liquid crystal alignment film as described in item 13 of the scope of patent application is contained on a liquid crystal holding substrate provided with electrodes facing the liquid crystal surface. 16 · —A composition for a liquid crystal alignment film, which is suitable for a 7L liquid crystal display device in a transverse electric field method, which is a reaction product containing polytetracarboxylic dianhydride and monodiamine—polyamic acid or polyimide The composition for polyimide-based liquid crystal alignment film is 20053〇77p12c, and is characterized in that the composition for liquid crystal alignment film contains at least one reaction product A and one reaction product B, and the reaction product A: the four A reaction product of a carboxylic dianhydride and the diamine containing a compound of the formula [1] as an essential component, the polyfluorenic acid or the polyimide; H2N — Xj — NH2 [1] the reaction product B: the Tetracarboxylic dianhydride and compound containing formula [2] An essential component of the reaction product of the diamine is the polyfluorene acid or the polyfluorene imine; Η2Ν-χ-χ2-χ_ΝΗ2 [2] where X is a divalent organic group contained, and X is benzene Cyclo or cyclohexane, X2 is a divalent organic group containing _ (CH2) nj-〇-, and n is an integer from 2 to 7. P. The composition for a liquid crystal alignment film according to item 16 of the scope of the patent application. In formula [1], X! Is a divalent group represented by formula [4]; [4] ^, a is Or _ (CH2) r_, Y is single 〇 Jian, S: or -〇-, u is 〇 or Bu is 0 when q is 0, q is 1, 1 or 2 when u is 1, r is 2 ~ 1 An integer of 〇. 18. The composition for a liquid crystal alignment film according to item 17 of the scope of the patent application, wherein the divalent group represented by the formula [4] is a divalent group represented by the formula [5] or the formula [6]; 61 [5] 2ΟΟ53ι03ρ12 ^ s— (CH2) —s [6] In the formula, t is 1, 2 or 3, and rl is an integer of 2 to 7. 19. The composition for a liquid crystal alignment film according to item 17 of the scope of patent application, wherein the group represented by the formula [4] is a divalent group represented by the formula [7]. 20. The composition for a liquid crystal alignment film according to item 16 of the scope of the patent application, in formula [2], X2 is a divalent group represented by formula [8]; —Y — (Z —Y) m— [ 8] Y is -0-, a benzene ring, a cyclohexane ring, a single bond, a divalent group represented by formula [9] or formula [10], Z is an alkylene group having 2 to 7 carbon atoms, and m is 0 or 1, and p is 1 or 2, wherein when m is 0, Y is -0-, a group represented by formula [7] or formula [8]. 21. The composition for a liquid crystal alignment film according to item 20 of the scope of patent application, in the formula [8], Y is a single bond. 22. The composition for a liquid crystal alignment film according to item 20 of the scope of patent application, in the formula [8], Y is a divalent group represented by the formula [9]. 62 200530 ¾¾¾ 23. According to the composition for a liquid crystal alignment film described in item 20 of the scope of patent application, in formula [8], Υ is a divalent group represented by formula [10]. 24. The composition for a liquid crystal alignment film according to item 16 of the scope of application for a patent, In the polyimide-based liquid crystal alignment film composition, the content of the reaction product A is 50 to 95 mole%. The content of the reaction product β is 5 mol% to 50 mol%. 25. The composition for a liquid crystal alignment film according to item 16 of the scope of the patent application, wherein the tetra-acid dianhydride used in the reaction product A is composed of 20 to 80 mol% pyromellitic dianhydride and 80 ~ 20 moles of 0/0 cyclobutane tetraacid dianhydride. 26. The composition for a liquid crystal alignment film according to item 16 of the scope of application for a patent, wherein the tetra-acid dianhydride used in the $ H1 reaction product B is composed of 20 to 80 mol% pyromellitic dianhydride and 80 to 20 mol% of cyclobutane tetraacid dianhydride. ^ 27 · A liquid crystal alignment film formed of the liquid crystal alignment film composition described in item π of the patent application scope. 28. —A liquid crystal holding substrate 'characterized in that it contains a liquid crystal alignment film as described in item 27 of the patent application range. 29. A liquid crystal display element characterized in that a liquid crystal alignment film as described in item 27 of the scope of patent application is contained on a liquid crystal holding substrate provided with electrodes toward a liquid crystal surface. '' 63