TWI306529B - Composition for liquid crystal alignment film, liquid crystal alignment film, liquid crystal holding substrate and liquid crystal display device - Google Patents

Description

I30652SU IX. Description of the Invention: [Technical Field] The present invention relates to a transverse electric field method for displaying by an electric field which is dominant parallel to a surface of a substrate, that is, an Ips (InPlane Switching) type liquid crystal An alignment film formed using the composition, an alignment film formed using the composition, a liquid crystal holding substrate containing the alignment film, and a lateral electric field type liquid crystal display element including the liquid crystal holding substrate (hereinafter, It is called IPS type liquid crystal display element). Φ [Prior Art] The liquid crystal display element was originally used for various liquid crystal displays such as a .4 thief of a notebook computer or a desktop computer, a viewfinder of a portable video recorder, and a projection type display device. The device has recently also been used as a display element for televisions. In addition, it is also used in optical printing system nozzles, optical Fourier transform elements and "grating optoelectronic components. In the past, liquid crystal display elements were mainly used as display elements using nematic liquid crystals, and now TN (Twisted Nematic) liquid crystal display elements with a twist of 9 degrees, and STNs that are usually twisted by i8 or more • SuperTwisted Nematic The column type> night crystal display element, and a thin film transistor called a TFT (Thin_fUm transist〇r thin film transistor) type liquid crystal display element are being gradually put into practical use. However, such a liquid crystal display element can correctly recognize the viewing angle of an image, and when viewed from an oblique direction, there is a decrease in brightness or contrast and a half color. Half tone has a shortcoming such as redundancy reversal. In recent years, this viewing angle problem is being achieved by using optically compensated TN Weijing display components and MVA (Multi d〇main I306S2@ifd〇c = ca subgnment, multi-quadrant vertical) using vertical alignment and protrusion structure technology. For example, the technique of the eigen-type device display device or the IPS-type liquid crystal display device of the electric field type is improved and can be used. For example, refer to Japanese Patent Laid-Open Publication No. SHO-121907, Japanese Patent No. (4) - Bulletin No. 1.8 and Japanese Patent Early Disclosure. Among them, the method of using an optical compensation film in the conventional TN type liquid crystal display device is easy to realize because the burden of the miscellaneous projection (4) is small, but the improvement effect of the half angle hue (halft_) display towel viewing angle is not good. The aspect of the vertical alignment mode liquid crystal display device represented by an MVA type liquid crystal display device is such that a negative dielectric constant anisotropic nematic nematic liquid crystal is aligned with respect to a normal direction of a substrate surface, and an electric field is applied to tilt the liquid crystal. Perform the display (four). Since there is no Weijia electric field, the liquid crystal tends to match, and no birefringence is generated at all. Therefore, the polarized surface of the human light is almost unchanged through the liquid crystal: therefore, the orthogonal display is sed Nic〇1, and the black display can be easily realized, so the liquid crystal display The component achieves high contrast. Such an MVA ship crystal display element is a vertical alignment type liquid crystal display element which is very advantageous in terms of degree. However, the MVA type liquid crystal display element is the same as the above-described material additive merging method, and _ is a halftone_tone), the liquid crystal is inclined with respect to the substrate surface, and the visibility is deteriorated. The MVA Weijing_ component is due to the formation of the protrusion structure on the substrate and the tilt direction of the control ship crystal. (4) Less visual dependence or defect occurrence. There is room for improvement in the viewing angle characteristics. The IPS type liquid crystal display element is such that the liquid crystal is aligned substantially parallel to the substrate surface, and the electric field substantially parallel to the surface of the 8 I3 〇 6529 Pifd 〇 c substrate is generated by the hanging electrode formed on the substrate, so that the liquid crystal rotates in the surface of the substrate. Displayed. 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 does not substantially change greatly depending on the viewing angle. Therefore, the IPS type liquid crystal display element can obtain a very desirable viewing angle characteristic including a halftone tone display.

In the case of the IPS type liquid crystal display element, since the black display is obtained at the orthogonal polarization extinction position, the alignment state of the liquid crystal is sensitive, and the contrast is lowered due to the occurrence of the light exposure. This contrast problem is particularly serious in comparison with MVA type display elements which do not produce birefringence at all by vertical alignment. As described above, the IPS liquid crystal display element is superior in quality to other methods in terms of viewing angle, but is inferior to the MVA type liquid crystal display element known as a wide viewing angle type liquid crystal display element in contrast, for example, Device (Japanese Y経 夕口, 〆彳乂),,, 2, 3, May, p71. The contrast ratio of the white display luminance to the black display luminance ratio is used as one of the indexes for expressing the performance of the liquid μ display element. In general, the white display brightness does not change much, so the contrast is largely determined by the brightness of the display as the denominator. Therefore, in order to improve the contrast, it is important to reduce the black display brightness. 0 * IPS type liquid crystal display element, generally, the direction of the single polarizing plate is aligned with the alignment direction of the liquid crystal by orthogonal polarization, and black display is performed when no electric field is applied. Normally black display. In the case of constituting such an element, if the uniaxial alignment property of the alignment film is insufficient, deterioration of the photoluminescence characteristic and deterioration of contrast due to the liquid crystal alignment direction distribution indicated by the molecular arrangement rank I306529pif.doc sequence occur. Further, it is also possible to impart an alignment film to the alignment film by rubbing treatment: 4, and the step side region having the comb electrode is difficult to be treated. Two-two configuration Single-axis alignment is not complete. Due to this area, the appearance of the alignment film deteriorates. [Organization of ordered alignment to produce photo-optical as described above] It is important to improve the uniaxial alignment of the IPS-type liquid helium alignment film.曰曰'", the contrast of the yak is not further controlled. As a problem common to IPS-type liquid crystal display elements, it can be cited that the same image is displayed for a long time: When the previous image is left as an afterimage remains, it is called: Very 2 get the quality of the liquid crystal display element 'improve this residual 现:;;; the problem. The remaining reason is considered to be the surface of the alignment film::: 2 pure ions and other charge accumulation, or due to residual Dc liquid crystal The voltage applied above cannot be eliminated. _ The mode is different from the electric field direction of the IPS method, in the liquid crystal layer

The tired voltage elimination process is also different. In summary, TN film m electricity (four) straight to the substrate direction 'hiding layer and alignment film or insulating film or insulation: connect two: r) fIPS mode liquid crystal horizontal direction expansion force ί into the knife king juxtaposed, which can be electric field along the substrate Therefore, since the electric 'lps mode between the liquid crystal layer and the other cell components is different from the TN mode, the X-Crystal display element must take a unique measure to reduce the accumulated charge. 130652ft if.doc For example, refer to the non-patent literature, Liquid Crystal", 1998. At present, there is a proposal to disclose a TN-type liquid crystal display element in a volume = 1: a sulfur-bonded polyimine can be used to form less than two. The liquid crystal alignment agent of the piece 'but does not explain the reduction of the accumulation in the liquid day and the liquid crystal display element; and the sum == can refer to the Japanese Patent Early Publication No. 5 - 2_^

In the case of the IPS, the sulphur bond and the IPS method are in the form of a contrast ratio, for example, the Japanese Patent Laid-Open Publication No. Hei. 7

[Non-Patent Document 2] Liquid crystal, 1998, Table 2, Ή; UA. SUMMARY OF THE INVENTION Niu Di 2 volumes P3H can be formed into a directional alignment mold and an IPS type liquid crystal display element having the alignment film and the shape retention substrate, which has excellent contrast and is excellent. , how to reduce the power of the hair%% of the solution to solve the problem of the 麟 麟 ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢 醢The liquid crystal display element having the composition t:: liquid crystal alignment film, the liquid crystal holding substrate containing the alignment film, and the 2 t liquid crystal holding substrate is very effective in solving the problem. ^ I30653Qif.doc The constitution of the present invention is as follows. (1) A composition for a polyfluorene-based liquid crystal alignment film which is suitable for a liquid crystal display device of a transverse electric field type, and contains a reaction product of a tetracarboxylic dianhydride and a diamine, a polyamine or a polyimine. 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]. [1] [2] Η2Ν — Xj — NH2 H2N —X — X2 — X — NH2

[3] wherein X1 is a divalent organic group containing -s-, each of which is a benzene ring or a cyclohexane, and X2 is a divalent organic group containing -(CH2)n- or. η is an integer of 2 to 7, and each of R and R2 is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

(2) The liquid crystal alignment composition according to Item 1, wherein Xi is a divalent group represented by the formula [4]. [4] where A is ^, or -(CH2)r-, Y is a single bond, -S· or -0, u is 0 or: when I'U is 0, q is 〇, uJg q Is 0, 1 or 2, and r is an integer of 2 to 10. The liquid crystal alignment composition according to the item 2, wherein the divalent group represented by the formula [4] is a group represented by the formula [5] or the formula [6].

(10) The composition for liquid crystal alignment film according to Item 5, wherein Y is a divalent group represented by the formula [10]. (9) The liquid crystal alignment film composition according to any one of the first to eighth aspects, wherein in the formula [3], each of '1^ and R2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or an alkoxy group. . (10) The liquid crystal alignment film composition according to any one of the preceding claims, wherein the position of the two amine groups in the formula [3] is para. (11) The liquid crystal alignment film composition according to any one of 1 to 10, wherein a compound of the formula [1] and the formula [2], a formula [1], a compound of the formula, or a formula [1] is used in the diamine. In combination with the compound of the formula [2] and the compound of the formula [3], the content of the formula [η is 30 to 99 mol%, and the total content of the compound represented by the formula [2] and the formula [3] is (12) The liquid crystal alignment film composition according to any one of the items 1 to 11, wherein the tetracarboxylic dianhydride in the pot is composed of 20 to 80 mol% of pyromellitic dianhydride and 8 Å to 2 Torr of Mohr% cyclobutane IV. It is composed of acid dianhydride. (13) A liquid crystal alignment film formed from the liquid crystal alignment film composition according to any one of items 1 to 12. (14) 3 The liquid crystal alignment liquid crystal holding substrate as described in the item π. (15) A liquid crystal display element comprising the liquid crystal alignment film according to item 13 on the liquid crystal holding substrate provided with the electrode on the liquid crystal surface. (10) A liquid crystal alignment "object" suitable for a horizontal electric field type liquid crystal display element contains a reaction product of a tetracarboxylic dianhydride and a diamine, polyamine H«imine, which is characterized in that the liquid crystal alignment is at least 13 I3065S9iw〇c has the following reaction product A and reaction product B. Reaction product A: a reaction product of tetracarboxylic dianhydride and a diamine containing a compound of the formula [1] as an essential component, polyglycine or poly醯imine. Reaction product B: a reaction product of a tetracarboxylic dianhydride with a diamine containing a compound of the formula [2] as an essential component, a polyamine or a polyimine. H2N — X — X 2 — X — NH 2 [2]

Wherein X is a divalent organic group containing -S-, X is a stupid ring or a cyclohexene, and X2 is a divalent organic group having a -(CH2)n- or -0- 2~7 Integer. (17) A composition for a liquid crystal alignment film according to the above formula, wherein X! is a divalent group represented by the formula [4].丫[4] where 'A is or -(CH2)r-, γ is a single bond, -S- or -0_, u is 0 or 1, when U is 0, q is 0, and u is 1 when q Is 0, 1 or 2, and r is an integer of 2 to 10. (18) The composition for 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]. fO~ is set to [5] ^^-S-(CH2)-S-^y [6] where t is 1, 2 or 3, and rl is an integer of 2 to 7. (19) A composition for a liquid crystal alignment film according to the above item, wherein the tetracarboxylic dianhydride used in the reaction product A is from 20 to 80 mol?/? It is composed of pyromellitic dianhydride and 80 to 20 mol% cyclobutane tetracarboxylic dianhydride. The liquid crystal alignment film composition according to any one of the items 16 to 25, wherein the tetracarboxylic dianhydride used in the reaction product B is 20 to 80 mol% of pyromellitic dianhydride and 80 ～20 mol% cyclobutane tetraacid dianhydride. (27) A liquid crystal alignment film formed from the liquid crystal alignment film composition according to any one of the items 16 to 26. (28) A liquid crystal holding substrate comprising the liquid crystal alignment film according to item 27. (29) A liquid crystal display element comprising the liquid crystal alignment film according to item 27, which is provided on the liquid crystal holding substrate provided with the electrode toward the liquid crystal surface. The present invention can provide an IPS type liquid crystal display element which has particularly excellent contrast ratio and which reduces residual charge reduction which does not cause residual DC, and an alignment film which can achieve the object and a composition for a liquid crystal alignment film which can form the alignment film. * To make the above and other objects, features and advantages of the present invention more apparent

It is to be understood that the preferred embodiments are described below and are described in detail with reference to the accompanying drawings. [Embodiment] A preferred embodiment of the composition for a liquid crystal alignment film of the present invention is a composition for a reaction product of an amine, a poly-acid or a polyimine-imparting film, wherein the poly-proline or poly-primary A composition of a polyimine-based liquid crystal alignment film which is characterized by a copolymerization reaction of a diamine and a tetracarboxylic dianhydride, which is characterized by a composition of 8 16 I30652 Sfd, and which is suitable for a horizontal electric field type liquid crystal display device. In the present invention, the diamine represented by the formula [1] includes the following compounds.

R, R-H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, 〇H

R, R'=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, 〇H

8 11I30652Skd〇 9 10 h2n

12

16 17

ζ, /S-R -NH 2

H2N R=CH3, C2H5, C3H7, C4H9, C5Hll, C6Hl3, C7Hl5

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 0CH3,0C2H5,0C3H7,Cl,Br,I,0H 18

H2N

R=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 0CH3, 0C2H5, 0C3H7, Cl, Br, I, 0H

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 OCH3,OC2H5,OC3H7,Cl,Br,I,OH 20

R

R 2 H, CH3, C2H5, C3H7, C4H9, C5Hll 0CH3, 0C2H5, 0C3H7, Cl, Br, I, 0H

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 OCH3,OC2H5,OC3H7,Cl,Br,I,〇H 18 23 23

13 065!29?>? d〇c 22 H2 h2

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

R=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 0CH3, 0C2H5, 0C3H7, Cl, Br, I, 0H

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 ◦CH3,OC2H5,OC3H7,Cl,Br,I,OH 26 27

8 130652^>fd〇c 28 29

8 I30652ftifd〇c

40 (CH2)-S-p

n=2~10

44

H2N〇_S_(CH2irS^0)~S_(CH2n"'S

2

45 h2n〇~s_(CH2!t° 46 O—(CH2)—S n

H2N〇^S_(CH2iTS n=2~10

n=2~10 S—(CH2)—s n

21 2 I306527Qif.doc 47

48

49

50

51 ~^—^NH2

S-s h2n The preferred diamine represented by the formula [1] includes the following compounds. 22 52 13 Ο652® if d〇c

H2N

NH 2

54 53 ΧΧχχχΓ2 H2N~^ ^~S—(CH2)2-S—^ ^—1 —^ ^-s—(CH2)3-S—^ ^-nh2 56 H2N~^ ^~s—(ch2)4 -s-^ ^-1 —^ ^-s—(ch2)5-s—^ ^-nh2 58 H2N~^ ^~s—(ch2)6-s—^ ^—1 —^ ^-S—( CH2)7'S—^ ^—nh2 60 H2N~^ ^~SS~^ ^-NH2 NH 2 NH 2 NH 2

H2N 55

H2N 57 h2n 59 The more preferable diamine represented by the formula [1], the following compounds h2nQ-S^NH2 The particularly preferred diamine 1-1 represented by the formula [1] can be exemplified by the following compounds. 1-2

H2N 0S{^NH2 η2ν νη2 The diamine represented by the formula [1] may be used, or two or more kinds may be used in combination. 23 1306SQi 9p*f d〇c The diamine represented by the formula [2] may be exemplified by the following compounds.

69 70

71 .〇-(CH2)

H?N- n=2 ～7

(D 24 13065 妙 ifdoc 72 h2n ο-°-α (ch2) r : 2 ~*7

NH 2 73

(CH2) α nh2

74 H〇N

76

H2N

Nh2 h2n n=2~7 n=2~7, P=1 ～2

25 3 130652ft if.doc The preferred diamines of the formula [2] include the following compounds 84 h2n-nh2 85 H2N87 H2N89 H2N91 h2n -a- (ch2)4 ~Qr J^r (ch2)6 <y %

86 H2N88 H2N90 H2N -o- (ch2)3 <y (CH2)5 Or JOr (ch2)7 92 —<~(CH2)2-〇—^~>—NH2 H2N—~o—(CH2) 3-Q-^~^)-nh2 93 94 H2N—〇一(CH2)4-〇—NH2 H2N—^~^-〇-(CH2)5-〇—nh2 95 96 o—(ch2)6-o乂]^nh2 h2n-^^- o-(ch2)7-o ^Q^nh2 97 98 26 10013065妙 if.doc 99 101 102 h2N—〇Ή^^>—(CH2)6-^^)— NH2 H2N^~^^〇一(CH2)7H^^h-NH2 103 h2n104 h2n105 h2n <y (ch2)2 <y (ch2)2^D^0^O^(ch2)2HO^°^j ^ 106 H2N107 h2n108 h2n109 h2n \ I0^〇_O^(ch2)7{^〇_<0^ no h2nh〇cH2{^· (CH2)3 {^ch2{^nh2 27 I3065i29pifd〇c 111 h2n (ch2 ) 2 JOr (CH2)6 (ch2)2 112 h2n (CH2)2 JOr (ch2)7 o (ch2)2 113 h2n114 (CH2)3 (ch2)2 (CH2)3

NH 丨2

H2n115 H2N (CH2)3 (CH2)3 JOr (CH2)3 JOr Ό- (CH2)3 <y (CH2)4 <y (CH2)3

NH '2

116 H2N ) _ _ _ _ <y (CH2)3 (CH2)5 JOr (CH2)3 Hair H2 117 h2n JOr (CH2)3 (ch2)6 (ch2)3 118 h2n (CH2)3 <y ( Ch2)7 (CH2)3 〇~nh2 The more preferable diamine represented by the formula [2], the following compounds 8 28 120 Ι3065®9ρ_ 119 η2ν 122 Η2Ν 121 η2ν <y (CH2)3 η2ν <y ( Ch2)4 123 124 h2N—^~^-(ch2)5-<^^>-nh2 h2n—(ch2)2-^^>—(Ch2)2-^^>—

NH 2 2

125 H2N—0——(CH2)2-(^^—0—ζ^ NH

126 H2N

NH 2 2 2 129 H2N ch2 (ch2) 3 <y ch2 <y nh2 The diamine represented by the formula [2] may be used, or two or more kinds may be used in combination. The following compounds are exemplified as the diamine represented by the formula [3]. 8 Ι306539ρϋ 130 131

132

R=CH3, C2H5, C3H7, C4H9, C5Hl 1 133

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, C5Hl 1 Preferred examples of the diamine represented by the formula [3] include the following compounds. 135 136 !η3 137 H2N Η2Ν h2n 1 1

138 139 C2H5 H2N H2fS I V^NH2^^CH3 ^ CQu

C2h5 141 142 93H7 143 h2n JL ) 1 T 1 JL 2, h2n l '^^NH2kv/kc2Hs 1 ecu

C3H7

C3H7 8 147I30652ftifd〇c 145

146

H2N

Och3 148 OC2H5 149 H2N H2N rvT"YOC2H5 I nh2 I u. U nh2 150

H2N

〇c2h5 153

151

152

H2N

OC3H7 154 155

159 160

OH H2N

H2N

OH OH 31 130652ft if.doc

OCH-, 166

Preferred diamines of the formula [3] include the following compounds

171

9CH,

0CH, 172

A diamine represented by the formula [3] may be used, or two or more of the two may be used in combination to enhance the black display property when no voltage is applied, and the two amine groups in the diamine represented by the formula may be used. It is preferred that the position is more ortho or meta-positioned to the aligner: in the present invention, the diamine represented by the formula [1] is used in combination with the amine of the formula [2] or the formula [3], or with the formula [2] and The diamines shown in [3] are used in combination. In this case, the diamine content of the formula (1) is 3 in combination with the amine of the formula [2], the formula (1), and the formula [1 or the formula [2]:]. Moore%~99 Mo is better inside Guangwei. When the content is 3 Gmol% or more, the liquid crystal display element using the obtained composition for a polyimine-based liquid crystal alignment film clearly exhibits a remarkable effect of a charge accumulation or a residual DC reduction. In the diamine represented by the formula [1], the liquid crystal display element of the composition of the obtained polyimine-based liquid crystal alignment film is used in combination with the diamine represented by the formula [3] and/or the formula [3], and black is not applied. The effect of the display characteristics being improved is obvious. The content of the diamine of the formula [2] and/or the formula [3] can increase the black display property while considering the reduction of the residual DC effect, and the total of the content is preferably in the range of i mole% to 7 〇mol%. Inside. Further, in the present invention, a diamine other than the above formula [1], formula P] and formula [3] (hereinafter referred to as "other diamine") may be further included, and the ratio of other diamines in this case is preferably When it is 30% or less of the total amount of the diamine, and more than 3% by weight, the liquid crystal display element using the composition for the obtained polyimine-based liquid crystal alignment film does not have an effect of reducing DC reduction or contrast. Examples of the compound which can be used as the other diamines other than the above formula [1], formula [2] and formula [3] are as follows. 4,4'-diaminodiphenyl decane, 3,3,-diaminodiphenyl decane, 3,3'-dimercapto-4,4,-diaminodiphenyl decane , 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4.aminophenoxy)phenyl] • hexafluoropropane, Phenyldiamine, p-styldiamine, m-diphenylphenyldiamine, p-xylyldiamine, 2,2'-diaminodiphenylpropane, p-diaminobiphenyl, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, U bis[4-(4-aminophenoxy)phenyl]-4-mercaptocyclohexane, Bis[4-(4-aminophenylhydrazino)phenyl]decane, 1,1-bis[4.(4-aminophenylmethyl)phenyl]cyclohexane, 1,1_2[4 -(4-.Amino-Alkyl)phenyl]-4-indolylcyclohexane, 1,1-bis[4-(4.aminophenylphenyl)phenyl]cyclohexane, 1,1 - bis[4-(4-aminophenylhydrazino)phenyl]-4-mercaptocyclohexene, 1,1-bis[4-(4-aminophenylhydrazino)phenyl]methane. 33 13 Ο 6 5 2^pif.d〇c One of the above other diamines may be used, or two or more of the above other diamines may be used in combination. Further, the present invention is not limited to the above diamine as long as the object of the present invention can be attained. 'As a reading acid dianhydride', it is preferable to use a pyromellitic acid dioxime in a ratio of 20 mol% or more of the four dicarboxylic acid dixan used, and 'heart set 1 soil is 20~Sn moir/ The proportion of bismuth is stupid tetracarboxylic dianhydride. The tetracarboxylic dianhydride which is stupid tetrasuccinate ditetrahydronaphthyl diacid is cyclobutane tetracarboxylic dianhydride, 1 24 <...-needle, and the anhydride is formed, 4-(2) , 5-dihydrotetrahydrofuran-3-yl)-1,2,3,4-acetic anhydride, 5-(2,5-dioxotetradecanoyl)-3-mercapto-3-cyclohexyl: and preferably. The amount of use of pyromellitic dianhydride is 80% by mole of phthalic anhydride or the like; 2 is more than 2% by mole, and it is easy to use the obtained liquid crystal display element of the composition of y = yttrium. The liquid crystal is referred to as a reduction in residual DC. Only the accumulated charge and the limit of the characteristics of the present invention do not impair the characteristics of the present invention, tetracarboxylic dianhydride, alicyclic tetracarboxylic acid two needles, furnace & dual use /, his cold fragrant family of 丄 heart fine aliphatic tetracarboxylic acid ~ &amp The pyromellitic dianhydride which can be used in the present invention. As follows. ~ 乂 dianhydride example column 8 34 130652 苏 if.doc -ίτο r\ η Λ7Λ

35 130652ft if.doc 185 186

188 187

190 189

193

194 195

8 36 130652ft if.doc

200 202

203 204

37 213 212 I3065i29pif.doc 211

214

217

use. Carboxylic acid anhydride may be used alone or in combination of two or more kinds.

The alkylene diamines of the formula [1], the formula [2] and the formula [3] which are used in the above-mentioned two compounds can be used. The oxygen-containing alkyloxy group can be suitably used in the present amine, such as the formula [11], h2n fR5^Si--〇)_S|^R5t_NH2 R4 R4 [11] 3 alkyl group Or phenyl, phenylene. X is a formula [11], and R3 and R4 are each an integer of 1 to 6 in which a carbon number of 1 to R5 is a methylene group, a phenylene group or an alkyl group, and y is an integer of 1 to 1 Å. 8 38 I3065i29pif.doc Another suitable form of the composition for a liquid crystal alignment film of the present invention is a polyimine-based liquid crystal alignment film containing a reaction product of a tetracarboxylic dianhydride and a diamine, a polyamine or a polyimine. In the composition for liquid crystal alignment film, the composition for liquid crystal alignment film contains at least the following reaction product A and reaction product B, and is suitable for a liquid crystal alignment film composition of a horizontal electric field type liquid crystal display element. Reaction product A: Polyamine or polyimine which is a reaction product of tetracarboxylic dianhydride and a diamine containing an essential component of the compound of the formula [1]. H2N - Xj - NH2 [1] Lu reaction product B: a polyamine or polyimine which is a reaction product of a tetracarboxylic dianhydride and a diamine containing an essential component of the compound of the formula p]. H2N — X — X2 — X — NH2 [2] In the formula [1 ] and in the formula [2], Χι is a divalent organic group containing -S-, and X is a benzene ring or a cyclohexane respectively. X2 is contained - The (CH2)n- or -0-divalent organic group 'n is an integer of 2 to 7. In addition, the composition for a liquid crystal alignment film may contain only the reaction product Α and the reaction product Β, and may further contain the reaction product A and the reaction product B, if necessary, and without impairing the φ effect of the present invention. Polylysine or polyimine. The diamine used in the reaction product A may have a compound of the formula [丨] as an essential component, and may further be used in combination with the formula [2], the formula [3], the above-mentioned "other diamine, or, as shown in the formula [11]. Further, the diamines which can be used in combination may be used in combination of two or more kinds. In this case, the diamine content of the formula π] in the combination of the above diamines is formed by reaction in the composition for liquid crystal alignment film. The content of the substance and the reaction product is different, and 39 I3065i39pifd〇c is preferably 30 mol/〇~100 mol%, more preferably 51 mol% to i〇〇mol%. The larger the diamine content, the more the effect of reducing the accumulated charge and the residual DC is more remarkable, and it is suitable. When the content is 30 mol% or more, it can be suitably used as the polyimide-based liquid crystal alignment film of the present invention. The composition of the tetracarboxylic dianhydride used in the reaction product A is the same as the tetracarboxylic dianhydride described in the above description of the tetracarboxylic dianhydride. Preferably, the pyromellitic dianhydride is a ratio of 20 mole% or more of the total amount of the tetracarboxylic dianhydride used. More preferably, pyromellitic dianhydride is used in a ratio of 20 to 80 mol%, and tetracarboxylic dianhydride other than pyromellitic dianhydride is cyclobutane tetracarboxylic dianhydride, 1, 2, 4, 5- Cyclohexanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthyl-1,2-dianhydride, 5-(2,5 - dioxetanyl alcohol) - 3 - mercapto-3- lysyl-1,2-dianhydride, etc. Preferably, the tetracarboxylic dianhydride used in the reaction product A is preferred. 20 to 80% of pyromellitic dianhydride and 80 to 20% of cyclobutanetetracarboxylic dianhydride. The diamine used in the reaction product B is compounded with the compound of the formula [2] as a necessary component. a formula [1], a formula [3], the above-mentioned 'other diamine, or a diamine as shown in the formula [11]. And the various diamines which can be used in combination may be used in one type or in a mixture of two or more types. In this case, the content of the diamine of the formula P] in the combination of the above diamines is different from the content of the reaction product A and the reaction product B in the liquid crystal alignment film composition, and is 30 mol% to 1 mol%. Preferably, the amount of diamine in the formula [2] is greater than the range of 51% Mohr% to 1 〇〇 Mohr °/〇. The black display characteristic of the liquid crystal display element is improved, and it is suitable. When the content of 1 is 30 mol% or more, the I306529 pif.doc is preferably used as the polyimine-based liquid crystal alignment composition of the present invention.

The tetrakisperic acid di-needle used in the reaction product B may be exemplified by the tetra-wei (four)-like example described in the above description of the tetracarboxylic dianhydride. The sound is 'four new two when the benzene is read in the second field (four) using the acid 2 ^ total amount of 20% Moore% or more, more preferably 2 〇 ~ 8 〇 Moll% ratio using stupid tetracarboxylic acid Two if. The two needles of benzene tetracarboxylic acid are the cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 4_(2 5 dioxane tetrahydronethane) - tetrahydronaphthyl-anthracene ^^dioxytetramethylene alcohol)_3-mercapto-3-cyclohexyl-1,2-dianhydride or the like is suitable. It is preferred that the tetracarboxylic dianhydride used in the reaction product A is composed of 2 Torr to 8 〇% of stearidonic acid, a needle and 80 to 20% of cyclobutane sulphuric acid dianhydride. Further, the reaction product B is different from the raw material composition of the above reaction product a. The reaction raw material of the reaction product A and the reaction product B may be the same raw material composition as the tetracarboxylic dianhydride and the diamine. However, the reaction product at this time necessarily becomes the above-mentioned copolymerization product. The composition for liquid crystal alignment film containing the reaction product A and the reaction product B is a polymerization II, a reaction product B, and a reaction product A and a reaction product B added as necessary. Amines ^^ < Polyimine mixed to prepare. The content of a mixed reaction product A is preferably from 50 to 95 mol% of the total polyamine@ or polyamidomine. When the content is 5 〇 Mohr 0/ =, the obtained polyimine-based liquid crystal alignment film for the obtained yttrium crystal display element clearly exhibits an accumulated charge and a significant decrease in residual DC. _

(D 130652 § pifdoc The content of the reaction product B to be mixed is preferably 5 to 50 mol% of the total polyamine or polyimine. If the content is 5 mol% or more, the obtained is obtained by using The black display property of the liquid crystal display device of the composition for a polyimine-based liquid crystal alignment film is improved. [amino silicon] Further, in order to improve the adhesion between the liquid crystal alignment film material of the present invention and the substrate, the composition of the liquid crystal alignment film Amino decane (£ compound may be added to the compound. Examples of the amino decane compound include amino phenyl trimethoxy decane, p-aminophenyl triethoxy decane, and m-aminophenyl trimethoxy sulphate. , m-aminophenyl triethoxy decane, amine propyl trimethoxy decane, amine propyl triethoxy decane, etc. 分子 molecular grouping of poly-proline or soluble polyimine used in the present invention: For example, gel permeation chromatography (Gpc), polystyrene-equivalent weight: average molecular weight (Mw) is 1 〇, 〇〇〇~5 〇〇, 〇〇〇, more preferably 2 〇〇〇〇 ~ 200, 〇〇〇〇' Benmao's high score in the composition of polyimine liquid crystal alignment film The concentration of the component polyamic acid or soluble polyimine is not particularly limited, and is 0.140% by weight. When the composition is applied to a substrate, it is necessary to carry out the dissolution of the county. When the wave height of the high knife is 4% by weight or less, the composition for the liquid crystal alignment film can be appropriately transferred, and it is necessary to dilute the liquid crystal alignment to adjust the film thickness, and the composition is used. When the solvent is easily mixed with the liquid composition, it is suitable for use in order to maintain a good film drought during the spin coating method or the printing method, and is usually 10% by weight or less. Other coating methods, For example, infiltration method or 8 I306S3Qif.doc ^ ink ^! / to lower concentration m polymer concentration of 0.1% of the weight of the cloth, the work is easy to get the most appropriate alignment film thickness. Therefore, through the hanging The concentration of the ruthenium or the printing method is (U% by weight or more, preferably 0.5% to 10% by weight. Pulling, thinning, and by this varnish coating method, it is also possible to use a more uniform In the composition for the brewing imine liquid crystal alignment film, together with the above = two, j two The solvent used is limited by the ability to dissolve the polymer. This solvent covers the solvent used in the process or use of poly-acid, soluble polymer, deer, or dilute. An example of such a solvent is shown below. A polystyrene, which is a miscible material, an organically soluble f-caprolactone, a pyrrolidone, a dinonyl imidazolidinone, and an N-based di- = propionate amine, N,N-dimethyletheneamine, dimethylacetamide, butyl::ir can, N count diethyl amide, dimethyl sulphate, special purpose. Examples of cap + solvent are calcined lactic acid vinegar, 3 =; =, other naphthalenes of the purpose, isophora, ethylene glycol monobutyl "V, butanol, tetrahydroethylene glycol, single ethyl shunt, etc. Alcohol mono I ethyl alcohol monoalkyl ether, diacetic acid vinegar, triethylene glycol monoalkyl bond, diol mono or phenyl alkyl ether, malonic acid diethyl vinegar, etc. a dipropylene glycol monoalkyl group such as a base bond, and among the 2 groups of dipropylene glycol monomethyl, preferably Ν_methyl~ than "di" alcohol monoethyl hydrazine, propylene glycol monobutyrolactone, ethylene glycol single Butyl , Diethyl meters soil sit pyrrolidone, γ · butyl ether and dipropylene glycol monomethyl ether and the like. 43 13 〇652^ifdoc This is a composition of a poly-imine-based liquid crystal alignment compound. It is necessary to contain various additives. For example, it is desirable to increase the applicability of the surfactant which can be mixed for the purpose, and it is necessary to improve the antistatic property. When the static electricity is prevented from being mixed with the adhesion of the substrate, the Wei coupling sword or the silver coupling agent is mixed. In the IPS type liquid crystal display device according to the present invention, the film is composed of the formed first-period plate, and the liquid crystal sandwiched between the two plates and the substrates. The first transparent substrate has a halogen electrode such as an alternating comb-shaped electrode and a common electrode plate having a black matrix for shielding light outside the halogen region, a color filter, a flat-shaped electrode, a transparent electrode such as a glass electrode, and the like. Use _ method to stack chrome and other shapes! The photoresist pattern is formed by etching the mask. The liquid crystal alignment film is coated on the two transparent substrates obtained for the film group, and the product H is then dried and the ring is subjected to a heat treatment process. In the coating method in the coating process of the de-kneading and de-blocking, the conventional method is a method of a heat treatment process necessary for a square-turn coating method, a printing method, a wetting method water, and a closed-nuclear reaction, Or a method of heat treatment in an infrared furnace, a method of heating on a table, and, =. These methods are equally applicable to the present invention. The temperature of the solvent is carried out at a sublime temperature, preferably in the range of i5Q~d, d) 44 I3〇652«kdoc 曰 subsequent implementation of the alignment treatment process of the obtained liquid crystal alignment film, the obtained liquid曰曰=The substrate is manufactured by a process in which the spacers are opposed to each other, a process of sealing the liquid crystal material, and a process of attaching the polarizing film to manufacture a liquid crystal display element. In the alignment processing method in the gas processing, the f-method is a friction method or a photo-matching method (t). These methods are equally applicable to the present invention in achieving the scope of the present invention. The alignment treatment method particularly suitable for use in apricot is a rubbing method, and any rubbing treatment condition can be used within the range of the purpose of the ruby. The condition of the special 5 is that the fiber pushing amount G.2 to G.8 mm, the moving speed of the sample stage, the rotation speed of the roller shaft, 500 to 2,000 rpm. The cleaning liquid inlet type liquid crystal display 7^1 pieces can be cleaned or ultrasonically cleaned before and after the alignment treatment. These parties, ^^, _, _, benzene, dimethyl _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The IP S-type liquid crystal display of the present invention has no special _, and can be made into a f-crystal composition. Examples of suitable liquid crystal compositions are various liquid crystal group reports, and Japanese Patent No. 2635435, Japanese Patent No. 3, 862, 862, and Japanese Patent No. 5-50173535, Japanese Patent No. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Japanese Laid-Open Patent Publication No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-235552, Japanese Laid-Open Patent Publication No. Hei 9-255956, Japanese Patent Laid-Open Publication No. Hei 9-241643 (Patent No. EP 885 271 A1), Japanese Patent Laid-Open Publication No. Hei No. Hei 10-204016 (Embodiment No. EP 844 229 A1) The patent of the earlier publication of the Japanese Patent Laid-Open No. 10-2, No. 2 Bulletin, Japanese Patent Special Employment - 〇87_, Japanese Patent Early Disclosure Japanese Laid-Open Patent Publication No. 2001-48822, 碣f can be used for each of the Weijing = night crystal compositions having a dielectric anisotropy of 贞, for example, refer to Japanese Patent Laid-Open Publication No. 532 ίί, Japanese Patent Early publication of the special opening of the Kaiping 2 - 4725 h report, 曰 专利 专利 专利 早期 早期 4 4 4 4 4 4 4 4 4 4 4 4 公 公 公 公 公 公 公 公 公 公 公 公 公 公 公 公 、 、 、 、 、 、 、 、 、 、 、 、 、 、 H_76, Japanese Patent Laid-Open No. 1_, Japanese Patent Laid-Open Patent Publication No. 2369%, Early Publication Kaiping 1G-236993G^6/92, No. Special Kaikai -2%994 bulletin, day ^ = early publication of this patent - No. of the public pro- 曰 专利 专利 早 早 早 早 早 曰 曰 曰 曰 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 〇 刼 刼 刼 曰 46 46 46 10 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 日本 日本 日本 日本 日本 日本 日本 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 〇 〇 〇 〇 〇 〇 〇 〇 〇 = 〇~ 237075, Japanese Patent No. H. s237448 pf6 Japanese Patent Early Disclosure Patent Early Publication βΓΓ (EP967261A1 Specification), Japan Kaiping 10-2919 #u么报, 曰本专利早公开第特-029581号八钼〜么报, Japanese Patent Early Disclosure Special Kaiping 11 , 日 m 特开平n-〇_ Japanese special patent It patent early open special opening 2_-256307 bulletin, early eight-door public open special 2GG1 - G19965 bulletin, Japanese patent J仏 two system ___6 bulletin The Japanese patent was first published in the "192 Milk Bulletin" and the like. j The dielectric anisotropy is positive or negative in the liquid day and day composition. There is no difference in the use of the optically active compound on the substrate. , the step of the polyimine-based liquid crystal alignment film of the present invention: 'in the range which does not impair the characteristics of the present invention (preferably within 2% Mohr%), = mixed use of poly-acids containing other compositions A polymer component such as a soluble polyacrylic acid polymer or a polymer. In the composition for a polyacrylonitrile-based liquid crystal alignment film of the present invention, a t-component of a liquid crystal alignment composition such as a carboxylic acid or a derivative thereof is added to the range which does not impair the object of the present invention. The reaction product of the diamine is a polymer component such as polyamine or a thief, a dicarboxylic acid, a reaction product of a touch with a triamine, and a polyamidoximine. The diamine at this time includes, in addition to the diamine represented by the formula [1], the formula [2] and the formula [3] of the present invention, the above-mentioned diamine which can be used in combination with the diamine. And a mixture of such diamines. [Examples] Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples. The names of the tetracarboxylic dianhydride, the diamine and the solvent used in the examples and the comparative examples are represented 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-butyric acid dianhydride: BBDA diamine

4,4'-diaminodiphenyl decane : DDM

4,4'-Diaminodiphenyl sulfide: ASD

4,4'-Diamino-1,2-diphenylethane: DDET

2-Azainyl-1,4-diphenyldiamine: 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-aminophenylthio)ethane : DDSE

4-bis(4-aminophenyloxy)butane :DDOB

1.3- bis(4-aminophenyloxy)propane: DDOP 48 130652 points if.doc

:DD0E :ΑΡΕ :APDS :ΝΜΡ :GBL :BC 1,2-bis(4-aminophenyloxy)ethane 4,4'-diaminodiphenyl ether 1,3'-di(3- Amine propyl) tetradecyl bismuth sulphate solvent component N-mercapto-2-° ratio ketone γ-butyrolactone butyl cellulose solvent Example 1

1) Poly=Amine-based liquid crystal alignment film composition A1 (varnish Α(10) is prepared with a thermometer, a stirrer, a raw material, a 20-tetra π flask, and a solution of i.28g, 1 and 2 == gas flow, and the solution is dissolved. The temperature of the second; into 2 Zheng c, GBL ', m ^ 3G minutes, add tyrosine of tyrosine lacquer" raw material read the reaction temperature of 5% by weight of the polymerization reaction rate of 7 to; = = make = When rising, 'control two in = (four) check two: add ==

^月= 35η^ (Use MM, react with MO, stop, and store at low temperature. The average molecular weight obtained is obtained. Among them, the weight average molecular weight and the (company name) GPC measurement device (Chr〇mat〇Pack c_r7a) , product name) The column temperature is measured at 50 ° C. The varnish obtained as described in the stomach is diluted with a mixed solvent of nmp / BC / GBL (= 60 / 25 / 15 ' weight ratio) to adjust the total polymer composition The concentration of 49 I3065i29pifd〇c was 3% by weight, and it was used as a varnish for coating. 2) Preparation of contrast and residual DC measurement group (cd) 1 Using a glass substrate with a comb electrode as shown in Fig. i And two glass substrates such as a glass substrate without electrodes. The obtained coating varnish was applied onto the glass substrate having the comb electrodes described above by a spin coating film under the conditions of 23 Å. : After the film is suspected, it is heated for 3 minutes. (4) A liquid crystal alignment film of about 8 inches. The obtained polyimine = the friction treatment device manufactured by Standard Scale Co., Ltd. in a friction cloth (fiber length: 19 mm: acetate), the speed of the fiber push table is 60 Å/sec, and the speed of the light shaft is 1000 rpm. Perform rubbing treatment. The obtained liquid crystal holding substrate was ultrasonically cleaned in ethanol for 5 minutes, and after cleaning the film, 12 (rc drying minutes) in the oven. The above IPS was placed on the glass substrate with the electrode to spread a spacer of 4 mm size. After the inner side is opposed to the electrodeless glass substrate, 钽H and the main agent are loosely sealed to form a parallel cell having a spacing of 4 μΠ1. The above-mentioned liquid crystal material is filled with a fine seal, and then (10). ^, I, 3G, and the two sides of the opposite side of the Lang substrate are attached with two pieces of milk for H-degree and residual DC measurement. In addition, the phase is mismatched; the electrode glass substrate and the electrodeless glass substrate are oriented in two directions. In the same direction, the polarized light transmission axis of one side is perpendicular to the other side of the motor. The composition of the liquid crystal material is as follows: The composition of the composition is as follows: The defect of this composition is 50 3 I306539piM〇 〇

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

!7wt.% 17wt.%

C2h5 ο c2h4. 16wt.%

10wt.°/〇

C3H7

5wt.% 10wt.% C5H11

6wt.% 6wt.% 13wt.% (1) Measurement of Contrast After the use of the liquid crystal panel evaluation device (LCD-5100, product name) manufactured by Otsuka Electronics Co., Ltd., the composition for contrast measurement prepared as described above was used. The transmittance-applied voltage curve calculates a contrast ratio of 195 from the ratio of the luminance displayed in white to the luminance displayed in black. Furthermore, alignment spots or alignment defects such as rubbing marks are not found at all, and a very uniform display is obtained. Among them, the conditions for contrast measurement are drive voltage 〇~l〇Vp_p, drive frequency 70 Hz, and rectangular wave. 8 1306533⁄4 if.doc (2) Determination of residual DC 30Hz, 3V rectangular wave superimposed lv DC voltage 3 () minutes immediately after the test (four) Shuo elimination voltage, the value of this value left DC the smaller the residual, is considered good. When the measurement residual Dc prepared as described above was measured by the above-described method, the residual DC was 45 mV. Examples 2 to 36, Comparative Examples 1 to 6 The varnishes A2 to a36 and the varnishes B1 to B6 were prepared by the raw material compositions shown in the following Table 1, respectively, and the varnish A in Example i was subjected to the same contrast as in Example i. Evaluation of residual DC voltage. Production of TN assembly shown in Comparative Example 5 A pair of glass substrates with an IT0 (indium tin oxide) transparent electrode were formed using a spacer of 4 μm; and were formed in a rubbing direction of 9 Å. In combination with the liquid crystal composition A to which the optically active compound is added, in addition to the normal black mode-attached polarizing film, the TN assembly is produced by the same method as the contrast and residual DC voltage measurement cassette. Example 1 The evaluation of the residual DC voltage was also performed. Preparation of various varnishes, varnishes A2 to A36 and varnishes B1 to B6 were 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 be about 7 〇 C or less to cause a reaction. In addition, when preparing a varnish of poly-proline, the viscosity of the reactant is checked during the progress of the reaction, and the viscosity of the varnish after adding BC and GBL reaches 30 to 35 mPa.s (using an E-type viscometer, 25. When the reaction is terminated) Stored at low temperature. 4 I306529pifd. This means that the initial poly-proline is synthesized only in NMP, followed by the addition of BC and GBL. The final adjustment of the varnish has a polyamine concentration of 5% by weight. The raw material molar ratio and weight average molecular weight of the examples are shown in Tables 1 to 4. [Table 1]

Lacquer acid dianhydride ^ Diamine molecular weight ^ Formation PMDA CBDA ASD DDET P1PDA ΒΖ 3 ΑΡΕ DDM Example Α 1 25 25 25 25 63,000 IPS Example 2 Α 2 25 25 25 25 54,000 IPS Example 3 A3 25 25 25 25 65,000 IPS Example 4 Α4 25 25 25 15 10 58,000 IPS Example 5 Α5 25 25 25 25 68,000 IPS Example 6 Α6 25 25 25 !5 10 65,000 IPS Comparative Example 1 Β1 25 25 25 25 55,000 IPS Comparative Example 2 Β2 25 25 50 57,000 IPS Comparative Example 3 Β3 25 25 50 70,000 IPS Comparative Example 4 Β4 25 25 50 51,000 IPS Comparative Example 5 Β5 25 25 25 25 48,000 IPS Comparative Example Β6 25 25 25 25 63,000 TN Note·· 1) Tetracarboxylic dianhydride 2 ) Weight average molecular weight [Table 2]

Lacquer acid dianhydride 11 - amine weight molecular composition 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 63,000 IPS Example 11 All 25 25 25 25 58,000 IPS Example 12 A12 25 25 25 25 57,000 IPS Example 13 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 Π 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]

Varnish acid dianhydride "Diamine molecular weight 2) Formation PMDA CBDA ASD DDOB DDOP DDOE DDET DDPB Example 19 A19 25 25 20 10 20 71,000 IPS Example 20 A20 25 25 20 10 20 68,000 IPS Example 21 A21 25 25 20 10 20 69,000 IPS Example 22 A22 25 25 20 10 20 68,000 IPS Example 23 A23 25 25 20 10 20 64,000 IPS Example 24 A24 25 25 20 10 20 65,000 IPS 53 I30652i9) pif.d〇c Note: 1) Tetracarboxylate Acid dianhydride 2) Weight average molecular weight [Table 4]

Lacquer bis-diamine molecule 2> PMDA BBD A ASD DDSB DDSP DDSE DDET DDPB Lean application 25 A25 25 25 10 15 25 58,000 IPS Example 26 A26 25 25 10 15 25 56,000 IPS Example 27 A27 25 25 10 15 25 55,000 IPS Example 28 A28 25 25 25 25 65,000 IPS Example 29 A29 25 25 25 25 63,000 IPS Lean Example 30 A30 25 25 25 25 000 IPS Example 31 A31 25 25 Ϊ0 15 25 55 000 IPS Appreciation Example 32 A32 25 25 10 15 25 54,000 IPS _ Example 34 Reward Example 35 Example 36 A33 25 25 10 15 25 51 000 IPS A34 A35 A36 25 25 25 25 25 25 30 30 30 20 20 20 65.000 62.000 61,000 IPS IPS IPS Note: 1) tetracarboxylic dianhydride 2) weight average molecular weight varnishes A1 to A36 and varnishes B1 to B5, the results of evaluation of residual DC and residual DC evaluation results of B6 are shown in Table 5. Among them, in the test method of the examples of the present invention, a preferable contrast value is 150 or more, and a preferable residual Dc is 7 〇 mV or less.

54 I3065i29pifd〇 [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 8 Ι3065ι29ρ if.doc Preparation of various varnishes, varnishes A37 to A41 and varnish B7 were 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 be about 70 C or less to cause a reaction. In addition, when the varnish of poly-proline is prepared, the viscosity of the reactant is checked during the progress of the reaction, and the viscosity of the varnish after adding BC and GBL reaches 30 to 35 mPa.s (using an E-type viscometer, 25. When the reaction is terminated) It is stored at low temperature. That is, the original poly-proline is synthesized only in NMP, and then Lu BC and GBL are added, and finally the lysine concentration of the varnish is adjusted to 5% by weight. The raw materials of the respective examples and comparative examples The molar ratio and weight average molecular weight are shown in Table 6. [Table 6]

Synthesis Example 1 Varnish A37 Acid II "Diamine Molecular Weight 2) Box PMDA 25 CBD A 〇5 APDS 10 DDM B23 DDET DDPB ddbu Synthesis Example 2 A38 25 25 10 40 --- 46,000 IPS 45 〇〇〇 Synthesis Example J 25 25 10 40 40,000 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 to 40 ''··.J 40,000 IPS Note: 1) tetracarboxylic dianhydride 2) weight average molecular weight Examples 37 to 42 and Comparative Example 7 Varnishes A37 to 42 and varnish B7 were respectively prepared with varnish B2 in the polymer composition shown in Table 7 below, using this and In the examples, the contrast and the residual DC voltage were evaluated in the same manner. Among the test methods of the examples of the present invention, a preferred contrast ratio is 150 or more, and a preferred residual DC is 70 mV or less. 56 13 Ο652ft if doc [Table 7] Reaction product A Reaction product B Mix ratio contrast residual DC/mV Example 37 B2 A37 A37/B2=l/9 200 50 Example 38 B2 A38 A38/B2=l/9 190 55 Example 39 B2 A39 A39/B2=l/9 210 58 Example 40 B2 A40 A40/B2-1/9 220 60 Example 41 B2 A41 A41/B2=l/9 210 60 Example 42 B2 A37 A37 /B2=2/8 220 60 Comparative Example 7 B2 B7 B7/B2=l/9 120 40 The results of Examples 1 to 42 and Comparative Examples 1 to 7 show that a varnish having a contrast ratio of 150 or more and having a DC of 70 mV or less can be used. A good IPS type display element is obtained. Further, the results of Example 1 and Comparative Example 6 show that the cumulative charge lowering effect of the sulfur-containing ASD is not remarkable in the TN type liquid crystal display element, and is unique to the IPS type liquid crystal display element. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a comb electrode structure for IPS. [Main component symbol description] No. 8

Claims (1)

1306529 Revision period: 97 years 1! Month 26th is the Chinese patent scope of No. 94104802. No slash correction 16170pif.doc X. Patent application scope: 1. A composition for liquid crystal alignment film, which is a polyimine system. The utility model relates to a cross-electricity, a liquid crystal display element, and a composition for a polyimine-based liquid crystal alignment film containing a reaction product of a retinoic acid and a two-saddle, a polyamine or a poly-imine. It is characterized in that the diamine includes a compound of the formula [i] as an essential component, and further includes at least one of the compounds of the formula [2] and the formula [3], H2N-X!-NH2 [l] ^ H2N-X-X2- x_NH2 [2] H2n 1 [3] where 'X is a divalent organic group containing -S-, each X is a ring or a % singular 'X2 is a divalent organic containing _(CH2)n- or _0· The group n is an integer of 2 to 7, and the core and I are each a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 5 carbon atoms. 2. The composition φ of the liquid crystal alignment film according to the first aspect of the patent application, in the formula [1], is a divalent group represented by the formula [4], -YV^As)r〇" 4) where A is either _(CH2)r-, γ is a single bond, -S- or 'u is 〇 or i'u is 〇, q is 〇, u is 1 when 9 is 〇, 1 or 2 ' r is an integer of 2 to 1 。. 3. The liquid crystal alignment film composition according to the second aspect of the invention, wherein the divalent group represented by the formula [4] is a group represented by the formula [5] or the formula [6], 58 [5] ] 1306529 16170pif.doc [6] where 't is 1, 2 or 3, and rl is an integer of 2 to 7. 4. The composition for liquid crystal alignment film according to the second aspect of the invention, wherein the group represented by the formula [4] is a divalent group represented by the formula [7]. 5. The composition for liquid crystal alignment film according to any one of claims 1 to 4, wherein Χ2 is a divalent group represented by the formula [8], - Y) m - Γ 81 [10] Y is a -O-, benzene ring, cyclohexane ring, single bond, a divalent group represented by the formula [9] or the formula [10], and each is an alkylene group having 2 to 7 carbon atoms, and m is 〇 or 1'卩 is 1 or 2, wherein, when 111 is 〇, 丫 is a group which is not represented by _〇_, formula [9] or formula [1〇]. 6. In the liquid crystal alignment composition according to item 5 of the patent application, in [8], Y is a single bond. 7. The composition for liquid crystal alignment film according to claim 5, wherein Y is a divalent group represented by the formula [9]. 8. The composition for liquid crystal alignment film according to claim 5, wherein the Y is a divalent group represented by the formula [10〇], in the formula [8]. 9. The composition for a liquid crystal alignment film according to claim 1, wherein in the formula [3], Ri and R2 each independently represent a hydrogen atom or a carbon group having 1 to 3 carbon atoms or an alkoxy group. 10. The composition for a liquid crystal alignment film according to claim 1, wherein the position of the two amine groups in the formula [3] is para. 11. The composition for liquid crystal alignment film according to claim 1, wherein the compound of the formula [1] and the formula [2], the compound of the formula [1] and the formula [3] ® are made in the diamine. Or a combination of the formula [1] and the compound of the formula [2] and the formula [3], the content of the compound of the formula [1] is 30 to 99 mol%, represented by the formula [2] and the formula [3]. The total content of the compound is from 1 to 70 mol%. 12. The liquid crystal alignment film composition according to claim 1, wherein the tetracarboxylic dianhydride is composed of 20 to 80 mol% of pyromellitic dianhydride and 80 to 20 mol/〇 The hospital consists of four acids and two livers. A liquid crystal alignment film formed by pre-sintering and heating a liquid crystal alignment film composition according to claim 1 of the patent application. A liquid crystal holding substrate characterized in that the liquid crystal alignment film according to claim 13 is provided on the substrate. A liquid crystal display device comprising: an electrodeless substrate; a liquid crystal holding substrate provided with an electrode; and a liquid crystal material disposed between the electrodeless substrate and the liquid crystal holding substrate provided with the electrode, wherein the liquid crystal surface is oriented The liquid crystal holding substrate provided with the electrode is provided with a liquid 1306529 16170pif.doc crystal alignment film as described in claim 13 of the patent application. 16. A liquid crystal alignment film composition suitable for a horizontal electric field type liquid crystal display element, which is a polymerization product containing a tetracarboxylic dianhydride and a diamine, a polyamine or a polyamidene And a composition for a liquid crystal alignment film containing at least one reaction product A and a reaction product B, the reaction product A: the four-reagent a reaction product of the diamine containing the compound φ of the formula [1] as an essential component of the polyamine or the polyimine; H2N-X plant ΝΗ 2 [η The reaction product B: the tetracarboxylic dianhydride a reaction product of the diamine containing the compound of the formula [2] as an essential component of the polyamine or the polyimine; Η2Ν-Χ-Χ2-χ-ΝΗ2 [2] wherein Χι is contained - The divalent organic group of S-, X is a benzene ring or a cyclohexane, and X2 is a divalent organic group containing _(CH2)n- or -〇-, and n is an integer of 2 to 7. 17. The composition for a liquid crystal alignment film according to claim 16 of the invention, wherein the 'X' in the formula [1] is a divalent group represented by the formula; 〇-"A_YV~(As)^^ [4 ] j, A is respectively "" or _(CH2)r-, γ is a single bond, -S- or -0·, u is 〇 or i'u is 0, q is 〇, u is 1 When q is 0, 1 or 2, r is an integer of 2 to 1 。. 1306529 16170pif.doc 18. The liquid crystal alignment film composition according to claim 17, wherein 2 is represented by the formula [4] The valence group is a divalent group represented by the formula [5] or the formula [6]; S-(CH2)prS [6] wherein t is 1, 2 or 3, and rl is an integer of 2 to 7. The composition for a liquid crystal alignment film according to claim 17, wherein the group represented by the formula [4] is a divalent group represented by the formula [7]. [7] 20. The liquid crystal alignment film composition according to claim 16, wherein in the formula [2], X2 is a divalent group represented by the formula [8]; -Y-(ZY)m- [8] [9] [10] Y is a 2-valent group represented by -〇-, benzene ring, cyclohexane ring, single bond, formula [9] or formula [10], respectively, carbon number 2 a sub-alkyl group of -7, m is 0 or 1, and p is 1 or 2, wherein, when m is 0, Y is a group represented by -0-, formula [9] or formula [10]. o^ (C%-62 1306529. The method of the liquid crystal alignment film according to claim 20, wherein Y is a single bond in the formula [8]. In the formula [8], γ is a divalent group represented by the formula [9], and the composition for a liquid crystal alignment film according to claim 20, In the formula [8], Y is a divalent group represented by the formula [10]. 24. The composition for liquid crystal alignment film according to claim 16 of the invention is used in the polyaniline liquid crystal alignment film. In the composition, the content of the reaction product A is 50 to 95 mol%, and the content of the reaction product B is 5 mol% to 50 mol%. 25. The liquid crystal according to claim 16 of the patent application. The composition for an alignment film, wherein the tetracarboxylic dianhydride used in the reaction product A is composed of 20 to 80 mol% of pyromellitic dianhydride and 80 to 20 mol% of cyclobutane tetracarboxylic dianhydride. The liquid crystal alignment film composition according to claim 16, wherein the tetracarboxylic acid dianhydride used in the reaction product B is • 20 to Mohr% benzene. And the composition of the liquid crystal alignment film is pre-sintered by the liquid crystal alignment film composition described in claim 16 of the patent application scope. 28. A liquid crystal holding substrate, characterized in that a liquid crystal alignment film according to item 27 of the patent application No. 27 is provided on the substrate. 29. A liquid crystal display element comprising: no electrode a liquid crystal holding substrate provided with an electrode; and a liquid crystal material disposed between the electrodeless substrate and the liquid crystal holding substrate provided with the electrode, wherein the liquid crystal holding substrate is provided with an electrode facing the liquid crystal surface The liquid crystal alignment film described in the above patent application is provided. 64