TW200909479A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device - Google Patents

Abstract

The technologies for improving the performance of a liquid crystal display by adding an additive to polyamic acid are proposed in the current market, but the problems of voltage holding ratio (VHR) and long-term reliability are not solved fully through those prior arts. The object of the present invention is to solve the aforesaid problems by providing a liquid crystal aligning agent which is a composition that contains a compound having allyl groups and at least one polymer selected from polyamic acid and derivatives thereof. The weight ratio of the compound having the allyl groups to the polymer is 0.01-1.0. Moreover, the compound having the allyl groups is at least one selected from the groups represented by formulas (A-1)-(A-7). Z1 is a single bond, -O-, alkylene, and etc; Z2 is -CH2CH2- or 1,4-phenylene; Q1 is a group represeted by a formula (B-1); Q2 is a group represeted by a formula (B-2); Q3 is hydrogen or a group represeted by a formula (B-3).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent containing a polyamic acid and a compound having a plurality of allyl groups and the use of the liquid crystal alignment agent. [Prior Art] Liquid crystal display elements are being used in various liquid crystal display devices such as a viewfinder or a projection display of a notebook computer or a desktop computer. The liquid crystal display element is used for a television set. Further, the liquid crystal display element is also used as an optoelectronic related element such as an optical print head, an optical Fourier transform element, and a light valve. The liquid crystal display device usually has a pair of substrates arranged in the opposite direction of D, 2) electrodes formed on one surface or both surfaces of the surfaces facing the pair of substrates, and 3) formed on each of the pair of substrates a liquid crystal alignment film on the opposite surface, and 4) a liquid crystal layer formed between the pair of substrates. Among the liquid crystal display elements before θ, the display elements using nematic liquid crystals are the mainstream, and the practical applications of τν (Twisted Nematic) type liquid crystal display elements, which are twisted by 9 degrees, 2) pass = A coffee liquid crystal display element with a thickness of (10) or more, and a so-called "I") ) type liquid crystal display element. Inversion of brightness occurs under brightness or contrast (halftone). Thousands 2000909479 In recent years, the viewing angle problem has been improved by the following techniques: 1) TN_TFT type liquid crystal display elements using optical compensation films, 2) VA (Vertical Alignment) type liquid crystals using vertical alignment and optical compensation films Display element, 3) MVA (Multi-Horizon Vertical Alignment) type liquid crystal display element for vertical alignment and protrusion structure, or 4) transverse electric field IPS (In_plane)

Swltchlng, coplanar switching) liquid crystal display device, 5) ECB (Electrically Controlled Birefringence) liquid crystal display device, 6) Optically Compensated Bend or Optically Computated Birefringence (OCC) type liquid crystal display Components, etc. Moreover, the improved technology is currently being applied to practice or the practical application of the technology is being studied. Improvements in the driving method of the liquid crystal display element, the improvement of the element structure, and the improvement of the components for the liquid crystal display element have led to the development of the technology of the liquid crystal display element. Among the constituent members used for the liquid crystal display element, in particular, the liquid crystal alignment film is an important factor related to the display quality of the liquid crystal display element. With the improvement in the quality of the liquid crystal display element, the effect of the liquid crystal alignment film is increasing year by year. The liquid crystal alignment film can be prepared by a liquid crystal alignment agent. At present, the main liquid crystal used is to dissolve poly-unicorn or soluble polyimine in an organic solvent. After coating such a solution on a substrate, a film can be formed by heating or the like to form a polyimide film. At present, although the Weijing alignment agent for poly-proline is also studied, heat resistance, chemical resistance (liquid crystal resistance), coating property, liquid crystal alignment, 200909479 electrical characteristics, optical characteristics, display characteristics, etc. In terms of aspect, the liquid crystal alignment agent hardly finds practical use.

In order to improve the display quality of the liquid crystal display device, as an important characteristic required for the liquid crystal alignment film, a voltage holding ratio can be cited. If the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame time is lowered, resulting in a decrease in redundancy and a failure in normal gray scale display. In addition, 7 is also a problem in that the initial voltage holding ratio is high and the voltage holding ratio (long-term reliability) after the high-temperature acceleration test is still lowered. As an attempt to solve the problem described, various methods have recently been proposed.丨,) A polyamic acid composition containing a polyglycine having a different physical property for forming a liquid crystal alignment film (for example, Patent Documents 1 and 2) is known. 2) A varnish composition containing a polymer component containing a poly-acid and an amine, and a ling agent is known (for example, refer patent document 3). 3) A varnish composition containing two or more types of polyamic acid and a polymerized solvent and a solvent having different physical properties is known (for example, see Patent Document 4). A phthalocyanine-specific varnish composition containing a diamine having a predetermined structure is known (for example, see Patent Document 5). Oxygen is known as a technique of adding a low molecular weight oxime resin to a miscellaneous kiwi varnish varnish (see, for example, Patent Document 6). There are a number of intentions to solve the problem, including improving the performance of liquid crystal display elements by adding to additives: in the technology: _: Containing "New Zealand, and (4) 唪ϊ 200909479 Liquid Crystal Alignment (for example, refer to Patent Document 7), a liquid crystal alignment agent containing a polyamic acid and a dilute-substituted mono-imine compound (for example, Patent Documents 8 and 9) and a polyglycine and an epoxy group. A liquid crystal alignment agent of a compound of a group (for example, refer to Patent Documents 10 and 11). Further, various techniques for solving the problems including improving the performance of a liquid crystal display element by adding an additive to a compound for photo-alignment have been proposed. For example, a photo-alignment composition containing a dichroic molecule and a compound having a dimercaptoamine group as a radical polymerizable group (for example, see Patent Document 12). However, voltage retention and long-term reliability issues have not been adequately addressed by these prior art techniques. For example, in Patent Document 7, the curing accelerator evaporates, sublimes, and decomposes during the imidization of the liquid crystal alignment film, and the needle is cured in the liquid crystal alignment film produced by using the liquid crystal alignment film. The influence of the accelerator on the electrical properties of the liquid crystal alignment film has not been studied. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. No. 2_16263 No. [Patent Document 6] Japanese Patent Laid-Open No. Hei 2 〇〇 5_18927 No. 丨 利 $ Li Document 7] Japanese Patent Special Opening + 9_3 () 2225 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Hei. No. Hei 9-9234. Japanese Patent Laid-Open Publication No. 2002-323701 [Patent Document 12] Japanese Patent Laid-Open No. 2003-270638 [Draft of the Invention] It is a matter of the case that the industry expects that the heating has improved the electrical characteristics for the temporal change of the electric castle retention rate. A liquid crystal alignment agent for liquid crystal alignment agents, a liquid crystal alignment layer formed by using the liquid crystal alignment agent for liquid crystal display elements, and a liquid crystal display element including the liquid crystal alignment film. The present inventors conducted intensive studies to solve the above problems. As a result, it has been found that a liquid crystal containing a polymer selected from the group consisting of polyphosphoric acid and a derivative of such polyamic acid, and a compound having a plurality of compounds having an allyl group in the molecule are used. When the liquid crystal alignment film is produced by the alignment agent, the liquid crystal display element having the alignment film can have good long-term reliability, and the present invention has been completed. The liquid crystal alignment agent of the present invention is as shown in the following item [1]. [1] A liquid crystal alignment agent characterized by comprising a composition comprising at least one polymer selected from the group consisting of polyaminic acid and a derivative thereof and a compound having a plurality of allyl groups, having a plurality of allyl groups The ratio of the ratio of the compound to the polymer is 〇.〇1 to 1.0, and the compound having a plurality of allyl groups is selected from the compounds represented by the formula (A-1) to the formula (A-7). At least one of the ethnic groups. 11 200909479 H2C=HCH2C\n j^Z"ON,CH2CH=CH2 (to) h2c=hch2c/ xch2ch=ch2

(A-2) (A-3) (A-4) (A-5) Q2——Z2—N—Z2—Q2 (A-6)

Q3

(A-7) 12 200909479

Ii

OH | 0-1-ch2 Η > (Bl) —c— •CH2 in (B-2) (B-3) t > , -CO-, -CONH-'-NHCO-' -C(CH3) 2-, -C(CF3)2-, -(CH2)t-, or_0-(CH2)f〇-, t is an integer from 1 to 8; Z2 is -CH2CH2- or 1,4-benzene ( Uphenylene) ; Q1 is a group represented by the formula (B1); Q2 is a group represented by the formula (B-2); Q3 is a hydrogen atom or a group represented by the formula (B-3); and, any hydrogen of the benzene ring The atom may be substituted by a fluorine atom, a methyl group or -OH. )

By using the liquid crystal alignment agent of the present invention to produce a liquid crystal alignment film, the decrease in the voltage holding ratio of the liquid crystal display element can be remarkably suppressed. [Embodiment] ~ The terminology used in armor is explained. In some cases, the compound represented by the formula (A·!) is also represented by the same formula: 2) The difference is the term "arbitrary" as used in the formula. Yiyi Chemical can be arbitrary. And ^, for example, "not only refers to the position but also refers to the number substitution, this expression refers to the case where the eight can be replaced by B, C or D, and the arbitrary A can be replaced by B.13 200909479. Any case where A can be replaced by C, any case where A can be replaced by D, and a case where a plurality of A can be substituted by at least two of B to D. Among them, any -CH2- can be - 〇-substituted, excluding a plurality of consecutive substitutions by -0. The symbols B, C, etc. in the hexagon represent ring B, ring C, etc., respectively, and are not fixedly bonded to the ring structure group. A substituent or a radical at a certain position of a carbon atom means that the substituent or the radical has a bonding position with the ring structural group arbitrarily. The bonding position of the substituent on the diimine group described below is 1. 5 or 7 digits.

0 N- 0 The allyl-substituted di-iminoimine compound represented by the formula (A-6) or the formula (a-7) can be obtained by having three or four maleimine groups , the compound is reacted with allyl cyclopentadiene, or a compound having three or four amino groups is added with a dipropyl bicyclo [221] heptano-5_ene-2,3_dimethyl Obtained by the reaction. New, propyl bicyclo [221] Geng Shou, no, ^ dimethyl anhydride, can be obtained by making allyl cyclopentadiene and maleic anhydride. Gp'-dilute cyclopentadiene is an intermediate product necessary for the manufacture of a propyl substituted. By making the allyl gas and the bonding position = the allyl cyclopentadiene obtained by the reaction, the possibility of a mixture of allyl compounds of the allyl compound is greater than that of the single-mixture * single_ "New" is very difficult to distinguish between the two, and it is very difficult to distinguish this 'chemicals'. In addition, the use of this 14 200909479 single compound is not a necessary condition for achieving the object of the present invention. In this case, even if the allyl-substituted diquinone imine compound is a mixture of compounds having different substitution positions of the allyl group, the same effect can be obtained, and thus, the possibility of retaining the allylcyclopentadiene as a mixture can be obtained. The use of propyl propylcyclopentadiene is desirable under the condition of f. Therefore, it is more likely that the allyl-substituted diquinone imine compound is a mixture of compounds having different ally-bonded positions. Because 'in the formula representing the allyl-substituted diquinone imine compound, the substitution position of the allyl group is not fixed on any of the carbons constituting the ring. Regarding the side chain type diamine and the non-side chain type II Amine, which is made in relation to the present invention The definition of these terms is set forth in the beginning of the description of the diamine. The present invention is constituted by the above item [1] and the items [2] to [22] shown below. [2] According to [1] The liquid crystal alignment agent is characterized in that it is a composition containing at least one polymer selected from the group consisting of polyaminic acid and a derivative thereof and a compound having a plurality of allyl groups, and a compound having a plurality of allyl groups It is at least one compound selected from the group of compounds represented by the formula (A-1), the formula (A-2), the formula (A-6), and the formula (A-7).

Ch2ch=ch2

H2C=HCH2Cv H2C=HCH2C

(A-1) (A-2) 15 200909479 Q2—Z2-N—Z2-Q2 z2 (A-6)

I Q2

(A-7) (here, Z1 is independently a single bond, -O-, -(CH2)t-, or 0-(CH2)r0_, and t is an integer of 1 to 8; and any hydrogen atom of the benzene ring The liquid crystal alignment agent according to the item [1], which is characterized in that it contains at least one polymer selected from the group consisting of polylysine and a derivative thereof and has a plurality of A composition of an allyl compound, a compound having a plurality of allyl groups is a formula (A-1-1), a formula (A-2-1), a formula (A-6-1), and a formula (A-6) -2) A compound represented by the formula (A-7-1) or the formula (A-7-2).

H2C—HCH2〇x /=\ H2C=HCH2C/N-〇CH2 分 N /CH2CH=CH2 , ch2ch=ch2

Q2^^Hn—〇-q2

(A-6-1 ) (A-2-1 ) Q2——H2CH2C\ /CH2CH2—Q2 Ϊ 2

CH2CH2—Q (A-6-2) 16 200909479

[4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the poly-proline is obtained by formula (2), formula (2), formula (5) to 7) A polymer obtained by reacting at least one of the aromatic tetracarboxylic dianhydride represented by the formula (14) with a monoamine.

[5] The liquid crystal alignment agent according to any one of [1] to [3] wherein the polyamic acid is an aromatic tetracarboxylic acid dianhydride and a diamine represented by the formula (1) The polymer obtained by carrying out the reaction.

(1) The liquid crystal alignment agent according to any one of [1], wherein the polyamic acid is obtained by formula (1), formula (2), and formula (5). a mixture of at least one of the aromatic tetracarboxylic dianhydrides represented by the formulas (7) and (14) and a tetra-tooacid dianhydride other than the aromatic compound, and a polymer obtained by reacting with a diamine.

(1) (2)

[7] The liquid crystal alignment agent according to any one of [1], wherein the poly-acid is obtained by the aromaticity represented by the formula (1), the tetrazoic acid and the aromatic surface (tetracarboxylic acid). a mixture of acid di and diamine

The polymer obtained by the reaction.

(1) It is characterized in that [8] is based on the liquid crystal of the household item [6]: the poly-proline is obtained by making the aromatic four represented by the formula (1) and the acid (14) A mixture of tetracarboxylic dianhydride other than the carboxy oxime anhydride, and a diamine is added to the diamine, and 四 18 200909479 = tetrazed dianhydride of the formula is a formula (19), a formula (23), ^ 式 (37), (39), (44), and (49) are less than five of the combinations of t.

(39) (44)

[9] The liquid crystal alignment agent according to the above [7], wherein the polyacrylic acid is an aromatic tetracarboxylic dianhydride represented by the formula (1) and a tetracarboxylic dianhydride other than the aromatic compound. a mixture obtained by reacting with a diamine, and a tetracarboxylic dianhydride other than aromatic is a formula (19), a formula (23), a formula (25), a formula (35) to a formula (37), and a formula. (39) at least one of the compounds represented by the formula (44) and the formula (49). 19 200909479

[10] The liquid crystal alignment agent according to [7], wherein the polyphthalic acid is an aromatic tetracarboxylic dianhydride represented by the formula (1) and a tetracarboxylic dianhydride other than the aromatic compound. The mixture obtained by the reaction with the diamine, and the tetracarboxylic dianhydride other than the aromatic compound are the compounds represented by the formula (19).

The liquid crystal alignment agent according to any one of [4], wherein the diamine is a non-side chain type selected from the group consisting of formula (丨) to formula (VII). At least one of the diamine groups; 20 200909479 h2n-x1-nh2

2

(I) (II) (III) (IV) h2n nh2

(V) (VI) h2n NH 2

^nh2 (VII)

Here, X1 is a linear alkylene group having a carbon number of 2 to 12; x2 is a linear alkylene group having a carbon number of 1 to 12; and X3 is independently a single bond, _c〇_, '_c〇nH_, -NHCO- , -C(CH3)2-, -C(CF3)2_, _〇_(CH, Qing, -ice, Gu(4), two t is an integer of b2, % hexanyl or benzene_any hydrogen atom can be _f [12] The liquid crystal alignment agent according to any one of [4] to [10]: characterized in that it is replaced by - OH, _C00H, ugly, ρ〇3 η2, or a benzyl group. The diamine is selected from the group consisting of formula (IV-1), wu (|ΝΛ2), 3)2) (IV) (ΝΜ)~ (5) 2), (\Λ33) and (VN-2) At least one of the non-side chain diamines represented - <^^-ΝΗ2 H2N-|^V-NH2 (IV'1) _

(IV-15) (IV-16) 21 200909479

(V-1) nh2 h2n

Nh2 h2n (V-2)

(V-3)

NH 2

3 nh2 3

Nh2

/tch2

The liquid crystal alignment agent according to any one of [4] to [i], wherein the diamine is selected from the group consisting of formula (丨) and formula (v丨丨). At least one of the non-side chain type diamines, and an alkoxy group having an alkyl group having a carbon number of 3 or more, an alkoxy group having a carbon number of 3 or more, a carbon number of 3 or more, and a steroid skeleton a group having a side group having a carbon number greater than 22, 200909479 equal to 3, an alkoxy group having 3 or more carbon atoms, or a side group having a carbon number of 3 or more a mixture of at least one of chain diamines; h2n-x1-nh2 η2ν八一^ νη2

Γ/λ-χ3-ϋ-χ3

(I) (II) (III) (IV) (V) η2ν ΝΗ,

(V,,) (VI) (. Here, 'Χ is a linear alkylene with a carbon number of 2 to 12; X2 is a linear burning support with a carbon number of 1 to 12' χ3 is a single bond, _〇_ , _c〇_, (〇ΝΗ·, -NHCO-, _〇(cH2)r〇, s·, each s_, ' _S_(eH2VS_& a linear alkylene with a carbon number of 1 to 12, t is 1~ An integer of 12; any hydrogen atom of the cyclohexane ring can be replaced by -F, -CH3, -OH, ·==〇3Η, milk, and fresh silk. ^ @13] An alignment agent characterized in that: the side chain type diamine is a compound selected from the group consisting of diamines of the formula (V丨丨丨, 丄/, ^ group. (化合物)~ (χ丨丨) represented by the compound 23 ( VIII) 200909479

f (wherein R1 is a single bond, _〇_, _C〇_, -COO_, -OCO-, -CONH-, -CH2〇-, -CF2〇-, or an alkylene group having a carbon number of 1 to 6, Any -CH2· of this alkane may be substituted by -〇-, -CH=CH- or -CeC-; R2 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having a hindrance a phenyl group having 3 to 30 alkyl groups or an alkoxy group having a carbon number of 3 to 3 Å as a substituent or a group represented by the formula (D-1), and any _Ch2_ in the alkyl group may be - Substituted by Ο-, -CH=CH- or -CeC-;

Here, R13, R14, and R15 are independently a single bond, _〇_, _c〇〇_, _〇c〇·,

_C〇NH_, an alkylene group having a carbon number of 1 to 4, an oxyalkylene group having a carbon number of 1 to 3, or an alkyleneoxy group having a carbon number of 1 to 3; the ring B and the ring ^ are independently 1 > 4_ Benzene or M-cyclohexene; R16 and R]7 are independently a fluorine atom or a fluorenyl group, and ml and m2 are independently 〇, 1 or 2; and e, f and g are independently an integer of 〇~3, & The leaf is greater than or equal to 1; R18 is a burnt group having a number of 3 to 3 Å, an alkoxy group having a carbon number of 3 to 30, or an alkoxyalkyl group having a carbon number of 3 to 30, and these alkyl groups and alkoxy groups. And an alkoxyalkyl group, any hydrogen atom may be substituted by a fluorine atom, and any -CH2_ may be substituted by a difluoromethylene group or a group represented by the formula (D_2); 24 200909479 R19 I Si- I R20

(D-2) 10 base or m!; two = number is

(IX) = / nh2 (here, R3 is independently a hydrogen atom or a methyl group; R4 is an alkyl group having 1 to 30 carbon atoms, or a dilute group having a carbon number of 2 to 3 Å is a single bond, -CO- or - CH2-.K independent

H2n

m. (X) (here, R3 is independently a hydrogen atom or a fluorenyl group; R4 is a hydrogen atom, a carbon group having a carbon number of 1 to 30, or a dilute group having a carbon number of 2 to 30; and r5 is independently a single bond, -CO- or -CIV; and 'R6 and R7 are independently a hydrogen atom, the latter number is a base of 30, or a phenyl group.) ~ 25 (XI) 200909479

(here, r8 is a carbon number of 3~3G fluorenyl group, and any _CH2• of the leg base can be replaced by 〇_, _CH=CH, bC_; R9 is independently _〇 or the stone inverse is 1~ 6 rot; ring A is M_phenylene or M•cyclohexene; a is 0 or l; b is 0, 1 or 2; and, c is independent. or

(here, =1 G is an alkyl group having a carbon number of 3 to 3 Å or a fluoroalkyl group having a carbon number of 3 to 3 Å; and R 11 is a hydrogen atom, an alkyl group having a carbon number of 丨~, or a carbon number i a fluoroalkyl group of ～30; R12 is independently _〇_ or an alkylene group having a carbon number of 1 to 6; and d is independently ruthenium or 1. (15) The liquid crystal alignment agent according to [13], It is characterized in that the side chain type diamine is selected from the group consisting of formula (vim-2), formula (vm-4), formula (vm-5), formula (vm-6), formula (X丨·2) and formula (二) A diamine in the compound represented. 26 200909479

H2N

R23 H2N (VIII-2)

H2N

H2n R24 (VI11-4)

(In this case, R23, R24, 尺29 and R3〇 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms.)

[16] The liquid crystal alignment agent according to [13], wherein the non-side chain type diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), and formula (IV). 16) a diamine in the compound represented by the formula (V·1) to the formula (V-12), the formula (V-33) and the formula (VII-2), and the side chain type diamine is selected from the group consisting of a diamine in the compound represented by (vm-2), formula (vm-4), formula (vm-5), formula (vm-6), formula (xi-2) and formula (Xb 4). 27 200909479

H0\ /0H h2m^^ ^〇fCH2^〇K 乂HNH: (V-33) (VII-2) 28 200909479

R24 (VI |丨-4)

R24

(Vlll-6) R29

The liquid crystal alignment agent according to any one of (1) to (1), wherein the polymer is selected from the group consisting of: (1), (2), (5) to (7), and (14) At least one of the aromatic tetracarboxylic dianhydrides represented by the formula (19), the formula (23), the formula (25), the formula (35) to the formula (37), the formula (39), the formula (44) and the formula (49) a mixture of at least one of tetrahydro acid dianhydrides other than aromatic, and formula (IV-1), formula (ιν_2), formula (IV-15), formula (IV-16), formula ( V-1)~ Poly(Amino acid) obtained by reacting at least one of non-side chain type diamines of 29 200909479 represented by formula (V-12), formula (V_33) and formula (v丨丨_2) a derivative, and by reacting the tetracarboxylic dianhydride with a compound selected from the group consisting of formula (VIH-2), formula (vm_4), formula (VIN-5), formula (VIH-6), formula (XI- 2) reacting at least one of the side chain type diamines represented by the formula (XI-4) with at least one of the non-side chain type diamines to obtain at least one of an amine acid and a derivative thereof One. Ο 〇

30 200909479

HO OH

(V-33)

(VI1-2) 31 200909479

Η2Ν

R23 (Vlll-2)

R24 | H2N

(Vi I

(Vlll-6)

― (In this case, R23, r24, R29 and R30 are independently a burnt group having a carbon number of 3 to 3 Å or a gas-bearing base having a carbon number of 3 to 30.) [18] The liquid crystal according to [17] The alignment agent is characterized in that the polymer is obtained by mixing at least one of an aromatic acid, at least one, and at least one of a tetracarboxylic dianhydride other than an aromatic, and a non-side chain diamine. The money is obtained (4) poly-stangic acid. The liquid crystal alignment agent according to the item [1], wherein the polymer is a mixture of at least one of aromatic tetracarboxylic dianhydride and at least one of tetracarboxylic dianhydrides other than aromatic, Poly-proline acid 'obtained by reacting with at least one of non-side chain type diamines' and at least one and side bond type 32 by a mixture of the four tetramines and the non-side bond type diamines 2009 2009479 A mixture of polylysines obtained by reacting a mixture of at least one of diamines. The liquid crystal alignment agent according to the item [17], wherein the t compound is at least one selected from the group consisting of at least one of aromatic tetraphthalic dianhydride and tetracarboxylic dianhydride other than aromatic. And a mixture of at least one of the non-side chain type diamine and at least one of the side chain type diamines is reacted to obtain at least one of the polylysine and a derivative thereof. [21] A liquid crystal alignment film which is coated on a substrate by the liquid crystal alignment agent according to any one of [1] to [20], and is preferably baked in a film state. form. [22] A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; and electrodes forming one surface or both surfaces of a surface on which the pair of substrates face each other, formed in the pair a liquid crystal alignment film on a surface of each of the substrates, and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to [21]. The liquid crystal alignment agent ' of the present invention' is a compound containing at least one polymer selected from the group consisting of polyacrylic acid and its derivatives, and a compound having a plurality of allyl groups. Further, the compound having a plurality of allyl groups is at least one compound selected from the group consisting of the compounds represented by the formula (Α·7). 33 200909479

H2C=HCH2C\ h2c=hch2c oh2ch=ch2

Nx ch2ch=ch2 (A-l)

/N

(A-2)

(A-3) Q1

Q2 Z2—N—Z2_Q2

Q3

(A-4) (A-5) (A-6)

In the formula (Al) to the formula (A-7), Z1 is independently a single bond, -O-, -CO-, -CONH- > -NHCO- '-C(CH3)2- '-C(CF3)2 - ' -(CH2)t- > A 34 200909479 ^• 仰士0...1 is an integer from 1 to 8; Z2 is -CH2CH2- or 1,4-benzene floor; Q3 is represented by (B-1) Q2 is a group represented by the formula (B_2); ^ is a hydrogen atom or a group represented by the formula (B-3); and any hydrogen atom of the 'benzene ring may be substituted by a fluorine atom, a fluorenyl group or _〇H. These groups are selected -OH. 〇

OH I -C-H h2c~ch-ch2-c-o-ch2-c-ch2 .N- (B-l) H2C=CH-CH2-C-O-CHo-c-CH;

OH (B-2) (B-3)

A preferred example of the compound having a plurality of dilute propyl groups is at least one compound selected from the group consisting of compounds represented by the formula (H), the formula (A-2), the formula (A-6), and the formula (Α·7). . (A-l) H2C=HCH2C, j^N/CH2CH=CH2 h2c=hch2c/N xch2ch=ch2

(A-2) 35 200909479 Q2——Z2- -N-Z2-Q2 (A-6)

Q3

(here, Z1 is independently a single bond, -O-, -(CH2)t-, or -0-(CH2)t-0-, and t is an integer of 1 to 8; the meanings of Q1 and Q2 are the same as described Further, any hydrogen atom of the benzene ring may be substituted by -OH.) Specific examples of the compound (A-1) are shown below.

CH2 (A-l-1 )

N

N

I :nhQCH2

(A-l-2)

N

I (A-l-4) (A-l-3 ) l· J\JT^

I

N

(A-l-5) I

I (A-l-7)

(A-l-6) HO I

I (A-l-8 ) 36 V^. 200909479 Ν <y (A-1-9) Specific examples of the compound (Α-2) are shown below. 0 OH ΟΗ 0

(Α-2-1) n^〇^ch2^}^ Ο OH OH Ο

(Α-2-2) (Α-2-3) (Α-2-4)

(Α-2-5)

Ο ΟΗ

ΟΗ Ο (Α-2-6 ) 37 200909479

(A-2-7)

Specific examples of the compound (A-3) are shown below. 0 OH ΟΗ Ο (A-3-1 )

OH

:N^^CH2{^fCH Ο OH

(A-3-2) OH Ο

:N^-〇^^CH

OH

CH3 (A-3-4) The compound (A-6) and the compound (A_7) are allyl substituted bisimine compounds. Specific examples of the allyl-substituted diquinone imine compound are shown below. 38 200909479

Q2~HH2CH2C, n/CH2CH2~~q2 I CH2CH2—Q2 (A-6-2)

,: The meaning of Q2 is the same as that of the other. A more preferred example of the compound of the formula ί-ι-dC is a selected compound. ~2) At least one of the compound groups represented by the present invention will be described for the scorpion ship and its charm used in this day (4).

Polylysine is a polymer obtained by reacting two needles of tetradecanoic acid with a diamine. The polymer is dissolved in a solvent, coated on a substrate, and heated to form a surface on the substrate. A liquid crystal hard film composed of a polyimide film. Examples of such derivatives of poly-proline are: soluble polyimine, polyphthalate, and polyamidamine. More specifically, a polyimine which is obtained by completely dehydrating a guanamine bond of a poly-aracine and a carboxyl group to form a ring, and a partial polyazide obtained by dehydrating a guanamine bond and a carboxyl moiety of a poly phthalic acid into a ring are exemplified. Poly-proline 39 which is converted into an ester of an amine or poly-proline, 200909479 s曰, a polyfluorene obtained by reacting a part of tetra-dianhydride with a dinuclear (or its tooth or anhydride) An amino acid-polyamine copolymer and a polyamidoximine obtained by partially or completely dehydrating the polyamido-polyamide copolymer into a ring. Further, in the case where a tetracarboxylic dianhydride and a dicarboxylic acid are used in combination as an acid component, not only a poly-proline-polyamine copolymer but also a polyamine and/or a poly-proline may be obtained. The mixture, in the present invention, is referred to as a poly-proline-polyamine copolymer based on this possibility. The present invention uses at least one polymer selected from the group consisting of polylysine and derivatives thereof. And ' preferably at least two of such polymers are used in combination. The tetracarboxylic dianhydride can be selected by dissolving the polyamic acid obtained by using the tetracarboxylic dianhydride in a solvent used for the liquid crystal alignment agent as a condition. Further, it is preferable to use at least one of the aromatic tetracyclic dianhydrides among the four tetra-oxo-acid needles. Preferred examples of the aromatic tetracarboxylic dianhydride are shown below.

40 200909479

i

More preferably, the compound (1), the compound 2, the compound (5), the compound (6), the compound (7), and the compound 4) are particularly preferably a compound (丨) (isophenyl). Tetracarboxylic acid dianhydride). In the invention, a preferred example of the tetracarboxylic dianhydride other than at least one of the tetracarboxylic dianhydrides other than the aromatic tetra dianhydride may be shown in the following square tube. 41 200909479

42 200909479

/

(45) (46)

(49)

43 200909479

Among the above-mentioned tetracarboxylic acid dianhydrides other than the aromatic compound, the compound (19) to the compound (39) and the compound (49) are more preferable, and the compound (19), the compound (23), the compound (25), and the compound (35) are more preferable. - Compound (37), Compound (39), Compound (44) and Compound (49). Further, the compound (19) (1,2,3,4-cyclobutanetetracarboxylic dianhydride) is particularly preferable. On the other hand, in order to form the polyaminic acid or a derivative thereof in the present invention into a polyimine which is soluble in a solvent, it is preferred to use the formula (24), the formula (35) to the formula (44), and the formula (49). And a tetracarboxylic dianhydride represented by the formula (50), the formula (53), and the formula (60). 44 200909479 Further, in the present invention, it is preferred to use at least one of the above aromatic tetra-orthocarboxylic dianhydrides in combination with at least one of tetracarboxylic dianhydrides other than aromatics, and it is particularly preferable to use compound (1) (isophenyl tetra It is used in combination with the compound (19) (1,2,3,4-cyclobutane tetraphthalic acid dianhydride). When a liquid crystal alignment film containing the polyamic acid and the compound (A) thus obtained is used to form a liquid crystal alignment film, the liquid crystal display element containing the liquid crystal alignment film can have good long-term reliability in terms of voltage holding ratio. . Further, as the tetracarboxylic dianhydride in the present invention, a compound (other than tetracarboxylic dianhydride other than the compound (67)) may be used. Other four oxonic acid bismuth, if it is within the range in which the object of the present invention can be attained For example, a tetracarboxylic acid dianhydride having a side chain structure may be mentioned, and a polyfluorene having a side chain structure and a tetracarboxylic dianhydride may be used. When the amine acid is used for the liquid crystal alignment agent, the liquid crystal alignment film formed by the liquid crystal alignment agent can increase the pretilt angle of the liquid crystal display having the liquid crystal alignment film. The tetracarboxylic acid dianhydride is not particularly limited, and examples thereof include a compound having a steroid frame and a compound (69).

45 200909479 Use this will = acid anhydride "quote into _ and anti-hemp end. * New-needle-type-substituting into Weixuan can make the polymerization go down, and the reaction can no longer be measured by the termination of the polymerization reaction. The molecular weight of the obtained polyaxid can be easily controlled: the ratio of the tetracarboxylic dianhydride can be 10, which does not damage the secret of this hair, and the amount of the four thieves (four) Rensi's diamine can be used in the middle of the month. However, in the case of the VA type liquid crystal f = ', it is required to be 8 多. ~9〇. The big pre-dip around. In the case of a CB type liquid crystal display element, it is required to be 7. ~2〇 Pre-tilt angle, 纟TN type liquid crystal display element or (4) type liquid crystal display: In most cases, it is required to be 3. ~1G. The left and right pretilt angles; and in the case of ips type liquid crystal display elements are mostly required. . ~3. A small pretilt angle to the left and right. Therefore, it is necessary to consider adjusting the pretilt angle. However, diamines can be classified into two types depending on their structures. That is, when the skeleton in which two amino groups are bonded is regarded as a domain, a diamine having a side chain group which is a group branched from the main chain, and a diamine having no side chain group. By reacting a diamine having a side chain group with a tetracarboxylic dianhydride, polyamic acid or polyimine having a plurality of side chain groups in the main chain of the polymer can be obtained. When a polyamic acid or a polyimine having a side chain group on the polymer main chain is used, the liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer can increase the pretilt angle of the liquid crystal display element. . That is, this side chain group is a group having an effect of increasing the pretilt angle, and may be selected from an alkyl group having a carbon number of 3 or more, an alkoxy group having a carbon number of 3 or more, and an alkoxyalkyl group having a carbon number of 3 or more. Base, having a group of steroid frames, and an alkyl group having a carbon number of 3 or more at the terminal, an alkoxy group having a carbon number of 3 or more, or an alkoxyalkyl group having a carbon number of 3 or more. Group. In the present invention, a diamine having such a side chain group is referred to as a side chain type diamine. A diamine having no such a side chain group is referred to as a non-side bond type diamine. Further, by appropriately combining the side chain type diamine and the non-side chain type diamine, the pretilt angle required for each of the various display elements can be matched. That is, at least one of the non-side chain type diamines can be used without requiring a large pretilt angle. In the case of use of the VA liquid crystal display device, the 〇CB liquid crystal display device, or the STN liquid crystal display device, at least one of the non-side bond-type amine and at least one of the side chain type diamines may be used in combination. In this case, the blending ratio of the non-chain type diamine to the side chain type diamine can be determined according to the target pretilt angle. Of course, by appropriately selecting the side chain groups, it is also possible to use only the side chain type - amine to correspond to the required pretilt angle. Thus, the liquid crystal alignment agent of the present invention can be applied to any type of liquid crystal display. Further, the effect of such a side chain group is also the same in the tetracarboxylic dianhydride. Specific examples of the side chain groups are as follows. Hundreds of first, for example, alkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, alkyl, alkyl, silk amino, alkenyl, diloxy, miscellaneous, occupational, County oxynonyl, alkenylamine, carbon, silk, silk, silk, alkyne, fast oxy group, silk ammonia scale. Further, the alkyl group, the alkenyl group and the alkynyl group of these group towels are all groups having a carbon number of 3 or more. Here, the total carbon number in the alkoxy group may be 3 or more. In addition, these groups can be either linear or branched in the form of 2009 2009479. a ring larger than Ιΐί has a cyclyl group having a carbon number of 3 or more, and a carbon number substituent is a ruthenium alkyl group as m · · a base, a phenyl alkyl group, a phenyl alkoxy group, a r phenyl group, a phenyl group a carbonyloxy group, a phenoxycarbonyl group, a phenylaminooxy group, a cycloalkyl group having a carbon number of 3 or more, a cyclohexylcyclohexyloxy group, a cyclohexylphenyl group, a ring tH, a cyclohexylphenoxy group, a double (cyclohexyl)oxy, bis(cyclohexanyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexane=^ soil rebel, bis(3⁄4 hexyl)phenyloxy, and ring The hexyl bis(phenyl) fluorenyl group is a ring-like structural group. The bis(cyclohexyl) and bis(phenyl) groups can be bonded through an alkene phase instead of a single bond. η. It can be exemplified that: a stupid ring or a cyclohexane ring of two or more is carried by a single bond, -0-, -COO-, -OCO-, _C0NH• or a carbon number of 丨~3, and the last ring has Wei Daqi is a stagnation atom of 3, a carbon atom having a carbon number of 3 or more, an alkoxy group having a carbon number of more than 3, or a ring assembly group having a Wei or higher than 3 oxirane as a substituent. Of course, having a steroid Skeleton group It can be effectively used as a pendant non-side chain type Preferred examples of the diamine are listed below.

(I) (II) (III) 48 (IV) 200909479

(V)

(VI)

(VII)

In the formula (丨)~ (VII), X1 is a linear burnt-iron having a carbon number of 2 to 12; X2 is a linear alkylene having a carbon number of 1 to 12; and X3 is independently a single bond, _〇_, -CO- > -CONH- > -NHCO- ' -C(CH3)2- ^ -C(CF3)2- ' -0-(CH2)r0-, -S-, _S_S_, _s〇2·, _s_(CH2)t_s_ or the number of obstacles is! 〜12的直链烧楼, t is an integer from 1 to 12; any hydrogen atom of a cyclohexane ring or a benzene ring may be -F, -CH3, -OH, -COOH, -S03H, -Ρ03Η2, or a base group or Replaced by the base group. Preferred examples of the diamine represented by the formula (?) are shown below. Η2_2)2ΝΗ2 H2N(CH2)4NH2 H2N(CH2)6NH2 η2ν_12νη2 (Ι·1) (Ι-2) (Ι-3) (Μ) A preferred example of the diamine represented by the formula (Ν) is shown below. H2N^yNH2 Η2Νη^ρΝΗ2 (H-1) (II-2) Preferred examples of the diamine represented by the formula (丨丨I) are shown below. 49 200909479

Preferred examples of the diamine represented by the formula (ιν) are shown below. Me h2n^^nh2 h2m^-NH2 Me (iv-1) (IV-2) (IV-3) Me Me OH HO NH 2 h2n H2N—/)—Nhb

(IV-4) H2N-NH2 Me Me (IV-5)

H2N y 'nh2 (IV-6)

Nhb (IV-7)

COOH

H2N v, nh2 (IV-8) HOOC h2n-nh2

S03H

H2N ^ 'NH, (IV'10) (IV-9)

NH 2 PO3H2

H2N v, nh5 (IV-12) c.

NH 2

(IV, 14) (IV-15) (IV-16) Preferred examples of the diamine represented by the formula (V) are shown below. 50 200909479

NH2

H2n^^0^°^^nh2 h2N-<^^〇^0^^NH2 (V-16) (V-17) (V-18) (V-19) 51 200909479 h2nhQ^0'^^x ^°^j>-nh2 h2n-^)"s 乂)-nh, (V-20) (V-21) H2N-S_s-NH2 H2N-NH2 (V-22) (V-23) (V- 24) (V-25)

H2N (V-27) 2 (V-26)

Chk

\J>_NH2 H2N~^~~^~S02— (V-31) (V-32) H0\ /0H ?H fl h2n^^- -〇-nh^ (V-33) (V-34) - NH〇 shows a preferred example of the diamine represented by the formula (VI) as follows 52 200909479

(VI-5) (VI-6) Preferred examples of the diamine represented by the formula (VII) are shown below. 53 2 200909479

H2n

(VII-1)

(VII-2)

(VII-3)

(VII-10)

(Vli-16) More preferable examples of these diamines are the compound (IV_1) to the compound (IV-5), the compound (IV-15), the compound (IV-16), and the compound (V-1) 54 200909479~ a compound (V-12), a compound (V-26), a compound (V-27), a chemical person (V-31), a compound (V-33), a compound (Vl-i), a compound (^-2), Particularly preferred examples of the compound (VI-6) and the compound (VII-1) to the compound (V|U5) are a compound (丨V-1), a compound (丨\/_2), and a character (丨V-15). ), the compound (IV-16), the compound (V-1), the compound (V-12), the compound (V-33), and the compound (VII-2). ° The side chain type diamine used in the present invention specifically includes the following formula

(VIII) to a diamine represented by the formula (XII).

(VIII) In the formula (VIII), R1 is a single bond, _〇_, _c〇-, -COO-, _0C0_, -CONH-, -CH2〇-, -CF2〇-, or a carbon number of 1 to 6. Burning, any -CH2- in the calcination may be substituted by -0, _CH=CH- or -CeC-; R2 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, having a phenyl group having a reciprocal number of 3 to 30 or a phenyl group having a number of 3 to 30 alkyl groups as a substituent or a group represented by the formula (D-1), and any _CH2_ in the alkyl group may be used. It is replaced by -Ο-, -CH=CH- or -C^C-.

Here, R13, R14 and R15 are independently a single bond, _〇_, _c〇〇_, _〇c〇_, -CONH-, an alkylene group having a carbon number of 1 to 4, and an oxygen having a carbon number of 1 to 3. An alkylene group, 55 200909479 or an alkyleneoxy group having a carbon number of 1 to 3; ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexene; and R16 and R17 are independently a fluorine atom or a hydrazine. Base, ml and m2 are independently 0, 1 or 2; e, f and g are independent integers of 〇~3, and the total of these is greater than or equal to 1; R18 is a burning base having a carbon number of 3 to 30, and the number of obstacles is 3~ An alkoxy group of 30 or an alkoxyalkyl group having a carbon number of 3 to 30, and among these alkyl groups, alkoxy groups and alkoxyalkyl groups, any hydrogen atom may be substituted by a fluorine atom, and any - Αν may be substituted by a difluoroindenylene group or a group represented by the formula (D_2).

Here, R19, R20, R group or phenyl group, and η is an integer of 1 and R22 independently of the alkane 100 having a carbon number of 1 to 10.

Here, R3 is independently a hydrogen atom or a methyl group; R4 is a hydrogen atom, an alkyl group having a carbon number of 30, or an alkenyl group having a carbon number of 2 to 3 Å; and R5 is independently a single bond, -CO- or - CH2·. Preferably, one of the two aminophenyl-R5_〇• groups is bonded to the 3-position of the ketone (4) and the other group is bonded to the 6 position. Further, the bonding position of the two amino groups on the benzene ring is preferably the meta or para position of the bonding position of R5. Further, any hydrogen atom of the bond formed on the carbon forming the alcohol skeleton may be substituted by a methyl group.

Here, R is independently a hydrogen atom or a methyl group; Μ *,

1 to 30 of the dazzling:, the type of stone mountain to go q, for the wind atom, the number of carbon with a carbon number of 1 30 or the slave number is 2~3 heart _c〇_ or even ·; and, R6 and R7 are independently hydrogen atoms A burnt group of carbon 30 or a phenyl group. The bonding position of the two R7-substituted aminophenylhydrazines on the soil is preferably the alignment or para position of the carbon to which the alcohol skeleton is bonded. In addition, the meta position or alignment of the bonding sites of the two pure groups on the benzene ring. horse

Here, R is a hospital base of ♦3 to 30, and any •CH2- of this alkyl group may be replaced by _〇-, -CH=CH_ or c^c-; R9 is independently -0- or Alkane having a carbon number of 1 to 6; ring A is 1,4-phenylene or 1,4-cyclohexene; a is 0 or 1; b is 〇, 1 or 2; and, ^ is independently 0 or 1 . The bonding position of the two amino groups on the phenyl ring is preferably the meta or para position of R9. 57 200909479

Here, R1G is an alkyl group having a carbon number of 3 to 30 or a fluoroalkyl group having a carbon number of 3 to 30; and R11 is a halogen atom, an alkyl group having 1 to 30 carbon atoms or a fluorine having 1 to 30 carbon atoms. Alkenyl; R12 is independently -0- or an alkylene having a carbon number of 1 to 6; and, d is independently 0 or 1. The bonding position of the two amino groups on the phenyl ring is preferably the meta or para position of R12.

Examples of the diamine represented by the formula (vm) include a diamine represented by the formula (vm-i) to the formula (VIII-43).

(V1IM) (VII1-2) (VIII-3)

(VI1I-6) 58 200909479

(VIIM1) In the formula (vm-i) to the formula (vm-ii), each of r23 and r24 is preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably having a carbon number of 5 to 25 alkyl groups or alkoxy groups having 5 to 25 carbon atoms.

R25 R25 R25

(VIII-12) (VIII-13) (VIII-14) (VIII-15) R26 0〆

H2N (VIII-16) (VIII-17) NH2 In the formula (vm-12) to the formula (vm-15), R25 is preferably an alkyl group having a carbon number of 4 59 200909479 to 30, more preferably a carbon number of 6 to 25 Alkyl. In the formulae (VMI-16) and (VIM_17), R26 is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 25 carbon atoms.

H2n h2n (Vill-19)

(VHI-20) (Vill-21)

H2N h2n (VIII-22)

H2N h2n (VIII.23)

(Vlil-24)

(VIH-25)

HsN (VIH-26) 60 200909479 h2m < h2n , 〇

R28 (VIII-27)

(Vlll-28)

(VIII-29)

(VIII-30)

H2N h2n (VIII-31) (VIII-32)

(VIII-33)

(VIII-34) H2Nv O H2N 〇 仆27 分#

H2n h2N wide H (VIII-35) (VIII-36)

In the formulae (vm-18) to (Vm-37), R27 and R28 are each preferably an alkyl group having a carbon number of 3 to 30 or an alkoxy group having a carbon number of 3 to 30, more preferably a carbon 61 200909479 number of 5 An alkyl group of ～25 or an alkoxy group having a carbon number of 5 to 25.

Among these groups, a diamine represented by the formula (VIII-1) to the formula (VIII-11) is preferred, and a formula (vm-2), a formula (vm-4), a formula (vm-5) and a formula (preferably) are preferred. A diamine represented by any one of VMI-6). Examples of the diamine represented by the formula (IX) include a diamine represented by the formula (IX-1) to the formula (IX-4). 62 200909479

Examples of the diamine represented by the formula (X) include a diamine represented by the formula (x-1) to the formula (X-8). H2n

63 200909479 h2n

64 200909479

65 200909479

Examples of the diamine represented by the formula (XI) include a diamine represented by the formula (ΧΙ-1) to the formula (XI-8).

R30

66 200909479 \ R30

R30

(Xl-β) R30

R30

67 200909479 In the formula (ΧΙ-1) to the formula (XI-3), R29 is preferably an alkyl group having a carbon number of 3 to 30; and in the formula (XI-4) to the formula (XI-8), R3G is preferably a carbon number. A base of 3 to 20. Examples of the diamine represented by the formula (XII) include a diamine represented by the formula (XII-1) to the formula (XII-3).

C

In the above formula, R31 is preferably an alkyl group having 6 to 20 carbon atoms, and R32 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In the present invention, other diamines other than the diamine represented by the formula (?) to the formula (XN) may be used in combination. Examples of the other diamines include a naphthalene-based diamine having a naphthalene structure, an anthracene-based diamine having a fluorene structure, and a decane-based diamine having a decane-based bond, and these diamines may have a side chain group. . A preferred example of the decane-based diamine is a compound represented by the following formula (XV). P33 / ? \ R33 h2n—X4— h °} —Si—X4—NH2 (XV) \ r34 m R34 In the formula (XV), R33 and R34 are each independently an alkyl group having 1 to 3 carbon atoms or benzene. The group X4 is independently an alkylene group having 1 to 6 carbon atoms or a phenylene group, and m 68 200909479 is an integer of 1 to 10 carbon atoms. In addition, this stupid replacement is replaced by a 1 to 4 yard base.

335 and, independently, the carbon number is ^_ base. The polymerization allows the polymerization to use a monoamine. Thus, the polymerization obtained can be terminated: C; tyrosine;:: sub-[this: the ratio of easily controllable amines] can be achieved without impairing the effects of the present invention: =::7 is equal to the amount of 1 GmG1% As a standard. Within the _, preferably the poly-proline or its derivative in the small hair may have an arbitrary weight 69 200909479 average molecular weight. The weight average molecular weight of the polyamic acid or a derivative thereof is not particularly limited. When it is used as a component of a liquid crystal alignment agent, the weight average molecular weight is preferably 5 x 10 or more, more preferably 1 x 1 4 or more. The polyglycine or a derivative thereof having a weight average molecular weight of 5x10 or more does not evaporate at the stage of firing the liquid crystal alignment film, and has a preferable physical property as a component of the liquid crystal alignment agent. This weight average molecular weight can be passed through gel permeation

The chromatography ''GPC) method was used for the measurement. For example, a polyamic acid or a derivative thereof obtained by diluting dimethylformamide (DMF) in a manner of a polymer concentration of about 1 wt./〇, using Chromat〇pacC-R7A (manufactured by Shimadzu Corporation) DMF was used as a developing solvent, and it was measured by a gelation chromatography (=P, C) method, and converted into polystyrene to calculate the average knife amount. In addition, in order to measure poly= or polyacrylic acid by GpC with high precision, it may be prepared by dissolving phosphoric acid, hydrochloric acid, nitric acid, thiodithiolate acid, and chlorinated inorganic salt in DMF solvent. Solvent. The production of the amino acid or its derivative in the present invention can be carried out by at least the method of the diamine represented by the reaction vessel containing the raw material inlet, the nitrogen inlet, the thermometer, the search machine and the condenser. One, according to the ^~ formula (at least one ^ ^ 匮 而 自 自 自 自 自 选择 选择 ; ; : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The solvent (for example, guanamine is the second liver, the screaming is to be smashed 1^_, etc.) and the tetrahydrofuran's loading of the tetracarboxylic dianhydride is 200909479. The total amount is preferably approximately equal to the total number of moles of the diamine ( The molar ratio is about 9~u.) After stirring, the reaction is carried out for 1 to 48 hours at a temperature of 0 ° C to 7 Torr, thereby obtaining a solution of poly-proline. In addition, it is heated by heating. A high reaction temperature (for example, 50 ° C to 80 ° 〇, a polyglycine having a small molecular weight can be obtained. The obtained solution of polyglycine can be diluted with a solvent to adjust to a desired viscosity. Polylysine' can be precipitated by using a large amount of poor solvent (p〇〇r Solvent), by filtration, etc. The solid component is completely separated from the solvent and analyzed by IR and NMR, and then identified by using an aqueous solution of a strong base such as KOH or NaOH to extract the organic polyamine, and then extract it by an organic solvent, and then pass GC, The analysis can be carried out by HPLC or GC-MS, whereby the monomer to be used can be identified. Further, in the case where the polylysine in the present invention is made into a polyphthalic acid derivative, that is, a soluble polyimine, a polyaminic acid solution, an anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride as a dehydrating agent, and a tertiary amine such as triethylamine, pyridine or tridecylpyridine (C〇iHdine) as a dehydration ring-forming catalyst (tertiary amine), the hydrazine imidization reaction is carried out at a temperature of 20 ° C to 15 ° t to obtain a soluble polyimine. Or a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol or propanol or a glycol solvent) is used. The polyamic acid is precipitated from the polyaminic acid solution, and the precipitated polylysine is made the same in a solvent such as toluene or xylene at a temperature of from 20 ° C to 150 ° C. Dehydrating agent and dehydration to ring catalyst together The reaction is carried out to obtain a soluble polyimine. 71 200909479 In the oxime imidization reaction, the ratio of the dehydrating agent to the dehydrated ring-forming catalyst is preferably 0.1 to 10 (mole ratio), and the total amount of the two is preferably relative to The total amount of methic anhydride contained in the tetracarboxylic dianhydride used is 15 to 10 moles. By adjusting the chemical hydrazide dehydrating agent, the amount of the catalyst, the reaction temperature and the reaction time, it can be controlled. The degree of imidization

Part of the polyimine. I can separate the obtained poly-imine from the solvent and combine the polyimine with

Si re-dissolving the mercapto-substituted mono-imine compound in combination with at least one selected from the group of heterocyclic persons into a solvent to form a liquid crystal alignment agent for use. Or the obtained polyimine is separated from the solvent, and the modifier is added to prepare a liquid crystal alignment agent. Further, as described above, the - moiety of the anhydride used in the tetracarboxylic acid of the present invention may be replaced with an organic bis. If the timing of the acid and the tetrahydrofuran anhydride is used to produce the polypyrene of the present invention, the polyamic acid and the guanamine copolymer are obtained. Here, the ratio of the 'organic dicarboxylic acid to the four-week two-needle' can be used as a standard without impairing the range of the present invention. Inflammation, 4 10 By polymerizing this polyamic acid-polyamide copolymer, polyamidoquinone imine can be produced. The liquid helium alignment agent of Lin Yue may contain various additives contained in the crystal alignment agent from the viewpoints of the physical properties of the two grades, ease of handling, and simplification of the process. In addition, the content of the compound (4) in the liquid crystal alignment agent of the present invention is generally higher than that of the liquid crystal alignment agent when the liquid crystal alignment element is used for a liquid crystal display element for a long period of time. The weight ratio of the polyaminic acid or its derivative in the alignment agent is preferably 0.01 to 10, more preferably 〇 to 0.7', more preferably 0.01 to 0.5. A particularly preferred range for this weight ratio is ~0.5. The liquid crystal alignment agent of the present invention is a composition in a usual state, and further contains a solvent in addition to the compound (A) and the polyaminic acid or a derivative thereof, and further contains various additives as needed. The content of the poly-proline or a derivative thereof in the liquid crystal alignment agent of the present invention can be appropriately selected depending on the method of applying the liquid crystal alignment agent onto the substrate. For example, a printing machine used in a manufacturing process of a usual liquid crystal display element (including an offset printing machine or an inkjet printing machine, hereinafter sometimes simply referred to as "printing machine"). Polyacrylic acid in a liquid crystal alignment agent used or The content of the derivative is preferably 0.5 30 Wt/° of the total amount, more preferably 1 to 15% by weight based on the total amount, and can be appropriately adjusted depending on the relationship with the viscosity of the liquid crystal alignment agent.

The solvent used in the present invention may contain a solvent which is generally used for the production, order or use of a polymer component such as polyamido I, soluble polyimine, and polyamidoximine, and is suitably used depending on the purpose of use. select. The solvent is preferably a solvent-soluble mixed solvent containing υ Wei Lin or a heteropolymer = = = aprotic polar organic solution m) for changing the surface tension and changing the coating property. These solvents can be exemplified as follows. 1) For poly-proline or soluble polyimine, it is a good solvent for polar organic (4) (the town is called 轩 极 财 各 各 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , N-dimercaptoacetamide, dimercapto, di-N-N-73 200909479: base amine, hydrazine, hydrazine diethyl carbamide, diethyl acetamide, butyl phthalocyanine ^ 戊内g曰. Among these aprotic polar organic solvents, more preferably 不 Ν-曱-based 2 - such as each biting ketone, dimethyl sulphate, pudding vinegar, r - pentane Ester, etc. 2) Solvents (hereinafter referred to as other solvents) for changing the surface tension to improve coating properties and the like: for example, Wei Shiji, X-methyl-3-methoxybutanol, tetrachloronaphthalene ( Tetralin), isophoric acid, ethylene glycol monotop, etc., ethylene glycol monolithic (dithioglycol monoethyl ether, etc., ethylene glycol monoalkyl radical, ethylene glycol monoalkyl or acetic acid , triethylene glycol monoalkyl radical, propylene glycol monobutyl bond, etc., single-burning domain, malonic acid, diethyl vinegar, malonic acid, dialkyl vinegar, dipropanol monomethyl hydrazine, etc. _, these acetic acid from the purpose of the class and other vinegars More preferably, it is exemplified by: ethylene glycol single-pass test, diethylene glycol single-assay, propylene glycol single top, dipropylene glycol monoterpene_, etc. Types and ratios of non-beibei polar solvents and other solvents, liquid crystal alignment may be considered. The printing property, coating property, solubility, storage stability, etc. of the J, and the setting of the grounding. The aprotic polarity solvency and storage stability are relatively good (better than other, and other solvants and coatings) The liquid crystal alignment agent of the present invention may contain various additives. For example, the electrical properties or alignment of the formed liquid crystal alignment film can be controlled by adding a soluble polymer as an additive to an organic solvent. Examples of the examples include: amines, polyamines, polyurea H polyepoxides, polyacetates, lysine-modified polyurethanes, and lycopene-modified vinegars. Other additives, such as D, are intended to improve the coating. A surfactant for achieving the purpose can be used for the cloth, 2) an antistatic 74 200909479 agent can be used when antistatic is required, and 3) a decane coupling can be used when the adhesion to the substrate or the abrasion resistance is desired. Agent or titanium A coupling agent is used, and 4) a ruthenium imidization catalyst can be used for the ruthenium imidization at a low temperature. Examples of the decane coupling agent include vinyl trimethoxy decane, vinyl diethoxy decane, N-(2-aminoethyl)_3_aminopropyl decyl dimethoxy decane, and N-(2). -aminoethyl)_3_aminopropyldecyltrimethoxydecane, p-aminophenyltrimethoxyoxane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-aminophenyl Triethoxy decane, 1 aminopropyl decyloxydecane, 3-aminopropyltriethoxy oxime, 3_glycidoxypropyl decyloxydecane, 3_epoxypropoxy Propylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltri曱oxydecane, 3-mercaptopropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(l,3-didecylbutylene)_3_(triethoxydecane Base) - propylamine, and N,N-bis[3-(dimethoxy sec- yl)propyl]ethylenediamine. Preferable examples of the ruthenium imidization catalyst include aliphatic amines such as tridecylamine, triethylamine, dipropylamine, and dibutylamine; hydrazine, hydrazine-dimercaptoaniline, monoethylamine, and methyl group substitution. An aromatic amine such as a stilbene amine or a phenylamine substituted by a base; and a bite-bit, methyl-substituted hydrazine 1 bit, a hydrazine substituted with a hydrazine group, a quinoline, a methyl substituted quinoline, a hydroxy-substituted quinoline, an isoquinoline, a mercapto-substituted isoquinoline, a hydroxy-substituted isoquinoline, an imidazole, a mercapto-substituted imidazole, a hydroxy-substituted imidazole, and the like. Particularly preferred are N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxylamine, ortho-quinone, ruthenium, ruthenium, and ruthenium. 75 200909479 The amount of the coupling agent to be added is usually G 10% by weight, preferably G _% to 3 wt%, based on the total weight of the polyaminic acid or its derivative. The amount of the brewing imidization catalyst to be added is usually 0.01 to 5 equivalents, preferably 5 to 5 equivalents, per equivalent of the mercapto group of the polyglycine or its derivative. The amount of the other additives to be added varies depending on the use thereof, and is usually 〇3 to 3 wt%, preferably 〇·1 wt% to 10 wt%, based on the total weight of the poly-amic acid or its derivative. Another preferred embodiment of the liquid crystal alignment agent of the present invention is a composition containing two or more kinds of polyaminic acid. For example, one or both of the first polylysine containing no compound having a side chain group and the tetracarboxylic dianhydride and the diamine, and one or both of the tetracarboxylic dianhydride and the diamine may be used. A liquid crystal alignment agent for the second polyaminic acid of the compound. More specifically, one of the poly-proline acids is at least one of an aromatic tetracarboxylic dianhydride (preferably the compound (丨) to the compound (18)) and a tetra-neoxic acid two-needle other than the aromatic (preferably said Polyamide obtained by reacting one or both of at least one of the compound (19) to the compound (67)) with at least one of a non-side chain type diamine (preferably, the compound (I) to the compound (VII)) Acid or its street organism (hereinafter sometimes referred to as "poly-proline I"); and the other is one or both of the aromatic tetraphthalic acid dianhydride and tetracarboxylic dianhydride other than aromatic And reacting with at least one of a side chain type diamine (preferably a compound (Vm) to a compound (XM)), or a mixture of at least one of the side chain type diamines and at least one of the non-side chain type diamines Polylysine or a derivative thereof (hereinafter sometimes referred to as "polyammonium phthalate"). The composition containing polylysine I and polypyridic acid π of the present invention can be prepared by mixing the polyaminic acid i with polypyridic acid π at 76 200909479. The weight ratio of the mixed polyamic acid 1 to polyamidite is preferably I / Π = 99 Α 1 / 99 Å ' more preferably 1 / II = 95 / 5 to 10 / 90. This weight ratio can be appropriately adjusted in accordance with the pretilt angle obtained, and if the ratio of the polyruthenium phthalate is increased, the pretilt angle can be increased. Further, the liquid crystal alignment agent of the present invention may contain only poly-proline I and poly-aracine 11 ', and may further contain poly-proline or a derivative other than poly-proline. . On the other hand, the polyphosphonium amide has an effective pretilt angle which is effective for a liquid crystal display element having a liquid crystal alignment film formed using a liquid crystal alignment agent containing the polyphosphonium phthalate. In the case of synthesizing polyamic acid II, a diamine other than a diamine having a side chain may be used in combination. Examples of the diamine which can be used in combination include the compound (丨) to the compound (VII), an anthraquinone diamine, and an anthracycline-based diamine. The liquid crystal alignment agent of the present invention can have preferred characteristics by combining (blending) the polyamic acid I with poly-tylinic acid]J. Specifically, the 'liquid crystal alignment film formed by the composition of the present invention can be made to have a good long-term basis by appropriately selecting the type of the diamine to be used and the combination thereof as the diamine as the raw material of the polyaminic acid. Reliability and suitable pretilt angle. In the liquid crystal alignment film of the present invention, the liquid crystal alignment agent of the present invention can be applied, for example, to a substrate for a liquid crystal display element, or a substrate for measurement such as gasification or Shixia, and the film of the liquid crystal alignment agent is, for example, 150. It is preferably formed by heating at 180 to 280 ° C at ~4 ° C. Here, the film thickness of the liquid crystal alignment film 77 200909479 is preferably 10 to 3 Å nm, and more preferably 3 Å to just (10). The crystal alignment film is preferably subjected to a rubbing treatment. The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the liquid alignment agent or the liquid crystal alignment. Further, the film thickness of the liquid crystal alignment film can be measured. This ", into 77, can be treated with water hydrolysis, etc., and then analyzed by IR S MS analysis materials. Next, the liquid crystal display element of the present invention will be described. The substrate of the present invention having == to ==' to the substrate, 2) to the liquid sandwiched between the Γ-pair substrates: ===) is preferably a transparent substrate (for example, a glass substrate). - The surface of at least one or both of the substrates may be arranged according to the electrodes. Such an electrode is not particularly limited as long as it is formed on the substrate. Examples of such an electrode include rn) a secret film of the genus Diptera. The electrode can be formed on the entire surface of the base (4), and the liquid crystal of the present invention is formed on the surface of the plate. === The composition of the liquid crystal layer between the substrates can be made from a common liquid crystal composition: the electrical conductivity is positive. The liquid compound and the dielectric night crystal composition can be used. The liquid liquid which is negative in the state of the state of the art is disclosed in the following patent documents: Japanese Patent No. 10 (No. 10), Japanese Patent No. 263 No. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. 8_199168

9^,J#f^9'235552^' ^ $ = Kaiping 9·255956, Japanese Patent Special Open 9_24i643 = Newspaper (ΕΡ885271Α1), Japanese Patent Special Kaiping (4) 4〇 (deleted 42), Japanese Patent Special Kaiping !曰本本专利本开平1〇_231482号: Erxin嶋G Bulletin, Japanese Patent Specialist _4882== ^Wei Jingxian uses the liquid compound for the case, can be equal to two sub-negative ί various liquid crystal combinations Things. Preferred liquid crystal composition #八# 矛'J document · 专利 专利 专利 57 57 57 - - - - - - - - - - - - - - - - - - 57 - - Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Too straight: No. 9 bulletin, Japanese patent special Kaiping 1 (M68076 #UA newspaper, Japanese patent special Kaiping 1〇-Na 53! Tiger Gazette, 曰太直 following Kaiping 10-236989, Japanese special & Japanese special · ^ Japanese Patent Unexamined No. No., and \1G == This patent is open to the public. 1.--Gazette, 曰本79 200909479 3 ^ newspaper, Japanese patent Lang Ping 1G_237G24 bulletin, date ^0-237075 ^ ^ ^ ^ ^ ^ r特开平_t8=r=:~= ^Report: This patent is open to the public side of the 10th side of the 45th bulletin, Japan: 2, ?|Tai honey 9581 bulletin, Japanese patent special Kaiping 11__49 bulletin, Japanese patent special Japanese Laid-Open Patent Publication No. Hei. No. sho. No. sho. For the optical activity of the positive or negative liquid crystal composition - riding, there is no question about the liquid crystal display element when it has pure For example, in the TFT-type liquid W of the color display of the transistor, the first pole is formed into a thin film transistor, an insulating film, a protective film, a signal electric power, and the second transparent plate can have a shielding area. , black matrix, filter, flattening film, halogen electrode, etc. Type liquid crystal display element 'especially mva type liquid crystal display element' has formed a micro protrusion called a quadrant on the transparent substrate. Tb I can form a spacer (Sf) acer for adjusting a cell gap (cel1 gap) between the substrates. The liquid crystal display element of the present invention may be any method by any method, which comprises the following steps: 1) a process of coating a liquid crystal alignment agent on the two pieces = 200909479; 2) aligning the applied liquid crystal Process for drying the agent; 3) a process for performing the desired heat treatment for dehydrating and ring-forming the dry crystallizing alignment agent; 4) a process for aligning the obtained alignment film; 5) making the two substrates After the specific gap is bonded together, a process of sealing the liquid crystal into the gap between the substrates, or a process of laminating the liquid crystal on one substrate and bonding it to the other substrate. As the method of applying the liquid crystal alignment agent, there are generally the following methods: a square coating method, a printing method, a dip coating method, a dropping method, an inkjet method, and the like. These methods are also applicable to the present invention. The drying process and the process for performing the heat treatment required for the dehydration reaction generally include a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like. These methods can also be applied to the towels of the present invention. The drying process is preferably carried out at a lower/dish level (5GC to 14GC) in the temperature range of the evaporable solvent. The heat treatment process is usually carried out at a temperature of from about 150 ° C to about 300 ° C. In the case of the n>s Weijing display element, the OCB Weijing display element, the tn type liquid crystal display element, and the STN type liquid crystal display element, the alignment treatment of the liquid crystal alignment film is usually performed by rubbing treatment. The VA type liquid crystal display element is often not subjected to rubbing treatment, but may be subjected to rubbing treatment. Next, an adhesive is applied to one of the substrates to bond them, and the liquid crystal is injected into the air. In the case of using the drip method, the & liquid crystal is dropped on the substrate before bonding, and then the other substrate is attached thereto. It can be made into a liquid crystal display element which is too bright by heating or irradiating ultraviolet rays and hardening it with a bonding adhesive. ^ 200909479 The m τ of the present invention is a polarizing plate (polarizing film), a wavelength plate, a light scattering film, a driving circuit, and the like. [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited to these Examples. The compounds used in the examples are as follows. <tetracarboxylic dianhydride> Compound (1). Pyromellitic acid two-needle compound (19): 1,2,3,4-cyclobutanetetracarboxylic dianhydride compound (23): 1,2,3 , 4_butane tetraphthalic acid dianhydride <diamine> Compound (V-1) : 4,4,-diamino. Compound (V·7): bis(4·aminophenyl)ethane compound ( VII-2) : U_bis(4_(4-aminophenyl)phenyl)propane cyclohexane (like 1): U·double (4 ipidine) filament)·4·heptyl.4 II t=4_1) : U,M4·aminophenoxy)phenyl phenyl (inverse pentyl hexyl)cyclohexane <compound having multiple allyl groups> Compound (A small 1): Compound (Α· 2-1): ΡΗ 一ΟΗ 0 ο

-N

J

200909479 Compound (A-6-1 ):

Ο ο Ο ο Compound (Α_6-2):

83 200909479 Compound (A-7-2):

<Solvent> NMP : N-mercapto-2-pyrrolidone BC : butyl cellosolve (ethylene glycol monobutyl ether) GBL : 7-butyrolactone [Synthesis Example 1] <Synthesis of poly-proline > To a 100 mL four-necked flask equipped with a thermometer, a stirrer, a feed port, and a nitrogen inlet, compound (V-1) (2.919 g), dehydrated NMP (54 g), and dehydrated GBL (15 g) were added. Stirring was carried out under a stream of dry nitrogen to dissolve. Next, the compound (19) (1.155 g) and the compound (1) (1.9927 g) were added, and the mixture was reacted at room temperature for 30 hours. In the case where the reaction temperature is raised in the reaction, the reaction temperature is controlled to be less than or equal to 84 200909479 at 70 ° C to carry out the reaction. To the obtained solution, Bc (25 g) was added to obtain a polyglycine solution (PA1) having a polymer concentration of 6 wt%. The weight average molecular weight of the polymer in pAi was 58,000. The weight average molecular weight of polylysine is determined in the following manner. First, a solution having a polyglycine concentration of 6 wt% obtained by a synthesis reaction was diluted to prepare a solution having a polyglycine concentration of about 1 wt%. Next, this dilution was measured by the GPC method, and the measurement data was converted into polystyrene to obtain a weight average molecular weight. The diluted polyaminic acid solution was a phosphoric acid-DMF mixture (phosphoric acid/DMF weight ratio = 0.^00), and this mixture was also used as a developing agent for the GPC method. Further, the Gpc method was measured using Chromatopac C-R7A (manufactured by Shimadzu Corporation), and the column was GF-7HQ (manufactured by Showa Denko Co., Ltd.), and the column temperature was 50 C 'flow rate of 6.6 mL/min. [Synthesis Examples 2 to 5] As shown in Table 1, a polyaminic acid solution (PA2 to PA5) was obtained according to the method of Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed. The results including Synthesis Example 1 are summarized in Table 1. 85 200909479 <Table ι> Synthesis Example No. Polyamine acid solution tetracarboxylic dianhydride compound No. Mohr percentage -------- No. 0.50 --^ Weight average molecular weight 1 PA1 (1) ( 19) 0.30 0.20 (Vl) 2 PA2 (1) 0.40 58000 (19) 0.10 (V-7) 0.25 -~~~ - PA3 (1) 0.40 ^25 48000 (19) 0.10 (V-7) -——^ ----- 4 PA4 (1) 0.15 44000 (19) 0.35 (Vi) 0.25 ~~~—--- (1) 0.10 ^25 42000 5 PA5 (19) 0.25 (Vl) (23) 0.15 0.50 52000 〔 Example 1] 2

PA2 obtained in the oxime obtained in Synthesis Example 1 was mixed at a weight ratio of 8/2'. The weight ratio of 1 in the obtained mixture to the polyamine contained in the synthesis example corresponds to 〇' added relative to (A-2-1). Thereafter, a mixed solution liquid crystal alignment agent of NMP/BC = l/i (rethinking compound agent, a polypyridic acid concentration of up to 4 wt%) was added. According to Zhiqing, the obtained liquid crystal alignment agent was applied onto the glass substrate of the two ITO electrodes by a spin coating method to form a film having a thickness of 7 Å. After coating =, after drying at 80 ° C = heat for about 5 minutes, heat treatment was carried out at 21 (rc for 20 minutes, followed by rubbing treatment to form a liquid crystal alignment film. The liquid crystal alignment film formed on this glass substrate was Ultrasonic cleaning in ultrapure water for 5 minutes, drying in an oven at 12 (rc for 3 minutes). Next, on a glass substrate of 86 200909479, a gap of 7 μm was spread on the surface of the film as the inner side to the friction side. After the liquid crystal is placed opposite to the other substrate, the film is sealed to the periphery of the film, and the hardener is applied to the liquid crystal. The liquid crystal cell is injected as shown below. The second flat = and the production =: two, followed by the heat treatment 3. minutes ' <liquid crystal composition> 87 200909479 F C2H5

F 17wt. % 17wt. % 16wt. %

C5h F

10wt. % 5wt. %

10wt. % C2H5

6wt. %

C3H7_C^O

6wt. %

13 wt. % [Example 2] PA1 obtained in Synthesis Example 1 was mixed with PA3 obtained in Synthesis Example 3 at a weight ratio of 8/2. To the obtained mixture, a compound (A-2-1) having a weight ratio equivalent to 0.2 with respect to the polyglycine contained therein was added. 88 After 200909479, a mixed solvent of NMP/BC = l/l (weight ratio) was added, and the polyamic acid was diluted to 4 wt% to prepare a liquid crystal alignment agent. Use the obtained liquid crystal alignment agent to work with the examples! The liquid crystal display element is produced in the same manner. [Example 3] To the pA4 obtained in Synthesis Example 4, the compound (A_M) was added to the weight ratio of the polyglycine contained in it to 〇.2. Thereafter, a mixed solvent of MANMP/BC = 1/1 (weight ratio) was diluted to a concentration of 4 wt% of polyacrylic acid to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 使用 using the obtained liquid crystal alignment agent. [Example 4] To the PA4, a compound (A_2_1;) having a weight ratio of 0.2% to the polyglycine contained therein was added. Thereafter, a mixed solvent of NMp/BC = l/i (weight ratio) was added, and the polyamine acid concentration was diluted to 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal matching agent. [Example 5] The PA1 and PA2 were mixed in a weight ratio of milk. 'Addition of the compound (A-6-2) in an amount equivalent to 0.2 by weight relative to the poly-aracine contained therein. Thereafter, a mixed solvent of NMp/BC = 1/1 (weight ratio) was added to polyamine A liquid crystal alignment agent was prepared by diluting the acid concentration to 4% by weight, and a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 89 200909479 [Example 6]

NMP/BC = the PA5 obtained in Synthesis Example 5 and the PA2 are added relative to the polyamine contained therein

A mixed solvent of ruthenium was prepared by diluting 'concentration of polyglycolic acid' to prepare a liquid crystal alignment agent. A liquid crystal alignment agent obtained by diluting the liquid crystal display to 4 wt% in the same manner as in Example 1 was used. [Example 7] The PA1 and pA2 were mixed at a weight ratio of 8/2. To the obtained mixture, a compound (A-6-1) having a weight ratio of 0.2% to the polyglycine contained therein was added. Thereafter, a mixed solvent of nmP/BC = 1/1 (weight ratio) was added, and dilution was carried out so that the polyglycolic acid concentration reached 4 wt%, thereby preparing a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 8] The PA1 and PA2 were mixed at a weight ratio of 8/2. To the obtained mixture, a compound (A-6-1) having a weight ratio of 0.4 relative to the polylysine contained therein was added. Thereafter, a mixed solvent of NMP/BC = 1 Torr (by weight) was added, and the polyisamic acid concentration was diluted to 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent'. [Example 9] The PA5 and PA2 were mixed at a weight ratio of 8/2. To the obtained compound (A_6_1)0 with a weight ratio of 0.2 200909479 relative to the polyglycine contained therein, * after Tianyi, U, add NMP/BC = 1/1 (weight ratio) The mixed solvent 'diluted by a polyamine concentration of 4 wt%' to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 10] The PA1 and PA2 were weighed at a weight ratio of 8/2. To the obtained mixture, 'the compound (A-7-2) having a weight ratio relative to the polyamine contained therein is added. After that, NMP/BC = 1/1 (weight ratio) is added. The mixed solvent was diluted to a concentration of 4 wt% of polyglycine to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 1) The PA1 and PA2 are mixed at a weight ratio of 8/2. To the obtained mixture, a mixed solvent of NMP/BC = 1/1 (weight ratio) is added to obtain a polyglycine concentration of 4 wt. In the same manner as in Example 1, a liquid crystal display element was produced by diluting in a manner of %. A liquid crystal display element was prepared in the same manner as in Example 1. [Comparative Example 2] In a weight ratio of 8/2, The PA1 was mixed with PA3, and a mixed solvent of NMP/BC = 1 A (weight ratio) was added to the obtained mixture, and the mixture was diluted so that the polyglycine concentration was 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 91 200909479 [Comparative Example 3] A mixed solution crystallizing agent containing NMP/BC = 1/1 (heavy agent 'in a concentration of 4 wt% of a polypyrene concentration phase) was added to the PA4. The obtained liquid crystal alignment agent was produced in the same manner to produce a liquid crystal display element. The first embodiment [Test Examples 1 to 13] <Evaluation of electrical characteristics> !~!〇Compared with the liquid crystal display device produced, the measurement of the voltage rate and the measurement of the voltage holding ratio (%). Nurturing. The voltage retention rate was measured using a liquid crystal property evaluation manufactured by Toyo Corporation of Japan. The measurement conditions are: , set 6254 to 0.3 Hz, wave height secret v, load temperature frequency, the better the electrical characteristics. The results are shown in Table 2. The larger the value is. 2) Measurement of long-term reliability The time-dependent voltage was evaluated for the produced liquid crystal display element, and the retention characteristics were evaluated. The test method for the (four) nature is ', face' and the display element is at a temperature of 6 〇. (3) The gas environment towel is placed for an hour, and the crystal j is taken out over time, and the voltage holding ratio is measured. The smaller the voltage is kept (for example, 'Under the conditions of 500 hours, the reduction of low pressure retention rate is less than 2%.) The better the long-term stability. The ECG is shown in Table 2. The measured temperature is 6CTC., °°果不92 200909479 〈 Table 2 > Test Example No. Liquid crystal display element elapsed time (hours) 0 250 500 1 Example 1 94.6 94.5 94.3 2 Example 2 96.1 96.1 95.9 3 Example 3 92.7 92.6 91.5 4 Example 4 95.0 94.8 94.6 5 Example 5 95.5 95.1 94.8 6 Example 6 95.5 95.1 94.6 7 Example 7 95.2 95.2 94.8 8 Example 8 95.8 95.3 94.2 9 Example 9 95.9 95.3 94.5 10 Example 10 96.4 95.7 95.0 11 Comparative Example 1 94.8 93.9 ^92.8 12 Comparative Example 2 96.2 95.4 92.2 13 Comparison Example 3 95.0 94.2 92.4 As shown in Table 2, when the liquid crystal display element is obtained by using the liquid crystal alignment agent of the present invention, the decrease in the voltage holding ratio can be remarkably suppressed.

Claims (1)

200909479 X. Patent Application Scope 1. The liquid crystal alignment agent is characterized in that it is a composition containing at least one polymer selected from the group consisting of polyaminic acid and its derivatives and a compound having a plurality of allyl groups. The ratio of the ratio of the compound having a plurality of allyl groups to the weight ratio of the polymer is 0.01 to 1.0 ' and the compound having a plurality of dilute groups is selected from the formula (A-1) to the formula (A-1) At least one of the compound groups represented by A-7); h2c=hch2c, /ΟΗ2ΟΗ=ΟΗ2 (A-1) /N h2c=hch2c Ν\ ch2ch=ch2 (Α-2) (Α-3) (Α-4) (Α-5) 94 200909479 (A-6) Q2-Z2—N—Z2—Q2 I z2 I Q2 (A-7) ?H H2C—CH——CH〇——G—O—CH〇—C—CH〇H, H h^C^CH—CH2—c—o—ch2—C—CH ^ ,N- (Bl) I] OH (B-2) (B-3) Here, Z1 is independently a single bond, -〇-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2- , -(CH2)t•, or -〇-(CH2)t-0_, t is an integer from 1 to 8; Z2 is -CHfH2- or 1,4-stup; Q) is represented by formula (Bl) a group represented by the formula (B-2); q3 is a hydrogen atom or a group represented by the formula (b-3); and any hydrogen atom of the benzene ring may be a fluorine atom, a methyl group or a -OH group Replace. 2. The liquid crystal alignment agent according to claim 1, wherein the feature 95 200909479 is that at least one poly-sigma selected from the group consisting of poly-proline and a derivative thereof and having a plurality of dilute propyl groups The composition of the compound, the compound ant having a plurality of dilute propyl groups is selected from at least one compound of the compound group represented by the formula U_1), the formula (Α_2), the formula (Α_6), and the formula (Α-7), · (Al) H2C=HCH2C^jQ^-21^^N/CH2CH=CH2 h2c=hch2c/ nch2ch=ch2 Q—Zc-\ ~N—Z2—Q2 (A-2) (A-6) Here, Z is independently a single bond, _〇_, _(CH2)r, or _〇_(CH2)t_〇_, t is an integer from 1 to 8; and any hydrogen atom of the benzene ring can be _〇H is replaced. 3. If you apply for a patent scope! The liquid crystal alignment agent according to the invention, which is characterized in that it is a composition containing at least one polymer selected from the group consisting of polylysine and a derivative thereof and a compound having a plurality of dilute propyl groups, and having a plurality of propyl groups The compound is a formula (A-1-1), a formula (A-2-1), a formula (A-6-1), a 96 200909479 formula (Α-6·2), and a formula (A-7-1). Or a compound represented by the formula (A-7-2), /CH2CH=CH2, ch2ch=ch2 Η2〇= HCHpC, /=\ Q (A-2-1) q2-〇-N Q2 Q2 Q2—H2CH2C, /CH2CH2-Q2 N ch2ch2- -Q2 (A-6-1) f (A-6-2 ) —Q2 φ —Q2 (A-7-1) (A-7-2) Q2 4 The liquid crystal alignment agent according to claim 2, wherein the polyamic acid is obtained by formula (1), formula (2), formula (5) to formula (7), and 14) The polymer obtained by the reaction of at least one of the two stagnations of the scent of the scent of the scent of the scent of the scent 5. The liquid crystal alignment agent according to claim 3, wherein the polyamic acid is obtained by reacting an aromatic tetracarboxylic dianhydride represented by the formula (1) with a diamine. Polymer, 6. The liquid crystal alignment agent according to claim 2, wherein the polyamic acid is obtained by formula (1), formula (2), formula (5) to formula (7), and (14) A mixture of at least one of the aromatic tetracarboxylic dianhydrides and a tetracarboxylic dianhydride other than the aromatic compound, and a polymer obtained by reacting with a diamine, 98 200909479 7. The liquid crystal alignment according to Item 3 of the scope of the patent application is characterized in that the polyamic acid is an aromatic tetracarboxylic acid represented by (1) and four or more than aromatic. a mixture, a polymer obtained by reacting with a diamine, (1) 8. The liquid crystal alignment agent according to Item 6, wherein the amino acid is a polymer obtained by using the formula (1), the formula (7), and the formula (5) to the di-tetra, to be known as a diamine. f reaction and formula (2)), formula (25), formula (5) - New reading is formula (19), = (four) shows two 99 200909479 (19) at least one of the compounds represented by the formula (23), the formula (25), the formula (35) to the formula (37), the formula (39), the formula (44), and the formula (49), (39) (37) (39) 9. The liquid crystal alignment agent according to claim 7, wherein the poly bribe is obtained by making the formula (1) silky (four) aromatic tetradecanoic acid a mixture of four ships and two needles other than aromatic, a polymer obtained by reacting with a diamine, and the tetracarboxylic dianhydride other than aromatic is a formula 100 200909479 10. The liquid crystal alignment agent according to claim 7, wherein the polyamic acid is an aromatic tetracarboxylic dianhydride represented by the formula (1) and a tetracarboxylic acid other than the aromatic compound. a mixture of acid dianhydride and a polymer obtained by reacting with a diamine, and the tetracarboxylic dianhydride other than aromatic is a compound represented by the formula f (19). The liquid crystal alignment agent according to any one of claims 4 to 10, wherein the diamine is selected from the non-sides represented by the formula (丨) to (VII) At least one of a chain diamine group; H2n-x1-nh2 (I) (II) (III) (IV) (V) 101 200909479 Here, 'X1 is a linear alkylene group having a carbon number of 2 to 12; χ2 is a linear alkylene group having a carbon number of 1 to 12; X3 is independently a single bond, -〇-, -CO-, -CONH-, - NHCO-, -C(CH3)2_, -C(CF3)2_, -0-(CH2)t-0-, -S-, -SS-, -S02-, -S-(CH2)tS- or carbon a linear burn-up of 1 to 12, t is an integer of 1 to 12; any hydrogen atom of a cyclohexane ring or a benzene ring may be _p, OH, -COOH, -S〇3H, -P〇3H2 Substituted or replaced by a base group. 12. The liquid crystal alignment agent according to any one of the items 4 to 1G, wherein the diamine is a non-form represented by the formula (V-33) and the formula (VII-2). At least one of the side-bonded diamines, (V-2) (V-3) 102 200909479 The liquid crystal alignment agent according to any one of claims 4 to 10, wherein the diamine is selected from the group consisting of the formula (丨) and the formula (vf). a mixture of at least one of an amine and at least one of a side chain type diamine having an alkyl group selected from a carbon number of 3 or more, an alkoxy group having a carbon number of 3 or more, and a carbon number greater than An alkoxyalkyl group equal to 3, a group having a steroid skeleton, and an alkyl group having a carbon number of 3 or more at the terminal, an alkoxy group having a carbon number of 3 or more, or an alkoxy group having a carbon number of 3 or more Side bond groups in the group; 103 200909479 h2n-x1-nh2 (I) (II) h2n (III) (IV) (V) (VI) Here, X1 is a linear alkylene group having a carbon number of 2 to 12; x2 is a linear alkylene group having a carbon number of i to 12, and X3 is independently a single bond, _〇_, _c〇_, , -NHCO-, -C(CH3)2...C(CF3)2_, _〇_(CH2)t 〇, _s s each, Two whole ~, air support, ...: -OH, -C00H, ·8〇3η', helium atom can be replaced by -F, 311屮〇3, benzyl or carboxybenzyl. 14. A liquid crystal alignment agent as claimed in the patent application, which is characterized in that: said side chain type, two from the group of compounds represented by $(V丨丨丨)~(XII). h2n 104 (VIII) 200909479 In formula (VIII), R1 is a single bond, _〇_, _c〇_, _c〇〇_, 〇c〇, -CONH-, _CH2〇_, _CF2a, or carbon number is跋, any -CH2- in this building can be replaced by ...CH=CH_ or _c Ξ c_; R2 is a group having an _ol skeleton, a carbon number of 3~3G, having a carbon number a phenyl group having a 3 to 3 fluorene group or a phenyl group having a carbon number of 3 to 3 Å as a substituent, and a group represented by the formula (D-1), and any _Ch2_ in the alkyl group may be -〇-, _CH=CH- or substituted; f Meal and servant, 5 © 'In the formula (D_l), 'R13, R14& Rn are independently a single bond, -0_, -C00-, -OCO-, -CONH-, alkane with a carbon number of 1 to 4, An alkylene group having a carbon number of i to 3 or an alkylene group having a carbon number of 1 to 3; the ring B and the ring c are independently 1,4-phenylene or 1,4-cyclohexene; Rn is independently a fluorine atom or a sulfhydryl group, and ml and m2 are independently 0, 1 or 2; e, f and g are independently an integer of 〇~3, \the total of these is greater than or equal to 1; and the rule 18 is a carbon number of 3 to 3 An alkyl group having a carbon number of 3 to 30 or an alkoxy group having a carbon number of 3 to 3 Å, and any hydrogen atom in the sulfo group, the alkoxy group and the alkoxy group may be used. Substituted by a fluorine atom' and any -CHr may be substituted by a difluoroindenylene group or a group represented by the formula (D_2); R-si T'R20 1 2 Tsi--R2 105 200909479 In the formula (D-2) In the above, R19, R2〇, r21 and r22 are independently a group or a base having a carbon number of 10, and n is an integer of 1 to 1〇〇; Η2ν ΝΗ, (X) In the formula (X), a hydrogen atom or a fluorenyl group; R4 is a gas atom; a group of 1 to 30 or an alkenyl group having a carbon number of 2 to 3 Å;独:,,·〇)· or _CH2_ ; and 'foot 6 and r7 are independently alkyl groups with a hydrogen number of 1 to 30, or stupid base; anti-mer 106 (XI) 200909479 Any r8=3~3g filament, which is replaced by carbon number 1~6, ==CjC·; R9 independent support; a is 0 or nb is 0, A is Μ·phenylene Or M_cyclohexene is 〇, 1 or 2; and, c is independently 0 or J; In the formula (XII), 'is a carbon group having a carbon number of 3 to 3 Å or a fluoroalkyl group having a carbon number of 3 to 30; R11 is a hydrogen atom, a carbon number is a ruthenium group or a carbon number is 1 〜 a fluoroalkyl group of 30; R!2 is independently an alkyl group of _〇_ or a carbon number; and, d is independently 〇 or i. The liquid crystal alignment agent according to claim 13, wherein the side chain type diamine is selected from the group consisting of a formula (VIM-2), a formula (VUI-4), and a formula (vm-5). a diamine in the compound represented by the formula (vm-6), the formula (ΧΙ_2), and the formula (ΧΜ); 107 200909479 The f group or the alkoxy group having a carbon number of 3 to 30. The liquid crystal alignment agent according to claim 13, wherein the non-side chain type diamine is selected from the group consisting of formula (IV-1), formula (IV-2), and formula (IV-15). a diamine in the compound represented by the formula (IV-16), the formula (V-1) to the formula (V-12), the formula (V-33) and the formula (VN-2), the side chain type Diamine Is selected from the compounds represented by the formula (vm-2), the formula (vm-4), the formula (vm-5), the formula (vm-6), the formula (XI-2), and the formula (Xb 4). Diamine; 108 200909479 (IV-1) (IV-15) (IV-16) (V-3) 109 200909479 J- , (ΧΙ-4) Here, the R23, R24, 29 group or the carbon number A 3 ^ is independently an alkoxy group having a carbon number of 3 to 30 and having an ablation of 3 to 3 Å. The coating agent according to claim 3 to 3, wherein the liquid crystal according to any one of the negative polymers is selected from the group consisting of: At least one of the formulas (19), (23), (25), and (35) from the formula (5) to the formula (7) and the formula (14) (37), a mixture of at least one of tetracarboxylic dianhydrides other than aromatics represented by formula (%), formula (44) and formula (49), and formula (iv-i), formula (丨v_2), Non-side chain type diamine represented by formula (丨v_15), formula (丨ν·16), formula (V-1)~formula (V-12), formula (ν_33) and formula (VII-2) 110 200909479 At least one polylysine obtained by reacting and a derivative thereof; and by reacting the mixture of the tetracarboxylic dianhydride with a compound selected from the group consisting of the formula (VIII-2), the formula (VIII-4), and the formula (VIII) VIII-5), at least one of the side chain type diamines represented by the formula (VIII-6), the formula (XI-2) and the formula (X|_4), at least one of the above-mentioned types of amines Polypyrene obtained by carrying out the reaction (1) Private 酉^ and at least one of its bamboo creatures, 0 η 0 υ ο (19) (23) 111 200909479 (V-4) (V-7) h2n^ HO OH (V-33) (VII-2) 112 200909479 Here, R23, R24, R29 and R30 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. 18. The liquid crystal alignment agent according to claim 17, wherein the polymer is at least one of an aromatic tetracarboxylic dianhydride and at least one of a tetracarboxylic dianhydride other than an aromatic compound. a mixture of polylysine obtained by reacting with at least one of the non-side chain type diamines. 19. The liquid crystal alignment agent according to claim 17, wherein the polymer is at least one of an aromatic tetracarboxylic acid dianhydride and at least one of a tetracarboxylic dianhydride other than an aromatic compound. a mixture of polylysine obtained by reacting with at least one of the non-side chain type diamines, and a mixture of the above-mentioned tetra-retensive acid >-anhydride and a non-side-bonded diamine a mixture of at least one polylysine obtained by reacting a mixture of at least one of the side chain plastic diamines. 20. The liquid crystal alignment agent according to claim 17, wherein the polymer is selected from the group consisting of at least one of aromatic tetracarboxylic dianhydride and tetracarboxylic dianhydride other than aromatic. At least one of the mixture, at least one of the polylysine obtained by reacting with at least one of the non-side chain type diamine and at least one of the side chain type diamines and a derivative thereof. A liquid crystal alignment film which is formed by applying a liquid crystal alignment agent according to the first aspect of the invention to a substrate and baking it in a film state. 22. A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; and electrodes formed on one surface or both surfaces of a surface on which the pair of substrates face each other, formed in the one The liquid crystal alignment film on the surface on which the substrate faces each other and the liquid crystal layer formed between the pair of substrates is the liquid crystal alignment film according to claim 21. 114 200909479 VII. Designation of the representative representative: (1) The designated representative of the case: None. (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: