TW200808686A - Diamide, liquid crystal alignment agent,liquid crystal alignment film and liquid crystal display - Google Patents

Abstract

A liquid crystal display having superior voltage holding rate and inhibition for residual DC is provided in this invention. Moreover, this invention further provides a liquid crystal alignment film for fabricating the liquid crystal display, a liquid crystal alignment agent for fabricating the liquid crystal alignment film, polymer in the liquid crystal alignment agent and new compound for synthesizing the polymer. A composition includes diamide represented by following formula (I) and one or more polymer. The composition is a polymer prepared by reaction of tetracarboxylic acid dianhydride as an acid constituent and diamide represented by following formula (I) as a amine constituent. A liquid crystal alignment agent includes the prepared polymer. A liquid crystal alignment film is fabricated by the liquid crystal alignment agent. A liquid crystal display is fabricated by the liquid crystal alignment film. (In the formula(I), A1 and R1 are defined the same as those in Claim.)

Description

200808686 IX. Description of the Invention: [Technical Field] The present invention relates to a diamine having a side chain structure and a polymer (polyproline or a derivative thereof) using the same, which is obtained by dissolving in a solvent. A liquid crystal alignment device and a liquid crystal display device including a liquid crystal alignment film formed of the liquid crystal alignment agent. [Prior Art] Liquid crystal display devices are used in various types of liquid crystal display devices such as monitors for notebook computers and desktop computers, viewfinders for video earners, and projection display devices. Recently, liquid crystal display devices have also been used in televisions. Further, the liquid crystal display device is also used as an optical printer related device such as an optical printer head, an optical fourier transform device, and a light valve. Conventionally, a liquid crystal display device is mainly used as a display device using nematic liquid crystal, and a liquid crystal display device which has been put to practical use has a Twisted Nematic (TN) liquid crystal display device which is twisted by 90 degrees; 2) Usually 18 A super Twisted Nematic (STN) type liquid crystal display device having a twist or a twist of 180 degrees or more; and a thin film transistor (TFT) type liquid crystal display device using a thin film transistor. The liquid crystal display device described above has the disadvantage that the image can be appropriately visualized with a narrow viewing angle; when viewed from an oblique direction, a luminance or contrast reduction and an intermediate brightness conversion phenomenon occur. In recent years, the problem of the above viewing angle has been improved by the following techniques: u using an optical TN-TFT type liquid crystal display device, vertical alignment and optical compensation = 200808686 jJll Vertical Alignment (VA) Liquid crystal display device, 3) Multi-domain vertical alignment (MVA) liquid crystal display device using vertical alignment and protrusion structure technology, or 4) transverse-field coplanar conversion (In-Plane Switching, IPS) a liquid crystal display device, 5) an electrically controlled birefringence (ECB) type liquid crystal display device, and 6) an optically compensated Bend or an Opticically Self-Compensated Birefringence (OCB) type liquid crystal display device, Improved technology has been or is being studied. The development of liquid crystal display device technology has not only been achieved by improving the above-described driving method or device structure, but also by improving the components used in the display device. Among the components used in the display device, in particular, the liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display device, and the function of the liquid crystal alignment film becomes important year by year as the display device is improved in quality. stand up. The liquid crystal alignment film is prepared from a liquid crystal alignment agent. Currently, the liquid crystal alignment agent mainly used is a solution in which polylysine or soluble polyimine is dissolved in an organic solvent +. After the solution is applied onto the substrate, a polyimide film is formed into a film by heating or the like. Although it is also studying the addition of phthalic acid in addition to proline or ketone, it is based on the chemical properties (liquid crystal resistance), coating properties, liquid crystal alignment, and electricity. Back to the display quality of the LCD display device, the liquid crystal alignment film needs 7 200808686 characteristics can be listed as: electric house retention rate and residual dc. If electricity = ancient, f is low, the voltage applied to the liquid crystal during combustion decreases, and the two parties fall again, which brings obstacles to the normal harmonic display. On the other hand, if =DC is large, the image that is erased will remain after the Wengjia turn, and the so-called "afterimage" will appear. As an attempt to solve the above problems, several methods have recently been proposed. 1) A poly-aracine group which is known to be used for forming a liquid crystal alignment film in combination with two or more kinds of poly-II acids having different physical properties. Document 1: Japanese special Kaiping u_1933 Kui uj-te Kaiping warfare bulletin) 45 Report, Special 2: Japan 2) A varnish composition using a polymer component and a solvent is known, and a polymer component is a polyamic acid and a polyamine (see, 00/61684).駄3. W0 3) Already 4 uses two or two different physical H shells to dissolve the varnish silk with acid and poly

Bulletin 01/000733). 4 · WO 4) A varnish composition using a polymer material is known, and a sub-material using an amine component having a specific structure is 77 (refer to Patent Document 5: 曰本特开2002_16263口〇号公^胺酸酸, etc.) However, in the prior art, there is room for research on the problem of the voltage remaining residual DC. In addition, as the amine component used in the liquid crystal _ ==, the retention (I) structure of the present invention has the =2 and the residue The amine component with improved DC is not known. The rabbit pressure retention rate [Patent Document π曰本特开平u_193345号

200808686 ΖΗ 〇 ) ) ) ) ) Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ WO WO WO WO WO WO WO WO WO WO WO WO WO 2000 2000 2000 2000 2000 SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal alignment agent for a liquid crystal display device which is improved in voltage holding ratio and residual DC. Further, another object of the present invention is to provide a liquid crystal display device comprising a liquid crystal alignment film formed using the above liquid crystal alignment agent. Further, another object of the present invention is to provide a novel polymer (diamine) which is a novel polymer for synthesizing the above liquid crystal alignment d and which is a raw material of the above polymer. In order to solve the above problems, the inventors of the present invention conducted intensive studies. As a result, a specific tetrahydetic di-hepatic liver is used as an acid component, and a thidium diamine including a diamine represented by the following general formula (1) is used as an amine component, and they are reacted to obtain a polymer, and a substance or A liquid crystal alignment film of two or more of the above polymers is used to prepare a liquid crystal alignment film which can impart a good voltage holding ratio and a remarkable residual DC to the liquid crystal n having the same, and a salty effect is obtained, thereby completing the present invention. invention. Further, it has been found that by appropriately selecting the above polymer (polyglycine or keto), the liquid crystal alignment film which is difficult to use by using the above 4 liquid crystal alignment is suitable for liquid crystal display devices of various display driving methods. The present invention includes the following constitutions. [1] A diamine having a side chain structure represented by the formula (I). 200808686 Z^f6J jpil R1 H2N0^c'hhOnh2 (I) [In the formula (I), A represents a single bond, -O---COO-, -0C0_, -CO-, -CONH- or -(CH2)nr m is an integer of 1 to 6; R is a group represented by the following formula (II-A) or a group represented by the following formula (IKB). ]

R4 (Π-Α)

(Π-Β) [In the formula (II-A), A and A3 independently represent a single bond, _〇__c〇〇_, _〇c〇_, -CONH-, -CH=CH- or a carbon atom The number of alkylenes is from j to 12; R2 and R3 each independently represent -Η, -F or _〇13; ring S represents 1,4-phenylene, α-cyclohexylene, u_dioxin _25·diyl, pyrimidine-2,5-diyl, pyridine_2,5-diyl, naphthalene], 5-diyl, naphthalene_2:7-diyl or fluoren-9,10-diyl; R4 A fluoroalkyl group having a -C, a carbon atom number of 丨, a carbon atom number of 〜30, -OCH2F, -〇CHF2 or _〇(^3; a and b each independently represent an integer of 〇~4 10 200808686 jpir c, d and e respectively represent integers of 〇~3; when e is 2 or 3, multiple rings S may be the same group or different groups; and f and g are respectively represented independently 〇~2 integer, and c+(j+ q 1.] [In the formula (II-B), A2 and A*" respectively represent a single bond, _q_, -C〇〇_, -CONH-, -CH =CH- or an alkylene group having 1 to 12 carbon atoms; R represents _H, -F or -CH3; R5 independently represents -H or -CH3; R6 represents -Η, the number of carbon atoms is 〜2 The alkyl or carbon number of hydrazine is 2 20; fcffj base; a and b respectively represent integers of 〇~4; c and d respectively represent integers of 0~3; e is an integer of 〇~2; ring T represents cyclohexane or cyclohexene.] [2] The diamine according to [1], wherein, in the above formula (1), A] is a single bond, and R1 is a group represented by the following formula (Π-A). [(严), /--V (f ) g) Ten % C X 3V d -R4 (Π-Α) g [In the formula (Π-A), A2, A3, R2, R3, R4, meaning the same as above. 1 Ring S, a, b, c, d And the alkylene group of the formula [II], wherein in the above formula (II_A), ¥ and a3 each independently represent a single bond, _◦_, _c(8)...〇(1). or a carbon number.卜12 11 200808686 Ring S represents 1,4-phenylene or 1,4-cyclohexylene; R4 represents -F, an alkyl group having 1 to 30 carbon atoms, -OCH2F, -OCHF2 or -ocf3; And b respectively represent 0 or 1 independently; c, d and e respectively represent 0 or 1; f and g are 0, and c+d+e-1. [4] The diamine described in [3], characterized in that The diamine is a diamine represented by the following formula (Μ), (1-8) or (1-4).

[wherein, R7 and R8 represent an alkyl group having 1 to 30 carbon atoms. [5] a polymer which is a tetracarboxylic dianhydride as an acid component and a diamine having a side chain structure as described in any one of [1] to [4]. They are obtained by reacting them. [6] The polymer according to [5], wherein the tetracarboxylic dianhydride comprises any of an aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride. One or two. [7] The polymer according to [6], wherein the aromatic tetracarboxylic dianhydride is selected from the following structural formulae (1), (2), (5), (6), and (7). One or more kinds of the constituent groups; the aliphatic tetracarboxylic dianhydride or the alicyclic tetracarboxylic dianhydride is a group selected from the following structural formulae (14) to (29) and (60); 12 200808686 One or more of the two-τ υ汐dp丄丄 groups.

(twenty two)

(twenty three)

(twenty four)

(2 5)

(2 6) CH3 〇

(2 7)

The polymer according to the above aspect, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the above structural formula (1); the aliphatic tetracarboxylic dianhydride or The alicyclic tetracarboxylic dianhydride is a compound represented by the above structural formula (14). The polymer according to any one of the above-mentioned items, wherein the amine component is further selected from the group consisting of diamines represented by the following formulas (ΠΙ) to (XIV). One or more of the groups. Η2ν-α4~νη2 (Hi) a(IV; “ νη2 〇-χ^Ο (ν) η2ν^~1 '~^νη2

[In the formula (III), Α4 represents -(CH2)m-, wherein m is an integer of 1 to 6; in the formulae (IV) to (IX), X represents a single bond, -〇_, -S_, _S-S -, _S02-, _CO_, -CONH·, 14 200808686 -NHCO- > -C(CH3)2- > -C(CF3)2- ' -(CH2)m- > -〇_(CH -S -(CH2)m_S_, where m is an integer from !~6; m<)... Y is independently representing a single bond, -Ο, -S_, -C(CF3)2- or a carbon number of 1 to 3 The alkylene; 3 r, % hexane ring or hydrogen bonded to the benzene ring may be substituted by _f, _Ch, -COOH, s〇3H, _p〇3H2. Moreover, the hydrogen of the formula can be combined with (iv) silk. Everything on this

H2N R1 person 1

^ nh2 [In the formula 0, (X) C〇-, -C〇NH_ A1 represents a single bond, _〇_, -COO-, _0C0- or _(CH2)m-, where m is an integer from 1 to 6 Or a group represented by a steroid skeleton, a group represented by the following formula, or a positional relationship of two amino groups bonded to the oxime 1 is relative, and R1 is an alkyl group having 1 to 3 carbon atoms; Or when the above positional relationship is phase-to-phase, Γ R is an alkyl group or a phenyl group having 1 to 30 carbon atoms; 3 of the above-mentioned groups, any _CH2_ may be _CF2_, _CHF_, _〇- (but 疋Non-connected, ,), { and sink or _CEC^ _ f, _CHF4CF3 are substituted; the hydrogen bonded to the carbon forming the above phenyl ring may be independently _F, CH3 - 〇CH3, -〇CH2F, -CHF2 or -〇 Replaced by CF3. ] 15 200808686 (Π) [In the formula (Π), A2 and A3 independently represent a single bond, _〇•, -c〇〇-, _〇c〇_, CONH-, -CH=CH- or the number of carbon atoms Is an alkylene group of 丨12; R2 and R3 independently represent _H, $ or -Ch3;

R4 % S represents not 1,4-phenylene, ι, 4_cyclohexylene, dioxane 2,5_diyl, t-but-2,5-diyl, such as determinate-2,5_2 Base, saponin 5_diyl, oxa-2-deyl or oxime-9,10-diyl; , -H, -F, an alkyl group having 1 to 30 carbon atoms, 1 carbon atom a fluoroalkyl group of ～30, an alkoxy group having a carbon number of 5%, a collar, 〇ch2f, -〇CHF2 or _〇邙3; a and b each independently representing an integer of ο4; c, d and e Individuals representing 〇~3 are independently represented; when e is 2 or eve, 75: the same group may be a different group; f and g respectively represent integers of 〇~2, and e+d+e ^

R5 R6 a J η2ν-4-

16 200808686 [In the formulae (XI) to (XII), R5 independently represents _H or -CH3, and R6 is independently represented or an alkyl group or an alkenyl group having 1 to 20 carbon atoms; A5 independently represents an early bond. And _CO_ or -CH]-, and R7 and R8 each independently represent - an anthracene, an alkyl group having 1 to 20 carbon atoms or a phenyl group. ]

[In the formula (XIII), R9 represents -Η or an alkyl group having 1 to 20 carbon atoms, and any -CH2- of the alkyl group having 2 to 20 carbon atoms in the alkyl group may be -0- (but not Continuous), -CH=CH_*_C, three C-substituted; A6 independently represents -0- or an alkylene group having 1 to 6 carbon atoms; A7 represents a single bond or an alkylene group having 1 to 3 carbon atoms; ; Ring U represents 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1. In the formula (XIV), R1Q is an alkyl group having 6 to 22 carbon atoms; R11 is -H or an alkyl group having 1 to 22 carbon atoms; 17 200808686 A6 independently represents -O- or a carbon number of 1 ~6 of the sub-burning base. The polymer according to [9], wherein the amine component is selected from the group consisting of the following general formulae (VI-1) to (VI-5) and (VI-14) to (VI-16). ), formula (VII-1)~〇/ΙΙ·15), formula (VII-26), formula (VII-27), formula (VII-31), formula (VIII-1), formula (VIII_2), formula (VIII-6) and one or more groups of the diamines represented by the formula (ΙΧ-1) to (ΙΧ-5).

18 200808686 厶*to J JjJil

[11] The polymer according to [10], wherein the amine component is selected from the group consisting of the above formula (VI-1), (VI-2), (VII_1) to (VII-12), and (IX-). 2) One or more types of the group consisting of diamines. [12] A liquid crystal alignment agent comprising a polymer obtained by using a diamine having a side chain structure represented by the following formula (I). 19 200808686 R1 h2n〇-c'h-Qn (I) [in formula (I),

To represent a single key, do, -COO-, oco_, _co_, C0NH· or -(CH2V; 11! is an integer of _~6; R is a base expressed by the following formula (II_A) or the following formula (n_B) Group.]

(Π-Β) [In the formula (π· Α), Α2 and Α3 independently represent a single bond, _〇_, _c〇〇_, _〇(7)_, -CONH_, _CH=CH_ or the number of carbon atoms is i~ 12 alkylene; R2 and R3 independently represent -H, -F or -CH3; % S represents 1,4_phenylene, 1,4-cyclohexylene, dioxane_2,5_ Base, t-deno-2,5-diyl H2,5-diyl, diyl, ca-2,7-diyl or fluoren-9,10-diyl; R represents -OH, -H, -F, carbon An alkyl group having an atomic number of 丨~3〇, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having a carbon number of 丨~3〇, -CN, -〇CH2F, -OCHF2 or -〇CF3 ; a and b respectively represent an integer not 0 to 4; 20 200808686

HU J JpJLJL c, d and e respectively represent an integer of 0 to 3; when e is 2 or 3, a plurality of rings S may be the same group or different groups; f and g respectively represent 〇 An integer of ~2, and. [In the formula (II-B), A2 and A" independently represent a single bond, _〇_, _c〇〇_, _〇c〇_, -CONH_, -CH=CH- or the number of carbon atoms is bu; Alkylene; R2 represents -H, -F or -CH3; R5 independently represents -Η or -CH3; R6 represents -Η, the number of carbon atoms is! 〜2〇 of an alkyl group or a carbon atom having a carbon number of 2 to 20; a and b each independently represent an integer of 〇~4; c and d each independently represent an integer of 〇~3; and e is an integer of 〇~2; Ring T represents cyclohexane or cyclohexene. [13] The liquid crystal alignment agent according to [12], wherein, in the diamine having a side chain structure represented by the above formula (1), AI is a single bond, and R1 is a group represented by the following formula (Π_Α). Earth (R2).

(R3)

-R4 (Π-Α) [In the formula (II-A), g A2, A3, V, 圮, r4, ring s, a, b, c, d, e, f have the same meanings. ]

[14] The liquid crystal alignment agent according to [13], wherein, in the above formula (Π-A) of the diamine having the chain structure represented by the above formula (1), A2 and A3 are independently represented by a single bond, -〇- , -c〇〇-, -〇co- or an alkylene group U 21 having a carbon number of 1 to 12 200808686 i s s represents 1,4_phenylene or anthracene, 4_cyclohexylene; 4 represents -〇 1^, _11, _17, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -0CH2F, -OCHF2 or _〇CF3; a and b are independently represented ο or 1 ; C, 4 and e respectively represent 0 or 1; f and g are 0, and c+d+e^b is a liquid crystal alignment agent according to [15] [14], characterized in that the above-mentioned The diamine having a side chain structure represented by the formula (I) is a diamine represented by the following formula (1-1), (1-8) or (1-4). (1 -1) h2N-〇X〇-NH2 h2N-^-cTh-^_, (I-8) (1-4) [wherein R and R8 represent a burnt group having 1 to 30 carbon atoms; The alkoxy group having a number of 1 to 30 is used. The liquid crystal alignment of any one of [16] [12] ~ [15]! The polymer is obtained by using tetra Wei dianhydride as an acid component to obtain any one of i-poly-indenyl*tetracarboxylic dianhydride and aliphatic tetracarboxylic acid di-flat tetracarboxylic dianhydride. Or two.酊 曰裱 曰裱 [18]-[17], a liquid crystal alignment agent, characterized in that the quaternary acid dianhydride is selected from the group consisting of the following structural formula (1), (= The above-mentioned aliphatic four-way operation: 22 200808686 The cyclic tetracarboxylic dianhydride is one or more selected from the group consisting of the following structural formulas (14) to (29) and (60).

23 200808686 ^-ru ^ ^ ριχ

[19] The liquid crystal alignment agent according to the above aspect, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the above structural formula (1); the aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic acid; The acid dianhydride is a compound represented by the above structural formula (14). The liquid crystal alignment agent according to any one of the above aspects, wherein the polymer is further composed of a diamine selected from the group consisting of the following general formulae (III) to (XIV); One or more of the resulting groups of polymers. H2n-a4-nh2

Ο-χ-Ο η2ν^χ Ν~^νη2

(in) (ιν) (V) (VI) (VII) (VIII) η2ν

24 (IX) 200808686 [In the formula (πι), Α4 represents _(CH2)m-, where m is an integer of 1 to 6; in the formulae (IV) to (IX), X represents a single bond, -〇-, - S-, -SS-, -S02-, -CO-, -CONH-,

-S-(CH2)mS-; wherein m is an integer from 1 to 6; Y independently represents a single bond, -〇-, -C〇_, -C (CF3V or a subunit having 1 to 3 carbon atoms) An alkyl group; a hydrogen bonded to a cyclohexane ring or a benzene ring may be substituted by -F, <Ή3, _QH, -COOH, -SOgH, and the hydrogen bonded to the benzene ring in the formula (VT) may be benzyl. Substituted.]

[In the formula (X), A1 represents an early bond, -〇_, -COO_, -0C0_, -CO-, _CCXNTI_ or _(CH2)nr, where m is an integer from 1 to 6; R1 represents a steroid skeleton a group, a group represented by the following formula (II), or when the positional relationship of two amino groups bonded to a benzene ring is relative, r1 is an alkyl group having 1 to 30 carbon atoms; or when the above positional relationship is interphase When R1 is an alkyl group or a phenyl group having 1 to 30 carbon atoms; in the above-mentioned alkyl group, any -CH2· may be -CF2-, -CHF-, -〇- (but not continuous), -CH= CH- or -CeC-substitution; _CH3 may be substituted by _ch2F, -〇^2 or <卩3; 25 200808686 ZH-0 J jpil The hydrogen bonded to the carbon forming the above phenyl ring may be independently _F, - CH3, -OCH3, 〇CH2F, -〇CHF2 or -〇Cf3 are substituted. ]

[In the formula (II), A and A*5 independently represent a single bond, -〇_, _c〇〇_, _〇c〇_, ^_CONH...-CH=CH- or a carbon number of 丨~12 Alkylene; R2 and R3 are each independently represented, _F or seven%; ring S represents 1,4-phenylene, anthracene, 'cyclohexylene, anthracene, 3_dioxane-2,5_diyl, t-fixed -2,5-diyl, _2,5-diyl, naphthyldiyl, ca _2,7-di-diyl or fluoren-9,10-diyl; r4--H, -F An alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having a carbon number of 丨~3〇, _CN, -〇CH2F, and -OCHF2 4-〇 CF3; a and b respectively represent an integer of o~4; c, d and e respectively represent integers of 〇~3; when e is 2 or 3, the rings S may be the same group or different The group; f and g respectively represent an integer of 0 to 2, and c+d+ed. ]

26 200808686

[In the formulae (XI) to (XII), R5 independently represents -H or -CH3; R6 is independently represented or the number of carbon atoms is 丨~2() hetero group or olefin A5 independently represents a single bond, _c〇^_CH _ ; R7 and R8 each independently represent _H, a carbon atomic number of U or a phenyl group. ]

[In the formula (XIII), R9 represents _H or an alkyl group having a carbon number, and any _CH2_ of the alkyl group having 2 to 20 carbon atoms in the above alkyl group may be _〇_ (but not continued), -CH=CH- or -CeC_ substitution;

Ay independently represents -〇- or an alkylene group having 1 to 6 carbon atoms, and A represents a single bond or an alkylene group having 1 to 3 carbon atoms; and ring U represents 1,4-phenylene or anthracene. , 'Cyclohexylene; 27 200808686 Two jh for 〇 or 1. In the formula (XIV), • R]0 represents an alkyl group having a carbon number of ό22; R]1 represents an anthracene or an alkyl group having 1 to 22 carbon atoms; Α6 independently represents _〇• or carbon The number of atoms is the sub-hospital base of Bu. [21] The liquid crystal alignment agent according to [20], wherein the diamine is selected from the group consisting of the following general formulae (VI-1) to (VI-5), (VI-14) to (VI-16), Formula (VII-1)~(VII_15), Formula (VII-26), Formula (VII-27), Formula (VII-31), Formula (VIII-1), Formula (VIII-2), Formula (VIII- 6) One or more types of the group consisting of diamines represented by (IX-1) to (IX-5).

(VI -1) (V I -2) (V I -3) (V I -4)

28 200808686

[22] The liquid crystal alignment agent according to [21], wherein the diamine is selected from the group consisting of the above formula (VI-1), (VI-2), (VII-1) to (VII-12), and (IX-2) 29 200808686 One or more of the groups consisting of one amine. The I amine is a second polymer obtained by using an amine other than a monoamine having a side chain structure represented by the above formula (1). [24] The liquid crystal alignment agent according to [23], wherein the composition is obtained by using _acid dianhydride as an acid component. [25] The liquid crystal alignment agent according to [24] or [24], wherein the diamine other than the diamine having a side chain structure represented by the above formula (I) includes the following formula (III) to ( XIV) One or more groups of the diamines of the table tr. (III) (IV) h2n-a4-nh2 η η2ν^—^νη2 Η2νΟΧ-^ ΝΗ 2 (V)

(VI) η2ν νη2

(VII)

(VIII) 30 (IX) 200808686 [In the formula (m), A represents -(CH2)m-, wherein an integer of 1 to 6 is represented; in the formulae (IV) to (IX), X represents a single bond, _〇... S_, each s...SCV, -CO...CONH-, -NHCO ... C(CH3)2~c(CF3)2~(CH2)m~〇_(CH2k4, -S-(CH2)mS-, where m is An integer of j~6;

Y independently represents a single bond...〇-, _S_, _c〇_, -C(CH3)2... -C(CF3)2· or an alkylene group having 1 to 3 carbon atoms; a cyclohexane ring or a benzene ring The superposed hydrogen can be substituted by -F, -CH3, -OH, -COOH, _S〇3H, -P〇3ii2. Further, the nitrogen bonded to the benzene ring in the formula (5) may be substituted by a benzyl group. ]

[In the formula (X), A represents a single bond, -〇-, -COO-, -OCO-, -CO-, or -(CH2)m-, wherein m is an integer of from 1 to 6; represents a steroid skeleton a group, a group represented by the following formula (II); or when the positional relationship of two amino groups bonded on a stupid ring is relative, R1 represents an alkyl group having 1 to 30 carbon atoms; or when the above positional relationship is interphase When R1 represents an alkyl group or a phenyl group having 1 to 30 carbon atoms; among the above alkyl groups, any -CH2- may be _CF2-, -CHF-, -〇_ (but not continuous), -CH= CH- or -CEC-substitution; -CH3 may be substituted by _CH2F, -CHF2 or -CF3; the hydrogen bonded to the carbon forming the above phenyl ring may be independently _F, 31

200808686-CH ", -OCH3, -〇CH2F, -〇CHF2 or seven-step substitution.] (/R2)f ^ one

-A2_

-A3- p

-R4 (π) [In the formula (II), A2 and A·3 independently represent a single bond, _〇_, _c〇〇-, -〇c〇_, -CONH-, -CHCH- or the number of carbon atoms is Alkylene; R2 and R3 each independently represent $, _F or _CH3; ring S represents 1,4-phenylene; [,4_cyclohexylene, I, dioxane-2,5_diyl, Pyrimidine _2,5_diyl" than bite _2,5-diyl, naphthalene 4,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl; 'R4 represents -H , -F, an alkyl group having a carbon number, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having a carbon number of 丨~刈, _CN, -〇CH2F, -OCHF2 4-〇CF3; a and b respectively represent integers of 〜4; c, d and e respectively represent integers of 0 to 3; when e is 2 or 3, plural rings S may be the same group or different groups. Group; f and g respectively represent an integer of 0~2, and c+d+1.]

32 200808686

[In the formulae (XI) to (XII), R5 independently represents -H or -CH3; R6 independently represents -anthracene or an alkyl or alkenyl group having 1 to 20 carbon atoms; Α5 independently represents a single bond, _CO_4 -CH2-; R7 and R8 each independently represent - an anthracene, an alkyl group having 1 to 20 carbon atoms or a phenyl group. ]

[In the formula (XIII), R9 represents -Η or an alkyl group having 1 to 20 carbon atoms, and any -CH2- of the alkyl group having 2 to 20 carbon atoms in the above alkyl group may be -0- (but not Continuous), -CH=CH- or -CeC_ substituted; A6 independently represents -0- or an alkylene group having 1 to 6 carbon atoms; A7 represents a single bond or an alkylene group having 1 to 3 carbon atoms ; Ring U represents 1,4-phenylene or 1,4-cyclohexylene; 33 200808686 h is 0 or i. The formula (XIV) towel, which represents a carbon atom having a carbon number of 6 to 22, R]6] represents -H or an alkyl group having a carbon number, and T represents _〇_ or a carbon number of 1 to 61 [ 26] a liquid crystal alignment film, the alignment film f. ] The liquid crystal alignment agent described in the item - item is added to the 'shaped soil [U] ~ [25]

P7] A liquid crystal display device, the spoon. To the membrane. 1 includes [26], the liquid crystal is provided by the present invention, and the above-mentioned TM*VA liquid crystal display capable of providing voltage holding suppression is obtained. The above description is merely an overview of the technical solution of the present invention, and the technique of the present invention is understood. The shooting section can be described in detail in accordance with the preferred embodiment of the present invention and in conjunction with the accompanying drawings. [Complex application method] The liquid crystal alignment agent of the present invention is a composition containing one or two or more kinds of polymers. The polymer of the present invention is a polyaminic acid or a derivative thereof obtained by reacting and reacting an acid component with a specific amine component. <1. The diamine having a side chain structure of the present invention> The diamine of the present invention is a monoamine having a side chain structure represented by the following formula (1). By using the diamine of the present invention, it is possible to obtain a liquid crystal matching agent which is improved in the problem of voltage retention and residual DC, in particular, 0 34 200808686

[In the formula (i), A1 represents a single bond, _0-, -COO-, -OCO-, -CO-, -CONH- or -(CH2)m-; m is an integer from 0 to 6; R] is lower a group represented by the formula (II-A) or the following formula (Π-Β). ]

(Π-Β) [In the formula (II-Α), Α and Α3 independently represent a single bond, _〇_, _c〇〇_, 々CO-CONH-, -CH=CH- or the number of carbon atoms][ ~ 〇 〇 亚 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; R R R ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ^ Diyl or 蒽-9,10-diyl; Mountain R4 is preferably: Guanyixin ^The number of carbon atoms is the base of the ruthenium, the fluorination of the number of atoms of W30, the number of carbon atoms is 3 () Oxygen stone CL_〇CH2F, _〇CHF2 or Na3; particularly preferred, F, ^ F ~% of the alkyl group, fluoroalkyl group having 1 to 3 carbon atoms, -〇CH2F, -〇CHF2 Or -〇CF3; 35 200808686 a and b respectively represent integers of 〇~4; c, d and e respectively represent integers of 0~3; when e is 2 or 3 B, 'the ring § can be the same The groups may also be different groups; f and g each independently represent an integer of 〇~2, and c+d+e-1. [In the formula (II-B), A2 and A3 each independently represent a single bond, _〇_, _c〇〇_, -〇c〇_, '_CH=CH- or an alkylene group having a carbon number of 丨~12 R2 represents, -F or _ch3; R independently represents -Η or -CH3; R6 means -Η or the number of carbon atoms is! ~? Alkyl or alkenyl; a and b each independently represent an integer of 〇~4; c and d each independently represent an integer of 〇~3; e is an integer of 〇~2; cyclohexane represents cyclohexane or cyclohexene . The diamine represented by the formula (I) may, for example, be the following diamine.

36 200808686 R7 R7 R8 H2N-"^ ~NH2 (1-7) h2n—<^^·οη^^-νη2 h2n-Bu R8 (1-8) R7 :1-9) R7 H2N-'^ CH —^ —NH2 H2N-“^~CH~^~NH2 H2N—1 (1-10) (1-1 1) (1-12) R8 R8 f Λ Λ H2N-<f~"Y-ChHf"""^-NH2 (1-13) H2N-<f~y~cHHf"""V~NH2 (1-14) H2N—^""Y-ChH^yH (1-15 NH2 NH〇

H2N U U i[ -^^-CHH^^-NH2 H2N-^^-ChH^^-nh2 h2n- NH〇 (1-16) (1-17) (1-18) 37 200808686

In the formula, R7 is preferably an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 2 carbon atoms or a carbon number of 3 to 20 carbon atoms. Alkoxy. R8 is preferably _H, _F, a carbon group having a carbon number of 30, an alkoxy group having 1 to 3 carbon atoms, _qh, -CN, -OCHJ'-OCHF2 or -〇CF3, more preferably a carbon number. It is an alkyl group of 3 to 20 or an alkoxy group having 3 to 20 carbon atoms.

In the formulae (1-20) to (1-22), R9 is preferably an alkyl group having 4 to 3 carbon atoms, and more preferably an alkyl group having 5 to 20 carbon atoms. 38 200808686 R10 R10

R 11 〇

0=C 〇=c H2N—NH2 H2N'~"<^3K"ChH^3>~NH2 Η2Ν"'"<^3^α"Η(^3^"ΝΗ2 (1-2 6 ) (1-2 8)

H2n i-hQ-chh^nh2 h2n-^Xq_NH2 h2n-^-^-^〇^nh2 (1-2 9) ( 1-3 0) (Bu 31) wherein R1G preferably has 1 to 30 carbon atoms The hospital group or an alkoxy group having 1 to 3 Å carbon atoms, more preferably an alkyl group having 3 to 2 carbon atoms or an alkoxy group having 3 or 2 carbon atoms as κ^20. Preferably, RU is -H, -F, and the number of carbon atoms is ^ -〇ch^.〇chp2S, -〇cF3, ^^; 4'A CN' group or alkoxy group having 3 to 20 carbon atoms. Sigh for 3 to 20 alkane 39 200808686

Η2ν-^^οη-^^-νη2 h2n-^^>-ch-<^^>-nh2 η2ν-<^^>-ch-^^>-nh2 (1 -3 2) (1-3 3) (1-3 4)

Η2Ν -^“^~CH-~—ΝΗ2 Η2Ν-“^>~CH—^ΝΗ2 Η2Ν—* “^-CH—^”—ΝΗ2 (1-35) (1-36) (1-37)

Η2Ν ~y^-CH—^~~—ΝΗ2 Η2Ν-“CH~^”ΝΗ2 Η2Ν-“CH-^”—ΝΗ. (1-38) (1-39) (1-40) 40 200808686 ^—TVJ U yj LL· ^ 1 The diamine (the compound represented by the formula CD) can be used by any means, for example, The synthesis was carried out by the method shown in the following scheme.

2. The method described in JP-A-2002-267934, wherein the compound represented by the formula, the aniline hydrochloride and the aniline are heated and stirred to obtain a diamine compound of 2 tables. The method for synthesizing the compound represented by 1 is described in Japanese Patent Publication No. 2002-121190, 〇rganic Functi〇nai Gr0Up Preparations Second Edition, ν〇1·i P(10)~'(1983) ' Academic Press and other literature. In the above reaction, a solvent which does not affect the reaction may be used. The above agents include aromatic solvents such as toluene and diphenylbenzene; aliphatic hydrocarbon solvents such as pentane and hexane; and dichloromethane and dichloroethane. A halogen-based solvent, an aprotic polar solvent such as N,N-dimethylamine, dimethylacetamide, N-methylpyrrole, or monomethylhydrazine. The amount of the above solvent used is arbitrary. However, in order to increase the yield of the product and suppress the side reaction, it is desirable to carry out the reaction in an excess amount of the aniline used as a raw material. The amount of the aniline used is 1 to 2 Torr, preferably 3 to 10 moles per mole of the compound represented by 1. In the present invention, the reaction temperature of the above reaction is 80. (: in the range of 300 ° C, preferably in the range of 100 ° C to 20 CTC. 41 200808686 In the present invention, the reaction time of the above reaction is usually 0.5 hours to 3 inches, but if the reaction is carried out for a long time, The formation of by-products is increased and the yield of the target compound is lowered. Therefore, the reaction time is preferably from 1 hour to 15 hours. <2. Polymer of the present invention> At least one of the polymers included in the liquid crystal alignment agent of the present invention It is a polyamine which is obtained by reacting a diamine having a side chain structure represented by the above formula (1) as an amine component and tetractylic dianhydride as an acid component, and is obtained from the reaction of an amine derivative. The acid component of the present invention includes one or two or more kinds of tetrazoic acid dianhydride, but a part of the tetracarboxylic dianhydride may be replaced with a dicarboxylic acid, wherein, in order to prevent the molecular weight from being excessively lowered, relative to the total The ratio of the acid component dinonanoic acid is preferably 10 mTorr/〇. The amine component of the present invention includes one or two or more kinds of diamines, but a part of the diamine may be substituted with a monoamine. The amount is not excessively lowered, and the ratio of the monoamine to the total amine component is preferably 10 mTorr/0 or less. The polymer of the present invention includes the following polyamine derivatives in addition to polyglycine: a polyimine obtained by dehydration ring-closing reaction of all amino groups of poly-proline and carboxylic acid; 2) a partial polyimine obtained by partial dehydration ring-closing reaction; 3) a carboxylic acid of poly-proline a polyamidamine obtained by conversion to an ester; 4) a poly-proline-polyamine copolymer obtained by replacing a part of a dianhydride contained in an acid component with an organic diacid and reacting it; and 5) A part or all of the poly-proline-polyamine copolymer is a polyamine amine produced by a closed-loop reaction of 2008-08686 jpil. It is known that the polymer of the present turtle is a polyglycine or a derivative thereof obtained by reacting an amine component and using tetrazoic acid dianhydride as an acid component, wherein at least one of the above amine components is used. The above-mentioned diamine. The amine component of the invention may include one or more of the above-mentioned general formula (4) to the above-mentioned one amine, and may also include two or more kinds. An amine other than the diamine represented by the formula (1) included in the amine 2 of February 4. The female &quot;Μ任思延选' is preferably listed as a diamine represented by the formula (ΠΙ)~(IX), which can be enumerated as Κ111·!)~(ΙΠ-3) No diamine. NH2 (II 1-3) Η2Μ ～η2ν-^^νη2 (II 1-2) (111-*!) Dry $$(IV) The diamine of Table 717 can be exemplified by: (ΐν·1), (ΐν·2) indicates the _amine. Η2ν V-1 H2N- (I V-2) 1) to (V-3) The diamine represented by the formula (v) may, for example, be a diamine.

(V-1

(V-2)

(V-3) 43 200808686 The diamine represented by the formula (VI) may be, for example, the formula (VI_1) to (VI-16).

H2n ^ nh2 (V I -6) The diamine shown. HpN~~<"~~NH2 nh2 h2n-&lt;^-nh2 hA-^^-nh: (V 1-1) (VI-2) (VI-3) (V 1-4) OH C〇〇H HO nu H2N—^ ^—NH2 (V 1-5)

H2N (VI-7)

H2N v NH2 (VI-8) H〇〇C H2N nh2 (V I -9)

H03S H2N-jj-NH2

PO3H2

H2〇3p H2N—4 —NH2

(V I -1 3)

H2I\T V, nh2 (V I -1 1 ) (V I -1 2)

H2n hh2 (V 1-1 5)

Nh2 nh2 (VI-16) The diamine represented by the formula (VII) may, for example, be a diamine represented by the formula (VII-1) to (VII-32). 44 200808686 Z呌0Jjpi丄

(V I I - 2 〇) (V ! 1-21) 45 200808686 j —

HO OH (VI 1-3 1) (VI 1-3 2) The diamine represented by the formula (VIII) may, for example, be a diamine represented by the formula (VIII-1) to (VIII-6).

(VI ! I - 5 ) (VIII-6) The diamine represented by the formula (IX) may, for example, be a diamine represented by the formula (IX-1) to (IX-11). 46 200808686 u u y a

H2N

NH2 X- 1 )

(CH2)3 (

Nh2 h2n

(ch2)6

Nh2 I X-2)

Nh2 (I X-3)

Nh2

Nh2

(I X-9)

Nh2 wherein, more preferably, the formulae (VI-1) to (VI-5), (VI_14) to (VI-16), the formula (VIM) to (VII-15), the formula (VII-26), and the formula (VII) VII-27), a diamine represented by the formula (VII-31), the formula (VIII-1), (VIII-2), the formula (VIII-6), and the formula (IX-1) to (IX-5); Preferable are the diamines represented by the formula (VI-1), the formula (VI-2), the formulae (VII-1) to (VII-12), and the formula (IX-2). The amine component of the present invention may be used alone or in combination of two or more kinds of the diamines represented by the above formulas (III) to (IX). In the total amine component of the present invention, the molar ratio of the diamine represented by the above formula (ΙΠ) to (IX) may be based on the structure of the diamine represented by the above-mentioned general formulae (III) to (IX) and 200808686 The required voltage holding ratio and residual DC reduction effect are adjusted by 1 to 95%, more preferably 5 to 80%. As described above, the amine component of the present invention includes one or two or more kinds of monoamines, but particularly in a VA type liquid crystal display device, (10) a crystallizer device, an STN type liquid crystal display device, etc. The pretilt angle is added to it. Further, other diamines having a side chain structure are used. The amine component of the present invention has a side bond structure (the diamine represented by the general formula (I) and other The ratio of the diamine of the side chain structure is determined according to the structure of the selected diamine having a side chain structure and the desired pre-expansion angle, preferably (10)%, more preferably 5 to 8%. In the book, the diamine of the instrument structure refers to a diamine having two amino groups and having a side chain in the main chain. That is, the diamine with a side chain structure; the four-ship dianhydride reaction can be used to collect the poly-proline or poly-imine (chain-polymerized) of the chain group relative to the polymer backbone. Proline or ηη: Contains a liquid crystal alignment film formed by a liquid crystal alignment agent having a side chain group π, w acid or a poly-light amine relative to the polymer main chain. In the above-mentioned patent document 1 (曰本特开平; Π493345), the side chain in the diamine having a side bond structure can be appropriately selected according to the required angle. For example, the above side The chain may preferably be a group having a carbon number of 3 or more. Specific examples thereof include the following: !) a phenyl group which may have a substituent, and a cyclohexyl group which may have a substituent 48 200808686 a bis(cyclohexyl) stilbene group having a substituent or an alkyl group, an alkenyl group or an alkynyl group having 3 or more carbon atoms; 2) a phenoxy group which may have a substituent, a cyclohexyloxy group which may have a substituent, Bis(cyclohexyl)oxy group which may have a substituent, phenyl% hexyloxy group which may have a substituent, cyclohexylbenzene which may have a substituent An alkoxy group, an alkenyloxy group or an alkynyloxy group having a carbon number of 3 or more; 3) a phenylcarbonyl group or an alkylcarbonyl group, an olefinylcarbonyl group or a fast-carbon group having 3 or more carbon atoms; 4) a phenylcarbonyloxy group Or an alkylcarbonyloxy group, an olefinic carbonyloxy group or an alkyneoxy group having a carbon number of 3 or more; 5) a pnnyicarbonyioxy group which may have a substituent, a cyclohexyloxycarbonyl group which may have a substituent, may have a bis(cyclohexyl)oxycarbonyl group of a substituent, a bis(cyclohexyl)phenoxycarbonyl group which may have a substituent, a cyclohexyl bis(phenyl)oxycarbonyl group which may have a substituent or a pyrolylcarbonyl group having 3 or more carbon atoms , an oxycarbonyl group or an alkynyloxycarbonyl group; 6) an aniline carbonyl group or an alkylamine carbonyl group, an enaminocarbonyl group or a block amine group having 3 or more carbon atoms; 7) a cyclic alkylene group having 3 or more carbon atoms; a cyclohexylalkylene group which may have a substituent, a phenylalkylene group which may have a substituent, a bis(cyclohexyl)alkylene group which may have a substituent, a cyclohexylphenylalkylene group which may have a substituent, Bis(cyclohexyl)phenylalkylene which may have a substituent, phenylalkoxy group which may have a substituent, alkyl group Oxycarbonyl or alkylbiphenyloxycarbonyl; 9) alkyl, fluoroalkyl or phenyl or cyclohexyl substituted by alkoxy; 49 200808686 and two (four) two or more benzene or cyclohexyl ring Bonding or by -0-, -COO-, -0C0_, _C0NH_ or a sub-alkyl group-bonding group having a carbon number of (a), (4) a silk filament group, or a group having a steroid skeleton, etc., but Without being limited to the alkyl group J, the "substituent" may be exemplified by a hospital base, an alkoxy group or a halogen.

= Outer 'bis(cyclohexyl) or bis(phenyl) can be used. In the specification, the group can be either linear or branched. For example, amines can be listed in the 3 and 5 or 2 and 5 positions. (9) The combination of two subtractions represents tf. The diamine of Table 7 can be exemplified by the following formula (Χ·1)~(X-48)

50 200808686 24»jipil

In the formula, R12 is preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms, more preferably an alkyl group having 5 to 12 carbon atoms or an alkyl group having 5 to 12 carbon atoms. Oxygen.

R13 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 3 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms. R 14

Nh2 h2n ^ nh2 R15 h2n

R15 R 14

R14 νη2 η

(x-1 5)

(X-1 6) nh2 h2n

(X-1 7) nh2 51 200808686

«yj^JLX In the formula (X-12) to (X-15), R14 is preferably an alkyl group having 4 to 16 carbon atoms, more preferably an alkyl group having 6 to 16 carbon atoms. In the formula (X-16) and the formula (X-17), R15 is preferably an alkyl group having 6 to 20 carbon atoms, more preferably a terminal having 8 to 20 carbon atoms.

\ I

R16

H2N

^17 (X- 2 3)

16

H2n

(X — 2 7) h2n

52 16 200808686 Ζ4δ^3ρΐΙ

R17

In the formula, R16 is preferably a group having 1 to 12 carbon atoms and having 1 to 12 carbon atoms, more preferably a carbon atom having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. R17 is preferably _H, _F, a calcined group having a carbon number of from 12 to 12, an alkoxy group having a number of broken atoms of from 1 to 12, _cn, -〇CH2F, -0CHF2 or -OCF3, more preferably a carbon atom of 3~ The alkyl group of 12 or an alkoxy group having 3 to 12 carbon atoms. A9 represents an alkylene group having 1 to 12 carbon atoms.

53 200808686

(X-A A)

(X-4 3)

Among them, a diamine represented by the formula (x-1) to the formula (x-ll) is preferably used. More preferably, the diamines represented by the formula (X-2), the formula (X-4), the formula (X-5) and the formula (X-6) are listed. In the above formula (XI), it is preferred that one of the two "NH2-Ph-A5-0-" is bonded to the 3-position of the wrong core and the other is bonded to the 6-position. The two amino groups are bonded to the carbon of the phenyl ring, preferably in the meta or para position relative to the binding position of A5. The diamine represented by the formula (XI) may, for example, be a diamine represented by the following formulas (XI-1) to (XI-4). 54 200808686

In the above formula (XII), two "NH2_(R8-)Ph-A5-0_" are bonded to the carbon of the phenyl ring, respectively, preferably in the meta or para position relative to the carbon to which the leaving nucleus is bound. On the carbon. The two amino groups are bonded to the carbon of the phenyl ring, respectively, preferably in the meta or para position relative to A5. The diamine represented by the formula (XII) may, for example, be a diamine represented by the following formula (XII_1) to (XII-8).

55 200808686 厶_1&quot; U J J ριι

In the above formula (XIII), two amino groups are bonded to the carbon of the phenyl ring, respectively, and are preferably bonded to the meta or para position with respect to A6. The diamine represented by the formula (XIII) may, for example, be a diamine represented by the following formula (XIII-1) to (XIII-9).

56 200808686

R19

R19

In the formula, R18 is preferably -H or an alkyl group having 1 to 20 carbon atoms, and Ri9 is preferably an anthracene or an alkyl group having 1 to 1 ring of carbon atoms. In the above formula (XIV), the two amino groups are bonded to the carbon of the phenyl ring, respectively, and are preferably bonded to the meta or para position relative to the oxime 6. The diamine represented by the formula (XIV) may, for example, be a diamine represented by the formula (XIV-3).

(X I V - 3) 57 200808686 24«33ρΐί is -Η or a carbon atom. The base component of the present invention is preferably an amine component of the present invention, which may include two or more of the amines represented by the above formula (XIV). Chain bis::) Diamines of the general formula (1_ ΠΙ(ΠΙ)~(ΙΧ), general formula (X)~(XIV) Table:, diamines other than the structure of diamine Is arbitrary, but it can also

A naphtha-based diamine of the structure of a bovine, a naphthalene-based diamine, a ruthenium, a structure (4), a diamine, or a diamine or a diamine having a chain structure of ΧΙνμχ. The oxirane-based diamine is not particularly limited, and in the present invention, a diamine represented by the following formula (XV) can be preferably used. / R22 \ R22 _^Aioj_NH2 (χν) \ R23 / j R23 (wherein R22 and R23 independently represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, A1G represents a fluorenylene group, a strepylene group or an alkyl group-substituted phenylene group. 丨 represents an integer of 1 to 6, and j represents an integer of 1 to 10 Further, the other diamine is not particularly limited, and in the present invention, for example, a diamine represented by the following formula (Γ) to (8') can be preferably used.

58 200808686

►25

(wherein R24 and R25 independently represent an alkylene group having a carbon number of 3 to 2 Å. It should be noted that the amine component of the present invention includes a diamine and a formula (ΠΙ) of the formula The diamine other than ~(XIV) is not limited to the above-mentioned diamine, and of course, various other kinds of diamines are present within the range which achieves the object of the present invention. The above other diamines may be used singly or in combination of two or more of them. The amine component of the present invention can impart a suitable pretilt angle to the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention by appropriately selecting the kind of the diamine and the combination thereof. When it is a VA type liquid crystal display device, it is often required to be 80 to 90. Large pre-tilt angles on the left and right; when it is an OCB type liquid crystal display device, it is often required to be 7~2〇. When the left and right pretilt angles T are TN type liquid crystal display devices or STN type liquid crystal display devices, 3 to 15 are often required. Left and right pretilt angles. Therefore, the liquid crystal alignment agent of the present invention which can appropriately adjust the pretilt angle can be applied to any type of liquid crystal display device. 59 200808686 Hereinafter, the relationship between the amine component of the present invention and the driving mode and the pretilt angle of the liquid crystal display device will be described. 1) In the case of a VA liquid crystal display device, in order to impart a suitable large pretilt angle to the VA liquid crystal display device, a diamine having a side chain structure can be particularly preferably used: a diamine represented by the general formula (1), and A diamine having a phenylene diamine structure and a side chain structure, for example, a diamine represented by the above (X-1) to (X-48). When the diamine having a sub-diamine diamine structure is a main chain connecting two amino groups, for example, the molecular length of the main chain structural portion is changed as compared with the diamine represented by the above formulas (νΠ) to (IX). short. As a result, in the polymer obtained by reacting the diamine and the tetracarboxylic acid monoanhydride, the spatial density (side chain density) of the side bond structure can be increased, and thus it is more suitable for use as a VA type liquid crystal display device. Liquid crystal alignment agent. And 'diamines having a sub-base diamine structure and a side bond structure on the same day, and other diamines having a side chain structure, diamines or oxime diamines represented by the above formula (ΠΙ)~(Ιχ), 矽An oxane-based diamine or the like is used in combination.

w 2) In the case of a 0CB liquid crystal display device, a TN liquid crystal display device, or an STN liquid crystal display device, a liquid crystal display device such as an OCB liquid crystal display device, a TN liquid crystal display device, or an STN liquid crystal display device is appropriately pretilted. The diamine represented by the above formula (I) and the diamine having a side chain structure represented by the formula (X) to (XIV) can be preferably used. More preferably, the diamine having a side chain structure is used in combination with a diamine represented by the above formula (I), a diamine represented by the formula (111) to (Ιχ), or a fluorene-based oxazepine diamine. . The amine component of the present invention is selected by the type of diamine and its combination by 60 200808686. With a suitable pretilt angle. The above liquid crystal display device can be provided as described above, and a part of the present invention can be replaced with a monoamine. The termination of the polymerization reaction by the diamine included in the female knives can suppress the substitution of the diamine into a monoamine, and the reaction of the reaction other than the obtained poly-management can be easily controlled, and thus the total amine component is The ratio of monoamines is only the water molecular weight. It is preferable to use it as a standard: :::: The range of the damage of the present invention is 10 moles of the total amine component of the polymer of the present invention. /. . Any one may be selected from the above-mentioned tetracarboxylic dianhydride which may be a polymer of dianhydride or alicyclic tetrasole or 2) an aliphatic tetra-sweet component; . In order to make the tetrahydro dianhydride form of the present invention, it is preferable to appropriately select the 'four as an aromatic tetracarboxylic dianhydride contained in the acid component, and specific examples thereof can be expressed by the following formulas (1) to (13). Diacid anhydride. In the case of the following aromatic tetracarboxylic acid, the mono-anhydride represented by the formula (1), the formula (2), the formula (5), the formula (6), and the formula (7) is more preferable, and the pyromellitic acid represented by the formula (1) is most preferable. Diacid anhydride. 61 200808686 jpn

The above 2) aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride which is included in the acid component of the present invention is specifically a dianhydride represented by the following formulas (14) to (62). Among the tetracarboxylic dianhydrides described below, the dianhydrides represented by the formulae (14) to (29) and the formula (60) are more preferable, and the oxime, 2, 3, 4 represented by the formula (14) is particularly preferable. - 1,2,3,4-cyclobutane tetra carboxylic acid dianhydride. Further, when the polyamine 62 200808686 acid of the present invention is made into a solvent-soluble polyimine, it is preferred to use the formula (19), the formula (20), the formula (27) to (29), and the formula (60). ) represents the dianhydride.

63 200808686, °V V αα ϊ (34) 0 〇 (3 5) 乂0 / ·\

〇 〇

〇 〇

〇(4 6)

(4 9)

〇 〇

P i1 xc r (3 8) 〇 9 〇 °μ jC I;0 &amp; (A 1 ) 〇

〇

〇

(4 8) 64 200808686

CH3CH;

H3C

(CH2) 10 KJ 〇 (6 0 (60) w (6 1 ) - (6 2) The acid component of the present invention may be used alone as a four-rebel dianhydride represented by the formulas (1) to (62), and may also be used. Two or more combinations are used, including aromatic tetraphthalic acid dianhydride and aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic acid di-hepatic (particularly preferably pyromellitic dianhydride and/or 1,2 , 3, 4-cyclobutane-tetradecanoic acid dianhydride), the acid component of the present invention is synthesized into a poly-proline, and a liquid crystal alignment film containing the above polyamine can be used to impart a good retention ratio of fineness and smallness. The tetracarboxylic dianhydride other than the tetracarboxylic dianhydride of the formula (1) to the exposure 65 200808686 included in the acid component of the present invention is not particularly limited, but may be exemplified by a tetracarboxylic dianhydride having a chain structure. The tetracarboxylic acid dianhydride having a side chain structure is used to synthesize a polymer from the acid component of the present invention, and a liquid crystal alignment film formed by using a liquid crystal alignment agent containing the above polymer can be increased in its content. The tetracarboxylic dianhydride having a side chain structure in the liquid crystal display device is not particularly limited, and may be preferably used in the present invention. With steroid represented by the following formula (63), formula (64) four framework betray dianhydride.

In addition, the acid component of the present invention includes tetrakisonic acid dianhydride other than the tetracarboxylic acid dianhydride represented by (62), and the dicarboxylic acid dianhydride is in the range of the object of the present invention. Form of four resorcinic dianhydrides. The above other tetracarboxylic acid di-anhydride is not limited to the above four. However, other kinds of other acids may be present or two or more kinds may be used in combination. As described above, the tetracarboxylic acid dianhydride may be used as described above, and the acid component of the present invention may be replaced by a carboxylic acid anhydride. By arranging Weicheng, the polymerization reaction can be terminated: = 2: substitution 2, so that the obtained polymer can be easily controlled (poly-acid and i: the ratio of the target to the overall acid anhydride of the acid component as long as it is not Within f, as a standard, preferably less than or equal to =

The polymer of S. chinensis may have any weight average molecular weight, and is not particularly limited. When used as a component of the liquid crystal alignment agent, it is preferably w' or more preferably 1 x 104 or more. A polymer having an average molecular weight of &lt; 5 χ 103 or more does not evaporate in the step of sintering the alignment film. 'The composition as a liquid crystal alignment agent has satisfactory physical properties: ~ wherein 'the weight average molecular weight of the polymer is condensed Gel permeation chromatography (GPC) was used for the determination. For example, the obtained polymer is diluted with dimethylamine (DMF) to have a polymer concentration of about 1% by weight, and a chromatographic paper bundle (chr〇matopack) c_R7A (manufactured by Shimadzu Corporation) is used, and dmf is used as a developing solvent. It was measured by a gel permeation chromatography (GPC) method and obtained by conversion of polystyrene. Further, in order to accurately measure GPC such as polyacrylic acid or polyacrylic acid, an inorganic acid such as phosphoric acid, hydrochloric acid, nitric acid or sulfuric acid, or an inorganic salt such as lithium bromide or lithium chloride may be dissolved in a DMF solvent to prepare a developing solvent. The molecular weight distribution of the polymer of the present invention can be expressed by the degree of polydispersity, which means a value of a weight average molecular weight / number average molecular weight (jyfw / Mn), and the value is preferably 2 to 5. The molecular weight distribution was measured by the same GPC method as the molecular weight measurement. 67 200808686 The polymer ruthenium of the present invention is prepared by a known method. For example, one or two or more kinds of _amines represented by the above formula (I) are charged into a reaction vessel having a raw material inlet, a nitrogen inlet, a thermometer, a stirrer, and a condenser, and One or two or more kinds of other diamines represented by the general formulae (III) to (XIV) and, if appropriate, one or two or more kinds of diamines selected from other diamines, further added as needed The amount of monoamine required. Next, a solvent (for example, N-mercapto-2-pyrrolidone or decyl decylamine as a guanamine-based polar solvent) and one or two or more kinds of tetradecanoic acid dianhydride are added, and further added as needed. Resulphate. At this time, the total amount of the tetra-acid dianhydride is preferably approximately equal to the total number of moles of the diamine (the molar ratio is about 0.9 to U). Stir it at a temperature of 0 to 70. (: The next reaction is 1 to 48 hours, so that a polymer solution can be obtained. In addition, it is also possible to heat up to raise the reaction temperature (for example, 50 to 8 Torr. 〇, thereby obtaining a polymer having a small molecular weight. The present invention is made with a large amount of poor solvent. The polymer is precipitated, and the solid component and the solvent are completely separated by filtration, etc., and can be identified by IR and NMR analysis. Further, the solid polymer is decomposed by a strong alkali aqueous solution such as KOH or NaOH, and an organic solvent is used. The extraction is carried out and analyzed by GC, HPLC or GC-MS, whereby the monomers used can be identified. The obtained polymer solution can be diluted with a solvent to adjust to a desired viscosity before use. When it is made into soluble polyimine, 68 200808686: Sa:=3 A polymer solution and dehydrating agent acetic anhydride, propionic anhydride, tri-J anhydride and dehydration ring-closing catalyst triethylamine, pyridine, trimethyl sulphide From the temperature of 2Q~15叱, the Niyaminization reaction can be carried out using a large amount of poor solvent (methanol, ethanol, isopropanol W mountain agent) to make the polysf amide from the obtained poly The polyaminic acid which is precipitated in the solution is obtained by the imidization reaction at a temperature of 20 to 150 C in the same manner as described above, and is sprayed at a temperature of 20 to 150 C. In the above-mentioned brewing imidization reaction, a dehydrating agent and The ratio of the dehydration ring-closing catalyst is preferably (U 1 to 1 G (mole ratio). The total amount of the dehydrating agent and the dehydration agent is preferably 1.5 to 10 times the molar amount relative to the σ of the Si anhydride contained in the acid component to be used. By adjusting the above: learning = imidization of the dehydrating agent, the amount of the catalyst, the reaction temperature and the reaction time, the degree of imidization can be controlled to obtain a partial polyimine. The known polyimine can be obtained. Separating from the solvent, dissolving it by the following dissolution, and using it as a liquid crystal alignment agent; or using it as a liquid crystal alignment agent without separating the solvent, 'w, and, as described above, the acid component of the present invention The di-acid portion of the diacid can be replaced with an organic bile. If the acid component of the second acid is further used to prepare the polymer of the present invention, the acid-poly-copolymer can be used. Two of the total acid components The ratio of the acid &lt; is preferably within a range that does not impair the effects of the present invention, and is preferably 5% or less. #,不平69 200808686 ia, by copolymerizing the above polylysine_polyamine Further, a preferred embodiment of the liquid crystal alignment agent of the present invention described below is a liquid crystal alignment agent containing a composition comprising two or more kinds of polymers. One of the substances is the use of the acid component A1 and the amine component A2, such that their reaction polymer is also referred to as "polyaracine". The upper amine component A2 includes the side chain represented by the above formula (1). Structure - Amine. The other of the above polymers uses the acid component B1 and the amine component = and reacts them (4) _ polymer _ lower _ "poly _ Θ ΰ 〇 〇 〇 。 。 。 The shipyard Wei Linyi is a poly-acid or a poly-amine. The acid-forming bismuth and acid-forming fines of the present invention include one or two or two, but among them, a portion of the tetracarboxylic dianhydride can be placed. to make-_. Among them, the ratio of diWei is preferably 10 mol% or less with respect to the total acid component. The amine component Α2 and the amine component 32 of the present invention include one or two or more diamines, but wherein a part of the diamine may be substituted with a monoamine. And relative to the total ship, the monoamine of the transfer of the county to hold a special material ^, the poly-[the biological includes: 丨) poly-acid of all amino σ thiol dehydration ring closure reaction obtained by polyimine; 2 __ Partial dehydration ring closure reaction _ partial polySI imine; 3) Replace the sulphuric acid anhydride containing 70 200808686 in the acid component with the organic dicarboxylic acid, and react to obtain $Wurnic acid · Poly-mesh; and 4) a polyamicimide obtained by subjecting a part or all of the above poly-amino acid-poly-laid copolymer to a dehydration ring-closing reaction. It should be noted that the composition of the present invention may have a heteroamic acid a and B, and may further contain a polymer other than poly-acid #3. As described above, the poly-acid A of the present invention reacts with an acid component and an amine component to transmit a polymer, and the amine component A2 includes a diamine. The amine component A2 may contain two kinds of two or more kinds represented by the formula (1). The total 3 of the diamines represented by the formula (1) is a total of (9) mole % of the total composition. According to the == synthetic polymer of the present invention, the liquid crystal alignment agent containing the above polymer is oriented to the film to impart a good voltage holding ratio to the liquid crystal display device using the same and a residual DC reduction effect of the caller. Further, the present invention (four) compound A is a polymer obtained by using four oxime = anhydride as a component A1 to make a fine-grained ～ (linked-private as an amine component A2, and reacting them to obtain a polymer The amine component A2 includes one or two or more kinds of diamines, but includes the diamines represented by the above formulas (m) to (IX). The two represented by the above formulas (III) to (IX) are used. The amine component of the amine is a synthetic polymer, and the liquid crystal alignment film formed using the liquid crystal alignment agent containing the polymer can impart a good voltage reduction rate and a residual residual enthalpy reduction effect to the liquid crystal display device used. 71 200808686 Amine component A2 is based on Further, the other diamine may be further contained, and examples of the other diamines include diamines or oxime diamines represented by the above formulas (X) to (XIV), and decane-based diamines. In the above, the molar ratio of the diamine represented by the above formulas (III) to (IX) may be based on the structure of the diamine represented by the above-mentioned general formulae (III) to (IX) and the required voltage retention and residual. The DC reduction effect is adjusted, preferably from 1 to 95%, more preferably from 5 to 80%. The polymer B of the present invention may be a polymer obtained by reacting tetrahydro acid dianhydride as the acid component B1 and using at least the diamine represented by the above formulas (III) to (XIV) as the amine component B2. A liquid crystal alignment film formed using a liquid crystal alignment agent containing the above polymer can be used to impart a suitable pretilt angle to a liquid crystal display device using the same. The amine component B2 includes one or Two or more kinds of diamines, but at least including the diamine represented by the above formula (ΠΙ) to (XIV). The amine component B2 may further contain any other diamine, and other diamines may be enumerated. : an oxime diamine, a decane-based diamine, etc. In the amine component B2, the molar ratio of the diamine represented by the general formula (in) to (χ ν) is adjusted according to a desired pretilt angle, preferably It is 1 to 100%, more preferably 5 to 8 Å/〇. By combining (mixing) the polymer A and the polymer B of the present invention, it is possible to impart satisfactoryness as a component of the liquid crystal alignment agent of the present invention. Characteristics of B2 ^ body, about aggregation Starting amine component types and combinations of diamine and amine A2 by appropriately selecting components contained can be assigned 72 200 808 686

^β ^ Λ JL The liquid crystal alignment film formed using the composition of the present invention has better electrical tightness, opacity and significant residual DC reduction effect and a uniform pretilt angle. The weight average molecular weight and molecular weight distribution of the polyamic acid A and the polyamic acid B of the present invention are determined by the above-described polymer phase of the present invention. The preferred weight average molecular weight and polydispersity are also the same as those of the above-described polymer of the present invention.

The polymer A and the polymer b of the present invention can be produced by the same method as the above-mentioned polymer of the present invention. X < 3 · Liquid crystal alignment agent of the present invention> The liquid crystal alignment agent of the present invention includes the above-described polymer of the present invention or the combination of the above polymer A and polymer B, and a solvent, and may further include a usual liquid crystal alignment agent. Various additives contained in the product. It should be noted that the composition of the polymer A and the polymer B of the present invention is prepared by mixing the above polymer A and polymer B. The weight ratio of the polymer A to the polymer B to be mixed is preferably a/B = 99/1 to 50/50, more preferably A/B = 95/5 to 80/20. The reset ratio of the polymer a and the polymer β is in the above range in order to control the voltage holding ratio, residual DC, and a suitable pretilt angle. The above weight ratio can be appropriately adjusted according to the required pretilt angle. As long as the ratio of the polymer B is increased, the pretilt angle can be increased. The content of the polymer in the liquid crystal alignment agent of the present invention can be appropriately selected depending on the coating method of applying the liquid crystal alignment agent onto the substrate. For example, a printer (including a lithographic printing or an inkjet printer) used in a manufacturing process of a general liquid crystal display device. Hereinafter, it may be simply referred to as a "printer". Among the liquid crystal alignment agents used, a uniform and flat film is printed. , Polymerization 73 200808686 J jpi The content of the cockroach is preferably 4 0.5 to 3 〇 wt%, more %, the root wei ❺ contains the surface liquid 35 with (4) = relationship to be appropriately adjusted. Between the &lt;&gt;&gt; (described later), the use of the above-mentioned liquid crystal alignment agent for the production of the liquid crystal display device

In the diamine component, the diammonium ratio represented by the above formula (1) and the erbium ratio in the 〇CB mode are preferably 2 in the above-described Mohr_VA mode of TN. ~1. . . / == Like, ~100%. Υυ/. More preferably, the solvent used in the present invention employs a solvent such as a white imine and a lysine, a soluble polypolar organic solvent, and 2) by a reputation = non-beneficial purpose. Further, the surface tension to improve the coating property and the like are as follows: 1) For example, N-methyl is a good solvent with respect to polyglycolic acid or an aprotic polar organic solvent. · 2_ scale ^ for aprotic polar organic solvent) endo-amine, N-methyl propylamine, 3, dimethyl saponin, N-methylhexan, n-dithiol Indoleamine, N, N/_methylacetamide, dimethyl sulfoxide, &gt; butyrolactone, and pucanolide. Ethyl amide, diethyl ethanoamine, bismuth, dimethyl sulphonate are selected: N-methyl-2 "pyrrolidine" butyrolactone, γ-valerol and the like. 74 200808686 2) A solvent (hereinafter referred to as another solvent) for the purpose of improving the coating property by changing the surface tension, for example, an alkyl lactate, a 3-mercapto-3-3-methylbutanol, a tetralin Ethylene glycol monoalkyl ether such as isophorol, ethylene glycol monobutyl bond, etc., diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkane = or thioglycolate, a dipropylene glycol monoalkyl group such as diethylene glycol, a propylene glycol monobutyl ketone, a propylene glycol monoalkyl ether, a malonic acid monoethyl ester, a dipropylene glycol malonate, a dipropylene glycol monomethyl ether, and the like; The vinegar compound of the above-mentioned acetic acid g is preferably: ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc. Nonprotic polarities The type and ratio of the solvent and other solvents can be appropriately set in consideration of printability, coatability, solubility, storage stability, and the like of the liquid crystal alignment agent. The polar solubility solubility and storage stability are relatively excellent; while other solvents have a tendency to be excellent in brushability and coating properties. ^ As described above, the liquid crystal alignment agent of the present invention may contain various additives. The polymer compound S low molecular compound other than the polymer can be selected and used according to the purpose. 3 For example, a polymer compound soluble in an organic solvent can be used as an additive, and the formed compound can be controlled by adding the above two molecules. The electrical properties or the alignment properties of the alignment =. Examples of the above polymer compound include polyamine, polyurethane, polyurea, polyethylation, polyepoxide, poly-g-modified polyurethane, and rhodium-modified poly-self As an example of a low molecular compound additive, when it is desired to improve the birthday π ', it is possible to use a surfactant that follows the purpose involved; 2) when it is necessary to provide an antistatic (4); When it is desired to improve the enthalpy or rub resistance, it can be made into a silk, a forest, or a compound containing an epoxy group; When lining is imidized, it can make Lai Ya's age agent. Low, dish ^ 〗 〖Shi Xi k light mixture examples are: ethylene trimethoxy stone household, vinyl triethoxy stone court, N_ (2 _Amineethyl&gt;3_Aminopropylmethyldimethoxy hydrazine, ^(2-Aminoethyl)_3_aminopropyldecyltrimethoxydecane, amphoteric methoxy sulphur, ammonia Phenyltriethoxy sulphate, m-aminophenyltrimethoxy sulphate, sulphate, succinyldiethoxy sulphate, 3-aminopropyltrimethoxy sulphate, di- 3-aminopropyltriethoxy decane , 3_glycidoxypropyltrimethoxy oxysulfide, 3_glycidyloxypropyl fluorenyl dioxime oxime, oxime, 4·epoxycyclohexyl)ethyltrimethoxywei, 3_gas Propyl f-based ruthenium oxide, 3-chloropropyltrimethoxy-wet, 3-mercaptopropene-propyltrimethyloxyxanthine, 3-propylpropyltrimethoxy-Wei, N_ (1,3_di-f-butylidene acetophenone acesulfame-propylamine, y, bis[Μtrioxetylwei)propylethylenediamine, and the like. Examples of the epoxy compound are: ethylene glycol diglycidyl, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Dihydrate; oil ether, 1,6-hexanediol diglycidyl _, glycerol diglycidyl bond, 22 dibromo neopentyl glycol diglycidyl ether, u, 5,6_tetraglycidyl 2, 4_ 'Hexanediol, N,N,N',N'-tetraglycidyl-m-diphenylene diamine, -bis(NN_ diglycidylaminodecyl)cyclohexane, N,n,n,, n, - tetraglycol, y-4,4'-diaminodiphenylmethane, and the like. &lt;土76 200808686 Examples of the above ruthenium amide catalysts; an aliphatic amine such as propylamine or tributylamine; bis, 1,3-, triethylamine, triphenylaniline, methyl substituted aniline, thiol = Cn , n · 2 bite, methyl take fine, silk replace „ than two, two special =, hydroxy substituted quinoline, isoquinoline, keto i-methyl substituted quinoline, Lin, methyl substituted taste, :Based ==etc. 特别 嗤 。 。 。 。 。 。 。 。 。 。 。 。 。 。 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专- The amount of the sputum coupling agent is usually 10%, preferably 0.1 to 3%, based on the base material, the sputum ratio, the sputum ratio, and the sputum coupling agent.

The amount of the oxygen compound added is genus, preferably dime. The addition amount of the 0.1 醯 imidization catalyst of the total weight of the polymer is usually 0.01^5 ft (equivalent), and the amount of other additives added is usually the total weight of the polymer. 〜30〇/〇, preferably 0.1~1〇%.至里日7 ϋ~ The degree of dot of the liquid crystal alignment agent of the present invention is not the same as the coating method curvature, the type of the polymer (4), the type and ratio of the solvent, and the like, when coated by a printer, liquid crystal Orientation _ K) 〇mPa.S (more preferably 1 〇 8 〇 mPa ♦ If the liquid crystal alignment agent adheres to 5 mPa s, it is difficult to obtain a sufficient film thickness; if the liquid crystal alignment agent S exceeds _ mPa. S, printing When it is not available, it becomes large. When the coating is applied by spin coating, the viscosity of the liquid crystal alignment agent is 5 to 2 〇〇 mPa.s (more preferably 忉200808686 to 100 mPa's). The viscosity of the agent is determined by rotational viscosity measurement, for example

The measurement was carried out using a rotational viscometer (TVE_20L type manufactured by Toki Sangyo Co., Ltd.). (/JHL &lt; 4) Liquid crystal display device of the present invention The liquid crystal display device of the present invention includes: 丨) opposed arrangement a pair of substrates 2, 2) a liquid crystal matching film formed on a surface of each of the pair of substrates facing each other; and 3) a liquid crystal layer sandwiched between the pair of substrates. The liquid crystal alignment film is as described above A liquid crystal alignment film formed by applying the liquid crystal alignment agent of the present invention and heating thereon, wherein the liquid crystal alignment = is preferably from 10 to 300 nm, more preferably from 30 to 100 nm. Further, the liquid crystal alignment film used in the ruthenium mode is preferably used. The substrate is provided with a pair of electrodes having electrodes (for example, a glass plate). The liquid crystal layer sandwiched between the above-mentioned pair of substrates includes a liquid crystal composition. - The medium liquid crystal composition has no special It is also possible to define any composition in which the anisotropy is a positive crystal composition and a negative dielectric anion composition according to the driving mode. The dielectric anisotropy is positive. Examples of liquid crystal compositions are disclosed. Japanese Patent No. 228, Japanese Patent No. 298, 报, 曰本特表平, 5_501735, 曰本特开平8_157828 = Gazette, 曰本特开平8_2过0?虎Bulletin, 曰本特开平^ Side No. 4 bulletin _852驴), Japan Special Kaiping ^ Moving Secret No. (EP806466A1), 曰本特开平8_199168号78378 200808686 (EP722998A1), Japanese Special Kaiping 9_235552, Japan Japanese Laid-Open Patent Publication No. Hei 9-241643 (EP885271A1), Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. 2001-48822, and the like.

The liquid crystal composition used in the VA liquid crystal display device may be various liquid crystal compositions in which the dielectric directions are negative and 11 is negative. Examples of the preferred liquid crystal composition are disclosed in Japanese Patent Publication No. 57_1!4532, Japanese Patent Publication No. 4725, Japanese Patent Publication No. 4, No. 3, No. 3, and No. 3, No. 3, Japan. ^Μ_号公告,日本开平1Q_168453 本特开平10-236989妒公刼D ^ % 日报,曰本特开平^=^八曰/特开平1〇-2_号号号,日本特平平= 3, Japan's special Kaiping 236993 10-237000 bulletin, Japanese Taihao #u bulletin, Japan special opening flat purchase chest fine money, Japan special 10-23707?,,, ί 1〇 · 237035 'Tiger &amp; Japanese Patent Laid-Open No. 10-237076, Bulletin H 37448 (EP967261A1), Japanese Taiping Kaiping _287874, Japanese Special Kaiping 1〇28.i〇-291945 ^ g ^ - Gazette, 曰本特开平^ 〇29581唬 细 细 公报 、 、 、 、 、 、 、 、 、 公报 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 触 触 触 触 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖Or a negative liquid crystal composition may be added after adding one or more kinds of optically active compounds. The liquid crystal display device of the present invention may of course include other members.罟 Φ Example 2 1 In a color display TFT type liquid crystal device using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal, an electrode, a pixel electrode, and the like are formed on a transparent substrate; on the second substrate 2, there are peach w, color matrix, color filter,

A flattening film, a pixel electrode, and the like. Further, in the VA type liquid crystal head display device, particularly in the MVA type liquid crystal display device, the money is referred to as a microscopic projection of a domain on the first through the county plate. It is also possible to form a space control material for adjusting the interval _ gaP between the substrates. The liquid crystal display device of the present invention can be produced by any method, for example, by a method including the following steps: a step of applying a liquid crystal alignment agent onto the two transparent substrates; a step of drying the applied liquid crystal alignment agent; 3) a step of performing a necessary heat treatment for dehydration and ring closure reaction of the dried liquid crystal alignment agent; 4) a step of performing an alignment treatment on the obtained alignment film; and 5) a step of sealing the liquid crystal between the substrates after bonding the two substrates, or a step of laminating the liquid crystal on one of the substrates and bonding the film to the other substrate. In the step of applying the liquid crystal alignment agent, a coating method is generally known as a spin coating method, a printing method, a dip coating method, a dropping method, an ink jet method, or the like. The above method can also be used in the present invention. The drying step and the method of heating 80 200808686 = necessary for performing the dehydration and the ring closure reaction are generally known as a method of adding a baking-infrared material, a method of processing, and a method of performing heat treatment on a hot plate. Wait. The above can be used: The dry process is preferably carried out under conditions in which the solvent can be vaporized by a degree of (5 Torr to 1 Torr.). The heat treatment process is generally carried out at a temperature of about 150 to 300 °C. In the alignment processing, in the 0CB type liquid crystal display device, the liquid crystal is not placed, and the STN liquid crystal display device is subjected to rubbing treatment. in

The VA type liquid crystal display can be rubbed, but it can also be carried out. Then, a binder is applied to one of the substrates, bonded, and the liquid crystal is injected under vacuum. When the dropping injection method is employed, liquid crystal is dropped onto the substrate before bonding, and then laminated with another substrate. The liquid crystal display device of the present invention is produced by curing the adhesive used for bonding by heat or ultraviolet rays. In the liquid crystal display device of the present invention, a polarizing plate (polarizing film), a wavelength plate, a light scattering film, a driving circuit, and the like can be mounted. The liquid crystal alignment film used in the VA type liquid crystal display device preferably provides a pretilt angle of about 8 〜 to 90 Å; and the liquid crystal alignment film used in the OCB type liquid crystal display device preferably provides 5 to 45. Left and right, preferably 7 to 2 inches. The right and left pretilt angles; the liquid crystal alignment film used in the TN type liquid crystal display device or the stn type liquid crystal display device is preferably provided in the range of 3 to 15. Left and right pretilt angles. As described above, the pretilt angle is mainly adjusted by adjusting the type of the diamine having a side chain structure of the present invention and the molar ratio of the diamine having a side chain structure in the amine component of the present invention. 2) The weight ratio of polyamic acid A and B in the composition of the present invention is achieved. 81 200808686 The liquid crystal display device of the present invention has a feature that the voltage holding ratio is high and the residual DC is low. In this case, the liquid crystal alignment film of the liquid crystal display device of the present invention is formed by using an amine component including the diamine represented by the above formula (I) and reacting it to obtain a polymer, which is aligned by a liquid crystal containing the above polymer. Formed by the agent. The above case is also explained in the following embodiments. EXAMPLES Hereinafter, the present invention will be described by way of examples, but the invention should not be construed as limited. It should be noted that the names of the four-rebel dianhydride, the diamine, and the solvent used in the examples are sometimes indicated by the following short symbols. [Tetracarboxylic dianhydride] Pyromellitic dianhydride {Formula(1)} : PMDA Cyclobutane tetraphthalic acid dianhydride {Formula(14)} ·· CBDA [Diamine]

4,4'-diaminodiphenylmethane {Formula/11-1)} : DDM 4,4'-diaminodiphenylethane {Formula (乂11-7)} : DDET 1,1-Double (4-Aminophenyl)-4-pentyldicyclohexylmethylpyrazine (I-8)/R7=C5Hn} : 5HHDDM ^

1,1-bis(4-aminophenyl)-4-dodecancyclohexylcarbazide {Formula (I_1)/R7=C12H25} : 12HDDM 1,1-bis(4-aminophenyl)-4-十六烧基基基甲完完丨g (I_4)/R8=C16H33} : 16PDDM work 5-[4-(4_n-pentylcyclohexyl)cyclohexyl]phenylhydrazino],3_diaminobenzene { S(X-5)/R13=C5H„} : 5ChCh soil [solvent] 82 200808686 N-mercapto-2-pyrrolidone: NMP butyl cellulolytic (ethylene glycol monobutyl ether): BC &lt;1·diamine Synthesis&gt; [Synthesis of Diamine] (Example 1)

10 g (38 mmol) of 4-(4-pentylcyclohexyl)cyclohexanecarboxaldehyde, 12 g (92 min 〇p aniline hydrochloride and llg (114 mmol)) synthesized according to the method described in 曰本特特 2002-12119〇 The mixture of aniline was stirred at 16 (rc) for 12 hours. After cooling, the reaction solution was poured into a 2% aqueous sodium hydroxide solution (300 ml) and extracted with dichloromethane (3 mL). After washing twice with pure water (300 ml), anhydrous magnesium sulfate was added and dried. After the magnesium sulfate was passed through, the solvent was removed under reduced pressure. Column chromatography (dichloromethane: decyl alcohol &gt; 2 〇: 1 The separation and purification were carried out, and the obtained crude crystals were recrystallized from ethanol to obtain U-bis(4-aminophenyl)succinimide (4-('-pentylcyclohexyl)cyclohexyl)methanone (5HHDDM). Yield: 24 〇 / 〇. Melting point: 182.6 - 185.8 ° C 1H-NMR: 0-81-1-29 (m &gt; 2lH) &gt; 1-63-1 · 66 (m &gt; 9H) ^ 1.83-l-89 (m.iH)&gt;3.21 (d. J=10.55, 1H), 3.48 (br.S, 4H), 6.56

-6.58 (m, 4H), 6.99~7.9Ri L (25 (m, 4H) (Cheng 2) Use 34g (121mmol) according to the day of the day, the day, the day, the scorpion; the test opening 2002-121190 The 4-didecylcyclohexanone-furfural synthesized by the method described in the above was reacted and post-treated in the same manner as in the above Synthesis Example 1. The color field of the column was used. ; 83 200808686 10. 1) Separation and purification, the obtained crude crystals from the a a Μ). Yield I 7jg, yield 14%. Melting point: 1〇4.6~1〇7.3. (3 1H-NMR: 0 · 86-1 · 26 (m&gt; 2 7H) Ί · 58-1 66(m^7H) &gt;1.92(d^J=l〇.〇〇.1H).2.

22 (d, J = 10.00, lH), 3.60 (br. S, 4H), 6.5 〇 ~~6·66 (m, 4H), 7. 11-7.2 3 (m, 4H) (Example 3) The reaction and post treatment were carried out in the same manner as in the above-mentioned Synthesis Example 1 using 28 g (85 mmol) of 4-(n-hexadecyl)benzaldehyde synthesized according to the method described in JP-A-2002-121190. Separation and purification by column chromatography (toluene:methanol di 10 1 )', the obtained crude crystals were recrystallized twice from ethanol to give bis(4-aminophenyl)-(4-(n-hexadecyl)phenyl ) methane (16PDDM). The yield was 17 g and the yield was 41%. a few

Melting point: 90.9 - 92.8 °C 1H-NMR; 〇·88 (ΐ, 3Η, : ί=6·95), 1·25 ～ 1 · 30 (m, 2 8 Η), 2·55 (ΐ, 2Η, 】 = 8·15), 3·56 (br·s, 4H), 5·30 (s, 1H), 6 · 60 (d, 4H, J=8.30), 6.89 (d, 4H, J=8.20), 6· 94-7·26 (m, 4H) · &lt;2. Synthesis of poly-proline acid &gt; [Synthesis of poly-tylamic acid] (Example 4) 84 200808686 A thermometer, a stirrer, and a raw material inlet are provided. A 100 ml four-necked flask of a nitrogen inlet was charged with 666 g of 12HDDM, 0.258 g of DDET, and 15 g of dehydrated NMP, and stirred and dissolved under a dry nitrogen stream. Next, 471.471g of PMDA and 〇.l〇6g of CBDA were added and allowed to react at room temperature for 3 hours. In the reaction, when the reaction temperature rises, the reaction temperature is controlled to be less than about 70 ° C to carry out the reaction. To the resulting solution, 8.5 g of BC was added to synthesize a polymer solution (PA1) having a concentration of 6% by weight. The viscosity of the obtained PA1 was 19 mPa·s. The resulting polymer had a weight average molecular weight of 43,000. Wherein, the weight average molecular weight of the polymer is determined as follows: • The obtained polymer is diluted with a diluent «acid/DMF = 0.6/100: weight ratio) so that the polymer concentration is about i% by weight 'Using a chromatographic paper bundle (ch face) Atopack) C_R7A (manufactured by Shimadzu Corporation) was measured by a GPC method using the above-mentioned diluent as a developing solvent, and was obtained by polystyrene conversion. In addition, the column was measured using GF_7Hq (manufactured by Showa Denko Co., Ltd.) under the conditions of a column temperature of 50 ° C and a flow rate of 0.6 ml/min. Example 5, Example 6, Example 7, Synthesis Example i, Synthesis Example 2 A polymer was synthesized according to Example 4 except that the composition of the tetracarboxylic dianhydride, the diamine, and the solvent was changed in the proportions shown in Table 1. Solution (pA2, pA3 &amp; ^, ^, ^. Including the examples 彳 in 'Results summarized in the table! ^ In addition 'the synthesis of PA1, PA2, PA3 and pM each polymer = pure water again' will be The infrared absorption spectra of the samples obtained by heating and drying under vacuum are summarized in Fig. 2 and Fig. 34, respectively. Round 85 200808686

&lt;3. Production of liquid crystal display device&gt; (1) Preparation of ΤΝ-type liquid crystal display device A liquid ruthenium alignment agent was applied onto two glass substrates having ITO electrodes using a rotator to form a film thickness of 7 〇 nm. membrane. After coating, it was 8 〇. The underarm was heated and dried for about 5 minutes, and then heat-treated at 22 Torr: for 1 minute to form a liquid crystal alignment film. In the friction processing device manufactured by the company's rice cooker gage, the amount of the pile in the rubbing cloth (hair length 1.9 mm·rayon) is 〇4〇mm, and the moving speed of the stage is 6〇mm/ Under the condition of sec and light cylinder rotation speed of $1, the glass substrate on which one of the liquid crystal alignment films was formed was rubbed. For the other glass substrate, the rubbing direction was changed by 9 turns. The rubbing treatment was carried out in the same manner as perpendicular to the other direction. The substrate was ultrasonically washed in ultrapure water for 5 minutes, and then dried in a container at 12 Torr for 30 minutes. Spread a gap of 7 inches on one of the glass substrates ((4) 86 200808686. The faces with the alignment film formed on the inner side are arranged to face each other so that the rubbing direction is perpendicular, and then sealed with an epoxy curing agent to make a 9 μm interval. Rotating box (twist cel1). The following composition is injected into the box, that is, 5 parts by weight of the optically active substance cholesterol phthalic acid vinegar (g〇lesteric nonanoate) is added to 100 parts by weight of the liquid crystal composition A and homogenized. The composition was sealed with a light curing agent, and then a TN-type liquid crystal display device was produced by heating at a temperature of 11 Torr for 30 minutes. [Example 8] The concentration synthesized in Example 4 was 6 wt% of the polymer solution (PA1) and a polymer solution (PA5) having a concentration of 6% by weight synthesized in Synthesis Example 1 were mixed at a weight ratio of 1/9. The obtained mixture was used with NMp/Bc = 1/1 (weight). The mixed solvent of the ratio was diluted to a concentration of 4% by weight to obtain a liquid crystal alignment agent, and a tn liquid crystal display device was produced by the above-described production method using the obtained liquid crystal alignment agent. (2) A method of fabricating a VA liquid crystal display device using a rotator Two pieces A liquid crystal alignment agent was coated on a glass substrate having an ITO electrode to form a film having a film thickness of 70 nm. After the film was coated, it was dried by heating at 8 Torr for about 5 minutes, and then heat-treated at 22 〇〇c for 4 minutes to form a liquid crystal. Alignment film λ The glass substrate on which the alignment film is formed is ultrasonically washed in ultrapure water for 5 minutes, and then dried in an oven at 12 rc for 3 minutes. A 4 μm spacer is spread on one of the glass substrates to The surface on which the alignment film was formed was disposed on the inner side so that the rubbing direction was anti-parallel, and the film was sealed with an epoxy curing agent after 87 200808686 to form a box having a spacing of 4 μm. The following liquid crystal composition was injected into the box, and the light was used. The curing agent sealed the injection port, and then heat-treated at 110 ° C for 30 minutes to prepare a VA liquid crystal display device. [Example 9] A polymer solution (PA2) having a concentration of 6 wt% synthesized in Example 5 was prepared. The polymer solution (PA5) having a concentration of 6% by weight synthesized in Synthesis Example 1 was mixed at a weight ratio of 1/9. The resulting mixture was diluted to a concentration of 4 with a mixed solvent of NMP/BC = 1/1 (weight ratio). % by weight as a liquid crystal alignment agent. A VA liquid crystal display device was produced by the above-described production method using the above liquid crystal alignment agent. [Example 10] A polymer solution (PA3) having a concentration of 6 wt%/〇 synthesized in Example 6 and synthesized in Synthesis Example 1 were synthesized. A polymer solution (PA5) having a concentration of 6% by weight was mixed at a weight ratio of 1/9, and the resulting mixture was diluted with a mixed solvent of NMP/BC = (weight ratio) to a concentration of 4% by weight as a liquid crystal alignment agent. A liquid crystal alignment agent was used to produce a VA liquid crystal display device by the above-described production method. [Example 11] The polymer solution (PA4) having a concentration of 6 wt% synthesized in Example 7 and the concentration synthesized in Synthesis Example 1 were 6 wt. °/. The polymer solution (PA5) was mixed at a weight ratio of 1/9. The resulting mixture was diluted with a mixed solvent of NMP/BC = 18 (by weight) to a concentration of 4 耋 / ° as a liquid crystal alignment agent. A VA liquid crystal display device was produced by the above-described production method using the above liquid crystal alignment agent. 88 200808686 [Comparative Example 1] A polymer solution (PA6) having a concentration of 6% by weight synthesized in Synthesis Example 2 and a polymer solution (PA5) having a concentration of 6% by weight synthesized in Synthesis Example 1 were subjected to a weight ratio of 1/1. 9 mixed. The resulting mixture was diluted with a mixed solvent of NMP/BC = 1/1 (weight ratio) to a concentration of 4% by weight as a liquid crystal alignment agent. The above liquid crystal alignment type liquid crystal display device was used.

Liquid crystal composition A n_C3Hr^K^)^QK〇CF3 ~^^HDCF3

Manufactured by the above manufacturing method VA 7 wt% 7 wt% 9 wt% 10 wt% 10 wt% 12 wt% 11 wt% 5.5 wt% 89 200808686 〇5η" n-C3H7

n-CsH"·Liquid Crystal Composition B 4.5 wt% 9 wt% 15 wt% c3h7-^_ TV r -0-CH3 5wt% C5Hir~{^ X &gt; One c3h7 7wt% C3H7-K: &gt; C4H9 8wt% C3H7-/ C5H11 8wt% C3H7 C5H11 c2h5 C3H7 C3H7

〇-C2H5 12wt% 14wt% 14wt% 10wt% 10wt% R F C5H11

O - C2H5 12wt% 90 200808686 &lt;4. Evaluation of electrical characteristics&gt; [Test Examples 1 to 5]

V The evaluation of the electrical characteristics and the pretilt angle of the liquid crystal display devices produced in Examples 8 to 11 and Comparative Example 1 was carried out. The electric property evaluation specifically refers to 1) measuring the voltage holding ratio; 2) measuring the residual dc by the dielectric absorption method. The measurements were carried out as follows. 1) Measurement of voltage holding ratio The voltage holding ratio was measured using a 6254 liquid crystal physical property evaluation device manufactured by Dongyang Technica. The measurement conditions were: strobe pulse width 6 〇哗, frequency 0·3 Ηζ, and Bonan ± 5 V' measurement temperature was 60 °C. The larger the value, the better the electrical characteristics. 2) Measurement of residual dc by dielectric absorption method Residual DC was measured by a dielectric absorption method using a 6254 liquid crystal physical property evaluation apparatus manufactured by Toyo Technica. The measurement conditions were as follows: two DC voltages were applied to the cartridge, the application time was 】hours, and then 丨 seconds were terminated, and the potential difference was observed for 30 minutes. The table shows the maximum residual D c and the minimum residue &amp; (: The smaller the value, the better the electrical characteristics. 3) Measurement of the pretilt angle For the test example 1, the central fine mechanism 〇MS-CA3 type liquid enthalpy evaluation was used, and the apparatus was measured. With respect to Test Examples 2, 3, and 4 (Comparative Example), the &amp; screaming (four) transmission curve was obtained under crossed Nicols (_Nied), and the pretilt angle was calculated from the value of the sample rotation angle at which the transmittance was extremely small. 91 200808686 Table 2 Liquid crystal display skirt (complex solution: weight ratio) Voltage holding ratio (%) Determined by dielectric absorption method. Residual DC (V) Pretilt angle (.) Maximum yj, Test Example 1 Example Example 8 __(ΡΑ1/ΡΑ5 : 1/9) 93.8 0.47 4 0.12 12.4

As shown in Table 2, the voltage holding ratio was about 93 8% in the test example, about 92.3% in Test Example 2, and about 92.1 〇/〇 in Test Example 3. On the other hand, compared with Test Example 5 (Comparative Example), the residual DC was obtained in two steps. In terms of pretilt angle, test case! The value of the pretilt angle is suitable for the tilting crystal display device; the test example 2, the test example 3, and the test example 4 are preliminarily suitable for the VA type liquid crystal display device. Material, = as VA combined with 〇CB type liquid crystal display device. In Test Example 4, the voltage retention rate of the Πi liquid helium display device was slightly lower. One = PA6 having the same side chain as PA4 was subjected to the same test. (43⁄4 Example 5) It was found that the liquid of PA4 was used. The rate is high, and the residual DC is also significantly inhibited. The scoring solution can be used for the formation of the liquid crystal alignment enthalpy of the liquid crystal display device of each of the 2008 200808686 driving modes. In any of the liquid crystal display devices of the display driving method, the electric power is south and the residual DC is suppressed. The above description is only a preferred embodiment of the present invention, and the present invention has been described in the preferred embodiment. The technical person of this profession is in the sparseness of the hair program.

t=construction of the technical content to make some changes or modifications to the equivalent: the embodiment of the invention, but without any deviation from the technology of the present invention, any modification or specialization made to the above embodiment according to the technical essence of the present invention The same changes and modifications are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the external absorption spectrum of a polymer obtained by synthesizing chalk PA1 in Example 4 in an ultrapure re-draining chamber, which was filtered and dried under vacuum. Fig. 2 is a sample 1 external absorption spectrum obtained by reprecipitating a polymer of PA2 synthesized in Example 5 in ultrapure water, filtering it, and heating and drying under vacuum. %0: Fig. 3 is an infrared absorption spectrum of a sample obtained by reprecipitating the polymer of PA3 synthesized in Example 6 in ultrapure water, filtering it, and heating and drying under vacuum. Figure 4 is a graph showing the polymer of PA4 synthesized in Example 7 in ultrapure water.

The infrared absorption spectrum of the sample obtained by reprecipitation, which was filtered and dried by heating under vacuum. vX 93 200808686 [Main component symbol description] None

Claims (1)

200808686 X. Patent application scope: Show side chain link 1 · A monoamine characterized by: a general formula (diamine: 乂 R1 In the formula (1), A1 represents a single bond, -〇-, -COO, -CO-, -CONH or -(CH2)m-'m is an integer of 1 to 6; R is a group represented by the following formula (Π-A) a group represented by a group or the following formula (4): (Π -B) In the formula (π-A), A and A3 independently represent a single bond, _〇_, _c〇〇---〇ca&gt;, -CONH·, -CH=CH- or the number of carbon atoms is The sub-alkyl group of Bu 12; R and R respectively represent _H, _j7 or _ch3; 裱S represents 1,4_phenylene, anthracene, 4_cyclohexylene, anthracene, 3_dioxane_2 , 5_ diyl, t-t-2, 5-diyl, π ratio bite_2, 5_diyl, T.·5-diyl, Chuadiyl or En-9,10-diyl; R4 represents, carbon atom The number is 丨, the base, the number of carbon atoms is! 95 200808686 'i--- ~30 fluoroalkyl, _〇CH2F, -〇CHF2 or -〇CF3; a and b respectively represent integers of q~4; c, d and e respectively represent 〇~3 An integer; when e is 2 or 3, the plurality of rings S may be the same group or different groups; f and g respectively represent an integer of 〇~2, and c+d+egi; In Π-B), A and A3 independently represent a single bond, _〇-, -C〇〇_, seven c〇_, -CONH-, -CH=CH- or an alkylene group having a carbon number; R2 represents -H, -F or _CH3; R5 independently represents -Η or -CH3; r6 represents _H, and the number of carbon atoms is 1. 〜2〇 of an alkyl group or a carbon atom having a number of 2^20; '' a and b respectively represent an integer of 〇~4; c and d each independently represent an integer of 0 to 3; e is 〇~2 Integer; Jade T table is not burnt or ring thin. 2. The diamine as described in claim 5, wherein in the above, the single bond is a group represented by the following formula (II_A); (Π-A) In the formula (Π-A), A2, A3, R2, R3, R4, and ring have the same meanings. f and g3. The diamine according to claim 2, wherein in the above formula (II-Α), Α2 and Α3 independently represent a single bond, _〇_, &lt;〇〇_, _QeQ_ 96 200808686 Or a pyridylene group having a carbon number of 1 to 12; a ring S represents a 1,4-phenylene group or a 1,4-cyclohexylene group; and R4 represents a -F, an alkyl group having 1 to 30 carbon atoms, 〇CH2F, -〇CHF2 or -OCF3; a and b respectively represent 〇 or 1; c, d and e respectively represent 〇 or 1; f and g are 0, and c+d+ e-1. 4. The diamine according to claim 3, wherein the diamine is a diamine represented by the following formula (I-1), (1) 8) or (M): R8 (ΙΊ) h2n^&gt;-ch- &lt;^nh2 h2n-〇~ch^Q^NH2 (1-8) (1-4) wherein R7 and R8 represent an alkyl group having 1 to 30 carbon atoms. 5. The polymer of the present invention, characterized in that the polymer is a tetracarboxylic dianhydride as an acid component and a diamine having a side chain structure as described in any one of claims 1 to 4 as an amine component. And get them by reaction. 6. The polymer according to claim 5, wherein the tetracarboxylic dianhydride comprises any one of an aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic acid diterpene tetrazoic acid dianhydride. Or two. 7. The polymer according to claim 6, wherein the bismuth-tetracarboxylic dianhydride is a group selected from the group consisting of the following structural formulae (1), (2), (5), (6) and: - or more than one kind; the fat is swayed or sin = 97 200808686 The cyclic tetracarboxylic dianhydride is one or more selected from the group consisting of the following structural formulae (14) to (29) and (60) , 98 200808686 8. The polymer according to claim 7, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the above structural formula (1); the aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic acid The dianhydride is a compound represented by the above structural formula (14). 9. The polymer according to any one of claims 5 to 8, wherein the amine component further comprises a group consisting of diamines selected from the group consisting of the following general formulae (III) to (XIV); One or more; H2N-A4-NH2 (III) h2n (IV) nh2 (V) 〇-x-C&gt; h2n^f N~^nh2 (VI) (VII) (VIII) In the formula (III), 99 200808686 A4 represents -(CH2)m_, wherein m is an integer of 1 to 6; in the formulae (IV) to (IX), X represents an early bond, 0-, -S_S-, - S〇2-, -CO-, -CONH_, NHCO-, -C(CH3)2-, -C(CF3)2-, -(CH2)m-, 0-(〇!'-0·, -S -(CH2)m_S-, where m is an integer from i to 6; Y independently represents a single bond, -Ο, -S-, -CO-, _c(ch3)2-, -C(CF3)2- or carbon An alkylene group having an atomic number of 1 to 3; a hydrogen bonded to a cyclohexane ring or a benzene ring may be substituted by -F, -CH3, -OH, COOH, -S03H, _P〇3h2; and, in the formula (VI) The hydrogen bonded to the benzene ring can be substituted by a benzyl group; R1 In the formula (X), A represents a single bond, -〇_, .COO-, -0C0-, -CO-, _CONH~ or -(CH2)m- 'wherein in is an integer from 1 to 6; R1 represents a steroid a group of a skeleton, a group represented by the following formula (11); or when the positional relationship of two amino groups bonded to a benzene ring is relative, R1 represents an alkyl group having 1 to 30 carbon atoms; or when the above positional relationship is When it is phase-to-phase, R1 represents an alkyl group or a phenyl group having a carbon number of 丨~sun; in the above-mentioned alkyl group, 'arbitrary _CH2_ may be -CF2_, -CHF_, _〇_, -CH=CH- or -CeC - Substitution, but the above _〇 is discontinuous; _CH3 may be substituted by -CH2F, -CHF2 or _〇?3; the hydrogen bonded to the carbon forming the above phenyl ring may be independently -F, 100 200808686 -CH3, _OCH3, - 〇CH2F, -〇CHF2 4_〇CF3 are substituted; - turn (R3)g^ c -(-a34-1 Jb d Ki&gt;i k4 (Π) e where (A) and A3 independently represent single bonds , #,_c〇〇_,, -CONH-, -CH=CH- or an alkylene group having a carbon number; R2 and R3 are each independently represented, _F or -CH3; ring S represents fluorene-phenylene, anthracene , 4_cyclohexylene, dioxane-2,5_diyl, ♦-2,5_2 , 吼, _2,5-diyl, naphthalenediyl, bismuth-2,diyl or fluoren-9,10-diyl; ', R4 represents f, -F, an alkane having 1 to 30 carbon atoms a group I, a carbon atom having a carbon number of 1 to 3 Å, an alkoxy group having a carbon number of fluorene, _〇CH2F, and -OCHF2 4_〇CF3; a and b each independently represent an integer of ο 4 (4) and e respectively represent an integer of 0 to 3; when e is 2 or 3, a plurality of rings S may be the same group or different groups; hearts f and g respectively represent 〇~2 Integer, and c+d+ e ^ 1 ; 101 200808686 In the formulae (XI) to (XII), R5 independently represents or -CH3, and R6 independently represents -H or an alkyl group having 1 to 20 carbon atoms or an alkene A5 independently representing a single bond, -CO- or - CH2-; R7 and R8 each independently represent - an anthracene, an alkyl group having 1 to 20 carbon atoms or a phenyl group; In the formula (XIII), R9 represents -Η or an alkyl group having 1 to 20 carbon atoms, and any -CH2_ of the alkyl group having 2 to 20 carbon atoms in the above alkyl group may be _0-, _CH=CH - or -CeC-substitution, but the above -0_discontinuous; A6 independently represents -0- or an alkylene group having 1 to 6 carbon atoms; 102 200808686 A7 represents a single bond or a carbon number of 1 to 3 An alkylene group; a ring U represents a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1; in the formula (XIV), R1 () represents an alkyl group having 6 to 22 carbon atoms; R11 represents -H or an alkyl group having 1 to 22 carbon atoms; and A6 each independently represents -0- or an alkylene group having 1 to 6 carbon atoms. The polymer according to claim 9, wherein the amine component is selected from the group consisting of the following general formulae (VI_1) to (VI-5), (VI-14) to (VI-16), and formula (VII). -1)~(VII-15), formula (VII-26), formula (VII-27), formula (VII-31), formula (VIII-1), formula (VIII-2), formula (VIII-6) And a group of diamines represented by the formulae (IX-1) to (IX-5) or more than ^ Called H2N-QtNH2 (V 1-1) (V 1-2) 103 200808686 11. The polymer of claim 10, wherein the amine component is selected from the group consisting of the above formula (VI-1), (VI_2), (VII·1) to (VII-12), and (IX- 2) One or more of the groups consisting of the diamines indicated. 104 200808686 A liquid crystal alignment agent which comprises a polymer obtained by using a diamine having a side chain structure as described below; R1 In the formula (I), A1 represents a single bond, -0-, &lt;00-go (CH2)m_, and ❿ is an integer of 1 to $; R is a group represented by the following formula (Π-A) or the following formula ( Π-Β) indicates the group • OCO-, -CO· CONH- (Π-Β) In the formula (Π-A), Α2 and Α3 independently represent a single bond, _〇_, _c〇〇..._〇c〇/, •CON^i·, _CH=CH_ or the number of carbon atoms Is an alkylene group of i~12; R2 and R3 are independently represented by -F or -CH3; 裱S represents ι,4-phenylene, 1, cyclohexylene, fluorene-2,5-di Base, mouth-tight t2,5-diyl, H2,5-diyl, naphthalene-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl; R4 represents -OH, ·Η, - F, an alkyl group having a carbon number of 丨~刈, a fluoroalkyl group having 1 to 30 carbon atoms, an alkoxy group having a carbon number of 丨~刈, 105 200808686 CN, -OCH2F, -〇CHF2 or - 〇CF3; a and b respectively represent integers of 〇~4; c, d and e respectively represent integers of 〇~3; when e is 2 or 3, multiple rings S may be the same group or may be Different groups; f and g respectively represent an integer of 〇~2, and c+d+e-1; in the formula (Π-B), -0-, _COO_, -〇c〇_, 1~12 An alkylene group; the number of alkyl or carbon atoms is 2 Α and Α respectively represent a single bond, -CONH-, -CH=CH- or the number of carbon atoms is R2 for _H, _F or _ch3; R5 independently represents -Η or -CH3; R6 represents -Η, carbon atom The number is a thin base of ~20; a and b respectively represent an integer of 〇~4; 匕 and d are independent of the table * 整数~3 integers; e is an integer of 〇~2; 裱T represents cyclohexane or cyclohexane Alkene. The liquid crystal alignment agent according to claim 12, wherein the above-mentioned general formula (I) has a side chain έ 槿 — j 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , Αι is a single bond, and Rl is a group represented by the following formula (Π-A): iR2)fl Ten A2t c ' (f%) t〇J 十3V d 'R4 (Π-Α) Formula (Π-A) In the A2, A3, R2, r3, peg KR piers S, a, b, c, d, e, f and meaning the same as above. The liquid crystal alignment agent of claim 13, wherein in the above formula (Π-A) of the diamine having a side chain structure represented by the general formula (I), A2 and A3 are each independently Represents a single bond, -0-, -COO-, -OCO- or an alkylene group having 1 to 12 carbon atoms; ring S represents 1,4-phenylene or 1,4-cyclohexylene; R4 represents - OH, -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH2F, -OCHF2 or -OCF3; a and b each independently represent 0 Or 1; c, d and e are independently represented by 0 or 1; f and g are 0, and c + d + e - 1 〇 15. The liquid crystal alignment agent according to claim 14, wherein the formula The diamine having a side chain structure represented by (I) is a diamine represented by the following formula (1-1), (1-8) or (1-4): In the formula, R7 and R8 represent an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30:): a complete oxy group. The liquid crystal alignment agent according to any one of claims 12 to 15, wherein the polymer is a polymer obtained by using tetracarboxylic dianhydride as an acid component. The liquid crystal alignment agent according to claim 16, wherein the tetraphthalic acid dianhydride comprises an aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride. Any one or two of them. =I8·If the liquid crystal alignment agent described in claim 17 of the patent application, the bean four-in-one is selected from the following structural formulas (1), (2), (5) Γ (6) anhydride or alicyclic acid reading The type or group of the group consisting of the four sharps is I ^ 冓 (14) ~ (10) and (60) (1 8) 〇 0 (2 0) (2 1) 108 200808686 The liquid crystal alignment agent according to claim 18, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the above structural formula (1); the aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic acid The acid dianhydride is a compound represented by the above structural formula (14). The liquid crystal alignment agent according to any one of claims 12 to 15, wherein the polymer further comprises a group consisting of diamines selected from the group consisting of the following general formulae (III) to (XIV); One or more polymers obtained; 109 200808686 H2N—A4—NH2 (III) a h2n N^nh2 In the formula (in), A4 represents -(CH2)m-, wherein m is an integer of 1 to 6; in the formulae (IV) to (IX), X represents an early bond, 0_, -S,, -S_S_, _S〇2_, -CO,, -CONH_, -NHCO-, -C(CH3)2-, -C(CF3)2-, -(CH2)m-, -CKCH2)m-0-, -S-( CH2)mS·, where m is an integer from 1 to 6; Y independently represents a single bond, -Ο-, _S-, _CO_, -C(CH3)2-, -C(CF3)2_ or the number of carbon atoms is a sub-alkyl group of 1 to 3; a hydrogen bonded to a cyclohexane ring or a benzene ring may be substituted by -F, -CH3, -OH, -COOH, _S03H, -Ρ03Η2; and, on the benzene ring in the formula (VI) The bound hydrogen can be substituted by a benzyl group; 110 200808686 (X) H2N NH2 in formula (X), One (I丄丄2^m—~ I丄上丄@ 1 m— The whole owe of the 丨山丨句 i~6; When the positional relationship of the two amino groups bonded to the benzene ring is relative, r1 represents a filament having 1 to 30 carbon atoms; or when the above positional relationship is between phases, R1 represents an alkyl group having a carbon number of 丨~Deng Or phenyl; 'any -CH2_ in the above-mentioned alkyl group can be replaced by -CF2-, -CHF-, -〇·, _(^=(^_ or _(3 = (:_), but the above is not continuous ;-(::113 may be substituted by -CH2F, -CHF2 or _CF3; the hydrogen bonded to the carbon forming the above-mentioned present ring may be independently replaced by -CH3, -OCH3, -OCH2F, -〇CHF2 or -〇CF3 ; In the formula (II), A and A3 each independently represent a single bond, _〇_, _c〇q_, -OCO_, -CONH-, -CH=CH- or an alkylene group having a carbon number of 12; R2 and R3 Respectively represent -Η, -f or -CH3, respectively; ring S represents 1,4-phenylene, iota, 4-cyclohexylene, iota, dioxalate-2,5-diyl, pyrimidine_2, 5_diyl, pyridyl 2,5-diyl, naphthalene_ι,5-diyl, naphthalene_2,7·diyl or fluoren-9,10-diyl; ' 111 200808686 R表不-Η , -F, an alkyl group having a carbon number, a fluoroindenyl group having 1 to 30 carbon atoms, an alkoxy group having a carbon number of exemplified, (3), _〇CH2F, _ochf2 or _0CF3; a and b Independently representing an integer of ο~4; an integer of 3; when e is 2 or 3, f and g respectively represent integers of 〇~2, and c, d and e respectively represent an integer of 〇~3; when a plurality of rings S may be the same group, they may be different groups; In the formulae (XI) to (XII), R5 independently represents -Η or -CH3; R independently represents or an alkyl group having 1 to 2 carbon atoms or an olefin 5 each independently represents a single bond, _c〇_ or _ Cii2_ ; Stupid base; R7 and R8 respectively represent -Η, an alkyl group having 1 to 2 carbon atoms or 112 200808686 R9 represents - an anthracene or an alkyl group having 1 to 20 carbon atoms; any -CH2- of the alkyl group having 2 to 20 carbon atoms in the above alkyl group may be -0, -CH=CH- or -C3C - Substitution, but the above -0 is discontinuous; A6 independently represents -0- or a alkylene group having 1 to 6 carbon atoms; A7 represents a single bond or an alkylene group having 1 to 3 carbon atoms; 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1; in the formula (XIV), R1G represents an alkyl group having 6 to 22 carbon atoms; and R11 represents -H or the number of carbon atoms is An alkyl group of 1 to 22; A6 each independently represents -0 or an alkylene group having 1 to 6 carbon atoms. The liquid crystal alignment agent according to claim 20, wherein the diamine is selected from the group consisting of the following general formulae (VI-1) to (VI-5), (VI-14) to (VI-16) , (VII-1) to (VII_15), formula (VII-26), formula (VII-27), formula (VII-31), formula (VIII-1), formula (VIII-2), formula (VIII) -6) and one or more groups of diamines represented by formulas (IX-1) to (IX-5), 113 200808686 114 200808686 22: The liquid crystal finishing agent according to claim 21, wherein the monoamine is selected from the above formula (VI-1), (Vl-2), (νΙΙ_υ~(νΐΙ-12), and (ΙΧ) -2) A liquid crystal alignment agent according to any one of the above-mentioned diamines, which further comprises the use of the above formula. (II) A second polymer obtained by using a diamine other than a diamine having a side chain structure. The liquid crystal alignment agent according to claim 23, wherein the polymer is a four-rebel The liquid crystal alignment agent according to the above-mentioned general formula (I), wherein the diamine other than the diamine having a side chain structure represented by the above formula (I) is selected from the group consisting of the diamines having a side chain structure represented by the above formula (I). One or more groups of diamines represented by the following formulas (III) to (XIV); 115 200808686 H2N-A4—NH2 (III) h2n ^^nh2 In the formula (III), A4 represents -(CH2)m, wherein m is an integer of 1 to 6; in the formulae (IV) to (IX), X represents a single bond, -0-, -S_, -SS·, - S02-, -CO-, -CONH-, -NHCO-, -C(CH3)2_, -C(CF3)2_, -(CH2)m-, -0-(CH2)m_0-, _S_(CH2)mS ·, where m is an integer from 1 to 6; Y independently represents a single bond, -〇-, -S-, _CO-, -C(CH3)2_, -C(CF3)2- or a carbon number of 1~ An alkylene group of 3; a hydrogen bonded to a cyclohexane ring or a benzene ring may be substituted by -F, -CH3, -OH, -COOH, -S03H, ·Ρ03Η2; and 116 on the benzene ring in the formula (VI) 200808686 Binding hydrogen can be substituted by benzyl; R1 In the formula (X), 'A1' represents a single bond, _0-, -COO-, 〇, 社山, 匕. ...-C〇-, -CONH or -(CH2)nT ' ', where m is an integer from 1 to 6; R1 represents a group having an alcohol skeleton, and a positional relationship between two amino groups bonded to a benzene ring represented by the following formula (11) is a relative day ±^: a filament having a carbon number of 1 to 30; or when the above-mentioned position When ^ ^, R1 represents a carbon atom number A 1~30 or a / is a phase between the above alkyl groups - any -CHy can be substituted by -CF _ctI - Η - or -, but the above _ 〇 _ discontinuous ;-cHhP=substituted by -CH2F, -CHF2 4_CF3; the hydrogen bonded to the carbon forming the above phenyl ring may be independently substituted by _F, CH, , -OOH2F, :〇CHF2 *-〇cf3; ^(D) J c L Jd LJ e In the formula (II), A2 and A3 independently represent a single bond, _〇_, _c〇〇_, _〇c〇-, -CONH-, _CH=CH- or carbon A subunit of the atomic number; R2 and R3 independently represent Η, j or _CH3; ring S represents 1,4-phenylene, iota, 4-cyclohexylene, i,3-dioxane_2 , 5_ diyl, pyrimidine _2, 5_diyl, bite · 2,5-diyl, naphthalene_ι, 5-diyl, naphthalene-2,7-diyl or -9,10-di 127 200808686 The alkyl group of 30, the alkoxy group having a carbon number of -30, -CN, R4 represents -H, -F, the fluoroalkyl group having 1 to 30 carbon atoms, and the number of carbon atoms is } -och2f &gt; -ochf2 ^-〇cf3 ; a and b respectively represent integers of 〇~4; c, #e respectively represent integers of 〇~3; when e is 2 or 3, The same group may also be a different group; f and g respectively represent integers of 〇~2, and c+d+ e^l; R5 independently represents -Η or -CH3; R is a turn-by-turn or an atomic or dilute group whose atomic number is in addition; A5 independently represents a single bond, -C〇 or _CH^_; R and R Separately, the number of carbon atoms is an alkylphenyl group; 118 200808686 R9 R9 represents -H or an alkyl group having 1 to 20 carbon atoms; any -CH2- of the alkyl group having 2 to 20 carbon atoms in the above alkyl group may be -0-, -CH=CH- or -CeC- Substituted, but the above -0 - non-continuous; Α6 independently represents -0- or an alkylene group having 1 to 6 carbon atoms; Α7 represents a single bond or an alkylene group having 1 to 3 carbon atoms; Represents 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1; in the formula (XIV), R1G represents an alkyl group having 6 to 22 carbon atoms; and R11 represents -H or a carbon atom It is an alkyl group of 1 to 22; A6 each independently represents -0- or an alkylene group having 1 to 6 carbon atoms. A liquid crystal alignment film formed by coating and heating a liquid crystal alignment agent according to any one of claims 12 to 25. A liquid crystal display device comprising the liquid crystal alignment film of claim 26. 119