TW201030095A - Alignment agent and liquid crystalline polyimide used therein - Google Patents

Abstract

The invention provides an alignment film having excellent alignment property, high sensitivity and high stability. An alignment agent is a composition having polyamic acid and at least one polymer and a solvent of the polyimide obtained through a dehydration reaction of the polyamic acid. The concentration of the polymer in the composition is from 0.1 wt% to 40 wt%. The proportion of the polymer is from 50 wt% to 100 wt% based on the total weight of the film forming content in the composition. A film having a liquid crystal temperature ranging from 100 DEG C to 300 DEG C is formed by using the compostion.

Description

201030095 33384pif.doc VI. Description of the Invention: [Technical Field] The present invention relates to an alignment agent which is mainly used in the manufacture of a liquid crystal display element. [Prior Art] The liquid crystal display element is used for a viewfinder (view finder) of a video camera (vide〇camera) including a notebook (noteb〇〇k personal computer) or a desktop personal computer monitor (monitor). In various liquid crystal display devices such as projection display (projecti〇ri display), it has recently been used in television. Further, the liquid crystal display element is also used as an optoelectronics-related element such as an optical printer head, an optically Fourier transform device, and a light valve. The mainstream of the conventional liquid crystal display device is a display element using a nematic liquid crystal, and the alignment direction of the liquid crystal in the vicinity of one substrate and the alignment direction of the liquid crystal in the vicinity of the other substrate are 90 degrees. An angle-twisted Twisted Nematic (TN) mode, and a liquid crystal display element such as a Super Twisted Nematic (STN) mode in which the alignment direction is usually twisted at an angle of 180 degrees or more is being put into practical use. . Further, a liquid crystal display element of a so-called thin film transistor (TFT) mode using a thin film transistor is also being put into practical use. However, these liquid crystal display elements can appropriately recognize the angle of view of an image. 201030095 33384pif.doc A small 'there is a case where the brightness or contrast is lowered when viewed from an oblique direction' and sometimes a brightness inversion is generated with an intermediate tone. In recent years, the problem of this viewing angle has been adopted by a multi-domain vertical alignment (MVA) mode using a TN-type liquid crystal display element of an optical compensation film and a technique of using a vertical alignment and a convex structure (for example, refer to the patent document) 1) Or a planar electric field conversion (In_Plane Switching, IPS) mode (for example, refer to Patent Document 2) and the like. The development of the liquid crystal display element technology is achieved not only by improving the driving method or the element structure of these liquid crystal display elements, but also by improving the constituent members used in the display elements. Among the constituent members used in the display element, in particular, the liquid crystal alignment film is one of important factors relating to the display quality of the liquid crystal display element. As the display element is made higher in quality, the function of the liquid crystal alignment film is becoming more and more important. For such a liquid crystal alignment film, in order to uniformly display the molecular display of the liquid crystal display element, it is necessary to uniformly control the molecular arrangement of the liquid crystal. Therefore, it is required that the liquid crystal molecules on the substrate are uniformly aligned in one direction and additionally from the substrate surface. A fixed inclination (pretiltangle) is produced. As described above, the liquid crystal alignment film in which the directions of the liquid crystal molecules on the substrate are aligned is an important and indispensable technique in the manufacturing steps of the liquid crystal display element. The liquid crystal alignment film is prepared from a liquid crystal alignment agent. At present, a liquid crystal alignment agent mainly used is a solution obtained by dissolving polyamic acid or a soluble polyimide in an organic solvent. After coating such a solution on a substrate, it is formed into a film by heating or the like, and 201030095 33384pif.doc forms a polyimine-based liquid crystal alignment film. Various liquid crystal alignment agents other than polyglycolic acid have also been studied in the industry, but in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical properties, optical properties, display characteristics, and the like. In fact, it has hardly been put into practical use. A rubbing method which is simple and can perform high-speed processing of a large area is widely used in the industry as an alignment treatment method. The rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon (nylon), rayon, polyester, or the like are implanted, whereby liquid crystal can be obtained. Consistent alignment of molecules. However, the rubbing method is pointed out that there are problems such as generation of dust, static electricity, and the like. k. As for the alignment mechanism of the liquid crystal on the alignment film subjected to the alignment treatment by the rubbing treatment, the following two types are proposed: (1) The surface of the liquid crystal alignment film caused by the microgroove generated by the rubbing treatment Shape effect; (2) Intermolecular interaction of a uniaxially aligned liquid crystal alignment film and a liquid crystal monolayer in contact with the liquid crystal alignment film by rubbing treatment. In recent years, it has been confirmed that the contribution of the intermolecular interaction with a small contribution of the surface shape effect of (1) is dominant. It is known that when such a hybrid method is employed, it is generally possible to impart a large alignment regulating force to the liquid crystal for the neoprene film (an anchoring energy (gum ratio - gy)). However, when this rubbing method is employed, the following The problem is that, by observing the direction of the hair rubbing film in the rubbing cloth, if it is observed at a molecular level (m〇lecular level), then it is not uniform, and as a result, the liquid crystal alignment of the alignment film interface occurs. Correction, it is precisely because of the 201030095 33384pif.doc contact with the cloth, it is scarred in the shame, etc., when the liquid crystal display element is black display (normally black mode) when no voltage is applied (black level) ) is less than ideal, this phenomenon has been smashed by the industry. On the other hand, the photo-alignment method for performing the alignment treatment on the light is proposed to have a photodecomposition method, a silk formation method, a photodimerization method, and a photocrosslinking type. The alignment mechanism (for example, refer to Non-Patent Document 1, Patent Document 3, and Spear Document 4). In particular, it is considered that since the photo-alignment method is the same non-contact alignment method, the intermolecular interaction as the alignment mechanism (2) of the liquid crystal acts. The phenomenon that the alignment of the photo-alignment processing method is the same as the rubbing method, and the non-contact-alignment method is used, so that the film does not have a mark. It is easier to increase the dark level with respect to the rubbing method. Moreover, the f = treatment method can reduce the occurrence of dust or static electricity in the manufacture of liquid crystal display elements. Its advantages are more L-light alignment processing === This situation will cause a decrease in response speed or stay in order to overcome this The inventors of the present invention have a method of coating a liquid crystal alignment agent containing a tri-acid on a substrate by a method disclosed in Patent Document 3, and then irradiating the light, and burning. By this method, it is possible to obtain a liquid crystal alignment film having a large amount of energy == having sufficient _, and it is not necessary to "make it", and further improvement is required. [Patent Document 1] Japanese Patent No. 2947350 [Patent Document 2] Japanese Patent No. MAO354 (Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. 1] Liquid crystal, Vol. 3, No. 4, p. 262, 1999 [Summary of the Invention] The purpose of using 8? 2 is to provide a kind of uniformity of the uniformity of the alignment = comparison:: light::r In addition, research and development have been carried out with a good degree of sensitivity, and as a result, it has been found that a polyimine material having high passability and high heat resistance is imparted with heating to the octame, and then the polymerization is increased, whereby the alignment is increased. The present invention has been completed. The T liquid crystalline polyimine of the present invention is used as a retort material. The present invention is represented by the following item [1]. (1) An aligning agent which contains a polyphosphonic acid and In the (tetra) imine obtained by the dehydration reaction of the polyamine = At least one polymer and a two-component composition' is characterized in that the concentration of the polymer in the composition is 1 wt/〇40 wt/ο (% by weight), and the film-forming component contained in the composition The total amount is a ratio of 50 wt% to tenderness, and a film having a liquid crystal temperature range between c c and 300 C can be formed by forming the composition into a film.

[Effect of the Invention J] If the alignment agent of the present invention is used, for example, as a liquid crystal alignment agent, the terms used in the present invention can be explained by 201030095 33384pif.doc. m Lu will sometimes be represented by the formula (Ι_υ as the two \). Sometimes the terminology used in the definition of a chemical formula for a compound represented by another formula can be freely selected, and the number can be freely selected: the expression "Ac can be taken, taken in C, and replaced by E". The meaning of B, c, and the meaning of A, which can be replaced by A, which is substituted by A, and the meaning of being mixed by E. w, when any ® is taken (four), the preconditions are continued by multiple 2,, ', ancient replaced by other identical groups. In the St configuration of the group table, the base chart of the text (for example, A) is surrounded by hexagons. a group (ring A), Me represents a methyl group. The range of no chemical bonding problem with any of the carbons constituting the ring ^There is no chemical problem. The case where the same mark is used in the same table of the substituent table indicates that the group has a phase difference, but It does not mean that the same 201030095 33384pif.doc group must be the same in all formulas. In this case, the same group may be selected among a plurality of formulae, or a different group may be selected in each formula. The present invention is constituted by the above item [1] and the following items [2] to [22]. [2] The alignment agent according to [1], wherein the poly-proline is a polylysine having a photosensitive group in the main chain. [3] The aligning agent according to [2], wherein the photosensitive group is at least one of the groups represented by the formula (I) to the formula (VI): —R1—C^C~R2—(I) —R1—C^C~C^C~R2— (II) —R1—C^C~CH=CH—R2—(III) ——r1—c^c~R2~C^C~R3— (IV ) —r1—c^c~R2~~CH=CH—R3—(V)—N=N—— (VI) Here, R1, R2 and R3 are independently aromatic divalent groups. [4] The alignment agent according to the item [2], wherein the polyaminic acid having a photosensitive group in the main chain is a polyamic acid obtained by the following method, that is, by the formula (1-1)~ Formula (1-3), Formula (Π_1) to Formula (Π-3), Formula (111_1), Formula (IV-1) to Formula (IV-3), Formula (V-1), and Formula (VI-1) At least one of the diamines having a photosensitive group represented by the formula (VI-7) and a formula (Α-1), a formula (Α-2), a formula (Α-12), a formula (Α-14) , formula (Α-18), formula (Α-20), formula (Α-21), formula (Α-37), formula (VII-4), formula (VII-5), formula (VIII-7) 10 201030095 33384pif.doc and at least one of the tetracarboxylic dianhydrides represented by the formula (VIII-8) are reacted:

H2N—~nh2Η2ί\

(Μ ) (Ι-2) (Ι-3)

(11-1) (ΙΙ-2) (ΙΙ-3) (in-1) 11 20103009533384pif.doc H2

H2 (IV-1 ) h2

H2 (IV-2 ) h2

(IV-3)

NH 2 H2N~~~~CSC—~~CK==CH—~~NH2 (V-1)

(VI-1) (VI-2) (VI-3) (VI-4) (VI-5) (VI-6)

(VI-7) 12 201030095 33384pif.doc

13 201030095 33384pif.doc

(Vll-4) (Vll-5) (Vlll-7) (Vlll-8) where 'R5 is arbitrary _CH2- can be -〇-, -nh-n(ch3)-, Si(CH3)2OSi (CH3) 2- or -COO-substituted alkylene having 6 to 20 carbon atoms. [5] The aligning agent according to [2], wherein the polyacrylic acid having a photosensitive group in the main chain is obtained by the following formula (IV) valine acid 'g卩' from the formula (IV-4) and At least one species of four rebelic livers trapped by the heterogeneous photoreceptor represented by the formula (VI_8) and the formula (vii-i) to (VII_3) and (VIII-1) to (VIII-6) Reacts of at least one of the indicated diamines: 201030095 33384pif.doc

(IV-4)

H2N~R4—NH2 (VI-8) h2NHQ_rMQ_Nh2 (VII-2) h^n-〇^〇-r5-〇-〇-nh2 (v"-3> Here, R4 is a sub-carbon number of 6~20 Alkyl; R5 is any -CH2- may be substituted by -〇-, -NH-, -N(CH3)-, -Si(CH3)2OSi(CH3)2- or -COO-, the carbon number is 6~20 Alkylene. 15 201030095 33384pif.doc H2W—^^-νη2 (VIII-1) Me (VIII-2) Afl a Turtle·▲ (VIII-3) iw' Me (VIIM) (VIII-5) (VIII -6) [6] The polyaminic acid having a photosensitive group in the main chain of the alignment agent according to the item [2] is a polylysine obtained by, for example, making the item [4] From the formula (1-1) to the formula (1-3), the formula (II-1) to the formula (Π-3), the formula (111-1), and the formula (IV-1) to the formula (IV-1) IV-3), at least one of the diamine having a photosensitive group represented by the formula (V-1) and the formula (VI-1) to the formula (VI-7) and the formula (VII-1) to (VII) -3) and a mixture of at least one of the diamines represented by the formula (VIII-1) to the formula (VIII-6) and the formula (A-1) and the formula (A-2) disclosed in the item [4] ), Formula (A-12), Formula (A-14), Formula (A-18), Formula (A-20), Formula (A-21), Formula (A-37) At least 16 of the tetracarboxylic dianhydride represented by the formula (VII-4), the formula (VII-5), the formula (VIII-7) and the formula (VIII-8) 201030095 33384 pif.doc A reaction (VIM} (VII) -2) H2N~R4-NH2 h2nH〇-r5-Qknh2

(VII-3) Here, R4 is an alkylene group having a carbon number of 6 to 20; R5 is an arbitrary -CH2- which may be -〇-, -NH-, -N(CH3)-, -Si(CH3) 2OSi(CH3)2- or -COO-substituted alkylene having 6 to 20 carbon atoms. nhQm

Me (VIII-2)

(VIII-3)

(VIIM) (VIII-5)

[VIII] The aligning agent according to the item [2], wherein the polyaminic acid having a photosensitive group in the main chain is a polylysine obtained by the following method, that is, And at least one of the tetracarboxylic dianhydride having a photosensitive group represented by the formula (IV-4) and the formula (VI-8) disclosed in the item [5], and the formula (VII-4), a mixture of at least one of the tetracarboxylic acid two needles represented by the formula (VII-5), the formula (VIII-7) and the formula (VIII-8) and the formula (VII-1) disclosed in the item [5] -Formula (VII-3) and Formula (VIII-1) to Formula (VIII-6)

At least one of the represented diamines is reacted:

(VII-4) (VII-5)

(VIII-7) (VIII-8)

Here, R5 is an arbitrary -CH2- which may be substituted by -Ο-, -NH-, -N(CH3)-, -Si(CH3)2OSi(CH3)2- or -COO-, and the carbon number is 6-20 The alkylene 18 201030095 33384pif.doc base [8] according to the [2] item, the poly-proline is the one that has been disclosed in the article "The main chain has a sense group" The polylysine obtained is obtained by the formula [4] αη_υ, & ί ^ (1_3), (5)), (11·3), and (VI-7); IV-3), at least one of the diamines having a photosensitive group of the formula (V-1) and the formula (II), xi, and the coating, and the diamine represented by the item [4] At least one kind of mixing, 肀, 揭, 式, 式, 式, 式, 式, At least one of the four-two-needle represented by the formula (VII_4), the formula (VII-5), the formula (VIII-7), and the formula (νΐΙΙ·8) is reacted: h2丨

A4—NH, 4 Miao-Min 30 丫弋 _ Here A, a2, A3 and A4 are independently Cyd〇hexylene or phenyl; χ3 and χ4 are independent single bond, carbon number Is a sub-alkyl group or 〇_; χ5 and χ6 are independently a single bond, -CH2-^-CH2CH2-^-〇-^_s-; Y1 ^-CH2- > -C(RU)(R12 ), -CO- or -S02-, R" and Rn are independently hydrogen, a carbon number of 12 and a fluorinated alkyl group having a carbon number of 1 to 12; and a mAb m2, m3, m4 = n stands for 0 or 1. Further, in the cyclohexylene group and the sub-stack, any hydrogen may be substituted by an alkyl group or a benzyl group having a carbon number of 丨4, and the bonding positions of these groups are arbitrary; however, when A1, A2 When Α3 and 'α4α are 1,4-phenylene', X3, χ4, χ5 and χ6 are not single bonds: Wang 19 201030095 33384pif.doc Η ΝΗ 22N-〇l.

-COO-, -OCO-, _ΝΗ_, where X1 and X2 are a single bond, CONH-, or a sub-alkyl group having a carbon number of 12; & and "is a single bond, or contains a carbon number selected from 6 ~12's aromatic ring and carbon number is 3~! 2 to 3 ring divalent groups U in 2 alicyclic rings; R6 is argon, fluorine, -CN,

: a filament having a carbon number of 1 to 3 G, a fluorinated group having a carbon number of 1 to 30, or an alkoxy group having a stone anomaly of 1 to 30; and, when x1, G], x2, and "all are single bonds" When 'R6 is a burning base having a carbon number of 3 to 3 Torr, a chaotic burning base having a carbon number of 3 to 3 Torr, or a carbon number of 3 to 3 〇-like Wei, # is a single bond and ¥ is a single bond When it is not a base, V is hydrogen or a carbon number of 3 to 3 Å. When both G and G2 are single bonds, the total carbon number of χ1, χ2, and r6 is 3 or more:

Here, R is hydrogen or carbon number, Bayi's "heart palpitations, ring β is any tone ^: two: tender base substitution or any two bonds or carbon number w ~ two single W let Shen Tai, Moreover, s is a meal of 〇~3 | When 〆 is 2 or 3, multiple rings B may all be phase _ rings, or may be composed of 2 different rings from Tian to 20 201030095 33384pif.doc, and multiple χ0 may all be The same group may also be composed of at least two different groups; ζι and ζ2 are independently a single bond, -CH2·, _CH2CH2• or _〇_, ti and t2 are independently integers of Q~3; 'When 11 When 2 or 3, a plurality of Z] may be all the same group, or 1 may be composed of at least 2 different groups; when t2 is 2 or 3, a plurality of Z may all be the same group. The group may also be composed of at least two different groups. φ [9] The hydrazine t-guanidinium having a photosensitive group in the main chain of the aligning agent described in the item [2] is obtained by the following method. The proline acid, that is, the formula (I-1) to the formula (1-3), the formula () to the formula (π_3), the formula (ΠΙ-1), and the formula (IV-) disclosed in the item [4] 1)~(iv-3), (V-1), and (νΐ) -1) at least one of the diamines having a photosensitive group represented by the formula (VI-7), the formula (νπ·!) to the formula (νπ_3) and the formula (VIII-) disclosed in the item [6] 1) a mixture of at least one of the diamines represented by the formula (VIII-6) and at least one selected from the diamines represented by the formula (2) to the formula (4) disclosed in the item [8] and the first [4] From the formula (Α_1), ® formula (Α_2), formula (Α-12), formula (Α-14), formula (Α·18), formula (Α-20), formula (Α- 21), at least one of a tetracarboxylic dianhydride represented by the formula (Α-3 7 ), the formula (VIM), the formula (VII-5), the formula (VIII-7), and the formula (VIII-8). [10] The alignment agent according to [1], wherein the polyamine is at least one of a diamine represented by the formula (VII-1) to the formula (VII-3) and a formula (VIII-) 7) and the polyamic acid obtained by reacting at least one of the tetrazoic acid dianhydride represented by the formula (VIII-8), or by using the formula 21 201030095 33384 pif.doc (VIII-1) to the formula (VIII) -ό) at least one of the diamines represented by the formula and the tetracarboxylic acid represented by the formula (VII-4) and the formula (VII-5) Polylysine obtained by carrying out a reaction of at least one of dianhydride:

(VII-1) (VII-2)

(VH-3) Q (VII-4) (VII-5) Here, R4 is an alkylene group having a carbon number of 6 to 20; and, R5 is an arbitrary -CH2- which may be -Ο-, -ΝΗ- , -N(CH3)-, -Si(CH3)2OSi(CH3)2- or -COO-substituted alkylene having 6 to 20 carbon atoms. 22 201030095 33384pif.doc

H2 h2

(VIII-6) (VIII-7) (VIII-8) (VI11-1) (VIII-2) (VIII-3) (VIII-4) (VIII-5) [11] A liquid crystal alignment film which is It is obtained by imparting anisotropy to the film obtained by coating the alignment agent according to the item [1] on the substrate by rubbing or light irradiation, and then heating to the liquid crystal of the film 23 201030095 33384pif. The doc temperature range is Μ to increase the anisotropy. [12] seed liquid (4) to the film, that is, by applying light to the liquid crystal temperature range of the two of the aligned liquid crystals obtained by applying the agent obtained on the substrate to the substrate, the film is made large and then heated to Membrane Π 3 kinds of liquid crystal alignment film, which is over-cut, ie, is applied to the alignment agent according to item _]; ❹ == Γ, then heated to the film == to increase the anisotropy of the film . (4) [Γ] - seed liquid (four) showing element 'The liquid crystal film according to item [11]. [I5] A liquid crystal alignment film according to the item (10). [16-type liquid crystal display device] has the liquid crystal alignment film described in the above paragraph. ❹ [Π] - a kind of polyacrylamide or poly-brenic acid as its precursor, containing the constituent unit represented by =(IX), this ~. c has a liquid crystal temperature range:

24 201030095 33384pif.doc 〜Formula (1-3), Formula (II-1)~Formula (II-3), Formula (III-1), Formula (IV-1)~Formula (IV-3), Formula ( V-1) and a residue of any one of the diamines represented by the formula (VI-1) to the formula (VI-7).

H2n—~nh2 (Μ ) (1-2)

(1-3)

(11-1 > (ΙΙ-2) (ll-3) (IH-1) 25 201030095 33384pif.doc

(iv-1) {IV-2) (IV-3) (V-1)

NH, (VI-1)

H2I

NH; (VI-2) h2i

H3C h3c

'V«^-nh2 ch3 (VI-3) (VM)

H.

\-^-nh2 丨 3 #-och3

NH, (VI-5)

V"^^-nh2 f3c (VI-6) H2 (VI-7) 26 201030095 33384pif.doc

(X) ❹ , where R5 is an alkylene group having a carbon number of ό~I2; R9 is a formula (Ι_1}~(1-3), a formula (X:), a formula (11_3), a formula (ΙΙΙ_υ) Residues of any of the diamines represented by the formula (π") to the formula (IV·3), the formula (V-1), and the formula (VI-1) to the formula (VI-7). ❿ nh2 nh2 (Μ ) (1-2) h2i

(1-3) νη2 27 201030095 33384pif.doc

(11-1) (H-2) (H-3) (HI-1) H2

H2 (iv-1)

H2h

H2 (IV-2 ) h2i

(IV-3) NHo H2N""^~C^CCH==CH—~NH2 (V-1 )

28 201030095 33384pif.doc H2! h2i h2i H3C丨 H2l NH, (VI-1)

H3c NH, NH, CH, (VI-2) (VI-3) (VI-4) H.

NH^ (VI-5)

H2I

V-^^-nh2 f3c (VI-6) H2 (VI-7) [19] The polyimine according to [17] or the polyglycine as a precursor thereof, R9 is a formula ( VIII-1) a residue of any one of the diamines represented by the formula (VIII-6). 29 201030095 33384pif.doc

Me (VIII-2) (VIII-3)

H2 (VMM)

G

H2

[20] The polyamidiamine according to the item [18] or the polylysine as a precursor thereof, wherein R9 is a formula (VIII-1) to a formula (VIII) The residue of any of the diamines represented by VIII-6). 〇 30 201030095 33384pif.doc

>W=Ty^H2 (VIII-2) (VIII-3) (VIII-4) (VIII-5)

(VIII-6) [21] - a poly-iimine or a poly-proline as a precursor thereof, comprising a constituent unit represented by the formula (IX) and a constituent unit represented by the formula (XI), and HKTC~3, with liquid crystal temperature range: 201030095 33384pif.doc Here, R5 is a sub-alkyl group having a carbon number of 6~12; R9 is a formula (I_1) of formula (1-3), formula (Π-1) Any of the diamines represented by formula (III-3), formula (III-1), formula (ιγ_ι), formula (IV-3), formula (V), and formula (vw) to formula (VI-7) One kind of residue; R10 is a residue of any one of the diamine towels represented by the formula (Vm_l) to the work, (νΐΙΙ·6). (1,

32 201030095 33384pif.doc

H2I n~^〇-<^c-〇-ch=ch'~0-nhz

(iv-1) (IV-2) (IV-3) (V-1) (VI-1) (VI-2) (VI-3) (VM) (VI-5) (VI-6) (VI -7) 33 201030095 33384pif.doc H2 h2 (VIII-1) h2

H2 (VIII-2) (VIII-3)

(VIII-4) ❹ (VIII-5) (VIII-6) [22] - Polyimine or polyglycine as a precursor thereof, comprising a constituent unit represented by the formula (X) and a formula The constituent unit represented by (XII) and having a liquid crystal temperature range from 100 ° C to 300 ° C: ®

(XII) 34 201030095 33384pif.doc Here, R5 is an alkylene group having a carbon number of 6 to 12; R9 is a formula (μ) to a formula (1·3), a formula (ΙΙ-1) to a formula (11- 3) Any one of the diamines represented by the formula (111-1), the formula (IV_i), the formula (IV_3), the formula (V-1), and the formula (VI-1) to the formula (VI-7). The residue; R1〇 is a residue of any one of the diamines represented by the formula (VIII-6). (Μ) ❹

Η2 (1-2)

(1-3) ΝΗ

(Η-1) (Η-2) (Π-3) (IH-1) 35 201030095 33384pif.doc

(iv-1) (IV-2) (IV-3) (V-1)

36 20103009533384pif.doc (VI-1)

(VI-2) (VI-3) (VM) (VI-5) (VI-6)

(VI-7) 37 201030095 33384pif.doc H2

H2 h2

H2 (VIII-2) (vm-3) h2n-^^—

(VIIM) (VIII-5)

H2

H2 The alignment agent of the present invention is a composition containing at least one polymer selected from the group consisting of polylysine and a polyimine obtained by the dehydration reaction of the polyamic acid, and is contained in the composition. The ratio of the polymer based on the total amount of the film-forming component is from 50% by weight to 100% by weight. Further, it can be formed at 100 by forming this composition into a film. 〇 to 300. A film with a liquid crystal temperature range between turns. That is, the alignment agent is coated on a substrate to form a film, and anisotropy is imparted to the film by rubbing or irradiation, and then heated until the liquid crystal temperature range of the film is increased, whereby an alignment improvement can be formed. And has a higher alignment of the alignment film. By using an alignment agent containing the above-mentioned polymer as a main component, it is possible to produce a film having high stability of heat stability and chemistry 38 201030095 33384 pif.doc. When the polyamic acid used in the present invention is made into a polyimide, the glass transition point is smaller than the usual polyimine and less than or equal to the liquid crystal temperature because the polymer backbone is easily moved. Therefore, by using the alignment agent of the present invention containing such polylysine as a main component, a film having a high yield of ruthenium iodide can be obtained even at a relatively low temperature. In the following description, the "polylysine used in the present invention" & is only referred to as "polyglycolic acid" unless otherwise specified. As described above, the alignment film of the present invention exhibits its performance by heating to the liquid crystal temperature range of the material. When anisotropy is imparted to the film by a rubbing method, in order to prevent breakage of the film, generally, a treatment is applied to the substrate, and the solvent is removed by pre-sintering, and then the crucible is dried at about 200 ° C. Burn and then rub. However, if the film is prevented from being broken by the selection of the material, the friction is performed even after the pre-sintering, and then at 200. (It is also possible to carry out the sinter and the heat treatment for increasing the anisotropy at the same time.) Since the photo-alignment method can impart anisotropy to the alignment film in a non-contact manner, there is no need to worry about film breakage. Since the photo-alignment method can perform simultaneous thermo-imidization and heat treatment after photo-alignment using tyrosine, it is more preferable to impart anisotropy to the alignment film of the present invention. For this reason, it is preferred to select The temperature at which the temperature of the heat-imidization is in the range of the liquid crystal temperature. Sometimes, the limit temperature of the heat treatment is limited depending on the kind of the substrate, but by using the alignment agent of the present invention, it can be formed at 1〇(TC~39 201030095). 33384pif.doc 30? The range of the liquid crystal temperature range of the nematic liquid crystal used in the alignment A ^ is also relative to Γ 8 〇 ^ containing the photosensitive group of the group of people, the invention of the t agent is better known All photosensitive groups. Dance, 3 = use of light-polymerization or photo-decomposition to show the alignment ability. 化化=r:n:=Liquid temperature: Production: Isomerization type photosensitive group It is better to use the light base:: to η:: combine r with the following feeling on the main chain (I) (H) (III) (iv) (V) (VI) - R1~ ~C^C~C^C—R2-—r1—C^=C—CH=CH—R2-_ —R1—0=C~R2—C^Cr3~ R^ CH^^CH·—f^3 Preferred examples of the aromatic divalent group in which R^R2 and R3 are independently aromatic are 1,4_stupid, sub-stupid, 4,4L biphenylene, and di-based methyl ketone-4 , 4, · Diyl. Any hydrogen of these rings may be substituted by methyl, methoxy 201030095 33384pif.doc, difluoromethyl, methoxy, fluoro or chloro. And 'in this group More preferably, it is 1,4-phenylene and 1,3-phenylene, and most preferably phenylene. By selecting a photosensitive group represented by the formula (I) to the formula (VI), light alignment can be achieved. The characteristics of the photo-aligning agent of the present invention which is relatively large and highly sensitive are maximized. There are cis or trans in the double bond of the photosensitive group of the formula (ΠΙ) and formula (v) ( Trans) two isomers, but the photo-alignment agent of the present invention may use any of these isomers. In order to obtain the main chain having the formula (1)~ (4) The at least one kind of (tetra)amine acid of the photosensitive group represented by (VI), as long as the amine group and the acid saponin having such a photosensitive group are used as a raw material, in particular, in order to obtain a higher light alignment It is preferred to use a raw material having a photosensitive group in the gauze-like form. The second (four) and read acid two having such a first group are preferably == ~ conjugate (10), Compound (5)) to a compound (11 pulverized compound (m-oxime, compound (10)) to compound (ιν_4), compound (V-1), 2 compound Ο~ compound (10)). In addition, in the following description, there may be four Wei ___. H2f\ (1-1) (I-2)

(1-3)

NH 41 20103009533384pif.doc H2

(«1-1) h2

H2 (H-2 ) h2

NH 2 H2

—^~nh2

(iv-1) (IV-2) (IV-3) (IV-4) (V-1)

42 201030095 33384pif.doc

(VI-1) (VI-2) (VI-3) (VI-*) (VI-5) (VI-6) (VI-7)

(VI-8) When polylysine is produced, a diamine or an acid anhydride having no photosensitive group can be used in combination with the compound. At this time, in order to easily lower the Tg of the polyimine obtained by the dehydration reaction of the polyamic acid, it is preferred to introduce an alkylene group having a carbon number of 6 to 20 into the main chain of the polymer. II 43 201030095 33384pif.doc Amine or anhydride. In order to further lower the Tg, any -CH2_ of this alkylene group may be substituted by -〇-, -NH-, -N(CH3)-, -Si(CH3)2OSi(CH3)2- or -COO-. As such a diamine and an acid anhydride, a compound represented by the following formula (VII-1) to formula (VII-5) is particularly preferred.

H2n-^-~r5-^~nh2 (VII-2) ο (VII-3)

(VIM) (VII-5) Here, R4 is an alkylene group having 6 to 20 carbon atoms, and a carbon number of 6 Θ to 12 is preferable. R5 is an arbitrary -CH2_ subunit having a carbon number of 6 to 2 Å which may be substituted by _〇_, -Νη, N(CH", -Si(CH3)2〇Si(CH3)2 or -COO. Preferably, R5 is an alkylene group having a carbon number of 6 to = which may be substituted by _〇. Further, a more preferable example of R5 is that there is no substituted carbon associated with 7.2 in the group. An alkylene group having a number of 6 to 12, also printed 2, and in order to easily exhibit liquid crystallinity, and to bind the aromatic ring 44 201030095 33384 pif. doc body as much as possible with two amine groups or two carboxyl groups in a straight line A diamine or an acid anhydride is also preferable. As such a diamine and an acid anhydride, a compound represented by the following formula (VIII-1) to formula (VIII-8) is particularly preferable.

H2n

(VIII-6) (VIII-7) (VIII-8) (VI11-1) (VIII-2) (VIII-3) (VMM) (VIII-5) 45 201030095 33384pif.doc In the present invention 'may also In addition to the diamines other than the diamines listed in the description so far. For example, when an alignment film is used as an alignment film for a nematic liquid crystal composition in a liquid crystal display application, a so-called electric power indicating that a voltage holding ratio (VHR) is high and it is difficult to generate a residue or the like can be used. A well-known diamine with excellent properties. Preferable examples of such a well-known diamine include a diamine represented by the formula (2). H2N^At^x5-A^7fx3 十丫4^炒

2 ❿ In the formula (2), ai, a2, a3 and A4 are independently stupid; gas and X4 are independently a single bond, an alkylene group having a carbon number of 5 or γ, and X independently being a single bond or even ... is called, _ 〇 or each; γ only - coffee (four) V damage V, Rn and, the hydrogen number ^ ^ base, or a carbon number of 1 ~ 12 fluoride, preferably hydrogen 1 Ο :f 二Ί(10)(10), melon 4 and 11 independently represent 0 or 1. Moreover, in L cyclohexyl and phenylene, any hydrogen may be deuterated by carbon number, and the bonding sites of these substituents are 2 to 4 ^; however, when "and ~: sub;;, X, and X6 is not a single bond. The following table is a preferred example of the diamine represented by the formula: 46 201030095 33384pif.doc

(2-1)

H2

(2-3>

P-9}

H2^~O^0-NH2 (2-11) nih2 (2-12) (2-13) (2-14)

47 201030095 33384pif.doc (2-25) (2-24) h2*h〇AQ p/3^ nh2 h2n^ nh2 (2-26) (2-27) h2nhQ^vA/0_NH2 h2>^〇/Qs/ "v〇nQ^nh2

P-28) P-29)

(2*31) (2-30) h2n-^q^s'v/vOKNH2 h2n-〇^Sn/vSs〇-nh2 P*32) P-33}

(2-39) (2-41) 48 201030095 33384pif.doc ❿

(2-48) H2N~〇/As〇-(CH2)3-^/N^-NH2 (2-49) H2N-^^S^^^CH2)6—(2-50)

(2-51} (2-52) P-53)

49 201030095 Among these diamines, from the viewpoint of imparting a high VHR to the liquid crystal alignment film and suppressing the phenomenon of leaving marks, it is more preferable that the formula (2-6) to the formula (2-24) and the formula (2) -36), a diamine represented by formula (2-42), formula (2-43) or formula (2-48) to formula (2-52), and more preferably by formula (2-6), Formula (2-11), formula (2-12), formula (2-13), formula (2-17), formula (2-22), formula (2-23), formula (2-24), or A diamine represented by the formula (2-49). The ratio of use of the diamine of the formula (2) in the present invention can be arbitrarily selected depending on the orientation and electrical properties to be targeted. However, if this also has a large proportion of amines, the liquid crystallinity will decrease. Therefore, the proportion of these diamines used is preferably 0 mol% to 30% of the total amount of diamine used in the synthesis of polyamic acid. The range of mol% (molar percentage) is more preferably 〇m〇i% to 10 mol%. Further, another example of a diamine which is preferably used for producing a polyaminic acid having no photosensitive group is a side chain group represented by the formula (3) or the formula (4).

In the formula (3), X1 is independently a single bond of J and X2, _〇_,

50 201030095 33384pif.doc A carbon number of 1 is a fluorinated alkyl group having 30 or an alkoxy group having a carbon number of 2. However, when the animals X, G, X and G2 are all single bonds, R6 is a hospital base with a carbon number of 3 to 30, a stone base of 3 to 3 〇, or a carbon number of 3 to 30. When the gas-based 'field 〇疋 single bond and χ 2 is neither a single bond nor a sub-alkyl group, R6 is hydrogen 6 or a hospital base; and, when both G1 and g2 are single bonds, the total hindrance of χ1 and χ2 R is greater than Equal to 3. The formula (3) +, the two amine groups are bonded to the benzoic carbon, and the bonding position relationship of the two amine groups is preferably a metaposition or a pair, and when the bond of the χ1 is When the junction position is set to the station position, the two amine groups are bonded to the 3 and 5 positions, or the 2 and 5 positions, respectively, and it is particularly preferable to bond the 3 and 5 positions. Bit

In the formula (4), 'R7 is hydrogen or a carbon group having a carbon number of 1 to 12; and any hydrogen of the ring 疋 可以 may be substituted by an alkyl group having a carbon number of 1 to 4, i, 4-phenylene, or any hydrogen produced. Substituted U4·cyclohexylene which may be substituted by a carbon number of 1 to 4; X is a soap bond or a pyridene group having a carbon number of 1 to 5, and s is an integer of 〇~3; when s is 2 or 3 'Multiple _ may all be the same ring, or may be composed of at least two different rings, and a plurality of fluorenes may all be the same group or may be composed of at least two different groups; Ζ1 and Ζ2 are independent The key, -ch2-, -ch2ch2- or seven_, tl and t2 are independent of 51 201030095 33384pif.doc integer of 〇~3; when tl is 2 or 3, multiple Z1s may all be the same group, or It is composed of at least two different groups; when t2 is 2 or 3, a plurality of Z2 may be all the same group, or may be composed of at least two different groups. Preferred examples of the diamine represented by the formula (3) are shown below.

52 201030095 33384pif.doc

H2n 〇 H2IH 0 h2n 七 2 (3-12) p- h2n -O-R22 P-13) 53 201030095 33384pif.doc

(3-18) (3-19)

54 201030095 33384pif.doc In the formula (3-J) ^ (3-25) rf, alkyl or alkoxy, preferably protected, the ruler is 1~2〇 with a carbon number of 1~2〇 The base or alkoxy groups are opposite to the two groups. Two 21 is the carbon number

疋 = an alkyl group having a number of 4 to 20, preferably an alkyl group having a carbon number of 6 to i6. R23 is an alkyl group having a carbon number of 6 to 20, preferably a fluorenyl group having a carbon number of 8 to=. R24 is an alkyl group or alkoxy group having a carbon number of 3 to 20, preferably a group having a carbon number of 5 to π. R25 is a burnt group or a hospitaloxy group having a carbon number of 1 to 20, and the car is preferably a base having a carbon number of 3 to 10. Among these diamines, a more preferred example is a diamine represented by each of the formula (3-1), the formula (3-2), the formula (), the formula (3-5), and the formula (3-6). A more illustrative example is a diamine represented by each of formula (3-1) and formula (3-2). Preferred examples of the diamine represented by the formula (4) are shown below. 55 201030095 33384pif.doc

56 201030095 33384pif.doc

(4-16) 烧 In the formula (4-1) to the formula (4-16), the alkyl group or the calcined oxygen * is preferably a carbon number = H number of 1 in the formula (3) Η 4 in the present invention. ~7 yard base. Two faces of you ffl»·Bu Wr, I) or formula (4) with a side chain group tilting and cup sound I": according to the target of the orientation, electrical properties or anticipation "" . In particular, in order to exhibit a pretilt of 2 degrees or more, the angle of 201030095 is preferably such that the ratio of use of these diamines is 1 mol% to 50 mol of the total amount of diamine used in the production of polyglycine. %, more preferably set to 5 mol% ~ 3 〇 m 〇 i%. However, if the proportion of the diamine having a side chain group of the formula (3) or (4) is large, the liquid crystallinity is lowered, so that it is preferably set to the minimum necessary. Among the diamines having a side chain group of the formula (3) or (4), in order to maintain the liquid crystallinity of the alignment film of the present invention, it is preferred to select the formula (3·5), (3-6) or a diamine of the formula (3-10). In the present invention, in addition to the above diamine, at least one of a decane quinone diamine may be used. Preferable examples of the decane-based diamine include a diamine represented by the formula (15).

In the formula (15), R and r31 are each independently an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R32 is an alkylene group having 1 to 6 carbon atoms, a phenylene group substituted phenylene group, yh~Η) (four) number. The present invention may be exemplified by a specific example compound or polymer which is a diamine represented by the formula (15). 58 201030095 33384pif.doc

Me (15-1)

Me Si—(CH2)3-NH2 Me Me H2N-(CH2)3-Si- Me

(15-2) H2N-(CH2)3-Si-〇^

Me In these formulas, the amount of Me is please ~ delete. In the M group, a molecule of the formula (15·2) exhibits the above-described effect and prevents deterioration of other characteristics, and the amount of the addition of the diamine to the diamine is preferably 0.5 relative to the total amount of the amine in the production of the hetero (IV). M〇1%~3〇m〇1%, more preferably ~10 mol%. According to the required characteristics of the alignment film, when the polyglycolic acid is produced, the retention rate (VHR) of the two-member electric power can be made high and difficult. A well-known acid anhydride having excellent properties such as trace retention, etc. It is an acid anhydride that can be produced by a well-known compound as an acid anhydride for the production of a squid. The acid anhydride may be a fatty liver of a (four) heteroaromatic ring system. And an acid anhydride of an aliphatic group (including a heterocyclic system), which is an acid group of any one of the groups. Preferably, the polyamine or the (tetra)amine has a structure of oxygen or sulfur which does not contain a bond or an ether bond which is a property of the liquid crystal display tree. Therefore, the acid Xu has a structure that does not contain oxygen or sulfur. However, if it is a quantity within the range that does not adversely affect electrical performance even if it has such a structure, what is the problem. "There is no heat 59 201030095 33384pif.doc Anhydride is represented by formula (20).

A preferred example of R4G in the formula (20) is a tetravalent group represented by the formula (21) to the formula (29).

(21 > G3 is a single bond, an alkylene group having a carbon number of 1 to 12, 1,4-phenylene, or 1,4-cyclohexylene, and X7 is independently a single bond or -CH2-. r41r42

Point 43 is independently hydrogen, methyl, ethyl or phenyl from 44, 41, 42 and 43. (23) Ring D1 is a cyclohexane ring or a benzene ring. 60 201030095 33384pif.doc P4) G4 is a single bond, -CH2-, -CH2CH2-, -Ο-, -CO-, -s-, C(CH3)2-, or -C(CF3)2·, ring D2 Independently a cyclohexane ring or a benzene ring.

R45 is hydrogen or fluorenyl.

P6) X8 is independently a single bond or -CH2-, and V is 1 or 2.

(27} X6 is a single bond or -CH2-.

(28} 61 201030095 33384pif.doc R46 is hydrogen, decyl, ethyl or phenyl, and ring D3 is a cyclohexane ring or a benzene ring. (29) #w1 wl and w2 are independently 0 or 1. Specific examples of the acid anhydride.

G

62 201030095 33384pif.doc

63 201030095 33384pif.doc A-14

A-17 A-16

A-18 A-19

Α·20 A-21

64 201030095 33384pif.doc Α·28

Α·29

Α-30

Α·31

Α·32

Α-33

Α·35

Α-36

Α_40

Α-41

65 201030095 33384pif.doc A42

A-44

Among these acid anhydrides, in order to maintain the liquid crystallinity of the polyamic acid, it is preferred to use the formula (A-1), the formula (Α2), the formula (a-12), the formula (A-14), and the formula (A). Α-18), a compound of the formula (Α-20), formula (Α-21) or formula (Α-37). Further, from the viewpoint of improving the light alignment ability of the alignment film, it is preferred to use the formula (Α-1), the formula (Α-2), the formula (Α-12), the formula (Α-14), (Α-18), formula (Α_20), formula (Α-21), formula (Α-28), formula (Α-30), formula (Α-37) or formula (Α-40), especially good It is a compound of the formula (冬丨), formula (Α-12), formula (Α-14) or formula (Α-18). In addition, from the viewpoint of reducing the VHR of the liquid crystal alignment film or reducing the coloration, it is preferred to use the formula (Α-14), the formula (Α-18), the formula (Α-19), and the formula (Α-20). , formula (Α_21), formula (Α-28), formula (Α-29), formula (Α-30), formula (Α-32), formula (Α-39), formula (Α_40), formula (Α- 41), a compound of the formula (Α-43), or a formula (Α-44), particularly preferably a formula (Α-14), a formula (Α-18), a formula (Α-21), or a formula (Α) -44) compound. The acid anhydride is not limited to these compounds, and other well-known compounds may be used within the scope of achieving the object of the present invention. Further, these acid anhydrides may be used singly or as a combination of one or more compounds in the group of 2010 20109595 33384 pif.doc. In the present invention, polylysine is produced by appropriately combining the diamine and the acid anhydride. The first preferred example of the poly-proline is a compound (1-1) to a compound (1_3) which is a polyamine having a salty light group, and a compound obtained by the following method. ~ At least one of the compound (11-3), the compound (IIM), the compound Gvq) to the compound (IV-3), the compound (V-1), and the compound (VM) to the human Q is reacted with an acid anhydride. mouth

67 20103009533384pif.doc h2n~c=c-~~c=c-~~nh2

H2

H=CH ~hO_n H2 (iv-1) (IV-2 ) (IV-3 ) (V-1)

(VI-1) (VI-2) (VI-3) (VM) (VI-5) (VI-6)

(VI-7) 68 201030095 33384pif.doc A preferred example of the acid anhydride used at this time is selected from the group consisting of a compound (Al), a compound (A-2), a compound (A-12), a compound (A-14), and a compound (A). -18), compound (A-20), compound (A-21), compound (A-37), compound (VII-4), compound (VII-5), compound (VIII-7), and compound (VIII- The anhydride in 8). Further, particularly preferred are the compound (VII-4) and the compound (VII-5).

69 201030095 33384pif.doc

(VII-4) (VII-5) (VIII-7) (VIII-8) where 'r5 is an arbitrary -CH2• can be -0-, -NH-, -N(CH3)-, _Si(CH3 2〇Si(CH3)r or _c〇〇_ substituted alkylene group having 6~2〇 carbon number and R is preferably a sub-alkyl group having a carbon number of 6~a, that is, ~-C12H24- Any of them. The second preferred example of the reaction of the 12 kinds of 'polyamines' is a chitin acid, which is a poly(IV·4) and a formula (like) which is the acid having the photosensitive group. The acid represented by at least ^ from the amine of the formula 201030095 33384pif.doc <IV4>

(VI-8) O Preferred examples of the diamine used at this time are selected from the group consisting of formula (vii-i) to formula (VII-3) and formula (VIII-1) to formula (VIII-6). a diamine in the compound. H2N~R4—NH2 (VII-1) (VII-2) (v"_3> Here, R4 is an alkylene group having a carbon number of 6 to 20, and a carbon number is preferably 6 to 12. R5 is arbitrary. -CH 2 - an alkylene group having 6 to 20 carbon atoms which may be substituted by 0, -NH-, _N(CH3)_, -Si(CH3)2OSi(CH3)2- or -COO-. Moreover, R5 is preferred. Is any of -C6H12-~_C12H24-. 71 201030095 33384pif.doc

(VIII-1) (VIII-2) (VIII-3) (VIII-4) 6 (VIII-5) (VIII-6) The third preferred example of polylysine is a polyfluorene obtained by the following manner The amine acid, that is, the compound (Μ) to the compound (1-3), the compound (ΙΙ-1) to the compound (11-3), the compound (111-1), and the compound ◎ (IV-1) At least one of the diamines in the compound (IV-3), the compound (V-1), and the compound (VI-1) to the compound (VI-7) and the compound (VII-1) to the compound selected from the above (VII-3) and a mixture of at least one of the diamines in the compound (VIII-1) to the compound (VIII-6) and an acid anhydride are reacted. Preferred examples of the acid anhydride are selected from the group consisting of the compound (Α-1), the compound (Α-2), the compound (Α-12), the compound (Α-14), the compound (Α-18), and the compound (Α). -20), acid needle in compound (Α-21), compound (Α-37), compound 72 201030095 33384pif.doc (νΙΜ), compound (VII_5), compound (fox 7). Moreover, when a diamine capable of transducing a filament-diamine^ is selected from a compound (vί~匕口m_3) towel, the _ of the lin is a compound (νπι·7) or a compound ^=(4), when the compound is (VII(4)~compound (V = Φ at least one of the acid anhydride group-containing acid anhydrides is reacted with a mixture of the formula (vh_4), the formula (vΐΙΙ_7), and the acid represented by the formula (vm_8) and the diamine A preferred example of the diamine is the diamine in the compound represented by the formula (VII-1) to the formula (νπ_3) and the formula (vma) to the formula (VIII-6). Φ 73 201030095 33384pif.doc

(VII-4) (VII-5)

(Vlll-7) (Vlll-8)

(The meaning of R5 in these formulas is as described above.) 'The fifth preferred example of polylysine is polylysine obtained by the following method, that is, the above formula (1)) to (1_3) Formula (11-3), formula (mD, formula (m) to formula (IV_3), formula (5)) ❹ and diamine having a sensible group represented by formula (νΐ·1) to formula (νι_7) ^ At least one kind of reaction with a mixture and an acid anhydride selected from at least one of the amines represented by the formula (7) to the formula (4). A preferred example of the acid anhydride is selected from the group consisting of the formula (Α_υ, formula (Α_2), formula (Α_12), formula (Α-14), formula (Α-18), formula (Α_2()), formula (酸酐_21), an acid anhydride in the compound of the formula (Α_37), formula (.4), formula (VI1-5), formula (VIII-7) and formula (VIII-8). Moreover, the anhydride is particularly good. It is compound 74 201030095 33384pif.doc (VII-4) and compound (νΐΐ·5). Amidoxime _ The sixth best example is obtained by the following method, that is, by the formula ~, ~ At least one of the diamines having a (four)thing group represented by the formula (11.3), the formula (III-m (〗 〖Im) to the formula σν·3), and the formula (ν(4) to (VI_7) At least one of the diamines represented by the formula (purchased) to the formula (νιι_" and the formula (VIII-1) to the formula (vm_6), and the formula (2) to formula (4) selected from the above a mixture of at least one of the diamines represented and a reaction to ride. A preferred example of the break is selected from the group consisting of formula (A-1), formula (Α_2), formula (Α12), formula ( Α-14), formula (Α-18), formula (formula (Α-21), formula (Α-37), formula (VII-4), An acid anhydride in the compound represented by the formula (VII-5), the formula (VfI-7), and the formula (vm_8). The seventh preferred example of the poly-proline is obtained by the formula (VIM) to the formula (VI3) a polylysine obtained by reacting at least one of the diamines represented by at least one of the tetracarboxylic dianhydrides represented by the formula (VIII-7) and the ketone, or by the formula (viii_丨) - (VIII_6) The polyamine of the diamine which is represented by the reaction of the formula (VIM) and the formula (VII_5)= 201030095 33384pif.doc

H2 h2n~^-rM〇-nh2 (VII-1) (VII-2) (VII-3)

(VII-4) (VII-5) (The meanings of R4 and R5 in these formulas are as described above).

76 201030095 33384pif.doc

(VIII-2)

(VIII-3) (VMM) (VIII-5)

(VIII-6) (VIII-7) (VIII-8) Further, a preferred embodiment of the alignment agent of the present invention is a polyglycine containing one selected from the above 7 preferred polylysines or An alignment agent of the polyimine obtained by the dehydration reaction of the polyamic acid, but the selected polyamine 77 201030095 33384pif.doc

The acid may also be two or more kinds. Further, if it is within the range which does not impair the effects of the present invention, the alignment agent of the present invention may contain, in addition to at least one of the seven polylysines described above, a general polyaminic acid other than the above examples. . That is, in the present invention, as long as the conditions for forming a film having a liquid crystal temperature range between 100 ° C and 300 ° C are satisfied, it is possible to use no photoreceptor in the main chain in addition to the polylysine. The poly-proline of the group cannot be formed at 1 〇〇. 〇 to 300. (: a polylysine having a film having a liquid crystal temperature range therebetween, etc. When using such a polyamine other than the above examples, the ratio of the polyacrylic acid is smaller than the total amount of the film forming component G in the alignment agent 50 wt% of the amount, preferably less than 20 wt%. The alignment agent of the present invention may further contain an organic antimony compound from the viewpoint of adjusting the adhesion of the alignment film to the glass substrate. An example of the organic antimony compound is Aminopropyltrimethoxy silane, aminopropyltriethoxysilane, vinyl bis oxetine, N-(2-aminoethyl)_3_aminopropyl decyl dimethyl Gas-based stone burning, N-(2-aminoethyl)-3·aminopropyltrimethoxy oxime, ethyltriethoxy zeoxime, 3-mercaptopropene oxypropyltrimethoxy shi Burning, 3_glycidoxypropyltrimethoxy oxime, 3-glycidoxypropyl fluorenyl dioxime, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxygen stone Xiyuan and other stone shovel coupling agents, as well as dimethyl 〇 氧 氧 氧 (dimethylp〇lysil 〇 xane), polydimethyl Wei, polydiphenyl money The addition ratio of the organic cerium compound in the alignment agent is not particularly limited as long as it is a range in which the effects of the present invention can be obtained. However, if a large amount of the organic cerium compound is added, Then, when the alignment film is formed, the alignment of the liquid crystal of 78 201030095 33384pif.doc occurs. Therefore, when the organic ruthenium compound is added, the concentration of the organic ruthenium compound is compared with the polymer contained in the alignment agent. The amount is preferably in the range of from 1 wt% to 5 wt%, particularly preferably in the range of from 0.1 wt% to 3 wt%, in order to prevent degradation of properties over time or deterioration caused by the environment. In view of the above, the alignment agent of the present invention may further contain a compound having two or more functional groups reactive with a carboxylic acid residue of polyproline, a so-called crosslinking agent. Examples of the crosslinking agent include, for example, a poly-B epoxidation disclosed in Japanese Patent Laid-Open No. 3049699, Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei. , isocyanate (iS〇Cyanate) material, etc. • Moreover, if the crosslinking agent itself reacts to become a network of polymers, thereby increasing the membrane strength of the poly-proline or polyimine. It can also be used for the same purpose as the above-mentioned purpose. As such a crosslinking agent, for example, the polyfunctionality disclosed in Japanese Patent Laid-Open No. Hei 10-310608, Japanese Patent Laid-Open No. Hei. Ethylene 2: ether), maieimide, or bis-allyl-nadi-imide derivatives. The proportion of these crosslinking agents is preferably from 〇 wt% to wt%, more preferably from 0 wt% to 30 wt%, based on the total amount of the polymer components. The alignment agent of the present invention contains a solvent having the ability to dissolve polyamic acid. The solvent broadly includes a solvent which is generally used in the production or use of polyaminic acid or a derivative thereof, and may be appropriately selected depending on the purpose of use. If these solvents are listed, then the following. 79 201030095 33384pif.doc As an example of an aprotic polar organic solvent which is a good solvent with respect to polyamic acid, N-mercapto-2-0 pirone (N-Methyl) can be cited. -2-pyrrolidinone, NMP), dimethyl imidazolidinone, N-Methyl caprolactam, N-methyl propionamide , N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethyl formamide (DMF), N,N-diethyl formamide, ,, diethyl acetamide (N, N-diethylacetamide, DMAc), and γ-butyrolactone (γ-butyrolactone, GBL) is a lactone (lactone). Examples of other solvents for the purpose of improving coatability and the like other than the solvent include lactic acid alkyl group (alkyl lactate), 3-mercapto-3 methoxybutanol (3-methyl-). 3-methoxybutanol), tetralin, isophorone, ethylene glycol monobutyl ether (BCS), etc. Ethylene glycol monobutyl ether, ethylene glycol monoalkyl ether acetate and ethylene glycol monophenyl ether acetate, triethylene glycol monoalkyl radical, propylene glycol monobutyl ether and other propylene glycol monoalkyl ether A dialkyl glycol monoalkyl ether such as diethyl malonate or a dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, or an ester compound such as these ethylene glycol monoethers. Among these compounds, NMP, dimethylimidazolidinone, GBL, BCS, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether or the like can be particularly preferably used in the solvent. 201030095 33384pif.d〇c The alignment agent of the present invention can also be further added according to the f. For example, when it is desired to further improve the coatability, it is possible to add a surfactant-containing force according to the above purpose, and it is possible to contain an anti-static axis in a simple amount. A shouts electrostatic energy. The concentration of poly-proline in the alignment agent of the present invention is higher.

Learn ~ 40 wt%. When the alignment agent is coated on the substrate, = 疋 (U ^ thick, sometimes depends on the solvent previously passed =

Acid operation. 3 Negative Polyamide The concentration of the solid component in the alignment agent of the present invention is not limited to the optimum value selected by the various coating methods described below. Usually (疋, (pinhole) #, in /var paint (varmsh) reset, preferably 〇! wt%~3〇f good is 1 wt ° / 〇 ~ i 〇 wt%. 0 'more f invention The alignment film is obtained by heating gp, rubbing or light irradiation to increase the anisotropy until the anisotropic 'news obtained by applying the alignment agent on the substrate is heated to a range of mm. From the viewpoint of exhibiting sufficient orientation at this time, a preferable a is produced according to the following procedure: 疋 (1) by brush coating method, dipping method, spin coating method, spray method, printing method Etc. 'coating the varnish on the substrate; '(2) at 50 ° C ~ 120. 〇, preferably 8 (rc ~ 1 〇 (the film formed on the substrate is heated under rc, and the solvent is evaporated; (3) illuminating the film to align the poly-proline in the film; 81 201030095 33384pif.doc (4) at 15 (TC~30 (TC, preferably just Dc~25 (rc) The heat is used to make the alignment of the concentrating ship, and the ampere is imidized. In addition, 'when the liquid crystal display element using the alignment film is required to exhibit a predetermined inclination angle' can be performed by the following method That is, when the light is irradiated, the arbitrary angle of the plate is irradiated with linearly polarized light, or the substrate is subjected to linearly polarized light irradiation from the vertical direction and combined with the vibrating illumination. The door is again in the alignment film of the present invention. In the production, linearly polarized light is used for the alignment of the poly-aracine, and the irradiation of the main-linearly polarized light of the proline is aligned in a direction perpendicular to the direction of polarization of the linearly polarized light. The light which can align the poly-acid of the above-mentioned money is not particularly limited. The invention Chen Xiangcai aligns the film by light irradiation with a reduced amount. Therefore, the linear polarization in the photo-alignment treatment of the poly-proline The amount of light irradiation is preferably 〇5 core 2~1 (u/em2. Moreover, the wavelength of the linearly polarized light is preferably 300 nm to full. The linearly polarized light has no surface for the film. _ limited, but when it is desired to exhibit a strong alignment limiting force for liquid crystals, the angle of irradiation is preferably as perpendicular as possible to the surface of the film from the viewpoint of shortening the alignment treatment time. Moreover, the alignment film of the present invention System In the case where it is desired to exhibit a pretilt angle, the light of the film may be either a polarized light or an unpolarized light. = It is desired to express the surface (four). The irradiation amount of the light is preferably 0.5 J/ Cm2~1〇J/Cm2, the wavelength of the light is preferably 400 nm. There is no limitation on the irradiation angle of the light irradiated to the film when the pretilt angle is desired to be expressed, but The orientation of the alignment is preferably from 30 to 6 degrees. The alignment film of the present invention is characterized by having a particularly large alignment and anisotropy. The size of such anisotropy can be evaluated by a method using polarized light infrared rays (1 IR) as disclosed in Japanese Patent Laid-Open No. Hei 5-275364. Further, as shown in the following examples, the alignment film of the present invention can also be used as a liquid crystal composition by using an ellipsic polarization method (ellips) to form a liquid crystal composition with a larger film. Anisotropic materials limit the alignment of liquid crystals. The aligning film of the present invention can be used to control the alignment of an optical compensation material or all other liquid crystal materials in addition to the alignment of the liquid crystal composition for a liquid crystal display. Moreover, since the alignment film of the present invention has a large heterogeneity, it can be used alone for optical compensation materials. The present invention provides a liquid crystal display device in which an electrode pair of the pair of substrates is formed on the opposite side of the pair of substrates, and the opposite direction of the pair of substrates is formed. A liquid crystal alignment film and a liquid crystal layer between the pair of substrates, the liquid crystal alignment film being an alignment film of the present invention. The electrode is not limited as long as it is an electrode formed on the surface of the substrate. Examples of such an electrode include an indium oxide (indium) or a metal vapor film. Further, the electrode may be reversed over the entire surface, for example, the desired shape that can be formed into a pattern, for example, a comb-tooth type, a tooth, a structure, or the like. The electrodes may be formed on a substrate in a pair of substrates. 83 201030095 33384pif.doc may also be formed on two substrates. The form of formation of the electrode differs depending on the type of the liquid crystal display element, for example, in the case of an IPS type liquid crystal display element, and the electrode is disposed on the substrate, and the electrode is disposed in the case of the crystal display element. On both the pair of substrates. The liquid crystal alignment film is formed on the base. Λ $ 〇 The liquid crystal layer is formed by sandwiching a liquid crystal composition from the counter substrate which is opposed to the surface on which the liquid crystal alignment film is formed. When the liquid crystal sound is formed, a spacer or a resin sheet or the like may be interposed between the pair of squeegees as needed to form a spacer. There is no limit to the composition of the liquid composition. When the alignment film of the present invention is used as a liquid crystal alignment film to form a liquid crystal display element, it is possible to improve the characteristics of the liquid crystal ageing member with respect to all liquid crystal compositions known to the present invention. The alignment film is particularly effective in improving the alignment defects of the large-surface display which is difficult to perform the impurity treatment. This large-faced display is driven by tft. Further, the liquid crystal composition used in such a TFT-type liquid crystal display device is disclosed in Japanese Patent No. 6228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. Hei No. Hei. Revealed in the middle. Therefore, the present invention = alignment film is preferably used in combination with the liquid crystal composition disclosed in these publications. The pretilt angle in the liquid crystal display element can be evaluated using, for example, liquid crystal characteristics manufactured by a central precision machine, 裳MS_CA3 $, and using Journal of Applled Physics, V〇 1.48, No. 5, p. 1783-1792 (1977) 84 201030095 33384pif.doc (Crystal rotation method) The liquid crystal display element of the present invention is excellent in electrical properties which are reliable with respect to a liquid crystal display element. As such electrical properties, a voltage holding ratio and an ion density can be cited.

电压 The voltage holding ratio (VHR) is the ratio of the voltage applied to the liquid crystal display element during the frame period to the age of the liquid crystal display element. From the viewpoint of preventing display failure, the present invention is preferably a 5 V and a 3 GHz moment, and is (9). (3) The voltage holding ratio measured under temperature conditions is greater than or equal to 9〇〇%, or 5 volts and fine chops with a frequency of G.3 Hz are used, and the voltage holding ratio measured at 6 (rc temperature condition is greater than or equal to 85.0%) The ion density is a transient current other than the current caused by the liquid crystal driving generated when a voltage is applied to the liquid crystal display element. This ion density indicates the concentration of the ionic impurity contained in the liquid crystal in the liquid crystal display element. The ion density of the liquid crystal display element of the present invention is preferably 500 pC or less from the viewpoint of preventing the retention of the liquid crystal display element. [Embodiment] Hereinafter, the present invention is carried out by way of Examples and Comparative Examples. However, the present invention is not limited to these examples. Pyromellitic anhydride (PMDA, compound (A-1)), 1,2,3,4-cyclobutane tetracarboxylic acid (l 2,3,4-cyclobutanetetracarboxylic acid, 85 201030095 33384pif.doc CBTA, compound (A-14)), and compound (2-13) are purified by recrystallization to a commercially available compound and used in experiments. 8 -1,8-Diaminooctane (DAO, compound (VII-1-1)) is used after distilling the commercial product. Compound (II-1) and compound (A-21) are separately & The following compounds (VII-2-1), compounds (VII-2-2), and compounds (VII-5) are synthesized by the Japanese Patent Publication No. Hei 5-65530, and Japanese Patent Laid-Open Publication No. SHO-58-109479. -1) is a compound according to the method disclosed in Japanese Patent Laid-Open No. Hei 11-160712, and Bulletin de la Societe Chimique de France, 9-10, Pr. 2, 2195 (1975). -5) and the compound (VIII_6) were directly used in the experiment without purifying the commercial product. The compound (νπι_8) was used for the recrystallization of the commercial product from ethanol and used in the experiment. The compound (2_22) and the compound ( 3-5-1) is adopted with the journal 〇fp〇lymer Sdence A: -

Polymer Chemistry, 30 (6), synthesized in the same manner as disclosed in the method disclosed in Japanese Patent Laid-Open No. Hei. No. Hei. Chemical. The object (A-21) is synthesized in accordance with Japanese Patent Laid-Open Publication No. 58_1〇9479. The preparation of the polymer was carried out in a stream of nitrogen. 86 201030095 33384pif.doc η2ν^〇—°8Ηι6-^^-νη2 ^η2ν h2N-〇—°ι〇η2〇—〇-nh2 ^,,.2.2)

(VII-5-1) (VIII-5) (Vlll&lt;6) (VIII-8) (2-22) (3-5-1) Light irradiation is performed by using a 250 W high-pressure mercury lamp that is locked by the Shengrong Hall in the well. Ultraviolet light with a wavelength of about 300 nm to 380 nm. Irradiation is carried out at room temperature in air. 87 201030095 33384pif.doc The evaluation method of the liquid crystal display element used in the examples is shown below. &lt;Relation of the alignment film and film thickness measurement> Using a spectroscopic ellipsometer M-20GGU (LA; manufactured by Woollam Co. Inc.). In the present embodiment, the retardation value of the film increases in proportion to the degree of alignment of the polymer main chain. That is, 貘 having a larger retardation value has a larger degree of alignment. <Measurement of ultraviolet-visible spectrum (UV-Vis) spectrum> Using a UV-Vis spectrometer (Japan Spectroscopic v_66〇), a glass substrate on which an alignment film was formed was used as a reference. Determination. &lt;Voltage retention rate&gt; The measurement was carried out by the method disclosed in "Water Island, etc., 14th Liquid Crystal Symposium Preparation Draft p78 (1988)". The measurement is performed on a cell. A rectangular wave having a wave height of ±4.5 V is applied. The measurement is at 6 〇. Let's go under your arm. This value 疋 indicates how much the applied voltage is maintained after the frame period. If this value reaches 100%, it means that all charges are maintained. @ &lt;Ionicity Measurement in Liquid Crystal (Ion Density)&gt; Manufactured by Toyo C〇rporati〇n, according to the method disclosed in Applied Physics, Vol. 65, No. 1 and No. 65 (1996) The liquid crystal property measurement system 6254 type was measured. A triangular wave having a frequency of 〇〇1 Hz is used, and a voltage range of ±10 V is measured at a temperature of 6 (rc). If the ion cost is large, problems such as leaving marks caused by ionic impurities are liable to occur. In other words, the 'ion density is a property value of the index 88 201030095 33384pif.doc which is the index of the occurrence of the residual mark. &lt;Viscosity&gt; The measurement was carried out using a rotational viscometer (TV-22L, manufactured by Toki Sangyo Co., Ltd.). Weight-average molecular weight (Mw) &gt; Weight average molecular weight (Mw) of poly-proline in liquid crystal alignment agent using Gel Permeation chromatography (GPC) 'and using 0.6 wt% The phosphoric acid DMF was used as the eluate, and polystyrene was used as a standard solution at a column temperature of 50° C. The column was Shodex GF-7MHQ (manufactured by Showa Denko Co., Ltd.) &lt;Polymer liquid crystal disc recognition&gt; The film formed on the substrate (film thickness: about 70 nm) was calcined at 230 ° C for 10 minutes, and then observed by a polarizing microscope. Further, the temperature increase rate was set to 3 ° C / min. &lt;Glass transition temperature&gt; The measurement was performed by differential scanning calorimetry (DSC) using a differential display. The temperature increase rate was set to 8 〇 c/min. &lt;The dark level of the cell was confirmed&gt; The prepared unit was subjected to polarized light microscopy and judged according to the following table. 89 201030095 33384pif.doc State evaluation Photoalignment film without spots (mura) Very good tiny granular spots Good large granular spots Bad friction The film has almost no friction and has a good frictional flaw. [Synthesis Example 1] &lt;Synthesis of Compound (VII-2-3)&gt; C9H 18-^-N H2 (VII-2-3) with (VII-2- The compound of 2) was synthesized in the same manner. Melting point: 98.0 ° C to 99.2 ° C. [Synthesis Example 2] &lt;Synthesis of Compound (VII-4-1)&gt;

Diethyl 4-bromophthalate (50 g, 166 mmol), 1,7-octadiyne (8.7 g, 82 mmol), triphenylphosphine di-gasified Is (II) (290 mg, A mixture of 0.41 mmol) and copper molybdenum (158 mmol, 0.83 mmol) was refluxed for four hours in triethylamine (200 ml) under a nitrogen stream. To be reversed 201030095 33384pif.doc After the end, add toluene (500 ml) and pure water (5 〇〇 ml) for extraction. After the organic layer was washed once with pure water (3 〇〇 ml), it was dried using anhydrous sulfuric acid. Filtration and distillation of the solvent under reduced pressure gave 1,4-bis(3,4-dicarboxyphenyl)ethynylbutanetetraethyl ester as a target. The yield was 42 g and the yield was 95%. This compound was used in the next reaction without purification. Add 5 wt% palladium on carbon catalyst (pd/c) in I,4-bis(3,4-dicarboxyphenyl)ethynylbutane tetraethyl ester (42 g, 77 mmol) (2 iy, then in A In the present/ethanol mixed solvent (3〇〇ml/3〇〇mi), the hydrogenation reaction is carried out at a hydrogen pressure of 72Q Mpa. After the reaction is completed, the catalyst is removed, and the solvent is distilled off under reduced pressure. Column chromatography (c〇lumn chromatography) (Shixi gum / toluene: ethyl acetate = 1 〇: iv / v) was purified 'to obtain the target # bis(10) di-phenyl) octyl tetraethyl ester . The yield was 43 g and the yield was 100%. μ·bis(3,4-dicarboxyphenyl)octane tetraethyl vinegar (4)

Dissolve in ethanol (250 ml) towel and add 5.7% aqueous sodium hydroxide solution (250 ml) to reflux for 2 hours. After the reaction, the solvent was distilled off under reduced pressure and then concentrated hydrochloric acid was added until the pH reached. After the shoal of the transitional site, the quilted water (2 (8) _ clear ^ times = the obtained crystals were dried under reduced pressure, thereby obtaining M• bis (3,4 bis-pyro-phenyl) octane. 31 g, the yield is 9〇%., the soil is in bis(3,4-dibuylphenyl) octyl (1〇g, Μ mm〇i): vinegar "ml), then refluxed for 2 hours. After removing the acetic acid needle by steaming, cyclohexene (9) ml) was added to the residue, and the resulting 91 201030095 33384 pif.doc precipitate was filtered, and the obtained crystal was dried under reduced pressure to obtain a chemical compound (VII-4). -1 ). Yield 9.2 g, yield 97%. Melting point: 109.7-111.2 〇C. NMR (500 Hz, CDC13); δ(ρριη) 7.92 (d, 4H, J =

Hz), 7.70 (d, 4H, J = 8.1 Hz), 2.82 (t, 4H, J = 7.65 l-3-1.7 (m5 12H).

[Synthesis Example 3] &lt;Preparation of polyamic acid varnish A&gt; ® Compound (II-1) (0.1818 g, 0.7827 mmol) was dissolved in Νmethylpyrrolidone (NMP '3.0 g), and the compound ( VII-4 - (0.3182 g '0.7829 mmol) was kept at room temperature or below, and the dough was added. After one night of mixing, 'addition of NMP (3.5 g) and ethanedibutyl ether (BSC, 3.0 g) The varnish a is prepared. The viscosity of varnish A is 4 sense 8 'mPa's. The weight average molecular weight of the lysine of this varnish is 74, 〇〇0, in the range of 2 (K) ° c ~ 300 ° c in memory Liquid crystal phase.

[Synthesis Examples 4 to 14] Q &lt;Preparation of Polyacrylic Acid Varnish B~; L&gt;, according to the raw material composition shown in Table 1, the varnish B of polylysine was prepared by the same method as in the synthesis example. ~ Varnish L·, and in the same manner as in Synthesis Example 1, the physical properties were determined. Within the brackets, mol°/0 is indicated. Further, according to the measurement, all of the varnishes were subjected to confirmation of the liquid crystal phase, and as a result, the memory was in the liquid crystal phase in the range of rc~250 °C. 92 201030095 33384pif.doc &lt;Table 1&gt; Varnish name: Amine acid viscosity (mPa.s) # Average 3 A II-l \ϊ I -4-1 49.8 74,000 4 B Μ »1 VII ^4^1 2S.8 48,000 5 C \4 i&gt ;l~&quot;l(8〇) 1-1(20) VI1 卜8 33. 3 ss.ooo 6 D \ϊ 1 80) Μ-1 (20) νι π -e 28,3 50,000 γ E Μ 1 ^1^1(80) VI-1 (20) VI: I I-8(90) , Ατΐ4{ 10) S7.9 68,000 8 F Π-1(40) VI-1(40) (2-22) (20) 1 -*4^1 30,8 51,000 9 G Μ1-2 \ί i 1 -8 30.4 60,000 10 Η i I ~1 VI! - 4TM1 27.6 48,000 11 I \川, 5 V! I ^ 4^1 34:. 2 54,000 12 J νΠ!~6 \1 Bu 4_! 37. i 62,000 Ϊ3 κ Μ Π-6 \Α 1 -δ-1 19.2 28,000 14 L VI ~Ι \11-4-1( 90) Ατ21 (10) 28.7 Silver (10) 〇 [Example 1] 1.0 g of varnish A was weighed in a sample bottle, and NMP/BC = 1/1 (weight ratio) was added to reach 1.67 g. On the transparent glass substrate, about 3 wt% of polylysine solution was added dropwise and coated by a spin coating method (2, 〇 〇 rpm '15 seconds). After coating, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and the polarizing plate was irradiated with linearly polarized light (365 nm and energy was about 1.3 J/cm 2 ). In the oven, 21 〇. The substrate after the light irradiation was subjected to heat treatment for 15 minutes to obtain a retardation of a film thickness of about 1 〇〇 93 201030095 33384 pif.doc, and the result was 12.9 nm. The results obtained in the same manner as in Example 1 were obtained in the same manner as in Example 1 nm of the alignment film A. The alignment 臈a was measured. [Example 2 to Example 6] The varnish shown in Table 2 was used to form the alignment film B to the alignment film F. The results of the measurement extension are shown together. &lt;Table 2&gt; Example No. Varnish name Orientation film Name Delay 1 A A 12.9 2 B B 2?. 8 3 C C 13.7 4 D D 7,9 5 E E a. 6 6 F F ..... 24.0

[Example 7] An aligning film crucible was produced in the same manner as in Example 1 except that the varnish 5% in which varnish A and varnish B were each mixed with 5 g of varnish was used instead of varnish A. The retardation value of this alignment film is 3 〇 5 nm. [Comparative Example 1] Compound (11-1) (2.6432 g ' 11.38 mm 〇l) was dissolved in NMP (35.0 g) with PMDA (1.2410 g, 5.690 mmol) and €3 (1.1158 L'5.69). 〇111111〇1) It is added while being kept at room temperature or below. After stirring at room temperature for one night, NMP (35 g) and BSC (25 g) were added. The viscosity of this solution was 12 〇 mpa.s. This solution 94 201030095 33384pif.doc was stirred at 6 (TC for about 4 hours to obtain a varnish N having a viscosity of 28 〇mpa s. The weight average molecular weight of the lysine of the varnish = and the glass transition temperature (Tg) exceeded In the same manner as in Example i, the alignment 貘n was obtained in the same manner as in Example i, and the retardation of the alignment film N was measured. The result was 0.4 nm. [Comparative Example 2] Compound (VI-1) was used instead. In addition to the compound (IM), φ was obtained in the same manner as in Comparative Example 1 to obtain a varnish P having a viscosity of 34.0 mPa·s. The weight average molecular weight of the lysine of the varnish was 54 Å, which was broken. The temperature (Tg) exceeded 300 ° C. Using the varnish P, the alignment film p was obtained in the same manner as in Example 1, and the retardation of this alignment film P was measured. The result was 0.8 nm. If the examples were compared with Comparative Example 1, In Comparative Example 2, it is understood that the alignment film of the present invention obtained by using the polymer of the present invention has an alignment film made of a polymer having no liquid crystal property, even with less irradiation energy. Very large delay value. ❹ [Embodiment 8] An alignment film A having a film thickness of about 100 nm was obtained in the same manner as in Example i except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one surface. Two sheets were formed on the ITO electrode. The substrate of the alignment film is bonded in such a manner that the directions of polarization of the linearly polarized light irradiated to the respective alignment films are parallel, and the faces on which the alignment films are formed are opposed to each other and formed between the opposing alignment films. The voids of the liquid crystal composition were injected to assemble liquid crystal cells A having a cell thickness of 7 μm (liquid 95 201030095 33384 pif.doc crystal display elements). Further, the liquid crystal composition A shown below was injected into these cells. Liquid crystal composition A&gt;

11-C5H11

17 wt% 17 wt% 16 wt% 10 wt% 5 wt% 10 wt% 6 wt% 6 wt% 13 wt%

By visually observing this liquid crystal cell a, as a result, a so-called flow alignment in which liquid crystals were arranged in the direction in which the liquid crystal flows was not observed at all. If the polarized light microscope is set to a cross nicol state and the liquid crystal cell A is rotated, a clear light state and a dark state are observed. The pretilt angle of this liquid crystal cell A is 〇 〇. . Moreover, VHR (electricity 96 201030095 33384pif.doc pressure retention) was 99.0% (30 Hz), 85.0% (0.3 Hz), and the ion density was 120 pC. Moreover, as a result of observing the dark level of the liquid crystal cell A, smaller granular spots were observed in all of the observed regions, but were still good dark levels. [Example 9] A liquid crystal cell B was produced in the same manner as in Example 8 except that the varnish used was replaced with varnish B. This liquid crystal cell B has a pretilt angle of 0.0°. Moreover, VHR (voltage holding ratio) is 92.2% (30 Hz), 76.3% (0.3 Hz), and the ion density is 340 pC. Further, as a result of observing the dark level of the liquid crystal cell B, no grainy spots were observed at all in the observed region, and this dark level was a very good dark level. [Example 10] A liquid crystal cell F was produced in the same manner as in Example 8 except that the varnish used was replaced with varnish F. The liquid crystal cell F has a pretilt angle 10 of 0.0°. Moreover, VHR (voltage holding ratio) is 99.2% (30 Hz), 85.3% (0.3 Hz), and the ion density is 80 pC. As a result of observing the dark level of this liquid crystal cell F, no grainy spots were observed at all in the observed region, and this dark level was a very good dark level. [Example 11] A liquid crystal cell L was produced in the same manner as in Example 8 except that the varnish used was replaced with varnish L. The pretilt angle 97 201030095 33384pif.doc of this liquid crystal cell L is 0.0. Moreover, 'VHR (voltage holding ratio) is 99 4% (3 Hz), 88.2% (0.3 Hz), and the ion density is 35 pc. Moreover, the result of observing the dark level of the liquid crystal cell L is the king observed. No grainy spots are visible at all in the P region, and this dark level is a very good dark level. [Example 12] A liquid crystal cell m was produced in the same manner as in the above, except that the varnish used was replaced with a clear one. The liquid crystal cell μ has a pretilt angle of 2 〇 / ^ and 'VHR (voltage holding ratio) is &quot;.〇%(9)Ηζ), 82.1/. (0.3 Hz), the ion density was 12 〇 pC. The result of entering the dark level of the liquid crystal cell M is as good as observed. The granules were not visible at all. This dark level was very good. [Comparative Example 3] The enamel paint used in I s was replaced with varnish N ′. 5 = Production of liquid crystal cell N. The liquid crystal cell N has a pretilt angle 760 760%f 〇 3T^VHR (voltage holding ratio) of &quot;.1% (3 〇 Hz), 7 〇/° (〇.3 Hz), and an ion density of 3 〇 0 PC. The result of the dark level of all the =1N is compared with the liquid crystal display element of the observed film. = The varnish p is replaced with the compound of Comparative Example 4 of the present invention. The liquid crystal cell is defective. The pretilt angle of this liquid crystal cell 98 98 201030095 33384pif.doc is 0.0. . Moreover, 'VHR (voltage holding ratio) is 92.4% (30 Hz), 85.3% (0·3 Ηζ) ’ ion density is 11〇pC. Further, as a result of observing the dark level of the liquid crystal cell p, large granular spots were observed in all of the observed regions, which was a poor dark level as compared with the liquid crystal display element using the alignment film of the present invention. [Example 13] In the same manner as in Example 1, varnish A was spin-coated on a φ transparent glass substrate provided with an IT 〇 electrode on one side, and then the substrate was at 80. (: After heating for 3 minutes to evaporate the solvent, it was heated in an oven at 21 ° C. for a minute. The obtained film was about 1 〇〇 nm. The film was subjected to rubbing treatment (pressure). Input: 0.3 mm, platform conveying speed: 6〇m/s, rotation speed: 1000, friction cloth: YA_18_R (rayon). Then, after ultrasonic cleaning of the alignment film in ultrapure water for 5 minutes, in the oven The film was dried at 200 ° C for 15 minutes. Two sheets of the substrate on which the alignment film was formed on the ITO electrode were laminated in such a manner that the rubbing directions for the respective alignment films were antiparallel, and the alignment film was formed. The liquid crystal cells Ar having a cell thickness of 7 μm are assembled into a cell having a cell thickness of 7 μm, and the liquid crystal composition A is injected into the cells. ' The pretilt angle of this liquid crystal cell Ar is 〇.3., VHR (electric dust retention rate) is 98.7% (30 Hz), 80.2% (〇.3 Hz), and the ion density is 23〇pc. The result of the dark level of the liquid crystal cell Ar, No scratches caused by friction were observed at all in the entire area, and the dark level was 99 201030095 33384 pif.doc and then very good dark level. [Example 14] Varnish J was used instead of varnish a, except The liquid crystal cell Jr having a cell thickness of 7 μm was assembled in the same manner as in Example 13. The pretilt angle of the liquid crystal cell Jr was 〇5 degrees, and the vhR (voltage holding ratio) was 99.1% (30 Hz), 87.5% (0.3). Hz), the ion density is 78 pC. Moreover, as a result of observing the dark level of the liquid crystal cell jr, scratches caused by friction are not observed at all in the observed region, and this dark level 疋 is very good darkness. When the alignment film of the present invention is applied to an alignment film for a liquid crystal display device as described above, the dark level can be greatly improved. Further, it is understood that the alignment of the present invention is resistant to (4) sufficient electrical properties. The reading of this publication reveals the above, but it is limited to the general knowledge of the two, and does not deviate from the protection of the invention. The second is: the change and retouching 'this book' is simple: Defined Quasi. Benefits. The main element REFERENCE SIGNS 100

Claims (1)

201030095 33384pif.doc VII. Patent Application Range: 1. An alignment agent comprising at least one polymer selected from the group consisting of polylysine and polyethylenimine obtained by the dehydration reaction of the polyaminic acid, and a solvent a composition in which the concentration of the polymer in the composition is 〇·1 wt% to 40 Wt%, and the ratio of the polymer based on the total amount of the film-forming component contained in the composition is 50 From wt% to 100 wt%, a film having a ❿ liquid crystal temperature range between 1 〇〇 t: 390 ° C can be formed by forming this composition into a film. 2. The alignment agent according to claim 1, wherein the polyamic acid is a polylysine having a photosensitive group in the main chain. 3. The alignment agent according to claim 2, wherein the photosensitive group is at least one of the groups represented by formula (I) to formula (VI): ❹ —R1~C^C~~ R2- ~R1~ R2- R1~~~~CH=CH-R2· CH=CH—R3—R1~~&lt;^C~Rz —R1~~C^C~~R2· (I) (&quot;) (&quot;I) (IV) (V) (VI) Here, R1, R2 and R3 are independently aromatic divalent groups. 4. The alignment agent according to the second aspect of the invention, wherein the polyamic acid having a photosensitive group in the main chain is a polyamic acid obtained by the following formula (1-1) to (1-3), Formula (nj) to Formula (π_3), Formula 101 201030095 33384pif.doc (111-1), Formula (IV-1) to Formula (IV-3), Formula (V_1), and Formula (vi) -l) at least one of the diamine having a photosensitive group represented by the formula (VI-7) and the formula (A-1), the formula (A-2), the formula (A-12), and the formula (A- 14), formula (A-18), formula (A-20), formula (A-21), formula (A-37), formula (vil-4), formula (VII-5), formula (VIII-7) And reacting at least one of the four resorcinic dianhydrides represented by the formula (VIII-8): 102 201030095 33384pif.doc H2N~^~c=c~c^c—^~^~nh2 (iv-1) (IV-2) (IV-3) (V-1) (VI-1) (VI-2) (Vl-3) (VM) (VI-5) (VI-6) (VI -7) 103 201030095 33384pif.doc 104 201030095 33384pif.doc (VII-4) (VII-5) (VIII-7) (VIII-8) Here, R5 is an arbitrary -CH2- which may be substituted by -〇, -NH-, -N(CH3)-, -Si(CH3)2OSi(CH3)2- or -COO-, having a carbon number of 6-20 Alkylene. 5. The aligning agent according to claim 2, wherein the t-amine having a sensitizing group on the primary bond is represented by the formula (IV-4) and the formula (νι_8) by: At least one of the tetracarboxylic dianhydride of the polyamido group is carried out by the formula (νΐϊ, having a photosensitive group AU ～ (νττ η. \ and formula (VIII-1) to formula (VIII-6)) Reaction: 105 201030095 33384pif.doc (IV4&gt; (VI-8) h2n- -R4—ΝΗ2 (VI Μ) H2N-Qh (Vll-2) n-0—0^^0~hG)_nh2 (VI1-3) Here, R4 is an alkylene group having a carbon number of 6 to 20; R5 is an arbitrary -CH2- which may be -〇-, _NH-, -N(CH3)_, -Si(CH3)2OSi(CH3)2- Or -COO-substituted alkylene having 6 to 20 carbon atoms; 106 201030095 33384pif.doc (VIII-2) (VIIM) (VIII-5) (VIII-6) o 6. The aligning agent as described in claim 2, wherein the polyaminic acid having a photosensitive group in the main chain is a polylysine obtained by the following formula 1-1) to formula (1-3), formula (Π-1) to formula (11-3), formula (111-1), formula (IV-1) to formula (IV-3), formula (V) -1) and at least one of the diamines having a photosensitive group represented by the formula (VI-1) to the formula (VI-7) and the formula (VII-1) to the formula (VII-3) and the formula (VIII- 1) a mixture of at least one of the diamines represented by the formula (VIII-6) and a formula (H), a formula (A-2), a formula (A-12), a formula (a-14), and a formula (A) -18), the formula (A-20), the formula (A-21), the formula (A-37), the formula (VII_4), the formula (νπ_5), the formula (νπι·7), and the formula (VIII_8) At least the species of New II Xuan carried out the anti-107 201030095 33384pif.doc H2n—~c^c——nh2 (Μ ) (I-2) h2 (I-3) NH 2 H2 H2 h2 H2 NH 2 h2 H2 201030095 33384pif.doc h2n~c=c-c=c-~~nh2 Nh2 H2N~~^CSC~~CH=CH-~~NH2 (iv-1) (IV-2) (IV-3) (V-1) (VI-1) (VI-2) (VI-3) (VI-4) (VI-5) (VI-6) (VI-7) 201030095 33384pif.doc H2N~R4—NH2 h2n-Q&gt;—r5H〇--nh2 (VII-1) (VII-2) (v&quot;·3) Here, R4 is a carbon number of 6~ 20 alkylene; R5 is any -CH2- may be substituted by -〇-, -NH-, -N(CH3)·, -Si(CH3)2OSi(CH3)2- or -COO- 6 to 20 alkylene; h2 H2 h2 H2 (VIII-2) 〇_NHz (VIII-3) ❿ (VIIM) (VIII-5) (VIII-6) 110 201030095 33384pif.doc Il 201030095 33384pif.doc (VII-4) (VII-5) (VIII-7) (VIII-8) Here, R5 is an arbitrary -CH2- which may be substituted by -0-, -NH-, -N(CH3)-, -Si(CH3)2〇Si(CH3)2· or -COO-, and the carbon number is 6 ~20 of the sub-smoke base. 7. The polyaminic acid having a photosensitive group as in the second item of the patent application is obtained by the formula (IV-4) and the formula (Vi_8) by, for example, the acid of the scorpion scorpion. At least one of a tetracarboxylic dianhydride of a guanamine group and a mixture having the photosensitive formula (VIII-7) and the formula (VIII-8) = ^VI1-4), the formula (VII-5), and The reaction of the diamine represented by the formula (VII-1) to the tetracarboxylic dianhydride of the formula (VII-1) to the formula (VIII-6) and the formula (VIII-1) are carried out: 112 201030095 33384pif.doc &lt;ιν^) (VI-8) (VII-4) (VII-5) (VIII-7) (VIII-8) Here, R5 is an arbitrary -CH2- which may be substituted by -0, -NH, -N(CH3)_, -Si(CH3)2〇Si(CH3)2· or -COO- Sub-hospital based on carbon number 6~20; 113 201030095 33384pif.doc (VII-1) (VII-2) (VII-3) H2N-R4-NH2 h2n~^^~r5H〇&gt;~nh2 ΗζΝ-0 ~Η0^5-0~0ΚΝΗ2 Here, R4 is an alkylene group having a carbon number of 6 to 20; R5 is an arbitrary -CH2- which may be -〇-, -NH_, -N(CH3)-, -Si( CH3) 2OSi(CH3)2- or -COO-substituted alkylene having 6 to 20 carbon atoms; (VIII-2) (VIII-3) ❹ (VIII-4) (VIII-5) (VIII-6) 114 201030095 33384pif.doc 8. The aligning agent according to claim 2, wherein the main chain The polyaminic acid having a photosensitive group is a polyglycolic acid obtained by the following formula: (Expression (1-1) to Formula (1_3), Formula (π-D~ Formula (π·3), Formula (( 111-1), at least one of the diamines having a photosensitive group represented by the formula (IV-7), the formula (V-1), and the formula (VU) represented by the formula (VI-7) a mixture with at least one selected from the group consisting of diamines represented by formula (2) to formula (4) and formula (Α·1), formula (Α-2), formula (Α-12), formula (Α- 14), Formula (Α-18), Formula (Α-20), Formula (Α-21), Formula (Α-37), Formula (VII-4), Formula (VII-5), Formula (VIII-7) And at least one of the tetracarboxylic dianhydrides represented by the formula (VIII-8) is reacted: (Μ) (1-2) (1-3) &quot;&quot;&quot;NHz h2\ h2K ❷ 115 20103009533384pif.doc H2 H2 (11-1) (H-2) (II-3) &lt;11-1 &gt; (iv-1) (IV-2) (IV-3) h2n—(Q&gt;—c=c—^c=c—nh2 H2N-H0K-C^C—C^=CH-^—NH2 (V-1) 116 201030095 33384pif.doc (VI-1) (VI-2) (VI-3) (VI-4) (VI-5) (VI-6) (VI-7) 2 H2N^A^—(-X^A2^—^X3十Y十χ4^~(·α3—x6^—a4-nh2 Here, A1, A2, A3 and A4 are independently cyclohexylene or phenylene; X3 and X4 are independently a single bond, and the carbon number is 1 to 5. Alkylene or -Ο- ; X5 and X6 are independently a single bond, -CH2-, -CH2CH2-, -Ο- or -S-; Υ1 is -CH2-, -C(Rn)(R12)-, -CO - or -S02-, Rn and R12 are independently argon, 117 201030095 33384pif.doc Xu Fu ^ m2, m3, m4 2 base having a carbon number of 1 to 12: or a fluoride wire having a carbon number of 1 to 12; None of the ^ keys are all ^ benzene, X3, X4, X5 and X6 〇-, -COO-, -OCO-, -NH-, 12 alkylene; G1 and G2 are a single bond, a cyclohexyl group, and a sub-independence H G * 1; and, in the Suppose that the arbitrary hydrogen can be bonded to the alkyl group having a carbon number of 1 to 4 or the bonding position of the A2A A3 '~di substituent; however, when A1 -3⁄42 is a single bond or contains: from the money of 6~12:; ^, "and & is a single bond, in the alicyclic ring, such as, the scent ring and the carbon number is 3~12-ΟΗ, a divalent group having a carbon number of ~3 rings; 1&quot;6 is a nitrogen, fluorine, _CN, a fluorinated group having a carbon number of 1 to 30 μ fluorenyl group, a carbon number of 1 to 3 G, or an inverse number of 1 to 30 When the oxime is a single bond, R6 is reduced by 3 G, X is read by f all f ^ , 疋 is 3 to 30, the carbon number is 3 to 30 or the carbon number is 3~ Alkoxy group of 30, when G2 is a single bond and X2 is both 疋: when the bond is not an alkylene group, R6 is hydrogen or the alkane i having a carbon number of 3 to 3 Å is 2 and both are single bonds. The total carbon number of χι, χ2, and r6 is greater than or equal to 3; 118 (4) 201030095 33384pif.doc &amp; Here, R7 is hydrogen or a carbon group having a carbon number of 1 to 12; a ring group which may be substituted by an alkyl group having 1 to 4 carbon atoms; and a group having a carbon number of 1 to 4; a substituted bond or an alkylene group having a carbon number of 1 to 5, and an s hexyl group, when X 疋 is 2 or 3, a plurality of rings B may all be the same number, and 'when s is less than 2 different _, Multiple defects. All of the same ^ can be composed of at least 2 different groups; j is also -CH2-, code? or -〇-, tl and t2 are independent of the early bond, when tl is 2 or 3, more Each of Z1 may be an integer of ～3; consists of at least two different groups; #t2, the group 'may also be Ζ2 may all be the same group, or may be from 2 to 3 pm Composition; ^ 2 different groups 119 201030095 33384pif.doc 120 201030095 33384pif.doc ❿ (VII-4) (VII-5) (VIII-7) (VIII-8) Here, R5 is an arbitrary -CH2. The carbon number which may be substituted by -0, -NH-, -Si(CH3)2〇Si(CH3)2 or -COO. is 6-20 Affiliated base. 9. The alignment agent according to claim 2, wherein the polylysine having a photosensitive group in the main chain is a polylysine obtained by the following formula (1-1) (1-3), Formula (Π-1)~Formula (Π-3), Formula (111-1), Formula (IV-1)~Formula (ιν-3), Formula (V-1), and Formula ( VI-1) at least one of the diamines having a photosensitive group represented by the formula (VI-7), from the formula (VII-1) to the formula (VII-3) and the formula (VIII-1) to the formula (VIII) -6) at least one of the diamines represented, and a mixture selected from at least one of the diamines represented by the formulas (2) to (4) and from the formula (A-1), the formula 121 201030095 33384pif.doc (A-2), formula (A-12), formula (A-14), formula (A-18), formula (a-20), formula (in-21), formula (in-37), formula (乂11-4), at least one of the formula (¥11-5), the formula (¥111-7), and the tetracarboxylic dianhydride represented by the formula (VIII-8) are reacted. HzN~&quot;^3一&quot ;·^Η2H2V_ _ (Μ (1-2) (1-3} Η2 η2 Η2Ν—CSC—CH==CH—ΝΗζ (11-1) (Η-2) 〇 (ΙΙ-3) (IH-1) 122 201030095 33384pif.doc ❹ (iv-1) (IV-2) (IV-3) (V-1) (VI-1) (VI-2) (VI-3) (VI-4) (VI-5) (VI-6) (VI-7) 123 201030095 33384pif.doc (VII-1) (VII-2) H2N^0-R5-0~NH2^nO-〇-r5O-〇-nh^ (vm-3&gt; Here, R4 is an alkylene group having a carbon number of 6 to 20 ; R5 is any -CH2- may be substituted by -〇-, -NH-, -N(CH3)-, -Si(CH3)2OSi(CH3)2- or -COO· with a carbon number of 6~20 Alkyl; h2n--4^V-nh2 (VIII-2) (VIII-3) ◎ (VIII-4) (vm-5) (VIII-6) 124 201030095 33384pif.doc Here, A1, A2, a3, and a4 are independently cyclohexylene or sub-stack; X and X are independently a single bond, an alkylene group having a carbon number of 1 to 5 or _〇·; and $ and X6 are independently a single bond. , _CH2_, _CH2CH2_, _〇 or each; γ1 a -CH2-, _C(Rm...(3) or _s〇2_, Rll and r12 are independently a burning group having a carbon number of 1 to 12, or a carbon number of 12 a fluorinated alkyl group; mi, two, m3, m4, and η independently represent 0 or 1; and, in the exfoliated X and subunits, any fluorene may be burned with a carbon number of 1 to 4. Base H2N^At^X5' The bonding position of the fluorenyl group is Ren Lang; however, when α:, are not single bonds; all are 1,4·sub-stupid, χ3, χ4, χ5, and X6 Here, X1 and X2 are -CONH-, or the carbon number is! ~, ·〇-, -COO-, -OCO-, -NH-, or one selected from a carbon number of 6 to 12 = _alkylene; G1 and G2 are single bonds, one of the alicyclic rings ~ 3 ^ aromatic rings and -OH having a carbon number of 3 to 12, a valence group having a carbon number of 1 to 3 Å; R6 being hydrogen, fluorine, -CN, and having a carbon number of 1 to 30; When the alkoxylate is a fluorinated alkyl group having a carbon number of 1 to 3 Å or a single bond, R6 is carbon, and when X'G1, #, and G2 are all ... to 30, the carbon number is 3 ~30 of 125 201030095 33384pif.doc Fluorinated base or alkoxy having a carbon number of 3 to 30 'When G2 is a single bond and χ2 is neither a single bond nor an alkylene group, R6 is hydrogen or has a carbon number of 3 〜3〇 of the alkyl group' When both G1 and G2 are single bonds, the total number of stones of X], χ2, and r6 is greater than or equal to 3; (4) Q Here, R7 is hydrogen or a carbon group having a carbon number of 1 to 12; and ring b is a 1,4-phenylene group in which hydrogen of any member may be substituted with an alkyl group having 1 to 4 carbon atoms, or A dihydrocyclohexyl group which is substituted with an alkyl group having a carbon number of 1 to 4; a ^ bond or a thio group having a carbon number of 1 to 5, and s is Q 〜 3 ^ an integer H is 2 or At 3 o'clock, a plurality of rings B may all be the same ring field and two different rings constitute 'multiple X'. It may be composed of at least 2 (four)_base_;; and 22 independently as a single bond, ❹-CH2-, -CH2CH2- or -〇·, tl and q independent A ...... when ^ is 2 or 3 In the case, a plurality of zl may have an integer of ～3, which is composed of at least two different groups; when the mouth is 25:3, Z2 may all be the same group, or may be at least: V2 different groups 126 201030095 33384pif.doc 127 201030095 33384pif.doc (VII-4) (VII-5) (vm-7) where 'R5 is arbitrary -CH2· can be replaced by _〇_, _nh_, -N(CH3)-, si(ch3)2osi(ch3)2· or -coo- with a carbon number of 6 ~ 2 亚 sub-base. 10. The acidity as described in item i of the patent application is made by the formula (vn-D~-form (side) two: fine-type and species (νιΙΙ·7) and formula (νιΙΙ^== _ at least one of the dianhydrides is subjected to the anti-employment shame from π to the tetracarboxylic acid g by the formula (vm-D~ formula 'X:: valerine' or is i with formula (VII-4) and formula ( v = diamine of at least one body to obtain a reaction to obtain 妓 _ acid: called _ _ 轩 Xu j 128 201030095 33384pif.doc (VII-1) (VII-2) (VII-3) (VII-4) (Vil-5) Here, R4 is an alkylene group having a carbon number of 6 to 20; and, R5 is an arbitrary -CH2- An alkylene group having 6 to 20 carbon atoms which may be substituted by -0,, NH-, -N(CH3)-, -SiCCH^OSiCCH^-i-COO-; 129 201030095 33384pif.doc h2N-^^n h2 h2 H2 (VIII-2) h2n (VIII-3) (VIII4) (VIII-5) (VIII-6) (VIII-7) (VIII-8) ❹ 11. A liquid crystal alignment film obtained by rubbing or light irradiation for the alignment according to item 1 of the patent application scope The film obtained by coating the substrate on the substrate imparts anisotropy, and then is heated to the liquid crystal temperature range of the film 130 201030095 33384 pif.doc to make the film anisotropic 12. The liquid crystal alignment film is passed through The light irradiation is applied to the film obtained by coating the film obtained by applying the alignment agent described in the above-mentioned patent range to the substrate, and then heating the film to the temperature of the liquid crystal. As stated in 1G The obtained film imparts frictional anisotropy and is then heated to a liquid helium temperature range of the film to increase the anisotropy of the film. X 14. A liquid crystal display element comprising the liquid crystal alignment film according to item u of the patent application. A liquid crystal display element comprising the liquid crystal alignment film according to item 12 of the patent application. A liquid crystal display element comprising the liquid crystal alignment film according to item 13 of the patent application. 17. A polyimine or a polyglycine as a precursor thereof, comprising a constituent unit represented by the formula (IX), and having a liquid crystal temperature range of from 100 ° C to 300 3⁄4. (IX) Here, R5 is an alkylene group having a carbon number of 6 to 12; and R9 is represented by the formula (1_1) 131 201030095 33384 pif. doc 〜 (1-3), and the formula (II-1) to the formula (11- 3), the formula (ΙΠ-l), the formula (IV-1) to the formula (IV-3), the formula (ν·1), and the diamine represented by the formula (VI-1) to the formula (VI-7) Residues of any of the following: (Μ) (1-2) (1-3) (11-1) (H-2) (ll-3) (HI-1) 132 201030095 33384pif.doc (iv-1) (IV-2) (IV-3) (V-1) 133 201030095 33384pif.doc (VI-1) (VI-2) (VI-3) (VM) (VI-5) (VI-6) (VI-7) ❹ 18. A polyimine or a poly-proline which is a precursor thereof, which comprises a constituent unit represented by the formula (X) and has a liquid crystal temperature range at 100 ° C to 300 ° C. 134 (X) 201030095 33384pif.doc where 'R5 is an alkylene group having a carbon number of 6 to 12; R9 is a formula of 〇u~(1-3), formula (II-1)~(π- 3), in the diamine represented by the formula (111-1), the formula (IV-1), the formula (IV-3), the formula (ν·ΐ), and the formula (VI-1) to the formula (VI-7) Residues of any of the following species: H2N-〇-^c-〇-nh2 (Μ) (1-2) (1-3) nh2 (I·-" (11-2) {H-3) (IH-1) 135 20103009533384pif.doc (&gt;V-1) (IV-2) (IV-3) (V-1) 136 201030095 33384pif.doc (VI-1) (VI-2) (VI-3) (VI-4) (VI-5) (VI-6) (VI-7) 19. Polyimine according to claim 17 or polyproline as a precursor thereof, wherein R9 is represented by the formula (VIII-1) to (VIII-6) Residues of any of the amines: 137 201030095 33384pif.doc h2N_^^ h2 (VIII-1) h2 H2 (VIII-2) (VIII-3) (VIII-4) Θ (VIII-5) (VIII-6) 20. Polyimine as described in claim 18 or polyproline as a precursor thereof, wherein R9 is of formula (VIII) -1) The residue of any one of the diamines represented by the formula (VIII-6): 138 201030095 33384pif.doc H2n-^^-nh2 Me h2n—^^~nh2 (VIII-1) (VIII-2) (VIII-3) (VIIM) (VIII-5) (VIII-6) 21. A polyimine or a polyglycine as a precursor thereof, which comprises a constituent unit represented by the formula (IX) and represented by the formula (XI) It constitutes a unit and has a liquid crystal temperature range at 100 ° C to 300 ° C: 139 201030095 33384pif.doc where 'R5 is an alkylene group having a carbon number of 6 to 12; R9 is a formula (υ)~(1-3), a formula (π_ι)~(11_3), a formula (^) a residue of any one of the diamines represented by the formula (IV-3), the formula (^), and the formula (vw) to the formula (νι·7); R10 is represented by the formula (vm_i) 〜 η2ν-Η0^^〇_〇_^ H2 (1-1 ) Η 外 140 201030095 33384pif.doc ❹ H2 ch==ch^O^~nh2 (iv-1) (IV-2) (IV-3) (V-1) (VI-1) (VI-2) (VI-3) (VI-4) (VI-5) (VI-6) (VI-7) ^OTQrs^y^ 141 201030095 33384pif.doc H2 H2 h2 H2 (VIII-2) (vm-3} (VIII-4) (VIII-5) (VIII-6) 22. A polyimine or a polyglycine as a precursor thereof, which comprises a constituent unit represented by the formula (X) and represented by the formula (XII) It constitutes a unit and has a liquid crystal temperature range of 100 ° C to 300 ° C: (XII) 142 201030095 33384pif.doc Here, 'R5 is a sub-dotted group having a carbon number of 6 to 12, and R9 is a formula (I-1) to (1-3), and (II-1) to (Π-3), any of the diamines represented by the formula (111-1), the formula (IV_D to the formula (IV-3), the formula (vl), and the formula (VI-1) to the formula (VI-7) a residue of one type; Ri 〇 is a residue of any one of the diamines represented by the formula (¥111_1:) to (VIII-6): H2n H2n~^-c^c-c^o-^-mh2 (1-1) (I-2) (I-3) (11-1) (II-2) (in-1) 143 201030095 33384pif.doc (iv-1) (IV-2) (IV-3) (V-1) (VI-1) H2i H3c H3c (VI-2) (VI-3) 3 H ‘ Ch3 ^ nh2 -och3 (VM) NH, (VI-5) h2i V~^^-nh5 f3c (VI-6) (VI-7) 144 201030095 33384pif.doc Me (VIII-2) H2N_HC)_O_NH2 (VIII-3) (VIII-4) (VIII-5) (VIII-6) 145 201030095 33384pif.doc IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ❹ No 〇 201030095 is the Chinese manual of No. 98145370 without a slash correction page. (Please do not change the format and order of this manual. ※Please do not fill in the mark) (2000.01) ※Application number: 9 8 1 45 3 7 0 ※Application date: Classification: '2006.01, fiooe.on I. Name of the invention : Alignment agent and liquid crystal polyimine for use in the alignment agent ALIGNMENT AGENT AND LIQUID CRYSTALLINE POLYIMIDE USED THEREIN II. Abstract: The invention provides a good alignment, high sensitivity and high stability/high stability Alignment membrane. An alignment agent which is a composition containing at least one polymer selected from the group consisting of polylysine and a polyimine obtained by a dehydration reaction of the poly-proline, and a solvent, and polymerization in the composition The concentration of the substance is from 0.1% by weight to 40% by weight, and the ratio of the polymer based on the total amount of the film-forming component contained in the composition is from 50% by weight to 100% by weight, and can be made by The film is formed at 1 〇〇. 〇~3 〇 〇. There is a film with a liquid crystal temperature range between the crucibles. III. Abstract of the invention: The invention provides an alignment film having excellent alignment property, high sensitivity and high stability. An alignment agent is a composition having 201030095 33384pif] A case where the alignment of the liquid crystal is poor. Therefore, when adding the right-handed name of this organic stone shihua character, Qu Huo's Shishi compound, the total amount of points: compared with the polymer contained in the _ agent is about %~3 wt% (four) i ^ It is particularly good to prevent the deterioration of the characteristics with time or by the ring: the second two-way agent can also further contain a substance having more than one or more carboxylic acid residues of the polyamine. Crosslinker. As an example of such a crosslinking agent, for example, Japanese Patent No. 3,049,699, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese, Japanese Lu is responsible for the % bismuth compound, isocyanate material, etc. and, if the crosslinking agent itself reacts to become a polymer of the network structure, the film strength of the surface polyglycolic acid or polyimine is used for For the purpose of the above-mentioned purpose, the polyfunctional ethylene (10), which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. m (maleimide), or bis-di-imide derivative, etc. The ratio of these cross-linking agents relative to the total amount of the polymer component is preferably 〇wt%~5〇 The wt%, more preferably 0 wt% to 30 wt%. The alignment agent of the present invention contains a solvent having the ability to dissolve polylysine. The solvent is broadly included in the manufacture of polyaminic acid or a derivative thereof. Or the solvent commonly used in use, depending on the purpose of use When selecting these solvents, the following are listed. 79 201030095 33384pifl As an example of an aprotic polar organic solvent which is a good solvent (g〇〇cj s〇ivent) with respect to polyamic acid, it is exemplified: N _曱基_2_ mouth ketone (N&quot;Methyl-2-pyrrolidinone, NMP), dimethyl imidazolidinone, N-Methyl caprolactam, N -N-methyl propionamide, n,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimercaptomethyl hydrazine N,N-dimethyl formamide (DMF), N,N-diethyl formamide, hydrazine, hydrazine-diethylacetamide (DEAc) And a lactone such as γ-butyrolactone (GBL). Examples of other solvents for the purpose of improving coatability and the like other than the solvent include lactic acid-based vinegar (alkyl). Lactate ), 3-methyl-3-methoxybutanol, tetralin Ethylene glycol monoalkyl ether such as lin ), isophorone, ethylene glycol monobutyl ether (BCS), diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, Ethylene glycol monoalkyl ether acetate and ethylene glycol monophenyl ether acetate, triethylene glycol monoalkyl shrine, propylene glycol monobutyl ether and other propylene glycol monoalkyl ether, malonate diethyl ester, etc. A dipropylene glycol monoalkyl ether such as a dialkyl acid ester or a dipropylene glycol monoterpene ether, and a vinegar compound such as these ethylene glycol monoethers. Among these compounds, NMP, dimercapto pimilinone, GBL, BCS, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether or the like can be particularly preferably used in the solvent. 80 201030095 33384pifl Additive ==;:::=:rr step contains various surfactants according to the purpose, step = appropriate amount of force, you can contain anti-static agent in an appropriate amount and further in the city of electrostatic energy The concentration of polylysine is preferably 0.1 film ==〇. When the alignment agent is applied to the substrate, in order to adjust the acid licking operation, the polyamine contained in the solvent is diluted in advance by the solvent. The solid content in the alignment agent of the present invention is concentrated. The value is fine. Fortunately, the solid component Han = a ‘monthly varnish weight, better county ^, +0/ is good! .疋切%~3〇Wt%, the more aligning film is obtained by the following materials, and the film obtained by the alignment miscellaneous cloth on the substrate is given an increase in the anisotropy: after heating to the liquid crystal temperature of the film _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The method is to apply 'the varnish on the substrate; ^(2) at 5 ° ° C ~ 12 ° ° C, preferably 8 〇 t ~ 1 thief under the thief plated the film formed, and the solvent is evaporated (3) illuminating the film to align the poly-proline of the film; 81 201030095 33384pifl (4) at 150 ° C ~ 300 ° C, preferably 18 〇 t; ~ 25 〇 t : heating the membrane to which the Hi acid is aligned, and imidating the membrane. Further, when it is desired to exhibit a predetermined pretilt angle in a liquid crystal display element using an alignment film, it is possible to irradiate the substrate with linearly polarized light from an arbitrary angle when irradiating light, or to perform a substrate on the substrate. Linearly polarized light illumination from the vertical direction is combined with unpolarized light illumination from any angle. In the production of the alignment film of the present invention, linearly polarized light is used in the alignment B of the polyacrylic acid.聚轴社_ Linearly polarized light (4) _ Aligned in a direction perpendicular to the direction of polarization of linearly polarized light. The linearly polarized light is not particularly limited as long as it is a light that can align the poly-aracine in the film. The _ aligning film can align the film by low-energy illumination. Therefore, the irradiation amount of the I· linearly polarized light in the photo-alignment treatment of the poly-branze is preferably 〇·5 J/cm 2 丨〇 J/cm 2 . Further, the wavelength of the linearly polarized light is preferably from nm to gamma. The irradiation angle of the linearly polarized light to the surface of the film is not particularly limited. However, in the case of a strong alignment limiting force of the liquid crystal, the alignment time is shortened, and the irradiation angle is preferably as perpendicular as possible to the film surface. . Further, in the production of the alignment film of the present invention, it is intended to exhibit a premise. The light irradiated to the film at an oblique angle may be polarized light or may be non-polarized'. The amount of light irradiated to the film when it is desired to exhibit a pretilt angle is preferably 0.5 JW to 10 J/cm 2 . The wavelength of this light is preferably · nm 400 nm. The irradiation angle of the light irradiated to the film when the pretilt angle is desired to be expressed on the film surface is not particularly limited, but the alignment is shortened. 82 201030095 is the Chinese specification of No. 98145370. (Please do not change the format and order of this manual. ※Please do not fill in the mark) (2000.01) ※Application number: 9 8 1 45 3 7 0 ※Application date: Classification: '2006.01, fiooe.on I. Name of the invention : Alignment agent and liquid crystal polyimine for use in the alignment agent ALIGNMENT AGENT AND LIQUID CRYSTALLINE POLYIMIDE USED THEREIN II. Abstract: The invention provides a good alignment, high sensitivity and high stability/high stability Alignment membrane. An alignment agent which is a composition containing at least one polymer selected from the group consisting of polylysine and a polyimine obtained by a dehydration reaction of the poly-proline, and a solvent, and polymerization in the composition The concentration of the substance is from 0.1% by weight to 40% by weight, and the ratio of the polymer based on the total amount of the film-forming component contained in the composition is from 50% by weight to 100% by weight, and can be made by The film is formed at 1 〇〇. 〇~3 〇 〇. There is a film with a liquid crystal temperature range between the crucibles. Abstract, the invention provides an alignment film having excellent alignment property, high sensitivity and high stability. An alignment agent is a composition having 201030095 33384ρΐί1 polyamic acid and at least one polymer and a solvent of the polyimide obtained through a dehydration reaction The concentration of the polymer in the composition is from 0.1 wt% to 40 wt%. The proportion of the polymer is from 50 wt% to 100 wt% based on the total weight of the film forming content in the composition A film having a liquid crystal temperature ranging from 100°C to 300°C is formed by using the compostion.