TWI253464B - Varnish for liquid crystal alignment film and liquid crystal alignment film and liquid crystal film display device - Google Patents

Abstract

The objects of the present invention are to fabricate a liquid crystal alignment film that eliminates mechanical friction and has superior compatibility with glass substrate and to provide a varnish for fabricating stable and consistent liquid crystal alignment film. The varnish for fabricating liquid crystal alignment film comprises polymers from derivatives of silsesquioxane as indicated by molecular formula (1). Wherein, the polymer is made from at least one of the amide and imide to form a polymer chain. In molecular formula (1), R1 is selected from hydrogen, alkyl, aryl and arylalkyl. In addition, at least two Ys in molecular formula (1) are selected from one of the groups indicated by molecular formula (2-1) and (2-2), and the residue of Y is hydrogen. In molecular formula (2-1) and (2-2), Z1 is a radical that includes amide, Z2 is a radical that includes 2-oxapropanedioyl. Whereas, R2 and R1 are the same radicals.

Description

</ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> An alignment film produced using the varnish for producing a liquid crystal alignment film, and an invention relating to a liquid crystal display element comprising the alignment film. Moreover, the expression "sesquioxane derivatives" is expressed in accordance with the rules of the International Union of Pure and Applied Chemistry (IUPAC), in which each helium atom is combined with three oxygen atoms, each oxygen The substance name of a compound in which an atom is bonded to two deuterium atoms. However, in the present invention, a substance having a structure similar to that of a part of the sesquioxane derivative which is destroyed in the basket structure is also referred to as a "sesquioxane derivative". [Prior Art] The mainstream of liquid crystal display elements is a display element using nematic liquid crystal. Further, there are a twisted nematic (TN) type liquid crystal display element which is twisted by 90°, a torsion 18 (super twisted nematic (STN) type liquid crystal display element of Γ or more, and a so-called TN-TFT type liquid crystal display using a thin film transistor) In addition, recently, In Plane Switching (IPS) type liquid crystal display elements, Vertical Alignment (VA) type liquid display elements, and Optically Corrected Birefringence (OCB) have appeared. A liquid crystal display element, etc. The in-plane conversion type liquid crystal display element is a type of field effect transistor type liquid crystal display element, and is a lateral electric field type element which has improved visual characteristics. The vertical alignment 1253464s3pif.doc type liquid crystal display element is A device for utilizing a vertical alignment state. A light lift correction birefringence type liquid crystal display element is an element having a characteristic of fast response speed, wide viewing angle, and the like. In these liquid crystal display elements, the long axis of liquid crystal molecules is made. It is very important that the aspect is uniformly aligned. As a representative method for uniformly aligning liquid crystal molecules, The following rubbing method is known, that is, an aligning film composed of an organic coating film on the surface of a substrate, which is rubbed in a certain direction by a cloth such as cotton, nylon or polyester to cause liquid crystal molecules to rub in the rubbing direction. The method of aligning the above. With this rubbing method, stable uniform alignment can be obtained relatively easily, and it is excellent in productivity, so it has become the mainstream in the industry. As a material for the alignment film, there are known: polyethylene Polymers such as alcohol, polyoxyethylene, polyamine, polyamidiamine, polyamidimide, etc., from the perspective of stability and durability of industrial batch production, due to the Since it is excellent in chemical enthalpy and thermal stability, it is the most widely used as a varnish for constituting a liquid crystal alignment film. Further, in the following description, a varnish for liquid crystal alignment film production may be used. It is described separately with varnish. The alignment treatment method of the rubbing alignment film is simple and excellent in productivity. It is a kind of method that is very useful in industry. However, if the liquid crystal is used When used in each field, it will be pointed out that various problems are caused by the salty appearance of the liquid crystal display element. For example, it can be seen that the alignment defect of the _ injury caused by the friction on the surface of the alignment film, the use of the friction grinding to remove the alignment film After that, the friction debris will become a problem such as a defect in the display. The lack of friction caused by the friction even if there is only one in the _ face, the liquid crystal is a bad product, 125346^53pif.doc, so it becomes a pass rate. One of the reasons for the reduction is very large. With the development of large screens in recent years, the friction resistance is more strictly required than before. Moreover, in recent years, in order to reduce the manufacturing cost and pursue the lightweight, the plastic sheet is being trial-produced instead of the previous one. In the case of the glass substrate, the varnish is sintered at a low temperature of less than 2 ° C (for example, Japanese Patent Application Laid-Open No. Hei No. Hei-5-158047 . However, in particular, polylysine which is a precursor of polyimine is coated on a substrate, and when it is sintered at a low temperature, cyclization dehydration (imidization) of polyproline cannot be sufficiently performed, and the obtained poly is obtained. The mechanical strength of quinone imine is insufficient, and the problem of damage to the alignment film is more profound. In the example of the problem of the alignment film related to the rubbing method, 'the mechanical strength is insufficient, the friction generated by the rubbing method is unsuitable, and the bonding with the glass substrate is not good, resulting in falling off, etc., and these problems can be seen. The seat is caused by the organic polymer of the majority of the carbon atoms contained in the alignment film as the main component. Moreover, it is desirable to develop an alignment film that improves these problems. Insufficient mechanical strength can be improved to some extent by changing the molecular structure of the alignment film. However, since the structure is changed, the electronic characteristics of the alignment film and the pretilt angle of the liquid crystal tend to fluctuate. Therefore, many improvements may occur in the improvement. Moreover, for the bonding to the glass substrate, the decane crosslinking agent can be used to some extent to improve. However, the decane cross-linking agent is easily hydrolyzed, and there is a problem in the storage stability of the varnish containing the substance. If it is used excessively in order to prevent detachment, there is a problem that the performance of the liquid crystal display element is lowered. [Improved] It is an object of the present invention to provide an alignment film which is excellent in mechanical strength which can be adapted to friction generated by a rubbing method and which has excellent adhesion to a glass substrate, and also has a storage stability. Very good varnish. Further, it is also an object of the present invention to provide an alignment film obtained by using the varnish and a liquid crystal display element containing the alignment film. The inventors of the present invention have found that the varnish obtained by using a polymer having a sesquioxane derivative skeleton in the main chain can solve the above problems. That is, the liquid crystal alignment film obtained by using the varnish has great mechanical strength, excellent adhesion to a glass substrate, and high abrasion resistance. Moreover, the storage stability of the alignment film is also excellent. Since the sesquiterpene oxide derivative skeleton in the polymer used in the present invention is itself a highly crosslinked body, there is no site where hydrolysis occurs. Therefore, in terms of improving the bonding property with the glass substrate, the storage stability is excellent as compared with the varnish using the decane crosslinking agent. Further, it is possible to produce a highly reliable liquid crystal alignment film which does not adversely affect the display performance of the liquid crystal display element. The present invention has the following structure: [1] The material is a varnish for producing a liquid crystal alignment film, which is a constituent material containing a polymer obtained by using a sesquioxane derivative represented by υ, which is a polymer A polymer constituting a polymer chain using at least one of a guanamine bond and an imide bond, and may contain a polymer obtained without using a sesquiterpene gas derivative represented by the formula (1), or may contain other additives. , in all the polymer components, the ratio of the polymer obtained by using the molecular formula (1), the deuterium hemidecane derivative, is 0.1 to 1 〇 0% by weight, '125346^3pif.d〇c The ratio of the polymer obtained by using the sesquitaine derivative represented by the formula (1) in the polymer component is 〇 to 99.9% by weight, and the ratio of all the polymer components contained in the constituent material is ο.1. ～40% by weight, the other additive is used in an amount of 〇~5 wt% of all the polymer components, and the remaining component of the composition is a solvent. R1r1\ /° ? Si—0-ρSi— R1 I Right R1 Two Si —k&Gt; two Si, 1 l/° I/0 R R1/S 丨 0-si, r1 〇 (1) R2 - Si—Z1 R2 • Si—Z2 (2-1) (2-2)

In the formula (1), r1 is an arylalkyl group composed of hydrogen, a group of a group having a carbon number of i to 45, a group having an aryl group having a substituent, and an aryl group having a substituent and an alkylene group. The base selected in the group. In a hospital with a carbon number of 1 to 45, any chlorine atom may be replaced by g-germanium, and the CH2-CH2- may utilize a 〇-, -CH=CH-, a ring-substrate or a ring-thin The base is substituted. In the sub-hospital base of the aryl base, Ren Si’s hydrogen atom can

By replacing with fluorine, any -CH2 can also be substituted with - 〇-, one CH-CH-, or a sub-group or a ring-subunit. At least two Y are groups selected from a group of a group represented by the formula (2-1) and a group of a group represented by the formula (2-2), and the remaining Y is hydrogen; Z1 It is a group having an amine group. Z2 is a group having a 2-oxypropanedifluorenyl group. Further, R2 is a group independently of the same definition as R1 in the formula (1). [2] The varnish described in [1], where 'Rl is a group derived from hydrogen and a number of carbon atoms from 1 to 30 (where 'any hydrogen atom can be used as a fluorine atom 10 125346^3pif.doc Substituting, any one of ch2- may also be substituted with a fluorene---ch=ch-, cycloalkylene or cycloalkenylene group, a group of a phenyl group (wherein any hydrogen atom may utilize a halogen atom) Or a group substituted with an alkyl group having a carbon number of 1 to ίο, or a phenylalkyl group (a phenyl group and a carbon atom which may be substituted by a halogen atom or an alkyl group having 1 to ί of an arbitrary hydrogen atom) a group of 1 to 12 subunits) and a group independently selected by Cai Jizhong; in the alkyl group having 1 to 10 carbon atoms as a substituent of the group, any hydrogen atom may be substituted by a fluorine atom, and Any one of ch2—may be substituted by a 0, a CH=CH-, a cycloalkylene or a phenylene group; in the alkylene group of a phenylalkyl group, any hydrogen atom may be substituted with a fluorine atom, and ' Any one CH2- may be replaced by a 0-, -CH=CH-, or cycloalkylene; R2 is independent of each other, It is methyl, isopropyl, tert-butyl or phenyl. [3] The varnish according to [1], wherein R1 is a group having an alkyl group having 1 to 8 carbon atoms (wherein any hydrogen atom may be replaced by a fluorine atom, and any -CH2 may be used) a group of a phenyl group substituted with —0—, —CH=CH—, a cycloalkylene group or a cycloalkenylene group (wherein any hydrogen atom may be substituted with a halogen atom, a methyl group or a methoxy group), benzene a group of an alkyl group (a phenyl group substituted with a fluorine atom or an alkyl group having 1 to 4 carbon atoms, a vinyl group or a methoxy group, and a sub-group having 8 carbon atoms) And each of the independently selected groups in the naphthyl group; in the alkylene group of the phenylalkyl group, any one of the CH2 groups may be substituted with -〇1, -CH=CH-, or a ring-substituent; R2 is independent, It is methyl, isopropyl, tert-butyl or phenyl. [12] The varnish described in [1], wherein all of R1 is a group derived from an alkyl group having 1 to 8 carbon atoms (wherein any hydrogen atom may be substituted by a fluorine atom, optionally -CH2- may be substituted with -〇-, -CH=CH-, cycloalkylene or cycloalkenylene), a group of a phenyl group (wherein any hydrogen atom may utilize a halogen atom or a methyl group or a a group substituted with an oxy group and a phenylalkyl group (a phenyl group and a carbon atom which may be substituted with a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a methoxy group by any hydrogen atom) 1 to 8 alkylene group) and the same group selected from naphthyl group; in the sub-hospital group of the phenyl group, '---- 2-- can use a 0-, a CH=CH-, a cycloalkylene Substituent; R2 is independently of each other and is methyl, isopropyl, tert-butyl or phenyl. [5] The varnish according to [1], wherein all of R1 is a group derived from a phenyl group (in which a halogen atom, a methyl group or a methoxy group may be substituted with an arbitrary hydrogen atom), a phenylalkyl group a group (in which a phenyl group substituted with a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a methoxy group, and an alkylene group having 1 to 8 carbon atoms) may be used. And the same group selected from the naphthyl group; in the alkylene group of the phenylalkyl group, any one (: 112- may be substituted with a fluorene-, a CH=CH-, a cycloalkylene group; and R2 The varnishes described in the item [1], wherein all of Ri is a group derived from a phenyl group (where 'anything' The gas atom of ruthenium may be substituted with the same group selected from the atom, methyl or methyl group; and R2 is independently, and is methyl, isopropyl, tert-butyl or phenyl. Z1 is a molecular formula. (2-1-A) ~ a group represented by any one of the formula (2-1-G), and z2 is a formula 12 125346^3ρίΜ〇〇(2-2-Α)~ Group / == ^ NH2 any one of the sub-formula (2_2-D) represented by /) (pin 2 (2-1-B) - (- ch2) -nh2 ~ (CH:

, NH 2 (2-1-C) (2-1-D) , V^NH2 ^CH2tvy

, NH 2 (2-1-E) 一〇^cH2

m .NH〇 (2-1-F)

(2-1-G)

(2-2-Α) (2-2-Β) (2-2-C) (2-2-D) 13 125346l43pif.doc In these formulas, m is an integer from 1 to 10, an amine group and a benzene ring And the combination of the cyclohexyl ring is in any position; any hydrogen atom in the benzene ring may be substituted by a halogen atom or an alkyl group having 1 to 10 carbon atoms; wherein the alkyl group having 1 to 10 carbon atoms In the above, any hydrogen atom may be replaced by a fluorine atom, and any one of ch2 may be substituted by a 0-. [7] The varnish described in [6], wherein R2 is independently a methyl group or a phenyl group; and Z1 is any one of the formula (2-1-A) and the formula (2-1-B). The group represented by the formula; Z2 is a group represented by any one of the formula (2-2-A) and the formula (2-2-B). [8] The varnish described in the item [1], wherein all of R1 is a phenyl group; R2 is each a 'AL' or a radical, and Z1 is a formula (2-1-A-1) The base; Z2 is a group represented by the formula (2-2-A-1).

rCH ^Γ〇&quot;0^ΝΗ2 (2-1-Α-1) 4CH 七t^O (2 Ο In these formulas, m is an integer from 1 to 6. [9] [1] a varnish in which at least two Y are selected from the group of the group represented by the formula (2-2), and the remaining Y is hydrogen. The varnish described in the item [10Π1], wherein the polymer is At least one of polyaminic acid, soluble polyimine, polyamidamine, polyamidimide, and a copolymer comprising polylysine, soluble polyimine, polyamine, poly a polymer of at least two of the respective structural units of amidoxime. The varnish described in [11] wherein all of R1 is a halogen atom from any of the 14 125346^ls3pif.doc hydrogen atoms, The same group selected from the group consisting of a methyl group or a methoxy-substituted phenyl group; R2 is independently a methyl group, an isopropyl group, a tert-butyl group or a phenyl group; and Z1 is a molecular formula (2-1- A) a group represented by any one of the formula (2-1-G); Z2 is a group represented by any one of the formula (2-2-A) to the formula (2-2-D); the polymer is Polylysine At least one of a polyimine, a polyamine, a polyamidimide, and a copolymer, the copolymer being a polyglycine, a soluble polyimine, a polyamine, a polyamidimide Polymer of at least two of the respective structural units. (2-1-A) (2-1-B) (2-1-C) (2-1-D) (2-1-E) ( 2-1-F) (2-1-G)

—(-CH2)—NH2 ~(·〇Η:

,NH? -CH〇 K^NH2

NH〇

NH〇 15 I25346A3pif.doc I25346A3pif.doc

(2-2-A) (2-2-B) (2-2-C) (2-2-D) In these formulas, m is an integer from 1 to 10, an amine group with a benzene ring and cyclohexane The combination of the rings is in any position; any hydrogen atom in the benzene ring may be substituted with a halogen atom or an alkyl group having 1 to 1 ring of carbon atoms; in the alkyl group having 1 to 1 ring of carbon atoms, Any hydrogen atom may be substituted with a fluorine atom, and any one CH2- may be substituted with a fluorene-. [12] The varnish according to [11], wherein R2 is a methyl group or a phenyl group of each of the respective α; Z1 is a molecular formula (2-1-A) and a molecular formula (2-1-B) Any one of the groups represented; and Z2 is a group represented by any one of the formula (2-2-A) and the formula (2-2-B). [13] The varnish described in [1], wherein all of R1 is a phenyl group; R is a single methyl group or a phenyl group; Z1 is a molecular formula (2 -1 - A-1) The base of Z2, the molecular formula of (2 - 2 - A -1), 丨fi] and 'polymer is polyglycine, soluble polyimine, polyamine, polyamidimide And at least one of the interpolymers, wherein the interpolymer is at least two polymers of 125346i43pif.doc in the respective structural units of poly-proline, soluble polyamidiamine, polyamine, and polyamidoximine. .

〇 In these formulas, m is an integer of 1 to 6. [14] The varnish described in [1], wherein all R1 are available

a group selected from the group consisting of a phenyl group in which a halogen atom, a methyl group or a methoxy group is substituted with an arbitrary hydrogen atom; at least two Y groups are selected from the group of the group represented by the formula (2-2), The remaining Y is a hydrogen atom; R2 is independently a methyl group, an isopropyl group, a tert-butyl group or a phenyl group; and Z2 is a molecular formula (2-2-A) to a molecular formula (2-2-D). Any of the groups represented by the polymer; the polymer is at least one of polyamic acid, soluble polyamidiamine, polyamine, polyamidimide, and a copolymer, the copolymer being polyamic acid, soluble Polycondensation of at least two of the respective structural units of polyimine, polyamine, and polyamidoximine

(2-2-A) (2-2-B)

(2-2-C) - bite. (2-2-D) 17 0 125346^63pif.doc In these formulas, m is an integer of 丨~(7), and any hydrogen atom in the benzene ring may be a halogen atom or an alkyl group having a carbon number of 丨~(7) In the alkyl group having 1 to 10 carbon atoms, any hydrogen atom may be replaced by a rat atom, and 'CH2' may be substituted with -〇. [15] The varnish according to [14], wherein R2 is independently a methyl group or a benzyl group; and Z2 is a group represented by any one of the molecular formula (2_2_a) and the molecular formula (2_2_b).

[16] The varnish according to [1], wherein all of R1 is a phenyl group, and at least two Y are groups selected from the group represented by the formula (2-2), and the remaining Y is a hydrogen atom; R2 is independently a methyl group or a phenyl group; z2 is a group represented by the formula (2_2_A.l); and, a polymerized view, a fatty acid, a soluble polyamidiamine, a polyamidamine, a polyamidoxime At least one of an imide and a copolymer which is a polymer containing at least two structural units of each of polyamine, soluble polyimine, polyamine, and polyamidoximine.

〇 (2-2-A-1)

In the formula, m is an integer of 1 to 6. [17] The varnish according to [1], wherein the polymer obtained by using the sesquioxanes derivative represented by the formula (1) is selected from the group consisting of polylysine, polyimine, and polyamine. And at least one of the groups consisting of polyamidoximine. [18] The varnish described in the item [1], wherein the polymer obtained by using the sesquioxane derivative represented by the formula (1) is a polyacetamide, a polyamidimide, or a polyamine. At least one selected from the group consisting of polyamidoximine, 18 125346l 3 pif_doc The proportion of the polymer obtained from the sesquioxane derivative represented by the formula (1) among all the components of the polymer The ratio of the polymer obtained by using the sesquioxane derivative represented by the formula (1) in all the components of the polymer is from 30 to 98% by weight, in an amount of from 2 to 70% by weight, in the constituent material The ratio of all the polymer components is 〇·5 to 10% by weight. [19] A compound represented by the formula (1) is obtained as a raw material, and has a molecular formula (3-1), a molecular formula (3-2), a molecular formula (3-3), a molecular formula (3-4), and a molecular formula (3-5). ), molecular formula (3-6), molecular formula (3-7), molecular formula (3-8), molecular formula

(5-1), molecular formula (5-2), molecular formula (5-3), molecular formula (5-4), molecular formula (5-5), molecular formula (5-6), molecular formula (5-7), molecular formula ( 5-8), any one of the structural units represented by any one of the formula (7-1), the formula (7-2), the formula (9-1), and the formula (9-2) and the formula (4-1) a structural unit represented by any one of the formula (6-1), the molecular formula (8-1), and the molecular formula (HM), at least one of the polymers R1, R1 constituting the polymeric chain.

Si—0 /Y, 〆0/ /V Si—oL-si-R1 | 1R1—Si-4-0—:Si, R2 —Si—Z1 (2-1 ) (1) 〇0 'R1 R2 -Si One z2 (2-2)

R' 'R1

FT 19 lpif.doc

20 125346^63pif.doc

(5-3)

C〇〇H COOH NH- (5-4)

-Q —HN ~S〇 HOOC* 〇:

COOH COOH NH- 〇 Q2—HN-^I ^ (5-7) H〇〇C 〇 HN HOOC* 〇 〇 NH·

&quot;COOH

COOH NH- (5-8)

(6-1) 21 125346^3pif.doc

(10-1) In these formulas, R1 is an alkyl group derived from hydrogen, having 1 to 45 carbon atoms, or an aryl group (having a substituent or a group having an aryl group and 22 丨3pif.doc) a substituent independently selected from the group consisting of a substituent) and an alkylene group composed of an alkylene group; in the alkyl group having 1 to 45 carbon atoms, any hydrogen atom may be substituted with an arbitrary one by a gas atom. CH2 - may be substituted with -0 -, a CH = CH -, a cycloalkylene group or a cycloalkenylene group; in the alkylene group of the arylalkyl group, any hydrogen atom may be substituted with a fluorine atom, any -ch2 - It can be substituted with a hydrazine-, -CH=CH- or a cycloalkylene group. At least two of Y are groups selected from a group of a group represented by the formula (2-1) and a group of a group represented by the formula (2-2), and the remaining Y is a hydrogen atom. . Z1 is a group having an amine group; and Z1 is a group having a 2-oxypropanedifluorenyl group. R2 is independent of each other and is the same as R1 in the formula (1); Q1 is a residue obtained by removing an amine group from the molecular formula (1) which is a group represented by the formula (2-1) in Y; Q2 The residue after removing an amine group from the molecular formula (1) which is a group represented by the formula (2-1) in Y; Q3 is represented by the formula (2-2) from two of Y The residue after removing the 2-oxypropanedifluorenyl group in the molecular formula (1); Q4 is a 2-oxo removal from the molecular formula (1) which is a group represented by the formula (2-2) in Y. a residue after propane dimercapto; G1 is a residue after removing an amine group from a compound having two amine groups; G2 is a residue after removing a carboxyl group from a compound having two carboxyl groups; and G3 is from 3 A residue after removing a carboxyl group in a compound having a carboxyl group; and G4 is a residue obtained by removing a carboxyl group from a compound having four carboxyl groups. [20] The polymer according to [19], wherein the polymer is at least one of structural units represented by any one of the formula (3-1) to the formula (3-8), and the molecular formula (4) -1) The structural unit represented forms a polymeric chain of polyimine. The polymer described in the item [19], wherein the polymer is at least one of structural units represented by any one of the formula (5-1) to the formula (5-8). A polylysine which forms a polymeric chain with a structural unit represented by the formula (6-1). [22] The polymer according to [19], wherein the polymer is at least one of structural units represented by any one of the formula (7-1) and the formula (7-2), and the molecular formula (8) -1) The structural unit represented forms a polymeric chain of polyamidoximine. [23] The polymer according to [19], wherein the polymer is at least one of structural units represented by any one of the formula (9-1) and the formula (9-2), and the molecular formula (HM) The structural unit represented forms a polymeric chain of polyamine. [24] The polymer according to [20], wherein the polymer is at least one of structural units represented by any one of the formula (3-3) to the formula (3-4), and the molecular formula (4) -1) The structural unit represented forms a polymeric chain of polyimine. [25] The polymer according to [21], wherein the polymer is at least one of structural units represented by any one of the formulae (5-3) to (5-4), and the molecular formula (6) -1) The structural unit represented forms a polymeric chain polylysine. [26] The varnish according to [19], wherein the polymer is of the formula (3-3), the formula (3-4), the formula (3-5), the formula (3-6), and the formula (3) -7), molecular formula (3-8), molecular formula (5-3), molecular formula (5-4), molecular formula (5_5), molecular formula (5-6), molecular formula (5-7) and molecular formula (5-8) Any one of 24 125346453 pif.doc of the structural units represented by at least one of the structural units represented by one of the formula (4-1) and the formula (6-1) forms a copolymer of the polymer chain. [27] An alignment film produced by using a varnish for producing a liquid crystal alignment film according to any one of [1] to [18]. [28] A liquid crystal display element comprising the alignment film described in [27]. The present invention will be described in detail below. The sesquiterpene oxide derivative represented by the formula (1) is sometimes labeled as the compound (1). Compounds represented by other formulas are sometimes labeled with the same labeling method. The alkyl group and the alkylene group in the present invention may be either a linear group or a branched group in any case. In this case, even if any hydrogen atom in these groups is subjected to a substitution reaction with a halogen atom or a cyclic group, or an arbitrary one is replaced with -0-, -CH=CH-, a cycloalkylene group, a cycloalkenylene group or the like. When CH2- is the same. "Arbitrary" as used in the present invention means that the position and the number are arbitrary. Further, when a plurality of hydrogen atoms or a CH2- is substituted, it may be substituted with a different one. For example, in any one of CH2- which may utilize an 0- or a CH-disubstituted alkyl group, in addition to an alkyl group, an alkoxyalkyl group and an alkenyl group, an alkoxy alkenyl group or an alkene may be contained. A substance such as an oxyalkyl group. Any one of the alkoxy group, the alkenylene group, the alkenyl group, and the alkylene group at this time may be a linear group or a branched group. Further, in the present invention, when -CH2- is used instead of -CH2-, the -CH2-" which is a continuous plural is not used in the present invention, and the sesquiterpenes represented by the formula (1) are used. Oxylkane derivatives. 25 125346463pif.doc R1

R1 .Si—〇一Si. R〆\r1 In the formula, R1 is hydrogen, an alkyl group, an aryl group which may have a substituent, or an aryl group which may have a substituent and an aryl group and an alkylene group. alkyl. It is preferable that all of R1 are the same base, and it may be composed of two or more different bases. Examples of the case where each R1 is composed of a different group are: a case of two or more alkyl groups; a case of two or more aryl groups; a case of two or more aralkyl groups; a case where hydrogen is composed of at least one aryl group; a case where it is composed of at least one alkyl group and at least one aryl group; a case where at least one alkyl group is composed of at least one aralkyl group; and at least one aryl group and at least one aromatic group. The case of alkyl formation. Combinations other than these examples can also be used. When R1 is an alkyl group, the number of carbon atoms is from 1 to 45. It is preferably from 1 to 30; more preferably from 1 to 8. Further, any hydrogen atom may be substituted with a fluorine atom, and any -CH2- may be substituted with any one CH2- by one fluorene-, -CH=CH-, cycloalkylene or cycloalkenylene. Preferred examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 29 alkyl groups, and an alkyl group having 1 to 8 carbon atoms. One alkyl group is substituted with a group -CH2-, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxyalkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms. 26 12534 - an oxyalkenyl group, an alkyl group having 1 to 8 carbon atoms, which is obtained by substituting a cycloalkenylene group for a mono-CH2 group, and a gas atom for replacing an arbitrary gas atom with a suitable atom in a suitable group. base. The cycloalkylene group and the cycloalkenylene group preferably have 3 to 8 carbon atoms. Examples of the unsubstituted alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group and a methyl group. Ethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, U,2-trimethylpropyl, heptyl, octyl, 2,4,4- Trimethylpentyl, decyl, decyl, undecyl, dodecyl, tetradecyl, hexadecanyl, eighteen yards, -10 ten yards, 廿* yards and twenty Court base. Examples of the fluorinated alkyl group having 1 to 30 carbon atoms include 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-fluorenylhexyl, Tridecylfluoro-1,1,2,2-tetrahydrooctyl, heptadecylfluoro-1,1,2,2-tetrahydroindenyl, fluorinated-1H, 1H, 2H, 2H-ten Dialkyl and fluorinated-1 counter 111,211,211-tetradecyl. Examples of the alkenyloxyalkyl group having 2 to 29 carbon atoms include 3-methoxypropyl, methoxyethoxyundecyl, and 3-heptadecylfluoroisopropanol base. In the case of a group having 1 to 8 carbon atoms, 'as an example of substituting a mono-CH2 group with a cyclo-sub-protection group, there are cyclohexylmethyl, adamantylethyl, cyclopentyl, cyclohexyl, 2-linked ring. Heptyl, and cyclooctyl. The cyclohexyl group is an example in which a CH 2 - in the methyl group is substituted with cyclohexane. The cyclohexylmethyl group is an example in which one CH 2 - in the ethyl group is substituted with cyclohexane. Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 5-hexenyl group, a 7-octenyl group, and a 10-undecyl group. 125346^63pif.doc and 21-decanealkenyl. As an example of the alkenyloxy group having 2 to 20 carbon atoms, there is a storage propenyl undecyl group. Examples of a group having 1 to 8 carbon atoms, and examples of a group in which one mono-CH2- is substituted by a cycloalkenylene group are 2-(3-cyclohexenyl)ethyl and 5-(cycloheptanyl). Ethyl, 2-cycloheptyl, 3-cyclohexenyl, 5-norbornyl-2-yl, and 4-cyclooctenyl. As an example of the aryl group which may have a substituent in R1 in the formula (1), any hydrogen atom may be a vinyl group substituted with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and an unsubstituted naphthyl group. Preferred halogen materials are fluorine, chlorine, and bromine. In the alkyl group having a carbon atom of 1 to 1 Torr, any hydrogen atom may be substituted with a fluorine atom, and any one of CH 2 may be substituted with -0, a CH=CH- or a phenylene group. That is, preferred examples of the aryl group in which R1 may have a substituent are phenyl, naphthyl, alkylphenyl, alkoxyphenyl, alkenylphenyl, having a carbon number of 1 to 10. In the alkyl group, a vinyl group in which a phenylene group is substituted with an arbitrary mono CH2 group is used as a substituent, and in these groups, a hydrogen atom is substituted with a halogen atom. Further, in the present invention, there is no special case, and when it is simply referred to as a vinyl group, it means an unsubstituted vinyl group. The same is true for naphthyl. Examples of the ethylene include a pentafluorophenyl group, a 4-chlorophenyl group, and a 4-bromophenyl group. Examples of the pendant phenyl group are 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl, 4 - octylphenyl, 4-nonylphenyl, 4-nonylphenyl, 2,4-methylphenyl, 2,4,6-trimethyl 28 ipif.doc phenyl, 2,4, 6-Triethylphenyl, 4-(1-methylethyl)phenyl, 4-(l,1-dimethylethyl)phenyl, 4-(2-ethylhexyl)phenyl, and 2,4,6-Tris(1-methylethyl)phenyl. Examples of alkoxyphenyl groups are 4-methoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl, 4- Hepoxyphenyl, 4-decyloxyphenyl, 4-octadecyloxyphenyl, 4-(1-methylethoxy)phenyl, 4-(2-methylpropoxy)benzene And 4-(1,1-dimethylethoxy)phenyl. Examples of alkenylphenyl groups are 4-vinylphenyl, 4-(1-methylvinyl)phenyl, 4-(3-butenyl)phenyl. In the alkyl group having 1 to 10 carbon atoms, an example of a phenyl group having a substituent obtained by substituting an arbitrary -CH2- group with a phenylene group is 4-(2-phenylvinyl)phenyl group, 4 -phenoxyphenyl, 3-phenylmethylphenyl, biphenyl, and hexadecylphenyl. 4-(2-Phenylvinyl)phenyl is an example in which one of the ethylphenyl groups is substituted with a phenylene group, one CH 2 -, and one CH = CH - is substituted for the other - CH 2 -. An example of a phenyl group in which a halogen atom is substituted for a part of a hydrogen atom of a benzene ring, and a phenyl group is substituted with another hydrogen atom using a hospital group, a hospitaloxy group or an alkenyl group is 3-chloro-4-methylphenyl group, 2,5-dichloro group. 4-methylphenyl, 3,5-dichloro-4-methylphenyl, 2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methyl Phenylphenyl, 3-bromo-4-methylphenyl, 2,5-dibromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl, 2,3-difluoro- 4-methylphenyl, 2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl, 3,5-di Bromo-4-methoxyphenyl, 2,3-dibromo-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl, 2,3-difluoro-4-propene Oxybenzene 29 丨 63 pif. doc base, and 4-vinyl-2,3,5,6-trifluorophenyl. Then, an example in which R1 in the formula (1) is an arylalkylene group which may have a substituent group and an alkylene group is listed. In the alkylene group of the aryl group, any hydrogen atom may be substituted by a fluorine atom, and any _CH2 may be substituted with -Ο---CH=CH- or a cyclic subunit. A preferred example of the arylalkylene group is a phenylalkyl group. In this case, the alkylene group has preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. In the phenylalkyl group, any hydrogen atom in the phenyl group may be substituted with a halogen atom or an alkyl group having 1 to 10 carbon atoms. In the alkyl group having 1 to 10 carbon atoms, 'any hydrogen atom may be substituted with a fluorine atom', and any -CH2 may be any -〇-, -CH=CH-, cycloalkylene or phenylene. Substituted. Examples of the unsubstituted phenylalkyl group are phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl , 11-phenylundecyl, 1-phenylethyl, 2-phenylpropyl, methylphenylethyl, phenylphenyl, 3-phenylbutyl, 1-methyl-3 -Phenylpropyl, 2-phenylphenyl, 2-methyl-2-phenylpropyl, and phenylhexyl. An example of a phenyl group which may be substituted with a fluorine atom as an arbitrary hydrogen atom in the phenyl group, a heart-fluorinated phenylmethyl group, a penta-derived methyl group, 2-(2,3,4,5,6- Pentafluorophenyl)ethyl, 3-(2,3,4,5,6-pentafluorophenyl)propyl, 2-(2-fluorinated phenyl)propyl, and 2-(4-fluoro) Phenyl) propyl. An example of a phenylalkyl group in which any hydrogen atom in the phenyl group is substituted with a chlorine atom is a chlorinated phenylmethyl group, a 2-phenyl chloride methyl group, a 2,6-dichlorophenyl group, 2,4-diphenylmethyl dichloride, 2,3,6-trichlorophenyl 30 125346463 pif.doc methyl, 2,4,6-triphenylmethyl, 2,4,5- Phenylmethyl trichloride, 2.3.4.6-phenylmethyl tetrachloride, 2·3·4·5·6-pentachlorophenylmethyl, 2-(2-chlorinated phenyl)ethyl , 2-(4-chlorophenyl)ethyl, 2-(2,4,5-chlorophenyl)ethyl, 2-(2,3,6-chlorophenyl)ethyl, 3_( 3_phenylphenyl)propyl, 3-(4-phenylene)propyl, 3-(2,4,5-triphenyl)propyl, 3-(2,3,6·trichloro Phenyl)propyl, 4-(2-chlorophenyl)butyl, 4-(3-chlorophenyl)butyl, 4-(4-chlorophenyl)butyl, 4-(2 , 3,6-triphenylphenyl)butyl, 4-(2,4,5-triphenyl)butyl, 1-(3-chlorophenyl)ethyl, i-(4-chloro Phenyl)ethyl, 2-(4-chlorophenyl)propyl, 2-(2-chlorophenyl)propyl, and 1-(4-chlorophenyl)butyl. Examples of the phenylalkyl group in which any hydrogen atom in the phenyl group is substituted with a bromine atom are: 2-bromophenylmethyl group, 4-brominated phenylmethyl group, 2,4-dibrominated phenylmethyl group, 2,4,6-Phenylmethyl bromide, 2,3,4,5-tetrabromophenylmethyl, 2.3.4.5.6-Pentaphenylpentaphenyl, 2-(4-bromo) Phenyl)ethyl, 3-(4-brominated phenyl)propyl, 3-(3-bromophenyl)propyl, 4-(4-brominated phenyl)butyl, 1-(4 - phenyl bromide ethyl, 2-(2-bromophenyl)propyl, and 2-(4-bromophenyl)propyl. Examples of the phenylalkyl group in which any hydrogen atom in the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms are: h methylphenylmethyl, 3-methylphenylmethyl, 4-methyl Phenylmethyl, 4-dodecane-tert-phenylmethyl, 3,5-dimethylphenylmethyl, 2-(4-methylphenyl)ethyl, 2-(3-methylphenyl Ethyl, 2-(2,5-dimethylphenyl)ethyl, 2-(4-ethylphenyl)ethyl, 2-(3-ethylphenyl)ethyl, 2-(2) ,5-dimethylphenyl)ethyl, 2-(4-ethylphenyl)ethyl, 2-(3-ethylphenyl)ethyl, 1-(4-methylphenyl)ethyl , 1-(3-methylphenyl)ethyl, 31 l2534felpl, d〇c 1-(2-methylphenyl)ethyl, 2-(4-methylphenyl)propyl, 2-(2 -methylphenyl)propyl, 2-(4-ethylphenyl)propyl, 2-(2-ethylphenyl)propyl, 2-(2,3-monomethylphenyl)propyl , 2-(2,5-dimethylphenyl)propyl, 2-(3,5-dimethyl-based)propyl, 2-(2,4·-methylamino)propyl, 2-( 3,4-I. A certain benzene) propyl, 2-(2,5-dimethylphenyl)butyl, 4-(1-methylethyl)phenylmethyl 2- (4-(1) ,1-dimethylethyl)phenyl)ethyl, 2-(4-(1-A) Ethyl) phenyl) propyl, and 2- (3- (1-methylethyl) phenyl) propyl. An example of a phenylalkyl group in which an arbitrary hydrogen atom in the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom in the alkyl group is substituted by a fluorine atom: 3-trifluoromethylphenyl group Methyl, 2-(4-trifluoromethylphenyl)ethyl, 2-(4-trisuccinylmethylphenyl)ethyl, 2-(4-trifluorohexylphenyl) Ethyl, 2-(4-pyridyl zinc phenyl)ethyl, 1-(3-trifluoromethylphenyl)ethyl, 1-(4-trifluoromethylphenyl) Base, 1-(4-twencyfluorinated methylphenyl)ethyl, 1-(4-trifluorohexylphenyl)ethyl, 1-(4-heptadecafluorooctylphenyl) Ethyl, 2-(4-twencyfluorinated methylphenyl)propyl, 1-methyl-1-(4-twencyfluorinated butylphenyl)ethyl, 2-(4-ten Hexylphenyl)ethyl trifluoride, 2-(4-heptadecafluorooctylphenyl)propyl, and 1-methyl-1-(4-heptadecafluorosemisyl)ethyl. An example of a phenylalkyl group in which a hydrogen atom of any one of the phenyl groups is substituted with an alkyl group having 1 to 10 carbon atoms, and -CH 2 - in the alkyl group is substituted by a CH 2 CH- group is: 2-(4-ethylene Phenyl)ethyl, 1-(4-vinylphenyl)ethyl, and 1-(2-(2-propenyl)phenyl)ethyl. A phenylalkyl group in which any hydrogen atom in the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms, and a case where a ch2- is substituted by -0- in the alkyl group 32 i63pif.doc has: 4- Methoxyphenylmethyl, 3-methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2-(4-methoxyphenyl)ethyl, 3-(4-methoxy Phenyl)propyl, 3-(2-methoxyphenyl)propyl, 3-(3,4-dimethoxyphenyl)propyl, 11-(4-methoxyphenyl)-11 Alkyl, 1-(4-methoxyphenyl)ethyl, and (3-methoxymethylphenyl)ethyl. An example of a phenyl group in which any hydrogen atom in the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms, and one of -CH2 - in the phenyl group is substituted by Examples of the case where another one CH2- is substituted by 0-, including cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylbenzene Propyl, cyclohexyloxyphenylmethyl. An example of a phenylalkyl group in which any hydrogen atom in the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms, and one of -ch2- in the alkyl group is substituted with a phenylene group, if another one is included - Examples of the case where CH2- is substituted by 0-, there are 2-(4-phenoxyphenyl)ethyl, 2-(4-phenoxyphenyl)propyl, 2-(2-phenoxyphenyl) )propyl, 4-diphenylmethyl, 3-hydraethyl, 4-biphenylethyl, 4-biphenylyl, 2-(2-biphenyl)propyl, 2- (4-biphenyl) propyl. Examples of phenylalkyl groups in which at least two hydrogens in the phenyl group are substituted by different groups are: 3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propyl, 3 -Chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl, 5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl , 2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl, 2,3-dichloro-4-methylphenylmethyl, 2,5-dichloro- 4-methylphenylmethyl, 3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylbenzene 33 1253464, '63pif.doc methyl, 2,3,5,6-tetrachloro-4-methylphenylmethyl, 2,3,4,6-tetrachloro-5-methylphenylmethyl, 2,3,4,5-tetrachloro -6-methylphenylmethyl, 4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl, 2,4-dichloro-3 , 5-dimethylphenylmethyl, 2,6-dichloro-3,5-dimethylphenylmethyl, 2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl, 4-bromo-2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenyl , 3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl, 2,3,5-tribromo-4-methylphenylmethyl, 2, 3, 5,6-tetrabromo-4-methylphenylmethyl, and 11 &lt;3_chloro-4-methoxyphenyl) eleven. Further, a most preferable example of the phenyl group in the phenylalkyl group is an unsubstituted phenyl group, and as a substituent, an alkyl group having a fluorine, a carbon number of 1 to 4, a vinyl group, and a methoxy group. At least one phenyl group. Examples of the phenylalkyl group substituted as -CH2- in the alkylene group by -CH=CH- or a cycloalkylene group are: 3-phenoxypropyl group, 1-phenylvinyl group, 2-ben Ethiyl, 3-benyl-2-propenyl, 4-benyl-4-pentyl, benzylcyclohexyl, and phenoxycyclohexyl. Examples of the phenylalkyl group in which a hydrogen atom in the phenyl group is substituted by a fluorine atom or a methyl group are: 4-fluorinated phenylvinyl group, 2,3-difluorophenyl group, 2,3,4, 5,6-pentafluorophenylvinyl, and 4-methylphenylvinyl. Preferable examples of the above R1 examples include an alkyl group having 1 to 8 carbon atoms, a phenyl group which may have a substituent, a phenylalkyl group which may have a substituent, and a naphthyl group. More preferably, V is a phenyl group which may have a substituent, a phenylalkyl group which may have a substituent, or a naphthyl group. In the alkyl group having 1 to 8 carbon atoms, any hydrogen atom may be substituted by a fluorine atom, and any - 34 Ι 2534 φ 4 i ^ 3 〇 3 pif (J〇q CH2s may be - 〇 - CH ^ CU -, ring An alkylene group or a cycloalkenylene group. In a phenyl group which may have a substituent, any hydrogen atom may be substituted by a halogen atom, a methyl group or a methoxy group. Among phenyl groups which may have a substituent, benzene Any hydrogen atom in the ring may be substituted by a fluorine atom, a carbon atom, an alkyl group having 1 to 4, a vinyl group or a methoxy group. The alkylene group in the phenylalkyl group has 1 carbon atom. ～8, any -CH2 in the alkylene group may be substituted by a fluorene-, a ch=ch- or a ring-substituent. In these groups, when the phenyl group has a plurality of substituents, these groups It may be the same group or a different group. Further, all of R1 in the formula (1) is preferably the same group selected from the examples of these preferred R1. As a better R1 Specific examples are: phenyl, halogenated phenyl, phenyl having at least one methyl group, methoxyphenyl group, naphthyl group, phenyl group Base, phenylethyl, phenylbutyl, 2-phenylpropyl, 1-methyl-2-phenylethyl, pentafluorophenyl, 4-ethylphenylethyl, 3- Ethylphenylethyl, 4-(1,1 dimethylethyl)phenylethyl, 4-vinylphenylethyl, 1-(4-vinylphenyl)ethyl, 4-methoxy Phenyl propyl group, and phenoxy propyl group. Among these examples, phenyl is the most preferable. In the formula (1), 'at least two Y' are groups based on the formula represented by the formula (2-1). a group selected from any one of the groups of the group represented by the formula (2_2), and the remaining hydrazine is hydrogen. When at least two γ are a group represented by the formula (2-])-, these oximes are It may be a different group, but is the same: a group is preferred. When at least two fluorenes are a group represented by the formula (2-2), although these γ may be different groups, it is preferably the same group. At least two 35 I2534^4463 pif.doc Y are more preferably the same group selected from the group represented by the formula (2-2). R2I , Si-Z1 (2-1 )

Rz I -Si- -Z2 (2-2) In these formulas, R2 is independently independent and is the same as R1 in the formula (1). Z1 is a group having an amine group. Further, Z2 is a group having a 2-oxypropanedifluorenyl group. A preferred example of R2 is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms and a substituent. In this case, in the alkyl group having 1 to 8 carbon atoms, any hydrogen atom may be substituted by a fluorine atom, and any -CH2- may be substituted by -〇. Preferred examples of R2 are: methyl, isopropyl, tert-butyl and phenyl. More preferred examples of R2 are methyl and phenyl. Next, a group having an amine group and a group having a 2-oxypropanedifluorenyl group will be described. Preferred examples of the group having an amine group are an aminoalkyl group and an aminophenyl group. Preferable examples of the group having a 2-oxypropanedifluorenyl group include an aliphatic dicarboxylic anhydride group and an aromatic dicarboxylic anhydride group. These groups are preferably bonded to a ruthenium atom via a divalent group such as an alkylene group, an alkylcycloalkylene group, an alkylphenylene group, an alkylcycloalkylene group or an alkylphenylalkylene group. A preferred example of Z1 is a group represented by any one of the formula (2-1-A) to the formula (2-1-G) shown below. 36 125346A3pif.doc

—fcH2)—NH2

/=\^nh2 ^cH2tO as ^crNH

(2-1-A) (2-1-B) (2-1-C) (2-1-D) (2-1-E)

(2-1-F) (2-1-G) In these formulas, m is an integer of 1 to 10. Any hydrogen atom in the benzene ring may be substituted by a halogen atom or an alkyl group having 1 to 10 carbon atoms. Further, in the alkyl group having 1 to 10 carbon atoms, any hydrogen atom may be substituted by a fluorine atom, and any -CH2- may be substituted by -0-. A preferred example of Z2 is a group represented by any one of the formula (2-2-A) to the formula (2-2-G) shown below. 37 I2534^4P1f.d〇c -lCH Seven

(2-2-A) (2-2-B)

(2-2-C) (2-2-D) c

II 〇 In these formulas, m is an integer of 1 to 10 Å, and any hydrogen atom in the benzene ring may be substituted with a halogen atom or an alkyl group having 1 to 10 carbon atoms. Therefore, in the alkyl group having 1 to 10 carbon atoms, any hydrogen atom may be substituted with a fluorine atom, and any -ch2- may be replaced by -0. The compound (1) used in the present invention can be produced, for example, by the following method. The hydrazine compound having a trifunctional hydrolyzable group is hydrolyzed in an oxygen-containing organic solvent in the presence of a basic gold-water oxide to be polycondensed to obtain a compound (3). This compound (3) is used as a raw material, and reacted with a compound represented by the formula (4) to obtain a compound (5). Then, a compound having a functional group and an unsaturated alkyl group is subjected to a homophilic reaction with the compound (5) to obtain a compound (1) °, and M in the formula (3) is a valence basic metal atom. 38 I2534^4pif.d〇〇 R· R·

R

R

R

Si—0 yT/? /〇/T, Si—Si_Ri I ^R^Si-^O-Si^ |/° l/° , Si—〇—Si,, R1 3Μ (5)

2 - 2 R-s-RI CI Η 3 \-/ (4 R2 in the formula (4) is the same as R2 in the formula (2-1) or the formula (2-2). R1 and the formula (1) in the formula (7) R1 is the same. Further, at least two T are groups represented by the removal of C1 from the formula (4). The remaining T is hydrogen R2 I. -Si-Η compound (4) is a chloride, However, even other halides can be used in the same manner. Compound (4) is commercially available. When it is not commercially available, well-known synthetic techniques can be utilized, such as reacting _ decane with an organic compound. The reagent can be easily reacted, etc. 39 125343⁄4 3pif.doc. Examples of the preferred compound (4) are dimethyl chlorodecane, diethyl chlorodecane, methyl ethyl, in view of the simplicity of manufacture. Chlorinated decane, methylhexylphosphonium chloride, diisopropylphosphonium chloride, diter-butylphosphonium chloride, dicycloheptylphosphonium chloride, dicyclohexylphosphonium chloride, di-n-octyl chloride Decane, methylphenylphosphonium chloride and diphenylphosphonium chloride. Having an amine group and an unsaturated alkane Specific examples of the compound are shown below. Among these, preferred compounds are (Al), (A-2), and (A-3). ch2 = chch2 - nh2 (A-1) ch2 = chch2 - Nh-(ch2)2 - nh2 (A_2) • ch2=chch2—o-^^—nh2 (A-3) CH2=CHCH2~~<》—<〉—NH2 (A-4) CH2—CHCH2—〇 〉~CH2-〈〉—NH2 (A-5) ch2^chch2—0—^~^ch2ch2-^~^^nh2 (A-6) (:Η2=(:Η〇Η2—〇一〇-^^ —nh2 (A-7) • Examples of compounds having a 2-oxopropanedifluorenyl group and an unsaturated alkyl group are propenyl succinic anhydride, isobutyl succinic anhydride, isobutenyl succinic anhydride, bicyclo [2.2.2]- Caprylic acid-7-salt-2,3,5,6-tetracarboxylic dianhydride and 5-norbornene-2,3-dicarboxylic anhydride. Among these, the preferred compound is acrylic succinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. 40 •3pif.doc One of the unsaturated alkyl groups having the above functional group is reacted with the compound (5) to obtain a compound having the same functional group (1) °) To synthesize a compound (1) having the same functional group and having at least 2 different unsaturated alkyl groups, at least The reaction of the compound (5) with two unsaturated alkyl compounds having a functional group is carried out. In this case, in consideration of the difference in reactivity of the unsaturated alkyl compound having a functional group, these compounds may be mixed and reacted once. The reaction can be carried out one by one. When the reaction is carried out one by one, the reactivity of the functional group may be affected. In this case, a protective group such as trimethylmethanealkyl group may be used to protect the functional group in advance. Another method for producing the compound (1) using the compound (3) is a method of reacting the compound (3) with the compound (6). CI-Si-Z (6) In the formula (6), Z is a group having an amine group or a group having a 2-oxypropanedifluorenyl group. The compound (6) is commercially available, and when it is not commercially available, it can be synthesized by a well-known technique such as reacting a halogenated decane with an organic reaction reagent. This method is advantageous when the compound (6) is commercially available. This reaction can be carried out basically in accordance with the reaction method of the compound (3) and the compound (4). In order to increase the yield of the reaction, the compound (6) is preferably used in a molar ratio of 3 or more to the compound (3). If the compound (3) is combined with the compound (6), the compound (1) having the same functional group can be obtained. When compound (1) having at least two different functional groups is synthesized, at least 41 1253464 if. doc two compounds (6) can be reacted. At this time, in consideration of the difference in reactivity of the compound (6), these compounds may be mixed and reacted at the same time, or may be carried out one by one. When the reaction is carried out one by one, the reactivity of the functional group may be affected. In this case, the functional group may be protected by using a protective group such as trimethylmethane alkyl. When at least two compounds (6) are used, the molar ratio of the total amount/usage to the compound (3) is 3 or more. When the molar ratio is less than 3 or the reactivity of the compound (6) is low, a part of the compound (1) wherein Y is hydrogen can be obtained. This is because, after the reaction, washing with water is carried out, and hydrolysis of unreacted chlorinated decane is also carried out. # Instead of the compound (6), 3-cyanopropylmethylphosphonium chloride or 3-cyanopropylisopropylphosphonium chloride can be reacted with the compound (3), followed by reduction to obtain an amine group. Compound (1). Instead of using Z as a group having a 2-oxypropanedifluorenyl group, a compound having a group having two carboxyl groups may be used instead of the compound (6). Specific examples of the compound (1) defined by the formula (D) are shown in Table 1-1-1 to Table 5. The molecular formula (1-A) is an example when R1 in the formula (1) is a phenyl group (indicated by Ph). , 2a

Ph\ _ /Y /I1—〇 /Υ γ

Y=—Si—Z

Ph\ ./° ? /° ο7

Si—Ο—Si—Ph I I Ph-Si-I-O—Si , 2b i.y ?xXph /Si—〇—Si

Ph〆(2-A) (1-A) 42 1253464^ &lt;Table 1 — 1 — 1> N R2 R2 z 1 ch3 ch3 —(CH2)3-〇—nh2 2 ch3 ch3 —(ch2)3-〇 —〇^nh2 3 ch3 ch3 —(C^)3——Nhh 4 ch3 ch3 one (CH2)3 — 5 ch3 ch3 —(CH2)5~0~NH2 6 ch3 ch3 —(ch2)3-o—(ch2 ) 2—Q^nh2 7 ch3 ch3 —(CH2)3—C^NH2 8 ch3 ch3 —(CH2)7—^^~nh2 9 C3H7 C3H7 —(CH2)3-〇一^^-nh2 1 C3H7 c3h7 — (ch2)3-〇一^)-nh2 1 C3H7 c3h7 —(Chfc)3——Nhb 1 c4h9 c4h9 —(CH2)3-〇— 1 C4H9 C4H9 —(ch2)3-〇一(^-nh2 1 C4H9 C4h9 —(CH2)3——Nhfc 1 ch3 c3h7 —(ch2)7—Q^nh2 1 c4h9 ch3 —(Chh)3——Nhb 1 C3H7 c4h9 —(CH2)3-0—^^nh2 1 ch3 ch3 G ^NH2 1 ch3 ch3 —{^Η(^}-νη2 2 ch3 ch3 —~(CH2)2-*^^-nh2 2 ch3 ch3 ~0~O~nh2 43 ipif.doc <Table 1—1 — 2&gt;

No. R2a R2b z 2 2 ch3 ch3 a ^~(CH2)2-^~-NH2 2 3 ch3 ch3 2 4 ch3 ch3 —o(ch2)4o-&lt;^~~^—(ch2)5 a mh2 2 5 ch3 ch3 ^ch3 h3c _ —\_)~ch2~\3^v_/一ch2_nh2 2 6 ch3 ch3 -^^CH2q~^~^~-〇(CH2)3〇-~y~NH2 2 7 ch3 ch3 ~^ Q(ch2)3o-^ ^—(CH^O-^ ^—nh2 2 8 ch3 ch3 2 9 ch3 ch3 3 0 ch3 ch3 ^—^\ji^°^^^^°~~{y~^ \ ^~nh2 3 1 ch3 ch3 3 2 c3h7 c3h7 —^~~^)-(ch2)2-^~~^—nh2 3 3 c4h9 C4H9 3 4 ch3 c3h7 3 5 c3h7 c4h9 ~~~(CH2)2— y~NH2 3 6 c4h9 ch3 -^ ^~(CH2)2~^ ^~~NH2 3 7 ch3 ch3 0 - (CH2)3-|^C, 〇II 〇3 8 ch3 ch3 M e 〇—(CH2) 3〇-si—|^γ-°ν〇Me 〇3 9 ch3 ch3 (CH2)3〇^K:. δ 44 if. doc &lt;Table 1 — 1 — 3&gt;

No. R2a R2b z 4 0 ch3 ch3 -(CH2)3〇n〇c|〇M 〇4 1 ch3 ch3 0 —(〇Η2)3〇Η〇Κη〇-〇:〇M 〇4 2 ch3 ch3 〇- (CH2)3〇-^^C.〇ii 〇4 3 ch3 ch3 〇—(CH2)3t}r::〇〇4 4 ch3 ch3 0 —(CH2)3〇-^~^—CH2— • 9 〇 4 5 ch3 ch3 0 — (〇^2)3〇-^)-(〇Η2)2η^〇:〇0 4 6 ch3 ch3 0 —(ch2)3〇-(ch2)2o—^^-CH2—| Q^,〇0 4 7 c3h7 c3h7 0 -(CH2)30—||^j^Cx〇II 〇4 8 c4h9 c4h9 0 —(ch2)3〇一^&quot;^—ch2— 0 4 9 ch3 c3h7 o One (ch2)3—^c;〇II 〇5〇C3H7 c4h9 〇(CH2)3〇^^:〇6 45 I253144Plf.d〇c <Table 1- 1 —4&gt;

No. R2a R2b z 5 1 c4h9 ch3 〇 —(CH2)3t5^. II 〇5 2 ch3 ch3 5 3 ch3 ch3 5 4 ch3 ch3 5 5 ch3 ch3 &quot;^(CH2)2tD:&gt; 5 6 ch3 ch3 ^&quot;Η2〇~0;&gt; 5 7 ch3 ch3 -〇-〇 -α!&gt; 5 8 ch3 ch3 〇-^D^0(CH2)4°~i3C^0 / I 5 9 ch3 ch3 π 6 0 ch3 ch3 〇-^^~€H2〇-^^-〇(CH2 ) 3〇-~{}~jQj^〇/ A 6 1 ch3 ch3 o -^^〇 (called 3〇-{^-((^)2〇^^~|^^,〇46 1253 do if.doc &lt; Table 1- 1 to 5&gt;

No. R2a R2b z 6 2 c3h7 c3h7 -〇!&gt; 6 3 c4h9 c4h9 6 4 ch3 c3h7 6 5 c3h7 C4H9 6 6 c4h9 ch3 0 &quot;~^^(CH2)2_〇Oo Molecular formula (1-B) Specific examples of the defined compound (1) are shown in Table 1-2-1 to Table 1-2-2. Ph in the formula (1-B) is a phenyl group.

(1-B) R2a

Y=—Si—Z 丨2b R2b (2-A ) 47 I2534Mpifdoc <Table 1 — 2— 1 &gt;

No. R2a R 2b z 6 7 ch3 ch3 —(CH2)3Q—^~^—nh2 6 8 ch3 ch3 —(CH2)3〇—(3*nh2 6 9 ch3 ch3 -(CH2)3—NH2 7 0 c3h7 C3h7 —(ch2)3o-nh2 7 1 ch3 c3h7 —(CH2)7—nh2 7 2 ch3 ch3 7 3 ch3 ch3 7 4 ch3 ch3 ~^ ^~(CH2)2—nh2 7 5 C4H9 c4h9 7 6 c4h9 ch3 - ^~^~(c H 2)2&quot;^ ^NH 2 48 1253464- <Table 1 1-2 — 2>

No. R2a R2b z 7 7 ch3 ch3 0 -(CH2)3— II 〇7 8 ch3 ch3 T ^ —(CH2)3〇-Si—r^YCv Me o 7 9 ch3 ch3 —(ch2)3〇U^ :〇δ 8〇c3h7 c3h7 0 —(CH2)3〇— M 〇8 1 C3H7 C4H9 〇—(ch2)30— «9 〇8 2 ch3 ch3 8 3 ch3 ch3 8 4 ch3 ch3 8 5 c4h9 c4h9 CH3 H3C V 8 6 CM, c3h7 -〇-〇:&gt; 49 I2534^p,doc Specific examples of the compound (1) defined in the formula (1-C) are as shown in Table i-3-1 to Table 1-3-2. .

(1-C) (2-Α) φ H3C\ h3c〆

50 I2534643pif.doc <Table 1 — 3 — 1〉

No. R2a R2b z 8 7 ch3 ch3 (CH2)3nh2 8 8 ch3 ch3 —(CH2)5—Q-nh2 8 9 ch3 ch3 -(CH2)3—^~^νη2 9 0 C4H9 C4H9 —(CH2)30— 9 1 c4h9 c3h7 -(CH2)3-nh2 9 2 ch3 ch3 -^)~^^〇(CH2)3cM3H^^NH2 9 3 ch3 ch3 ch3 h3c \^^H2 \3^V_y-&quot;CH2'NH2 9 4 ch3 ch3 9 5 c3h7 c3h7 nh2 9 6 ch3 c3h7 9 7 ch3 ch3 0 —(CH2)3〇-^^—CH2—M 〇9 8 ci-i3 ch3 0 —(CH2)3〇-^^-(CH2 )2-[0j^,〇0 9 9 ch3 ch3 (CH2)3°^Jic;0 δ 10 0 c 3 H 7 c3h7 〇-(CH2)3〇—II 〇10 1 Cl!3 c4h9 〇-(ch2 ) 3 - ^ 己 , 〇 1 1 〇 51 12534l64pif.doc &lt; Table 1 - 3 - 2 > No. R2a R2b z 10 2 ch3 ch3 - o 10 3 ch3 ch3 - &lt; ^ H2-1Q ^ CH2) 2 〇 hQ^CH2-0^〇o 10 4 ch3 ch3 o -^)^~〇(ch2)4〇乂〉 / ί 10 5 c4h9 C4H9 10 6 c3h7 C4H9 ^&quot;Η2〇Ό:&gt; In the following description The sesquiterpene oxide is abbreviated as SQ and has an SQ skeleton. As a functional group, the compound (1) having an amine group is abbreviated as an SQ amine, and has a SQ skeleton, and has a compound having a 2-oxypropanedifluorenyl group as a functional group ( 1) Slightly recorded as SQ anhydride. First, the case of using an SQ amine will be described. The varnish of the present invention contains a polymer obtained by reacting at least two compounds having a functional group in which an SQ amine and an amine vine are reacted. Such a polymer, for example, can be made to react with the SQ family: a tetracarboxylic acid substance, a hydrazine: a carboxylic acid substance, or a: carboxylic acid substance. The tetracarboxylic acid is a generic term for a tetracarboxylic acid and a derivative thereof which do not contain an SQ skeleton, and represents a tetracarboxylic acid, a tetracarboxylic dianhydride, a tetracarboxylic acid tetrahalide or the like. The tricarboxylic acid is a total of I2534643pif.doc of a tricarboxylic acid and a derivative thereof, and represents a tricarboxylic acid, a tricarboxylic acid monohydride, a tricarboxylic acid trialkyl ester, a tricarboxylic acid trihalide or the like. The dicarboxylic acid compound is a generic term for a dicarboxylic acid and a derivative thereof, and represents a dicarboxylic acid, a dicarboxylic acid anhydride, a dialkyl dicarboxylate, a dicarboxylic acid dihalide or the like. In the following description, the tetracarboxylic acid substance, the tricarboxylic acid substance, and the dicarboxylic acid substance are collectively referred to as other polyvalent acids. Further, as a substance which reacts with the SQ amine, an SQ anhydride can also be used. Preferable examples of the polymer obtained by reacting the SQ amine with these organic acids include polylysine, soluble polyimine, polyamidoximine and the like. Polylysine can be obtained by reacting a tetracarboxylic acid with an SQ amine. The soluble polyimine can be obtained by a dehydration reaction of the polyamic acid. The polyamidoximine can be obtained by reacting a tricarboxylic acid with a SQ amine. The mixture of a tetracarboxylic acid substance and a dicarboxylic acid is reacted with an SQ amine, followed by a dehydration polycondensation reaction to obtain an interpolymer of a polyimine and a polyamine. The polymer may also be called a polyamidoximine. Polyamine can be obtained by reacting a dicarboxylic acid with an SQ amine. Among the polyamines, a polyamine which has a hydrogen atom of a guanamine bond (CONH) substituted with another group is preferred. Among them, polyamine can be obtained by reacting a SQ amine, an aromatic dihalide, and carbon monoxide using a transition metal catalyst. When these polymers are produced, a diamine other than the SQ amine can be used while using the SQ amine. In the following description, a diamine other than the SQ amine may be referred to as another diamine. (1) HL, a compound which reacts with an SQ amine to produce a ruthenium polymer, and is limited to the above-mentioned organic acid. It is almost possible to use all of the compounds having at least two functional groups reactive with an amine group. As a reaction with an amine group, 53 1253464 pifd〇c is exemplified by a group having an epoxy group, a fine acid group, a trans group, a thiol group, an isocyanate group or the like. For example, the SQ amine can be reacted with diisocyanate to give a polyurea. Next, the case of using SQ anhydride will be described. The varnish of the present invention contains a polymer obtained by reacting an SQ anhydride with a compound having at least two functional groups reactive with an acid anhydride. Examples of the functional group reactive with the 2-oxopropanedifluorenyl group of the SQ anhydride include a substance having a group of an active hydrogen, such as an amine group, a thiol group, a 5st acid group, a trans group, a phthalyl group, and a decylamine. Substrate, mercapto group, mercaptocarboxy group, thiol group and the like. Namely, the components of the polymer contained in the varnish of the present invention are selected from polymers obtained by reacting a monomer having these functional groups with an SQ anhydride. Preferred examples of the polymer include a soluble polyamidiamine obtained by reacting a polyphthalic acid or a polydecylamine obtained by reacting a SQ anhydride with a diamine, a dehydration reaction of polyamidamine, and the like, and an SQ anhydride and a dicarboxylic acid. A polyamidoximine obtained by reacting a mixture of acids with a diamine. Further, other polyvalent acids can be used in addition to the SQ anhydride. In view of the use in the liquid crystal alignment film, preferred polymers contained in the varnish of the present invention are the above polylysine, soluble polyimine, polyamine, and polyamidimide. Further, an interpolymer containing at least two of the constituents of these polymers may be used. Such a copolymer is obtained by adjusting the ratio of the above-mentioned polymer raw materials. In the following description, a polymer obtained by using SQ amine and / &amp; SQ acid field as polyglycolic acid, soluble hydrazine, poly phthalimide, oxime amide, or polyamidoximine. Or a copolymer containing two or more of these constituent units is referred to as "SQ polymer", and means a poly 54 I25346463 pif. doc compound having a sesquiterpene skeleton. The varnish in the present invention is a composition in which the SQ polymer and other components added as needed are dissolved in a solvent. The other components are components other than the SQ polymer, and are other polymers obtained by using no SQ amine and SQ anhydride, or additives other than the polymer. When a polyamine acid, a soluble polyimine, or a polyamine amine, a polyamidamine, or the like is produced using the SQ amine, the above may be used. Further, other diamines may be used while using the SQ amine. At this time, the use ratio of the SQ amine is 0.001 to 100% by mole based on the total amount of the diamine. Although not added in the examples of the present specification, the effect can be recognized in a very small proportion of the SQ amine, which can be confirmed by experiments. The ideal range of the ratio is 0. 〇1~7 5 moles The %' is preferably in the range of 0.01 to 50% by mole. The more preferable range is 〜1 to 50% by mole, and the most preferable range is 〇1 to 20% by mole. By using this ratio of s Q amine', it is possible to produce a crystallographic alignment which is balanced in terms of abrasion resistance, liquid crystal alignment, and display quality. When polyacrylic acid, soluble polyimine, polyamine or polyamidoximine are produced using SQ anhydride, other polyvalent acids may be used while using SQ anhydride, preferably tetracarboxylic acid. Acidic substances. At this time, the use ratio of the SQ anhydride is from 0.1 to 100 mol% based on the total amount of the organic acid. Although not added in the examples of this booklet, but in a very small proportion of SQ amines to recognize its effect '辺&quot; a point can be confirmed by inspection. The ideal range of this ratio is 〇·01~75 mol%, preferably _0.01~50 mol%, and the range of 佧 为 is 0.]~50 mol of the most guinea range is 〇. 1~2 〇mol% By using this ratio of s Q sour liver, a liquid crystal alignment film which maintains a balance of 55 I253464ifd〇c in terms of abrasion resistance, alignment of liquid crystal, and display quality can be produced. Specific examples of the above-mentioned tetracarboxylic acid substances, dicarboxylic acid substances and other diamines are described in the 5th to 9th pages of the Patent Cooperation Convention W098/31725A1, pages 15 to 31 of the Patent Cooperation Convention WO99/33902A1 manual, and W099/33923A1. Pages 16 to 35 of the Handbook, pages 17 to 36 of the Patent Cooperation Convention W099/34252A1, pages I to 39 of the Patent Cooperation Convention W001/0〇732A1, and pages 9 to 27 of the Patent Cooperation Convention WO01/14457A1. As a substitute for the dicarboxylic acid or the dicarboxylic anhydride in the examples described, a G acid dihalide having the same residue as those of the above can be used. The tetracarboxylic acid substance, the dicarboxylic acid substance, and other diamines which can be used in the present invention are not limited to these recording examples. Any of these examples can be arbitrarily selected and used as long as the object of the present invention is not impaired. The tetracarboxylic acid substance, the dicarboxylic acid substance, and other diamines may be used in combination of any two or more. Preferred examples of the tetracarboxylic dianhydride are shown below.

56 Ι25346Φ3ρ if.doc

12534646^^°°

58 I25346463pifdoc

In the above formula, Me represents a methyl group. Among these compounds (1 to 34), there are those in which structural isomers are present, and these may be one or a mixture of the isomers of the individual 59 I25346463P if.doc. Examples of preferred dicarboxylic acids are shown below. 2

Preferred examples of other diamines are shown below. Further, η in the specific W example described below represents an integer of 1 to 20. R represents an alkyl group having 1 to 20 carbon atoms, and a pleasant CH 2 group in the alkyl group may be substituted by one, one CH = CH - or one C ^ C. Any hydrogen in the cyclohexyl group and the phenyl group may be substituted with a hydrazine halide or an alkyl group having 1 to 5 carbon atoms. 60 I25346463pif.doc

61 I25346463P if.doc

62 Ι25346Φ63Ρίίά〇° 26

63 I25346463pifdoc

Bn in the formula 37 is biphenyl fluorene. 64 I25346463pif.doc

R

42

H2N

45

65 125346^3Pifd〇c

66 I25346463p if.doc A oxane diamine containing a hydrazine bond can also be exemplified as an example of other diamines. A preferred example of the dioxane-based diamine is a compound represented by the formula (7).

In the formula (7), R4 and R5 are each independently and are an alkyl group having 1 to 4 carbon atoms or a phenyl group. R6 is an alkylene group having 1 to 1 ring of carbon atoms, and any -CH2- in the alkylene group may be substituted with a mono or a phenyl group. Any hydrogen atom in the phenyl group may be substituted with an alkyl group having a carbon number of 丨~4. X is an integer of 1 to 10. Preferred examples of NH2-R6- in the formula (7) are: nh2 - (CH2)3 -, NH2 - C2H4 〇(CH2)2 -, NH2 - C2H4 〇(CH2)3 -, NH2 - (CH2) 3〇(CH2)2-, NH2 -(CH2)3〇(CH2)3 -, NH2 - (CH2)4〇(CH2)2—, NH2 —(CH2)4〇(CH:2)3 —, NH2 — (ch2)5〇(ch2)2—, nh2 — (ch2)5〇(ch2)3—, nh2 — (CH2)60(CH2)3- 'NH2-(CH2)60(CH2)2- &gt; NH2-Ph-C2H4 —, NH2 — Ph — 0(CH2)2 —, NH2 — Ph — 〇(ch2)3 —, nh2 — ch2—Ph—0(CH2)2—, NH2-CH2-Ph—〇 ( C11:)3—, NH2-Ph-CH2〇(CH2)2—, NH2-Ph—CH2〇(CH2)3—, NH2-Ph—C2H4〇(CH2)2—, NH2-Ph—C2H4〇(CH2 -3, NH2 - Ph(CH3) - 〇(CH2)2 -, NH2 - Ph(CH3) - 〇(CH2);; - ' / £ In these examples, Ph is phenyl and Ph(CH3) is A Phenyl group. As other diamines, a diamine having a side chain of 67 1253464^ if. doc having a steroid skeleton can also be cited. Examples of such diamines are: cholesteryl, androstino, /3 cholesteryl, epiguanosyl, ergoline, estradiol, 11α-hydroxymethyl thiol, 11 α-methyl fluorenyl, wool Retention base, melanilide, methyl hydrazine, gestic acid alkyl, /5-glutamyl, decyl, testosterol and cholesteryl acetate. A solution of the SQ polymer can be obtained by reacting the SQ amine with another polyvalent acid substance in a solvent. At this time, other diamines can be used while using the SQ amine. A solution of the SQ polymer can also be obtained by reacting the SQ anhydride with another diamine in a solvent. In this case, other polyvalent acids may be used together with the SQ anhydride, or SQ amines may be used together with other diamines. The order of the reaction can be carried out in accordance with the usual reaction examples of the polyvalent acid and the diamine. As described above, by appropriately selecting the kind of the organic acid or the molar ratio of the amine group to the carboxyl group, the SQ polymer can be made into a polylysine, a soluble polyimine, a polyamine, a polyamidimide, and the like. Any of two or more interpolymers of these structural units. This solution can be used directly as the varnish of the present invention. A solution obtained by dissolving a solid substance (hereinafter referred to as "reaction product") obtained by removing the solvent from the solution in a solvent different from the reaction solvent may be used as the varnish in the present invention. Hereinafter, an example of the SQ polymer obtained as described above is represented by a structural unit. In the structural unit described below, Q 1 is a residue obtained by removing an amine group from the molecular formula (1) in which two of the oximes are a group represented by the formula (2-1); Q: three of the oximes are The residue after removal of the amine group in the formula (1) of the formula (2-1) in the formula (1); Q 3 is removed from the molecular formula (1) in which two of Y are a group represented by the formula (2-2) Residue after 2-oxopropanedifluorenyl; Q4 is a molecular formula (1) from three of Y represented by the formula (2-2), wherein 2-68 Ι25346Φ63ρ if. doc oxypropane dimercapto group is removed Residues. G1 is a residue after removing an amine group from a diamine; G2 is a residue after removing a carboxyl group from a dicarboxylic acid; G3 is a residue after removing a carboxyl group from a tricarboxylic acid; and G4 is removed from a tetracarboxylic acid The residue after the carboxyl group.

R2 R2 I , I 2 -Si——Z1 ( 2-1 ) ——Si——Z2 ( 2-2 ) l2 l2 R2 R The SQ polymer as polyimine is represented by the following formula (3-1) The polymer represented by at least one of the structural units represented by any one of the molecular formulae (3-8) and the structural unit represented by the formula (4-1) constitutes a polymer chain. The structural positions represented by these formulas are obtained by reacting only a difunctional SQ amine, a trifunctional SQ amine, and other individual diamines, with a tetrafunctional SQ anhydride, a hexafunctional SQ anhydride, and each tetracarboxylic acid. The structural unit of the quinone imine bond in the structural unit. Since these are theoretically introduced structural units, in practice, the polymer may be included in the case where an acid group based on an amine group of a trifunctional SQ amine or an /1 hexafunctional s Q acid anhydride is unreacted. The structural unit obtained by the reaction. 69 I25346463pif.doc

70 I25346463pif.doc The SQ polymer as a poly-proline is at least one of the structural units represented by any one of the following formulas (5-1) to (5-8) and the structure represented by the formula (6-1). The unit constitutes a polymer of a polymeric chain. The structural unit represented by these formulas is a structure obtained by reacting only a difunctional SQ amine, a trifunctional SQ amine, and other respective diamines, a tetrafunctional SQ anhydride, a hexafunctional SQ anhydride, and each tetracarboxylic acid substance. The structural unit of the indoleamine in the unit. Since these are theoretically introduced structural units, in practice, the polymer may contain a structure obtained by a reaction in the case where an amine group of a trifunctional SQ amine or an acid anhydride group of a hexafunctional SQ anhydride is unreacted. unit. 125346i463pif.doc

C〇〇H 〇

(5-4)

(5-5)

r\ C〇〇H

(5-7)

The SQ polymer as the polyamidoximine is at least one of the structural units represented by any one of the following formula (7-1) to 72 I253464363 pif. doc (7-2) and the formula (8-1) The structural unit constitutes a polymer of a polymeric chain. The structural unit represented by these formulas is a structure having a difunctional SQ amine, a trifunctional SQ amine, and other individual diamines, a quinone bond and a guanamine bond in a structural unit obtained by reacting with a tricarboxylic acid substance. unit. Since these are theoretically introduced structural units, in practice, the polymer may contain structural units obtained by a reaction in the case where an amine group of a trifunctional SQ amine is unreacted. Further, a polyamidoximine having a structural unit in which a guanamine hydrogen is substituted with an alkyl group of a methyl group is preferred. # 〇 〇 〇 〇

Y 0 " (8-1) The SQ polymer as the polyamine is at least one of the following structural formula (9-1) and the formula (9-2), and at least one of the structural units of π, and the molecular formula (1) The structural unit represented by (M) constitutes a polymer of a polymer chain. These polymers represent structural units of a difunctional SQ amine, a trifunctional SQ amine, and other diamines and dicarboxylic acids of 73 12534$^63pif.doc. The structural unit obtained by the reaction of the substance. Since these are theoretically introduced structural units, in practice, the polymer may contain a structural unit obtained by a reaction in the case where an amine group of the trifunctional SQ amine is unreacted. Further, polyamine which has a structural unit in which amidide hydrogen is substituted with a methyl group alkyl group is preferred.

—Q

NH_-

—G1——NH

NH—

(10-1) The SQ polymer as the copolymer is any structural unit of the formula (3-1) to the formula 08), and the molecular formula (5-丨) to any of the formula (5-8) A structural unit of the table K, a molecular formula (7_丨), and a structural unit of any one of the bifurcation formulas (7-2), a molecular formula of the formula (9_1), and a formula 02), at least one selected from the structural units of the crucible The two structural units, at least one of the structural units represented by any one of the molecular formula (4-1), the molecular formula (6-1), and the molecular formula (8-1) constitute a polymer of a polymer chain. 74 125 3 46463Pifd〇c Further, in the above, an example of a preferred polymer is at least one of structural units represented by any one of the molecular formula (3-3) and the molecular formula (3-4), and the molecular formula (4-1) The structural unit represented by the polymerized chain forms a polyimine of a polymer chain, at least one of structural units represented by any one of the formula (5-3) and the formula (5-4), and forms a polyamine with a structural unit represented by the formula (6-1). Acid, and by formula (3-3), formula (3-4), formula (5-3) and formula Any one of the structural units represented by any one of 5 to 4), and at least one of the structural units represented by any one of the molecular formula (4_1) and the formula (6-1) forms a copolymer of the polymer chain. In the SQ polymer, also because the above structural unit is a theoretical structural unit, in practice, the polymer may contain an anhydride group utilizing an amine group or a hexafunctional SQ anhydride in the trifunctional SQ amine. The structural unit obtained in the case of the reaction. ^ 1), the molecular formula in all structural units of the SQ polymer (3, subformula (3-2), molecular formula (3 - 3), molecular formula (3 - 4) ), molecular formula (3 molecular formula (3-6), molecular formula (3-7), molecular formula (3-8), molecule '5)' 1), molecular formula (5-2), molecular formula (5-3), molecular formula ( 5 — 4), 八, 5, ～50 mol% more &lt; 0.1 to 20 mol% - 5), formula (5-6), formula (5-7), formula (5\-formula (7- 1), molecular formula (7~2), molecular formula (9-1) and molecular formula (any one of 9 knife households) The total ratio of the structural units is % of 〇.〇〇1 to 丨%^2). The ratio is 〇·〇1 to 75 mol%, and the ratio is preferably 0.1 to 50 mol%, and the ratio is 0.1 to 50 mol%. Green 1% 铎 Η, 丨卽 结 描

At this point, use three dozen SQ amines to get 丨/

The unit may contain structural units obtained by reaction using a face/M 在 of a trifunctional SQ amine to react in the case of 75 125346A63pif.doc. The structural unit obtained by using a hexafunctional SQ anhydride may contain a structural unit obtained by a reaction in the case where an acid anhydride group of a hexafunctional SQ anhydride is unreacted. In the production of the SQ polymer, an amine compound or a dicarboxylic anhydride may be used simultaneously in order to form a reaction terminal of the polymer. Examples of the dicarboxylic acid anhydride include maleic anhydride, phthalic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of the monoamine compound include aniline. Cyclohexylamine, η-butylamine, η-pentylamine, η-hexylamine, η-heptylamine, η-octylamine, η-decylamine, η-decylamine, η-undecylamine, η-Twelve Alkylamine, η-tridecylamine, η-tetradecylamine, η-pentadecaneamine, η-hexadecaneamine, η-heptadecaneamine, η-octadecylamine, and η-twenty Alkylamine. In the varnish of the present invention, other polymerizations obtained without using the sesquiterpene oxide derivative represented by the formula (1) can be used while using the SQ polymer as long as the effects of the present invention are not impaired. Things. Examples of the other polymer are polyglycine, polyimine, polyamine, and polyamidimide which are obtained without using SQ amine and SQ anhydride, and other polymers may be used. Among all the components of the polymer contained in the varnish, the ratio of the SQ polymer is 0.1 to 100% by weight, and the ratio of the other polymers is 0 to 99.9% by weight. 'i.e., when used in combination with other polymers, the varnish A preferred ratio of the other polymer in all the polymer components contained in the polymer is 0.01 to 99.9 % by weight based on the total amount of the components of all the polymers. The ratio of other polymers is preferably from 2 to 70% by weight. The range of from 1 to 50% is preferably from 4 to 50%. 〇 In the varnish of the present invention, other additives may be used. Other examples of the additives of 76 1253464363 pif.doc include: decane- or titanium-based coupling agents which further improve the bonding of the alignment film to the glass substrate. Examples of decane coupling agents are: aminopropyltrimethoxydecane, aminopropyltriethoxydecane, vinyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, vinyltriethoxydecane, 3-methylpropoxypropyltrimethyl Decane, 3-propoxytrimethoxytrimethyldecane, 3-propoxytrimethoxydimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrioxydecane. It is also possible to use an eucalyptus oil such as polydimethyl siloxane or polydiphenyl fluorene to achieve the same purpose as the coupling agent. The amount of the other additives such as the coupling agent and the eucalyptus oil is 〇 55% by weight based on the proportion of all the polymer components contained in the varnish. When other additives are used, a preferred ratio is from 0.01 to 5% by weight. A more preferable range of the ratio is 0.1 to 3% by weight. However, this range is a general standard when a substance such as a decane coupling agent is used, and is not a characteristic standard in the present invention. An example of an additive other than eucalyptus oil or a coupling agent is an surfactant. When it is desired to improve the sprayability and the property of preventing charging, an interface surfactant suitable for the purpose can be used in combination. Examples of the surfactant are anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, and these materials can be used within a range that does not impair the properties of the membranous film. The preferred concentration of the component of the polymer in the varnish of the present invention is 〇.1 to 4% by weight based on the total amount of the varnish. The concentration of the composition of the composition is within this range, and a varnish having an appropriate viscosity can be obtained. Moreover, since the dilution is very easy, it can be adjusted to the most appropriate coating film thickness. Use 1253464363pif.doc Spin method 'When printing method' In order to ensure a good coating film thickness, the concentration of the polymer component is often set to 1% by weight or less. Other coating methods, such as in the rubbing process, may also set lower concentrations. In the usual spin method or printing method, the concentration of the polymer component is 0 l% by weight or more, preferably 0.5 to 10% by weight. However, depending on the coating method of the varnish, a more dilute concentration can be used. The selection conditions of the solvent used in the varnish of the present invention are not particularly limited as long as they have the ability to dissolve the raw material used for the production of the polymer and the obtained polymer. Therefore, when producing a polyamic acid, a soluble polyimine, a polyamidimide, a polyamine or the like, a solvent which is usually used, and a solvent which is usually used in the use of these polymers are The purpose is chosen appropriately. Examples of such solvents are aprotic polar organic solvents which are parent solvents for polyglycolic acid, soluble polyimine, polyamidimide, and polyamidamine, for example: N-methyl-2- Pyridinone (NMP), dimethyl imidazolidinone, N-methyl caprolactam, N-methylpropionamide, N,N-dimethylacetamide (DMAc), dimethylsulfonate Oxide (DMS®), N,N-dimethylformamide (DMF), N,N-diethylformamidine, diethylacetamide, r-butyl inner vessel (GBL). These solvents can also be used in combination. For the purpose of improving coatability, ΐ is used simultaneously with other solvents. Such solvents are: alkyl lactate, benzyl-3-methoxybutane, 1,2,3, tetralin, isosymmetric isopropylene: 1, anthrone, ethylene glycol alkyl ether (for example: Ethylene glycol butyl ether (BC), diethylene glycol decyl ether (eg diethylene glycol ethyl ether), ethylene glycol acetate, ethylene glycol phenyl acetate, triethylene glycol alkyl Ether, 1253464l363pif.doc

A dialkyl acid ester (e.g., diethyl malonate), a propylene glycol acetate, a dipropylene glycol alkyl ether (e.g., dipropylene glycol methyl ether), and a dipropylene glycol acetate. These solvents can be used in combination. The alignment film of the present invention can be effectively used in all liquid crystal display elements. In order to obtain a strong alignment setting force, the effect of the present invention which does not cause frictional damage and poor alignment can be clearly confirmed even in a mode in which strong friction is applied. Examples of such modes are: in-plane conversion mode, super-twisted nematic mode, twisted nematic mode, optically corrected birefringence mode, strong inductive type, anti-inductive type, and the like. In the vertical calibration mode, friction is sometimes required for the purpose of controlling the skew of the liquid crystal molecules when the voltage is applied. However, in this mode, it is also confirmed that there is a remarkable effect. The method for producing the alignment film of the present invention is not particularly limited, and it can be produced in the following order. The varnish of the present invention is applied onto a glass substrate with a transparent electrode or a plastic substrate with a transparent electrode by a coating method, a dipping method, a spin method, a spray method or a printing method. Then, the temperature of the substrate with the electrode is set to 50 to 15 ° C, preferably 80 to 120 ° C, to evaporate the solvent. Thereafter, the temperature is set to 150 to 40 G: C, preferably 180 to 280 ° C, on the substrate with the electrode, and the film is formed on the glass substrate. In particular, when a rubber substrate is used, it is preferable to use a low-temperature paste of /H 120 to 160 ° C in consideration of the heat-resistant temperature of the substrate. Further, the alignment film of the present invention can be obtained by rubbing the surface of the coating film in the same direction with a cloth. 79 1253464363pif.doc Before the varnish of the present invention is applied onto a substrate or a plastic substrate with a transparent electrode, the surface of the substrate is treated with a sand-in-a-kind agent to further improve the bond between the alignment film formed on the surface of the substrate and the substrate. The liquid crystal composition material used in the liquid crystal display element of the present invention is not particularly limited. When a liquid crystal element such as a twisted nematic type, a super twisted nematic type, an in-plane conversion type, or an optically corrected birefringence type is used, a liquid crystal composition having positive conductivity anisotropy is used. Preferable examples of the liquid crystal composition material are disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei 9-241644 (EP 885 272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1), Japanese Patent Laid-Open No. Hei 9-235552 Japanese Laid-Open Patent Publication No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP 885 271 A1), Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei. Japanese Patent Laid-Open No. Hei 10-23M82, Japanese Patent Laid-Open Publication No. 2000- 087040, and Japanese Patent Laid-Open No. 2001-48822. When the liquid alignment film of the present invention is used for the production of a vertical alignment type liquid crystal display device, a liquid crystal composition having a negative conductivity anisotropy is used. A preferred example of the liquid crystal composition material is disclosed in Japanese Laid-Open Patent Publication No. SHO 57-114532, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. 2 - 4-25, Japanese Patent No. 1253464363 pif. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 10-236990, Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei 10-237004, Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 10-237448 (EP967261), Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. 287874, Japanese Patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. 2001-019965, Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. The extent of the scratches and the mechanical properties of the aligning film that was destroyed after the formation of the scratches were evaluated. That is, according to the experiments of the inventors of the present invention, it is possible to know the load and the orientation when the friction is applied while the ancestors are applied, the load on the alignment film is scratched, or the scratches are formed until the alignment strand is broken. The friction resistance of the film is related. Therefore, by comparing these defects, it is possible to evaluate the friction resistance of 81 I25346Apif.doc. At this time, for example, the load (wi) of the scratch of the alignment film (pi) formed using the polymer containing the sesquiterpene oxide derivative is caused to cause formation of a polymer containing no sesquioxane derivative. When the ratio (W-1/W-2) of the load (W-2) of the scratch of the alignment film (P-2) is 1.05 or more, it is considered that the friction resistance of the qualitative film of P-1 is higher than that of P- 2 high. The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] Hereinafter, the present invention will be described in detail by way of examples. However, the invention is not limited to these examples. In the chemical formula in the examples, Ph is a phenyl group. The NMR data in the examples are those measured in heavy chloroform. The molecular weight was determined by using GPC, polystyrene as a standard solution, and DMF as an effluent. The unit of the capacity "liter" is indicated by the symbol L. <Method for Evaluating Liquid Crystal Display Element> The evaluation method of the liquid crystal display element used in the examples is described below. Further, the measurement of various physical properties described in the examples was 値 at 25 °C. (1) Scratch caused by friction applies a voltage to the liquid crystal element, and when the display is performed, the portion where the 7K defect is observed by visual observation is observed, and (2) the adhesion between the liquid crystal inner film and the substrate and the adhesion of the substrate to the substrate are measured. The detachment load of the alignment film (the breaking load of the film &lt;3 pif. doc to the film) was measured using a scanning scratch detector SST101 manufactured by Shimadzu Corporation, and the ruthenium was used for the evaluation. The measurement of the shedding load is the bending curvature of the stylus 10//Μ • the friction speed 20//M/s • the amplitude 100 // Μ • the stylus pressing speed 5//M/s. (3) Pretilt angle ~ Perform according to the crystal detection method. The measurement wavelength was 589 nm. / (4) The voltage holding ratio is carried out in accordance with the method described in "Water Margin, 14th Liquid Crystal Symposium P78". The voltage applied to the element during the measurement was set to a gate width of 69//s, a wave height of ±4·5 V, and a frequency number of 30 Hz or 0.3 Hz. _ [Example 1] <Synthesis of SQ amine represented by the formula (1_5)> The SQ amine can be synthesized by the following method.

83 1253464·63ρΐί.άοο HO—^~y~N〇2

Br K2C03 N〇2

H el e Μ·δι丨 M

Phi Ph 84 1253464363 pif.doc [Example 2] <Synthesis of SQ acid anhydride represented by the formula (1-3)> SQ anhydride was synthesized by the following method.

Ph,

Si—0 y\ 八 〇 〇 ''Si—0-pSi~Ph I Iph-Si-I-O—Si.ΪΧ X Ph .Si—0—Si. Ph, 'Ph 3Na (1-1 )

Me

Cl-Si-H Me

<First stage: Production of SQ compound (1-2) In a reaction vessel having a titration funnel, a thermometer, and a mixer having an internal volume of 3 liters of 85 I63 pif.doc, compound (ll) (249 g) and toluene (2000 ml) were added. ), sealed with dry nitrogen. The dimethyl decane chloride (142 g) was stirred and titrated after about 50 minutes. During this period, the temperature of the solution should be kept at 2〇~4 (rc. After the end of the titration, the solution is heated to 65 ° C, after reaching 65 ° C, continue mixing for 3 hours. After the solution is cooled to 50 ° C, drip Ion-exchanged water (230 g) was allowed to stand for about 10 minutes, then stirred for 10 minutes, transferred to a separatory funnel, and separated into an organic layer and an aqueous layer. The organic layer obtained was repeatedly washed with 200 g of ion-exchanged water, and repeated three times. Then, the mixture was dehydrated by boiling to remove water, and then concentrated under reduced pressure to obtain 242 g of a white solid. Compound (1-1) can be hydrolyzed with p-phenyltrialkoxydecane to obtain a sesquioxane oxide oligomer. Then, it is obtained by reacting with sodium hydroxide in tetrahydrofuran. Compound (1-1) can also be hydrolyzed and condensed by phenyltrialkoxydecane in the presence of an oxygen-containing organic solvent, water and sodium hydroxide. The compound (1-1) can be produced in a short time and with high efficiency by any method (for example, refer to the Patent Cooperation Convention WO02/094839 manual). For the obtained white solid, infrared absorption is performed by the KBr tablet method. Spectral analysis confirmed the absorption based on Si-H stretching in 2134CM-1. Moreover, using heavy chloroform as a solvent, the old Isodecane was used as an internal standard substance for 29SI-NMR analysis. 2 · The signal of dimethylformamidin was confirmed in 76 PPM, and the average molecular weight of polystyrene was measured by GPC, and the number average molecular weight was 85 Å, and the weight average molecular weight was 860. The above data indicates the molecular formula (1-2). Structure: <Phase 2: Manufacture of SQ Anhydride (1_3)> 1253464363pif.doc A compound (1_2) was added to a three-necked flask having an internal volume of i〇〇mi equipped with a thermometer, a stirrer, a titration funnel, and a circulation cooler. (4 4g), allyl succinic anhydride (2.3g), and toluene (6.7g), sealed with dry nitrogen. While stirring with a magnetic stirrer, heat the solution to 8 (rc, then, in the micro cylinder Krusted catalyst (3.9//1) was added thereto, and after the catalyst was added, it was confirmed that the heat was generated, and the reaction was started. Further, after stirring for 1 hour, sampling was carried out, and infrared absorption spectrum analysis was performed to confirm 2134CHT1 derived from Si-H group. The peaks disappeared and the reaction was completed. Then, the reaction liquid was cooled to room temperature, and concentrated under reduced pressure using a rotary evaporator. In the obtained residue, added: towel|| (4.2 g), using a magnetic stirrer at room temperature After stirring for 15 hours, the solution was passed through a furnace and a formazan solution, and the obtained solution was concentrated under reduced pressure to obtain 5· lg of solid. For a light brown solid substance, heavy chloroform was used as a solvent, and [methyl sand yard] The 13C-NMR analysis was carried out as an internal standard, and as a result, a peak corresponding to the substituted succinic anhydride was confirmed in 17 〇.44 ppm and 144.04 ppm. Further, GPC analysis was carried out, and the number average molecular weight was 1,350, and the weight average molecular weight was 1,430. The light brown solid material which is not obtained in the above data sheet is the SQ anhydride represented by the formula (1-3). [Example 3] <Preparation of polyamic acid varnish (1)&gt; In a 200 ml four-necked flask, 4,4-diaminodiphenylmethane (hereinafter referred to as DDM) was added (2.9940 g; 1.51). (10-^01), and dehydrated N-methyl-2-[panelone ketone (hereinafter referred to as NMP) (54.00 g), 1/i: stirred and dissolved under a dry nitrogen gas stream. Then, the temperature of the hydrazine is kept at 5 ° C, SQ anhydride (l-3) (0.0600 g; 3.93x10-5 mol) is added, and the mixture is stirred until Sq 1253464 ό 3ρίί. phthalic anhydride is completely dissolved, and then added to the ring. Dingyuan tetracarboxylic dianhydride (hereinafter referred to as CBDA) (2.9500 g; 1.50 x l 〇 2 mol), and then it was allowed to react for 30 hours without specifically controlling the temperature. Finally, 4 g of ethylene glycol butyl diether (hereinafter referred to as BC) was added to obtain a polyamic acid varnish having a polymer component concentration of 6% by weight. This compound was used as varnish A1. In the embodiment of the present invention, the viscosity is measured while the viscosity is increased. Further, when the viscosity increase is small, BC is added to terminate the progress of the adhesion-promoting reaction. After the addition of BC, heating was carried out to adjust the viscosity of the varnish, and when it reached 55 to 65 mPa·s, the heating operation was stopped. The viscosity was measured at 25 ° C using an E-type viscometer. Moreover, the obtained varnish is kept at a low temperature. [Example 4] <Preparation of polyamic acid varnish (2)> The amount of use of SQ anhydride (1-3) was set to 〇.6000 g (3.93 x 1 (T 4 mol), and the amount of DDM used was set to 2.6443 g. (1.33 x 10 - 2 mol), and the amount of CBDA used was set to 2.5000 g (1.27 x 10 - 2 mol), and other polyacetin was obtained in the same manner as in Example 3. This material was used as varnish A2. [Example 5] <Preparation of polyamic acid varnish (3)> In addition to changing the raw material composition to 4,4'-diaminodiphenyl phenylene (hereinafter referred to as DDEt) (1.0720g; 5.05x10-3m〇l), 1,1-(4-((Aminophenyl)"P-)phenyl-M-heptylcyclohexane (hereinafter referred to as APMPH) (2.7512 g; 5.05x10-3 mol), SQ strontium dry ( 1-3) (0.06()0 g ' 3.93x10—'mol), and pyromellitic dianhydride (hereinafter indicated by PMDA table ►pif.doc) (2.1900 g; 1.00x10-2m〇l) other than In the same manner as in Example 1, polylysine was obtained, and this material was used as varnish B1. [Example 6] <Preparation of polyamic acid varnish (2)> In addition to changing the raw material composition to DDEt (l. 〇 845 g; 5.11x10 — 3mol), APMPH (2.7 833 g; 5.11xl (T1mol), SQ anhydride (1 -3) (0.0600 g; 3.93x10-2 mol), and PMDA (2.1000 g; 9.63x10-1 mol), otherwise identical to Example 1 Proline acid, this substance is used as varnish B2 ° [Example 7] <Polymerization of poly (proline varnish) (3)> In addition to changing the raw material composition to 5-((2_(2-(4-pentylcyclohexyl))) Cyclohexyl)phenyl)methyl-1,3-diaminobenzene (hereinafter referred to as HHPMB.) (3.9633 g; 9·16χ1〇-1M〇1), SQ anhydride (1-3) (0.0600 g; 3.93) Other than Example 3, except that x10-3M0 1 ) and PMDA (1.9850 g; 9.10x10-1M0 1 ), polylysine was obtained, and this material was used as varnish C1. [Example 8] Amino acid varnish formulation (6)&gt; 1 mo〇, SQ anhydride (1-3) (0.〇600 g; 3.93χ1〇2m〇!), and 2 PMDA (1.7300 g; 7.93xl (T1mol) raw material composition Other than the same as in the third embodiment 3, polylysine was obtained, and this material was used as the varnish C2. • pif.doc [Example 9] <Polymeric amidoxime formulation (1)> In a 50 ml three-necked flask, DDEt (1.0833 g; 5.10 χ 10 -3 mol) and hydrazine (2·7801 g; 5.1 〇 xl 〇 -3 mol), dissolved in 20 g of NMP, and stirred in a stream of dry nitrogen. The reaction temperature was maintained at 5 ° C while SQ anhydride (l-3) (0.0600 g; 3.93 x 10-5 mol) was added to completely dissolve it. Then, PMDA (1.1066 g; 5.07 x lO-3 mol) was introduced and stirred for 1 hour under a nitrogen stream. Then, p-terephthalic acid dichlorooxygen (hereinafter referred to as TPAC) (1.0300 g; 5.07 x 10 - 3 mol) and pyridine (Inil) were added, and the mixture was further stirred for 2 hours. After completion of the reaction, acetic anhydride (2 〇 ml) was added, and the mixture was reacted at 100 ° C for 1 hour. The cooled reaction solution was added to 300 ml of methanol to precipitate a product, which was filtered. The obtained crude product was boiled and washed twice with pure water (15 ml). The obtained crude product was boiled and washed once with methanol (15 ml), and washed for 30 minutes. The obtained material was vacuum dried at 120 ° C for 7 hours to obtain 4.8 g of polyamidoximine. The weight average molecular weight of the polymer was i.ix105. <Methylation of Polyamidourine Imine> The polyamidoquinone imine (i.Og) was placed in a three-necked flask to dissolve in NMP (20 ml). 94 mg (2 - 3 mmol) of 60-electrolyzed sodium hydride (protective substance: liquid paraffin) was added thereto, and the mixture was stirred at room temperature for 3 hours. To the solution was added 43 0 g of methyl iodide (3.0 mmol), which was further reacted for 2 hours in the room. The reaction liquid was added to 300 ml of pure water to precipitate the product again, and the resulting crude product was washed with pure water (15 〇ml) by 2 90 12534644363 pif.doc times, and then mixed with pure water-IPA ( The weight ratio i/1) (50 ml) was washed once. Wash strips using pure water are allowed to boil for 30 minutes. The washed product was vacuum dried at 120 ° C for 8 hours to obtain 960 mg of methylated polyamidoximine. The polymer had a weight average molecular weight of 4.3 x 104. Further, the substitution ratio to the methyl group of the amino hydrogen was 97%. This polymer was used as PAI-1. A varnish in which PAI-1 was dissolved in the same manner as in Example 3 was used as the varnish D1. [Example 1〇] <Polymerization of polyamidoquinone (2)> The amount of DDEt was set to 1.1030 g (5.20 x 10 -3 mol), and the amount of APMPH was 2.8308 g (5.20 x 10-3 m〇l), SQ The amount of the acid anhydride (1 - 3) was set to 〇.6000 g (3.93 x 1 (T4 mol), the amount of PMDA was set to 1.0690 g (4.90 x 1 (T3 mol), and the amount of TPAC was set to 0.9950 g (4.90 X10-3 mol)). Other, in the same manner as in Example 8, 4.8 g of polyamidoximine was obtained. The weight average molecular weight of the polymer was Hx 105. Then, methylation reaction of the amine hydrogen was carried out as in Example 8 to obtain 94 〇 mg. The methylated polyamidoximine. The weight average molecular weight of the polymer is 4.3 X 104. Moreover, the methyl group substitution rate to the amine hydrogen is 97%. The polymer is used as ΡΑΙ-2. And BC, the varnish dissolved in bismuth-2 was used as the varnish D2 ° in the same manner as in Example 3, and the polymer in the varnish of Example 3 to 〇 was relative to the ruthenium sample A; Just: Moore is as shown in Table 2. + 12534 Secret 63pif.doc <Table 2> Example No. Varnish name SQ anhydride accounts for the total amount of organic acids in the raw materials The ratio (mol-%) 3 A1 0.26 4 A2 2.99 5 B1 0.39 6 B2 3.92 7 C1 0.43 8 C2 4.72 9 D1 0.39 10 D2 3.86 [Comparative Example 1] Except that SQ anhydride (1-3) is not used, and only A polyamic acid varnish was obtained in the same manner as in Example 3 except that the amount of the SQ acid anhydride used in the raw material diamine component was removed. The varnish was used as the varnish A0. [Comparative Examples 2 to 4] In the methods of Examples 5, 7 and 9, varnishes BO, C0, and DO were obtained. That is, varnishes B0 and C0 were polyamic acid, and varnish DO was a varnish of methylated polyamidoximine. [Example 11 [Preparation of Mixed Varnish (1)] The varnish A1 and the varnish A0 were mixed to prepare a mixed varnish AL·A0 having a weight ratio of the polymer in the varnish A1 to the polymer in the varnish A0 of 1/9. 12~18] <Mixing varnish blending (2) to (8)&gt; As in Example 11, varnishes A2, Bl, B2, C1, and 1253464 "4363pif.doc C2, D1, and D2 were mixed with varnish AO, respectively. Blended to a mixed varnish A2 · AO, B1 · AO, B2 · AO, Cl · AO, C2 · AO, D1 · A0, and D2 • AO, the poly in these varnishes Weight of the polymer component was AO varnish component ratio of 1/9. [Comparative Examples 5 to 7] <Preparation of mixed varnish containing no polymer obtained by SQ anhydride (1-3)> The varnish B0 and varnish A0 were mixed to prepare a mixed varnish, and the polymer component in the varnish B0 was The weight ratio of the polymer component in the varnish A0 was 1/9. This mixture was used as a varnish BO/AO. Similarly, varnishes C0 to DO and varnish A0 were separately blended into mixed varnishes C0 · A0 and DO · A0. [Example 19] The varnish A1 obtained in Example 3 was diluted with a NMP-BC mixed solvent (weight ratio of 1/1) to adjust the concentration of the polymer component to 3% by weight. The diluted varnish was applied onto a substrate with a transparent electrode by a spinner, and pre-sintered for 5 minutes under conditions of 8 (TC). Then, it was sintered at 210 ° C for 30 minutes to form a coating film having a thickness of 60 nm. The rubbing method performs an overall alignment treatment on the surface thereof. Another identical substrate is fabricated, and 20 #Μ spacer material is spread on one side of the alignment film of the substrate, and the other substrate is relatively overlapped with the alignment film surface, and then cured by epoxy. The agent is sealed and made into an anti-coupling member with a spacing of 20//Μ. To this, the U!7 dip is injected with the liquid composition material A shown below, and the Kawasaki hardener seals the injection port. Then, at 11 ( Under the condition of TC, heat treatment was carried out for 30 minutes to prepare an element which was uniformly aligned. The element was sandwiched between two polarizing plates in a state of a cross polarizer, 93 I63pif.doc, and rotated therebetween to confirm that there was no The uniform and clear light and darkness of the alignment defect, the liquid crystal molecules are well aligned by the rubbing method, that is, the scratch caused by the friction on the alignment film in the element can be determined. The pretilt angle is 1.4 degrees. I63pif.doc

94 lpif.doc

Lpif.doc <Liquid Crystal Composition A> F

17 wt% 17 wt% 16 wt% 10 wt% 5 wt% 10 wt% 6 wt% 6 wt% 13 wt% Then, in addition to setting the spacer interval to 6.8//M, the liquid crystal was produced in the same process. The component was measured for the holding ratio of the liquid crystal element. As a result, the voltage holding ratios at 30 Hz and 0.3 Hz were 98.1% and 92.8%, respectively. Moreover, no Vth spots were found at all.

In the same manner as the sintering conditions for producing a liquid crystal element, it was used as a substrate for scratch test, except that a coating film having a thickness of 1 //M was applied onto a substrate with a transparent electrode by a spinner. The scanning force of the coating film formed on the substrate and the substrate was measured using a scanning scratch detector SST101. As a result, the shedding load was 1.13 kPa. [Examples 20 to 34] Using the varnish obtained in Examples 4 to 18, a liquid crystal display element was produced in accordance with Example 19. At this time, in some embodiments, the liquid crystal composition material B described below is used instead of the liquid crystal composition material A. The liquid crystal display elements were evaluated in the same manner as in Example 19, and the results are shown in Table 3.

96 12 5 3 4644363pif.doc &lt;Liquid Crystal Composition B&gt; c3H 〇ch2

C6H13 -o coo

〇C2H5 15wt.% 5wt.% 12wt.% 12wt.% 12wt.% 12wt.% 13wt.% 13wt.% 6wt.%

[Comparative Examples 8 to 14] A liquid crystal display device was produced by the method of Example 19 using a varnish of Comparative Examples 1 to 7 which did not contain a polymer obtained by using SQ anhydride. At this time, in some of the examples, the liquid crystal composition substance Β described below was used instead of the liquid crystal composition substance Α. These liquid crystal display elements were evaluated in the same manner as in Example 19, and the results are shown in Table 3. 97 125346^,. &lt;Table 3&gt; Class skin paint liquid crystal composition material with or without scratch spot pretilt angle (degree) Voltage retention rate (%) 30Hz 0.3Hz kPa A1 A No 1.3 98.1 92.8 1.13 A2 A No 1.3 98.5 93.8 1.23 — B1 I- 1Γ ^T6~~ 98.7 93.5 1.10 B2 A No 7.1 98.7 94.0 1.26 — C1 ~ΊΓ I ^89^2~ 98.6 93.8 1.11 C2 B No 89.3 98.7 94·1 1.25 dT^ 1Γ 6^ 9 97.8 92.9 1.10 D2 A No 6.9 97.9 93.0 1.23 A〇A There are 1.3 97.5 91.0 0.96 B〇A There are 7.1 97.2 91.5 0.93 C There are 89.1 97.2 91.3 0.91 〇0 A There are 6.9 96.4 90.1 0.89 ~7T No 'W ΰ~ 98.1 92.7 1·0" 2-AO A No 1.3 98.5 94.0 1.19 h〇- I- ΊΓ 6^9~ 98.7 93.7 1.12 2.AO A No 6.9 98.8 94.1 1.23 1-AO ^m~ 98·4— 93.8 1.10 2-AO B No 89.1 98.7 94.1 1.26 D.AO A No 6.8 97.8 93.3 1.08 2-AO A No 6.8 98.1 93.7 1.18 0-AO A There are 6.9 97.1 91.2 0.92 〇-A〇 There are 89.0 97.3 91.2 0.90 0-AO A Yes - 6.8 9, L 〇 - 90.3 0.92 Example

No. —19 20 25 26 lb Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 ~~27 __28 ~29&quot; 30

~~3T 32 ~~33~ 34 lb Comparative Example 12 Comparative Example 13 Comparative Example 14 In Table 3, "None" in the column with or without scratch indicates that there is no scratch caused by friction in the alignment film surface, and the alignment of the liquid crystal good. “Yes” means that there are scratches and scratches on the surface of the i (b), and that it is obscured in the is of the liquid crystal. "None" in the display spot indicates that no Vth spot was found. "There is a Vth spot found. It can be confirmed from Table 3. · In the liquid crystal display element showing a pretilt angle of 丨·3 to 89.3." SQ acid 98 Pif.doc 12534644363 Anhydride (1-3) is effective for scratches and scratches. [Industrial Applicability] The liquid crystal alignment film produced by the varnish of the present invention is excellent in mechanical properties suitable for friction, particularly The substrate with the transparent electrode is excellent in bonding. Moreover, the varnish of the present invention is excellent in storage stability. Moreover, such a liquid crystal alignment film can prevent scratches and scratches of the alignment film surface caused by the rubbing operation. The wound can improve the voltage holding ratio which is one of the characteristics of the liquid crystal element. That is, the twisted nematic liquid crystal display element, the super twisted nematic liquid crystal display element, the thin film transistor type liquid crystal display element, and the varnish of the present invention can be used. In-plane conversion type liquid crystal display element, vertical alignment type liquid crystal display element, optically corrected birefringence (type liquid crystal display element, strong conductive liquid Display elements, anti-strongly conductive liquid crystal display elements, and the like are improved as more display elements. Although the present invention has been disclosed in the preferred embodiments as above, it is not intended to limit the present invention, and anyone skilled in the art will not be able to The scope of the present invention is defined by the scope of the appended claims. Main component symbol description]

4fE

Claims (1)

1253464 i positive date: November 28, 1994 is the Chinese patent scope of No. 93312860 without a slash correction this year (10) Patent application scope ---- one ^ A varnish for producing a liquid crystal alignment film which is a composition containing a polymer obtained by using a sesquioxane derivative represented by the formula (1), wherein the polymer is a guanamine bond and an imide bond. At least one of the polymers constituting the polymer chain may also be selected from the group consisting of polyamic acid, polyimine, polyamine, and polyfluorene without using the sesquioxane derivative represented by the formula (1). The polymer of at least one of the groups consisting of the amine imide may also contain other additives, and the ratio of the polymer obtained by using the sesquioxane derivative represented by the formula (1) in all the polymer components is 0.1. ～100% by weight, the ratio of the polymer obtained by using the sesquioxane derivative represented by the formula (1) in all the polymer components is 0 to 99.9% by weight, and the ratio of all the polymers contained in the composition is 〇·1 to 4% by weight, the ratio of the amount of other additives used to the amount of all the polymers is 0 to 5% by weight, and the remaining component of the composition is the solvent R1 R2 RV Si—〇/ -Si —Z 丨(2-1) 〇vSi —O-pSi-R1 丄 R1—Si — —SiιΧ °\/ Rl/Si—o-Sj, Ri (1) R2 I . -Si—Z&quot; (2-2) In the formula (1), R1 is a group derived from an alkyl group having 1 to 8 carbon atoms (wherein any hydrogen atom may be substituted by a fluorine atom, and any -ch2 may be substituted by a cycloalkylene group), a group of a phenyl group (wherein any hydrogen atom may be substituted by a halogen atom, a methyl group or a methoxy group) and a group of a phenylalkyl group (a gas atom may be used from any hydrogen atom, and the number of carbon atoms is 1~) 4 100 1253464 14363pif.doc The alkyl, vinyl or methoxy-substituted phenyl group is the same as the one selected from the group consisting of 1 to 8 alkylene groups; at least two γ are from the formula (2- 1) a group represented by a group and a group selected from any one of the groups represented by the formula (2-2), and the remaining Y is hydrogen; Z1 is a group having an amine group; Z2 is a group having 2 The oxypropanediyl group; and R2 are each independently and are methyl, isopropyl, tert-butyl or phenyl. 2. The varnish for producing a liquid crystal alignment film according to the first aspect of the invention, wherein all of R1 is a group derived from a phenyl group (wherein a halogen atom, a methyl group or a methoxy group may be substituted by any one) a hydrogen atom) and a phenylalkyl group (wherein a phenyl group having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a methoxy group, and a carbon atom; The same group selected from the group consisting of 1 to 8 alkylene groups. 3. The varnish for producing a liquid crystal alignment film according to the first aspect of the invention, wherein all of R1 is a group derived from a phenyl group (wherein any hydrogen atom may be a halogen atom, a methyl group or a methoxy group). Substituting the same group selected in the formula; R2 is each independently, and is methyl, isopropyl, tert-butyl or phenyl; Z1 is a formula (2-1-A) to a formula (2-1-G) Any one of those represented by Lu, and Z2 is a group represented by any one of the formula (2-2-A) to the formula (HD); in these formulas, m is an integer of 1 to 10, an amine group The combination with the benzene ring and the cyclohexane ring is in any position; any hydrogen atom in the benzene ring may be substituted with a halogen atom or a group having 1 to 10 carbon atoms; and the number of carbon atoms is 1~ In the alkyl group of 10, any hydrogen atom may be substituted by a fluorine atom, and any -CH2- may be substituted by -. 101 1253464 14363pif.doc (2-1-A) (2-1-B) (2-1-C) (2-1-D) (2-1-E) (2-1-F) (2-1-G) ( 2-2-A) (2-2-B) (2-2-C) (2-2-D) 4. For the production of liquid crystal alignment film as described in claim 3 of the patent application 102 1253464 14363pif.doc a varnish, wherein R2 is each independently 'methyl or benzoquinone; Z is a group represented by any one of the formula (2-1-A) and the formula; and Z2 is a formula (2-2-A) and a molecular formula The base represented by any of (2_2_B). 5. The varnish for producing a liquid crystal alignment film according to the first aspect of the invention, wherein all of R1 is a phenyl group; R2 is each independently a methyl group or a phenyl group; and Z1 is a molecular formula (2-1). a group represented by -A-1); Z2 is a group represented by the formula (2-2-A-1); and in these formulas, m is an integer of 1 to 6. . 〇^CH2VT^:0 (2-2-A-1) Ο6·A varnish for producing a liquid crystal alignment film as described in claim 1, wherein at least two oximes are represented by the formula (2_2) The group selected in the group, and the remaining hydrazine moiety is hydrogen. 7. The varnish for producing a liquid crystal alignment film according to claim 1, wherein the polymer is polyamic acid, soluble polyimine, polyamine, polyamidimide, and copolymer. At least one of the copolymers is a polymer containing at least two of the respective structural units of polyglycolic acid, soluble polyimine, polyamine, and polyamidoximine. The varnish for producing a liquid crystal alignment film according to the first aspect of the invention, wherein all of R1 is a group of a phenyl group which may be substituted with a halogen atom, a methyl group or a methoxy group from any hydrogen atom. Select the same group; R2 is each independently, which is methyl, isopropyl, tert-butyl or phenyl; 103 1253464 14363pif.doc Z1 is a formula (2-1-A) ~ formula (2-1-G) a group represented by any one of the formulas; Z2 is a group represented by any one of the formula (2-2-A) to the formula (2-2-D); the polymer is a polylysine, a soluble polyimine, At least one of a polyamine, a polyamidimide, and a copolymer, wherein the interpolymer is in a structural unit containing polyglycolic acid, soluble polyimine, polyamine, or polyamidimide. At least two kinds of polymers; in these formulas, m is an integer of from 1 to 10, and the combination of an amine group with a benzene ring and a cyclohexane ring is in an arbitrary position; and any hydrogen atom in the benzene ring may utilize a halogen atom. Or an alkyl group having 1 to 10 carbon atoms; and an alkyl group having 1 to 1 ring of carbon atoms , Arbitrary hydrogen atom may be substituted with a fluorine atom, any one can be replaced by using a ch2- Ο-. 104 1253464 14363pif.doc (2-1-A) (2-1-C) (2-1-D) (2-1-E) (2-1-F) (2-1-G) (2-2-A) (2-2-B) (2-2-C) (2-2-D) 9. The varnish for producing a liquid crystal alignment film according to claim 8, wherein R2 is each independently a methyl group or a phenyl group; Z1 105 1253464 14363pif.doc is a group represented by any one of the molecular formula (2~1 -A) and the formula (2-1 -B); further, Z2 is a molecular formula (2_2-A) and a molecular formula (2-2-Β) Any of the ~ representations in the base. 10. A varnish for liquid crystal alignment film as described in claim 1, wherein 'all r1 are phenyl groups; r2 is each independently methyl or phenyl; Z1 is a molecular formula (2- 1-A-1) represents a group; Z2 is a group represented by the formula (2-2-Α-1); the polymer is polyglycine, soluble polyimine, polyamine, polyamidimide And at least one of the interpolymers, wherein the interpolymer is a polymer containing at least two of the respective structural units of polyphthalic acid, soluble polyamidiamine, polyamine, and polyamidoximine; In the formula, m is an integer of 1 to 6. 4ch2V〇-〇-nh^ (2-1-A-1) Ο 11 · A varnish for producing a liquid crystal alignment film as described in claim 1, wherein all of R1 is a group of a phenyl group which may be substituted with a halogen atom, a methyl group or a methoxy group from an arbitrary hydrogen atom. The same group selected in the middle; at least two Y are groups selected from the group represented by the formula (2_2), and the remaining Y is a hydrogen atom; R2 is each independently, and is methyl, isopropyl, tert - butyl or a base, Z is a group represented by any one of the formula (2-2-A) to the formula (2-2-D); the polymer is polylysine, soluble polyimine, polyfluorene At least one of an amine, a polyamidimide, and a copolymer, wherein the interpolymer is at least two of each structural unit containing a poly-proline, a soluble polyimine, a polyamine, or a polyamidoximine. a polymer; in these 106 1253464 14363pif.doc formula, m is an integer of 1 to 10, and any hydrogen atom in the benzene ring may be substituted with a halogen atom or an alkyl group having 1 to 1 ring of carbon atoms; In the alkyl group having 1 to 10 carbon atoms, any hydrogen atom may utilize a fluorine atom. Substituted, any one CH2 - may utilize a o - substituted. (2-2-A) (2-2-B) 〇(2-2-C) (2-2-D) 12. The varnish for producing a liquid crystal alignment film according to claim 11, wherein R2 is each independently and is a methyl group or a phenyl group. And Z2 is a group represented by any one of the molecular formula (2-2-A) and the molecular formula (2-2-B). The varnish for producing a liquid crystal alignment film according to the first aspect of the invention, wherein all of R1 is a phenyl group, and at least two Y are groups selected from the group represented by the formula (2-2). The remaining Y is a hydrogen atom; R2 is each independently a methyl group or a phenyl group; Z2 is a group represented by the formula (2-2-A-1); the polymer is a polylysine, a soluble poly At least one of phthalimide, polyamidamine, polyamidimide and copolymer, the copolymer is each containing polyglycolic acid, soluble polyimine, polyamine, polyamidimide 107 1253464 14363pif.doc A polymer of at least two of the structural units; and in the formula, Π1 is an integer of 〜6. 14. The varnish for producing a liquid crystal alignment film according to the first aspect of the invention, wherein the proportion of the polymer obtained by using the sesquioxane derivative represented by the formula (1) among all the components of the polymer 30 to 98% by weight, in all the components of the polymer, without using the formula (1) The proportion of the polymer obtained by the semi-oxane derivative is 2 to 7 % by weight, and the ratio of all the polymer components in the composition is 〇 5 to 10% by weight. I5·-a polymer obtained by using a compound represented by the formula (1) as a raw material 'from the formula (3-1), the formula (3-2), the formula (3-3), the formula (3-4), and the formula (3) -5), molecular formula (3-6), molecular formula (3-7), molecular formula (3-8), molecular formula (5-1), molecular formula (5-2), molecular formula (5-3), molecular formula (5- 4), molecular formula (5-5), molecular formula (5-6), molecular formula (5-7), molecular formula (5-8), molecular formula (7-1), molecular formula (7-2), molecular formula (9-1 Any one of the structural units represented by any one of the formula (9-2) and a structural unit represented by any one of the molecular formula (cardiac, molecular formula (6-1), molecular formula (8-丨), molecular formula (iod)) At least one polymer constituting a polymeric chain; /Si—Ο YR1, /〇ά X . Cut—r1 Ii/° ?y Y 'R' R2 I , •Si——Z1 (2-1) (1) R2 I 2 -Si——Zl (2- 2) 108 1253464 14363pif.doc N 109 1253464 14363pif.doc Ο C〇〇H ΥΝΗ 〇 (5-2) 〇〇人 C〇〇H / -Q2—HN^ QJ, /NH_ HN 〇人 C〇〇H -G1—HN Q: H〇〇C NH 〇 C〇〇H 〇 •Q2—HN- B4 (5-3) (5-4) (5-7) C〇〇HH〇〇C 〇NH- H〇〇C =〇&quot;COOH Y 〇(5-6) H〇〇C 〇hn h〇 〇c_ &gt;( NH- NH- 〇 / :〇COOH , NH- ΌΟΟΗ (5-8) 〇 A COOH / -G1——HN' G? NH /V H〇〇C II (6-1) 110 1253464 14363pif.doc (10-1) In these formulas, R1 is a group 111 1553464 14363pif.doc derived from an alkyl group having 1 to 8 carbon atoms (wherein any hydrogen atom may be substituted by a fluorine atom, and any one of ch2 may be used. a group substituted with a cycloalkylene group, a group of a phenyl group (wherein any hydrogen atom may be substituted by a halogen atom, a methyl group or a methoxy group) and a group of a phenylalkyl group (available from any hydrogen atom) a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a methoxy group substituted with a methoxy group and the same group selected from the group consisting of 1 to 8 alkylene groups; at least 2 Ys are a group selected from the group represented by the formula (2-1) and a group selected from any one of the groups of the group represented by the formula (2-2), and the remaining Y is a hydrogen atom; Z1 is a group having an amine group Z2 is a group having a 2-oxopropanedifluorenyl group; R2 is each independently a methyl group, an isopropyl group, a tert-butyl group or a phenyl group; Q1 is a molecular formula (2) from Y as a -1) The residue of the group of formula (1) after removal of the amine group; Q2 is from 3 of Y, which is the formula of formula (2-1) The residue after removal of the amine group in the formula (1); Q3 is after removing the 2-oxypropanedifluorenyl group from the molecular formula (1) which is a group represented by two molecular formulas (2-2) in Y Residue; Q4 is a residue obtained by removing 2-oxopropanedifluorenyl from the molecular formula (1) which is a group represented by three molecular formulas (2-2) in Y; G1 is a compound having two amine groups a residue after removal of an amine group; G2 is a residue after removing a carboxyl group from a compound having two carboxyl groups; G3 is a residue after removing a carboxyl group from a compound having three carboxyl groups; and G4 has four carboxyl groups The residue after removal of the thiol group in the compound. 16. The polymer according to claim 15, wherein the polymer is at least one of structural units represented by any one of the formulae (3-1) to (3_8), and the molecular formula ( The structural unit represented by 4-1) forms a polymeric chain of polyimine. The polymer according to claim 15, wherein the polymer is at least one structural unit represented by any one of the formula (5-1) to the formula (5-8). 'Polyamic acid which forms a polymeric chain with a structural unit represented by the formula (6-1). 18. The polymer according to claim 15, wherein the polymer is at least one structural unit represented by any one of the formula (7-1) and the formula (7-2), and the molecular formula (8) -1) The structural unit represented forms a polymeric chain of polyamidoximine. 19. The polymer according to claim 15, wherein the polymer is at least one structural unit represented by any one of the formula (9-1) and the formula (9-2), and the molecular formula Ο0· 1) The structural unit represented forms a polymeric chain of polyamine. 20. The polymer according to claim 16, wherein the polymer is at least one structural unit represented by any one of the formulae (3-3) to (3-4), and the molecular formula (4) -1) The structural unit of the representation forms a polymeric chain of polyimine. 21. The polymer as described in claim 17, wherein the polymer is at least one of structural units represented by any one of the formulae (5-3) to (5-4), and The structural unit represented by the formula (6-1) forms a polymeric chain polylysine. 22. The polymer according to claim 15, wherein the polymer is of the formula (3-3), the formula (3-4), the formula (3-5), the formula (3-6), Molecular formula (3-7), molecular formula (3-8), molecular formula (5-3), molecular formula (5-4), molecular formula (5-5), molecular formula (5-6), molecular formula (5-7) and molecular formula (5-8) 113 1253464 14363pif.doc Any one of the structural units represented by at least one of the structural units forming a polymeric chain with at least one of the structural units of the formula (4-1) and the formula (6-1). A liquid crystal alignment film produced by the varnish for producing a liquid crystal alignment film according to the first aspect of the invention. A liquid crystal display element comprising the liquid crystal alignment film of claim 23 of the patent application. 114