KR20090071448A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent is provided to produce a liquid crystal display device of various driving methods having low ion density and excellent long-term reliability. A liquid crystal aligning agent comprises a polyamic acid or their derivative which is a reaction product of diamine and tetracarboxylic dianhydride; and an epoxy compound having an epoxy group in which the average functional group number is more than 1. The diamine comprises the diamine represented by following chemical formula (I).

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT LAYER AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to the liquid crystal aligning agent containing a polyamic acid or its derivative (s), and an epoxy compound, the liquid crystal aligning film formed from the said liquid crystal aligning agent, and the liquid crystal display element provided with the same.

Liquid crystal display devices are used in various liquid crystal display devices such as monitors of notebook computers and desktop computers, view finders of video cameras, projection displays, and the like, and have recently been used as televisions. Liquid crystal display elements are also used as optoelectronics-related elements such as optical printer heads, optical Fourier conversion elements, and light valves.

The liquid crystal display device is usually 1) a pair of substrates arranged oppositely, 2) an electrode formed on one or both of the opposing surfaces of each of the pair of substrates, and 3) each of the pair of substrates. And a liquid crystal layer formed between the pair of substrates.

As a conventional liquid crystal display device, a display device using nematic liquid crystal is the mainstream, 1) a twisted nematic (TN) type liquid crystal display device twisted at 90 degrees, and 2) a super twisted nematic (STN) type liquid crystal twisted at least 180 degrees. Display element, 3) A so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor has been put into practical use. Such a liquid crystal display element has a drawback that the viewing angle which can visually recognize an image is narrow, and when it sees from an inclined direction, the fall of a brightness | luminance, contrast, and brightness inversion in halftone are produced.

Recently, this problem of viewing angle includes 1) TN-TFT type liquid crystal display element using an optical compensation film, 2) Vertical alignment and VA (Vertical Alignment) type liquid crystal display element using an optical compensation film, 3) vertical alignment and projection MVA (Multi Domain Vertical Alignment) type liquid crystal display device using the structure technology, or 4) IPS (In-Plane Switching) type liquid crystal display device of transverse electric field method, 5) Electrically Controlled Birefringence (ECB) type liquid crystal display device, 6) Optically compensated bends (Optically Compensated Bends or Optically Self-Compensated Birefringence (OCB) type liquid crystal display elements, etc. have been improved, and the improved technologies have been put into practice or examined.

The technical development of a liquid crystal display element is achieved not only by such an improvement of a drive system and an element structure but also the improvement of the structural member used for a liquid crystal display element. Among the constituent members used in the liquid crystal display element, in particular, the liquid crystal alignment film is one of important factors affecting the display quality of the liquid crystal display element, and the role of the liquid crystal alignment film is becoming important year by year with the improvement of the quality of the liquid crystal display element.

A liquid crystal aligning film is prepared from a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is the solution which melt | dissolved polyamic acid or soluble polyimide in the organic solvent. After apply | coating this solution to a board | substrate, it forms into a film by means, such as a heating, and forms a polyimide oriented film. As such a liquid crystal aligning agent, the tetracarboxylic dianhydride and diamine which are raw materials of a polyamic acid or its derivatives, and the liquid crystal aligning agent in which the pretilt angle expressed are prescribed | regulated are known (for example, refer patent document 1). Various liquid crystal aligning agents other than polyamic acid are also examined, but they are hardly put into practical use in terms of heat resistance, chemical resistance (liquid crystal resistance), coating property, liquid crystal alignment property, electrical characteristics, optical characteristics, display characteristics, and the like.

Ion density is mentioned as an important characteristic calculated | required by the liquid crystal aligning film in order to improve the display quality of a liquid crystal display element. If the ion density is high, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may interfere with normal gradation display. Moreover, even if the initial ion density is low, for example, it becomes a problem when the ion density (long-term reliability) after high temperature acceleration test increases.

As an attempt to solve the above problem, a liquid crystal aligning agent containing a polyamic acid or a derivative thereof and a compound having a specific amount of an oxazine structure is known (see Patent Document 2, for example), but is accompanied by the development of liquid crystal display element technology. Therefore, the provision of the liquid crystal aligning agent which can solve the said problem is increasingly requested | required.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2002-62537

[Patent Document 2] Japanese Patent Application Laid-Open No. 2007-286597

In view of the above situation, development of a liquid crystal aligning agent for a liquid crystal display element, a liquid crystal aligning film formed using the same, and a liquid crystal display element having the same has been desired in which problems of ion density and long-term reliability are improved.

The present inventors conducted intensive research in order to solve the said subject.

As a result, it was found that the liquid crystal aligning agent containing a polyamic acid or a derivative thereof and a specific epoxy compound can impart good ion density and long-term reliability to a liquid crystal display device having a liquid crystal aligning film produced using the same. Completed.

This invention consists of the following structures.

[1] A liquid crystal aligning agent containing a polyamic acid or a derivative thereof which is a reaction product of a diamine and a tetracarboxylic dianhydride, and an epoxy compound having an epoxy group having an average number of functional groups of more than one.

The said diamine contains the diamine represented by the following general formula (I), The liquid crystal aligning agent characterized by the above-mentioned.

In the general formula (I), X ¹ and X ² are each, -O-, or -CH ₂ - represents the, Y ¹ is -H, the following structural formula (II-1), general formula (II-2), or 4-substituted- ¹ represented by general formula (II-3), Z ¹ is alkylene having 1 to 12 carbon atoms which may have methyl, the general formula (III-1) or (III-2) shown below; 1-cyclohexylene is represented, and m, n, and p represent 0 or 1, respectively.

Provided that m + n + p is 0, 1, or 3,

When m + n + p is 0, Y ¹ represents general formula (II-1), (II-2), or (II-3),

is 1 when m + n + p, m and n represents 0, and X ² represents -O-, and X ² is an amino-phenylamino which is coupled with respect to the X ² bonded to the meta position,

When m + n + p is 3, X ¹ and X ² each represent -O- or -CH _2- , Y ¹ represents -H, and Z ¹ has 1 to 12 carbon atoms which may have methyl. Alkylene or 4-substituted-1,1-cyclohexylene represented by formula (III-1) or (III-2).

In General Formulas (II-2) and (II-3), Y ² and Y ³ each represent alkyl having 1 to 30 carbon atoms.

In General Formulas (III-1) and (III-2), Y ⁴ and Y ⁵ each represent alkyl having 1 to 30 carbon atoms.

[2] The diamine represented by General Formula (I) has m + n + p of 3, X ¹ and X ² each represent —O— or —CH ₂ —, and Y ¹ represents —H, Z ¹ is a diamine representing 4-substituted-1,1-cyclohexylene represented by the general formula (III-1) or (III-2), wherein the liquid crystal aligning agent according to [1].

[3] The liquid crystal aligning agent according to [2], wherein the diamine represented by General Formula (I) is one or both of the diamines of the following structural formulas A1 and A2.

[4] The diamine further includes at least one of the following diamines of the following structural formulas (VIII-3), (VIII-7), and (VIII-31), wherein the tetracarboxylic dianhydride is represented by the following structural formulas (1) and ( It is one or both of 14), The liquid crystal aligning agent as described in [2] or [3] characterized by the above-mentioned.

[5] The diamine represented by the general formula (I) is m + n + p, 3, X ¹ and X ² each represent -O- or -CH _2- , Y ¹ represents -H, Z <^1> is diamine which shows the C1-C12 alkylene which may have methyl, The liquid crystal aligning agent as described in [1] characterized by the above-mentioned.

[6] The diamine represented by General Formula (I) is a diamine in which X ¹ and X ² each represent -CH ₂ -and Z ¹ represents alkylene having 1 to 10 carbon atoms which may have methyl. The liquid crystal aligning agent as described in [5] characterized by the above-mentioned.

[7] The liquid crystal aligning agent according to [6], wherein the diamine represented by General Formula (I) is a diamine of the following structural formula B1.

[8] The above-mentioned diamine further includes a diamine of the following structural formula (VIII-13), wherein the tetracarboxylic dianhydride is one or both of the following structural formulas (1) and (14). The liquid crystal aligning agent in any one of [7].

[9] The diamine represented by General Formula (I) is m + n + p, and Y ¹ represents General Formula (II-1), (II-2), or (II-3). It is diamine, The liquid crystal aligning agent as described in [1] characterized by the above-mentioned.

[10] The diamine represented by general formula (I) is Y ² and Y ^{3 in} general formulas (II-2) and (II-3) are diamines each having 1 to 20 carbon atoms. The liquid crystal aligning agent as described in [9] characterized by the above-mentioned.

[11] The liquid crystal aligning agent according to [9] or [10], wherein the diamine represented by General Formula (I) is at least one selected from diamines of the following structural formulas C1 to C4.

[12] The diamine further includes one or both of the diamines of the following structural formulas (VIII-1) and (VIII-7), and the tetracarboxylic dianhydride is one of the following structural formulas (1) and (14) or It is both, The liquid crystal aligning agent in any one of [9]-[11] characterized by the above-mentioned.

[13] In the diamine represented by the general formula (I), m + n + p is 1, m and n are 0, X ² represents -O-, and amino of aminophenyl to which X ² is bonded. Is a diamine bonded to a meta position with respect to X ² , wherein the liquid crystal aligning agent according to [1].

[14] The liquid crystal aligning agent according to [13], wherein the diamine represented by General Formula (I) is one or both of the diamines of the following structural formulas D1 and D2.

[15] The liquid crystal aligning agent according to [13] or [14], wherein the tetracarboxylic dianhydride is one or both of the following structural formulas (1) and (14).

[16] In the diamine, m + n + p in the general formula (I) is 3, X ¹ and X ² each represent -O- or -CH _2- , and Y ¹ represents -H. And diamine which represents C1-C12 alkylene which Z <^1> may have methyl, and one or more selected from the following 4 types of diamines, The liquid crystal aligning agent as described in [1] characterized by the above-mentioned.

(1) the general formula (I), and m + n + p is 3 in, X ¹ and X ² are each -O- or -CH ₂ - represents a, Y ¹ represents a -H, also Z ¹ Diamine which represents 4-substituted-1,1-cyclohexylene represented by said general formula (III-1) or (III-2).

(2) Diamine in which m + n + p in the said General formula (I) is 0, and Y <^1> represents the said General formula (II-1), (II-2), or (II-3).

3 is the m + n + p is 1 in the formula (I), m and n is 0, and X ² represents an -O-, an amino-phenyl-amino is bonded to X ² X ² Diamine bound to the meta position relative to

(4) Diamine whose m + n + p in the said General formula (I) is 0, and Y <^1> is general formula (II-4).

In General Formula (II-4), Y ⁶ represents alkyl having 1 to 30 carbon atoms.

[17] The liquid crystal aligning agent according to [16], wherein the diamine represented by the general formula (I) contains at least one selected from the diamines of the following structural formula B1 and the following four diamines.

(1) Diamine represented by the following structural formula A1 or A2

(2) Diamine represented by the following structural formula C1 or C2

(3) Diamine represented by the following structural formula D1 or D2

(4) Diamine of the following structural formula (XI-47).

[18] The liquid crystal aligning agent according to any one of [1] to [17], wherein the polyamic acid or a derivative thereof is contained.

[19] m + n + p in the general formula (I) is 3, X ¹ and X ² each represent -O- or -CH _2- , Y ¹ represents -H, and Z ¹ Polyamic acid or a derivative thereof, which is a reaction product of a diamine representing an alkylene having 1 to 12 carbon atoms which may have methyl and tetracarboxylic dianhydride, and one or both of the following three kinds of polyamic acid or its derivatives The liquid crystal aligning agent as described in [17] characterized by the above-mentioned.

(1) the general formula (I), and m + n + p is 3 in, X ¹ and X ² are each -O- or -CH ₂ - represents a, Y ¹ represents a -H, also Z ¹ Polyamic acid or a derivative thereof, which is a reaction product of diamine and tetracarboxylic dianhydride represented by 4-substituted-1,1-cyclohexylene represented by the general formula (III-1) or (III-2).

(2) Diamine and tetra which m + n + p in the said General formula (I) is 0, and Y <^1> represents the said General formula (II-1), (II-2), or (II-3). Polyamic acid or a derivative thereof which is a reaction product of carboxylic dianhydride

3 is the m + n + p is 1 in the formula (I), m and n are 0, and X ² represents -O-, an amino-phenyl-amino bond to the X ² X ² The polyamic acid or its derivative which is a reaction product of diamine and tetracarboxylic dianhydride couple | bonded with the meta position with respect to.

[20] The epoxy compound is a glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic fat. The liquid crystal aligning agent in any one of [1]-[19] which is one or more selected from the group which consists of a group type epoxy compound.

[21] The epoxy compound is N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2- [4- (2,3-epoxy propoxy) phenyl] -2- [4- [1,1 -Bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, N-phenyl At least one selected from maleimido-glycidyl methacrylate copolymers, bisphenol A novolac type epoxy compounds, cresol novolac type epoxy compounds, and N, N, O-triglycidyl-p-amino phenols The liquid crystal aligning agent as described in [20].

[22] A liquid crystal aligning film formed by baking the film of the liquid crystal aligning agent according to any one of [1] to [21].

[23] Liquid crystals formed on opposing surfaces of a pair of substrates arranged on one side or on opposing surfaces of each of the pair of substrates, and on opposing surfaces of each of the pair of substrates A liquid crystal display device having an alignment film and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is a liquid crystal alignment film according to [22].

In addition, in this specification, when it says "alkyl", "alkenyl", and "alkynyl", it may be linear and may be branched.

This invention can provide the liquid crystal display element of various drive systems with low ion density and favorable long-term reliability.

The liquid crystal aligning agent of this invention contains the polyamic acid or its derivative (s), and the epoxy compound which has an epoxy group with an average number of functional groups more than one. The polyamic acid or derivatives thereof may be one kind or two or more kinds. The epoxy compound may be one kind or two or more kinds. It is preferable that it is 0.1-50 weight% in a liquid crystal aligning agent, and, as for content of the said polyamic acid or its derivatives, it is more preferable that it is 1-30 weight%. Moreover, it is preferable that it is 0.1-100 weight part with respect to 100 weight part of said polyamic acids or its derivatives, and, as for content of the said epoxy compound, it is more preferable that it is 0.5-80 weight part.

The polyamic acid and its derivatives are reaction products of diamine and tetracarboxylic dianhydride. The derivative of the said polyamic acid is a form melt | dissolved in the solvent when it is set as the liquid crystal aligning agent mentioned later, and is a component which can form the liquid crystal aligning film which has polyimide as a main component, when the liquid crystal aligning agent is used as the liquid crystal aligning film mentioned later. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, polyamic acid amides, and the like. More specifically, 1) polyimide in which all amino and carboxyl of the polyamic acid are subjected to dehydration ring closure; 2) partial polyimide partially dehydrated, 3) polyamic acid ester in which carboxyl of polyamic acid is converted to ester, and 4) reaction by replacing a part of acid dianhydride contained in tetracarboxylic dianhydride compound with organic dicarboxylic acid And polyamideimide obtained by dehydrating and ring-closing a part or all of the polyamic acid-polyamide copolymer.

In the polyamic acid or a derivative thereof, the tetracarboxylic dianhydride and the diamine are preferably in a molar ratio of 0.8: 1.2 to 1.2: 0.8, more preferably 0.9: 1.1 to 1.1: 0.9.

1 type may be sufficient as the said diamine, but 2 or more types may be included, but the diamine represented by following General formula (I) is included. 1 type may be sufficient as the diamine represented by this general formula (I), and 2 or more types may be sufficient as it. It is preferable that it is 0.5-100 mol%, and, as for the diamine represented by general formula (I) in the said diamine, it is more preferable that it is 1-100 mol%.

In the general formula (I), X ¹ and X ² are each, -O-, or -CH ₂ - represents the, Y ¹ is -H, the following structural formula (II-1), general formula (II-2), or 4-substituted- ¹ represented by general formula (II-3), Z ¹ is alkylene having 1 to 12 carbon atoms which may have methyl, the following general formula (III-1) or (III-2); 1-cyclohexylene is represented, and m, n, and p represent 0 or 1, respectively.

However, in the general formula (I), m + n + p is 0, 1, or 3, when m + n + p is 0, Y ¹ is a general formula (II-1), (II-2) , or represents a (II-3), m + n + p is when 1, m and n represents 0, and X ² represents -O-, an amino-phenyl-amino is bonded to X ² X ² Bound to the meta position relative to, and when m + n + p is 3, X ¹ and X ² each represent —O— or —CH ₂ —, Y ¹ represents —H, and Z ¹ represents methyl C1-C12 alkylene which may have, or 4-substituted-1,1-cyclohexylene represented by general formula (III-1) or (III-2) is shown.

The diamine represented by general formula (I) are, for example, and m + n + p is 3, X ¹ and X ² are each -O- or -CH ₂ - represents a, Y ¹ represents -H, In addition, Z <^1> is A-type diamine which shows the 4-substituted-1, 1-cyclohexylene represented by said general formula (III-1) or (III-2). A-type diamine can be used suitably mainly for a TN type liquid crystal display element.

As said A-type diamine, the diamine of following structural formula A1 and A2 is mentioned, for example.

In addition, in the diamine represented by the general formula (I), m + n + p is 3, for example, X ¹ and X ² each represent -O- or -CH _2- , and Y ¹ represents -H. Z <^1> is a B-type diamine which shows the C1-C12 alkylene which may have methyl. Type B diamine can be suitably mainly used for IPS and VA type liquid crystal display elements.

It is preferable that the said B type diamine is diamine which X <^1> and X <^2> respectively represent -CH <_2> -and Z <^1> represents C1-C10 alkylene which may have methyl, and such a B type diamine, For example, the diamine of the following structural formula B1 is mentioned.

In the diamine represented by General Formula (I), m + n + p is 0, and Y ¹ represents General Formula (II-1), (II-2), or (II-3). It is a C-type diamine shown. C-type diamine can be used suitably mainly for VA-type liquid crystal display elements.

It is preferable that said C type diamine is diamine which Y <^2> and Y <^{3> in the} said General formula (II-2) and (II-3) represent a C1-C20 alkyl, respectively. As such a C-type diamine, the diamine of following structural formula C1-C4 is mentioned, for example.

In the diamine represented by the general formula (I), m + n + p is 1, m and n are 0, and X ² represents -O-, and amino of aminophenyl to which X ² is bonded. Is a D-type diamine bonded to the meta position with respect to X ² . D-type diamine can be used suitably mainly for an IPS-type liquid crystal display element. As said D-type diamine, the diamine of following structural formula D1 and D2 is mentioned, for example.

The said diamine may further contain other diamine other than the diamine represented by the said general formula (I). As such other diamine, the linear diamine represented by the following general formula (IV)-(X) is mentioned, for example. The linear diamine may be one kind or two or more kinds.

In General Formula (IV), A ¹ represents-(CH ₂ ) _m- . M represents the integer of 1-12 here. In general formulas (VI) and (VIII), A ¹ is independently a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -N (CH ₃ )-(CH ₂ ) _m -N (CH ₃ )-, -S- (CH ₂ ) _m -S-. M represents the integer of 1-12 here.

In General Formula (IX), A ² independently represents —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or alkylene having 1 to 3 carbon atoms. .

In General Formula (X), A ¹ is, independently, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO-, -C (CF ₃ ) ₂ -,- O- (CH ₂ ) _m -O- and -S- (CH ₂ ) _m -S-. M represents the integer of 1-12 here. In General Formula (X), A ² is a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or 1 to 3 carbon atoms. Alkylene is represented.

In addition, hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulas (V) to (X) is independently -F, -Cl, -CH ₃ , -OH, -COOH, -SO ₃ H,- May be substituted with PO ₃ H ₂ , or 4-hydroxybenzyl.

As a linear diamine represented by general formula (IV), the diamine represented by structural formula (IV-1) (IV-3)-is mentioned, for example.

As a linear diamine represented by general formula (V), the diamine represented by structural formula (V-1) and (V-2) is mentioned, for example.

As a linear diamine represented by general formula (VI), the diamine represented by structural formula (VI-1) (VI-3)-is mentioned, for example.

As a linear diamine represented by general formula (VII), the diamine represented by structural formula (VII-1) (VII-14)-is mentioned, for example.

As a linear diamine represented by general formula (VIII), the diamine represented by structural formula (VIII-1) (VIII-31) is mentioned, for example.

As a linear diamine represented by general formula (IX), the diamine represented by structural formula (IX-1) (IX-6)-is mentioned, for example.

As a linear diamine represented by general formula (X), the diamine represented by structural formula (X-1) (X-6)-is mentioned, for example.

Among these, as a more preferable linear diamine, Structural Formulas (VII-1) to (VII-5), (VIII-1) to (VIII-13), (VIII-24), (VIII-25), and (VIII- The diamine represented by 29), (VIII-31), (IX-1), (IX-2), (IX-6), and (X-1) is mentioned, A more preferable linear diamine is a structural formula And diamines represented by (VII-1), (VII-2), (VIII-1) to (VIII-13), (VIII-29), and (VIII-31).

It is preferable that it is 1 to 90%, and, as for the molar ratio of the said linear diamine in the said diamine, in TN and IPS from a viewpoint of obtaining the suitable orientation at the time of using as a liquid crystal display element, it is more preferable that it is 5 to 80%.

In applications where large pretilt angles such as VA type liquid crystal display elements, OCB type liquid crystal display elements, and STN type liquid crystal display elements are required, it is preferable to include diamines having a side chain structure in the diamine, and thus, the above general formula (I) The diamine which has such a side chain structure can be used for diamines other than the diamine represented by these. As a diamine which has such a side chain structure, the side chain type diamine represented by the following general formula (XI)-(XV) is mentioned, for example. The branched diamine may be one kind or two or more kinds.

In formula (XI), A ³ represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or-(CH ₂ ) _m- . M represents the integer of 1-6 here. R <^7> represents group which has a steroid skeleton, group represented by the following general formula (XVI), or C1-C30 alkyl. In the alkyl, any -CH ₂ -may be independently substituted with -CF _2- , -CHF-, -O-, -CH = CH- or -C≡C-, and -CH ₃ is- It may be substituted with CH ₂ F, -CHF ₂ or -CF ₃ . However, in said alkyl, -O- does not neighbor.

In formula (XVI), A ⁴ and A ⁵ each independently represent a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH— or alkylene having 1 to 20 carbon atoms. Indicates. R ⁸ and R ⁹ each independently represent -F or -CH ₃ . Ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene- 1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl. R ¹⁰ represents a -F, alkyl of 1 to 30 carbon atoms, fluorine substituted alkyl of 1 to 30 carbon atoms, alkoxy having a carbon number of _{1~30 -CN, -OCH 2 F, -OCHF} 2 or -OCF _3. And a and b each independently represent an integer of 0 to 4, when a or b is 2 to 4, adjacent A ⁴ or A ⁵ is another group, and c, d and e are each independently 0 to 3 An integer is shown, and when e is 2 or 3, some ring S may be the same group, or may be another group. f and g each independently represent an integer of 0 to 2, and c + d + e ≧ 1.

Provided that when m in formula (XI) is 1, c, d, and e in formula (XVI) are each 1, or A ⁴ and A ⁵ are each a single bond or an alkylene having 2 carbon atoms Except that

In formula (XII), hydrogen bonded to the carbon forming the steroid skeleton may be independently substituted with —CH ₃ . In General Formulas (XII) and (XIII), each R ¹¹ independently represents —H or —CH ₃ , and R ¹² represents —H or alkyl or alkenyl having 1 to 20 carbon atoms. A ⁶ each independently represent a single bond, —C (═O) — or —CH ₂ —. In General Formula (XIII), R ¹³ and R ¹⁴ each independently represent —H, alkyl having 1 to 20 carbon atoms, or phenyl.

In general formula (XIV), R <^15> represents -H or C1-C30 alkyl.

Any -CH ₂ -of alkyl having 2 to 30 carbon atoms in the alkyl may be independently substituted with -O-, -CH = CH- or -C≡C-. However, in said alkyl, -O- does not neighbor. In formulas (XIV) and (XV), A ⁷ independently represents —O— or alkylene having 1 to 6 carbon atoms. In formula (XIV), A ⁸ represents a single bond or alkylene having 1 to 3 carbon atoms. Ring T represents 1,4-phenylene or 1,4-cyclohexylene. h represents 0 or 1; In general formula (XV), R <^16> represents C6-C22 alkyl and R <^17> represents -H or C1-C22 alkyl. However, in general formula (XIV), when h is 0, R <^15> is -H, and when h is 1, A <^8> is a single bond or R <^15> is -H.

In the side chain type diamine represented by said general formula (XI), it is preferable that the bond position relationship of the two amino groups couple | bonded with the carbon of a phenyl ring is meta or para. Moreover, it is preferable that the binding positional relationship of two amino groups is 3-position and 5-position, or 2-position and 5-position, when the bonding position of "R <^7> -A <^3->" is made into 1 position.

As diamine represented by said general formula (XI), the diamine represented by the following general formula (XI-1) (XI-9)-is mentioned, for example.

In the general formulas (XI-1), (XI-2), (XI-5) and (XI-6), R ¹⁸ is preferably alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and having 3 carbon atoms. More preferably, alkyl of 30 to 30 or alkoxy of 3 to 30 carbon atoms is more preferred, and alkyl of 5 to 25 carbon atoms or alkoxy of 5 to 25 carbon atoms is more preferred. In formulas (XI-3), (XI-4) and (XI-7) to (XI-9), R ¹⁹ is preferably alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms. More preferred are 3-25 alkyl or alkoxy having 3 to 25 carbon atoms.

Moreover, as a side chain type diamine represented by said general formula (XI), the diamine represented by the following general formula (XI-10)-(XI-15) is mentioned, for example.

In the general formulas (XI-10) to (XI-13), R ²⁰ is preferably alkyl having 4 to ³⁰ carbon atoms, and more preferably alkyl having 6 to 25 carbon atoms. In General Formulas (IX-14) and (IX-15), R ²¹ is preferably alkyl having 6 to 30 carbon atoms, and more preferably alkyl having 8 to 25 carbon atoms.

Moreover, as side chain type diamine represented by the said general formula (XI), the diamine represented by the following general formula (XI-16)-(XI-36) is mentioned, for example.

General Formulas (XI-16), (XI-17), (XI-20), (XI-22), (XI-23), (XI-26), (XI-28), (XI-29) In (XI-34) and (XI-35), R ²² is preferably alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, more preferably alkyl having 3 to 25 carbon atoms or alkoxy having 3 to 25 carbon atoms. Do. General Formulas (XI-18), (XI-19), (XI-21), (XI-24), (XI-25), (XI-27), (XI-30) to (XI-33) and in (XI-36), R ²³ is and is -H, -F, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF ₃ alkyl, preferably 1 to 30 carbon atoms of 1 to 30 carbon atoms, More preferred are alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons. In the formulas (XI-31) and (XI-32), A ⁹ represents alkylene having 1 to 20 carbon atoms.

Moreover, as side chain type diamine represented by the said general formula (XI), the diamine represented by the following structural formula (XI-37)-(XI-46) is mentioned, for example.

As for the side chain type diamine represented by said general formula (XI), the diamine represented by general formula (IX-1)-(IX-9) is preferable, and is represented by general formula (IX-2) or (IX-4). The diamine which becomes becomes more preferable.

The branched diamine represented by the general formula (XII) is one of two "NH ₂ -Ph-A ⁶ -O-" is bonded to the 3 position of the steroid nucleus, the other is bound to the 6 position desirable. Moreover, it is preferable that two amino groups couple | bonded with two phenyl, respectively, are couple | bonded with the meta position or the para position with respect to the bonding position of A <^6> .

As a side chain type diamine represented by said general formula (XII), the diamine represented by the following structural formula (XII-1) (XII-4)-is mentioned, for example.

In the branched diamine represented by the general formula (XIII), two "NH _{2- (} R ^14- ) Ph-A ⁶ -O-" are each bonded to carbon of phenyl, but the steroid nucleus is bonded to each other. It is preferable to be bonded to the meta position or the para position with respect to the carbon in phenyl. Moreover, it is preferable that two amino groups couple | bonded with two phenyl, respectively, are couple | bonded with the meta position or the para position with respect to the bonding position of A <^6> .

As side chain type diamine represented by said general formula (XIII), the diamine represented by the following structural formula (XIII-1) (XIII-8)-is mentioned, for example.

In the branched diamine represented by the general formula (XIV), two amino groups each bonded to two phenyls are preferably bonded to a meta position or a para position with respect to A ⁷ .

As a side chain type diamine represented by said general formula (XIV), the diamine represented by the following general formula (XIV-1) (XIV-9)-is mentioned, for example.

In Formulas (XIV-1) and (XIV-2), R ²⁴ is -H, and in Formulas (XIV-4) and (XIV-5), R ²⁵ is -H. In General Formula (XIV-3), R ²⁴ is preferably -H or an alkyl group having 1 to 30 carbon atoms. In Formulas (XIV-6) to (XIV-9), R ²⁵ is -H. Or it is preferable that it is a C1-C20 alkyl group.

In the branched diamine represented by the general formula (XV), two amino groups each bonded to two phenyls are preferably bonded to a meta position or a para position with respect to A ⁷ .

As a side chain type diamine represented by said general formula (XV), the diamine represented by the following general formula (XV-1) (XV-3)-is mentioned, for example.

In the above general formula, R ²⁶ is preferably an alkyl group having 6 to ²⁰ carbon atoms, and R ²⁷ is preferably -H or an alkyl group having 1 to 10 carbon atoms.

It is preferable that it is 1 to 90%, and it is more preferable that it is 5 to 80% in TN and VA from a viewpoint of obtaining the appropriate pretilt angle at the time of setting it as a liquid crystal display element in the said diamine. Do.

The diamine is a diamine other than the diamine represented by the general formula (I), which is a naphthalene diamine having a naphthalene structure, a fluorene diamine having a fluorene structure, or a siloxane diamine having a siloxane bond, or the general The diamine which has a side chain structure other than the side chain structure represented by Formula (XI)-(XV) may further be included. The other diamine can be used as the B component of the amine as long as it has a side chain structure, and can be used as the A component of the amine if it does not have it.

For example, as said siloxane diamine, the diamine represented by the following general formula (XVII) is mentioned, for example.

In formula (XVII), R ²⁸ and R ²⁹ independently represent alkyl or phenyl having 1 to 3 carbon atoms, and A ¹⁰ independently represents methylene, phenylene or alkyl substituted phenylene. i represents the integer of 1-6, j represents the integer of 1-10.

As a diamine represented by the said general formula (XVII), the diamine represented by the following structural formula (XVII-1) (XVII-7)-is mentioned, for example.

Moreover, it does not specifically limit as said other diamine, For example, the diamine represented by following General formula (1 ')-(8') is mentioned.

In the above general formula, R ³⁰ independently represents an alkyl group having ³ to ³⁰ carbon atoms, and in the general formulas (4 '), (6') and (8 '), R ³¹ represents an alkyl group having 3 to 30 carbon atoms.

On the other hand, the other diamine is not limited to the above-mentioned diamine, It goes without saying that various other types of diamine existing in the other diamine can be used within the range in which the objective of this invention is achieved.

Some of the diamines may be substituted with monoamines. Substituting a part of the diamine with a monoamine causes the termination of the polymerization reaction to produce the polyamic acid or its derivatives and inhibits the progress of further reactions, and therefore, from the viewpoint of easily controlling the molecular weight of the resulting polyamic acid or its derivatives. desirable. Although the ratio of monoamine with respect to diamine should just be a range which does not impair the effect of this invention, it is preferable that it is 10 mol% or less of approximately all amines.

The said tetracarboxylic dianhydride will not be specifically limited if it is tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be one kind or two or more kinds. It is preferable to select the said tetracarboxylic dianhydride suitably from a viewpoint of making the polyamic acid or its derivative (s) in this invention soluble form in a solvent. As said tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride are mentioned, for example.

As said aromatic tetracarboxylic dianhydride, the compound represented by following structural formula (1)-(13) is mentioned, for example.

The aromatic tetracarboxylic dianhydride is preferably a compound represented by the following structural formulas (1), (2), (5), (6) and (7), and pyromellitic dianhydride represented by structural formula (1) It is more preferable that is.

As said aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, the compound represented by following Structural formula (14)-(62) is mentioned, for example.

The aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are preferably compounds represented by the structural formulas (14) to (29) and (60), and 1,2,3 represented by the structural formula (14). It is more preferable that it is, 4-cyclobutane tetracarboxylic dianhydride.

Moreover, the said aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride are structural formulas (19), (20), and (27) from a viewpoint of making the polyamic acid or its derivative (s) in this invention the polyimide soluble in a solvent. It is preferable that it is a compound represented by)-(29) and (60).

In addition, the said tetracarboxylic dianhydride may contain the tetracarboxylic dianhydride which has a side chain structure. The tetracarboxylic dianhydride which has a side chain structure can enlarge the pretilt angle in a liquid crystal display element. As tetracarboxylic dianhydride which has a side chain structure, the compound which has a steroid skeleton represented by following structural formula (63) and (64) is mentioned, for example.

It is preferable that the said tetracarboxylic dianhydride contains one or both of the said aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride from a viewpoint of providing the favorable ion density in a liquid crystal display element. Do.

In addition, the said tetracarboxylic dianhydride contains the tetracarboxylic dianhydride of various forms, and is not limited to the above-mentioned tetracarboxylic dianhydride. As said tetracarboxylic dianhydride, various forms of tetracarboxylic dianhydride can be used within the range in which the objective of this invention is achieved.

A part of said tetracarboxylic dianhydride may be substituted by the carboxylic acid anhydride. Substituting a part of tetracarboxylic dianhydride with carboxylic anhydride causes termination of the polymerization reaction to produce the polyamic acid or its derivatives and inhibits the progress of further reactions, thereby easily controlling the molecular weight of the polyamic acid or its derivatives. It is preferable from a viewpoint. Although the ratio of carboxylic anhydride with respect to the said tetracarboxylic dianhydride should just be a range which does not impair the effect of this invention, it is preferable that it is about 10 mol% or less of the said tetracarboxylic dianhydride.

As for the combination of the above-mentioned diamine and the tetracarboxylic dianhydride, more specifically, the diamine is represented by the A-type diamine and the structural formulas (VIII-3), (VIII-7), and (VIII-31). It is preferable from the viewpoint of lowering ion density and improving orientation that the tetracarboxylic dianhydride contains one or more of the above-mentioned diamine, and the tetracarboxylic dianhydride contains one or both of the structural formulas (1) and (14).

Moreover, it is ion that the said diamine contains the said B-type diamine and the diamine represented by the said structural formula (VIII-13), and the said tetracarboxylic dianhydride contains one or both of the said structural formulas (1) and (14). It is preferable from a viewpoint of preventing a fall of a density, the improvement of orientation, and a sticking.

In addition, the diamine includes one or both of the C-type diamine and the diamines represented by the structural formulas (VIII-1) and (VIII-7), wherein the tetracarboxylic dianhydride is represented by the structural formulas (1) and (14). It is preferable to include either or both of them from the viewpoint of lowering the ion density and improving the orientation.

The diamine may include one or both of the D-type diamines represented by the above-mentioned structural formulas D1 and D2, and the tetracarboxylic dianhydride may include one or both of the above-mentioned structural formulas (1) and (14). It is preferable from the viewpoint of the decrease of the, the improvement of the orientation, and the prevention of seizure.

Although the weight average molecular weight of the said polyamic acid or its derivatives is not specifically limited, When used as a component of a liquid crystal aligning agent, it does not evaporate at the stage of baking a liquid crystal aligning film, and acquires preferable physical properties as a component of a liquid crystal aligning agent. Is preferably at least 5 × 10 ^{3 and} more preferably at least 1 × 10 ⁴ . Moreover, it is preferable that the said weight average molecular weight is 1 * 10 <^6> or less from a viewpoint of making easy handling as liquid crystal aligning agents, such as viscosity.

The weight average molecular weight of the polyamic acid or its derivatives is measured by gel permeation chromatography (GPC). For example, the obtained polyamic acid or derivatives thereof are diluted with dimethylformamide (DMF) so that the concentration of the polyamic acid or derivatives thereof is about 1% by weight, and using Chromapack C-R7A (manufactured by Shimadzu Corporation) And DMF as a developing solvent, are measured by gel permeation chromatograph analysis (GPC) method, and are required by polystyrene conversion. In addition, from the viewpoint of increasing the accuracy of the GP C measurement, a developing solvent in which inorganic acids such as phosphoric acid, hydrochloric acid, acetic acid and sulfuric acid, and inorganic salts such as lithium bromide and lithium chloride are dissolved in a DMF solvent may be prepared and used.

The said polyamic acid or its derivative can be manufactured using a well-known method. For example, the diamine is injected into a reaction vessel provided with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer, and a condenser, and a desired amount of monoamine is further added as necessary.

Subsequently, a solvent (for example, N-methyl-2-pyrrolidone, dimethylformamide, etc.), which is an amide polar solvent, and the tetracarboxylic dianhydride are added thereto, and a desired amount of carboxylic anhydride is further added, if necessary. . At this time, it is preferable that the total amount of tetracarboxylic acid dianhydride be set to a molar amount (a molar ratio of about 0.9 to 1.1) which is almost the same as the total moles of diamine.

The solution of polyamic acid can be obtained preferably by making it react for 1 to 48 hours at the temperature of 0-70 degreeC under stirring. Moreover, polyamic acid with a small molecular weight can also be obtained by heating and raising reaction (for example, 50-80 degreeC). The produced polyamic acid is obtained by precipitating with a large amount of poor solvent and completely separating the solid content and the solvent by filtration or the like.

The soluble polyimide, which is a polyamic acid derivative, usually contains a solution of polyamic acid, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoro acetic anhydride, which are dehydrating agents, and triethylamine, pyridine, and collidine, which are dehydrating ring closure catalysts. It can obtain by imidation reaction at the temperature of 20-150 degreeC with a tertiary amine.

Alternatively, polyamic acid is precipitated using a large amount of poor solvent (alcohol solvent or glycol solvent such as methanol, ethanol or isopropanol) as a solution of polyamic acid, and the precipitated polyamic acid is dissolved in a solvent such as toluene or xylene. It can also be obtained by imidation reaction at a temperature of 20 to 150 ° C with a dehydrating agent and a dehydrating ring-closure catalyst as described above.

In the said imidation reaction, it is preferable that the ratio of a dehydrating agent and a dehydration ring-closure catalyst is 0.1-10 (molar ratio). It is preferable that the total usage-amount of both is 1.5-10 times mole with respect to the total molar amount of the acid dianhydride contained in the tetracarboxylic dianhydride to be used. By adjusting the dehydrating agent, catalyst amount, reaction temperature, and reaction time of such chemical imidation, the degree of imidation can be controlled and partial polyimide can be obtained.

Moreover, when a part of said tetracarboxylic dianhydride is substituted by organic dicarboxylic acid, a polyamic-acid-polyamide copolymer can be obtained. Here, although the ratio of the organic dicarboxylic acid with respect to tetracarboxylic dianhydride should just be a range which does not impair the effect of this invention, it is preferable that it is about 10 mol% or less of the said tetracarboxylic dianhydride.

In addition, polyamideimide can be prepared by chemically imidating the polyamic acid-polyamide copolymer.

The polyamic acid or a derivative thereof can be identified by analyzing by IR and NMR. Furthermore, the monomer used can be identified by decomposing a solid polyamic acid or its derivative with aqueous solution of strong alkalis, such as KOH and NaOH, extracting with an organic solvent, and analyzing by GC, HPLC, or GC-MS.

The obtained polyamic acid or its derivative can be diluted and used with a solvent in order to adjust to desired viscosity.

Moreover, the obtained polyamic acid or its derivative can be used as a liquid crystal aligning agent, isolate | separates from a solvent and re-dissolves in the solvent mentioned later with the epoxy compound mentioned later, or adds an epoxy compound without separating with a solvent, and a liquid crystal aligning agent Can also be used as.

By using the diamine or tetracarboxylic dianhydride which has a side chain structure like the said side chain-type diamine, the said polyamic acid or its derivative can adjust the pretilt angle in a liquid crystal display element suitably, and can use any kind of liquid crystal display element Applicable to As the pretilt angle, a large pretilt angle of about 80 to 90 degrees in the case of a VA type liquid crystal display element, a pretilt angle of about 7 to 20 degrees in the case of an OCB type liquid crystal display element, a TN type liquid crystal display element or an STN type In the case of a liquid crystal display element, a pretilt angle of about 3 to 10 degrees, and in the case of an IPS type liquid crystal display element, a small pretilt angle of about 0 to 3 degrees is often required.

Like the pretilt angle described above, the properties expressed by the monomers of the polyamic acid or its derivatives are obtained by producing the polyamic acid or its derivatives using the monomers that bring about such properties. The characteristic according to the monomer can be obtained from one kind of polyamic acid or derivatives thereof obtained using plural kinds of monomers bringing about such characteristics, and two or more kinds of polya obtained using plural kinds of monomers bringing about such characteristics. It can be obtained from mic acid or a derivative thereof.

It is preferable from the viewpoint of providing the characteristic which is preferable as a liquid crystal aligning agent of this invention that 2 or more types of polyamic acid or derivatives from which some or all of a monomer differs are contained in a liquid crystal aligning agent. The mixing ratio of two or more types of polyamic acid or its derivatives should just be a grade from which the desired characteristic corresponding to the use of a liquid crystal aligning agent is obtained.

More specifically, by appropriately selecting the kind of diamine or tetracarboxylic dianhydride and combinations thereof, it is possible to impart desired properties such as more preferable ion density and preferred pretilt angle required for the liquid crystal aligning agent of the present invention. Can be improved.

As a combination of such 2 or more types of polyamic acids or its derivatives, it is (1) the polyamic acid containing the said type B diamine or its derivative (s), the polyamic acid containing the said A type diamine or its derivative (s), said C type A polyamic acid or derivative thereof comprising a diamine, or a combination thereof with a polyamic acid or derivative thereof comprising a D-type diamine, (2) a polyamic acid or derivative thereof comprising the B-type diamine, and the A-type diamine Combination of a polyamic acid or a derivative thereof, a polyamic acid or a derivative thereof containing the C-type diamine, and (3) a polyamic acid or a derivative thereof containing the B-type diamine, and the D-type diamine A polyamic acid or a derivative thereof and a polyamic acid or a derivative thereof containing the A-type diamine or a C-type diamine Polyamic may be mentioned a combination of the acid or a derivative thereof.

The said epoxy compound is a compound which has an epoxy group with more than one average functional groups, such as a compound which has two or more epoxy groups. 1 type may be sufficient as an epoxy compound, and 2 or more types may be sufficient as it. An epoxy compound is used by the kind and content which forms the solution of an epoxy compound, the said polyamic acid, or its derivative in a liquid crystal aligning agent. In addition, an epoxy resin means resin which has an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic fat. A group type epoxy compound is mentioned.

As said glycidyl ether, a bisphenol-A epoxy compound, a bisphenol F-type epoxy compound, a bisphenol S-type epoxy compound, a bisphenol-type epoxy compound, a hydrogenated bisphenol-A type epoxy compound, a hydrogenated bisphenol-F type epoxy compound, hydrogenation, for example Bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolak-type epoxy compound, cresol novolak-type epoxy compound, brominated phenol novolak-type epoxy compound , Brominated cresol novolac epoxy compound, bisphenol A novolac epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic Polyglycidyl Ether Compound, Polysulfy Type diglycidyl there may be mentioned ether compound, and biphenol type epoxy compound.

As said glycidyl ester, a diglycidyl ester compound and a glycidyl ester epoxy compound are mentioned, for example.

As said glycidyl amine, a polyglycidyl amine compound and glycidyl amine type epoxy resin are mentioned, for example.

As said epoxy-group-containing acryl-type compound, the homopolymer and copolymer of the monomer which has oxilanyl are mentioned, for example.

As said glycidyl amide, a glycidyl amide type epoxy compound is mentioned, for example.

As said linear aliphatic epoxy compound, the compound containing an epoxy group obtained by oxidizing the carbon-carbon double bond of an alkene compound is mentioned, for example.

As said cyclic aliphatic epoxy compound, the compound containing an epoxy group obtained by oxidizing the carbon-carbon double bond of a cycloalkene compound is mentioned, for example.

Examples of the bisphenol A epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, 1010 (all manufactured by Japan Epoxy Resin), Efototo YD-128 (manufactured by Toyo Chemical Co., Ltd.), DER-331, DER-332, DER-324 (all from Dow Chemical), Epiclone 840, Epiclone 850, Epiclone 1050 (all from Dainippon Ink, Inc.), Epomic R-140, Epomic R-301, and Epomic R-304 (all are manufactured by Mitsui Chemicals, Inc.) are mentioned.

Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by Japan Epoxy Resin Co., Ltd.), Efototo YDF-170, Efototo YDF-175S, and Efototo YDF-2001 (both from Tokyo. Products), DER-354 (manufactured by Dow Chemical), Epiclone 830, and Epiclone 835 (all manufactured by Dainippon Ink, Inc.).

As said bisphenol type epoxy compound, the epoxide of 2, 2-bis (4-hydroxy phenyl) -1,1,1,3,3,3-hexafluoro propane is mentioned, for example.

As said hydrogenated bisphenol-A epoxy compound, for example, Santoto ST-3000 (manufactured by Tosho Chemical Co., Ltd.), Licarazine HBE-100 (manufactured by Nippon Chemical Co., Ltd.), and Denacol EX-252 (manufactured by Nagase Chemtex Co., Ltd.) Can be mentioned.

As said hydrogenated bisphenol-type epoxy compound, the epoxide of hydrogenated 2, 2-bis (4-hydroxyphenyl) -1, 1, 1, 3, 3, 3- hexafluoro propane is mentioned, for example.

Examples of the brominated bisphenol-A epoxy compound include 5050, 5051 (all manufactured by Japan Epoxy Resin), Efototo YDB-360, Efototo YDB-400 (all manufactured by Toyo Chemical Co., Ltd.), DER-530, and DER. -538 (all manufactured by Dow Chemical Co., Ltd.), epiclon 152, and epiclon 153 (all manufactured by Dainippon Ink, Inc.).

As said phenol novolak-type epoxy compound, 152,154 (all are from Japan Epoxy Resin company), YDPN-638 (all from Tosho Chemical Co., Ltd.), DEN431, DEN438 (all from Dow Chemical company), and epiclon N-770, for example. (Made by Dainippon Ink and Chemicals, Inc.), EPPN-201, and EPPN-202 (all of which are manufactured by Nippon Kayaku Co., Ltd.).

As said cresol novolak-type epoxy compound, for example, 180S75 (made by Japan epoxy resin), YDCN-701, YDCN-702 (all manufactured by Tosho Chemical Co., Ltd.), epiclon N-665, and epiclon N-695 (all are Dainippon) Ink chemical products), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Fire Co., Ltd.).

As said bisphenol A novolak-type epoxy compound, 157S70 (made by Japan Epoxy Resin) and epiclon N-880 (made by Dainippon Ink and Chemicals, Inc.) are mentioned, for example.

As said naphthalene frame | skeleton containing epoxy compound, Epiclone HP-4032, Epiclone HP-4700, Epiclone HP-4770 (all are the Dainippon Ink & Chemicals Co., Ltd. product), and NC-7000 (made by Nippon Fire Co., Ltd.) ).

As the aromatic poly glycidyl ether compound, for example, hydroquinone diglycidyl ether (following formula 101), catechol diglycidyl ether (following formula 102), resorcinol diglycidyl ether (following formula 103) , 2- [4- (2,3-epoxypropoxy) phenyl] -2-4 [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane Structural Formula 104), Tris (4-glycidyloxyphenyl) methane (Structural Formula 105), 1031S, 1032H60 (all manufactured by Japan Epoxy Resin), TACTIX-742 (manufactured by Dow Chemical), Denacol EX-201 (Nagase Chemtex Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Fire Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemical Co., Ltd.), a compound represented by the following Structural Formula 106, and the following structural formula The compound represented by 107 is mentioned.

As said dicyclopentadiene phenol type epoxy compound, TACTIX-556 (made by Dow Chemical company), and Epiclone HP-7200 (made by Dainippon Ink & Chemicals, Inc.) are mentioned, for example.

As said alicyclic diglycidyl ether compound, a cyclohexane dimethanol diglycidyl ether compound, and ligazine DME-100 (made by Nippon Chemical Co., Ltd.) are mentioned, for example.

As the aliphatic polyglycidyl ether compound, for example, ethylene glycol diglycidyl ether (following formula 108), diethylene glycol diglycidyl ether (following formula 109), polyethylene glycol diglycidyl ether, propylene glycol Diglycidyl ether (following formula 110), tripropylene glycol diglycidyl ether (following formula 111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula 112), 1, 4-butanediol diglycidyl ether (following formula 113), 1,6-hexanediol diglycidyl ether (following formula 114), dibromoneopentyl glycol diglycidyl ether (following formula 115), denacol EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX- 313 (all manufactured by Nagase Chemtex Co., Ltd.), DD-503 (manufactured by Nippon Chemical Co., Ltd.), Lika Resin W-100 (New) Nippon Chemical Products), 1,3,5,6-tetraglycidyl-2,4-hexanediol (formula 116 below), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycid Dyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all manufactured by Nagase Chemtex).

As said polysulfide type diglycidyl ether compound, FLDP-50 and FLDP-60 (all are the Toray Thichol Co. product) are mentioned, for example.

As said non-phenol type epoxy compound, YX-4000, YL-6121H (all are manufactured by Japan Epoxy Resin Co., Ltd.), NC-3000P, and NC-3000S (all are the Nippon Fire Co., Ltd. product) are mentioned, for example.

As the diglycidyl ester compound, for example, diglycidyl terephthalate (formula 117 below), diglycidyl phthalate (formula 118 below), bis (2-methyloxylanylmethyl) phthalate (formula 119 below) ), Diglycidyl hexahydephnolate (former breakfast 120), a compound represented by the following structural formula 121, a compound represented by the following structural formula 122, and a compound represented by the following structural formula 123.

Examples of the glycidyl ester epoxy compound include 871 and 872 (all manufactured by Japan Epoxy Resin Co., Ltd.), epiclon 200, epiclon 400 (all manufactured by Dainippon Ink and Chemicals, Inc.), Denacol EX-711, And Denacol EX-721 (both manufactured by Nagase Chemtex).

As said polyglycidyl amine compound, for example, N, N- diglycidyl aniline (following formula 124), N, N- diglycidyl-o-toluidine (following formula 125), N, N-di Glycidyl-m-toluidine (formula 126), N, N-diglycidyl-2,4,6-triblemoaniline (formula 127), 3- (N, N-diglycidyl) amino Propyltrimethoxysilane (Formula 128), N, N, O-triglycidyl-p-aminophenol (Formula 129), N, N, O-triglycidyl-m-aminophenol (Formula 130) , N, N, N ', N'-tetraglycidyl-m-xylenediamine (TETRAD-X (Mitsubishi Gas Chemical), Structural Formula 132), 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane (TETRAD-C (Mitsubishi Gas Chemical), formula 133), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (formula 134), 1,3-bis ( N, N-diglycidylamino) cyclohexane (formula 135), 1,4-bis (N, N-diglycidylamino) cyclohexane (formula 136), 1 , 3-bis (N, N-diglycidylamino) benzene (formula 137), 1,4-bis (N, N-diglycidylamino) benzene (formula 138), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (formula 139), N, N, N ', N'-tetraglycidyl-4,4'-diaminodicyclo Hexylmethane (formula 140 below), 2,2'-dimethyl- (N, N, N ', N'-tetraglycidyl) -4,4'-diaminobiphenyl (formula 141 below), N, N , N ', N'-tetra glycidyl-4,4'-diaminodiphenylether (formula 142), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy Benzene (formula 143), 2,4,4'-tris (N, N-diglycidylamino) diphenylether (formula 144), tris (4- (N, N-diglycidyl) ) Aminophenyl) methane (formula 145), 3,4,3 ', 4'-tetrakis (N, N-diglycidylamino) biphenyl (formula 146), 3,4,3', 4 '-Tetrakis (N, N-diglycidylamino) diphenyl ether (formula 147 below), represented by formula 148 below The compound and the compound represented by following structural formula 149 are mentioned.

As a homopolymer of the monomer which has the said oxiranyl, polyglycidyl methacrylate is mentioned, for example. As a copolymer of the monomer which has the said silanyl, for example, N-phenylmaleimide glycidyl methacrylate copolymer, N-cyclohexyl maleimide glycidyl methacrylate copolymer, benzyl methacrylate -Glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-jade Cetanyl) methylmethacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

As a monomer which has the said oxylanyl, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate are mentioned, for example.

As a monomer other than the monomer which has the said oxiranyl in the copolymer of the monomer which has the said oxiranyl, it is (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl, for example. (Meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexyl Maleimide, and N-phenylmaleimide.

As said glycidyl isocyanurate, for example, 1,3,5-triglycidyl-1,3,5-triadine-2,4,6- (1H, 3H, 5H) -trione (following) 150), 1,3-diglycidyl-5-allyl-1,3,5-triadine-2,4,6- (1H, 3H, 5H) -trione (formula 151), and glyc A cyl isocyanurate type epoxy resin is mentioned.

As said chain aliphatic epoxy compound, epoxidized polybutadiene and epoxide PB3600 (made by Daicel Chemical Industries, Ltd.) are mentioned, for example.

Examples of the cyclic aliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (Celoxide 2021 (made by Daicel Chemical Industries, Ltd.)) 152), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (formula 153 below), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (formula 154 shown below), epsilon -caprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy Limonene (Celoxide 3000 (manufactured by Daicel Chemical Corporation), Structural Formula 155), a compound represented by Structural Formula 156, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY); EHPD-3150 (made by Daicel Chemical Industries, Ltd.), and a cyclic aliphatic type epoxy resin are mentioned.

It is preferable that the said epoxy compound is at least one of a polyglycidyl amine compound, a bisphenol A novolak-type epoxy compound, a cresol novolak-type epoxy compound, and a cyclic aliphatic type epoxy compound, N, N, N ', N'- Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'- Diaminodiphenylmethane, trade name "Techmore VG3101L", 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, N-phenylmaleimido-glycidyl methacrylate copolymer , N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac epoxy compound, and cresol novolac epoxy compound.

The liquid crystal aligning agent of this invention may further contain components other than the polyamic acid or its derivative (s) mentioned above, and an epoxy compound. As such a new component, the solvent and various additives contained in a normal liquid crystal aligning agent are mentioned, for example.

The said solvent contains the solvent normally used for the manufacturing process and use of high molecular components, such as a polyamic acid, soluble polyimide, and polyamideimide, and can be suitably selected according to a use purpose. For example, the said solvent can be used from a viewpoint of adjustment of physical properties, such as the viscosity of a liquid crystal aligning agent, ease of handling, process simplification, etc. The solvent may be one kind or two or more kinds. Examples of the solvent include an aprotic polar organic solvent which is easily dissolved in polyamic acid or a derivative thereof, and a coating property improving solvent for the purpose of improving the coating property by changing the surface tension. It is preferable that it is a mixed solvent containing these.

Examples of the aprotic polar organic solvents include N-methyl-2-pyrrolidone, N, N'-dimethylimidazolidinone, N-methylcaprolactam, N, N-dimethylpropionamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N, N ', N'-tetramethylurea, (gamma) -butyrolactone, and (gamma) -valerolactone are mentioned. The aprotic polar organic solvent is preferably at least one selected from N-methyl-2-pyrrolidone, N, N'-dimethylimidazolidinone, γ-butyrolactone, and γ-valerolactone. .

Examples of the coating property improving solvent include ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and the like. Propylene glycol monoalkyl ethers such as diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, and propylene glycol monobutyl ether; Dipropylene glycol monoalkyl ethers, such as a monomethyl ether, and ester compounds, such as these acetates, are mentioned. The coating property improving solvent is preferably at least one selected from ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

The kind and ratio of an aprotic polar solvent and a coating property improvement solvent can be set suitably in consideration of printability, applicability | paintability, solubility, storage stability, etc. of a liquid crystal aligning agent. Aprotic polar solvents are relatively superior in solubility and storage stability than applicability improving solvents, and applicability improving solvents tend to be excellent in printability and applicability.

The additive may be any component that can be used for the purpose of improving specific properties of the liquid crystal aligning agent, and may be one kind or two or more kinds. As said additive, the high molecular compound and the low molecular compound other than the polyamic acid or its derivative which can be used according to each objective are mentioned.

It is preferable that the said high molecular compound is a high molecular compound soluble in an organic solvent from a viewpoint of controlling the electrical property and orientation of the liquid crystal aligning film formed. As such a high molecular compound, polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone modified polyurethane, silicone modified polyester is mentioned, for example.

As said low molecular weight compound, surfactant, an antistatic agent, a silane coupling agent, a titanium-type coupling agent, and an imidation catalyst are mentioned, for example. Surfactant is preferable from a viewpoint of improving the applicability | paintability of a liquid crystal aligning agent. An antistatic agent is preferable from a viewpoint of improving the antistatic property of a liquid crystal aligning agent and a liquid crystal aligning film. A silane coupling agent and a titanium-based coupling agent are preferable from a viewpoint of improving adhesiveness and rubbing tolerance with the board | substrate of a liquid crystal aligning film. An imidation catalyst is preferable at the point which advances imidation at low temperature in formation of a liquid crystal aligning film.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3- Aminopropylmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloro Propylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3 -(Triethoxysilyl) -1-propylamine, and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenedia Min can be mentioned.

As said imidation catalyst, Aliphatic amines, such as trimethylamine, triethylamine, tripropylamine, and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline and hydroxy substituted aniline; Pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, etc. Cyclic amines may be mentioned. The imidation catalyst is preferably at least one selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline.

The addition amount of a silane coupling agent is 0 to 10 weight% of the total weight of a polyamic acid or its derivative normally, and it is preferable that it is 0.1 to 3 weight%.

The addition amount of the imidation catalyst is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or its derivatives.

Although the addition amount of another additive changes with the use, it is usually 0-30 weight% of the total weight of a polyamic acid or its derivative, and it is preferable that it is 0.1-10 weight%.

For example, the liquid crystal aligning agent of this invention may further contain an alkenyl substituted naziimide compound from a viewpoint of stabilizing the electrical property of a liquid crystal display element for a long time. The alkenyl substituted naziimide compound may be one kind of compound or two or more kinds of compounds. It is preferable that it is 0.01-1.00 by weight ratio with respect to the polyamic acid or its derivative in a liquid crystal aligning agent, as for content of the said alkenyl substituted naziimide compound, It is more preferable that it is 0.01-0.70, and it is 0.01-0.50 More preferred.

It is preferable that the said alkenyl substituted naziimide compound is a compound which can be melt | dissolved in the solvent which melt | dissolves the polyamic acid or its derivative which can be used by this invention. As an example of such an alkenyl substituted naziimide compound, the compound represented with the following general formula (Ina) is mentioned.

In General Formula (Ina), L ¹ and L ² each independently represent hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl or benzyl, and n is 1 or 2 is shown.

When n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, -Z ^1- (O) _q- ( Z ² O) _r -Z ³ -H (Z ¹ , Z ² and Z ³ independently represent alkylene having 2 to 6 carbon atoms, q represents 0 or 1, r represents an integer of 1 to 30) Group represented by-(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ⁵ independently represent alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms, B represents phenylene , s represents 0 or 1, -BTBH (B represents phenylene, T represents -CH _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S -Or SO _2- ), or a group in which 1 to 3 hydrogens of such a group are substituted with hydroxyl groups.

At this time, preferable W is C1-C8 alkyl, C3-C4 alkenyl, cyclohexyl, phenyl, benzyl, C4-C10 poly (ethyleneoxy) ethyl, phenyloxyphenyl, phenylmethylphenyl, phenyliso Propylidenephenyl, and groups in which one or two hydrogens of such groups are substituted with hydroxyl groups.

When n = 2 In one general formula (Ina), W is arylene, -O- -Z ¹ (Z ² O of the cycloalkylene, 6 to 12 carbon atoms in the alkylene group, having a carbon number of 5 to 8 of 2 to 20 carbon atoms ) is a group represented by _r -Z ^3- (where Z ^{1 to} Z ³ , and r have the same meaning as above), -Z ⁴ -BZ ^5- (where Z ⁴ , Z ⁵ and B have the same meaning as above) The group represented, -B- (OB) _s -T- (BO) _s -B- (B represents phenylene, T represents alkylene having 1 to 3 carbon atoms, -O- or -SO _2- , s represents 0 or 1), or group in which 1-3 hydrogen of such a group was substituted by the hydroxyl group.

In this case, preferred W is alkylene, cyclohexylene, phenylene, tolylene, xylylene, -C ₃ H ₆ -O- (Z ² -O) _r -OC ₃ H _6- ( Z ² represents an alkylene having 2 to 6 carbon atoms, r represents 1 or 2, -BTB- (B represents phenylene, and T represents -CH _2- , -O- or -SO _Group represented by-), group represented by -BOBC ₃ H ₆ -BOB- (B represents phenylene), and a group in which one or two hydrogen of such a group is substituted with a hydroxyl group.

Such alkenyl-substituted naziimide compounds are synthesized by maintaining the alkenyl-substituted naziic anhydride derivatives and diamines at a temperature of 80 to 220 ° C. for 0.5 to 20 hours, as described, for example, in Japanese Patent No. 2729565. The obtained compound and the commercially available compound can be used. As a specific example of an alkenyl substituted naziimide compound, the compound shown below is mentioned.

N-methyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-methyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-di Carboxylimide, N-Methyl-Metalyl Bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-methyl-Metalylmethylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-allyl-allylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide, N-allyl-allylmethylbicyclo [2.2.1] hepto-5-en-2,3-dicarboxyimide, N-allyl-metallylbicyclo [2.2.1] hepto -5-ene-2,3-dicarboxyimide, N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-allyl (methyl ) Bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide, N-cyclohexyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-phenyl-allylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-benzyl-allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide, N-benzyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-benzyl-metallylbicyclo [2.2.1] hepto-5-ene- 2,3-dicarboxyimide, N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl)- Allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl) -metallylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide,

N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2,2-dimethyl-3-hydroxy Oxypropyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyl Mead, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxycyclohexyl) -allyl (Methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N -(4-hydroxyphenyl) -metallmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} -allyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxy Oxyethoxy) ethyl} -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} -metallylmethylbicycle Rho [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] hepto-5 -Ene-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -metallylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {4- (4-ha De-hydroxyphenyl-isopropylidene) phenyl} - Metal rilbi [2.2.1] hept-5-ene-2,3-dicarboxyimide, and these oligomers,

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

1,2-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane, 1,2-bis {3'-(allylmethyl Bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane, 1,2-bis {3 '-(metallylbicyclo [2.2.1] hepto-5-ene- 2,3-dicarboxyimide) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] Ether, bis [2 '-{3'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether, 1,4-bis {3 ' -(Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} butane, 1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylylene-bis ( Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N ' -m-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metallylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide ) Phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylmethylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- ( Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone, bis {4- (allylmethylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfone,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone, 1,6-bis (allylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide) -3-hydroxy-hexane, 1,12-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3,6- Dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxy-cyclohexane, 1,5-bis { 3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene,

1,4-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2,5-dihydroxy-benzene, N, N'-p- (2- Hydroxy) xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p- (2-hydroxy) xylylene-bis (Allylmethylcyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide), N, N'-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyi mid),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenoxy} phenyl] propane, bis {4 -(Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide) -4-hydroxy-phenyl} ether, bis {3- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)- 5-hydroxy-phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)} phenoxymethylpropane, N , N ', N "-tri (ethylenemetallbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) isocyanurate, oligomers thereof and the like.

In addition, the alkenyl substituted naziimide compound which can be used for this invention may be a compound represented by the following structural formula containing an asymmetric alkylene phenylene group.

Among the alkenyl substituted naziimide compounds, preferred compounds are shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylylene-bis ( Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N ' -m-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), 2,2-bis [4- {4- (allylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylmethylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- ( Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone, bis {4- (allylmethylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfon, bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} Sulfone.

In addition, preferred alkenyl substituted naziimide compounds are shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylylene-bis ( Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N ' -m-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metallylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide ) Phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane .

As a particularly preferable alkenyl substituted naziimide compound, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl represented by the structural formula (Ina-1) shown below } Methane, N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by structural formula (Ina-2), and structural formula And N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by (Ina-3).

For example, the liquid crystal aligning agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond from a viewpoint of long-term stabilizing the electrical property of a liquid crystal display element. The compound having a radically polymerizable unsaturated double bond may be one kind of compound or two or more kinds of compounds. In addition, the said alkenyl substituted naziimide compound is not contained in the compound which has the said radically polymerizable unsaturated double bond. As for content of the compound which has the said radically polymerizable unsaturated double bond, from a viewpoint mentioned above, it is preferable that it is 0.01-1.00 by weight ratio with respect to polyamic acid or its derivatives, It is more preferable that it is 0.01-0.70, It is 0.01-0.50 More preferred.

On the other hand, the ratio of the compound which has a radically polymerizable unsaturated double bond with respect to an alkenyl substituted naziimide compound reduces the ion density of a liquid crystal display element, suppresses the increase of ion density with time, and also suppresses afterimages. It is preferable that it is 0.1-10 by weight ratio, and it is more preferable that it is 0.5-5.

As a compound which has the said radically polymerizable unsaturated double bond, (meth) acrylic acid derivatives, such as (meth) acrylic acid ester and (meth) acrylic acid amide, and bismaleimide are mentioned. As for the compound which has the said radically polymerizable unsaturated double bond, it is more preferable that it is a (meth) acrylic acid derivative which has 2 or more of radically polymerizable unsaturated double bonds.

As a specific example of (meth) acrylic acid ester, (meth) acrylic-acid cyclohexyl, (meth) acrylic-acid 2-methylcyclohexyl, (meth) acrylic-acid dicyclopentanyl, (meth) acrylic-acid dicyclopentanyloxyethyl, (meth) Isoboroyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

As a specific example of a bifunctional (meth) acrylic acid ester, For example, ethylene bisacrylate, the Aloneics M-210, the Alonix M-240 and Alonics M-6200, Nippon Kayaku which are products of Toago Seigagaku Kogyo Co., Ltd. (株) KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, V260, V312 and V335HP, which are major products, and Light Acrylate BA, which are manufactured by -4EA, light acrylate BP-4PA, and light acrylate BP-2PA.

As a specific example of a trifunctional or more than trifunctional (meth) acrylic acid ester, For example, 4,4'- methylenebis (N, N- dihydroxy ethylene acrylate aniline), an Alonex M-400, an Alonex M-405, Alonix M-450, Alonix M-7100, Alonix M-8030, Alonix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and 大阪 有機And VGPT, which is a chemical product.

As a specific example of a (meth) acrylic acid amide derivative, N-isopropyl acrylamide, N-isopropyl methacrylamide, Nn-propyl acrylamide, Nn-propyl methacrylamide, N-cyclopropyl acrylamide, N, for example -Cyclopropyl methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethyl methacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N -Ethyl-N-methylacrylamide, N, N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acrylic Loylpyrrolidine, N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide , N-phenyl methacrylamide, N-butyl methacrylamide, N- ( Small-butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] meta Krillamide, N- (methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N'-methylenebismethacrylamide Can be mentioned.

Among the (meth) acrylic acid derivatives, N, N'-methylenebisacrylamide, N, N'-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4'-methylenebis (N, N- Dihydroxyethylene acrylate aniline) is particularly preferred.

Examples of the bismaleimide include BMI-70 and BMI-80, manufactured by K-I Kasei, and BMI-1000, BMI-3000, BMI-4000, BMI-5000, and BMI-, manufactured by Daiwa Chemical Industries, Ltd., for example. 7000 may be mentioned.

For example, the liquid crystal aligning agent of this invention may further contain an oxazine compound from a viewpoint of the long-term stability of the electrical characteristic in a liquid crystal display element. The oxazine compound may be one kind of compound or two or more kinds of compounds. It is preferable that content of the said oxazine compound is 0.1-50 weight% with respect to the said polyamic acid or its derivative from said viewpoint, It is more preferable that it is 1-40 weight%, It is more preferable that it is 1-20 weight% desirable.

The oxazine compound is soluble in a solvent in which polyamic acid or a derivative thereof is dissolved, and further, an oxazine compound having ring-opening polymerization property is preferable.

The number of oxazine structures in the oxazine compound is not particularly limited.

Various structures are known in the structure of an oxazine. In this invention, although the structure of an oxazine is not specifically limited, The structure of the oxazine which has an aromatic group containing condensed polycyclic aromatic groups, such as benzoxazine and naphthooxazine, is mentioned as an oxazine structure in the said oxazine compound. Can be.

As said oxazine compound, the compound shown to the following general formula (a)-(f) is mentioned, for example. In addition, in the following general formula, the bond shown toward the center of a ring shows that it is couple | bonded with any carbon which can combine a substituent and constitutes a ring.

In said general formula (a)-(c), R <^1> and R <^2> represents a C1-C30 organic group. In General Formulas (a) to (f), R ³ to R ⁶ represent hydrogen or a hydrocarbon group having 1 to ⁶ carbon atoms. In formulas (c), (d) and (f), X is a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO -, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -S- (CH ₂ ) _m -S Indicates-. M is an integer of 1-6 here. In the above general formulas (e) and (f), Y is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -or C1-C3 alkylene is shown. Hydrogen bonded to the benzene ring and the naphthalene ring in Y may be independently substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ .

Moreover, the said oxazine compound contains the oligomer and polymer which have an oxazine structure in a side chain, and the oligomer and polymer which have an oxazine structure in a main chain.

As an oxazine compound represented by general formula (a), the following oxazine compounds are mentioned, for example.

In the formula, R ¹ is preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.

As an oxazine compound represented by general formula (b), the following oxazine compound is mentioned, for example.

In the formula, R ¹ is preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.

As an oxazine compound represented by general formula (c), the oxazine compound represented by the following general formula (I) is mentioned.

In the general formula (I), R ¹ and R ² are an organic group having 1 to 30 carbon atoms, R ³ to R ⁶ are hydrogen or a hydrocarbon group having 1 to ⁶ carbon atoms, X is a single bond, -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -SO ₂ -or -C (CF ₃ ) _2- . As an oxazine compound represented by said general formula (I), the following oxazine compound is mentioned, for example.

In the formula, R ¹ is preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.

As an oxazine compound represented by general formula (d), the following oxazine compound is mentioned, for example.

As an oxazine compound represented by general formula (e), the following oxazine compound is mentioned, for example.

As an oxazine compound represented by general formula (f), the following oxazine compound is mentioned, for example.

Among these, More preferably, Formula (b-1), Formula (c-1), Formula (c-3), Formula (c-5), Formula (c-7), Formula (c-9), And oxazine compounds represented by formulas (d-1) to (d-6), (e-3), (e-4) and (f-2) to (f-4). have.

The said oxazine compound can be manufactured by the method similar to what was described in international publication 2004/009708 pamphlet, Unexamined-Japanese-Patent No. 11-12258, and Unexamined-Japanese-Patent No. 2004-352670.

For example, the oxazine compound represented by general formula (a) is obtained by making a phenol compound, a primary amine, and an aldehyde react (refer the international publication 2004/009708 pamphlet).

Moreover, the oxazine compound represented by General formula (b) is obtained by making primary amine react with the formaldehyde gradually, and then adding and reacting the compound which has a naphthol type hydroxyl group (refer the international publication 2004/009708 pamphlet). ).

In addition, the oxazine compound represented by the general formula (c) is a secondary aliphatic amine containing at least 2 moles or more of aldehydes and 1 mole of primary amine per mole of a phenol compound, one phenolic hydroxyl group thereof in an organic solvent. It is obtained by reacting in the presence of a tertiary aliphatic amine or a basic nitrogen-containing heterocycle ring compound (see International Publication 2004/009708 Pamphlet and Japanese Patent Laid-Open No. 11-12258).

The oxazine compounds represented by the general formulas (d) to (f) include aldehydes such as diamine and formalin having a plurality of benzene rings such as 4,4'-diaminodiphenylmethane and an organic group bonding them, and phenol. Is obtained by dehydrating condensation reaction at a temperature of 90 ° C. or higher in n-butanol (see Japanese Patent Laid-Open No. 2004-352670).

For example, the liquid crystal aligning agent of this invention may further contain an oxazoline compound from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one kind of compound or two or more kinds of compounds. It is preferable that content of the said oxazoline compound is 0.1-50 weight% with respect to the said polyamic acid or its derivative from said viewpoint, It is more preferable that it is 1-40 weight%, It is more preferable that it is 1-20 weight% desirable. Or it is preferable from said viewpoint that content of the said oxazoline compound is 0.1-40 weight% with respect to the said polyamic acid or its derivative, when converting the oxazoline structure in an oxazoline compound into oxazoline.

The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Moreover, although the said oxazoline compound should just have one said oxazoline structure in one compound, it is preferable to have two or more. Moreover, the oxazoline compound may be a polymer having an oxazoline ring structure in the side chain, or may be a copolymer. The polymer which has an oxazoline structure in a side chain may be a homopolymer of the monomer which has an oxazoline structure in a side chain, and may be a copolymer of the monomer which has an oxazoline structure in a side chain, and the monomer which does not have an oxazoline structure. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more types of monomers having an oxazoline structure in the side chain, or a monomer not possessing an oxazoline structure with two or more monomers having an oxazoline structure in the side chain; It may be a copolymer of.

It is preferable that the said oxazoline structure is a structure which exists in an oxazoline compound so that the carbonyl group of a polyamic acid may react with one or both of oxygen and nitrogen in an oxazoline structure.

As said oxazoline compound, 2,2'-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene, for example 2-phenyl-4H-oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxa Zolyl) benzene, 2,3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis (iso Propyl-2-oxazolin-2-yl) pyridine, 2,2'-isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2 -Oxazoline), 2,2'-methylenebis (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline) are mentioned. In addition to these, the polymer and oligomer which have oxazolyl, such as Epocurose (brand name, the product made by Nippon Corporation) are mentioned.

As said more preferable oxazoline compound, 2,2'-bis (2-oxazoline) and 1, 3-bis (4, 5- dihydro-2- oxazolyl) benzene are mentioned, for example.

The content rate of the polyamic acid or its derivative in the liquid crystal aligning agent of this invention can also be selected by the coating method to the board | substrate of a liquid crystal aligning agent. For example, if it is a liquid crystal aligning agent used in the printing machine (including an offset machine and an inkjet printing machine which may be abbreviated as "printer" hereafter) which can be used in the manufacturing process of a normal liquid crystal display element, a polyamic acid or its It is preferable that it is 0.5-30 weight%, and, as for the content rate of a derivative, it is more preferable that it is 1-15 weight%, but it adjusts suitably in relationship with the viscosity (it demonstrates later) of a liquid crystal aligning agent.

The viscosity of the liquid crystal aligning agent of this invention is various in accordance with the method of apply | coating, the density | concentration of a polyamic acid or its derivative, the kind of polyamic acid or its derivatives used, and the kind and ratio of a solvent. For example, in the case of application | coating by a printing machine, it is preferable that it is 5-100 mPa * s, and, as for the viscosity of a liquid crystal aligning agent, it is more preferable that it is 10-80 mPa * s. When the viscosity of the liquid crystal aligning agent is smaller than 5 mPa · s, it becomes difficult to obtain a sufficient film thickness of the liquid crystal alignment film, and when it exceeds 100 mPa · s, printing unevenness may increase. In the case of application | coating by spin coating, it is preferable that it is 5-200 mPa * s, and, as for the viscosity of a liquid crystal aligning agent, it is more preferable that it is 10-100 mPa * s.

The viscosity of a liquid crystal aligning agent is measured by the rotational viscometry method, for example, it is measured using a rotational viscometer (The TVK-20L type | made by the Tokiko Corporation) (measurement temperature: 25 degreeC).

The liquid crystal aligning film of this invention is formed by baking the film of the liquid crystal aligning agent of this invention mentioned above. Formation and baking of the film of a liquid crystal aligning agent can be performed by the conventional method in a photoresist.

The said liquid crystal aligning film apply | coats the liquid crystal aligning agent of this invention to the board | substrate for liquid crystal display elements, or the measurement board | substrates, such as calcium fluoride and silicon, for example, and makes the film of this liquid crystal aligning agent 150-400 degreeC, Preferably, it can form by heating at 180-280 degreeC. It is preferable that it is 10-300 nm, and, as for the film thickness of a liquid crystal aligning film here, it is more preferable that it is 30-100 nm. Moreover, when the liquid crystal aligning film is a use of the liquid crystal display element of the transverse electric field system like an IPS type liquid crystal display element, it is preferable that it is rubbing.

The film thickness of the said liquid crystal aligning film can be adjusted with the viscosity of a liquid crystal aligning agent, and the coating method of a liquid crystal aligning agent. Moreover, the film thickness of a liquid crystal aligning film can be measured by well-known film thickness measuring devices, such as a stepmeter and an ellipsometer. In addition, the component in a liquid crystal aligning film can perform a process of hydrolysis etc. as needed, and can analyze using ordinary analysis means, such as IR and MS. For example, IR analysis of oxazine compounds in a film formed by imidating a polyamic acid is performed using "Performance improvement of polybenzoxazine by alloying with polyimide: effect of preparation method on the properties" (Tsutomu Takeichi et al., Polymer , 2005, 46, p. 4909-4916.

The liquid crystal display element of this invention opposes each of the pair of board | substrates arrange | positioned, the electrode formed in one or both of the opposing surfaces of each of the said pair of board | substrates, and each of said pair of board | substrates. It has the liquid crystal aligning film of this invention formed in the surface which exists, and the liquid crystal layer formed between the said pair of board | substrates.

It is preferable that the pair of substrates with electrodes arranged opposite to each other be a transparent substrate (for example, a glass substrate).

Electrodes are provided on the surfaces of at least one or both substrates of the pair of substrates corresponding to the shape of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one side of the substrate. As such an electrode, ITO, a vapor deposition film of a metal, etc. are mentioned, for example. The electrode may be formed in the whole surface of a board | substrate, for example, may be formed in the predetermined shape patterned. In addition, the electrodes may be provided only in one direction of the pair of substrates, or may be provided at both sides. For example, the liquid crystal aligning film of this invention is formed in the board | substrate with which an electrode is not provided, and the liquid crystal aligning film of this invention is formed on the electrode in the board | substrate with which an electrode is provided. Formation of the liquid crystal aligning film of this invention is as above-mentioned.

The liquid crystal layer interposed between the pair of substrates includes a liquid crystal composition. The liquid crystal composition is not particularly limited herein, and either of the liquid crystal composition having a positive dielectric anisotropy and the liquid crystal composition having a negative dielectric anisotropy can be used corresponding to the driving mode.

Examples of preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, Japanese Patent Application Laid-Open No. 8-157826, and Japanese Patent Application Laid-Open No. 8-231960. JP 9-241644 A (EP 885272 A1), JP 9-302346 A (EP 806466 A1), JP 8-199168 A (EP 722998 A1), JP 9-241 A 235552, Japanese Patent Laid-Open No. 9-255956, Japanese Patent Laid-Open No. 9-241643 (EP 885271 A1), Japanese Patent Laid-Open No. 10-204016 (EP 844229 A1), Japanese Patent Laid-Open No. 10-204436, Japanese Patent Laid-Open No. 10-231482, Japanese Patent Laid-Open No. 2000-087040, and Japanese Patent Laid-Open No. 2001-48822 are disclosed.

The liquid crystal composition which can be used in VA type liquid crystal display element can be set as the various liquid crystal composition whose dielectric anisotropy is negative. Examples of preferred liquid crystal compositions include Japanese Patent Application Laid-Open No. 57-114532, Japanese Patent Application Laid-Open No. 2-4725, Japanese Patent Application Laid-Open No. 4-224885, Japanese Patent Application Laid-Open No. 8-40953, and Japanese Patent Application Laid-Open No. 8-104869. JP-A-10-168076, JP-A-10-168453, JP-A 10-236989, JP-A 10-236990, JP-A 10-236992, JP-A 10-236993, Japanese Patent Laid-Open No. 10-236994, Japanese Patent Laid-Open No. 10-237000, Japanese Patent Laid-Open No. 10-237004, Japanese Patent Laid-Open No. 10-237024, Japanese Patent Laid-Open No. 10-237035 Japanese Patent Laid-Open Publication No. 10-237075, Japanese Patent Laid-Open Publication No. 10-237076, Japanese Patent Laid-Open Publication No. 10-237448 (EP 967261 A1), Japanese Patent Laid-Open Publication No. 10-287874, Japanese Patent Laid-Open Publication No. 10-287875 JP-A-10-291945, JP-A-11-029581, JP-A-11-080049, JP-A 2000-256307, It is disclosed, etc. The JP-A No. 2001-019965, Japanese Patent Application 2001-072626 discloses, Japanese Patent Laid-Open 2001-192657 discloses.

One or more optically active compounds may be added to the liquid crystal composition having the dielectric anisotropy positive or negative.

Of course, the liquid crystal display element of this invention may have another member.

For example, in the TFT-type liquid crystal device of color display using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, etc. are formed on a 1st transparent substrate, and on a 2nd transparent substrate And a black matrix, a color filter, a planarization film, a pixel electrode, and the like, which block light other than the pixel region.

Moreover, in VA type liquid crystal display element, especially MVA type liquid crystal display element, the minute protrusion called a domain is formed on the 1st transparent substrate. Moreover, the spacer may be formed for adjustment of the cell gap between board | substrates.

The liquid crystal display device of the present invention can be manufactured by any method, for example, 1) a step of applying a liquid crystal aligning agent on the two transparent substrates, 2) a step of drying the applied liquid crystal aligning agent, 3 ) The process of heat-processing necessary for dehydration and ring-closure reaction of the dried liquid crystal aligning agent, 4) The process of orientation-processing the obtained liquid crystal aligning film, 5) After bonding two board | substrates together, a liquid crystal composition is put in and sealed between board | substrates. It is manufactured by the method containing the process or the process of sticking with the other board | substrate after dripping a liquid crystal composition on one board | substrate.

As a coating method in the process of apply | coating the said liquid crystal aligning agent, the spinner method, the printing method, the dipping method, the dropping method, the inkjet method, etc. are generally known. Such a method is also applicable to the present invention.

Moreover, as a method of the heat processing required for the said drying process and dehydration reaction, the method of heat processing in oven or infrared furnace, the method of heat processing on a hotplate, etc. are generally known. Such a method is also applicable to the present invention. It is preferable to perform a drying process at comparatively low temperature (50-140 degreeC) in the range which can evaporate a solvent. It is preferable to perform the process of heat processing at the temperature of about 150-300 degreeC generally.

Orientation processing with respect to a liquid crystal aligning film performs a rubbing process normally in an IPS type liquid crystal display element, an OCB type liquid crystal display element, a TN type liquid crystal display element, and an STN type liquid crystal display element. Although many rubbing processes are not performed in VA type liquid crystal display elements, they can also be performed.

Subsequently, an adhesive agent is apply | coated and stuck on one board | substrate, and a liquid crystal is inject | poured in a vacuum. In the dropping injection method, the liquid crystal composition is dropped onto the substrate before being glued to each other, and then attached to the other substrate. The liquid crystal display element of this invention is manufactured by hardening the adhesive agent used for bonding mutually with heat or an ultraviolet-ray.

In the liquid crystal display element of this invention, a polarizing plate (polarizing film), a wave plate, a light scattering film, a drive circuit, etc. may be mounted.

EXAMPLE

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compound used in the Example is as follows.

<Tetracarboxylic acid dianhydride>

Compound: pyromellitic dianhydride: PMDA

Compound: 1,2,3,4-cyclobutane tracarboxylic acid dianhydride: CBDA

<Diamine>

Compound: 4,4'-diamino diphenylmethane: DDM

Compound: 4,4'-diaminodiphenylethane: DDET

Compound: 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (trans-4-n-pentylcyclohexyl) cyclohexane: 5HHBA

Compound: 1,1-bis [4- (4-aminophenolshi) phenyl] -4-[(4-n-heptylcyclohexyl) ethyl] cyclohexane: 7H2HBA

Compound: 1,1-bis [4- (4-aminophenylmethyl) phenyl] -4-n-heptylcyclohexane: 7HBZ

Compound: 1,3-bis [4- (4-aminophenylmethyl) phenyl] propane: BABZP3

Compound: 2,2-bis [4- (4-aminophenoxy) phenyl] propane: BAPP

Compound: 1-phenylmethyl-2,5-diamino benzene: 2,5-P1PDA

Compound: 1-phenylmethyl-3,5-diamino benzene: 3,5-P1PDA

Compound: 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethyl-1,3-diaminobenzene: 5HHP1PDA

Compound: 5- {[4- (4-n-heptylcyclohexyl) ethyl] cyclohexyl} phenylmethyl-1,3-diaminobenzene: 7H2HP1PDA

Compound: 5- [4- (n-hexadecyl) phenylmethyl] -1,3-diaminobenzene: 16P1PDA

Compound: 3,3'-diaminodiphenyl ether: 3,3'-DDE

Compound: 3,4'-diaminodiphenyl ether: 3,4'-DDE

Compound: 4,4'-diaminodiphenyl ether: 4,4'-DDE

<Epoxy compound>

Compound: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane: TGDDM

Compound: Bisphenol A novolak-type epoxy compound: 157S70 (brand name, the product made by Japan Epoxy Resin Co., Ltd., an epoxy compound which has an epoxy group with more than 1 functional group)

Compound: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate: Celoxide 2021P (brand name, the product made by Daicel)

Compound: Cresol novolak-type epoxy compound: EOCN-104S (trade name, product of Japan Chemical Co., Ltd., epoxy compound having an epoxy group of two or more functional groups)

<solvent>

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

<One. Synthesis of Polyamic Acid>

Synthesis Example 1

DDM 2.426g and dehydration NMP 54.0g were put into a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, and the mixture was dissolved by stirring under a dry nitrogen stream. Subsequently, 1.735 g of PMDA, 0.840 g of CBDA, and 15.0 g of dehydrated GBL were added thereto and allowed to react for 30 hours in a room temperature environment. When reaction temperature rose during reaction, reaction temperature was suppressed to about 70 degreeC or less, and it was made to react. BC 25.0g was added to the obtained solution, and the polyamic-acid solution whose density | concentration is 6 weight% was obtained. This polyamic acid solution is called PA1.

Synthesis Examples 2 to 19

As shown in Table 1, except having changed tetracarboxylic dianhydride and diamine, polyamic-acid solution PA2-PA19 was prepared according to the synthesis example 1. Table 1 summarizes the results including Synthesis Example 1.

TABLE 1

<2. Manufacturing of Liquid Crystal Display Elements>

Comparative Example 1

PA1 and PA2 were mixed at a weight ratio of 8/2. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of a polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured as follows.

<Method for Manufacturing Liquid Crystal Display Element (Examples 1 to 12, Comparative Examples 1 to 13)>

The liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes with the spinner, and the film | membrane with a film thickness of 70 nm was formed. After heating and drying at 80 degreeC for about 5 minutes after coating film, it heat-processed at 210 degreeC for 20 minutes, and formed the liquid crystal aligning film. Next, the surface of the board | substrate with which the liquid crystal aligning film was formed was rubbed with the rubbing device, and the alignment process was performed. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C. for 30 minutes.

After spread | dispersing a 7 micrometers gap material on one glass substrate, the surface in which the liquid crystal aligning film was formed, and facing it so that a rubbing direction may become antiparallel, sealed with an epoxy hardening | curing agent, and the antiparallel cell of a gap of 7 micrometers Prepared. The liquid crystal composition shown below was injected to the said cell, and the injection hole was sealed with the photocuring agent. Next, heat processing was performed at 110 degreeC for 30 minutes, and the liquid crystal display element was manufactured.

Example 1

20 weight part of TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 1 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 2

20 weight part of 157S70 was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 1 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 2

PA1 and PA3 were mixed at a weight ratio of 8/2. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 3

20 weight part of TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 2 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 4

In the 4 weight% liquid crystal aligning agent obtained by the comparative example 2, 20 weight part of celloxide 2021P was dissolved with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 3

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA4, and the whole was diluted so that the density | concentration of a polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 5

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 3 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 6

EOCN-104S was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 3 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

[Comparative Example 4]

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA5, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 7

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 4 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 8

EOCN-104S was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 4 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

[Comparative Example 5]

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA6, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 9

20 weight part of TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 5 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 10

EOCN-104S was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 5 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 6

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA7, and the whole was diluted so that the density | concentration of a polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 11

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 6 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 7

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA8, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Example 12

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 7, with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 8

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA9, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 9

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 8 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 10

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA10, and the whole was diluted so that the density | concentration of a polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 11

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 10 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured as follows.

Comparative Example 12

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA11, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. The liquid crystal display element was manufactured as mentioned above using the obtained liquid crystal aligning agent.

Comparative Example 13

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 12 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured as follows.

Comparative Example 14

PA6 and PA12 were mixed at a weight ratio of 9/1. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured as follows.

<Method for Manufacturing Liquid Crystal Display Element (Examples 13 to 20, Comparative Examples 14 to 21)>

The liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes with the spinner, and the film | membrane with a film thickness of 70 nm was formed. After heating and drying at 80 degreeC for about 5 minutes after coating film, it heat-processed at 210 degreeC for 20 minutes, and formed the liquid crystal aligning film. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C. for 30 minutes.

After spread | dispersing the gap material of 4 micrometers to one glass substrate, and arrange | positioned the surface which formed the liquid crystal aligning film inside, it sealed with the epoxy hardening | curing agent, and produced the cell of gap 4 micrometers. The liquid crystal composition shown below was injected to the said cell, and the injection hole was sealed with the photocuring agent. Next, heat processing was performed at 110 degreeC for 30 minutes, and the liquid crystal display element was manufactured.

Example 13

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 14 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 10.

Comparative Example 15

PA6 and PA13 were mixed at a weight ratio of 9/1. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Example 14

20 weight part of TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 15 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

[Comparative Example 16]

PA6 and PA14 were mixed in a weight ratio of 9/1. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Example 15

20 weight part of 157S70 was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 16 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

[Comparative Example 17]

PA15 and PA16 were mixed at a weight ratio of 9/1. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Example 16

20 weight part of TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 17 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Example 17

In the 4 weight% liquid crystal aligning agent obtained by the comparative example 17, 20 weight part of celloxide 2021P was melt | dissolved with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

[Comparative Example 18]

PA15 and PA17 were mixed in a weight ratio of 9/1. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Example 18

20 weight part of EOCN-104S was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 18 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Comparative Example 19

The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to PA18, and the whole was diluted so that the density | concentration of a polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Example 19

20 weight part of TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 19 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Example 20

EOCN-104S was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 19 with respect to 100 weight part of polyamic acid, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

[Comparative Example 20]

PA15 and PA19 were mixed at a weight ratio of 9/1. The mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted so that the density | concentration of polyamic acid might be 4 weight%, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

Comparative Example 21

TGDDM was melt | dissolved in the 4 weight% liquid crystal aligning agent obtained by the comparative example 20 with respect to 100 weight part of polyamic acids, and the liquid crystal aligning agent was obtained. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like the comparative example 14.

<3. Evaluation of Electrical Characteristics>

About the liquid crystal display element manufactured in Examples 1-20 and Comparative Examples 1-21, the measurement of ion density and the measurement of long-term reliability were performed as follows.

1) Measurement of ion density

The ion density was measured using the Toyo Technica made liquid crystal physical property evaluation apparatus 6254 type. Measurement conditions were waveform: triangle wave, frequency: 0.01 Hz, voltage: ± 10 V, and the measurement temperature was 60 ° C. The smaller this value, the better the electrical characteristics. The results are shown in Table 2 and Table 3.

2) Measurement of Retention Characteristics of Ion Density

About the produced liquid crystal display element, ion density [pC] was calculated | required over time and its retention characteristic was evaluated. As a test method of a retention characteristic, the method of leaving a liquid crystal display element in the atmosphere of temperature 100 degreeC, taking it out over time and measuring ion density [pC] was employ | adopted. It can be said that the smaller the value of the ion density after 200 hours is, the better the retention property of the ion density is, and the longer term reliability of the electrical property is. Data after 100 hours and after 200 hours are shown in Tables 2 and 3.

TABLE 2

TABLE 3

As shown in Table 2 and Table 3, with the liquid crystal display element using the liquid crystal aligning agent of Examples 1-20 which added the epoxy compound, the increase of ion density over time could be suppressed.

<4. Evaluation of Orientation Characteristics

In the liquid crystal display elements manufactured in Examples 1,3,5,7,9,11,12 and Comparative Examples 1-13, the said element before heat processing after injecting a liquid crystal composition is joined to two deflection plates, and the backlight Were aligned, the alignment state of the liquid crystal was observed, and evaluated by the presence or absence of the flow orientation. It can be said that there is no flow orientation, and orientation property is favorable. The results are shown in Table 4.

TABLE 4

Test Example Number Liquid crystal aligning agent Flow orientation 42 Comparative Example 1 radish 43 Example 1 radish 44 Comparative Example 2 radish 45 Example 3 radish 46 Comparative Example 3 radish 47 Example 5 radish 48 Comparative Example 4 radish 49 Example 7 radish 50 Comparative Example 5 radish 51 Example 9 radish 52 Comparative Example 6 radish 53 Example 11 radish 54 Comparative Example 7 radish 55 Example 12 radish 56 Comparative Example 8 radish 57 Comparative Example 9 U 58 Comparative Example 10 radish 59 Comparative Example 11 U 60 Comparative Example 12 radish 61 Comparative Example 13 U

As shown in Table 4, the liquid crystal aligning agent which added the epoxy compound developed this time cannot confirm a flow orientation even if an epoxy compound is added, and can maintain high orientation.

Claims (23)

As a liquid crystal aligning agent containing the polyamic acid which is a reaction product of diamine and tetracarboxylic dianhydride, or its derivative (s), and the epoxy compound which has an epoxy group with an average number of functional groups more than one, The diamine includes a diamine represented by the following general formula (I):

(In General Formula (I), X ¹ and X ² each represent —O— or —CH ₂ —, and Y ¹ represents —H, the following structural formula (II-1), general formula (II-2), Or 4-substituted-1 represented by general formula (II-3), Z ¹ is alkylene having 1 to 12 carbon atoms which may have methyl, and represented by the following general formula (III-1) or (III-2): , 1-cyclohexylene, m, n, and p each represent 0 or 1, Provided that m + n + p is 0, 1, or 3, When m + n + p is 0, Y ¹ represents general formula (II-1), (II-2), or (II-3), is 1 when m + n + p, m and n represents 0, and X ² represents -O-, and X ² is an amino-phenylamino which is coupled with respect to the X ² bonded to the meta position, When m + n + p is 3, X ¹ and X ² each represent -O- or -CH _2- , Y ¹ represents -H, and Z ¹ has 1 to 12 carbon atoms which may have methyl. Alkylene of the above or 4-substituted-1,1-cyclohexylene represented by the general formula (III-1) or (III-2):

(In General Formulas (II-2) and (II-3), Y ² and Y ³ each represent alkyl having 1 to 30 carbon atoms.)

(In formula (III-1) and (III-2), Y ⁴ and Y ⁵ each represent alkyl having 1 to 30 carbon atoms). The method of claim 1, The diamine is represented by formula (I), m + n + p is a 3, X ¹ and X ² are each -O- or -CH ₂ - represents a, Y ¹ represents -H, also Z ¹ Is a diamine which represents 4-substituted-1,1-cyclohexylene represented by said general formula (III-1) or (III-2), The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 2, The diamine represented by general formula (I) is one or both of the diamines of the following structural formulas A1 and A2:

The method according to claim 2 or 3, The diamine further comprises at least one of the following diamines of the formulas (VIII-3), (VIII-7), and (VIII-31), wherein the tetracarboxylic dianhydride is represented by the following formulas (1) and (14) Liquid crystal aligning agent, characterized in that one or both:

The method of claim 1, The diamine is represented by formula (I), m + n + p is a 3, X ¹ and X ² are each -O- or -CH ₂ - represents a, Y ¹ represents -H, also Z ¹ Silver is a diamine which represents a C1-C12 alkylene which may have methyl, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 5, The diamine represented by the general formula (I) is a diamine in which X ¹ and X ² each represent -CH ₂ -and Z ¹ represents an alkylene having 1 to 10 carbon atoms which may have methyl. Liquid crystal aligning agent. The method of claim 6, The diamine represented by said general formula (I) is the diamine of following structural formula B1, The liquid crystal aligning agent characterized by the above-mentioned:

The method according to any one of claims 5 to 7, Wherein said diamine further comprises a diamine of the following structural formula (VIII-13), wherein said tetracarboxylic dianhydride is one or both of the following structural formulas (1) and (14):

The method of claim 1, The diamine represented by the said general formula (I) is m + n + p is 0, and Y <^1> is the diamine which represents the said general formula (II-1), (II-2), or (II-3). A liquid crystal aligning agent characterized by the above-mentioned. The method of claim 9, The diamine represented by the general formula (I) is a diamine wherein Y ² and Y ³ in the general formulas (II-2) and (II-3) represent alkyl having 1 to 20 carbon atoms, respectively. Positive alignment agent. The method of claim 9 or 10, The diamine represented by the said general formula (I) is at least one chosen from the diamine of following structural formula C1-C4, The liquid crystal aligning agent characterized by the above-mentioned:

The method of claim 9, The diamine further comprises one or both of the diamines of the following structural formulas (VIII-1) and (VIII-7), wherein the tetracarboxylic dianhydride is one or both of the following structural formulas (1) and (14) Characteristic liquid crystal aligning agent:

The method of claim 1, In the diamine represented by the general formula (I), m + n + p is 1, m and n are 0, X ² represents -O-, and the amino of the aminophenyl to which X ² is bonded is X ^2. It is a diamine couple | bonded with a meta position with respect to, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 13, The diamine represented by the general formula (I) is one or both of the diamines of the following structural formulas D1 and D2:

The method according to claim 13 or 14, Said tetracarboxylic dianhydride is one or both of the following structural formulas (1) and (14):

The method of claim 1, The diamine, the general formula (I), and m + n + p is 3 in, X ¹ and X ² are each -O- or -CH ₂ - represents a, Y ¹ represents a -H, also Z ¹ A liquid crystal aligning agent containing diamine which shows the C1-C12 alkylene which may have this methyl, and one or more selected from the following four types of diamines: (1) m + n + p in the general formula (I) is 3, X ¹ and X ² each represent -O- or -CH _2- , Y ¹ represents -H, and Z ¹ is Diamine which represents 4-substituted-1,1-cyclohexylene represented by said general formula (III-1) or (III-2), (2) diamine in which m + n + p in said general formula (I) is 0, Y <^1> represents the said general formula (II-1), (II-2), or (II-3), 3, in the general formula and m + n + p is 1 in the (I), m and n is 0, and X ² represents an -O-, X ² is an amino-phenyl-amino is bonded to X ² of A diamine bound to a meta position relative to, and (4) a diamine in which m + n + p in formula (I) is 0 and Y ¹ is formula (II-4):

(In general formula (II-4), Y ⁶ represents alkyl having 1 to 30 carbon atoms.). The method of claim 16, The diamine represented by the said general formula (I) contains the diamine of following structural formula B1, and the 1 or more selected from the following 4 types of diamines, The liquid crystal aligning agent characterized by the above-mentioned: (1) the diamine represented by the following structural formula A1 or A2, (2) a diamine represented by the following structural formula C1 or C2, (3) a diamine represented by the following structural formula D1 or D2, and (4) diamine of the following structural formula (XI-47):

The method of claim 1, A liquid crystal aligning agent containing 2 or more types of polyamic acid or its derivative (s). The method of claim 18, M + n + p in the general formula (I) is 3, X ¹ and X ² each represent -O- or -CH _2- , Y ¹ represents -H, and Z ¹ has methyl A liquid crystal comprising a polyamic acid or a derivative thereof, which is a reaction product of a diamine and tetracarboxylic dianhydride, which may represent alkylene having 1 to 12 carbon atoms, and one or both of the following three types of polyamic acid or a derivative thereof. Alignment agent: (1) m + n + p in the general formula (I) is 3, X ¹ and X ² each represent -O- or -CH _2- , Y ¹ represents -H, and Z ¹ is Polyamic acid or a derivative thereof, which is a reaction product of diamine and tetracarboxylic dianhydride represented by 4-substituted-1,1-cyclohexylene represented by the general formula (III-1) or (III-2); (2) Diamine and tetracarboxylic acid in which m + n + p in the general formula (I) is 0, and Y ¹ represents the general formula (II-1), (II-2), or (II-3). Polyamic acid or a derivative thereof which is a reaction product of a dianhydride, and 3 in the formula is a m + n + p is 1 in the (I), m and n are 0, and X ² represents -O-, X ² is an amino-phenyl-amino is bonded to X ² The polyamic acid or its derivative which is a reaction product of diamine and tetracarboxylic dianhydride couple | bonded with the meta position with respect to it. The method of claim 1, Glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound Liquid crystal aligning agent which is one or more selected from the group which consists of. The method of claim 20, The epoxy compound is N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [ 4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, N-phenylmaleimide- Liquid crystal orientation characterized in that it is at least one selected from glycidyl methacrylate copolymer, bisphenol A novolak type epoxy compound, cresol novolak type epoxy compound, and N, N, O-triglycidyl-p-aminophenol. My. The liquid crystal aligning film formed by baking the film of the liquid crystal aligning agent in any one of Claims 1-21. A pair of substrates arranged oppositely, an electrode formed on one or both of the opposing surfaces of each of the pair of substrates, a liquid crystal alignment film formed on the opposing surfaces of each of the pair of substrates, and In the liquid crystal display device having a liquid crystal layer formed between the pair of substrates, The said liquid crystal aligning film is a liquid crystal aligning film of Claim 22, The liquid crystal display element characterized by the above-mentioned.