TWI458754B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent containing polyglycine or a derivative thereof, a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film.

The liquid crystal display element is used for various liquid crystal displays such as a viewfinder and a projection display of a video camera represented by a note personal computer or a desktop personal computer. In the device, it has recently been used in television. Further, the liquid crystal display element is also used in an optoelectronic related element such as an optical printer head, an optical Fourier transform device, or a light valve.

Various components are known for liquid crystal display elements, but the technical development of liquid crystal display elements can be achieved not only by the driving method of the liquid crystal display element or the structure of the liquid crystal display element, but also by the composition used in the liquid crystal display element. The components are improved to achieve. In general, a liquid crystal display element has a liquid crystal alignment film for aligning a liquid crystal composition in a liquid crystal layer in a specific direction. The liquid crystal alignment film is an important factor related to the display quality of the liquid crystal display element, and the function of the liquid crystal alignment film becomes important year by year as the quality of the liquid crystal display element is improved.

The liquid crystal alignment film is prepared from a liquid crystal alignment agent. At present, the main liquid crystal alignment agent used is polylysine or soluble polyimine. (polyimide) A solution obtained by dissolving in an organic solvent. After such a solution is applied onto a substrate, film formation is performed by a method such as heating to form a liquid crystal alignment film.

Regarding a liquid crystal alignment film, for example, a liquid crystal alignment film using diamine tetraacetic acid dianhydride is known, and the liquid crystal alignment film is disclosed to improve a Super Twisted Nematic (STN) mode, an active matrix display. The voltage holding ratio in (refer to the specification of US Pat. No. 5,520,845).

Further, a method of improving crosstalk by using a liquid crystal alignment film of ethylenediaminetetraacetic acid dianhydride has been disclosed (refer to Japanese Laid-Open Patent Publication No. Hei 6-75229).

Further, a liquid crystal alignment film using a copolymer of a polymer material having a photoreactive group bonded to an acid anhydride in ethylenediaminetetraacetic acid dianhydride is disclosed (refer to Japanese Laid-Open Patent Publication No. 2006-350347).

As a parameter governing the electro-optic property of the liquid crystal display element, a retardation (R) of the liquid crystal alignment film can be cited. The higher the value of the retardation (R), the higher the uniaxial alignment property of the liquid crystal alignment film, and the black display of the liquid crystal display element becomes good. For this reason, a technique of using a liquid crystal alignment film having a high uniaxial alignment property to more uniformly align liquid crystal molecules in a liquid crystal display element to enhance black display characteristics has been known (Japanese Patent Laid-Open Publication No. Hei No. 2005-258397). Further, as one type of display failure of the liquid crystal panel which is produced in the manufacturing process of the liquid crystal panel, a phenomenon in which liquid crystal molecules are fixed in the flow direction at the time of injection when liquid crystal molecules are injected into the liquid crystal panel is known. That is, the flow alignment, but as a liquid crystal display element, it is required not to generate a flow alignment.

However, there is a need for a technique for further improving characteristics relating to retardation and flow alignment of liquid crystal display elements.

The present invention provides a liquid crystal display element having excellent performance in retardation and flow alignment, a liquid crystal alignment film which achieves the above-described characteristics in the liquid crystal display element, and a liquid crystal alignment agent which can form the liquid crystal alignment film.

The present inventors have found that a composition containing polyamic acid or a derivative thereof using a specific tetracarboxylic dianhydride and a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride as a raw material is used for The liquid crystal alignment element having the liquid crystal alignment film formed by the liquid crystal alignment agent has a desired property, thereby completing the present invention.

The present invention includes the following constitutions.

[1] A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent characterized in that the tetracarboxylic acid The dianhydride contains one or more kinds of tetracarboxylic dianhydride represented by the following general formula (TC-1) to (TC-14), and one or more kinds of other tetracarboxylic dianhydrides.

(In the formula (TC-1), X represents -(CH ₂ ) _m -, and two or less -CH ₂ - may be independently -O- (but not continuous), -S-, -COO -, -OCO-, -CO-, -CONH-, -C _n H _2n N(C _m H _2m COOH)C _n H _2n -, -CH(C _m H _2m OH)-, -CH(C _n H _2n+1 )-, -CH=CH- or -C≡C- is substituted (m independently represents an integer from 0 to 30, and n independently represents an integer from 1 to 30). Formula (TC-4)~ In the formula (TC-7), Y independently represents a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -NH-, -N (CH ₃ )-(CH ₂ ) _m -N(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH _{2 m} -O-, -S-(CH ₂ ) _m -S- (m represents an integer of 1 to 6). In the formula (TC-5), Z represents a single bond or does not exist. In the general formula (TC-7), the hydrogen bonded to the cyclohexane ring or the benzene ring is independent and can be -F, -CH ₃ , -CF ₃ , -OH, - Substituting COOH, -SO ₃ H, -PO ₃ H ₂ , the hydrogen bonded to the benzene ring in the formula (TC-3) may be substituted by benzyl. General formula (TC-2)~ in the general formula (TC-8), R ¹ independently represents - (CH _{2) m} -, or both of the following two -CH ₂ - may independently be -O- (but not even ), - S -, - COO -, - OCO -, - CO -, - CONH -, - CH (C m H 2m OH) -, - CH (C m H 2m + 1) -, - CH = CH- Or -C≡C- is substituted (m independently represents an integer of 0 to 30). In the formula (TC-8), A ^{1 is} independently an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. Alkoxy, acetamide, fluorine, chlorine or bromine, A ² independently represents an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 3, and n represents an integer of 0 to 4. In (TC-9), R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and A ³ independently represents a methylene group or a phenylene group or a subphenyl group substituted with an alkyl group, wherein l represents an integer of 1 to 6, and m represents an integer of 1 to 10. In the formula (TC-10), A ³ represents a single bond, -O-, -COO-, -OCO -, -CO-, -CONH- or -(CH ₂ ) _m - (m represents an integer of 1 to 6), and R ¹ represents a group having a steroid skeleton or a group represented by the following formula (B) When the positional relationship of two amino groups bonded to the benzene ring is para, R ¹ further contains an alkyl group having 1 to 30 carbon atoms, and when its positional relationship is meta, R ¹ further contains carbon. a number of 1 to 30 alkyl or phenyl, in the alkyl, any -CH ₂ - may be independently _{-CF 2 -, - CHF -,} - O- ( but not continuously), - CH = CH- or -C≡C- substituted, -CH ₃ may be -CH ₂ F, Substituted by -CHF ₂ or -CF ₃ , the hydrogen of the phenyl group is independently and may be substituted by -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ .

In the general formula (B), A ⁴ and A ⁵ each independently represent a single bond, -O- (but not continuous), -COO-, -OCO-, -CONH-, -CH=CH- or a carbon number of 1~. 12 alkylene, R ² and R ³ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexene (1,4- Cyclohexylene), 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine -1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluorene-9,10- Anthracene-9,10-diyl, R ⁴ represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, and an alkyl group having 1 to 30 carbon atoms. Oxy, -C≡N, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , a and b represent integers from 0 to 4, respectively, c, d and e represent integers from 0 to 3, respectively, and f and g are independent The ground represents an integer from 0 to 2, and c+d+e≧1. In the formula (TC-11) and the formula (TC-12), R ⁵ independently represents -H or -CH ₃ , R ⁶ represents -H, or an alkyl group having 1 to 20 carbon atoms or a carbon number of 2 to 20 Alkenyl, A ⁶ independently represents a single bond, -CO- or -CH ₂ -. In the formula (TC-12), R ⁷ and R ⁸ each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group. In the formula (TC-13) and the formula (TC-14), A ⁷ independently represents -O- or an alkenyl group having 1 to 6 carbon atoms. In the formula (TC-13), R ⁹ represents -H or an alkyl group having 1 to 30 carbon atoms, and in the alkyl group, any -CH ₂ - of the alkyl group having 2 to 30 carbon atoms may be -O-( But discontinuous), -CH=CH- or -C≡C- is substituted, A ⁸ represents a single bond or an alkylene group having 1 to 3 carbon atoms, and ring T represents a 1,4-phenylene group or 1,4- Cyclohexene, h represents 0 or 1. In the formula (TC-14), R ¹⁰ represents an alkyl group having 6 to 22 carbon atoms, and R ¹¹ represents -H or an alkyl group having 1 to 22 carbon atoms.

[2] The liquid crystal alignment agent according to [1], wherein the other tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride.

[3] The liquid crystal alignment agent according to [2], wherein the aromatic tetracarboxylic dianhydride is a structural formula (1), a structural formula (2), and a structural formula (5) to a structural formula (7) At least one of the compounds represented by the structural formula (10), the structural formula (13) and the structural formula (14).

[4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the tetracarboxylic dianhydride comprises an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. One or both of them.

[5] The liquid crystal alignment agent according to [4], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the following structural formula (15), structural formula (16) At least one of the compounds represented by Structural Formula (21) to Structural Formula (25) and Structural Formula (29) to Structural Formula (31).

[6] The liquid crystal alignment agent according to any one of [1] to [5] wherein the diamine further comprises a side represented by the following general formula (I) and formula (II) One or more of the diamines of the chain structure.

(In the general formula (I) and the general formula (II), A ⁹ independently represents -O- or an alkylene group having 1 to 6 carbon atoms, and in the general formula (I), R ¹² represents -H or a carbon number of 1~. An alkyl group of 30, wherein any -CH ₂ - of the alkyl group having 2 to 30 carbon atoms may be substituted by -O- (but not continuous), -CH=CH- or -C≡C-. A ¹⁰ represents a single bond or an alkenyl group having 1 to 3 carbon atoms, a ring T represents a 1,4-phenylene group or a 1,4-cyclohexene, h represents 0 or 1, and in the formula (II), R ¹⁵ It represents an alkyl group having 6 to 22 carbon atoms, and R ¹⁶ represents an alkyl group having 1 to 22 carbon atoms.

[7] The liquid crystal alignment agent according to [6], wherein the diamine having a side chain structure is selected from the group consisting of the following general formula (I-1), general formula (I-2), and general formula At least one of (I-4) and a compound represented by the formula (I-7).

(In the above formula, R ¹³ and R ¹⁴ each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms).

The liquid crystal alignment agent according to any one of [1], wherein the diamine further comprises the following general formula (III) to general formula (X), and general formula (N). And a diamine having no side chain structure represented by the formula (a).

(In the formula (III), X represents -(CH ₂ ) _m - (m represents an integer of 1 to 6), and in the formula (V) and the formula (VII) to the formula (IX), Y independently represents Single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH ₃ )-(CH ₂ ) _m -N (CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH _{2 m} -S-(m represents an integer of 1 to 6), and in the formula (VII), Z represents a single bond or does not exist, and in the formula (X), R ¹⁹ and R ²⁰ each independently represent a carbon number of 1~ An alkyl group or a phenyl group, A ¹¹ independently represents a methylene group, a phenylene group or an alkyl group-substituted subphenyl group. i represents an integer of 1 to 6, and j represents an integer of 1 to 10, and the formula (IV) In the formula (IX), the bond to the cyclohexane ring or the benzene ring may be independently -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , the hydrogen bonded to the benzene ring in the formula (VI) may be substituted by a benzyl group. In the formula (N), A ¹ independently represents an alkyl group having 1 to 4 carbon atoms and a carbon number. The alkoxy group, acetamide, fluorine, chlorine or bromine of 1 to 4, A ² independently represents an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 3, and n represents an integer of 0 to 4. In the general formula (a), L ¹ represents Hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group).

[9] The liquid crystal alignment agent according to [8], wherein the diamine having no side chain structure is selected from the following structural formula (VI-1), structural formula (VI-2), and structure. Formula (VI-15)~Structure Formula (VI-17), Structural Formula (VII-1)~Structure Formula (VII-13), Structural Formula (VII-32), Structural Formula (VII-34)~Structure Formula ( VII-36), structural formula (XI-2), structural formula (X-3), structural formula (N)-1, structural formula (N)-2, structural formula (N)-14, and structural formula (a- 1) at least one of the compounds represented.

[10] The liquid crystal alignment agent according to any one of [6], wherein the poly-proline or a derivative thereof comprises two polyamine acids or derivatives A and B thereof The polyaminic acid or derivative A thereof comprises the diamine One or more of the diamines having a side chain structure represented by the general formula (I) and the general formula (II), and one of the polycarboxylic acid or derivatives of the derivatives A and B of the tetracarboxylic dianhydride or Both of them contain one or more kinds of tetracarboxylic dianhydrides represented by the above formula (TC-1) to formula (TC-14) and other tetracarboxylic dianhydrides.

[11] The liquid crystal alignment agent according to any one of [1], which further comprises a nadic ylidene compound selected from an alkenyl group, having a radical polymerizable unsaturated group. One or more of a compound of a double bond, an oxazine compound, an oxazoline compound, and an epoxy compound.

[12] A liquid crystal alignment film which is formed by heating a coating film of the liquid crystal alignment agent according to any one of [1] to [11].

[13] A liquid crystal display element comprising: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode applying a voltage to the liquid crystal layer; and a liquid crystal alignment film to cause the liquid crystal The molecular alignment is in a predetermined direction; the liquid crystal display element is characterized in that the liquid crystal alignment film is the liquid crystal alignment film according to [12].

According to the present invention, it is possible to provide a liquid crystal display element having a desired property such as retardation and flow alignment in terms of retardation and flow alignment.

The above described features and advantages of the present invention will be more apparent from the following description.

The liquid crystal alignment agent of the present invention contains polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine. The derivative of polylysine is dissolved in a solvent when it is prepared as a liquid crystal alignment agent to be described later containing a solvent. When the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later, it is possible to form a component of a liquid crystal alignment film containing polyimine as a main component. Examples of such a derivative of the polyaminic acid include soluble polyimine, polyamic acid ester, and polyamic acid amide. More specifically, 1) Polyimine which is obtained by dehydration ring-closure reaction of all amino groups of poly-proline and carboxyl group, 2) Partial polyimine which is partially subjected to dehydration ring-closure reaction, and 3) Polyfluorene A polyphthalate obtained by converting a carboxyl group of an amino acid into an ester, and 4) a polylysine obtained by replacing a part of the acid dianhydride contained in the tetracarboxylic dianhydride compound with an organic dicarboxylic acid to carry out a reaction. Further, examples of the polyamide copolymer include 5) a polyamide-imide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyaminic acid or a derivative thereof may be one compound or two or more compounds. Further, the polyamic acid or a derivative thereof may be a compound having a structure of a reaction product of a tetracarboxylic dianhydride and a diamine, and may be a tetracarboxylic dianhydride and a diamine by using another raw material. The reaction product obtained by the reaction other than the reaction.

<1. Tetracarboxylic dianhydride used in the present invention>

The tetracarboxylic dianhydride (hereinafter also referred to simply as acid dianhydride) used in the present invention contains one of tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14) or More than one.

The tetracarboxylic dianhydride represented by the formula (TC-1) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of X is 0 to 20, for example, The acid dianhydride represented by the following structural formula is used.

In the general formula, the number of carbon atoms of the alkenyl group as a main chain of R ¹ is from 0 to 10, and examples thereof include the following structural formula. Indicated acid dianhydride.

The tetracarboxylic dianhydride represented by the formula (TC-3) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of R ¹ is from 0 to 10, and examples thereof include the following structural formula. Indicated acid dianhydride.

The tetracarboxylic dianhydride represented by the formula (TC-4) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of R ¹ is from 0 to 10, and examples thereof include the following structural formula. Indicated acid dianhydride.

In the general formula, the number of carbon atoms of the alkenyl group as a main chain of R ¹ is from 0 to 10, and examples thereof include the following structural formulas. Indicated acid dianhydride.

The tetracarboxylic dianhydride represented by the formula (TC-6) is preferably a compound having a carbon number of from 0 to 10 as a main chain of R ¹ , and examples thereof include the following structural formula. Indicated acid dianhydride.

The tetracarboxylic dianhydride represented by the formula (TC-7) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of R ¹ is from 0 to 10, and examples thereof include the following structural formula. Indicated acid dianhydride.

The tetracarboxylic dianhydride represented by the formula (TC-8) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of R ¹ is from 0 to 10, and examples thereof include the following structural formula. Indicated acid dianhydride.

The tetracarboxylic dianhydride represented by the formula (TC-9) is, for example, an acid dianhydride represented by the following structural formula.

The tetracarboxylic dianhydride represented by the formula (TC-10) may, for example, be an acid dianhydride represented by the following formula or structural formula.

(In the above formula, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms).

The tetracarboxylic dianhydride represented by the formula (TC-11) is, for example, an acid dianhydride represented by the following structural formula.

The tetracarboxylic dianhydride represented by the formula (TC-12) is, for example, an acid dianhydride represented by the following structural formula.

The tetracarboxylic dianhydride represented by the formula (TC-13) is, for example, an acid dianhydride represented by the following formula.

(R ²⁹ represents -H, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms).

The tetracarboxylic dianhydride represented by the formula (TC-14) is, for example, an acid dianhydride represented by the following formula.

(R ²⁹ represents an alkyl group having 6 to 22 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms; R ³⁰ represents an alkyl group having -H or a carbon number of 1 to 22, more preferably -H or a carbon number of 1~ 10 alkyl).

Examples of the other tetracarboxylic dianhydride include acid dianhydride represented by the following formula.

(R ³⁵ and R ³⁶ each independently represent an alkyl group having 3 to 30 carbon atoms).

The tetracarboxylic dianhydride which is particularly suitable for use in the present invention is a tetracarboxylic dianhydride represented by the general formula (TC-1) to the general formula (TC-7), and among them, particularly preferably represented by the following structural formula Carboxylic dianhydride.

In addition, from the viewpoint of exhibiting a desired retardation in the liquid crystal display element and suppressing the flow alignment of the liquid crystal display element, it is preferable that the acid dianhydride of the polyamic acid which constitutes the liquid crystal alignment agent of the present invention contains Mo The ear ratio is from 10% to 99.5%, and the tetracarboxylic dianhydride represented by the above (TC-1) to the above (TC-14), more preferably contains 20% to 95% of the (TC- 1) to the tetracarboxylic dianhydride represented by the above (TC-14).

In the present invention, as the tetracarboxylic dianhydride, in addition to the tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14), other tetracarboxylic acid II is further used. anhydride. Expressed by the above formula (TC-1) to formula (TC-14) The tetracarboxylic dianhydride other than the tetracarboxylic dianhydride shown may be one type or two or more types. From the viewpoint of making the polyproline or the derivative thereof in the present invention into a solvent-soluble form, it is preferably suitably selected from the above formula (TC-1) to formula (TC-14). The tetracarboxylic dianhydride other than the tetracarboxylic dianhydride.

Examples of the tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14) include aromatic tetracarboxylic dianhydride and fat. Group of tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides. Thus, tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14) and tetracarboxylic dianhydride other than the tetracarboxylic dianhydride are used as the liquid crystal alignment agent of the present invention. The raw material of the polyaminic acid or its derivative contained therein, thereby exhibiting an increase in retardation and suppression of flow alignment of the liquid crystal alignment agent.

Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following structural formulae (1) to (14).

The aromatic tetracarboxylic dianhydride preferably has the structural formula (1), the structural formula (2), the structural formula (5) to the structural formula (7), the structural formula (10), the structural formula (13), and the structure. The compound represented by the formula (14) is more preferably pyromellitic dianhydride represented by the above structural formula (1).

Examples of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride include compounds represented by the following structural formulae (15) to (64).

The aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride preferably have the structural formula (15), the structural formula (16), the structural formula (21) to the structural formula (25), and the structural formula (29). a compound represented by the formula (31), more preferably 1,2,3,4-cyclobutane tetracarboxylic dianhydride represented by the formula (15) (1,2,3,4-cyclobutane tetracarboxylic dianhydride) ).

Further, from the viewpoint of making the polyproline or the derivative thereof in the present invention into a solvent-soluble polyimine, the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are preferably used. The structural formula (15) to the structural formula (18), the structural formula (21) to the structural formula (25), the structural formula (28) to the structural formula (30), and the structural formula (44) to the structural formula (47) The compound represented.

Further, the tetracarboxylic dianhydride may also contain a tetracarboxylic dianhydride having a side chain structure. Tetracarboxylic dianhydride having a side chain structure can increase liquid crystal display The pretilt angle in the component. Examples of the tetracarboxylic dianhydride having a side chain structure include compounds having a steroid skeleton represented by the following structural formula (65) and structural formula (66).

The tetracarboxylic dianhydride preferably contains the aromatic tetracarboxylic dianhydride, the aliphatic tetracarboxylic dianhydride, and the alicyclic tetracarboxylic dianhydride from the viewpoint of reducing the residual voltage in the liquid crystal display device. One or both parties.

The tetracarboxylic dianhydride also contains other various forms of tetracarboxylic dianhydride, and is not limited to the tetracarboxylic dianhydride. The tetracarboxylic dianhydride may use other various forms of tetracarboxylic dianhydride within the scope of achieving the object of the present invention.

It is also possible to replace a part of the tetracarboxylic dianhydride with a carboxylic anhydride (carboxylic anhydride). The replacement of a part of the tetracarboxylic dianhydride with a carboxylic acid anhydride causes termination of the polymerization reaction for producing the polyamic acid or a derivative thereof, thereby suppressing further progress of the reaction, and therefore, the polyamine can be easily controlled. It is preferable from the viewpoint of the molecular weight of an acid or a derivative thereof. The ratio of the carboxylic anhydride to the tetracarboxylic dianhydride may be within a range that does not impair the effects of the present invention, and is preferably equal to or less than 10 mol% of the tetracarboxylic dianhydride.

From the viewpoint of increasing the retardation value and suppressing the flow alignment, the acid dianhydride constituting the poly-proline in the liquid crystal alignment agent is represented by the above formula (TC-1) to formula (TC-14). The content of the tetracarboxylic dianhydride other than the tetracarboxylic dianhydride to be expressed is preferably 10% to 90%, more preferably 10% to 80%, still more preferably 30% to 70%, in terms of a molar ratio.

Further, in the acid dianhydride constituting the polyphthalic acid in the liquid crystal alignment agent, the content of the aromatic tetracarboxylic dianhydride is preferably 0% to 80%, more preferably 0% to 60% by mol ratio. % is further preferably 5% to 50%.

<2. Diamine used in the present invention>

As the diamine used in the present invention, a diamine having a side chain structure represented by the following general formulae (I) to (II) (hereinafter also referred to as a side chain type diamine) can be preferably used.

In the formula (I), R ¹² represents -H or an alkyl group having 1 to 30 carbon atoms. In the alkyl group, any -CH ₂ - of the alkyl group having 2 to 30 carbon atoms may be independently substituted by -O-, -CH=CH- or -C≡C-. Wherein -O- is not adjacent in the alkyl group. In the general formula (I) and the general formula (II), A ⁹ independently represents -O- or an alkenyl group having 1 to 6 carbon atoms. In the formula (I), A ¹⁰ represents a single bond or an alkenyl group having 1 to 3 carbon atoms. Ring T represents 1,4-phenylene or 1,4-cyclohexene. h means 0 or 1. In the formula (II), R ¹⁵ represents an alkyl group having 6 to 22 carbon atoms, and R ¹⁶ represents -H or an alkyl group having 1 to 22 carbon atoms.

In addition, examples of the side chain type diamine represented by the above formula (I) include diamines represented by the following formula (I-1) to formula (I-9).

In the above formulae (I-1) and (I-2), R ¹³ represents -H or an alkyl group having 1 to 30 carbon atoms, and in the above formulae (I-4) and (I-5), R ¹⁴ represents -H or an alkyl group having 1 to 30 carbon atoms. Further, in the above formula (I-3), R ¹³ represents -H or an alkyl group having 1 to 30 carbon atoms, and in the above formula (I-6) to formula (I-9), R ¹⁴ represents -H or an alkyl group having 1 to 20 carbon atoms.

As the diamine represented by the above formula (I), for example, the above formula (I-1), formula (I-2), formula (I-4) and formula (I) can be preferably used. -7) The diamine represented.

The side chain type diamine represented by the above formula (II) is preferably bonded to the two phenyl groups, respectively, in a meta or para position with respect to A ⁹ .

Examples of the side chain type diamine represented by the above formula (II) include a diamine represented by the following formula (II-1) to formula (II-3).

In the above formula, R ¹⁷ represents an alkyl group having 6 to 20 carbon atoms, and R ¹⁸ represents -H or an alkyl group having 1 to 10 carbon atoms.

The molar ratio of the diamine having a side chain structure to the diamine constituting the polylysine in the liquid crystal alignment agent of the present invention is from the viewpoint of obtaining an appropriate alignment property when the liquid crystal display element is formed. In-plane switching (In-Plane Switching, IPS) is preferably 0% to 50%, more preferably 0% to 20%, and preferably 0% to 90%, more preferably 3% to 70% in Twisted Nematic (TN) and STN. %.

The other diamines other than the diamines represented by the above formula (I) and the formula (II) may be preferably further exemplified by the following formula (III) to formula (X) and formula (N). And a diamine (hereinafter also referred to as a linear diamine) having no side chain structure represented by the formula (a). The diamine having no side chain structure may be one type or two or more types.

(In the formula (III), X represents -(CH ₂ ) _m - (m represents an integer of 1 to 6), and in the formula (V) and the formula (VII) to the formula (IX), Y independently represents Single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH ₃ )-(CH ₂ ) _m -N (CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH _{2 m} -S-(m represents an integer of 1 to 6), and in the formula (VII), Z represents a single bond or does not exist, and in the formula (X), R ¹⁹ and R ²⁰ each independently represent a carbon number of 1~ Alkyl or phenyl of 3, A ¹¹ independently represents a methylene group, a phenylene group or a subphenyl group substituted by an alkyl group. i represents an integer of 1 to 6, and j represents an integer of 1 to 10, and the formula (IV) In the general formula (IX), the hydrogen bonded to the cyclohexane ring or the benzene ring is independent, and may be -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, - Substituted by PO ₃ H ₂ , the hydrogen bonded to the benzene ring in the formula (VI) may be substituted by a benzyl group. In the formula (N), A ¹ independently represents an alkyl group having 1 to 4 carbon atoms. , alkoxy group having a carbon number of 1 to 4, acetaminophen, fluorine, chlorine or bromine, A ² independently represents an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 3, and n represents 0 to 4 Integer. In general formula (a) L ¹ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group).

The linear diamine represented by the formula (III) may, for example, be a diamine represented by the structural formula (III-1) to the structural formula (III-3).

As the linear diamine represented by the formula (IV), for example, The diamine represented by the structural formula (IV-1) and the structural formula (IV-2).

Examples of the linear diamine represented by the formula (V) include diamines represented by the structural formula (V-1) to the structural formula (V-3).

The linear diamine represented by the formula (VI) may, for example, be a diamine represented by the structural formula (VI-1) to the structural formula (VI-17).

The linear diamine represented by the formula (VII) may, for example, be a diamine represented by the structural formula (VII-1) to the structural formula (VII-36).

The linear diamine represented by the formula (VIII) may, for example, be a diamine represented by the structural formula (VIII-1) to the structural formula (VIII-6).

The linear diamine represented by the formula (IX) may, for example, be a diamine represented by the structural formula (IX-1) to the structural formula (IX-16).

Among these diamines, as the more preferable linear diamine, the structural formula (VI-1), the structural formula (VI-2), and the structural formula (VI-15) to the structural formula (VI-17) ), Structural Formula (VII-1)~Structure Formula (VII-13), Structural Formula (VII-32), Structural Formula (VII-34)~Structure Formula (VII-36) and Structural Formula (IX-2) The diamine represented by the formula (VI-1), the structural formula (VI-15), the structural formula (VI-16), and the structural formula (VII-1) are further preferred as the linear diamine. And a diamine represented by the formula (VII-7).

Examples of the diamine represented by the above formula (X) include diamines represented by the following structural formula (X-1) to structural formula (X-7). Among these diamines, a diamine represented by the following structural formula (X-3) is particularly preferably used.

Examples of the diamine represented by the above formula (N) include the following structural formula (N)-1, structural formula (N)-2, and structural formula (N)-5~ structural formula (N)- 7. Structural formula (N)-9, structural formula (N)-10, structural formula (N)-14, structural formula (N)-17, structural formula (N)-18, structural formula (N)-21~ The diamine represented by the structural formula (N)-23, the structural formula (N)-26, and the structural formula (N)-28. Among these diamines, a diamine represented by the following structural formula (N)-1, structural formula (N)-2, and structural formula (N)-14 is particularly preferably used.

Examples of the diamine represented by the above formula (a) include diamines represented by the following structural formulae (a-1) to (a-3). Among these diamines, a diamine represented by the following structural formula (a-1) is particularly preferably used.

The molar ratio of the linear diamine to the diamine constituting the polyglycolic acid in the liquid crystal alignment agent of the present invention is in the IPS from the viewpoint of obtaining an appropriate alignment property when the liquid crystal display element is formed. It is preferably 50% to 100%, more preferably 80% to 100%, and preferably 10% to 100%, more preferably 30% to 97% in TN and STN.

In addition, the other diamine is not particularly limited, and examples thereof include diamines represented by the following general formulae (1') to (8').

In the above formula, R ²¹ independently represents an alkyl group having 3 to 30 carbon atoms, and in the general formulae (4'), (6') and (8'), R ²² represents an alkane having 3 to 30 carbon atoms. base.

In the diamine of the polyglycolic acid constituting the liquid crystal alignment agent of the present invention, the other diamine can be used to the extent that the effects of the present invention are not impaired.

For the diamine, a part of the diamine may be replaced with a monoamine in a range in which the ratio of monoamine to diamine is 40 mol% or less in each diamine. Such substitution can cause termination of the polymerization reaction when polyamic acid is formed, so that further progress of the polymerization reaction can be suppressed. Therefore, by such substitution, the molecular weight of the obtained polymerization (polylysine or its derivative) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The diamine substituted with a monoamine may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, and n-glycan. Amine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecane, positive Octadecylamine and n-dodecylamine.

The monomer of the polyaminic acid or a derivative thereof may further comprise a monoisocyanate compound. By including a monoisocyanate compound in the monomer, the terminal of the obtained polyaminic acid or its derivative is modified, and the molecular weight is adjusted. By using the terminal-modified polyglycine or a derivative thereof, for example, the effects of the present invention can be prevented without being impaired. Improve the coating properties of the liquid crystal alignment agent. From the above viewpoints, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

In the present invention, other diamines other than the diamines represented by the above formula (III) to formula (X) and formula (N) may be used as long as the effects of the present invention are not impaired. A diamine having a side chain structure (hereinafter also referred to as a side chain type diamine) is shown. Examples of such a diamine having a side chain structure include diamines having a side chain structure represented by the following general formula (XI), general formula (XIII), and general formula (XIV). The diamine having a side chain structure may be one type or two or more types.

In the formula (XI), A ¹² represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _m - (m represents an integer of 1 to 6), R ²⁷ represents a group having a steroid skeleton, a group represented by the following formula (XII), and when the positional relationship of two amino groups bonded to the benzene ring is para, R ²⁷ further contains a carbon number of 1~ The alkyl group of 30, when its positional relationship is meta, R ²⁷ further contains an alkyl group having 1 to 30 carbon atoms or a phenyl group. In the alkyl group, any -CH ₂ - is independently and may be substituted by -CF ₂ -, -CHF-, -O- (but not continuous), -CH=CH- or -C≡C-, -CH ₃ may be substituted by -CH ₂ F, -CHF ₂ or -CF ₃ . Further, the phenyl group is independently hydrogen and may be substituted by -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ .

In the formula (XII), A ¹³ and A ¹⁴ each independently represent a single bond, -O- (but not continuous), -COO-, -OCO-, -CONH-, -CH=CH- or a carbon number of 1~. Alkenyl group of 12, R ³⁰ and R ³¹ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexene, 1,3-dioxane -2,5-diyl, pyrimidine-2,5-diyl, pyridine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluorene-9,10- Dibasic, R ³² represents -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkyl group substituted with fluorine having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -C≡N, - OCH ₂ F, -OCHF ₂ or -OCF ₃ , a and b respectively represent integers of 0 to 4, c, d and e represent integers of 0 to 3, respectively, and f and g each independently represent an integer of 0 to 2, and c+d+e≧1. Further, when c + d + e = 1, R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an alkyl group substituted with fluorine having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms.

In the formula (XIII), hydrogen bonded to the carbon forming the steroid skeleton is independently and may be substituted by -CH ₃ . In the general formula (XIII) and the general formula (XIV), R ³⁷ each independently represents -H or -CH ₃ , and R ³⁸ represents -H or an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. A ¹⁵ independently represents a single bond, -CO- or -CH ₂ -. In the formula (XIV), R ³⁹ and R ⁴⁰ each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group.

For the side chain type diamine represented by the above formula (XI), the bonding positional relationship of the two amino groups preferably bonded to the two amino groups on the carbon of the benzene ring is meta or para. Further, when the bonding position of "R ²⁷ -A ¹² -" is taken as one position, the bonding positional relationship of the two amino groups is preferably 3 bits and 5 bits, or 2 bits and 5 bits.

As the diamine represented by the above formula (XI), for example, A diamine represented by the following formula (XI-1) to formula (XI-9).

In the above formula (XI-1), formula (XI-2), formula (XI-5) and formula (XI-6), R ⁴¹ represents an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 The alkoxy group of ~30 is preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms or an alkoxy group having 5 to 25 carbon atoms. Further, in the above formula (XI-3), formula (XI-4) and formula (XI-7) to formula (XI-9), R ⁴² represents an alkyl group or carbon having 1 to 30 carbon atoms. The alkoxy group having 1 to 30 is more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In addition, examples of the side chain type diamine represented by the above formula (XI) include diamines represented by the following formula (XI-10) to formula (XI-15).

In the above formula (XI-10) to formula (XI-13), R ⁴³ represents an alkyl group having 4 to 30 carbon atoms, and preferably an alkyl group having 6 to 25 carbon atoms. In the above formula (XI-14) and formula (XI-15), R ⁴⁴ represents an alkyl group having 6 to 30 carbon atoms, and preferably an alkyl group having 8 to 25 carbon atoms.

In addition, examples of the side chain type diamine represented by the above formula (XI) include diamines represented by the following formula (XI-16) to formula (XI-36).

The general formula (XI-16), the general formula (XI-17), the general formula (XI-20), the general formula (XI-22), the general formula (XI-23), the general formula (XI-26), In the formula (XI-28), the formula (XI-29), the formula (XI-34), and the formula (XI-35), R ⁴⁵ represents an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30. The alkoxy group is more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

The general formula (XI-18), the general formula (XI-19), the general formula (XI-21), the general formula (XI-24), the general formula (XI-25), the general formula (XI-27), In the formula (XI-30) to the formula (XI-33) and the formula (XI-36), R ⁴⁶ represents -H, -F, an alkyl group having 1 to 30 carbon atoms, and an alkyl group having 1 to 30 carbon atoms. The oxy group, -C≡N, -OCH ₂ F, -OCHF ₂ or -OCF ₃ is preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. In the above formula (XI-31) and formula (XI-32), A ¹⁶ represents an alkenyl group having 1 to 20 carbon atoms.

In addition, examples of the side chain type diamine represented by the above formula (XI) include the following structural formula (XI-37) to structural formula (XI-46). Diamine.

The side chain type diamine represented by the above formula (XI) is preferably a diamine represented by the formula (XI-1) to the formula (XI-9), and more preferably a formula (XI-2). Or a diamine represented by the formula (XI-4).

The side chain type diamine represented by the above formula (XIII) preferably has one of two "NH ₂ -Ph-A ¹⁵ -O-" groups bonded to the 3 position of the steroid core, and the other side is bonded to the 6 position. Further, the two amino groups respectively bonded to the two phenyl groups are preferably bonded to the meta or para position with respect to the bonding position of A ¹⁵ .

Examples of the side chain type diamine represented by the above formula (XIII) include diamines represented by the following structural formula (XIII-1) to structural formula (XIII-4).

Two "NH ₂ -(R ⁴⁰ -)Ph-A ¹⁵ -O-" of the side chain type diamine represented by the above formula (XIV) are bonded to the carbon of the phenyl group, respectively, but preferably with respect to The carbon in the phenyl group to which the steroid nucleus is bonded is bonded to the meta or para position. Further, the two amino groups respectively bonded to the two phenyl groups are preferably bonded to the meta or para position with respect to the bonding position of A ¹⁵ .

Examples of the side chain type diamine represented by the above formula (XIV) include diamines represented by the following structural formula (XIV-1) to structural formula (XIV-8).

The diamine has a side chain structure represented by the above formula (XI), formula (XIII) and formula (XIV) from the viewpoint of obtaining an appropriate orientation when the liquid crystal display element is produced. Diamine relative to the constituents of the invention The molar ratio of all the diamines of the polyamic acid in the liquid crystal alignment agent is preferably 0% to 50%, more preferably 0% to 20% in IPS, and preferably 0% to 90% in TN and STN. More preferably, it is 3% to 70%.

The polyamic acid or a derivative thereof can be used in addition to the tetracarboxylic dianhydride represented by the general formula (TC-1) to the general formula (TC-14) and other tetracarboxylic dianhydrides. A well-known poly-proline or a derivative thereof used for the formation of a membrane of ruthenium is produced in the same manner. The total addition amount of the tetracarboxylic dianhydride is preferably approximately equal to the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

The molecular weight of the polyaminic acid or its derivative is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, in terms of polystyrene-reduced weight average molecular weight (Mw). The molecular weight of the polyaminic acid or its derivative can be determined by measurement by a gel permeation chromatography (GPC) method.

The polyaminic acid or a derivative thereof can be confirmed by the method of infrared spectroscopy (IR), nuclear magnetic resonance (NMR), and precipitation by using a large amount of poor solvent. The solid components were analyzed. In addition, gas chromatography (GC), high performance liquid chromatography (GC) can be performed on an extract of an organic solvent of a decomposition product of the polyaminic acid or a derivative thereof with an aqueous solution of a strong base such as KOH or NaOH. High Performance Liquid Chromatography (HPLC) or Gas Chromatograph-Mass Spectrometer (GC-MS) analysis was performed to confirm the monomers used.

The liquid crystal alignment agent of the present invention may further contain other components than the polyamic acid or a derivative thereof. The other components may be one type or two or more types.

For example, from the viewpoint of stabilizing the electrical properties of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain a nadic quinone imine compound substituted with an alkenyl group. The naphthylamine compound substituted with an alkenyl group may be one compound or two or more compounds. From the viewpoint of the above, the content of the alkenyl imino compound substituted by the alkenyl group is preferably 0.01 to 1.00 by weight based on the weight ratio of the polyglycine or the derivative thereof in the liquid crystal alignment agent. It is more preferably 0.01 to 0.70, still more preferably 0.01 to 0.50.

The naphthylamine compound substituted with an alkenyl group is preferably a compound which can be dissolved in a solvent which dissolves the polyamic acid or a derivative thereof used in the present invention. Examples of such an alkenyl imine compound substituted with an alkenyl group include compounds represented by the following formula (Ina).

In the general formula (Ina), L ¹ and L ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a aryl group. An aryl or benzyl group, and n represents 1 or 2.

When n=1, W represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, and - Z ¹ -(O) _q -(Z ² O) _r -Z ³ -H (Z ¹ , Z ² and Z ³ independently represent an alkenyl group having 2 to 6 carbon atoms, q represents 0 or 1, and r represents a group represented by an integer of 1 to 30), and -(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ⁵ independently represent an alkenyl group having 1 to 4 carbon atoms or a cycloalkane having 5 to 8 carbon atoms; Alkenyl, B represents a phenyl group, and s represents a group represented by 0 or 1), with -BTBH (B represents a phenyl group, and T represents -CH ₂ -, -C(CH ₃ ) ₂ -, -O a group represented by -, -CO-, -S- or SO ₂ -), or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group.

In this case, preferred W is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, and a poly(ethyleneoxy) group having 4 to 10 carbon atoms. Poly(ethyleneoxy)ethyl, phenyloxy phenyl, phenyl methyl phenyl, phenyl isopropylidene phenyl, and 1 of these groups One or two hydrogen-substituted groups.

When n=2 in the general formula (Ina), W represents an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, and an arylene having 6 to 12 carbon atoms. -Z ¹ -O-(Z ² O) _r -Z ³ - (Z ¹ ~Z ³ and the meaning of r are as described above), represented by -Z ⁴ -BZ ⁵ -(Z ⁴ , Z ⁵ and The meaning of B is as described above. The group represented by -B-(OB) _s -T-(BO) _s -B- (B represents a subphenyl group, and T represents an alkenyl group having 1 to 3 carbon atoms, - O- or -SO ₂ -, s represents a group represented by 0 or 1), or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group.

In this case, preferred W is an alkenyl group having 2 to 12 carbon atoms, cyclohexene, phenylene, tolylene, xylylene, and -C ₃ H ₆ -O. -(Z ² -O) _r -OC ₃ H ₆ - (Z ² represents a carbon 2 to 6 alkenyl group, r represents 1 or 2), and -BTB- (B represents a subphenyl group, Further, T represents a group represented by -CH ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (B represents a phenylene group), and one of these groups or Two groups in which hydrogen is replaced by a hydroxyl group.

Such an alkenyl imino compound substituted with an alkenyl group can be used, for example, as described in Japanese Patent No. 2729565, by using an alkenyl substituted nadecic anhydride derivative and a diamine at 80 ° C to 220 ° C. The compound obtained by the synthesis at a temperature of 0.5 hour to 20 hours or a commercially available compound is maintained. Specific examples of the nadicilimine compound substituted with an alkenyl group include the compounds shown below.

N-methyl-allyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxyimide), N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-methyl-methylallylbicyclo[2.2.1 Gh-5-ene-2,3-dicarboxy quinone imine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine , N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2-ethylhexyl)-allyl ( Methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-allyl-allylmethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-allyl-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-isopropenyl-allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-iso Propenyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-cyclohexyl-allylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine, N-cyclohexyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-A Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-phenyl-allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allyl bicyclo [ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine, N-benzyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-hydroxyethyl)-allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine, N-(2-hydroxyethyl)-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2,2- Dimethyl-3-hydroxypropyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2,3-dihydroxypropane -Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2,3-dihydroxypropyl)-allyl (methyl)bicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-Dicarboxy quinone imine, N-(4-hydroxycyclohexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-( 4-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(4-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-hydroxybenzene -Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxyphenyl)-methylallylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindenine, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(3-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(p-hydroxybenzyl) )-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allyl (methyl)bicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallyl bicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-[2-{2-(2- Ethyloxy)ethoxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-[2-{2- (2-hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-{4-(4 -hydroxyphenylisopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-{4-(4-hydroxyphenyliso) Propylene)phenyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isophthalamide Propyl)phenyl}-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, and their oligomers, N,N'-ethylidene- Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicar boxyimide), N,N'-ethylidene-bis(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-ethylidene-bis(methylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-double ( Allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, N'-docamethylene-bis(allyl bicyclo [2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine), N,N'-cyclohexene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N'- Cyclohexene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 1,2-bis{3'-allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane (1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxyimide)propoxy}ethane), 1,2-double {3'- Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, 1,2-bis{3'-methylallylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, bis[2'-{3'-allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxyindolimine)propoxy}ethyl]ether (bis[2'-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy} Ethyl]ether), bis[2'-{3'-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, 1,4-double {3'-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}butane (1,4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxyimide)propoxy}butane), 1,4-bis{3'-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)propoxy Butane, N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide) (N,N'-p- Phenylene-bis (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine (N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)), N,N'-metaphenyl-bis(allylmethyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)(N,N'-{(1-methyl)-2,4-phenylene}--bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxyimide)), N,N'-p-xylyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine) (N, N'-p-xylylene-bis (allylbic Yclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)), N,N'-p-xylyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine), N, N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) (N , N'-m-xylylene-bis (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-xylylene-bis(allylmethylbicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane (2,2- Bis(4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane), 2,2-bis[4-{4-(allylmethyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxyindolimine)phenyl}methane (bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane), double {4-(allyl) Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) Phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)phenyl}ether (bis{4-(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxyimide)phenyl}ether), bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindole Amine)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)phenyl}ether, bis{4-(ene Propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} hydrazine (bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxyimide)phenyl}sulfone), bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}indole, double {4-(A Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine) phenyl} hydrazine, 1,6-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)-3-hydroxy-hexane (1,6- Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-3-hydroxy-hexane), 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinoid imine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imino)-5-hydroxy-cyclohexane, 1,5-bis{3'-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) propoxy }-3-Hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)-2-hydroxy-benzene, 1,4 - bis (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)-2,5-dihydroxy-benzene, N,N'-pair (2-hydroxyl Benzyl dimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) (N,N'-p-(2-hydroxy)xylylene-bis ( Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)), N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylmethylcyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine), N, N'-inter (2-hydroxy Benzyl-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-(2,3-dihydroxy) Benzyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2,2-bis[4-{4-(allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenoxy}phenyl]propane, bis{4-(allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine)}phenoxymethylpropane, N,N',N"-tris(ethethylenemethylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine) Isocyanurates, their oligomers, and the like.

Further, the alkenylimine compound substituted with an alkenyl group used in the present invention may be an asymmetric compound containing an alkenyl group or a phenylene group represented by the following structural formula.

Preferred compounds among the alkenylimine compounds substituted with an alkenyl group are listed below.

N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-ethylidene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-ethylidene-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-cyclohexene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N '-Cyclohexene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine), N, N'-time Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-xylyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine), N,N'-p-xylyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N, N'-m-phenylenedi-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarthazomine), N,N'-m-xylylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), 2,2-bis[4-{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]g -5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imino)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane, double {4- (Methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, double {4-(A Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy fluorene Amine) phenyl} hydrazine, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}indole, double {4-(A Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene.

More preferred naphthyl imine compounds substituted with alkenyl groups are listed below.

N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-ethylidene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-ethylidene-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N, N'-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarthazomine), N,N'-dichteen Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-cyclohexene-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-cyclohexene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine), N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N' - p-Phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide), N,N'-m-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine), N,N'-p-xylylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-xylyl-bis(allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), 2,2 - bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4 -{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{ 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} methane, bis {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinolinimine)phenyl}methane.

Further, as a particularly preferable naphthyl imine compound substituted with an alkenyl group, a bis{4-(allylbicyclo[2.2.1]g which is represented by the structural formula (Ina-1) as shown below can be cited. -5-ene-2,3-dicarboxy quinone imine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2] represented by the formula (Ina-2) .1]hept-5-ene-2,3-dicarboxyindenine), and N,N'-hexamethylene-bis(allylbicyclo[2.2] represented by the structural formula (Ina-3) .1]hept-5-ene-2,3-dicarboxyinlimine).

Further, for example, from the viewpoint of stabilizing the electrical properties of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond. The compound having a radical polymerizable unsaturated double bond may be one compound or two or more compounds. Further, the naphthylamine compound substituted with an alkenyl group is not included in the compound having a radical polymerizable unsaturated double bond. In view of the above, the content of the compound having a radical polymerizable unsaturated double bond is preferably from 0.01 to 1.00, more preferably from 0.01 to 0.70, based on the weight ratio of the polyaminic acid or its derivative. Further, it is preferably 0.01 to 0.50.

Further, in terms of reducing the ion density of the liquid crystal display element, suppressing an increase in ion density with time, and further suppressing the afterimage, a compound having a radical polymerizable unsaturated double bond is substituted with an alkenyl group. The ratio of the diclosan compound is preferably from 0.1 to 10, more preferably from 0.5 to 5, by weight.

Examples of the compound having a radical polymerizable unsaturated double bond include (meth)acrylic acid ester, (meth)acrylic acid amide, and the like ((meth)acrylic acid amide) ( Methyl)acrylic acid derivatives and bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dialkylpentyloxyethyl acrylate, (meth)acrylic acid Isobornyl ester, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the difunctional (meth) acrylate include, for example, ethylene diacrylate, Aronix M-210, Aronix M-240, and Aronix M-6200 of the East Asian Synthetic Co., Ltd. ) Products KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and products of Kyoritsu Chemical Co., Ltd. Light Acrylate BA- 4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA.

Specific examples of the trifunctional or trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4'-methylenebis(N,N-dihydroxyethylene phenyl aniline), Aronix M -400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 And VGPT, the product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylamide derivative include, for example, N-isopropyl acrylamide, N-isopropylmethacrylamide, and N-n-propyl propylene. Indoleamine, N-n-propylmethyl acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxy Ethyl methacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide , N,N-diethyl acrylamide, N- Methyl-N-n-propylpropenylamine, N-methyl-N-isopropylpropenylamine, N-propenyl acridine, N-propenylpyrrolidine, N,N'-methylene Bisacrylamide, N,N'-ethylidene bis decyl decylamine, N,N'-dihydroxyethenyl bis acrylamide, N-(4-hydroxyphenyl)methacrylamide, N- Phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl)methacrylamide, N-[2-(N,N-dimethylamino)ethyl] Methyl acrylamide, N,N-dimethyl methacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-(methoxymethyl)methyl Acrylamide, N-(hydroxymethyl)-2-methylpropenylamine, N-benzyl-2-methylpropenylamine, and N,N'-methylenebismethacrylamide.

Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethenyl-bispropenylamine, ethylene diacrylate, and 4 are particularly preferable. 4'-methylenebis(N,N-dihydroxyethylene phenyl aniline).

Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by KI CHEMICAL INDUSTRY, and BMI-1000, BMI-3000, BMI-4000, and BMI manufactured by Daiwa Kasei Kogyo Co., Ltd. -5000 and BMI-7000.

Further, for example, from the viewpoint of long-term stability of electrical properties in the liquid crystal display element, the liquid crystal alignment agent of the present invention may further contain an oxazine compound. The oxazine compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the oxazine compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, based on the polyamic acid or a derivative thereof. The step is preferably from 1% by weight to 20% by weight.

The oxazine compound is preferably soluble in a solvent in which polyacrylic acid or a derivative thereof is dissolved, and has a ring-opening polymerizable oxazine compound.

Further, the number of the oxazine structure in the oxazine compound is not particularly limited.

The structure of the oxazine is known in various structures. In the present invention, the structure of the oxazine is not particularly limited, and the oxazine structure in the oxazine compound may include a benzoxazine or a naphthoxazine having a condensed polycyclic aromatic group. The structure of the aromatic-based oxazine.

Examples of the oxazine compound include compounds represented by the following formulas (a) to (f). Further, in the following formula, the bond shown toward the center of the ring means that it is bonded to any of the carbons constituting the ring and which may bond the substituent.

In the above formulae (a) to (c), R ¹ and R ^{2 each} represent an organic group having 1 to 30 carbon atoms. Further, in the above formulae (a) to (f), R ³ to R ⁶ represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. Further, in the above formula (c), formula (d) and formula (f), X represents 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-. Here, m is an integer of 1 to 6. Further, in the above formula (e) and formula (f), Y independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF _{3 2} - or an alkenyl group having 1 to 3 carbon atoms. The hydrogen in the Y bond to the benzene ring and the naphthalene ring is independent, and may be substituted by -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ .

Further, the oxazine compound includes an oligomer or a polymer having an oxazine structure in a side chain, an oligomer or a polymer having an oxazine structure in the main chain.

Examples of the oxazine compound represented by the formula (a) include the following oxazine compounds.

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

Examples of the oxazine compound represented by the formula (b) include the following oxazine compounds.

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

The oxazine compound represented by the following formula (c-I) is exemplified as the oxazine compound represented by the formula (c).

In the above formula (cI), R ¹ and R ² represent an organic group having 1 to 30 carbon atoms, R ³ to R ⁶ represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and X represents a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, -SO ₂ - or -C(CF ₃ ) ₂ -. Examples of the oxazine compound represented by the above formula (cI) include the following oxazine compounds.

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

As the oxazine compound represented by the formula (d), for example, The underlying oxazine compound.

Examples of the oxazine compound represented by the formula (e) include the following oxazine compounds.

The oxazine compound represented by the formula (f) includes, for example, the following oxazine compounds.

Among these oxazine compounds, formula (b-1), formula (c-1), formula (c-3), formula (c-5), formula (c-7), and formula (c-9) are more preferable. An oxazine compound represented by the formula (d-1) to the formula (d-6), the formula (e-3), the formula (e-4), and the formula (f-2) to the formula (f-4).

The oxazine compound can be produced by the same method as that described in the International Publication No. 2004/009708, the Japanese Patent Application Laid-Open No. Hei 11-12258, and the Japanese Patent Publication No. 2004-352670.

For example, the oxazine compound represented by the formula (a) can be obtained by reacting a phenol compound, a primary amine, and an aldehyde (refer to International Publication No. 2004/009708).

Further, the oxazine compound represented by the general formula (b) can be obtained by adding a naphthol-based hydroxyl group by a method in which a primary amine is gradually added to formaldehyde (formaldehyde). The compound is reacted (refer to International Publication No. 2004/009708).

Further, the oxazine compound represented by the formula (c) can be used as follows Obtained in the organic solvent, a 1 mol phenol compound, an aldehyde of at least 2 mol or more with respect to one phenolic hydroxyl group, and 1 mol of a primary amine in the aliphatic secondary amine ( The reaction is carried out in the presence of an aliphatic secondary amines, an aliphatic tertiary amines or a basic nitrogen-containing heterocyclic compound (refer to the International Publication No. 2004/009708, and Japanese Patent Laid-Open No. Hei 11-12258).

Further, the oxazine compound represented by the general formula (d) to the general formula (f) can be obtained by having a plurality of benzenes such as 4,4'-diaminodiphenylmethane or the like in n-butanol. The ring and the aldehyde such as a diamine, a formalin, and the like which bond to the organic group of the benzene ring, and the phenol are subjected to a dehydration condensation reaction at a temperature of 90 ° C or higher (refer to Japanese Laid-Open Patent Publication No. 2004-352670).

Further, for example, from the viewpoint of long-term stability of electrical properties in the liquid crystal display element, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the oxazoline compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably 1% by weight relative to the polyaminic acid or a derivative thereof. %~20wt%. Or, in view of the above, the content of the oxazoline compound is preferably relative to the poly-proline or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to an oxazoline It is from 0.1 wt% to 40 wt%.

The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more types in one compound. The oxazoline structure. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more oxazoline structures. Further, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure on the side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a monomer having an oxazoline structure in a side chain and having no oxazoline structure. Copolymer of monomer. The copolymer having an oxazoline structure on the side chain may be a copolymer of two or more kinds of monomers having an oxazoline structure in a side chain, or two types having an oxazoline structure in a side chain or A copolymer of two or more monomers and a monomer having no oxazoline structure.

The oxazoline structure preferably has a structure in which one or both of oxygen and nitrogen in the oxazoline structure are allowed to react with a carbonyl group of polyphthalic acid in the oxazoline compound.

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tri-(2- Oxazolinyl-2)-benzene (1,2,4-tris-(2-oxazolinyl-2)-benzene), 4-furan-2-ylmethylene-2-phenyl-4H-oxazole- 5-keto-2-ylmethylene-2-phenyl-4H-oxazole-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene (1,4- Bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2- Oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine , 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2, 2'-methylenebis(4-tert-butyl-2-oxazole Porphyrin) and 2,2'-methylenebis(4-phenyl-2-oxazoline). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group such as Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.) may be mentioned. Among these compounds, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is more preferable.

Further, for example, from the viewpoint of long-term stability of electrical properties in the liquid crystal display element, the liquid crystal alignment agent of the present invention may further contain an epoxy compound. The epoxy compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the epoxy compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably 1% by weight, based on the polyaminic acid or a derivative thereof. ~20wt%.

Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having an epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, and 3,3,3-trifluoromethyl propylene oxide (3, 3, 3-trifluoro propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxy propyl trimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-glycidyl phthalimide, (nonafluoro-n-butyl) epoxide ((nonafluoro-N-butyl)epoxide), perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N,N-diglycidylaniline, and 3-[2-(all Fluoryl)ethoxy]-1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl glycol. Ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane.

As a compound having three epoxy rings in the molecule, for example, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4- ([2,3-Epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Techmore VG3101L", manufactured by Mitsui Chemicals Co., Ltd.).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl. Base-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'- Diaminodiphenylmethane and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

In addition to the above compounds, examples of the compound having an epoxy ring in the molecule include an oligomer or a polymer having an epoxy ring. Examples of the monomer having an epoxy ring include, for example, glycidyl (meth)acrylate, (meth)acrylic acid 3,4-epoxycyclohexyl ester, and (meth)acrylic acid. Glycidyl ester.

As another monomer copolymerized with the monomer having an epoxy ring, for example, (meth)acrylic acid, methyl (meth)acrylate (methyl) (meth)acrylate), ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, Cyclohexyl methacrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methyl styrene, chlorine Methylstyrene, (3-ethyl-3-epoxypropenyl)methyl (meth)acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Preferable specific examples of the polymer having a monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexyl horse.醯imino-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxy methacrylate Ethyl ester-glycidyl methacrylate copolymer, (3-ethyl-3-epoxypropyl)methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymerization Things.

Among these examples, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N are particularly preferred. , N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Techmore VG3101L", 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

More systematically, as the epoxy compound, for example, it can be listed For example: glycidyl ether, glycidyl ester, glycidyl amine, epoxy-containing acrylic resin, glycidyl amide, glycidyl isocyanurate (glycidyl) Isocyanurate), a chain aliphatic epoxy compound, and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, and a hydrogenated bisphenol- A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol- F-type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolac type epoxy compound, brominated cresol novolac type epoxy Compound, bisphenol A novolak type epoxy compound, epoxy compound containing naphthalene skeleton, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic poly A glycidyl ether compound, a polysulfide type diglycidyl ether compound, and a biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

As the glycidylamine, for example, a polyglycidylamine compound can be mentioned.

As the epoxy group-containing acrylic compound, for example, it can be listed Homopolymers and copolymers of monomers having oxiranyl groups.

As the glycidylamine, for example, a glycidylamine type epoxy compound can be mentioned.

Examples of the chain aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an alkene compound.

Examples of the cyclic aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cycloolefin compound.

Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, and 1010 (all manufactured by Japan Epoxy Resins Co., Ltd.), and Epotohto YD-128. (Dongdu Chemical Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by Dow Chemical Japan), Epiclon 840, Epiclon 850, Epiclon 1050 (all manufactured by DIC), Epomic R- 140, Epomic R-301 and Epomic R-304 (all manufactured by Mitsui Chemicals Co., Ltd.).

Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by Nippon Epoxy Co., Ltd.), Epotohto YDF-170, Epotohto YDF-175S, and Epotohto YDF-2001 (both Dongdu Chemical Co., Ltd.), DER-354 (manufactured by Dow Chemical Japan), Epiclon 830 and Epiclon 835 (both manufactured by DIC).

Examples of the bisphenol type epoxy compound include epoxides of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

As the hydrogenated bisphenol-A type epoxy compound, for example, Suntohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rikaresin HBE-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), and Denacol EX-252 (manufactured by Nagase Chemtex).

Examples of the hydrogenated bisphenol type epoxy compound include an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the brominated bisphenol-A type epoxy compound include 5050 and 5051 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epotohto YDB-360, and Epotohto YDB-400 (both are Dongdu Huacheng). )) DER-530, DER-538 (all manufactured by Dow Chemical Japan), Epiclon 152 and Epiclon 153 (all manufactured by DIC).

Examples of the phenol novolak-type epoxy compound include 152 and 154 (all manufactured by Japan Epoxy Resin Co., Ltd.), YDPN-638 (manufactured by Toshiro Kasei Co., Ltd.), and DEN431 and DEN438 (both are Dow). Chemical Japan (manufactured by Chemical Japan Co., Ltd.), Epiclon N-770 (manufactured by DIC), EPPN-201 and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by Nippon Epoxy Resin), YDCN-701, and YDCN-702 (both manufactured by Tohto Kasei Co., Ltd.), Epiclon N-665, and Epiclon N. -695 (both manufactured by DIC), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the bisphenol A novolak-type epoxy compound include 157S70 (manufactured by Nippon Epoxy Resin Co., Ltd.) and Epiclon N-880 (manufactured by DIC Co., Ltd.).

Examples of the epoxy compound containing a naphthalene skeleton include Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (all manufactured by DIC), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.). .

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following structural formula E101), and catechol diglycidyl ether ( The following structural formula E102), resorcinol diglycidyl ether (the following structural formula E103), tris(4-glycidyloxyphenyl)methane (the following structural formula E105), 1031S , 1032H60 (all manufactured by Japan Epoxy Resin Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Japan), Denacol EX-201 (manufactured by Nagase Chemtex), DPPN-503, DPPN-502H, DPPN -501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals Co., Ltd.), a compound represented by the following structural formula E106, and a compound represented by the following structural formula E107.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by Dow Chemical Japan Co., Ltd.) and Epiclon HP-7200 (manufactured by DIC Co., Ltd.).

Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and a Rikaresin DME-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula E108), diethylene glycol diglycidyl ether (the following structural formula E109), and polyethylene glycol. Diglycidyl ether, propylene glycol diglycidyl ether (structure E110 below), tripropylene glycol diglycidyl ether (structure E111 below), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (described below) Structural formula E112), 1,4-butanediol diglycidyl ether (structure E113 below), 1,6-hexanediol diglycidyl ether (structure E114 below), dibromo neopentyl glycol Glycidyl ether (Formula E115 below), 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), DD-503 (made by ADEKA), Rikaresin W-100 (made by New Japan Physical and Chemical Co., Ltd.), 1, 3, 5, 6-four Glycidyl-2,4-hexanediol (structure E1 16 below), glycerin polyglycidyl ether, sorbitol polyglyl Cidyl ether), trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321 and Denacol EX-411 ( Both are manufactured by Nagase Chemtex.

Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toray Thiokol Co., Ltd.).

Examples of the biphenol-type epoxy compound include YX-4000 and YL-6121H (all manufactured by Japan Epoxy Resin Co., Ltd.), NC-3000P and NC-3000S (both are Japanese chemical products). Manufacturing).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following structural formula 117) and phthalic acid condensed water. A glyceride (the following structural formula E118), bis(2-methyloxiranylmethyl) phthalate (the following structural formula E119), a compound represented by the following structural formula E121, and the following structure A compound represented by the formula E122 and a compound represented by the following structural formula E123.

Examples of the glycidyl ester epoxy compound include 871 and 872 (all manufactured by Nippon Epoxy Resin Co., Ltd.), Epiclon 200 and Epiclon 400 (all manufactured by DIC Co., Ltd.), and Denacol EX-711 and Denacol EX-721 (both manufactured by Nagase Chemtex).

Examples of the polyglycidylamine compound include N,N-diglycidylaniline (the following structural formula E124) and N,N-diglycidyl-o-toluidine (the following structural formula E125); N,N-diglycidyl-m-toluidine (structure E126 below), N,N-diglycidyl-2,4,6-tribromoaniline (structure E127 below), 3-(N , N-diglycidyl)aminopropyltrimethoxydecane (structure E128 below), N,N,O-triglycidyl-p-aminophenol (structure E129 below), N,N,O - triglycidyl-m-aminophenol (structure E130 below), N,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.), The following structural formula E132), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.), the following structural formula E133), 1, 4-bis(N,N-diglycidylaminomethyl)cyclohexane (structure E134 below), 1,3-bis(N,N-diglycidylamino)cyclohexane (structure described below) Formula E135), 1,4-bis(N,N-diglycidylamino)cyclohexane (structure E136 below), 1,3-bis(N,N-diglycidylamino)benzene (under Structure E137) 1,4-Bis(N,N-diglycidylamino)benzene (structure E138 below), 2,6-bis(N,N-diglycidylaminomethyl)bicyclo[2.2.1]g Alkane (structural formula E139 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (structure E140 below), 2,2'-dimethyl Base-(N,N,N',N'-tetraglycidyl)-4,4'-diaminodiphenyl (structural formula E141 below), N,N,N',N'-tetraglycidyl Base-4,4'-diaminodiphenyl ether (structure E142 below), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (described below) Structural formula E143), 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether (structure E144 below), three (4-(N,N-diglycidyl)aminophenyl)methane (Strong formula E145 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)biphenyl (Structure E146 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl ether (Structure Formula E147 below), represented by the following structural formula E148 A compound and a compound represented by the following structural formula E149.

Examples of the homopolymer of the monomer having an oxiranyl group include polyglycidyl methacrylate. Examples of the copolymer of the monomer having an oxiranyl group include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexylmaleimide-A. Glycidyl acrylate copolymer, benzyl methacrylate-methyl methacrylate Oil ester copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3-ethyl-3-ring Oxypropanyl)methyl ester-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having an oxiranyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidol (meth)acrylate. ester.

Examples of the monomer other than the monomer having an oxiranyl group in the copolymer of the oxiranyl group-containing monomer include (meth)acrylic acid and (meth)acrylic acid. Methyl ester, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) Cyclohexyl acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methyl styrene, chloromethyl styrene, ( (3-Ethyl-3-epoxypropenyl)methyl (meth)acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

As the glycidyl isocyanurate, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)- Triketone (1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione) (Structure E150 below), 1,3-diglycidyl 5--5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (structure E151 below) and glycidyl isocyanurate type Epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolead PB3600 (manufactured by Daicel Chemical Industry Co., Ltd.).

Examples of the cyclic aliphatic epoxy compound include 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3', 4'-epoxycyclohexylcarboxylic acid. Ester (structure E153 below), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (structure E154 below), ε-caprolactone modification 3,4- Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2:8,9-diepoxylimene (Celloxide 3000 (manufactured by Daicel Chemical Industry Co., Ltd.), 3,4- Epoxycyclohexenylmethyl-3, '4'-epoxycyclohexene carboxylate (Celloxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), the following structural formula E155), represented by the following structural formula E156 Compounds, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY), EHPD-3150 (manufactured by Daicel Chemical Industry Co., Ltd.), and cyclic aliphatic epoxy resins.

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include polymer compounds and low molecular compounds other than polyglycine and derivatives thereof, and can be selected and used according to various purposes.

For example, examples of the polymer compound include a polymer compound which is soluble in an organic solvent. From the viewpoint of controlling the electrical properties or the alignment property of the liquid crystal alignment film formed, it is preferred to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, and fluorenone. Modified polyurethane and anthrone modified polyester.

Further, as the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant suitable for the purpose may be mentioned, 2) an antistatic agent may be mentioned when it is necessary to improve the antistatic property, and 3) when it is desired to improve the substrate. The adhesion or rubbing resistance may be exemplified by a silane coupling agent or a titanium coupling agent, and 4) when the hydrazine imidization is carried out at a low temperature, a ruthenium amide catalyst may be mentioned.

Examples of the decane coupling agent include vinyl trimethoxysilane, vinyl triethoxy decane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxy. Baseline, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxy Baseline, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-shrinkage Glyceroxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyl Trimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylidene)-3-(triethoxy Methyl decyl)-1-propylamine and N,N'-bis[3-(trimethoxycarbamidino)propyl]ethylenediamine.

Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-diethyl Aromatic amines such as aniline, methyl substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, a quinoline substituted with a hydroxy group, an isoquinoline, an isoquinoline substituted with a methyl group, an isoquinoline substituted with a hydroxy group, an imidazole, an imidazole substituted with a methyl group, a cyclic amine such as an imidazole substituted with a hydroxy group . The ruthenium amide catalyst is preferably selected from one of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine and isoquinoline or Two or more.

The amount of the decane coupling agent to be added is usually from 0% by weight to 50% by weight, preferably from 0.1% by weight to 20% by weight based on the total amount of the polyaminic acid or its derivative.

The amount of the ruthenium imidization catalyst added is usually from 0.01 equivalents to 5 equivalents, preferably from 0.05 equivalents to 3 equivalents, per equivalent of the carbonyl group of the polyglycine or a derivative thereof.

The amount of other additives to be added varies depending on the use thereof, and is usually from 0% by weight to 30% by weight, preferably from 0.1% by weight to 10% by weight based on the total amount of the polyamido acid or its derivative.

Further, for example, the liquid crystal alignment agent of the present invention may further contain an acrylic polymer, an acrylate polymerization, in a range not detracting from the effects of the present invention (preferably within 20% by weight of the polyaminic acid or a derivative thereof) And other polymer components such as polyamidoximine which is a reaction product of tetracarboxylic dianhydride, dicarboxylic acid or a derivative thereof and a diamine.

Further, for example, from the viewpoint of adjusting the coatability of the liquid crystal alignment agent or the concentration of the polyaminic acid or its derivative, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve a polymer component. The solvent widely includes a solvent which is usually used in the production step or use of a polymer component such as polyglycolic acid or soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be a solvent or a mixed solvent of two or more solvents.

Examples of the solvent include a good solvent of the polyaminic acid or a derivative thereof, or another solvent for the purpose of improving coatability.

Non-quality for a good solvent for the polyaminic acid or its derivative The polar polar organic solvent may, for example, be N-methyl-2-pyrrolidone, dimethyl imidazolidinone or N-methyl caprolactam. ), N-methyl propionamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide (N, Lactones such as N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrolactone.

Examples of the other solvent for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, and tetralin. ), isophorone, ethylene glycol monobutylether, ethylene glycol monoalkyl ether, diethylene glycol monoethyl ether, etc. Propylene glycol monoalkyl ether such as alkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monobutyl ether; malonate dioxane such as diethyl malonate An ester compound such as a dipropylene glycol monoalkyl ether such as a base ester or a dipropylene glycol monomethyl ether or an acetate thereof.

Among these compounds, the solvent is particularly preferably N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, Propylene glycol monomethyl ether and dipropylene glycol monomethyl ether.

In the present invention, the concentration of the polymer component containing the polyamic acid or a derivative thereof in the liquid crystal alignment agent is not particularly limited, but is preferably 0.1% by weight to 40% by weight. When the liquid crystal alignment agent is applied onto a substrate, it may be necessary to use a solvent in advance to adjust the film thickness. The operation of ingredient dilution. In this case, the viscosity of the liquid crystal alignment agent is adjusted to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent, and the concentration of the polymer component is preferably 40% by weight or less.

Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted depending on the method of applying the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polymer component is usually usually 10% by weight or less. For other coating methods, such as dipping or ink-jet, it is possible to further reduce the concentration. On the other hand, if the concentration of the polymer component is 0.1% by weight or more, the film thickness of the obtained liquid crystal alignment film tends to be an optimum thickness. Therefore, in the usual spin coating method, printing method, or the like, the concentration of the polymer component is 0.1% by weight or more, preferably 0.5% by weight to 10% by weight. However, depending on the method of applying the liquid crystal alignment agent, it may be used at a lower concentration.

Further, when the liquid crystal alignment agent of the present invention is used for producing a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined according to the mechanism or method of forming the film of the liquid crystal alignment agent. For example, when a printing machine is used to form a film of a liquid crystal alignment agent, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa or more from the viewpoint of obtaining a sufficient film thickness. s, in addition, from the viewpoint of suppressing printing unevenness, the viscosity of the liquid crystal alignment agent of the present invention is preferably 100 mPa or less. s, more preferably 10 mPa. s~80mPa. s. When the liquid crystal alignment agent is coated by a spin coating to form a film of the liquid crystal alignment agent, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa from the same viewpoint. s~200mPa. s, more preferably 10 mPa. s~100 mPa. s. The viscosity of the liquid crystal alignment agent can be reduced by dilution of the solvent or aging with stirring.

The liquid crystal alignment agent of the present invention may be in the form of a polyglycine or a derivative thereof, or a form of a so-called polymer blend in which two or more kinds of polyaminic acid or a derivative thereof are mixed. The liquid crystal alignment agent of the form of the polymer blend may, for example, be a liquid crystal alignment agent containing polylysine or derivatives A and B thereof, and the polyamine or its derivative A contains a diamine. One or more of the diamines having a side chain structure represented by the above formula (I) and formula (II), and one of the tetracarboxylic dianhydrides of polyglycine or derivatives A and B thereof Or both of them may contain one or more kinds of tetracarboxylic dianhydrides represented by the above formula (TC-1) to formula (TC-14) and one or more kinds of other tetracarboxylic dianhydrides.

Polylysine or its derivative A is preferably a polyamine or a derivative thereof containing the diamine having a side chain structure. The polyproline or its derivative B is preferably a polyamine or a derivative thereof containing a diamine other than a diamine having a side chain structure. The tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14) and the other tetracarboxylic dianhydride are at least one polyamine which is mixed in the polymer blend. The acid or a derivative thereof may be contained in the poly-proline or its derivatives A and B, or may be contained in all the polyamines or their derivatives mixed in the polymer blend. .

The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can form a liquid crystal alignment agent of the present invention. The step of coating the film and the step of heating and calcining the coating film are obtained. For the liquid crystal alignment film of the present invention, the film obtained in the calcining step may be subjected to a rubbing treatment as needed.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention onto a substrate of a liquid crystal display element, similarly to the production of a usual liquid crystal alignment film. The substrate may be a glass substrate such as an electrode such as an Indium Tin Oxide (ITO) electrode or a color filter.

As a method of applying a liquid crystal alignment agent onto a substrate, a spin coating method, a printing method, a dipping method, a falling-drop method, an inkjet method, and the like are generally known. These methods are equally applicable in the present invention.

The calcination of the coating film can be carried out under the conditions required for the dehydration and ring closure reaction of the polyaminic acid or its derivative. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. These methods are equally applicable in the present invention. It is usually preferably carried out at a temperature of from about 150 ° C to about 300 ° C for from 1 minute to 3 hours.

The rubbing treatment can be carried out in the same manner as the rubbing treatment which is usually used for the alignment treatment of the liquid crystal alignment film, as long as it is a condition that a sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. Particularly preferred conditions are a hair injection amount of 0.2 mm to 0.8 mm, a platform moving speed of 5 mm/sec to 250 mm/sec, and a drum rotation speed of 500 rpm to 2,000 rpm. As a method of the alignment treatment of the liquid crystal alignment film, in addition to the rubbing method, a photoalignment method, a transfer method, or the like is generally known. In the range in which the effects of the present invention can be obtained These other alignment treatment methods can be used in combination in the rubbing treatment.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further including steps other than the above steps. As such another step, a step of drying the coating film or a step of washing the film before and after the rubbing treatment using a cleaning liquid may be mentioned.

The drying step is generally known as a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like, as in the step of calcining. These methods can also be applied in the drying step as well. The drying step is preferably carried out at a temperature within a range in which the solvent can evaporate, more preferably at a relatively low temperature compared to the temperature of the calcining step.

Examples of the cleaning method for cleaning the liquid crystal alignment film before and after the alignment treatment using a cleaning liquid include brushing, jet spray, steam cleaning, or ultrasonic cleaning. These methods can be performed separately or in combination. As the cleaning solution, pure water, various alcohols such as methanol (mehtyl alcohol), ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, and methylene chloride (methylene) can be used. A halogen-based solvent such as chloride), a ketone such as acetone or methyl ethyl ketone, but is not limited to these cleaning solutions. Of course, these cleaning liquids can use a cleaning liquid which is sufficiently purified with less impurities. Such a cleaning method can also be applied in the cleaning step of forming the liquid crystal alignment film of the present invention.

The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm. Liquid crystal matching of the invention The film thickness of the film can be measured using a well-known film thickness measuring device such as a surface profiler or an ellipsometer.

The liquid crystal display device of the present invention has: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode applying a voltage to the liquid crystal layer; and a liquid crystal alignment film aligning the liquid crystal molecules In the intended direction. The liquid crystal alignment film is a liquid crystal alignment film of the present invention.

The substrate may use the glass substrate described above for the liquid crystal alignment film of the present invention, and the electrode may use the ITO electrode formed on the glass substrate described above for the liquid crystal alignment film of the present invention.

The liquid crystal layer is formed of a liquid crystal composition sealed in a gap between a pair of opposing substrates, wherein the pair of substrates are formed such that a liquid crystal alignment film is formed on one of the pair of substrates The faces are facing toward the other substrate.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A preferred liquid crystal composition having a positive dielectric anisotropy is exemplified by the liquid crystal composition disclosed in the following patents: Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735 Japanese Patent Laid-Open No. Hei 8-- No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1) Japanese Patent Laid-Open Publication No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (E. Japanese Patent Laid-Open No. Hei 10-204436, Japanese Patent Laid-Open No. Hei 10-231482, Japanese Patent Laid-Open Publication No. 2000-087040, and Japanese Patent Laid-Open No. 2001-48822.

A preferred liquid crystal composition having a negative dielectric anisotropy is exemplified by the liquid crystal composition disclosed in Japanese Patent Laid-Open Publication No. SHO 57-114532, Japanese Patent Laid-Open No. Hei 2-4725, and Japanese Patent. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei 10-236989, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei 10-236990, Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Japanese Patent Laid-Open No. Hei 10-237004, Japanese Patent Laid-Open No. Hei 10-237004, Japanese Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, Japanese Patent Japanese Laid-Open Patent Publication No. Hei 10-237076, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei 10-237448 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, and the like.

Even if one or more optically active compounds are added to the liquid crystal composition having positive or negative dielectric anisotropy for use, there is no influence at all.

The liquid crystal display device of the present invention is obtained by forming a liquid crystal alignment film of the present invention on at least one of a pair of substrates, and bringing the liquid crystal alignment film inward so that the obtained pair of substrates pass through the spacer ( In the relative direction, a liquid crystal composition is sealed in a gap formed between the substrates to form a liquid crystal layer. In the production of the liquid crystal display device of the present invention, a step of attaching a polarizing film or the like to the substrate may be further included as needed.

The liquid crystal display element of the present invention can form various liquid crystal display elements for electric field mode. The liquid crystal display element for the electric field method includes a liquid crystal display element for applying a voltage to the liquid crystal layer in a direction in which the electrode is in a level with respect to a surface of the substrate, or the electrode is opposite to The surface of the substrate is a vertical electric field mode liquid crystal display element that applies a voltage to the liquid crystal layer in a vertical direction.

The liquid crystal display element of the transverse electric field method does not have a large pretilt angle. Therefore, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a transverse electric field method, wherein the liquid crystal alignment agent of the present invention contains Polylysine or a derivative thereof having no side chain structure such as polylysine or a derivative thereof which does not contain a diamine having a side chain structure.

The vertical electric field mode liquid crystal display element needs to exhibit a large pretilt The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a longitudinal electric field mode, wherein the liquid crystal alignment agent of the present invention contains a polycondensation product obtained from a diamine containing a diamine having a side chain structure. Polylysine having a side chain structure or a derivative thereof such as valine or a derivative thereof.

As described above, the liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material can be suitably used for liquid crystal display elements of various display driving methods by appropriately selecting a polymer which is a raw material.

The liquid crystal display element of the present invention may further have elements other than the constituent elements. As such other constituent elements, a constituent element which is generally used in a liquid crystal display element such as a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, and a driving circuit can be mounted on the liquid crystal display element of the present invention.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. The compounds used in the examples are as follows.

<tetracarboxylic dianhydride>

Compound: Ethylenediaminetetraacetic acid dianhydride: EDDA

Compound: 1,4-phenylenediamine tetraacetic acid dianhydride: PhDDA

Compound: ethylene glycol-bis-(2-aminoethyl ether) tetraacetic acid dianhydride: EGDA

Compound: 1,2-bis-(aminomethyl)-cyclohexanetetraacetic acid dianhydride: CDA

Compound: pyromellitic dianhydride: PMDA

Compound: cyclobutane tetracarboxylic dianhydride: CBDA

Compound: Butane tetracarboxylic dianhydride: BUTDA

Compound: 3,3'-4,4'-benzophenonetetracarboxylic dianhydride: BTDA

Compound: 3,3'-4,4'-diphenyltetracarboxylic dianhydride: BPDA

Compound: Naphthalene-2,3,6,7-tetracarboxylic dianhydride: NTCA

Compound: naphthalene-1,4,5,8-tetracarboxylic dianhydride: NPDA

<Diamine>

Compound: 4,4'-diaminodiphenylmethane: DDM

Compound: 4,4'-diaminodiphenylethane: DDET

Compound: 4,4'-diaminodiphenyl ether: DDE

Compound: 2,2-bis{4-[4-aminophenoxy]phenyl}propane: BAPP

Compound: 4-bis(4-aminophenyl)-1,4-diazacyclohexane: DAC

Compound: N,N'-bis(4-aminophenyl)-N,N'-dimethylethylenediamine:DMEDA

Compound: 1,3,5-diamino-1,2,4-triazole: DATA

Compound: 1,1-bis((aminophenoxy)phenyl)-4-(pentylcyclohexyl)cyclohexane: 5HHBA

Compound: 1,1-bis{4-[(4-aminophenyl)methyl]phenyl}-4-n-heptylcyclohexane: 7HBZ

Compound: 1,1-bis(4-(4-aminophenoxy)phenyl)-4-n-heptylcyclohexane: 7HBA

Compound: 1,1-bis((aminophenoxy)phenyl)-4-(heptylcyclohexyl)ethyl)cyclohexane: 7H2HBA

<solvent>

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

<1. Synthesis of polyaminic acid>

[Synthesis Example 1]

2.7320 g of DDM and 75.0 g of dehydrated NMP were placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet, and stirred and dissolved in a dry nitrogen stream. Next, 1.7652 g of EDDA and 1.5028 g of PMDA were added, and after reacting for 30 hours, 19.0 g of BC was added to synthesize a polyglycine solution (hereinafter also referred to as varnish) (A1) having a concentration of 6 wt%. When the temperature rises due to the reaction temperature in the reaction of the raw material, the reaction is carried out by suppressing the reaction temperature to about 70 ° C or lower. Further, the obtained polyaminic acid in A1 had a weight average molecular weight of 70,700.

The weight average molecular weight of polylysine is determined in such a manner that the obtained polylysine is diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100:weight ratio) to make the polyglycine concentration After about 1 wt%, the mixture solution was measured using a 2695 separation module and a 2414 differential refractometer (manufactured by Waters), and the mixture was used as a developing solvent by a GPC method, and then converted into polystyrene. Further, the column was measured using HSPgel RT MB-M (manufactured by Waters) under the conditions of a column temperature of 40 ° C and a flow rate of 0.35 mL / min.

[Synthesis Example 2 to Synthesis Example 47]

In addition to the tetracarboxylic dianhydride and the diamine as shown in Tables 1 to 4, a polylysine solution (A2) to a polyaminic acid solution (A44) and a polyaminic acid solution were prepared according to Synthesis Example 1. B1) ~ Polyaminic acid solution (B3). Including Synthesis Example 1, the results are summarized in Tables 1 to 4.

The polyamine liquid solutions (A23, A36, and A30) having a concentration of 6 wt% synthesized in Synthesis Example 23, Synthesis Example 36, and Synthesis Example 30 and the concentrations synthesized in Synthesis Examples 45 to Synthesis 47 were 6 wt%. The polyaminic acid solution (B1 to B3) was mixed at a weight ratio of 20/80 (the former/the latter) to prepare a liquid crystal alignment agent (A45 to A51). The composition of A45~A51 is summarized in Table 5.

To a polyglycine solution (A4, A14, and A32) having a concentration of 6 wt% synthesized in Synthesis Example 4, Synthesis Example 14, and Synthesis Example 32, respectively, a double {4-(ene group) having an average polymer weight of 10% by weight was added. Propylbicyclo[2,2,1]hept-5-ene-2,3-dicarboxyindolimide)phenyl}methane, N,N-(1,2-dihydroxyethylidene)bispropenylamine , 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, ammonia Propyltriethoxydecane, 4,4'-methylenebis(N,N-diglycidylaniline) and 1,3-bis(4,5-dihydro-2-oxazolyl)benzene Thus, a liquid crystal alignment agent (A52 to A60) was prepared. The composition of A52~A60 is summarized in Table 6.

(2. Production of liquid crystal display elements)

[Reference Example 1]

To the polyglycine solution (A1) having a concentration of 6 wt% synthesized in Synthesis Example 1, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and the whole was diluted to 4 wt% to prepare a liquid crystal alignment. Agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner.

(Manufacturing method of liquid crystal display element)

The liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode by a spinner to form a film having a film thickness of 70 nm. After coating, the film was dried by heating at 80 ° C for about 5 minutes, and then heat-treated at 210 ° C for 20 minutes to form a liquid crystal alignment film. Next, the surface of the substrate on which the liquid crystal alignment film was formed was subjected to a rubbing treatment using a rubbing device to carry out an alignment treatment. Then, the liquid crystal alignment film was subjected to ultrasonic cleaning for 5 minutes in ultrapure water, and then dried in an oven at 120 ° C for 30 minutes.

A gap material of 7 μm was spread on one of the glass substrates so that the surface on which the liquid crystal alignment film was formed was inside and rubbed direction The opposite arrangement was carried out in an antiparallel manner, and then sealed with an epoxy hardener to prepare an antiparallel cell having a gap of 7 μm. The liquid crystal composition shown below was injected into the unit, and a light curing agent was used to seal the injection port.

[Examples and Reference Examples 2 to 51]

Add a mixed solvent of NMP/BC=1/1 (weight ratio) to A2~A5, A10~A29, A31~A37, A39, A40, A42, A43, A45~A50 and A52~A60 and dilute to make polyfluorene The concentration of the amine acid is 4.0 wt% to 5.0 wt% as a whole, thereby preparing a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Reference Example 1 using the obtained liquid crystal alignment agent.

[Comparative Example 1 to Comparative Example 9]

Adding a mixed solvent of NMP/BC=1/1 (weight ratio) to A6~A9, A30, A38, A41, A44 and A51 and diluting to make the concentration of polyproline acid 4.0wt%~5.0wt as a whole. %, thereby preparing a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Reference Example 1 using the obtained liquid crystal alignment agent.

(confirmation of flow alignment)

The liquid crystal display element produced by the above method was sandwiched between polarizing plates disposed on a crossed nicol, and it was visually confirmed whether or not the flow alignment could be seen.

(Production of substrate for retardation measurement)

A transparent glass substrate is used as the substrate of the measurement substrate.

The varnish A1 obtained in Synthesis Example 1 was coated on the transparent glass substrate by a spinner. The coating conditions were 2,000 rpm and 15 seconds. After coating, the film was pre-baked at 80 ° C for about 3 minutes, and then heat-treated at 210 ° C for 20 minutes to form a liquid crystal alignment film having a film thickness of about 70 nm. Using a friction treatment device made by Iinuma-gauge Co., Ltd., the amount of friction in the rubbing cloth (hair length 1.8 mm: rayon) The obtained polyimide film was subjected to a rubbing treatment at 0.40 mm, a stage moving speed of 60 mm/sec, and a drum rotation speed of 1,000 rpm to obtain a substrate for measurement.

(delay (R) measurement)

The retardation (R) of the alignment film was determined using a spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.). The larger the value of R, the more the liquid crystal alignment film extends in the rubbing direction, thereby having high uniaxial alignment. As a result, it can be said that the black display is good. In the test method of the embodiment of the invention, the retardation is preferably 0.3 nm or more.

As shown in Tables 7 and 8, in the liquid crystal display element using the liquid crystal alignment film obtained by the liquid crystal alignment agent described below, the flow alignment was eliminated, The effect of extremely high retardation is that the liquid crystal alignment agent is a liquid crystal alignment agent containing a polyamic acid containing EDDA and other tetracarboxylic dianhydride in a monomer.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (10)

A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent characterized in that the tetracarboxylic dianhydride contains the following One or more of the tetracarboxylic dianhydride represented by the formula (TC-1) to the formula (TC-14) and one or more other tetracarboxylic dianhydrides, and the other tetracarboxylic dianhydride is The aromatic tetracarboxylic dianhydride represented by the following structural formula (5) and structural formula (14) has the following structural formula (15), structural formula (16), structural formula (21) to structural formula (25), and At least one of the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride represented by the structural formula (31): In the formula (TC-1), X represents -(CH ₂ ) _m -, and at most two -CH ₂ - may be independently -O-, but here -O-discontinuous, -S-, -COO- , -OCO-, -CO-, -CONH-, -C _n H _2n N(C _m H _2m COOH)C _n H _2n -, -CH(C _m H _2m OH)-, -CH(C _n H _{2n +1} )-, -CH=CH- or -C≡C- is substituted, wherein m of X in the above formula (TC-1) independently represents an integer of 0 to 30, and n independently represents an integer of 1 to 30; In the formula (TC-4) to the formula (TC-7), Y independently represents a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, - NHCO-, -NH-, -N(CH ₃ )-(CH ₂ ) _m -N(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH ₂ ) _m -S-, _m of Y in the above formula (TC-4) to formula (TC-7) represents 1~ An integer of 6; in the formula (TC-5), Z represents a single bond or is absent; in the formula (TC-2) to formula (TC-7), bonded to a cyclohexane ring or a benzene ring Hydrogen can be independently substituted by -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , and the bond in the formula (TC-3) is bonded to the benzene ring. hydrogen may be substituted with a benzyl group; formula (TC-2) ~ in formula (TC-8), R ¹ independently represents - (CH _{2) m} -, up to two -CH ₂ - may independently be -O-, -O- here but discontinuous, -S -, - COO -, - OCO -, - CO -, - CONH -, - CH (C m H 2m OH) -, - CH (C m H Substituting _2m+1 )-, -CH=CH- or -C≡C-, m of R ¹ in the above formula (TC-2) to formula (TC-8) independently represents an integer of 0 to 30; In the formula (TC-8), A ^{1 is} independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, acetaminophen, fluorine, chlorine or bromine, and A ² independently represents a carbon number of 1 An alkyl group of ~3, m represents an integer of 0 to 3, and n represents an integer of 0 to 4; in the formula (TC-9), R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 3 carbon atoms or benzene. A, A ³ independently represents a methylene group, a phenylene group or a subphenyl group substituted by an alkyl group, 1 represents an integer of 1 to 6, and m represents an integer of 1 to 10; in the formula (TC-10), A ³ represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _m -, and _m of A ³ in the above formula (TC-10) represents 1 to 6 An integer of R ¹ represents a group having a steroid skeleton or a group represented by the following formula (B), and when the positional relationship of two amino groups bonded to the benzene ring is para, R ¹ further contains a carbon number of 1 The alkyl group of ~30, when its positional relationship is meta, R ¹ further contains an alkyl group having 1 to 30 carbon atoms or a phenyl group. In the alkyl group, any -CH ₂ - may be independently -CF ₂ -, -CHF-, -O-, but here -O-discontinuous, -CH=CH- or -C≡C- Substituted, -CH ₃ may be substituted by -CH ₂ F, -CHF ₂ or -CF ₃ , which is hydrogen independent and may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, - Replaced by OCHF ₂ or -OCF ₃ ; In the general formula (B), A ⁴ and A ⁵ each independently represent a single bond, -O-, but here -O-discontinuous, -COO-, -OCO-, -CONH-, -CH=CH- or Alkenyl groups having 1 to 12 carbon atoms, R ² and R ³ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexene, 1,3 - Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or hydrazine- 9,10-diyl, R ⁴ represents -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkyl group substituted with fluorine having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -C ≡N, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , a and b represent integers from 0 to 4, respectively, c, d and e represent integers from 0 to 3, respectively, and f and g independently represent 0 to 2, respectively. Integer, and c+d+e≧1; in the formula (TC-11) and formula (TC-12), R ⁵ independently represents -H or -CH ₃ , and R ⁶ represents -H, or carbon number An alkyl group of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms, and A ⁶ independently represents a single bond, -CO- or -CH ₂ -; in the formula (TC-12), R ⁷ and R ⁸ are each independently And -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group; in the formula (TC-13) and the formula (TC-14), A ⁷ independently represents -O- or an alkene having 1 to 6 carbon atoms group; general formula (TC-13), R ⁹ denotes -H An alkyl group having 1 to 30 carbon atoms, and the alkyl, any alkyl group having 2 to 30 carbon atoms in -CH ₂ - -O- can be, but here the discontinuity -O-, -CH = CH- or -C≡C-substituted, A ⁸ represents a single bond or an alkylene group having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexene, and h represents 0 or 1; In the formula (TC-14), R ¹⁰ represents an alkyl group having 6 to 22 carbon atoms, and R ¹¹ represents -H or an alkyl group having 1 to 22 carbon atoms; The liquid crystal alignment agent according to claim 1, wherein the other tetracarboxylic dianhydride is represented by the structural formula (15), the structural formula (16), and the structural formula (21) to the structural formula (25). And at least one of an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride represented by the structural formula (31). The liquid crystal alignment agent according to claim 1 or 2, wherein the diamine further comprises a diamine having a side chain structure represented by the following general formula (I) and formula (II) Or more than one, In the general formula (I) and the general formula (II), A ⁹ independently represents -O- or an alkenyl group having 1 to 6 carbon atoms, and in the formula (I), R ¹² represents -H or a carbon number of 1 to 30. An alkyl group in which any -CH ₂ - of an alkyl group having 2 to 30 carbon atoms may be -O-, but here -O-discontinuous, -CH=CH- or -C≡C- Substituted, A ¹⁰ represents a single bond or an alkenyl group having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexene, and h represents 0 or 1, in the formula (II) R ¹⁵ represents an alkyl group having 6 to 22 carbon atoms, and R ¹⁶ represents an alkyl group having 1 to 22 carbon atoms. The liquid crystal alignment agent according to claim 3, wherein the diamine having a side chain structure is selected from the group consisting of the following general formula (I-1), general formula (I-2), and general formula (I- 4) and at least one of the compounds represented by the formula (I-7), In the above formula, R ¹³ and R ¹⁴ each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. The liquid crystal alignment agent according to claim 1 or 2, wherein the diamine further comprises the following general formula (III) to general formula (X), general formula (N), and general formula (a) a diamine represented by a side chain structure, In the formula (III), X represents -(CH ₂ ) _m -, and in the above formula (III), m of X represents an integer of 1 to 6, and the formula (V) and the formula (VII) to the formula (IX) In the formula, Y independently represents a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -NH-, -N(CH ₃ )- (CH ₂ ) _m -N(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O- , -S-(CH ₂ ) _m -S-, _m of Y in the above formula (V) and formula (VII) to formula (IX) represents an integer of 1 to 6, and in the formula (VII), Z Represents a single bond or absent. In the general formula (X), R ¹⁹ and R ²⁰ each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and A ¹¹ independently represents a methylene group, a phenylene group or an alkyl group. a sub-substituted phenyl group; i represents an integer of 1 to 6, and j represents an integer of 1 to 10, and hydrogen in the formula (IV) to formula (IX) bonded to a cyclohexane ring or a benzene ring may be used. Substituted independently by -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , the hydrogen bonded to the benzene ring in the formula (VI) can be Substituted by a benzyl group; in the formula (N), A ¹ independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, acetamide, fluorine, chlorine or bromine, and A ² Independently indicates that the carbon number is 1~3 Alkyl group, m represents an integer of 0 to 3, n is an integer of 0 to 4; in the general formula (a), L ¹ represents a hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group. The liquid crystal alignment agent according to claim 5, wherein the diamine having no side chain structure is selected from the group consisting of the following structural formula (VI-1), structural formula (VI-2), and structural formula (VI). -15)~Structure Formula (VI-17), Structural Formula (VII-1)~Structure Formula (VII-13), Structural Formula (VII-32), Structural Formula (VII-34)~Structure Formula (VII-36) ), structural formula (XI-2), structural formula (X-3), structural formula (N)-1, structural formula (N)-2, structural formula (N)-14, and structural formula (a-1) At least one of the compounds represented, The liquid crystal alignment agent according to claim 3, wherein the polyaminic acid or a derivative thereof comprises two polylysines or derivatives thereof A and B, the polyaminic acid or a derivative thereof A contains the diamine in the pass One or more of the diamines having a side chain structure represented by the formula (I) and the formula (II), and one or both of the polycarboxylic acid or derivatives of the derivatives A and B of the tetracarboxylic dianhydride One or more kinds of tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14) and other tetracarboxylic dianhydrides are contained, and the other tetracarboxylic dianhydride is The aromatic tetracarboxylic dianhydride represented by the structural formula (5) and the structural formula (14), the structural formula (15), the structural formula (16), and the structural formula (21) to the structural formula (25) And at least one of an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride represented by the structural formula (31). The liquid crystal alignment agent according to claim 1 or 2, further comprising a nadic ylidene compound selected from an alkenyl group, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, One or more of an oxazoline compound and an epoxy compound. A liquid crystal alignment film which is formed by heating a coating film of the liquid crystal alignment agent according to any one of claims 1 to 8. A liquid crystal display element having: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and aligning the liquid crystal molecules in a predetermined direction The liquid crystal display element is characterized in that the liquid crystal alignment film is a liquid crystal alignment film according to item 9 of the patent application.