KR102043699B1 - Liquid crystal aligning agent, liquid crystal alignment film, phase difference film, manufacturing method for the phase difference film, polymer, and compound - Google Patents

Abstract

(식 중, R¹∼R⁸은 수소 원자 등이고, R⁹ 및 R¹⁰은 할로겐 원자 등이고, Z¹ 및 Z²는 단결합, -O-, -COO-, -CO-, -NHCO- 또는 -O-CH₂-이고, Z¹ 및 Z²가 동시에 단결합이 되는 일은 없고; X¹은 2가의 유기기, m¹ 및 m²는 0∼4의 정수이고, n은 0 또는 1임).(Problem) The liquid crystal aligning agent which can express the various characteristic calculated | required by the liquid crystal display element in a balanced manner is provided.
(Solution means) A liquid crystal containing at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide obtained by reacting tetracarboxylic dianhydride and the diamine containing a compound represented by the following formula (d): It is contained in an alignment agent:

(Wherein, R ¹ to R ⁸ are hydrogen atoms, R ⁹ and R ¹⁰ are halogen atoms, etc., Z ¹ and Z ² are a single bond, -O-, -COO-, -CO-, -NHCO- or- O-CH _2- , and Z ¹ and Z ² do not become a single bond at the same time; X ¹ is a divalent organic group, m ¹ and m ² are integers of 0 to 4, and n is 0 or 1.

Description

LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM, PHASE DIFFERENCE FILM, MANUFACTURING METHOD FOR THE PHASE DIFFERENCE FILM, POLYMER, AND COMPOUND }

This invention relates to the polymer which can be used suitably as a component of a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, a retardation film, and a retardation film, and a compound used for manufacture of the said polymer.

Conventionally, as the liquid crystal display element, various driving methods having different electrode structures, physical properties of liquid crystal molecules to be used, manufacturing processes, and the like have been developed. For example, TN type, STN type, VA type, in-plane switching type (IPS type) Various liquid crystal display elements, such as FFS type, are known. These liquid crystal display elements have a liquid crystal aligning film for orienting liquid crystal molecules. As a material of a liquid crystal aligning film, polyamic acid and polyimide are generally used from the point which various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable.

In order to obtain a liquid crystal display device having high display quality, the liquid crystal cell exhibits a high voltage holding ratio, a burn-in phenomenon is hard to occur (afterimage hardly occurs), good heat resistance, and good rubbing resistance. It is desired that various characteristics are satisfactory, such as, for example, and various liquid crystal aligning agents for obtaining high quality liquid crystal display elements have been proposed (for example, see Patent Documents 1 and 2). PTL 1 uses polyamic acid obtained by reacting a diamine having an aromatic ester structure such as di (4-aminophenyl) hexane-1,6-dioate and a tetracarboxylic acid derivative as a polymer component of a liquid crystal aligning agent. Is disclosed. Further, Patent Document 2 discloses polyamic acid obtained by reacting a diamine and a tetracarboxylic acid derivative in which two aromatic rings, such as 1,3-bis (4-amino-2-methylphenyl) propane, are linked by an alkylene spacer structure. Use as a polymer component of a liquid crystal aligning agent is disclosed.

Moreover, various optical materials are used for a liquid crystal display element, The retardation film has the objective of eliminating the coloring of a display, and the resolution of viewing angle dependence, such that a display color and contrast ratio change with a visual direction. It is used. As such a retardation film, what has a liquid crystal aligning film formed in the surface of substrates, such as a TAC film, and the liquid crystal layer formed by hardening a polymeric liquid crystal on the surface of this liquid crystal aligning film is known. Moreover, in recent years, in the preparation of the liquid crystal aligning film in retardation film, the photo-alignment method which gives a liquid-crystal orientation capability by irradiating the radiation-sensitive organic thin film formed in the surface of a board | substrate with polarization or non-polarization radiation is used. The liquid crystal aligning agent for retardation films for producing a liquid crystal aligning film by these methods is proposed variously (for example, refer patent document 3).

As a method of producing a retardation film on an industrial scale, the roll-to-roll system is proposed (for example, refer patent document 4). This method unwinds a film from the winding body of a elongate base film, the process of forming a liquid crystal aligning film on the unwinded film, the process of apply | coating and hardening a polymeric liquid crystal on a liquid crystal aligning film, and protection as needed. It is a method of performing the process of laminating | stacking a film in a continuous process, and collect | recovering the film after having passed those processes as a winding object.

Japanese Patent No. 4415435 Japanese Patent No. 4779339 Japanese Laid-Open Patent Publication No. 2012-37868 Japanese Laid-Open Patent Publication No. 2000-86786

Background Art In recent years, liquid crystal display elements are not only used for display terminals such as personal computers, but also used for various types of applications such as liquid crystal televisions, car navigation systems, mobile phones, smart phones, information displays, and the like. From such a background, the demand for the high performance of a liquid crystal display element is increasing, and as a liquid crystal aligning film, the thing which can make various characteristics in a liquid crystal display element more favorable is calculated | required.

In addition, while adopting said roll-to-roll method with respect to retardation film, it can produce easily on an industrial scale, When the adhesiveness of a liquid crystal aligning film and a base film is insufficient, the film was made into a winding body after completion | finish of a process. In this case, the liquid crystal alignment film may be peeled off from the substrate film. In such a case, a problem may occur that product yield is lowered.

This invention is made | formed in view of the said subject, and can form the liquid crystal aligning film which can express favorable liquid-crystal orientation, and expresses the various characteristics calculated | required by the liquid crystal display element, such as high voltage holding ratio, heat resistance, and an afterimage, in a balanced manner. It is one object to provide a liquid crystal aligning agent which can be used. Moreover, another object is to provide the liquid crystal aligning agent which can form the liquid crystal aligning film for retardation films with favorable liquid crystal orientation and favorable adhesiveness with a board | substrate.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the subject of the said prior art, As a polymer component of a liquid crystal aligning agent, the polyamic acid obtained by polycondensation of diamine which has a specific structure, tetracarboxylic dianhydride, etc., By containing the polymer of at least one of a polyamic acid ester and a polyimide, it discovered that the said subject could be solved and came to complete this invention. Specifically, the following liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, retardation film, its manufacturing method, a polymer, and a compound are provided by this invention.

In an aspect, the present invention provides at least one compound selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester compound, and a compound represented by the following formula (d): It provides a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide obtained by reacting with a diamine comprising:

(In formula (d), R <^1> -R <^8> is respectively independently a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkenyl group, or a C1-C20 alkyl group or an alkenyl group A substituent is a monovalent group introduced; R ⁹ and R ¹⁰ are each independently a halogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxy group; and Z ¹ and Z ² are each independently a single bond, -O -, * -COO-, * -OCO-, -CO-, * -NHCO-, * -CONH- or * -O-CH _2- , where "*" represents a bond to X ¹ Provided that Z ¹ and Z ² do not become a single bond at the same time; X ¹ is a divalent organic group; m ¹ and m ² are each independently an integer of 0 to 4, n is 0 or 1; However, when two or more R <^9> , R <^10> exists, some R <^9> , R <^10> may be same or different, respectively).

This invention provides the liquid crystal aligning film formed using the said liquid crystal aligning agent in another aspect. Moreover, the liquid crystal display element provided with the said liquid crystal aligning film, and the retardation film provided with the said liquid crystal aligning film are provided. Moreover, in another aspect, the process of apply | coating the said liquid crystal aligning agent on a board | substrate to form a coating film, the process of light-irradiating the said coating film, and apply | coating and hardening a polymeric liquid crystal on the coating film after the light irradiation are carried out. It provides a method for producing a retardation film comprising a step. Further, at least one selected from the group consisting of a compound represented by the formula (d) and a diamine containing the compound, a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride and a tetracarboxylic acid diester compound A polymer obtained by reacting a compound of a species is provided.

By using the liquid crystal aligning agent containing polymers, such as polyamic acid synthesize | combined using the diamine represented by said formula (d), the liquid crystal aligning film with favorable liquid-crystal orientation can be obtained. Moreover, since the liquid crystal aligning film obtained using the liquid crystal aligning agent of this invention is high in voltage retention of a liquid crystal cell, and also excellent in heat resistance and afterimage characteristic, a high quality liquid crystal display element can be manufactured. Moreover, the adhesiveness with respect to a board | substrate of the liquid crystal aligning film obtained using the liquid crystal aligning agent of this invention is favorable. Therefore, even when this is preserve | saved as a winding object, a liquid crystal aligning film and a board | substrate are hard to peel, Therefore, the fall of a product yield can be suppressed at the time of manufacture of retardation film, for example.

1 is a schematic configuration diagram of an FFS type liquid crystal cell.
Fig. 2 is a plan schematic view of the top electrode, Fig. 2 (a) is a plan view of the top electrode, and Fig. 2 (b) is a partially enlarged view of the top electrode.

(Form to carry out invention)

The liquid crystal aligning agent of this invention contains at least 1 sort (s) of polymer (henceforth a polymer (A)) chosen from the group which consists of a polyamic acid, a polyamic acid ester, and a polyimide. Below, each component contained in the liquid crystal aligning agent of this invention, and the other component arbitrarily mix | blended as needed are demonstrated.

<Polymer (A); Polyamic Acid>

The polyamic acid (hereinafter also referred to as polyamic acid (A)) as the polymer (A) of the present invention can be obtained by, for example, reacting tetracarboxylic dianhydride and diamine.

[Tetracarboxylic dianhydride]

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid in this invention, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. . As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane 2: 3,5: 6-2 anhydride, bi Cyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclo Hexanetetraka An acid dianhydride, and bicyclo [2.2.2] loam-7-ene-2,3,5,6-tetracarboxylic acid dianhydride;

As aromatic tetracarboxylic dianhydride, For example, pyromellitic dianhydride etc .; In addition to each of them, tetracarboxylic dianhydride described in JP 2010-97188 A can be used. Moreover, as tetracarboxylic dianhydride used for the synthesis | combination of polyamic acid, these 1 type can be used individually or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesizing the polyamic acid (A) of the present invention, bicyclo [2.2.1] heptane-2,3, from the viewpoint of improving liquid crystal alignment and solubility in a solvent. 5,6-tetracarboxylic acid 2: 3,5: 6-2 anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1, 3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1 , 3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1, 3-dione, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride And it is preferable to contain the specific tetracarboxylic dianhydride which is at least 1 sort (s) chosen from the group which consists of pyromellitic dianhydride. Moreover, it is preferable to make the usage-amount of the said specific tetracarboxylic dianhydride into 5 mol% or more with respect to the total amount of the tetracarboxylic dianhydride used for the synthesis of polyamic acid, and it is more preferable to set it as 10 mol% or more. And it is especially preferable to set it as 20 mol% or more.

Moreover, the said tetracarboxylic dianhydride is poly which can form the liquid crystal aligning film which is excellent in various characteristics, such as liquid crystal aligning property, voltage preservation characteristic, and heat resistance, by polycondensation reaction with the diamine containing the compound represented by a following formula (d). All have the same effect in that a dark acid can be obtained. Therefore, even if it is not described in the following example, it can use in this invention.

[Diamine]

The compound represented by said formula (d) is contained in the diamine used for the synthesis | combination of the polyamic acid (A) of this invention.

With respect to the formula (d), R ¹ ~R ⁸ halogen atoms in the ^{(R 1, R 2, R} 3, R 4, R 5, R 6, R 7 and R ^8), for example, a fluorine atom , Chlorine atom, bromine atom, iodine winza and the like. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, Octadecyl group, eicosyl group, etc. are mentioned, These may be linear or branched form. As a C1-C20 alkenyl group, a vinyl group, an allyl group, a propenyl group, a hexenyl group, etc. are mentioned, for example, These may be linear or branched form. In addition, R <^1> -R <^8> may be a monovalent group in which a substituent was introduce | transduced into said C1-C20 alkyl group or C1-C20 alkenyl group. As a substituent in this case, For example, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine winza; Alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group etc. are mentioned. In addition, R <^1> -R <^8> may mutually be same or different.

Examples of R ¹ ~R ^8, it is preferable that the steric hindrance is small structure in terms of liquid crystal alignment property and rubbing resistance. Specifically, it is preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and all of R ¹ ~R ⁸ are hydrogen atoms are particularly preferred.

As R ⁹ and R ¹⁰ in the formula (d), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine winza. The alkyl group having 1 to 6 carbon atoms may be linear or branched, and examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. Moreover, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example. In addition, R <^9> and R <^10> may mutually be same or different. In addition, when two or more R <^9> exists in said Formula (d), these some R <^9> may mutually be same or different, and when two or more R <^10> exists in said Formula (d), these some R <^10> mutually exist It may be same or different.

As R <^9> and R <^10> , among these, it is preferable that they are a C1-C4 alkyl group, an alkoxy group, or a fluorine atom. R ⁹ and R ¹⁰ can be introduced in the (m ^1, m ^2), it is preferable that each is an integer of 0 to 2 is preferred, and 0 or 1;

Z ¹ and Z ² are a single bond, -O-, * -COO-, * -OCO-, -CO-, * -NHCO-, * -CONH- or * -O-CH _2- , and the same as each other Although they may differ, Z <^1> and Z <^2> do not become a single bond simultaneously. In addition, "*" represents the bond with X <^1> . Among them, Z ¹ and Z ² are preferably -O-, * -COO-, * -OCO-, -CO-, * -NHCO-, * -CONH- or * -O-CH _2- , and It is more preferable that it is O-, * -COO-, * -OCO-, -CO-, * -NHCO-, or * -CONH-. In addition, when at least any one of Z <^1> and Z <^2> is -O-, * -COO-, * -OCO-, -CO-, * -NHCO- or * -CONH-, it is represented by said formula (d) A phenethyl structure is introduced into the compound. More preferably, it is * -COO- or * -CONH-, Especially preferably, it is * -COO-.

X ¹ is a divalent organic group, for example, a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group, and -O-, -COO-, The divalent group which has -CO-, -NHCO-, -S- etc., and the divalent group into which the substituents, such as a halogen atom and an alkoxy group, were introduce | transduced, are mentioned, for example in the said hydrocarbon group. In addition, a chain hydrocarbon group means the saturated hydrocarbon group and unsaturated hydrocarbon group which consist of only a chain structure, without including a cyclic structure in a principal chain. However, both of a linear hydrocarbon group and a branched hydrocarbon group are included. In addition, an alicyclic hydrocarbon group means a hydrocarbon group which contains only the structure of an alicyclic hydrocarbon as a ring structure, and does not contain an aromatic ring structure. However, it does not need to consist only of the structure of an alicyclic hydrocarbon, but includes the thing which has a linear structure in one part. An aromatic hydrocarbon means the hydrocarbon group which contains an aromatic ring structure as ring structure. However, it is not necessary to be comprised only with an aromatic ring structure, and the structure of a linear structure and an alicyclic hydrocarbon may be included in one part.

Examples of X ^1, in view of maintaining a good liquid crystal alignment retention, particularly alkanediyl group or a carbon number of _{1~18 - [(CH 2) 2} O] a - (CH 2) 2 - ( However, a is 1 to 3 Is an integer of). Here, as an example of a C1-C18 alkanediyl group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, decandiyl group, etc. are mentioned, for example. These may be linear or branched form. As X <^1> , it is preferable that it is a C1-C10 alkanediyl group among the above from a viewpoint of making liquid crystal aligning property and rubbing tolerance favorable, and it is more preferable that it is a C2-C8 alkanediyl group.

Although the bonding position of the primary amino group on a benzene ring is not specifically limited about two aminophenyl groups in Formula (d), It is preferable that it is 3-position or 4-position with respect to another group (ethylene structure), and 4-position More preferably. n is 0 or 1, and it is especially preferable that it is 1.

As a specific example of a compound represented by said formula (d), the compound etc. which are represented by each of following formula (d-1) (d-11)-are mentioned, for example.

In the synthesis | combination of the polyamic acid (A) of this invention, 1 type of compounds represented by said formula (d) can be used individually or in mixture of 2 or more types. In addition, all the compounds represented by said formula (d) have the same effect | action in the point which can obtain the polymer which shows the effect of this invention. Therefore, even the compound which is not described in the following example can be used in this invention.

In the synthesis | combination of a polyamic acid (A), although only the compound represented by said formula (d) may be used as a diamine, you may use other diamine together with the said compound.

As other diamine which can be used here, an aliphatic diamine, an alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. As these specific examples, As aliphatic diamine, For example, m-xylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1, 5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7- Diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene ) Bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl , 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3, 6-diaminocarbazole, N- Tyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl ) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy- 2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2, 5-diaminobenzene, tetradecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5- Diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2, 4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4 -Aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1 -Bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1- Bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-amino Benzylamine, 1- (2,4-diaminophenyl) piperazin-4-carboxylic acid, 4- (morpholin-4-yl) benzene-1,3-diamine, 1,3-bis (N- (4 -Aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5 -Amines, 1- (4-aminophenyl) -2,3 -Dihydro-1,3,3-trimethyl-1H-inden-6-amine, 4-aminophenyl-4'-aminobenzoate, 4,4 '-[4,4'-propane-1,3-diyl Bis (piperidine-1,4-diyl)] dianiline and the following formula (D-1);

(In formula (D-1), X <^I> and X <^II> are single-bond, -O-, -COO-, or -OCO-, respectively, R <^I> is a C1-C3 alkanediyl group and a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, n is 0 or 1, provided that a and b do not become 0 at the same time)

Compounds represented by these;

As diamino organosiloxane, For example, 1, 3-bis (3-aminopropyl)-tetramethyl disiloxane, etc .; In addition to each of them, the diamines described in JP 2010-97188 A can be used.

The expression in (D-1) ^{"-X I - (R I -X Ⅱ} ) n - " As the divalent group represented by, alkanediyl group having a carbon number of 1~3, * -O-, * -COO- Or * -OC ₂ H ₄ -O-, provided that the bond to which "*" is attached is combined with a diaminophenyl group.

Specific examples of the group "-C _c H _{2c +1",} for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl group , n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octade A practical group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. It is preferable that two amino groups in a diaminophenyl group exist in 2, 4-position or 3, 5-position with respect to another group.

As a specific example of a compound represented by said formula (D-1), the compound etc. which are represented by each of following formula (D-1-1) (D-1-3) are mentioned, for example.

In addition, as other diamine used for the synthesis | combination of the said polyamic acid, these compounds can be used individually by 1 type or in combination of 2 or more types.

As a diamine used for the synthesis | combination of the polyamic acid (A) of this invention, from the viewpoint of obtaining a liquid crystal aligning film with favorable liquid-crystal orientation, heat resistance, and an afterimage characteristic, the diamine which uses the use ratio of the compound represented by said formula (d) for synthesis | combination is used. It is preferable to set it as 1 mol% or more with respect to whole quantity of, It is more preferable to set it as 5 mol% or more, It is more preferable to set it as 10 mol% or more, It is especially preferable to set it as 20 mol% or more. In addition, about the upper limit of the use ratio of the compound represented by said Formula (d), what is necessary is just to set suitably according to the drive mode of the liquid crystal display element to apply, etc., and to set arbitrarily in 100 mol% or less with respect to all the diamines used for synthesis | combination. Can be.

When providing liquid-crystal orientation by the photo-alignment method with respect to the coating film produced using the liquid crystal aligning agent of this invention, one or all of the polymer (A) of this invention may be used as a polymer which has a photo-alignment structure. Here, the photo-alignment structure is a concept including both the photo-alignment group and the resolved photo-alignment unit. Specifically, as the photo-alignment structure, groups derived from various compounds exhibiting photo-alignment by photoisomerization, photodimerization, photolysis, etc. may be employed. For example, azobenzene containing azobenzene or a derivative thereof as a basic skeleton. Benzoconium-containing groups, benzophenones or derivatives thereof, containing a cinnamic acid structure containing a containing group, cinnamic acid or a derivative thereof as a basic skeleton, a chalcone or a derivative thereof, as a basic skeleton And a coumarin-containing group containing a phenone-containing group, coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing a polyimide or a derivative thereof as a basic skeleton, and the like.

When the polymer (A) contains a polymer having a photo-alignment structure (hereinafter also referred to as a photo-alignment polymer (A)), the polymer (A) is preferably a polymer including a decomposable photo-alignment portion, specifically Is preferably a polymer having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton. By having such specific frame | skeleton, the liquid crystal alignability of a coating film can be made more favorable. The polymer having the specific skeleton is, for example, at least one of cyclobutanetetracarboxylic dianhydride and bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride. It can obtain by making tetracarboxylic dianhydride containing and the diamine containing the compound represented by said formula (d) react.

When providing liquid crystal aligning ability to a coating film by the photo-alignment method, it is preferable that the use ratio of a photo-alignment polymer (A) shall be 10 weight% or more with respect to the total amount of a polymer (A), and 30- It is more preferable to set it as 100 weight%, and it is further more preferable to set it as 50-100 weight%.

[Molecular Weight Control Agent]

At the time of synthesis | combination of polyamic acid (A), you may make it synthesize | combine a terminal-modified polymer using a suitable molecular weight modifier with tetracarboxylic dianhydride and diamine as mentioned above. By setting it as such a terminal modified polymer, the coating property (printability) of a liquid crystal aligning agent can be improved further, without impairing the effect of this invention.

As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As these specific examples, as an acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back; As a monoamine compound, For example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc .; As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, respectively.

It is preferable to set it as 20 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine to be used, and, as for the usage ratio of a molecular weight modifier, it is more preferable to set it as 10 weight part or less.

<Synthesis of Compound Represented by Formula (d)>

The compound represented by said formula (d) can be synthesize | combined by combining suitably the method of organic chemistry. As an example, the dinitro body which has two nitrophenyl groups instead of two aminophenyl groups in said Formula (d) is synthesize | combined, and then, the nitro group of the obtained dinitro body is aminated using a suitable reducing system. How to do this.

Here, the method for synthesizing the dinitro body is not particularly limited and can be appropriately synthesized according to Z ¹ , Z ² , n and the like, for example. Specifically, for example, when a compound of n = 1 is represented, when Z ¹ and Z ² are "* -CO-NH-", a primary amine compound containing nitrophenethyl groups such as nitrophenylethylamine and the like; And can be synthesized by reacting an acid chloride of dicarboxylic acid having a corresponding X ¹ . In addition, when Z <^1> and Z <^2> are "* -NH-CO-", it can synthesize | combine by reacting the acid chloride containing nitrophenethyl group, and the diamine which has corresponding X <^1>, for example.

When Z <^1> and Z <^2> are "* -CO-O-", it is synthesize | combined, for example by making nitro phenethyl group containing alcohols, such as nitrophenyl ethanol, react with the acid chloride of the dicarboxylic acid which has corresponding X <^1> . Can be. Also, Z ¹ and Z ² may be synthesized by a "* -O-CO-", in the case of, for example, reacting the diol with an acid chloride having a nitro containing a phenethyl group, corresponding to X ^1.

When Z ¹ and Z ² are "-O-" or "* -O-CH _2- ", for example, a nitrophenethyl group-containing alcohol such as nitrophenylethanol, nitrophenylpropanol, and the corresponding X ¹ are represented. It can synthesize | combine by making reacting the dihalide which has. When Z <^1> and Z <^2> are "-CO-", the Grignard reagent obtained by reaction of dihalogenated alkyl and metal magnesium, for example with respect to aldehyde containing nitrophenethyl groups, such as nitro phenethyl aldehyde, is mentioned. It can be synthesize | combined by making it react, and synthesize | combining the secondary alcohol compound obtained, and oxidizing the obtained secondary alcohol compound using a suitable oxidation reagent.

The reaction for obtaining the dinitro body as the intermediate is preferably performed in an organic solvent. The organic solvent may be any solvent which does not affect the reaction, for example, methanol, ethanol, tetrahydrofuran, toluene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone Etc. can be mentioned. In addition, you may perform the said reaction in presence of a catalyst as needed.

The reduction reaction of the dinitro body is preferably carried out using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel in an organic solvent. As an organic solvent used here, ethyl acetate, toluene, tetrahydrofuran, an alcohol type, etc. are mentioned, for example. However, the synthesis sequence of the compound represented by said formula (d) is not limited to the said method.

Synthesis of Polyamic Acid (A)

The use ratio of tetracarboxylic dianhydride and diamine provided in the synthesis reaction of the polyamic acid (A) of this invention becomes 0.2-2 equivalent of the acid anhydride group of tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of a diamine. A ratio is preferable, More preferably, it is a ratio which becomes 0.3-1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably performed in an organic solvent. At this time, the reaction temperature is preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. Moreover, 0.1-24 hours are preferable and, as for reaction time, 0.5-12 hours are more preferable.

Here, examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.

Specific examples of these organic solvents include, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and γ-buty as aprotic polar solvents. Rolactone, tetramethylurea, hexamethylphosphortriamide and the like; As the phenol solvent, for example, phenol, m-cresol, xylenol, halogenated phenol and the like;

As alcohol, For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc .; As a ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonic acid, isoamyl propio Nate, isoamyl isobutyrate, etc .; As the ether, for example, diethyl ether, diisopentyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene Glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, tetrahydrofuran and the like; As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like; As said hydrocarbon, For example, hexane, heptane, octane, benzene, toluene, xylene, etc .; Each can be mentioned.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenolic solvents (a first group of organic solvents), or at least one selected from a first group of organic solvents, alcohols, Preference is given to using mixtures with at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group of organic solvents). In the latter case, the use ratio of the second group of organic solvents is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total amount of the organic solvent of the first group and the organic solvent of the second group. More preferably, it is 30 weight% or less. The amount (a) of the organic solvent is preferably such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight relative to the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving the polyamic acid (A) is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after isolating the polyamic acid (A) contained in a reaction solution, or refine | purified the isolated polyamic acid (A). You may provide to preparation of a liquid crystal aligning agent later. In the case where the polyamic acid (A) is dehydrated and closed to form a polyimide, the reaction solution may be used as it is for dehydration ring closure, or may be used for dehydration ring closure after isolation of the polyamic acid (A) contained in the reaction solution. Alternatively, the isolated polyamic acid (A) may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of polyamic acid can be performed according to a well-known method.

<Polymer (A); Polyamic Acid Ester>

The polyamic acid ester (hereinafter also referred to as polyamic acid ester (A)) as the polymer (A) of the present invention is, for example, [I] a polyamic acid (A) obtained by the above-described synthesis reaction, a hydroxyl group-containing compound, or a halogen. It can obtain by the method of synthesize | combining by making a cargo, an epoxy-group-containing compound, etc. react, the method of making [II] tetracarboxylic acid diester compound, and a diamine react, and the method of making [III] tetracarboxylic acid diester dichloride, and diamine react. .

Here, as a hydroxyl-containing compound used by method [I], For example, Alcohol, such as methanol, ethanol, a propanol; Phenols, such as a phenol and a cresol, are mentioned. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodineethane, and the like, and examples of the epoxy group-containing compound For example, propylene oxide etc. are mentioned. The tetracarboxylic acid diester used by method [II] can be obtained by ring-opening tetracarboxylic dianhydride illustrated by the synthesis of the said polyamic acid (A), for example using said alcohol. In addition, the tetracarboxylic-acid diester dichloride used by method [III] can be obtained by, for example, reacting the tetracarboxylic-acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. As diamine used by method [II] and [III], the compound represented by said formula (d) is included, You may use the said other amine as needed. In addition, the polyamic acid ester may have only a dark acid ester structure, and the partial esterified product which a dark acid structure and a dark acid ester structure coexist together may be sufficient as it.

<Polymer (A); Polyimide>

The polyimide (hereinafter also referred to as polyimide (A)) as the polymer (A) of the present invention can be obtained by, for example, dehydrating and ring closing the polyamic acid (A) synthesized as described above.

The said polyimide may be the complete imide which dehydrated and closed all the dark acid structures which the polyamic acid (A) which is the precursor has, and only the part of the dark acid structure is dehydrated and closed, and the part of the dark acid structure and the imide ring structure coexists. Imide may be sufficient. It is preferable that the imidation ratio of the polyimide in this invention is 30% or more, It is more preferable that it is 40 to 99%, It is further more preferable that it is 50 to 99%. This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. Here, part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. . Among these, it is preferable by the latter method.

In the method of adding a dehydrating agent and a dehydrating ring-closure catalyst in the solution of the polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing the polyimide (A) is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, and may provide it to preparation of a liquid crystal aligning agent after isolating polyimide. After refine | purifying the isolated polyimide, you may provide for preparation of a liquid crystal aligning agent. These purification operations can be performed according to a well-known method. In addition, a polyimide (A) can also be obtained by imidating by dehydrating and ring-closing a polyamic acid ester (A).

<Solution Viscosity and Molecular Weight of Polymer>

When the polyamic acid, polyamic acid ester, and polyimide as a polymer (A) obtained as mentioned above are made into the solution of 10 weight% of concentration, it is preferable to have a solution viscosity of 10-800 mPa * s, and it is 15-500 mPa *. It is more preferable to have a solution viscosity of s. In addition, the solution viscosity (mPa * s) of the said polymer is the density | concentration 10weight prepared using the quantity solvent (for example, (gamma) -butyrolactone, N-methyl- 2-pyrrolidone, etc.) of the said polymer. It is the value measured at 25 degreeC using the E-type rotational viscometer about% polymer solution.

The weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) of the said polyamic acid, a polyamic acid ester, and a polyimide becomes like this. Preferably it is 1,000-500,000, More preferably, it is 2,000-300,000. Moreover, molecular weight distribution (Mw / Mn) represented by the ratio of Mw and the number average molecular weight (Mn) of polystyrene conversion measured by GPC becomes like this. Preferably it is 15 or less, More preferably, it is 10 or less. By being in such a molecular weight range, the favorable orientation and stability of a liquid crystal display element can be ensured.

<Other ingredients>

Although the liquid crystal aligning agent of this invention contains the above polymer (A), it can contain another component as needed. For example, when using the liquid crystal aligning agent of this invention for manufacture of the liquid crystal aligning film in a liquid crystal display element, as another component which may be added to the said liquid crystal aligning agent, other polymers other than the said polymer (A), molecule The compound which has at least 1 epoxy group in it (henceforth "epoxy group containing compound"), a functional silane compound, a metal chelate compound, a hardening accelerator, surfactant, etc. are mentioned.

[Other polymers]

The said other polymer can be used for the improvement of a solution characteristic and an electrical property. As such another polymer, the polyamic acid (henceforth "other polyamic acid") obtained by making the above-mentioned tetracarboxylic dianhydride and said other diamine react, for example, is formed by dehydrating and ring-closing the said other polyamic acid. Polyimide (hereinafter also referred to as "other polyimide"), polyamic acid ester synthesized using the above-mentioned other diamine (hereinafter also referred to as "other polyamic acid ester"), polyester, polyamide, polysiloxane, cellulose derivative, Polyacetal, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like.

In addition, when making the liquid crystal aligning agent of this invention for retardation films, as said other polymer, the polymer which has a photo-alignment structure can be used preferably. It is preferable to include the polymer which has a photo-alignment group specifically, and it is more preferable to include the polymer which the group which has the cinnamic acid structure was introduce | transduced as a photo-alignment group. Especially, since the introduction of the photo-orientation group into a polymer is easy, it is preferable that it is polyorganosiloxane which has a cinnamic acid structure.

In addition, the polymer which has a photo-alignment group can be synthesize | combined by a conventionally well-known method. For example, the polyorganosiloxane which has a photo-alignment group as another polymer contains the polyorganosiloxane which has an epoxy group, and the carbonic acid which has a photo-alignment group, Preferably it is 4 in organic solvents, such as an ether, ester, and a ketone. It can synthesize | combine by making it react in presence of catalysts, such as a quaternary ammonium salt.

When adding another polymer to a liquid crystal aligning agent, it is preferable to set it as 50 weight part or less with respect to 100 weight part of all the polymers in the said composition, It is more preferable to set it as 0.1-40 weight part, 0.1- More preferably, it is 30 parts by weight.

Epoxy-containing Compounds

An epoxy group containing compound can be used in order to improve adhesiveness with the board | substrate surface in a liquid crystal aligning film. Here, as an epoxy group containing compound, For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglyci Dyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol di Glycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, N, Preferred N-diglycidyl-cyclohexylamine, epoxy group-containing polyorganosiloxane as described in International Publication No. 2009/096598 It can be mentioned as.

When adding these epoxy group containing compounds to a liquid crystal aligning agent, 40 weight part or less is preferable with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent, and 0.1-30 weight part is more preferable.

[Functional silane compound]

The said functional silane compound can be used in order to improve the printability of a liquid crystal aligning agent. As such a functional silane compound, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate , 9-triethoxysilyl-3,6-methyl diazanonan, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxy Silane, glycidoxy methyl triethoxy silane, 2-glycidoxy ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, etc. are mentioned. .

When adding a functional silane compound to a liquid crystal aligning agent, 2 weight part or less is preferable with respect to a total of 100 weight part of polymers, and, as for the compounding ratio, 0.02-0.2 weight part is more preferable.

[Metal Chelate Compounds]

The said metal chelate compound is a liquid crystal aligning agent (especially the liquid crystal aligning agent for retardation films) for the purpose of ensuring the mechanical strength of the film | membrane formed by low temperature processing, when the polymer component of a liquid crystal aligning agent has an epoxy structure. It is contained in. As the metal chelate compound, it is preferable to use an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium. Specifically, for example, diisopropoxyethylacetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis ( Acetylacetonate) titanium, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, and the like. The use ratio of the metal chelate compound is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and 1 to 30 parts by weight based on 100 parts by weight of the total components of the epoxy structure. More preferred.

[Hardening accelerator]

When the polymer accelerator in a liquid crystal aligning agent has an epoxy structure, the said hardening accelerator is a liquid crystal aligning agent (especially liquid crystal aligning for retardation film), in order to ensure the time-dependent stability of the mechanical strength and liquid crystal aligning property of the liquid crystal aligning film formed. It is contained in first). As said hardening accelerator, the compound which has a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carbonic anhydride group, etc. can be used, for example, The compound which has a phenol group or a silanol group is especially preferable. Do. As the specific example, As a compound which has a phenol group, For example, cyanophenol, nitrophenol, methoxy phenoxy phenol, thiophenoxy phenol, 4-benzyl phenol; As the compound having a silanol group, for example, trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene , Triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, and the like. The use ratio of the curing accelerator is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and more preferably 1 to 30 parts by weight based on 100 parts by weight of the total of the constituent components including the epoxy structure. Do.

[Surfactants]

The said surfactant can be contained in a liquid crystal aligning agent (especially the liquid crystal aligning agent for retardation films) for the purpose of improving the applicability | paintability to the board | substrate of a liquid crystal aligning agent. As such surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant etc. are mentioned, for example. It is preferable to set it as 10 weight part or less with respect to 100 weight part of total amounts of a liquid crystal aligning agent, and, as for the usage ratio of surfactant, it is more preferable to set it as 1 weight part or less.

In addition, antioxidants, such as a phenolic antioxidant and an amine antioxidant; Polyfunctional (meth) acrylates such as ethylene glycol diacrylate and 1,6-hexanediol diacrylate; You may add etc. in a liquid crystal aligning agent.

<Solvent>

The liquid crystal aligning agent of this invention is prepared as said liquid composition which disperse | distributes or melt | dissolves the said polymer (A) and other components used as needed, preferably in a suitable solvent.

As the organic solvent to be used, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydride Roxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl Propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These can be used individually or in mixture of 2 or more types.

Solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is chosen suitably in consideration of viscosity, volatility, etc., Preferably Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of this invention is apply | coated to the board | substrate surface as mentioned later, Preferably, it heats, and the coating film which becomes a coating film which is a liquid crystal aligning film, or a liquid crystal aligning film is formed. At this time, when solid content concentration is less than 1 weight%, the film thickness of a coating film becomes small and a favorable liquid crystal aligning film becomes difficult to obtain. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and a favorable liquid crystal aligning film is hard to be obtained, and also the viscosity of a liquid crystal aligning agent increases and there exists a tendency for applicability | paintability to fall.

The range of especially preferable solid content concentration changes with the use of a liquid crystal aligning film, and the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, when apply | coating to a board | substrate with a spinner method about the liquid crystal aligning agent for liquid crystal cells, solid content concentration (the ratio which the total weight of all components other than the solvent in a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent) It is especially preferable that it is the range of 1.5 to 4.5 weight%. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC. Moreover, about the liquid crystal aligning agent for retardation films, it is preferable that solid content concentration of a liquid crystal aligning agent is the range of 0.2-10 weight% from a viewpoint of making applicability | paintability of a liquid crystal aligning agent, and the film thickness of the coating film formed. It is more preferable that it is the range of 3 to 10 weight%.

<Liquid crystal display element and retardation film>

A liquid crystal aligning film can be manufactured by using the liquid crystal aligning agent of this invention demonstrated above. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention can be preferably applied to the liquid crystal aligning film for liquid crystal display elements (for liquid crystal cells), and the liquid crystal aligning film for retardation films. Below, the liquid crystal display element and retardation film of this invention are demonstrated.

[Liquid Crystal Display Element]

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type It can be applied to various driving methods. The liquid crystal display element of this invention can be manufactured by the process of the following (1-1)-(1-3), for example. In the step (1-1), the substrate used differs depending on the desired operation mode. Process (1-2) and (1-3) are common to each operation mode.

[Step (1-1): Formation of Coating Film]

First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface.

(1-1A) For example, when manufacturing a TN type, STN type, or VA type liquid crystal display element, first, two board | substrates with which the patterned transparent conductive film is formed are paired, and each transparent conductive film formation is carried out. On the surface, the liquid crystal aligning agent of this invention is apply | coated preferably by the offset printing method, the spin coating method, the roll coater method, or the inkjet printing method, respectively. As a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. Can be. To obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern; A method of using a mask having a desired pattern when forming a transparent conductive film; Or the like. At the time of application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface and a transparent conductive film and a coating film more favorable, a functional silane compound, a functional titanium compound, etc. are previously made to the surface which forms a coating film in the board | substrate surface. Pretreatment to apply may be performed.

After apply | coating a liquid crystal aligning agent, preheating (prebaking) is preferably performed for the purpose of liquid flow prevention of the apply | coated liquid crystal aligning agent. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25-10 minutes, More preferably, it is 0.5-5 minutes. Thereafter, the solvent is completely removed and a firing (postbaking) step is performed for the purpose of thermally imidizing the dark acid structure present in the polymer as necessary. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes. Thus, the film thickness of the film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

 (1-1B) When manufacturing an IPS type or FFS type liquid crystal display element, the electrode formation surface of the board | substrate in which the electrode which consists of the transparent conductive film or metal film patterned by the comb-tooth type is formed, and the electrode is not formed The coating film is formed by apply | coating the liquid crystal aligning agent of this invention each to one surface of a counter substrate, and then heating each coating surface. In this case, the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after the coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film have the same meanings as in the above (1-1A). to be. As a metal film, the film which consists of metals, such as chromium, can be used, for example.

In any of said (1-1A) and (1-1B), after apply | coating a liquid crystal aligning agent on a board | substrate, the coating film used as an oriented film is formed by removing an organic solvent. In this case, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and a dark acid structure, further dehydration ring closure reaction is performed by further heating after coating film formation. It is good also as a coating film more imidated.

[Step (1-2): Orientation Performance Providing Treatment]

When manufacturing a liquid crystal display element of TN type, STN type, IPS type, or FFS type, as a process which gives a liquid-crystal orientation ability to the coating film formed at the said process (1-1), the said coating film is nylon, rayon, for example. The rubbing process which rubs in a fixed direction is performed with the roll which wound the cloth which consists of fibers, such as cotton. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. On the other hand, when manufacturing a VA type liquid crystal display element, although the coating film formed by the said process (1-1) can be used as a liquid crystal aligning film as it is, you may perform a rubbing process with respect to the said coating film. About the liquid crystal aligning film after a rubbing process, the rubbing process mentioned above after the process which changes the pretilt angle of the one part area | region of a liquid crystal aligning film by irradiating a part of liquid crystal aligning film, or a part of the surface of a liquid crystal aligning film, After performing a rubbing process in a different direction, the process of removing a resist film may be performed and a liquid crystal aligning film may have a different liquid crystal aligning ability for every area | region. In this case, it is possible to improve the viewing characteristic of the liquid crystal display element obtained. Moreover, the liquid crystal aligning film suitable for VA type liquid crystal display element can be used suitably also for the PSA (Polymer sustained alignment) type liquid crystal display element. As a process which gives a liquid-crystal orientation ability to a coating film, you may employ | adopt the process by the photo-alignment method instead of a rubbing process.

[Step (1-3): Construction of Liquid Crystal Cell]

The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged to face each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealing agent, and the substrate surface and the sealing agent are partitioned. After injecting and filling a liquid crystal in a cell gap, a liquid crystal cell can be manufactured by sealing an injection hole. The second method is a method called ODF (One Drop Fill) method. After apply | coating an ultraviolet-ray curable sealing compound to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, and dropping a liquid crystal in predetermined several places on the liquid crystal aligning film surface, a liquid crystal aligning film The liquid crystal cell can be manufactured by bonding another board | substrate so that this may oppose, spreading a liquid crystal on the whole surface of a board | substrate, and then irradiating ultraviolet light to the whole surface of a board | substrate and hardening a sealing compound. Also by any method, it is preferable to remove the liquid crystal orientation at the time of liquid crystal filling by gradually cooling to the temperature which liquid crystal cell used as mentioned above also takes the isotropic phase of the used liquid crystal, and then cools to room temperature. Do.

As a sealing agent, the epoxy resin etc. which contain the aluminum oxide sphere as a hardening | curing agent and a spacer can be used, for example. Moreover, as a liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, Especially, a nematic liquid crystal is preferable, For example, a sieve base liquid crystal, a cyanide liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, ester Type liquid crystals, terphenyl type liquid crystals, biphenylcyclohexane type liquid crystals, pyrimidine type liquid crystals, dioxane type liquid crystals, bicyclooctane type liquid crystals, cuban type liquid crystals, and the like. Moreover, for these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agent sold as brand names "C-15" and "CB-15" (made by Merck); Ferroelectric liquid crystals, such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, may be added and used.

And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine, and extended | stretched polyvinyl alcohol by the cellulose acetate protective film, or the H film itself is mentioned. Can be.

[Retardation Film]

The liquid crystal aligning film formed using the liquid crystal aligning agent of this invention can be applied to the liquid crystal aligning film for retardation films. Below, the method of manufacturing retardation film using the liquid crystal aligning agent of this invention is demonstrated. In manufacture of the retardation film of this invention, it is possible to form a uniform liquid crystal aligning film, suppressing generation | occurrence | production of dust and static electricity during a process, and the liquid crystal aligning direction on a board | substrate is used by using a suitable photomask at the time of irradiation of a radiation. It is preferable to use the optical alignment method in that a plurality of different regions can be arbitrarily formed. Specifically, it can manufacture by going through the following process (2-1)-(2-3).

[Step (2-1): Formation of Coating Film by Liquid Crystal Alignment Agent]

First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and a coating film is formed. As a board | substrate used here, the transparent substrate which consists of synthetic resins, such as a triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate, etc. Can be suitably illustrated. Among these, TAC is generally used as a protective layer of the polarizing film in a liquid crystal display element. Moreover, polymethyl methacrylate can be used suitably as a board | substrate for retardation films from the point where the hygroscopicity of a solvent is low, the optical characteristic is favorable, and the point is low cost. In addition, about the board | substrate used for application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface and a coating film further favorable, the conventionally well-known pretreatment may be given to the surface which forms a coating film in the board | substrate surface.

In most cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to precisely control the angle with respect to the polarization axis of a polarizing film in a specific direction so that the expected optical characteristic can be exhibited, and to bond a retardation film. Therefore, here, the process of bonding a retardation film on a polarizing film, controlling the angle by forming the liquid crystal aligning film which has liquid crystal aligning ability in the direction of a predetermined angle on substrates, such as a TAC film and a polymethylmethacrylate, Can be omitted. Moreover, this can contribute to the improvement of the productivity of a liquid crystal display element. In order to form the liquid crystal aligning film which has liquid crystal aligning ability in the direction of a predetermined angle, it is preferable to carry out by the photo-alignment method using the liquid crystal aligning agent of this invention.

The application of the liquid crystal aligning agent onto the substrate may be made by an appropriate coating method, for example, a roll coater method, spinner method, printing method, inkjet method, bar coater method, extrusion die method, direct gravure coater method, or chamber. Doctor coater method, offset gravure coater method, one roll kiss coater method, reverse kiss coater method using small gravure roll, three reverse roll coater method, four reverse roll coater method, slot die method, air The doctor coater method, the forward rotation roll coater method, the braid coater method, the knife coater method, the impregnation coater method, the MB coater method, and the MB reverse coater method can be adopted.

After coating, the coating surface is heated (baked) to form a coating film. It is preferable to set it as 40-150 degreeC, and, as for the heating temperature at this time, it is more preferable to set it as 80-140 degreeC. The heating time is preferably 0.1 to 15 minutes, more preferably 1 to 10 minutes. The film thickness of the coating film formed on a board | substrate becomes like this. Preferably it is 1-1,000 nm, More preferably, it is 5 nm-500 nm.

[Step (2-2): Light Irradiation Step]

Subsequently, by irradiating light to the coating film formed on the board | substrate as mentioned above, liquid crystal aligning ability is provided to a coating film, and it is set as a liquid crystal aligning film. Here, as light to irradiate, the ultraviolet-ray, visible light, etc. which contain the light of a wavelength of 150-800 nm are mentioned, for example. Of these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. Irradiation light may be polarized or non-polarized light. As polarized light, it is preferable to use light containing linearly polarized light.

When the light to be used is polarized light, irradiation of light may be performed from the direction perpendicular | vertical to a board | substrate surface, or may be performed from an oblique direction, or it may combine them. When irradiating non-polarization, it is necessary to carry out from the direction oblique with respect to the board | substrate surface.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a mercury-xenon lamp (Hg-Xe lamp) etc. are mentioned, for example. Polarization can be obtained by means of using these light sources in combination with a filter, a diffraction grating, or the like, for example.

The irradiation dose of light is preferably 0.1 mJ / cm 2 or more and less than 1,000 mJ / cm 2, more preferably 1 to 500 mJ / cm 2, and even more preferably 2 to 200 mJ / cm 2. Moreover, when the liquid crystal aligning agent of this invention is used, even if the amount of light irradiation is 500 mJ / cm <2> or less and 200 mJ / cm <2> or less, favorable liquid crystal aligning ability can be provided by the photo-alignment method, and it can reduce the manufacturing cost of a liquid crystal aligning film. Contribute.

 [Step (2-3): Formation of Liquid Crystal Layer]

Next, a polymeric liquid crystal is apply | coated and hardened on the coating film after light irradiation as mentioned above. Thereby, the coating film (liquid crystal layer) containing a polymeric liquid crystal is formed. The polymerizable liquid crystal used herein is a liquid crystal compound or a liquid crystal composition which polymerizes by at least one treatment of heating and light irradiation. As such a polymerizable liquid crystal, a conventionally well-known thing can be used, For example, Nonpatent literature 1 ("UV curable liquid crystal and its application", a liquid crystal, Vol. 3, No. 1 (1999), pp34). The nematic liquid crystal described in -42) is mentioned. In addition, cholesteric liquid crystal; Discotic liquid crystals; A twisted nematic alignment type liquid crystal to which chiral agent was added may be sufficient. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may further be a composition containing a known polymerization initiator, a suitable solvent, or the like.

In order to apply | coat the polymeric liquid crystal as mentioned above on the formed liquid crystal aligning film, the appropriate coating methods, such as the bar coater method, the roll coater method, the spinner method, the printing method, the inkjet method, can be employ | adopted, for example.

Next, the coating film is cured by forming at least one treatment selected from heating and light irradiation on the coating film of the polymerizable liquid crystal formed as described above to form a liquid crystal layer. It is preferable to perform these processes in a superimposition at the point by which favorable orientation is obtained.

The heating temperature of a coating film should be suitably selected according to the kind of polymeric liquid crystal to be used. For example, when using RMS03-013C by Merck Co., Ltd., it is preferable to heat at the temperature of 40-80 degreeC. Heating time becomes like this. Preferably it is 0.5 to 5 minutes.

As irradiation light, the ultraviolet-ray of non-polarization which has a wavelength of 200-500 nm can be used preferably. As irradiation amount of light, it is preferable to set it as 50-10,000mJ / cm <2>, and it is more preferable to set it as 100-5,000mJ / cm <2>.

As thickness of the liquid crystal layer formed, it sets suitably by a desired optical characteristic. For example, when manufacturing a 1/2 wavelength plate in visible light with a wavelength of 540 nm, thickness is selected so that the phase difference of the formed retardation film may be 240-300 nm, and if it is a 1/4 wavelength plate, phase difference will be The thickness to be 120-150 nm is selected. The thickness of the liquid crystal layer from which the target phase difference is obtained varies depending on the optical properties of the polymerizable liquid crystal to be used. For example, when using Merck Co., Ltd. RMS03-013C, the thickness for manufacturing a quarter wave plate is 0.6-1.5 micrometers.

The retardation film obtained as mentioned above can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film manufactured using the liquid crystal aligning agent of this invention is applied does not have a restriction | limiting in the drive system, For example, well-known, such as TN type, STN type, IPS type, FFS type, VA type, etc. It can be applied to various methods. As for the said retardation film, the surface by the side of the board | substrate in a retardation film is adhere | attached with respect to the outer surface of the polarizing plate arrange | positioned at the visual recognition side of a liquid crystal display element. Therefore, it is preferable to set it as the aspect which makes the board | substrate of a retardation film a TAC or an acrylic base material, and makes the board | substrate of the said retardation film also function as a protective film of a polarizing film.

The liquid crystal display element of this invention can be effectively applied to various apparatuses, For example, a clock, a portable game, a word processor, a notebook PC, a car navigation system, a camcorder, a PDA, a digital camera, a mobile telephone, It can be used for various display devices, such as a smart phone, various monitors, a liquid crystal television, and an information display.

EXAMPLE

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

In the following synthesis examples, the weight average molecular weight Mw, imidation ratio, and epoxy equivalent of the polymer, and the solution viscosity of the polymer solution were measured by the following method.

[Weight Average Molecular Weight Mw of Polymer]

Mw is polystyrene conversion value measured by the gel permeation chromatography on the following conditions.

Column: Toso Co., Ltd., TSKgelGRCXLⅡ

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

[Imidation Rate of Polymer]

The solution containing a polyimide was put into pure water, the obtained precipitate was dried under reduced pressure sufficiently at room temperature, it was dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio was determined using the following formula (1):

Imidation ratio (%) = {(1-A ¹ ) / (A ² × α)} × 100. (One)

(In Formula (1), A <^1> is the peak area derived from the proton of the NH group which shows around 10 ppm of chemical shifts, A <^2> is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polymer. Number ratio of other protons to one proton of NH group).

[Epoxy equivalent]

Epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[Solution Viscosity of Polymer Solution]

The solution viscosity (mPa * s) of the polymer solution was measured at 25 degreeC using the E-type rotational viscometer.

Synthesis of Diamine

[Example A-1; Synthesis of Compound (d-1)]

Compound (d-1) was synthesized according to Scheme 1 below.

In a 2 L three-necked flask equipped with a dropping lot, 332.36 g of 2- (4-nitrophenyl) ethylamine and 1,000 mL of pyridine were mixed, and a solution in which 154 g of succinyl chloride was dissolved in 500 mL of tetrahydrofuran was slowly added dropwise from the dropping lot. did. During dropping, the system was cooled so as not to exceed 30 ° C. After completion of the dropwise addition, the mixture was stirred at 45 ° C. for 2 hours to react. After reaction, 2000 mL of ethyl acetate was added and extracted, 200 mL of distilled water was added, and liquid-separation was carried out. After repeating the extraction and purification five times, 320 g of a nitro intermediate (compound represented by the formula (d-1-1)) was obtained by removing the solvent from the organic layer by distillation under reduced pressure.

Subsequently, after adding 16 g of said nitro intermediate 320g and 5% Pd / C, 500 mL of ethanol, and 500 mL of tetrahydrofuran to a 2 L three neck flask under nitrogen stream, it substituted with hydrogen again and made it react at room temperature in presence of hydrogen. . The reaction was traced in HPLC and filtered after confirming the progress of the reaction. Ethyl acetate 3000mL was added to the filtrate, distilled water 200mL was added, and liquid-separation was carried out. After repeating the extraction purification five times, the solid was precipitated by removing the solvent from the organic layer by distillation under reduced pressure. 219g of compounds (d-1) were obtained by recrystallizing the precipitated solid from ethanol.

Example A-2; Synthesis of Compound (d-5)]

Compound (d-5) was synthesized according to Scheme 2 below.

In a 2 L three-necked flask with a dropping lot, 334.32 g of 2- (4-nitrophenyl) ethyl alcohol and 1,000 mL of pyridine were mixed, and a solution in which 183 g of adipic acid dichloride was dissolved in 500 mL of tetrahydrofuran was added from the dropping lot. I dripped slowly. During dropping, the system was cooled so as not to exceed 30 ° C. After completion of the dropwise addition, the reaction was carried out by stirring at 45 ° C for 2 hours. After reaction, 2000 mL of ethyl acetate was added and extracted, 200 mL of distilled water was added, and liquid-separation was carried out. After repeating the said extraction purification 5 times, 306g of nitro intermediates (compound represented by said formula (d-1-2)) were obtained by removing a solvent from the organic layer by vacuum distillation.

Subsequently, 306 g of the above-mentioned nitro intermediate, 15.3 g of 5% Pd / C, 500 mL of ethanol and 500 mL of tetrahydrofuran were added to a 2 L three-necked flask under nitrogen stream, and then substituted again with hydrogen, and reacted at room temperature in the presence of hydrogen. I was. The reaction was traced in HPLC and filtered after confirming the progress of the reaction. Ethyl acetate 3000mL was added to the filtrate, distilled water 200mL was added, and liquid-separation was carried out. After repeating the extraction purification five times, the solid was precipitated by removing the solvent from the organic layer by distillation under reduced pressure. 220g of compound (d-5) was obtained by recrystallizing the precipitated solid from ethanol.

[Example A-3; Synthesis of Compound (d-9)]

Compound (d-9) was synthesized according to Scheme 3 below.

In a 2 L three-necked flask equipped with a dropping lot, 362.38 g of 3- (4-nitrophenyl) propanol and 1600 ml of tetrahydrofuran were mixed and dissolved, and cooled in an ice bath. Next, the mixture of 400 ml of tetrahydrofuran and 84 g of sodium hydride was slowly added to the solution obtained above from the dropping lot, and it stirred at room temperature for 1 hour. In addition, it cooled by the ice bath so that it might not exceed 30 degreeC during dripping. Next, 229.94 g of 1,5-dibromopentane and 6.45 g of tetrabutylammonium bromide (TBAB) were added, mixed, and reacted at 40 ° C for 20 hours. After reaction, 5000 mL of ethyl acetate was added and extracted, 200 mL of distilled water was added, and liquid-separation was carried out. After repeating the extraction and purification five times, the solvent was removed from the organic layer by distillation under reduced pressure to obtain a crude product. 327g of nitro intermediate (compound represented by said formula (d-1-3)) was obtained by refine | purifying the obtained crude product by silica column chromatography.

Subsequently, after adding 327 g of said nitro intermediate, 16.35 g of said 5% Pd / C, 500 mL of ethanol, and 500 mL of tetrahydrofuran to a 2 L three neck flask under nitrogen stream, it substituted by hydrogen again and reacted at room temperature in presence of hydrogen. I was. The reaction was traced in HPLC and filtered after confirming the progress of the reaction. Ethyl acetate 3000mL was added to the filtrate, 200 mL of distilled water was further added, and liquid-separation was carried out. After repeating the extraction purification five times, the solid was precipitated by removing the solvent from the organic layer by distillation under reduced pressure. 190 g of compounds (d-9) were obtained by recrystallizing the precipitated solid from ethanol.

Synthesis of Polymer

[Example B-1; Synthesis of Polyamic Acid]

10.18 g of pyromellitic dianhydride and 9.16 g of 1,2,3,4-cyclobutanoic acid dianhydride as tetracarboxylic dianhydride and 13.25 g of compound (d-1) as diamine, with the following formula (1-1) 6.39 g of the compound represented and 11.00 g of the compound represented by the following Formula (1-2) were dissolved in 200 g of N-methyl-2-pyrrolidone (NMP), and the reaction was performed at room temperature for 6 hours. A small amount of the reaction solution was collected and the solution viscosity was measured. As a result, it was 1,810 mPa · s. The reaction mixture was then poured into excess methanol to precipitate the reaction product. After wash | cleaning the collect | recovered precipitate with methanol, 47.5g of polyamic acid (P-1) was obtained by drying at 40 degreeC under reduced pressure for 15 hours.

[Example B-2; Synthesis of Polyimide]

10.5 g of 2,3,5-tricarboxycyclopentylacetic dianhydride and 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 as tetracarboxylic dianhydride 11.7 g of anhydride and 13.18 g of compound (d-9) as a diamine, 9.32 g of 4,4'-diaminodiphenylmethane and 5.2 g of the compound represented by the following formula (1-3) are dissolved in NMP 200 g, at room temperature The reaction was carried out for 6 hours. A small amount of the reaction solution was collected and the solution viscosity was measured. As a result, it was 1,670 mPa · s.

Subsequently, NMP250g was added to the obtained polyamic acid solution, pyridine 14.88g and 19.20g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 90 degreeC for 6 hours. The reaction mixture was then poured into excess methanol to precipitate the reaction product. Methanol wash | cleaned the collect | recovered deposit, and it dried at 40 degreeC under reduced pressure for 15 hours, and obtained 46.9g of polyimides (P-2) of 94% of imidation ratios.

[Example B-3; Synthesis of Polyamic Acid]

9.11 g of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride as tetracarboxylic dianhydride and bicyclo [2.2.1] heptan-2,3,5,6-tetracarboxylic acid 2: 3,5: 9.60 g of 6-2 anhydride and 31.28 g of compound (d-5) as diamine were dissolved in 200 g of NMP, and the reaction was carried out at room temperature for 6 hours. A small amount of the reaction solution was collected and the solution viscosity was measured. As a result, it was 1,250 mPa · s. The reaction mixture was then poured into excess methanol to precipitate the reaction product. After wash | cleaning the collect | recovered precipitate with methanol, 48.1g of polyamic acid (P-3) was obtained by drying at 40 degreeC under reduced pressure for 15 hours.

Example B-4; Synthesis of Polyamic Acid]

Tetracarboxylic acid dianhydride as 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] furan-1,3-dione 13.11 g and 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho 12.52 g of [1,2-c] furan-1,3-dione and 3.10 g of compound (d-9) as a diamine, 11.43 g of a compound represented by the following formula (1-1), and the following formula (1-2) 9.83 g of the compound represented by) was dissolved in NMP 200 g, and the reaction was carried out at room temperature for 6 hours. A small amount of the reaction solution was collected and the solution viscosity was measured. As a result, it was 1,450 mPa · s. The reaction mixture was then poured into excess methanol to precipitate the reaction product. 48.7g of polyamic acid (P-4) was obtained by wash | cleaning the collect | recovered deposit with methanol, and drying at 40 degreeC under reduced pressure for 5 hours.

Example B-5; Synthesis of Polyamic Acid]

3.88 g of pyromellitic dianhydride and 13.98 g of 1,2,3,4-cyclobutanoic dianhydride as tetracarboxylic dianhydride and 30.98 g of compound (d-1) as diamine and the following formula (1-4): 1.15 g of the compound shown was dissolved in 200 g of NMP, and the reaction was performed at room temperature for 6 hours. A small amount of the reaction solution was collected and the solution viscosity was measured. As a result, it was 1,680 mPa · s. The reaction mixture was then poured into excess methanol to precipitate the reaction product. After wash | cleaning the collect | recovered precipitate with methanol, 49.1g of polyamic acid (P-5) was obtained by drying at 40 degreeC under reduced pressure for 15 hours.

Synthesis Example 1; Synthesis of Polyamic Acid]

10.18 g of pyromellitic dianhydride and 9.15 g of 1,2,3,4-cyclobutanoic acid dianhydride as tetracarboxylic dianhydride and 30.66 g of a compound represented by the following formula (1-5) as diamine: NMP 200 g It melt | dissolved in and reacted at room temperature for 6 hours. The reaction solution was aliquoted in small portions, and the solution viscosity was measured. As a result, it was 1,220 mPa · s. The reaction mixture was then poured into excess methanol to precipitate the reaction product. After wash | cleaning the collect | recovered precipitate with methanol, 46.7g of polyamic acid (P-6) was obtained by drying at 40 degreeC under reduced pressure for 15 hours.

Synthesis Example 2; Synthesis of Polyamic Acid]

12.58 g of pyromellitic dianhydride and 11.31 g of 1,2,3,4-cyclobutanoic acid dianhydride as tetracarboxylic dianhydride, and 26.11 g of compound represented by the following formula (1-6) as diamine: NMP 200 g It melt | dissolved in and reacted at room temperature for 6 hours. A small amount of the reaction solution was collected and the solution viscosity was measured. As a result, it was 980 mPa · s. The reaction mixture was then poured into excess methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried at 40 ° C. for 15 hours under reduced pressure to obtain 47.1 g of polyamic acid (P-7).

Table 1 shows the types and molar ratios of tetracarboxylic dianhydride and diamine used in Examples B-1 to B-5 and Synthesis Examples 1 and 2.

In addition, the numerical value of Table 1 shows the use ratio (mol%) with respect to the total amount of tetracarboxylic dianhydride used for reaction about tetracarboxylic dianhydride, and about diamine, to the total amount of diamine used for reaction The use ratio (mol%) to the following is shown.

The abbreviated-name of Table 1 is the following meaning.

(Tetracarbonic acid 2 anhydride)

t-1: 1,2,3,4-cyclobutanoic acid dianhydride

t-2: pyromellitic dianhydride

t-3: 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride

t-4: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

t-5: 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride

t-6: bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-2 anhydride

t-7: 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1 , 3-dione

t-8: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c Furan-1,3-dione

(Diamine)

da-1: the compound represented by said formula (1-1)

da-2: the compound represented by said formula (1-2)

da-3: the compound represented by Formula (1-3)

da-4: 4,4'-diaminodiphenylmethane

da-5: the compound represented by said formula (1-4)

da-6: the compound represented by said formula (1-5)

da-7: compound represented by the formula (1-6)

Synthesis Example S-1; Synthesis of Polyorganosiloxane]

Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were added thereto. Mix at room temperature. 100 g of deionized water was dripped here over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an oxiranyl group. Obtained as a viscous transparent liquid. As a result of ¹ H-NMR analysis of the polyorganosiloxane having the oxiranyl group, a peak based on the oxiranyl group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and the reaction of the oxiranyl group was carried out during the reaction. It was confirmed that no side reaction occurred. It was 186 g / equivalent when the epoxy equivalent of the polyorganosiloxane which has this oxiranyl group was measured.

Subsequently, in a 100 mL three-necked flask, 9.3 g of polyorganosiloxane having an oxiranyl group obtained above, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid, and 0.10 g of UCAT 18X (trade name, manufactured by San Apro Co., Ltd.) Was added, and reaction was performed at 80 degreeC for 12 hours, stirring. After completion of the reaction, the reaction mixture was poured into methanol to recover the precipitate, which was dissolved in ethyl acetate to form a solution. The solution was washed three times with water, and then the solvent was distilled off to remove the oxyranyl group and the liquid crystal aligning group. 6.3g of obtained polyorganosiloxane (S-1) was obtained as white powder. The weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography about this polyorganosiloxane (S-1) was 3,500.

<Preparation and evaluation of liquid crystal aligning agent>

Example 1: FFS liquid crystal display device

(1) Preparation of liquid crystal aligning agent

100 parts by weight of the polyamic acid (P-1) obtained in Example B-1 as a polymer is a mixed solvent consisting of γ-butyrolactone (GBL), NMP and butyl cellosolve (BC) (GBL: NMP: BC = 40: 40:20 (weight ratio)), and it was set as the solution whose solid content concentration is 4.0 weight%. The liquid crystal aligning agent was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

(2) Evaluation of applicability

After apply | coating the liquid crystal aligning agent prepared above using the spinner on a glass substrate, and prebaking for 1 minute by 80 degreeC hotplate, it heats in 200 degreeC oven which nitrogen-substituted the inside of tube for 1 hour (post-baking) By doing so, a coating film having an average film thickness of 1,000 kPa was formed. This coating film was observed under the microscope of 20 times magnification, and the film thickness nonuniformity and the presence or absence of the pinhole were investigated. The evaluation is based on the case where neither the film thickness nonuniformity nor the pinhole is observed, and the case where at least one of the coating property "goodness", the film thickness nonuniformity, and the pinhole is slightly observed among the applicability "a", the film thickness nonuniformity, and the pinhole. The case where at least one was observed clearly was performed as applicability "failure." In the present Example, neither a film thickness nonuniformity nor a pinhole was observed, and coating-film property was "good."

(3) evaluation of rubbing resistance

About the coating film obtained above, the rubbing process was performed 5 times by the rubbing machine which has the roll which rolled the cotton cloth by roll rotation speed 1000rpm, stage movement speed 20cm / sec, and hairpin indentation length 0.4mm. The foreign material (fragment of a coating film) by rubbing abrasion on the obtained board | substrate was observed with the optical microscope, and the foreign material number in the area | region of 500 micrometers x 500 micrometers was measured. Evaluation was performed when the number of foreign matters was 9 or less as rubbing tolerance "good", and when 10 or more was regarded as rubbing tolerance "bad". As a result, the rubbing resistance of this coating film was "good".

(4) Fabrication of FFS liquid crystal display device

The liquid crystal cell of the FFS type liquid crystal display element shown in FIG. 1 was produced. First, the bottom electrode 15 having no pattern, the silicon nitride film as the insulating layer 14, and the top electrode 13 patterned in a comb-tooth shape were formed in this order in two pairs of electrode pairs ("electrode A" and " The glass substrate 11a which has electrode B ") on one side, and the opposing glass substrate 11b in which an electrode is not formed are made into a pair, and the surface which has an electrode of the glass substrate 11a, and the opposing glass substrate 11b On one surface of), the liquid crystal aligning agent prepared above was apply | coated using the spinner, respectively, and the coating film was formed. Subsequently, this coating film was prebaked at 80 degreeC hotplate for 1 minute, and then heated (postbaked) at 230 degreeC for 15 minutes in oven which carried out the nitrogen substitution of the inside of the tube, and formed the coating film of average film thickness of 1,000 Pa. The top schematic of the top electrode 13 is shown in FIG. 2A is a top view of the top electrode 13, and FIG. 2B is an enlarged view of the portion C1 surrounded by the broken line in FIG. 2A. In the present Example, the board | substrate which has the top electrode 13 whose line | wire width d1 of a transparent electrode is 4 micrometers, and the distance d2 between electrodes is 6 micrometers was used.

Next, each surface of the coating film formed on the glass substrates 11a and 11b was subjected to a rubbing treatment with cotton in the direction of the arrow f in FIG. 2 (b) to obtain a liquid crystal alignment film 12. These board | substrates 11a and 11b were bonded together through the spacer of 3.5 micrometers in diameter so that the rubbing direction of each board | substrate might be reversed, and the empty cell of liquid crystal non-injection was produced. Liquid crystal MLC-6221 (made by Merck) was injected into this cell, and the liquid crystal layer 16 was formed. Moreover, the liquid crystal display element 10 of Example 1 was produced by bonding the polarizing plate (not shown) to the outer both surfaces of the board | substrates 11a and 11b so that the polarization direction of two polarizing plates may mutually orthogonally cross. This series of operations were repeated, and three FFS type liquid crystal display elements were produced in total, and each was provided for evaluation of the following liquid crystal orientation, evaluation of heat resistance, and evaluation of the relaxation rate of residual DC.

(5) Evaluation of liquid crystal alignment

With respect to the FFS liquid crystal display device manufactured above, the presence or absence of an abnormal domain in the change in contrast when the voltage of 5 V was turned on and off (applied and released) was determined by the microscope 100 times magnification and 50 times magnification. Observed by ship. In the evaluation, the liquid crystal alignment property "good" and the magnification of the case where the abnormal domain was not observed even at the magnification 100 times, the abnormal domain was observed at the magnification 100 times, but the abnormal domain was not observed at the magnification 50 times. The case where abnormal domain was observed also at 50 times was performed as liquid crystal aligning "poor". In this liquid crystal cell, it was liquid crystal orientation "excellent".

(6) evaluation of heat resistance

For the FFS type liquid crystal display device manufactured above, after applying a voltage of 5 V in an application time of 60 microseconds and a span of 167 milliseconds, the voltage holding ratio (initial voltage holding ratio (VHR _BF )) 167 milliseconds after the release of the application was applied. It measured using "VHR-1" by the Toyo Technica Corporation. Next, the liquid crystal display element after VHR _BF measurement was left to stand in 100 degreeC oven for 1,000 hours. Then, after leaving this liquid crystal display element to stand at room temperature and allowing it to cool to room temperature, voltage holding ratio (VHR _AF ) was measured on the conditions similar to the measurement of initial stage voltage holding ratio VHR _BF . Moreover, the change rate ((DELTA) VHR (%)) of the voltage holding ratios before and behind provision of thermal stress was calculated | required by following formula (2).

ΔVHR (%) = ((VHR _BF -VHR _AF ) ÷ VHR _BF ) x 100. (2)

Evaluation was performed when the change rate (DELTA) VHR was less than 5% as heat resistance "good" and 5% or more as heat resistance "failure." As a result, VHR _BF was 99.2% and the heat resistance of the liquid crystal display element was "good".

(7) Evaluation of relaxation rate of residual DC (evaluation of afterimage characteristic)

About the liquid crystal display element manufactured above, the relaxation rate of residual DC was measured by the dielectric absorption method using the 6254C type liquid crystal physical property evaluation apparatus by a Toyo Technica Corporation. The measurement was performed under an environment of 60 ° C, after applying a DC voltage of 10V to the cell for 30 minutes, the battery was discharged for 1 second, and then the residual DC for 30 minutes was measured. The relaxation rate of residual DC was calculated | required by calculating average residual DC relaxation rate from the residual DC value 1 minute after the time which showed the maximum value and maximum value of residual DC. The evaluation is performed when the residual DC relaxation rate is 4 kV / sec or more when the residual DC relaxation "good", and when the residual DC relaxation "good" is less than 4 kV / sec. Was performed as residual DC loosening "bad". In addition, the higher the relaxation rate, the less likely that an afterimage is generated and the better the afterimage characteristic. The relaxation rate of residual DC of the liquid crystal display element of a present Example was 5.2 kV / sec, and it was judged as residual DC relaxation "good".

[Examples 2 and 3 and Comparative Examples 1 and 2]

In the said Example 1, the liquid crystal aligning agent was prepared like Example 1 except having used each of the kind shown in following Table 2 as a polymer, and produced and evaluated the FFS type liquid crystal display element. The evaluation results are shown in Table 2 below.

As shown in Table 2, in an Example, all were favorable results about the applicability | paintability of a liquid crystal aligning agent, the rubbing tolerance of a coating film, and the relaxation rate of liquid crystal alignability, initial stage voltage holding ratio, heat resistance, and residual DC in a liquid crystal display element. Was obtained. On the other hand, in Comparative Examples 1 and 2, the initial voltage holding ratio of the liquid crystal display element was less than 99%, which was lower than that of the examples. In Comparative Example 1, the heat resistance of the liquid crystal display element was “poor”, and in Comparative Example 2, the relaxation property of residual DC was “poor”.

Example 4 TN Liquid Crystal Display Element

(1) Preparation of liquid crystal aligning agent

As a polymer, 100 parts by weight of the polyimide (P-2) obtained in Example B-2 was dissolved in a mixed solvent of NMP and BC (NMP: BC = 50: 50 (weight ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. . After fully stirring this solution, the liquid crystal aligning agent was prepared by filtering by the filter of 0.2 micrometer of pore diameters.

(2) evaluation of printability

The liquid crystal aligning agent prepared in said (1) is apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printer (made by Nippon Shashin Insatsu Co., Ltd.), and it is on a 80 degreeC hotplate After heating (prebaking) for 1 minute and removing a solvent, it heated (postbaking) for 10 minutes on the 200 degreeC hotplate, and formed the coating film of average film thickness of 600 Pa. This coating film was observed with the microscope of 20 times the magnification, and the printing nonuniformity and the presence of pinholes were investigated. The evaluation is based on a case where at least one of printability "good", print nonuniformity, and pinhole is slightly observed in the case where neither printing nonuniformity nor pinhole is observed, at least one of printability "possible", printing nonuniformity, and pinhole. The case where a lot was seen was performed as printability "defect". In the present Example, neither printing nonuniformity nor the pinhole was observed, and printability was "good."

(3) Preparation of TN type liquid crystal cell

The liquid crystal aligning agent prepared in said (1) is apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printer (made by Nippon Shashin Insatsu Co., Ltd.), and it is on a 80 degreeC hotplate After heating (prebaking) for 1 minute and removing a solvent, it heated (postbaking) for 10 minutes on the 200 degreeC hotplate, and formed the coating film of average film thickness of 600 Pa. About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound the rayon cloth, at the roll rotation speed of 500 rpm, the stage moving speed of 3 cm / sec, and the seedling indentation length of 0.4 mm, and the liquid crystal aligning ability was provided. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. Moreover, said operation was repeated and the pair (two sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Next, after apply | coating the aluminum-oxide-containing epoxy resin adhesive of 5.5 micrometers in diameter to the outer edge of the surface which has one liquid crystal aligning film among the said pair of board | substrates, a liquid crystal aligning film surface has a counterpart of a pair of board | substrates. It crimped | bonded so that it might overlap, and hardened the adhesive agent. Subsequently, after filling a nematic liquid crystal (MLC-6221 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the TN type liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocurable adhesive.

By repeating the above series of operations, a total of three TN liquid crystal cells were produced, and each liquid crystal cell was used for evaluation of liquid crystal orientation, evaluation of pretilt angle stability, and heat resistance.

(4) Evaluation of liquid crystal alignment

About the liquid crystal cell manufactured by said (3), the presence or absence of the abnormal domain at the time of turning on / off the voltage of 5V under cross nicol was observed by the microscope 100 times magnification and 50 times magnification. Evaluation was performed similarly to (5) of the said Example 1. As a result, in this liquid crystal cell, it was liquid crystal orientation "excellent".

(5) Evaluation of pretilt angle stability

About the liquid crystal cell manufactured by said (3), the angle of inclination from the board | substrate surface of a liquid crystal molecule is measured by the crystal rotation method which uses a He-Ne laser beam, and this value is made into the initial pretilt angle (theta) _IN . did. The crystal rotation method is described in Non Patent Literature 1 (TJ Schffer et al., J. Appl. Phys. Vol. 48, p1783 (1977)) and Non Patent Literature 2 (F. Nakano et al., JPN. J. Appl. Phys. Vol. 19). , p2013 (1980)).

Next, an alternating voltage of 5 V was applied to the liquid crystal cell after measuring the initial pretilt (θ _IN ) for 100 hours. Then, the pretilt angle was measured again by the same method as the above, and this value was made into the pretilt angle (theta _AF ) after voltage application. These measured values were substituted into the following formula (3), and the change amount (Δθ (°)) of the pretilt angle before and after voltage application was obtained.

Δθ = | θ _AF -θ _IN | (3)

When this value (DELTA) (theta) is less than 0.05 degree, it evaluated as the pretilt angle stability "good", and when it is 0.05 degree or more and less than 0.2 degree, the pretilt angle stability "good", and when it is 0.2 degrees or more, it evaluated as pretilt angle stability "bad". As a result, the amount of change Δθ in the pretilt angle in the liquid crystal cell was less than 0.2 °, and the pretilt angle stability was “good”.

(6) evaluation of heat resistance

In the same manner as in Example 6 (6), the initial voltage holding ratio VHR _BF was measured, and heat resistance was evaluated by the rate of change of the voltage holding ratio before and after applying thermal stress. As a result, the initial voltage holding ratio VHR _BF was 99.1%. In addition, heat resistance was "good".

Example 5 VA Type Liquid Crystal Display Element

(1) Preparation of liquid crystal aligning agent

As polymer, 100 parts by weight of polyamic acid (P-5) obtained in Example B-5 was added with NMP and BC to prepare a solution having a solid content concentration of 6.5% by weight and a solvent mixing ratio of NMP: BC = 50: 50 (weight ratio). After fully stirring this solution, the liquid crystal aligning agent was prepared by filtering by the filter of 0.2 micrometer of pore diameters.

(2) evaluation of printability

Using the liquid crystal aligning agent prepared in said (1), the printability was investigated similarly to (2) of the said Example 4, and neither the printing nonuniformity nor the pinhole was observed, and printability was "good."

(3) Preparation of VA type liquid crystal cell

The liquid crystal aligning agent prepared above is apply | coated using the liquid crystal aligning film printer (made by Nippon Shashin Insatsu Co., Ltd.) on the transparent electrode surface of the glass substrate (1 mm of thickness) with a transparent electrode which consists of an ITO film, and 80 degreeC It heated on the hot plate for 1 minute (prebaking), and further heated (post-baking) for 60 minutes on the 200 degreeC hotplate, and formed the coating film (liquid crystal aligning film) of average film thickness 800 Pa. This operation was repeated and the pair (two sheets) of glass substrates which have a liquid crystal aligning film on the transparent conductive film was obtained.

Next, after apply | coating the 5.5-micrometer-diameter aluminum oxide containing epoxy resin adhesive agent on the outer edge of the surface which has one liquid crystal aligning film among the said pair of board | substrates, a pair of board | substrates are overlapped so that a liquid crystal aligning film surface may face and crimp | compression-bonded. And the adhesive was cured. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, VA type liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

(4) Evaluation of liquid crystal alignment and heat resistance

The liquid crystal aligning property of this liquid crystal cell was "good" as a result of evaluating similarly to (4) of Example 4 about the liquid crystal cell manufactured by said (3). In addition, the initial voltage holding ratio VHR _BF was measured in the same manner as in Example 6 (6), and heat resistance (rate of change in voltage holding ratio before and after applying thermal stress) was evaluated. As a result, initial stage voltage retention VHR _BF was 99.4%, and heat resistance was "good".

Example 6: Retardation Film

(1) Preparation of liquid crystal aligning agent

100 parts by weight of polyamic acid (P-1) obtained in Example B-1 and 5 parts by weight of polyorganosiloxane (S-1) obtained in Synthesis Example S-1, a mixed solvent consisting of NMP and BC (NMP: BC = 50:50 (weight ratio)), and it was set as the solution whose solid content concentration is 3.5 weight%. The liquid crystal aligning agent was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

(2) Preparation of Retardation Film

The liquid crystal aligning agent prepared above was apply | coated to the one surface of the TAC film as a board | substrate using the bar coater, and it baked at 120 degreeC in oven for 2 minutes, and formed the coating film with a film thickness of 100 nm. Subsequently, 10 mJ / cm <2> of polarized ultraviolet-ray containing 313 nm bright line was irradiated perpendicularly from the board | substrate normal line on the surface of this coating film using the Hg-Xe lamp and the glan tailor prism, and the liquid crystal aligning film was formed. Subsequently, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck Co., Ltd.) was filtered with a filter having a pore size of 0.2 μm, and then the polymerizable liquid crystal was applied onto the liquid crystal alignment film by a bar coater to form a coating film of the polymerizable liquid crystal. After baking for 1 minute in the oven adjusted to the temperature of 50 degreeC, the ultraviolet-ray 1000mJ / cm <2> of unpolarized light containing 365 nm bright line was irradiated using the Hg-Xe lamp from the direction perpendicular | vertical to a coating-film surface, and superposed | polymerized. The retardation film was manufactured by hardening | curing a crystalline liquid crystal and forming a liquid crystal layer.

(3) Evaluation of liquid crystal alignment

About the retardation film manufactured by said (2), liquid-crystal orientation was evaluated by observing the presence or absence of an abnormal domain with the naked eye under a cross nicol, and a polarization microscope (2.5 times magnification). The evaluation was performed when the orientation was good with the naked eye and the abnormal domain was not observed with the polarization microscope, but the liquid crystal alignment "excellent" and the abnormal domain was not observed with the naked eye, but the abnormal domain was observed with the polarization microscope. , And the case where the abnormal domain was observed with the naked eye and a polarization microscope were performed as liquid crystal aligning "poor". As a result, this retardation film was evaluated by liquid-crystal orientation "excellent".

(4) adhesion

The adhesiveness with the board | substrate of a liquid crystal aligning film was evaluated using the retardation film manufactured by said (2). First, using the equally spaced spacer with a guide, the cutter knife cut | disconnected from the surface of the retardation film side of the liquid crystal layer side, and formed the 10x10 lattice pattern. The depth of each cut was made to reach to about the middle of the substrate thickness from the liquid crystal layer surface. Subsequently, the cellophane tape was brought into close contact with the entire surface of the lattice pattern, and then the cellophane tape was peeled off. The incision part of the lattice pattern after peeling was observed by visual observation under cross nicol, and adhesiveness was evaluated. Evaluation is based on the adhesion "goodness" in the case where peeling is not confirmed at the intersection of the cut line and the lattice pattern, and the number of lattice eyes observed at the peeling part is less than 15% with respect to the whole lattice pattern. The case where adhesiveness "good | favorableness" and the number of grating | lattices which peeling was observed in the said part was 15% or more with respect to the number of whole grating patterns was made as adhesive "poor". As a result, this retardation film was adhesive "excellent".

10 liquid crystal display element
11a, 11b: glass substrate
12: liquid crystal aligning film
13: top electrode
14: insulation layer (silicon nitride film)
15: bottom electrode
16: liquid crystal layer
f: rubbing direction

Claims (10)

It is obtained by making at least 1 sort (s) of compound chosen from the group which consists of a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride, and a tetracarboxylic acid diester compound, and the diamine containing the compound represented by following formula (d) react. Liquid crystal aligning agent containing at least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid, a polyamic acid ester, and a polyimide:

(Wherein (d) of, R ¹ ~R ⁸ are, each independently, a hydrogen atom, a halogen atom, an alkenyl group of an alkyl group of 1 to 20 carbon atoms, having 1 to 20 carbon atoms, or alkyl or alkenyl groups of 1 to 20 carbon atoms A substituent is a monovalent group introduced; R ⁹ and R ¹⁰ are each independently a halogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxy group; and Z ¹ and Z ² are each independently a single bond, -O -, * -COO-, * -OCO-, -CO-, * -NHCO-, * -CONH- or * -O-CH _2- , where "*" represents a bond to X ¹ ; However, Z ¹ and Z ² are not do that a single bond simultaneously; X ¹ is, or any of the divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group, a hydrocarbon group, the carbon of such a hydrocarbon group A divalent group having —O—, —COO—, —CO—, —NHCO— or —S— between carbon bonds, or a divalent group having a halogen atom or an alkoxy group introduced as a substituent to the hydrocarbon group ; M ¹ and m ² are, each independently an integer of 0~4, n is 0 or 1; stage, R ^9, R ¹⁰ if a plurality is present, a plurality of R ^9, R ¹⁰ are, respectively, may be the same May be different). The method of claim 1,
Liquid crystal aligning agent whose said n is 1. The method of claim 1,
X ¹ is a C 1-18 alkanediyl group or-[(CH ₂ ) ₂ O] _a- (CH ₂ ) _2- (where a is an integer of 1 to 3). The method of claim 1,
The said polymer is a polymer obtained by making tetracarboxylic dianhydride and diamine react,
As the tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-2 anhydride, 1,2,3,4-cyclobutanetetra Carboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6 : Liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of: 8-2 anhydride, cyclohexane tetracarboxylic dianhydride, and pyromellitic dianhydride. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-4. The liquid crystal display element provided with the liquid crystal aligning film of Claim 5. Retardation film provided with the liquid crystal aligning film of Claim 5. The process of apply | coating the liquid crystal aligning agent in any one of Claims 1-4 on a board | substrate, and forming a coating film,
Irradiating the coating film with light;
The manufacturing method of retardation film containing the process of apply | coating and hardening a polymeric liquid crystal on the coating film after said light irradiation. It is obtained by making at least 1 sort (s) of compound chosen from the group which consists of a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride, and a tetracarboxylic acid diester compound, and the diamine containing the compound represented by following formula (d) react. polymer:

(Wherein (d) of, R ¹ ~R ⁸ are, each independently, a hydrogen atom, a halogen atom, an alkenyl group of an alkyl group of 1 to 20 carbon atoms, having 1 to 20 carbon atoms, or alkyl or alkenyl groups of 1 to 20 carbon atoms A substituent is a monovalent group introduced; R ⁹ and R ¹⁰ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group; and Z ¹ and Z ² are each independently a single bond,- O-, * -COO-, * -OCO-, -CO-, * -NHCO-, * -CONH- or * -O-CH _2- , where "*" represents a bond with X ¹ and; stage, Z ¹ and Z ² is at the same time does not work that this single bond; X ¹ is, or any of the divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group, a hydrocarbon group, of such a hydrocarbon group A divalent group having —O—, —COO—, —CO—, —NHCO— or —S— between carbon-carbon bonds, or a divalent group having a halogen atom or an alkoxy group introduced as a substituent to the hydrocarbon group And; m ¹ and m ² are, each independently an integer of 0~4, n is 0 or 1; stage, R ^9, R ¹⁰ if a plurality is present, a plurality of R ^9, R ¹⁰ are the same respectively May be different). Compound represented by the following formula (d):

(Wherein (d) of, R ¹ ~R ⁸ are, each independently, a hydrogen atom, a halogen atom, an alkenyl group of an alkyl group of 1 to 20 carbon atoms, having 1 to 20 carbon atoms, or alkyl or alkenyl groups of 1 to 20 carbon atoms A substituent is a monovalent group introduced; R ⁹ and R ¹⁰ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group; Z ¹ and Z ² are each independently a single bond,- O-, * -COO-, * -OCO-, -CO-, * -NHCO-, * -CONH- or * -O-CH _2- , where "*" represents a bond with X ¹ and; stage, Z ¹ and Z ² is at the same time does not work that this single bond; X ¹ is, or any of the divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group, a hydrocarbon group, of such a hydrocarbon group A divalent group having —O—, —COO—, —CO—, —NHCO— or —S— between carbon-carbon bonds, or a divalent group having a halogen atom or an alkoxy group introduced as a substituent to the hydrocarbon group And; m ¹ and m ² are, each independently an integer of 0~4, n is 0 or 1; stage, R ^9, R ¹⁰ if a plurality is present, a plurality of R ^9, R ¹⁰ are the same respectively May be different).

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