CN107022358A - Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, a polymer, and a diamine, which can obtain a liquid crystal element with good AC afterimage characteristics and voltage retention. A liquid crystal aligning agent contains the polymer which has the partial structure represented by following formula (0) at least 1 sort(s) chosen from the group which consists of a polyamic acid, a polyamic acid ester, and a polyimide. (R ¹ is a divalent group having a cyclic group and at least one of "-NR ³ -" and an alkanediyl group, or "-X ²⁰ -R ²⁰ -* ¹ " (X ²⁰ is a single bond, an ether bond, etc., R ²⁰ is alkanediyl), R ² is a divalent organic group, R ⁶ is a cyclic group. In the case of R ¹ being "‑X ²⁰ ‑R ²⁰ ‑* ¹ ", R ² is a urea bonded divalent organic group, divalent chain hydrocarbon group or divalent alicyclic hydrocarbon group).

Description

Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal element, polymer and diamine

technical field

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, a polymer and a diamine.

Background technique

The liquid crystal cell includes a liquid crystal alignment film to control alignment of liquid crystal molecules in the liquid crystal cell. Polyamic acid or polyimide is generally used as a material of a liquid crystal aligning film at the point that various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable.

In recent years, in order to seek further improvement of the display performance of a liquid crystal panel, various liquid crystal aligning agents are proposed (for example, refer patent document 1, patent document 2). Patent Document 1 proposes improving voltage retention characteristics or reducing burning by making a liquid crystal aligning agent contain polyamic acid or polyimide obtained using 4,4'-diaminodiphenylamine. In addition, Patent Document 2 discloses that by making the liquid crystal aligning agent contain a polyimide precursor or polyimide obtained by using a diamine having a urea bond, it is possible to obtain good liquid crystal orientation and rubbing resistance, A liquid crystal aligning film having a small ion density and little accumulated charge in a fringe field switching (Fringe Field Switching, FFS) mode liquid crystal display element.

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent No. 4052307

[Patent Document 2] International Publication No. 2013/008906

Contents of the invention

[Problems to be Solved by the Invention]

The rubbing method, which is one of the methods for discovering anisotropy in a liquid crystal aligning film, is generally used because it is simple and has good orientation of liquid crystal molecules. However, the conventional liquid crystal aligning agent with good rubbing resistance tends to generate afterimage or fall in voltage retention rate by charge accumulation accompanying the application of AC voltage in many cases, ie, AC afterimage characteristic and voltage retention ratio are in a trade-off.

This invention is made|formed in view of the said subject, and one object is to provide the liquid crystal aligning agent which can obtain the liquid crystal element with favorable AC afterimage characteristics and voltage retention.

[Technical means to solve the problem]

As a result of diligently studying to achieve the above-mentioned subject, the present inventors found that the above-mentioned subject can be solved by making the liquid crystal aligning agent contain the polymer which has a specific structure, and completed this invention. Specifically, the following means are provided.

<1> A liquid crystal aligning agent containing at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and having a partial structure represented by the following formula (0) Polymer[P];

[chemical 1]

(In formula (0), R ¹ is a divalent group having at least one of a cyclic group and "-NR ³ -" (where R ³ is a hydrogen atom or a monovalent organic group) and an alkanediyl group, or "-X ²⁰ -R ²⁰ -* ¹ " (wherein, X ²⁰ is a single bond, an ether bond, a thioether bond, an ester bond or -CONR ^b - (R ^b is a hydrogen atom or a monovalent organic group), R ²⁰ is an alkanediyl group; "* ¹ "represents the bond bonded to the nitrogen atom in the urea bond), R ² is a divalent organic group, and R ⁶ is a cyclic group; wherein, in R ¹ is "-X ²⁰ - In the case of R ²⁰ * ¹ ", R ² is a divalent organic group having a urea bond, a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group; "*" represents a bond).

<2> Liquid crystal aligning film formed using the liquid crystal aligning agent of said <1>.

<3> A liquid crystal element including the liquid crystal aligning film of the above <2>.

<4> a polymer, which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and has a compound derived from the compound represented by the following formula (1) Structural units;

[Chem 2]

(In formula (1), R ¹ is a divalent group having at least one of a cyclic group and "-NR ³ -" (where R ³ is a hydrogen atom or a monovalent organic group) and an alkanediyl group, Or "-X ²⁰ -R ²⁰ -* ¹ " (wherein, X ²⁰ is a single bond, an ether bond, a thioether bond or an ester bond, and R ²⁰ is an alkanediyl group; "* ¹ " means that the bond of nitrogen atom), R ² is a divalent organic group; wherein, when R ¹ is "-X ²⁰ -R ²⁰ -* ¹ ", R ² is a divalent organic group having a urea bond, a divalent chain hydrocarbon group or divalent alicyclic hydrocarbon group).

<5> Diamine represented by said formula (1).

[Effect of the invention]

According to the present disclosure, a liquid crystal element having good voltage retention and afterimage characteristics can be obtained. The said effect is acquired also when performing the heating at the time of forming a liquid crystal aligning film at relatively low temperature, and it is preferable at the point that low-temperature baking can be performed.

detailed description

Hereinafter, each component contained in the liquid crystal aligning agent of this indication, and other components arbitrarily blended as needed are demonstrated.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of the present disclosure contains at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide and has a polymer [P ].

In the formula (0), the alkanediyl group in R1 preferably has ¹ to 6 carbon atoms, for example, methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexamethylenediyl Wait. These alkanediyl groups may be linear or branched, and are preferably linear.

The cyclic group is a group obtained by removing two hydrogen atoms from a substituted or unsubstituted ring. Examples of the ring include aromatic rings, aliphatic rings, and heterocyclic rings, and specifically, benzene rings, naphthalene rings, anthracene rings, cyclohexane rings, pyridine rings, piperidine rings, and piperazine rings. , pyrimidine ring, etc. Moreover, as a substituent which these rings may have, the alkyl group which has 1-5 carbons, the alkoxyl group which has 1-5 carbons, a halogen atom etc. are mentioned, for example. The cyclic group of R ¹ is preferably a substituted or unsubstituted phenylene group or a piperidinyl group in terms of improving the electrical characteristics of the obtained liquid crystal device and the friction resistance of the coating film.

The monovalent organic group of R ³ in "-NR ³ -" (where R ³ is a hydrogen atom or a monovalent organic group) is preferably a monovalent hydrocarbon group or a protecting group having 1 to 5 carbon atoms. Examples of the protecting group include a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, and a sulfonamide-based protecting group, among which a t-butoxycarbonyl group is preferred. Furthermore, "-NR ³ -" may constitute a part of an amide bond, a urea bond, or a urethane bond.

R ¹ in the formula (0) is preferably a group represented by the following formula (2), a group represented by the following formula (3), or a group represented by the following formula (4).

[Chem 3]

(In formula (2), ^A is a divalent organic group with a cyclic group, a single bond, methylene, ethylene, ether bond, thioether bond or ester bond, and a is an integer of 1 to 6. Wherein , in the case of A ¹ being a single bond, methylene, ethylene, ether bond, thioether bond or ester bond, the R ² is a divalent chain hydrocarbon group or an alicyclic hydrocarbon group. In the formula (3) , B ¹ is a single bond or a divalent linking group, A ² is a single bond or a cyclic group, R ³ is a hydrogen atom or a monovalent organic group, and b is an integer of 1 to 6. In formula (4), A ³ is A divalent organic group having a cyclic group, c is an integer of 1 to 6. "*" represents a bond with a nitrogen atom in a urea bond).

In the formula (2), preferred examples of A ¹ include, for example, groups represented by the following formula (2-1). In addition, regarding the cyclic group of A ¹¹ in the following formula (2-1), the description of the cyclic group that R ¹ has can be applied.

[chemical 4]

(In formula (2-1), A ¹¹ is a cyclic group, X ¹ is a single bond, methylene, ethylene, ether bond, thioether bond, ester bond or -CONR ^b -(R ^b is a hydrogen atom , a monovalent hydrocarbon group or protecting group with 1 to 6 carbons, the same below), Y1 is a single bond, an ether bond, an ester bond, a thioether bond, -CONR ^b - or -NR ^b -. p is 0 or 1, "*" indicates a bond with an alkanediyl group).

In the formula (3), the divalent linking group of B1 is preferably an alkanediyl group having ¹ to 6 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms. Regarding the cyclic group contained in A ² of the formula (3) and the cyclic group contained in A ³ of the formula (4), the description of the cyclic group contained in the R ¹ can be applied. In addition, the divalent organic group which has the cyclic group ^of A3 may have only one cyclic group, and may have two or more.

Examples of the organic group for R include: a hydrocarbon group having ¹ to 40 carbon atoms, a group containing a heteroatom-containing group between carbon-carbon bonds of the hydrocarbon group, and a bond between the hydrocarbon group and a heteroatom-containing group. The base and so on. In addition, at least one hydrogen atom of these groups may be substituted with a substituent such as a halogen atom, a nitro group, a cyano group, or a hydroxyl group, for example. However, when R ¹ is "-X ²⁰ -R ²⁰ -*", R ² is a divalent organic group having a urea bond, a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group.

Examples of the cyclic group for R ⁶ include those exemplified in the description of the cyclic group for R ¹ above. Preferably ^R6 is phenylene or pyridyl, more preferably phenylene.

Here, in this specification, a "chain hydrocarbon group" means a linear or branched hydrocarbon group that does not contain a cyclic structure but only consists of a chain structure. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group including only an alicyclic hydrocarbon structure as a ring structure. However, it is not necessary to be composed only of an alicyclic hydrocarbon structure, and a part thereof may have a chain structure. The term "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure. The term "organic group" refers to a group comprising a hydrocarbon group, which may also contain heteroatoms in the structure. The "heteroatom-containing group" refers to a group having a heteroatom with a valence of two or more, for example: -O-, -CO-, -COO-, -CONR ^b -, -NR ^b -, -NR ^b CONR ^b -, -OCONR ^b -, -S-, -COS-, -OCOO-, -SO ₂ -, etc.

The polymer [P] is only required to have a partial structure represented by the above-mentioned formula (0), and it is particularly preferable to have a structure derived from a diamine represented by the above-mentioned formula (1) (hereinafter simply referred to as "specific diamine"). unit. In the case where R in the formula ( ¹ ) is a group represented by the formula (2), preferred specific examples of specific diamines include compounds represented by the following formula (11) and the following A compound represented by formula (12), etc.

[chemical 5]

(In formula (12), R ⁴ is a divalent chain hydrocarbon group or alicyclic hydrocarbon group with 1 to 10 carbons, and p is 0 or 1. In formula (11) and formula (12), a is 1 to 6 Integer. A ¹¹ , X ¹ and Y ¹ have the same meaning as the formula (2-1), respectively. A plurality of A ¹¹ , a plurality of X ¹ , a plurality of Y ¹ and a plurality of a in the formula (11) can be respectively same or different).

Regarding the formula ( ¹¹ ), the cyclic group of A11 is preferably 1,4-phenylene, 1,4-pyridinyl, 1,4-cyclohexylene, 1,4-piperidinyl or 1, 4-piperazinyl, these cyclic groups may be substituted by methyl or fluorine atoms. Particular preference is given to 1,4-phenylene or 1,4-piperidinyl. a is preferably 2-4.

As a preferable specific example of the compound represented by the said formula (11), the compound etc. which are respectively represented by following formula (1-1) - a formula (1-5) are mentioned, for example.

[chemical 6]

(In formula (1-1) ~ formula (1-5), R ⁸ is a hydrogen atom, an alkyl group with 1 to 3 carbons, or tert-butoxycarbonyl. R ⁹ is a hydrogen atom or a methyl group. a is 1 to 3 an integer of 6. In the formula, a plurality of a, a plurality of R ⁸ , and a plurality of R ⁹ may be the same or different).

Regarding the formula (12), X ¹ is preferably an ethylene group, an ester bond, or -CONR ^b -. ^Y1 is preferably a single bond or an ether bond. The cyclic group of A ¹¹ is preferably 1,4-phenylene, 1,4-pyridinyl, 1,4-cyclohexylene, 1,4-piperidinyl or 1,4-piperazinyl, these rings The aliquots may be substituted by methyl or fluorine atoms. R ⁴ is preferably an alkanediyl group having 2 to 6 carbon atoms or a group represented by the following formula (6).

[chemical 7]

(In the formula (6), d is an integer of 1 to 3. "*" represents a bonding bond to a primary amino group).

As a preferable specific example of the compound represented by the said formula (12), the compound etc. which are each represented by following formula (2-1) - a formula (2-7) are mentioned, for example. Among these compounds, compounds represented by the following formula (2-1) and compounds represented by the following formula (2-3) are preferable.

[chemical 8]

(In formula (2-1) ~ formula (2-7), R ¹⁰ is a hydrogen atom, an alkyl group with 1 to 3 carbons or tert-butoxycarbonyl. a is an integer of 1 to 6, and e is 1 to 10 integer).

In the case where R in the formula ( ¹ ) is a group represented by the formula (3), preferred specific examples of specific diamines include compounds represented by the following formula (13) and the following: A compound represented by formula (14), etc.

[chemical 9]

(In formula (13) and formula (14), R ⁵ is a divalent organic group, and g and k are each independently an integer with 1 to 6 carbons. R ³ and b have the same meaning as in formula (3). Multiple R ³ 's and multiple b's in the formula may be the same or different respectively).

In the formula (13), R ³ is preferably a hydrogen atom, a methyl group or a tert-butoxycarbonyl group. b is preferably 1-4.

As the divalent organic group of R5, for example, a hydrocarbon group having ¹ to 40 carbon atoms, a group containing a heteroatom-containing group between carbon-carbon bonds of the hydrocarbon group, a group containing a heteroatom-containing group between the hydrocarbon group and a heteroatom-containing group Bonded bases, etc. In addition, at least one hydrogen atom of these groups may be substituted with a substituent such as a halogen atom, a nitro group, a cyano group, or a hydroxyl group, for example. Preferable examples of R ⁵ include groups represented by the following formula (7), and the like.

[chemical 10]

(In formula (7), A ¹³ is a cyclic group, X ³ is a single bond, methylene, ethylene, ether bond, thioether bond, ester bond or -CONR ^b -, Y ³ is a single bond, ether bond, ester bond, thioether bond, -CONR ^b - or -NR ^b -. "*" represents a bond to a primary amino group. h, r, q and s are independently integers from 0 to 6) .

As a preferable specific example of the compound represented by the said formula (13), the compound etc. which are each represented by following formula (3-1) and a formula (3-2) are mentioned, for example. h in the following formula (3-1) and formula (3-2) is preferably 1 or 2.

[chemical 11]

(In formula (3-1) and formula (3-2), b is an integer of 1 to 6, and h is an integer of 0 to 6).

In the formula (14), R ³ is preferably a hydrogen atom, a methyl group or a tert-butoxycarbonyl group. b, g, and k are each preferably 1-3. As a preferable specific example of the compound represented by the said formula (14), the compound etc. which are each represented by following formula (4-1) and a formula (4-2) are mentioned, for example.

[chemical 12]

(In formula (4-1) and formula (4-2), b, g, and k are each independently an integer having 1 to 6 carbon atoms).

In the case where R ¹ in the formula (1) is a group represented by the formula (5), preferred specific examples of the specific diamine include compounds represented by the following formula (15), and the like.

[chemical 13]

(In the formula (15), R ¹¹ is a divalent organic group, and c is an integer of 1 to 6. A plurality of c in the formula may be the same as or different from each other).

R in the formula ( ¹⁵ ) is preferably a divalent chain hydrocarbon group with 1 to 10 carbons, a group containing a heteroatom-containing group between the carbon-carbon bonds of the chain hydrocarbon group, or the hydrocarbon group A group bonded to a heteroatom-containing group. c is preferably 1-3. As a preferable specific example of the compound represented by the said formula (15), the compound etc. which are each represented by following formula (5-1) and a formula (5-2) are mentioned, for example.

[chemical 14]

(In formula (5-1) and formula (5-2), c is an integer of 1 to 6, and x and y are each independently an integer of 2 to 6. A plurality of c in the formula may be the same or different).

Specific diamine can be synthesize|combined by combining well-known methods suitably. As an example, it can be enumerated, for example: synthesizing a nitro intermediate having a nitro group to replace the primary amino group in the formula (1), and then using an appropriate reducing agent to aminate the nitro group of the obtained nitro intermediate the method for synthesizing the primary amino in the formula (1) through tert-butoxycarbonyl and other protected intermediates, and then the method for deprotecting the obtained intermediates, etc.

The method for synthesizing the nitro intermediate can be appropriately selected according to the target compound. For example, there may be mentioned: a method of reacting ^a nitrobenzene derivative having R1 in the presence of bis(4-nitrophenyl)carbonate; making a urea group ^- containing derivative having ^a partial structure derived from R1 and R2 A method of reacting a compound of a compound with a halide such as nitrobenzoyl chloride; a method of reacting an isocyanate compound having R ¹ or R ² with an amine compound having R ² or R ¹ , etc. However, the synthesis method of specific diamine is not limited to the said method.

(polyamic acid)

In the case where the polymer [P] is a polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid [P]") can be obtained by, for example, combining tetracarboxylic dianhydride with the specific diamine obtained by the reaction of diamines.

As tetracarboxylic dianhydride used for synthesis|combination of polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride etc. are mentioned, for example. As a specific example of these tetracarboxylic dianhydrides, 1,2,3,4- butane tetracarboxylic dianhydride etc. are mentioned, for example as aliphatic tetracarboxylic dianhydrides.

Examples of alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic Acid dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3- Furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2, 5-dioxo-3-furyl)-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-furyl)-3-methyl-3-cyclohexene -1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethyl norbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[ 3.3.0] octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, Cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.

As an aromatic tetracarboxylic dianhydride, pyromellitic dianhydride etc. are mentioned, for example, In addition, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can also be used. In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesis, what contains an alicyclic tetracarboxylic dianhydride is preferable at the point which makes the electric characteristic of a liquid crystal element more favorable in combination with specific diamine. With respect to the total amount of tetracarboxylic dianhydride used in the synthesis of polyamic acid, the usage ratio of alicyclic tetracarboxylic dianhydride is preferably 5 mol % or more, more preferably 10 mol % or more, and still more preferably 30 mol % to 100 mol%.

When synthesizing polyamic acid [P], specific diamine may be used independently, and diamine (henceforth abbreviated as "other diamine") other than specific diamine may be used.

As other diamines, aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane etc. are mentioned, for example. As specific examples of these other diamines, aliphatic diamines include, for example, m-xylylenediamine, 1,3-propylenediamine, pentamethylenediamine, hexamethylenediamine, etc.; alicyclic diamines For example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc. are mentioned.

Aromatic diamines include, for example, dodecyloxydiaminobenzene, myristyloxydiaminobenzene, octadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, and cholesteryloxydiaminobenzene. , Cholesteryl Diaminobenzoate, Cholesteryl Diaminobenzoate, Lanostyl Diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3, 6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, the following formula (E-1) Alignment group-containing diamines such as the compounds shown.

[chemical 15]

(In formula (E-1), X ¹ and X ¹¹ are each independently a single bond, -O-, -COO- or -OCO-, R ¹ is an alkanediyl group with 1 to 3 carbons, R ¹¹ is a single A bond or an alkanediyl group with 1 to 3 carbons, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. Among them, a and b cannot be 0 at the same time ).

p-Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'- Diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, bis[2-(4-aminophenyl)ethyl]adipic acid, N,N-bis(4-aminophenoxy) base) methylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 4,4'-(p-phenylene diisopropylidene)bisaniline, 4,4'-(m-phenylene Diisopropylidene) bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, N,N'-bis(4 -aminophenyl)-benzidine, 1,4-bis-(4-aminophenyl)-piperazine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 3,5-diaminobenzoic acid and other non-side chain diamines Wait.

Examples of diaminoorganosiloxane include: 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc., in addition to that described in Japanese Patent Laid-Open No. 2010-97188 can also be used of diamines.

Specific examples of the compound represented by the formula (E-1) include, for example, compounds represented by the following formula (E-1-1), compounds represented by the following formula (E-1-2), etc. .

[chemical 16]

When synthesizing polyamic acid [P], from the viewpoint of sufficiently obtaining the effect of improving the friction resistance of the coating film, the electrical characteristics of the liquid crystal element, and the afterimage characteristics, compared with the two compounds used in the synthesis of polyamic acid [P], It is preferable that the total amount of amines and the usage ratio of a specific diamine shall be 5 mol% or more. More preferably, it is 10 mol% - 70 mol%, More preferably, it is 10 mol% - 50 mol%. In addition, specific diamine and other diamine can use individually by 1 type, respectively, or can select and use 2 or more types suitably.

(Synthesis of polyamic acid)

The polyamic acid [P] can be obtained by making the above-mentioned tetracarboxylic dianhydride and diamine react together with a molecular weight modifier as needed. It is preferable that the usage ratio of the tetracarboxylic dianhydride and diamine used for the synthesis reaction of a polyamic acid is the ratio of 0.2 equivalent - 2 equivalents of the acid anhydride group of tetracarboxylic dianhydride with respect to 1 equivalent of amino groups of a diamine. Examples of molecular weight regulators include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; isocyanate compounds, etc. It is preferable that the usage ratio of a molecular weight modifier is 20 mass parts or less with respect to a total of 100 mass parts of tetracarboxylic dianhydrides and diamines used.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C. The reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Regarding the particularly preferred organic solvent, it is preferred to use a solvent selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butylene One or more of the group consisting of lactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol and halogenated phenol is used as a solvent, or more than one of these solvents is used together with other organic solvents (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.). It is preferable that the usage-amount (a) of an organic solvent is the quantity which becomes 0.1 mass % - 50 mass % of the total amount (b) of tetracarboxylic dianhydride and diamine with respect to the total amount (a+b) of a reaction solution.

In this manner, a reaction solution in which polyamic acid is dissolved can be obtained. The said reaction solution may be used for preparation of a liquid crystal aligning agent as it is, and may be used for preparation of a liquid crystal aligning agent after separating the polyamic acid contained in a reaction solution.

(polyamic acid ester)

The polyamic acid ester which is a polymer [P] can be obtained by the method of making tetracarboxylic-acid diester dihalide and diamine react, for example.

The tetracarboxylic-acid diester dihalide used can be obtained by making tetracarboxylic-acid diester react with an appropriate chlorinating agent, such as thionyl chloride. The tetracarboxylic-acid diester can be obtained by making the tetracarboxylic-acid dianhydride illustrated in the synthesis|combination of a polyamic acid, and alcohols, such as methanol or ethanol, react, for example. As diamine, specific diamine may be used independently, and other diamine may be used together. As a specific example of the diamine used, the specific diamine illustrated in the description of the synthesis|combination of a polyamic acid, and other diamines are mentioned.

The ratio of the tetracarboxylic acid diester dihalide and diamine used in the synthesis reaction of the polymer [P] is preferably 1 equivalent of the amino group of the diamine, and the group of the tetracarboxylic acid diester dihalide "-COX- (X is a halogen atom)" in a ratio of 0.2 equivalents to 2 equivalents. It is preferable to carry out the reaction of tetracarboxylic-acid diester dihalide and diamine in an organic solvent in the presence of a base. The reaction temperature at this time is preferably -30°C to 150°C, and the reaction time is preferably 0.1 hour to 48 hours. As the organic solvent used in the reaction, the description of the organic solvent usable in the synthesis reaction of polyamic acid can be applied. As the base used in the reaction, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine; sodium hydride, potassium hydride, sodium hydroxide, Alkali metals such as potassium hydroxide, sodium, and potassium. It is preferable that the usage-amount of a base shall be 2 mol - 4 mol with respect to 1 mol of diamine.

The reaction solution which melt|dissolved polyamic acid ester can be obtained as mentioned above. The said reaction solution may be used for preparation of a liquid crystal aligning agent as it is, and may be used for preparation of a liquid crystal aligning agent after separating the polyamic acid ester contained in a reaction solution. The polyamic acid ester may have only an amic acid ester structure, and may be a partial esterification thing which an amic acid structure and an amic acid ester structure coexist. Furthermore, the polyamic acid ester as the polymer [P] is not limited to the above synthesis method, for example, it can also be obtained by the following method, such as making polyamic acid [P], alcohols or alkyl halides A method of reacting a radical, a method of reacting a tetracarboxylic acid diester with a diamine, and the like.

(Polyimide)

The polyimide which is a polymer [P] can be obtained, for example by dehydrating and ring-closing the polyamic acid [P] synthesized above, and imidating it. When the polyamic acid is dehydrated and ring-closed to form a polyimide, the reaction solution of the polyamic acid can be directly used for the dehydration ring-closing reaction, or it can be used after separating the polyamic acid contained in the reaction solution. Dehydration ring closure reaction.

The polyimide may be a complete imide obtained by dehydrating and ring-closing all the amic acid structures of the polyamic acid as its precursor, or it may be a part of the amic acid structure that is dehydrated and ring-closed to make the amic acid structure A partial imide compound that coexists with an imide ring structure. The imidization rate of the polyimide used for reaction becomes like this. Preferably it is 20 % or more, More preferably, it is 30 % - 99 %. The said imidization rate represents the ratio of the number of imide ring structures with respect to the total number of the number of amic acid structures of a polyimide, and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

The dehydration and ring closure of polyamic acid is preferably carried out by the following method. The method is to heat the polyamic acid, or dissolve the polyamic acid in an organic solvent, and add a dehydrating agent and a dehydration ring closure catalyst in the solution, Method of heating as needed. Among them, the method using the latter is preferable. In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamic acid solution, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01 mol - 20 mol with respect to 1 mol of amic-acid structures of a polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. It is preferable that the usage-amount of a dehydration ring closure catalyst shall be 0.01 mol - 10 mol with respect to 1 mol of dehydrating agents used. Examples of the organic solvent used in the dehydration ring-closing reaction include those exemplified as the organic solvent used in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0°C to 180°C. The reaction time is preferably 1.0 hour to 120 hours.

In this manner, a reaction solution containing polyimide can be obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, and can also be used for the preparation of the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can also be used for the liquid crystal alignment agent after the polyimide is separated. Alignment agent preparation.

The solution viscosity of the polymer [P] is preferably a solution having a solution viscosity of 10 mPa·s to 800 mPa·s, more preferably a solution having a solution viscosity of 15 mPa·s to 500 mPa·s when it is prepared as a solution having a concentration of 10% by mass. Viscosity. Furthermore, the solution viscosity (mPa·s) of the polymer [P] is obtained by using an E-type rotational viscometer, and the solution viscosity (mPa·s) of the polymer [P] (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) etc.) to prepare a polymer solution with a concentration of 10% by mass and measure it at 25°C.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer [P] measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Also, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.

(other ingredients)

The liquid crystal aligning agent of this disclosure may contain other components other than polymer [P]. Examples of such other components include: polymers different from the above-mentioned polymer [P] (hereinafter referred to as "other polymers"), compounds having at least one epoxy group in the molecule (hereinafter also referred to as "containing Epoxy compounds"), etc.

These other polymers can be used for the purpose of improving various properties such as afterimage and transparency, or for cost reduction. As such other polymers, for example, it can be cited: at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide does not have the The structural units of the compound are polymers, polyorganosiloxanes, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives things etc. It is preferable that the compounding ratio of another polymer shall be 95 mass % or less with respect to the total amount of the polymer component contained in a liquid crystal aligning agent, More preferably, it shall be 10 mass % - 90 mass %.

An epoxy group-containing compound is used for improving the adhesiveness with the board|substrate surface of a liquid crystal aligning film, or an electrical characteristic. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trihydroxy Methyl propane triglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane , N, N, N', N'-tetraglycidyl[4,4'-methylenebisaniline], N,N-diglycidyl-benzylamine, N,N-diglycidyl- Aminomethylcyclohexane, N,N-glycidyl-cyclohexylamine and the like are preferred. In addition, the epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can also be used. When compounding an epoxy group-containing compound in a liquid crystal aligning agent, the compounding ratio is preferably 40 parts by mass or less, more preferably 40 parts by mass or less with respect to a total of 100 parts by mass of polymers contained in the liquid crystal aligning agent. It is 0.1 mass part - 30 mass parts.

Furthermore, in addition to the above, other components include functional silane compounds, compounds having at least one oxetanyl group in the molecule, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, Dispersants, photosensitizers, etc. The compounding ratio of these other components can be suitably selected according to each compound as long as the effect of this disclosure is not impaired.

Regarding the liquid crystal aligning agent of the present disclosure, the compounding ratio of the polymer [p] relative to the total amount of the polymer components contained in the liquid crystal aligning agent is from the point of realizing the improvement of the electrical characteristics and afterimage characteristics of the liquid crystal element Preferably it is 5 mass % or more, More preferably, it is 10 mass % or more. Moreover, when other polymers are contained in a liquid crystal aligning agent, it is preferable to mix the polymer [p] with respect to 100 mass parts of total amounts of the polymer [p] contained in a liquid crystal aligning agent and other polymers The ratio is 5 to 99 parts by mass, more preferably 10 to 95 parts by mass, and still more preferably 10 to 80 parts by mass.

The polymer [p] preferably has a structural unit derived from a specific diamine, specifically, preferably has a partial structure represented by the following formula (p-1) and a compound represented by the following formula (p-2). At least one partial structure in the group of partial structures.

[chemical 17]

(In formula (p-1) and formula (p-2), R ⁵¹ is a tetravalent organic group, R ⁵² is a hydrogen atom or a monovalent organic group, R ⁵³ is the removal of two primary diamines from the specific diamine The remaining groups formed from amino groups. A plurality of R ⁵² may be the same or different).

Examples of the monovalent organic group of R ⁵² in the formula (p-1) include a monovalent hydrocarbon group having 1 to 10 carbon atoms, a group having a cinnamic acid structure, and the like. The tetravalent organic group of ^R51 is the remaining group obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. As a specific example of the said tetracarboxylic dianhydride, the tetracarboxylic dianhydride etc. which were illustrated above are mentioned.

(solvent)

The liquid crystal aligning agent of the present disclosure is prepared in the form of a polymer [P] and other components used if necessary, preferably as a liquid composition dispersed or dissolved in an appropriate solvent.

As the organic solvent used, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ -butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-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-isopropyl 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, diethyl Glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether , Ethylene carbonate, propylene carbonate, etc. These organic solvents may be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1% by mass to 10% by mass. That is, as described below, a liquid crystal aligning agent is applied to the substrate surface, and preferably heated to form a coating film as a liquid crystal aligning film or a coating film serving as a liquid crystal aligning film. At this time, when solid content concentration is less than 1 mass %, the film thickness of a coating film becomes too small, and it becomes difficult to obtain a favorable liquid crystal aligning film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large, making it difficult to obtain a good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases to reduce the applicability. tendency.

<Liquid crystal element>

The liquid crystal element of this disclosure contains the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, for example, it can be applied to twisted nematic (Twisted Nematic, TN) type, super twisted nematic (Super Twisted Nematic, STN) type, vertical alignment (Vertical Alignment, VA) type (including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-patterned vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), coplanar switching (In -Plane Switching (IPS) type, FFS type, Optically Compensated Bend (Optically Compensated Bend, OCB) type and other operating modes. When it is applied to TN-type, STN-type, IPS-type, FFS-type or OCB-type liquid crystal elements, etc., the coating film formed by using a liquid crystal aligning agent must be treated to give liquid crystal alignment ability, even if the rubbing method is used. It is preferable also at the point which can obtain the liquid crystal element which shows favorable voltage retention rate and afterimage characteristic. The liquid crystal element of this disclosure can be manufactured by the method including the following steps 1-3, for example. Step 1 uses different substrates depending on the desired mode of operation. Step 2 and Step 3 are common in all operation modes.

[Step 1: Formation of coating film]

First, a liquid crystal aligning agent is apply|coated on a board|substrate, and a coating film is formed on a board|substrate by heating an application surface next. As the substrate, for example, glass such as float glass and soda glass; including polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, and polycarbonate, can be used. , poly(alicyclic olefin) and other plastic transparent substrates. As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG Corporation of the United States) containing tin oxide (SnO ₂ ), a film containing indium oxide-tin oxide (In ₂ O _s -SnO ₂ ) can be used. indium tin oxide (Indium TinOxide, ITO) film, etc. In the case of manufacturing a TN-type, STN-type or VA-type liquid crystal cell, two substrates provided with patterned transparent conductive films are used. When manufacturing an IPS type or FFS type liquid crystal element, a substrate provided with an electrode including a comb-shaped transparent conductive film or a metal film and a counter substrate provided with no electrode are used. As the metal film, for example, a film containing metal such as chromium can be used. Coating on the substrate is preferably performed on the electrode formation surface by an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method.

After apply|coating a liquid crystal aligning agent, it is preferable to implement preheating (prebaking) for the purpose, such as preventing the sagging of the applied liquid crystal aligning agent. The prebaking temperature is preferably 30°C to 200°C. The prebaking time is preferably 0.25 minutes to 10 minutes. Then, the solvent is completely removed, and a calcining (post-baking) step is performed if necessary for the purpose of thermally imidizing the amic acid structure present in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80° C. to 300° C., and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film thus formed is preferably 0.001 μm to 1 μm. After coating a liquid crystal aligning agent on a board|substrate, an organic solvent is removed, and a liquid crystal aligning film or the coating film used as a liquid crystal aligning film is formed.

[Step 2: Orientation Processing]

When manufacturing a TN type, STN type, IPS type, FFS type, or OCB type liquid crystal element, the coating film formed in the said step 1 is given the process (orientation process) which imparts liquid crystal orientation capability. Thereby, the orientation ability of a liquid crystal molecule is given to a coating film, and it becomes a liquid crystal aligning film. As orientation treatment, can enumerate: Utilize the roll that is wound with the cloth that comprises fiber such as nylon, rayon, cotton for example, rub toward fixed direction to coating film is carried out rubbing treatment to give liquid crystal alignment capability to coating film; The formed coating film is irradiated with light, and the photo-alignment process etc. which provide liquid crystal orientation ability to a coating film are performed. On the other hand, in the case of producing a vertical alignment type liquid crystal element, the coating film formed in the above step 1 can be used as a liquid crystal alignment film as it is, but an alignment treatment may be performed on the coating film.

[Step 3: Construction of the liquid crystal cell]

A liquid crystal cell is manufactured by preparing two board|substrates on which the liquid crystal aligning film was formed as mentioned above, and arrange|positioning a liquid crystal between two board|substrates arrange|positioned facing each other. As a method of manufacturing a liquid crystal cell, for example, (1) arrange two substrates facing each other through a gap (cell gap) in such a manner that the liquid crystal aligning films face each other, and bond the peripheral parts of the two substrates with a sealant. Combined, after filling the liquid crystal into the substrate surface and the cell gap divided by the sealant, the method of sealing the injection hole; (2) Coating, for example, UV curable sealant, and then drop the liquid crystal on the prescribed several positions on the surface of the liquid crystal alignment film, then attach another substrate in such a way that the liquid crystal alignment film faces each other, and spread the liquid crystal on the entire surface of the substrate, and then place the The method of hardening the sealant, etc.

As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers, or the like can be used. As liquid crystal, nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal) can be mentioned, among them, nematic liquid crystal is preferable, for example, can use: Schiff base (Schiff base) liquid crystal, azoxy (azoxy) system Liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals Liquid crystals, cubane-based liquid crystals, and the like. In addition, these liquid crystals may be used by adding, for example, cholesteric liquid crystals (cholesteric liquid crystals), chiral agents, ferroelectric liquid crystals (ferroelectric liquid crystals), and the like.

Next, a liquid crystal element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary. Examples of the polarizing plate include: a polarizing plate in which a polarizing film called “H film” is interposed between cellulose acetate protective films, or a polarizing plate including the H film itself. Vinyl alcohol is stretched and oriented while absorbing iodine into the film.

Here, in transverse electric field type liquid crystal elements such as FFS, when anisotropy is found in the liquid crystal aligning film due to rubbing treatment, in order to further improve the display quality by improving the contrast or reducing the afterimage, the application is started. Increase friction. Therefore, there exists a problem that a liquid crystal aligning film is thinned at the time of a rubbing process, and an orientation defect generate|occur|produces easily. On the other hand, conventional liquid crystal aligning agents having good rubbing resistance tend to generate afterimages or lower voltage retention ratios due to charge accumulation accompanying application of AC voltage in many cases, and AC afterimage characteristics and voltage retention ratios are in a trade-off. In this respect, according to the liquid crystal aligning agent containing a polymer [P], the rubbing resistance of a coating film is favorable, the orientation defect by a rubbing process is few, and the liquid crystal element which AC afterimage characteristic and voltage holding ratio are favorable can be obtained.

Moreover, for example, in a color liquid crystal display element, troubles, such as discoloration of the fuel contained in a color filter, generate|occur|produce by the heat at the time of forming a liquid crystal aligning film. In addition, it is also considered that if high-temperature heat treatment is necessary at the time of formation of a liquid crystal aligning film, the application of substrates with insufficient heat resistance such as plastic substrates in the manufacture of liquid crystal elements is limited. In this respect, even when the liquid crystal aligning agent of the present disclosure containing the polymer [P] is heated at the time of post-baking at a relatively low temperature, it is possible to obtain a high voltage retention rate and a low afterimage. Words are also preferred.

In addition, the reason why the said effect is acquired is not clear depending on the liquid crystal aligning agent containing polymer [P], For example, it thinks as follows. The monomer having the partial structure represented by the formula (0) has a relatively large monomer size, and when compared at the same molecular weight, the concentration of carboxylic acid in the polymer [P] is low. From this, it is presumed that one of them is that the influence of the decrease in voltage retention due to low imidization accompanying low-temperature calcination is suppressed, and the AC afterimage is reduced due to the urea bond in the above formula (0), thereby obtaining A liquid crystal element that exhibits good voltage retention and AC afterimage characteristics. In addition, in the case of doping polymer [P] with other polymers, it is also considered that the polymer [P] caused by the low concentration of carboxylic acid is easily distributed in the upper layer, thereby showing good voltage retention and AC Afterimage properties. However, this is only speculation and does not limit the content of the present disclosure.

The liquid crystal element of the present disclosure can be effectively applied to various devices, for example, it can be used in clocks, portable games, word processors, note type personal computers, car navigation systems (car navigation system), camcorder (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart phone, various monitors, LCD TV and other display devices, or Dimming film, etc. Moreover, the liquid crystal element formed using the liquid crystal aligning agent of this disclosure can also be applied to a retardation film.

[Example]

Hereinafter, although an Example demonstrates further in detail, this invention is not limited to these Examples.

In the following examples, the imidation rate of a polymer, the solution viscosity of a polymer solution, the weight average molecular weight Mw of a polymer, and epoxy equivalent are measured by the following methods. Hereinafter, the compound represented by formula (X) may be abbreviated as "compound (X)".

[Imidation rate of polymer] A solution containing polyimide was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and the Using methylsilane as a reference substance, ¹ H-NMR was measured at room temperature. From the obtained ¹ H-NMR spectrum, the imidation rate was calculated|required using the following numerical formula (1).

Imidization ratio (%)=(1-A ¹ /A ² ×α)×100...(1)

(In formula (1), A ¹ is the peak area derived from the proton of the NH group that appears near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the number of other protons relative to the polymer The ratio of one proton of the NH group in the precursor (polyamic acid).)

[Solution Viscosity of Polymer Solution (mPa·s)] Measured at 25° C. using an E-type rotational viscometer.

[The weight-average molecular weight Mw of the polymer]: Using the following device, the result obtained by gel permeation chromatography under the following conditions was determined as a polystyrene-equivalent value using monodisperse polystyrene as a standard substance .

Measuring device: manufactured by Tosoh Co., Ltd., model "8120-GPC"

Column: manufactured by Tosoh Co., Ltd., "TSK gel (TSKgel) GRCXLII"

Solvent: Tetrahydrofuran

Sample concentration: 5% by weight

Sample injection volume: 100μL

Column temperature: 40°C

Column pressure: 68kgf/cm ²

[Epoxy unit amount]: Measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

<Synthesis of Compound>

[Synthesis Example 1: Synthesis of Compound (1-1-1)]

Compound (1-1-1) was synthesized as shown in Scheme 1 below.

[chemical 18]

·Synthesis of compound (1-1-1A)

12.2 g of hydroxybenzaldehyde, 18.1 g of nitrophenylacetic acid, and 17.0 g of piperidine were placed in a 200 mL three-necked flask equipped with a nitrogen gas inlet tube, a thermometer, and a reflux tube, and reacted at 140° C. for 4 hours. After the reaction was completed, 100 mL of ethanol was added, the precipitate was filtered, washed with ethanol, recrystallized from a mixed solvent of tetrahydrofuran and ethanol, and dried to obtain 19.3 g of compound (1-1-1A) crystallization.

·Synthesis of compound (1-1-1C)

Add compound (1-1-1A) 19.3g, compound (1-1-1B) 24.4g, potassium carbonate 13.2g and N, N-dimethyl 400 mL of methyl formamide was stirred at room temperature for 12 hours. After the reaction was completed, the precipitate formed by pouring the reaction liquid into 2 L of water was filtered and dried. Next, 39.8 g of the precipitate, 200 mL of tetrahydrofuran, 200 mL of ethanol, and 9.61 g of hydrazine monohydrate were added to a 1000 mL three-necked flask equipped with a nitrogen gas inlet tube, a thermometer, and a reflux tube, and reflux was performed for 5 hours. After the reaction was completed, 1 L of tetrahydrofuran and 500 mL of toluene were added, and after liquid separation washing with water, drying with magnesium sulfate, concentration under reduced pressure, and filtration and drying of the resulting precipitate were obtained to obtain 19.2 g of the compound ( 1-1-1C).

·Synthesis of compound (1-1-1D)

19.2 g of compound (1-1-1C), 9.58 g of bis(4-nitrophenyl) carbonate, 1200 mL of tetrahydrofuran, 40.6 g of triethylamine and N , 1.63 g of N-dimethylaminopyridine, stirred at room temperature for 12 hours. After the reaction, the precipitate was filtered, washed with water and methanol, recrystallized with a mixed solvent of tetrahydrofuran and ethanol, filtered, and dried to obtain 12.0 g of compound (1-1-1D) .

·Synthesis of compound (1-1-1)

Add 12.0 g of compound (1-1-1D), 6.03 g of 5% palladium carbon, 240 mL of tetrahydrofuran, 120 mL of ethanol, and 6.03 g of hydrazine monohydrate into a 500 mL three-necked flask equipped with a reflux tube, a nitrogen gas inlet tube, and a thermometer, and carry out 4 hour reflux. After the reaction was completed, the filtrate obtained by filtering through celite was concentrated under reduced pressure to 120 mL, poured into 1.2 L of water, and the resulting precipitate was filtered, washed with methanol, and vacuum-dried to obtain 9.74 g of compound (1-1-1).

[Synthesis Example 2: Synthesis of Compound (1-2-1)]

Compound (1-2-1) was synthesized as shown in Scheme 2 below. It synthesize|combines similarly to compound (1-1-1) except having used 4-nitrobiphenol as a raw material instead of compound (1-1-1A) like following scheme 2.

[chemical 19]

[Synthesis Example 3: Synthesis of Compound (1-3-1)]

Compound (1-3-1) was synthesized as shown in Scheme 3 below.

[chemical 20]

·Synthesis of compound (1-3-1B)

23.6 g of compound (1-3-1A), 400 mL of tetrahydrofuran, 15.2 g of bis(4-nitrophenyl) carbonate, 20.2 g of triethylamine and N , N-dimethylaminopyridine 1.22g, reacted at room temperature for 4 hours. After the reaction, the precipitate obtained by pouring into 4L of water was filtered, vacuum-dried and the obtained substance was transferred to a 500mL eggplant-shaped flask, and 200mL of dichloromethane and 100mL of trifluoroacetic acid were added. React for 2 hours. After the reaction was completed, after drying with an aspirator, 200 mL of tetrahydrofuran and 200 mL of ethyl acetate were added, once with a saturated aqueous sodium carbonate solution, and three times with water for liquid separation and washing, and then the organic layer was dried with magnesium sulfate. After concentration, the precipitated crystals were filtered and dried to obtain 11.4 g of compound (1-3-1B).

·Synthesis of compound (1-3-1C)

Add 11.4 g of compound (1-3-1B), 300 mL of tetrahydrofuran, 14.0 g of 4-fluoronitrobenzene, and 10.0 g of triethylamine to a 500 mL three-necked flask equipped with a thermometer, a reflux tube, and a nitrogen gas introduction tube, and heat at 40° C. Respond all day and night. After the reaction was completed, 300 mL of ethyl acetate was added, and water was used for liquid separation and washing three times, and then the organic layer was dried with magnesium sulfate, concentrated under reduced pressure, and the precipitated crystals were filtered and dried to obtain 19.9 g of Compound (1-3-1C).

· Synthesis of compound (1-3-1)

Add 19.9 g of compound (1-3-1C), 1.0 g of 5% palladium on carbon, 200 mL of tetrahydrofuran, 100 mL of ethanol, and 12 g of hydrazine monohydrate into a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen gas inlet tube, and carry out the process for 2 hours. reflow. After the reaction was completed, the filtrate obtained by filtering through diatomaceous earth was concentrated under reduced pressure to 200 mL, poured into 1 L of water and the obtained precipitate was filtered, washed with ethanol, and vacuum-dried to obtain 15.7 g Compound (1-3-1).

[Synthesis Example 4: Synthesis of Compound (1-4-1)]

Compound (1-4-1) was synthesized as shown in Scheme 4 below.

[chem 21]

·Synthesis of Compound (1-4-1A)

After adding 14.9 g of compound (R-1) and 300 mL of pyridine to a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen gas inlet tube, 20.4 g of 4-nitrobenzoyl chloride was added, and the mixture was refluxed for 6 hours. After the reaction was completed, it was poured into 3 L of water and the precipitate was filtered and vacuum-dried, then recrystallized using N,N-dimethylacetamide, filtered, and vacuum-dried to obtain the compound ( 1-4-1A).

·Synthesis of compound (1-4-1B)

Add 26.8 g of compound (1-4-1A), 2.20 g of N,N-dimethylaminopyridine, 300 mL of dimethyl sulfoxide, and tert-butyl dicarbonate into a 1 L three-necked flask equipped with a thermometer and a nitrogen inlet tube 29.4g, reacted at 40°C for a whole day and night. After completion of the reaction, it was poured into 3 L of water, and the deposited precipitate was filtered, washed with methanol, and vacuum-dried to obtain 34.1 g of compound (1-4-1B).

·Synthesis of compound (1-4-1)

34.1 g of compound (1-4-1B), 1.70 g of 5% palladium on carbon, 300 mL of tetrahydrofuran, and 200 mL of ethanol were added to a 1 L autoclave, hydrogen gas was blown in to 0.4 MPa, and the mixture was reacted at room temperature for 4 hours. After the reaction was completed, the filtrate obtained by filtering through diatomaceous earth was concentrated under reduced pressure to 200 mL, 1000 mL of ethyl acetate was added and washed with water three times, the organic layer was concentrated under reduced pressure and the precipitated solid was By filtering and vacuum-drying, 29.5 g of compound (1-4-1) was obtained.

[Taiwan Cheng Example 5: Synthesis of Compound (2-1-1-1)]

Compound (2-1-1-1) was synthesized as shown in Scheme 5 below.

[Chem 221

·Synthesis of compound (2-1-1-1A)

19.0 g of 4-nitrophenylethyl isocyanate and 200 mL of tetrahydrofuran were placed in a 1 L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen gas introduction tube. 16.0 g of N-(tert-butoxycarbonyl)-1,2-diaminoethane and 200 mL of tetrahydrofuran were placed in the dropping funnel and added dropwise over 1 hour, followed by stirring at room temperature for 1 hour. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the precipitate was filtered, washed with ethanol, and vacuum-dried to obtain 33.5 g of compound (2-1-1-1A).

·Synthesis of compound (2-1-1-1)

Add 33.5 g of compound (2-1-1-1A), 1.68 g of 5% palladium carbon, 300 mL of tetrahydrofuran, and 150 mL of ethanol to a 500 mL three-necked flask equipped with a reflux tube and a nitrogen gas introduction tube, and then slowly add 28.5 g of hydrazine monohydrate , to reflux for 2 hours. After the reaction was completed, the solution obtained by filtering through diatomaceous earth was concentrated to 300 mL under reduced pressure, 300 mL of ethyl acetate was added, liquid separation and washing were performed three times with water, and then the organic layer was concentrated under reduced pressure and the resulting precipitate Filtration and vacuum drying were performed to obtain 16.9 g of compound (2-1-1-1).

[Synthesis Example 6: Synthesis of Compound (2-1-2)]

Compound (2-1-2) was synthesized as shown in Scheme 6 below.

[chem 23]

· Compound (2-1-2A)

17.6 g of compound (2-1-1-1A), 0.88 g of 5% palladium on carbon, 200 mL of tetrahydrofuran, and 100 mL of ethanol were added to a 1 L autoclave, hydrogen gas was blown in to 0.4 MPa, and the reaction was carried out at room temperature for 4 hours. After the reaction was completed, the filtrate obtained by filtering through diatomaceous earth was concentrated under reduced pressure to 150 mL, 300 mL of ethyl acetate was added, and water was used to separate and wash three times, and the organic layer was concentrated under reduced pressure, dried and dried in vacuo. , thus obtaining 14.5 g of compound (2-1-2A).

· Compound (2-1-2B)

Add 14.5 g of compound (2-1-2A), 10.7 g of 4-(tert-butoxycarbonylamino)benzoic acid, and 400 mL of dichloromethane to a 1 L three-necked flask equipped with a nitrogen introduction tube and a thermometer, and cool in an ice bath to 5 below ℃. Next, add 9.49 g of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and 1.10 g of N,N-dimethylaminopyridine, and react at 5° C. for 2 hours, React overnight at room temperature. After the reaction was completed, 1 L of ethyl acetate was added, and water was used to separate and wash three times. After drying the organic layer with magnesium sulfate, it was concentrated and dried, and then dissolved in tetrahydrofuran again. ; Chloroform:ethanol=9:1), concentrated and dried to obtain 14.6 g of compound (2-1-2B).

· Compound (2-1-2)

14.6 g of compound (2-1-2B), 200 mL of dichloromethane, and 100 mL of trifluoroacetic acid were added to a 500 mL eggplant-shaped flask equipped with a nitrogen gas introduction tube, and reacted at room temperature for 2 hours. After the reaction was completed, concentrated under reduced pressure and dried to solid, added 300 mL of ethyl acetate and 300 mL of tetrahydrofuran, and carried out once with saturated aqueous sodium carbonate solution and washed with water three times, then concentrated the organic layer, dried and solidified in a vacuum. By drying, 9.24 g of compound (2-1-2) was thus obtained.

[Synthesis Example 7: Synthesis of Compound (3-1-1)]

Compound (3-1-1) was synthesized as shown in Scheme 7 below.

[chem 24]

· Compound (3-1-1A)

16.0 g of N-(tert-butoxycarbonyl)-1,2-diaminoethane, 300 mL of acetonitrile, 12.1 g of triethylamine and 4 - 14.1 g of fluoronitrobenzene was reacted at 50° C. for a whole day and night. After the reaction was completed, it was concentrated under reduced pressure to 50 mL, and the target substance was fractionated using an alumina column (developing solvent; chloroform:ethanol=8:2), then concentrated under reduced pressure, and dried to a solid. Next, 300 mL of dichloromethane and 150 mL of trifluoroacetic acid were added and reacted at room temperature for 2 hours. After the reaction is completed, concentrate under reduced pressure and dry to solid, add 200 mL of ethyl acetate and 200 mL of tetrahydrofuran, perform once with saturated aqueous sodium carbonate solution, wash with water three times, then dry with magnesium sulfate, and then concentrate under reduced pressure , dried, and vacuum-dried to obtain 14.5 g of compound (3-1-1A).

· Compound (3-1-1B)

15.4 g of 4-nitrophenylethyl isocyanate and 200 mL of tetrahydrofuran were placed in a 1 L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen gas introduction tube. 14.5 g of the compound (3-1-1A) and 200 mL of tetrahydrofuran were placed in the dropping funnel and added dropwise over 1 hour, followed by stirring at room temperature for 1 hour. After completion of the reaction, it was concentrated under reduced pressure, and the precipitate was filtered, washed with ethanol, and vacuum-dried to obtain 28.4 g of compound (3-1-1B).

· Compound (3-1-1)

Into a 500mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube, 28.4g of compound (3-1-1B), 1.42g of 5% palladium carbon, 300mL of tetrahydrofuran and 150mL of ethanol were charged, and then 20.4g of hydrazine monohydrate was slowly added, Reflux for 2 hours. After the reaction was completed, the filtrate obtained by filtering through diatomaceous earth was concentrated to 300 mL under reduced pressure, 300 mL of ethyl acetate was added, and water was used to separate and wash three times, then the organic layer was concentrated under reduced pressure and the resulting precipitate The resultant was filtered and vacuum-dried to obtain 20.4 g of compound (3-1-1).

[Synthesis Example 8: Synthesis of Compound (4-1-1)]

Compound (4-1-1) was synthesized as shown in Scheme 8 below.

[chem 25]

· Compound (4-1-1A)

14.9 g of compound (R-1), 300 mL of tetrahydrofuran, and 24.0 g of tert-butyl dicarbonate were added to a 500 mL eggplant-shaped flask equipped with a nitrogen gas introduction tube, and stirred at room temperature overnight. After the reaction was completed, the reaction solution was concentrated under reduced pressure to 200 mL, poured into 2 L of methanol, and the generated precipitate was filtered, washed with methanol, and dried in vacuo to obtain 22.4 g of the compound (4-1-1A ).

· Compound (4-1-1B)

Add 22.4 g of compound (4-1-1A) to a 1 L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen inlet tube, repeatedly perform vacuum/nitrogen replacement and dehydrate the system, then add 200 mL of tetrahydrofuran and 1.3 M bis( 70 mL of tetrahydrofuran solution of lithium trimethylsilyl)amide was cooled in an ice bath to below 5°C. Next, after slowly adding dropwise a solution in which 41.4 g of 4-nitrophenethyl bromide was dissolved in 400 mL of tetrahydrofuran, 70 mL of methanol was slowly added to stop the reaction. Next, 400 mL of water and 600 mL of ethyl acetate were added, and the water layer was removed, followed by liquid separation washing with water three times. Next, after drying the organic layer with magnesium sulfate, it concentrated under reduced pressure, filtered and dried the deposited precipitate, and obtained 28.7 g of compound (4-1-1B).

· Compound (4-1-1)

28.7 g of compound (4-1-1B), 1.44 g of 5% palladium on carbon, 300 mL of tetrahydrofuran, and 150 mL of ethanol were added to a 1 L autoclave, hydrogen gas was blown in to 0.4 MPa, and the mixture was reacted at room temperature for 4 hours. After the reaction was completed, the filtrate obtained by filtering through celite was concentrated under reduced pressure to 200 mL, poured into 2 L of methanol, and the resulting precipitate was filtered, washed with methanol, and vacuum-dried to obtain 23.9 g Compound (4-1-1).

[Synthesis Example 9: Synthesis of Compound (1-5-1)]

Compound (1-5-1) was synthesized as shown in Scheme 9 below.

[chem 26]

· Compound (1-5-1A)

Add 24.9 g of compound (4-1-1A) to a 1 L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen inlet tube, repeatedly perform vacuum/nitrogen replacement and dehydrate the system, then add 250 mL of tetrahydrofuran and 1.3 M bis( Lithium trimethylsilyl)amide tetrahydrofuran solution 77mL, ice bath cooling to below 5 ℃. Next, after slowly adding dropwise a solution obtained by dissolving 37.1 g of 4-nitrobenzoyl chloride in 400 mL of tetrahydrofuran, 80 mL of methanol was slowly added to stop the reaction. Next, 500 mL of water and 600 mL of ethyl acetate were added, and the water layer was removed, followed by liquid separation washing with water three times. Next, after drying the organic layer with magnesium sulfate, it concentrated under reduced pressure, filtered and dried the deposited precipitate, and obtained 31.9 g of compound (1-5-1A).

· Compound (1-5-1)

39.1 g of compound (1-5-1A), 1.60 g of 5% palladium on carbon, 300 mL of tetrahydrofuran, and 150 mL of ethanol were added to a 1 L autoclave, hydrogen gas was blown in to 0.4 MPa, and the mixture was reacted at room temperature for 4 hours. After the reaction was completed, the filtrate obtained by filtering through celite was concentrated under reduced pressure to 200 mL, poured into 2 L of methanol, and the resulting precipitate was filtered, washed with methanol, and vacuum-dried to obtain 26.5 g of Compound (1-5-1).

<Synthesis of Polymer>

[polymerization example 1]

100 mole parts of 1R, 2S, 4S, 5R-1,2,4,5-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 30 moles of compound (1-1-1) as diamine Parts and 70 molar parts of the compound represented by the following formula (D-1) were dissolved in N-methyl-2-pyrrolidone (N-methy1-2-pyrrolidone, NMP), and reacted at room temperature for 6 hours to obtain A solution containing 20% by mass of polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured with a solution having a polyamic acid concentration of 10% by mass was 95 mPa·s. Here, let the obtained polyamic acid be a polymer (PAA-1).

[chem 27]

[Polymerization Example 2 to Polymerization Example 11, Comparative Polymerization Example 1, Comparative Polymerization Example 2]

Except having changed the kind and quantity of the tetracarboxylic dianhydride and diamine used like following Table 1, it carried out similarly to the said polymerization example 1, and synthesize|combined polyamic acid, respectively. Moreover, about polymerization example 9, 100 mol parts of pyridine and 100 mol parts of acetic anhydride were added to the obtained polyamic-acid solution, and chemical imidation was performed at 90 degreeC over 8 hours. The reaction solution after chemical imidation was concentrated, and it prepared by NMP so that the density|concentration might become 10 mass %.

[Table 1]

In Table 1, the numerical value of a monomer composition shows the usage ratio [mol part] of each compound with respect to 100 mol parts of the total amount of the tetracarboxylic dianhydride used for superposition|polymerization. The abbreviations of the compounds are as follows.

A-1: 1R, 2S, 4S, 5R-1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride

D-2: a compound represented by the following formula (D-2)

D-3: a compound represented by the following formula (D-3)

D-4: 2,2′-Dimethyl-4,4′-diaminobiphenyl

[chem 28]

[Example 1]

<Preparation of liquid crystal aligning agent>

To 20 parts by mass of the polymer (PAA-1) obtained in the polymerization example 1 as a polymer, and 80 parts by mass of the polymer (BPA) obtained in the polymerization example 10, and as an epoxy additive N, N, N', N'-tetraglycidyl [4,4'-methylene bis-aniline] (compound represented by the following formula (e-1)) 5 parts by mass (with respect to the polymer A total of 100 parts by mass) was added as organic solvent NMP and butyl cellosolve (butyl cellosolve, BC) to make a solvent composition of NMP:BC=50:50 (mass ratio) and a solid content concentration of 4.0% by mass. solution. A liquid crystal aligning agent (G-1) was prepared by filtering the said solution using the filter of 1 micrometer of pore diameters.

[chem 29]

<Evaluation of amount of foreign matter generated by rubbing treatment>

The prepared liquid crystal aligning agent (G-1) is coated on the transparent electrode surface of a glass substrate with a transparent electrode comprising an ITO film by spin coating, and heated (pre-baked) on a hot plate at 80° C. for 1 minute After removing the solvent, it was heated (post-baked) for 15 minutes in a clean oven at 230° C. under nitrogen gas to form a coating film with an average film thickness of 100 nm. Using a rubbing machine with a cotton cloth-wrapped roller, the coating film was rubbed five times at a roller speed of 1000 rpm, a table moving speed of 2 cm/sec, and a fluff indentation length of 0.4 mm to obtain a substrate for evaluation of the amount of foreign matter. . Foreign matter on the obtained substrate for evaluation of the amount of foreign matter was observed with an optical microscope, the number of foreign matter in a region of 500 μm×500 μm was counted, and rubbing resistance was judged by the following criteria.

Amount of foreign matter ×: The number of foreign matter in the area of 500 μm × 500 μm is 10 or more

Amount of foreign matter △: The number of foreign matter in the area of 500μm×500μm is 5 to 10

Amount of foreign matter ○: The number of foreign matter in the area of 500 μm × 500 μm is 4 or less

As a result, in Example 1, foreign matter was not confirmed, and the abrasion resistance of the coating film was favorable.

<Manufacture of liquid crystal cell for rubbing alignment>

On a glass substrate having a two-system metal electrode (electrode A and electrode B) comprising comb-shaped chromium on one side as the substrate, the liquid crystal aligning agent (G-1) prepared by utilizing a spinner is coated. ), and after prebaking for 1 minute on a hot plate at 80° C., post-baking was performed on a hot plate at 230° C. for 10 minutes to form a coating film with a film thickness of about 80 nm. Using a rubbing machine with a roller wrapped with nylon cloth, a rubbing treatment is carried out on the formed coating film surface at a roller rotation speed of 1000 rpm, a platform moving speed of 25 mm/sec, and a fluff indentation length of 0.4 mm to impart liquid crystal orientation. ability. Furthermore, the substrate was ultrasonically cleaned in ultrapure water for 1 minute, and dried in a clean oven at 100° C. for 10 minutes to manufacture a substrate having a liquid crystal alignment film on a surface having comb-shaped chromium electrodes. Let the board|substrate which has the said liquid crystal aligning film be "substrate A."

In addition, on one side of a glass substrate with a thickness of 1 mm that does not have an electrode, a coating film of a liquid crystal aligning agent is formed in the same manner as described above, rubbed, washed and dried, and a liquid crystal aligning film is produced on one side. the substrate. Let the board|substrate which has the said liquid crystal aligning film be "substrate B."

Then, after the outer edge of the surface with the liquid crystal alignment film of the rubbing treatment on the substrate was coated with an epoxy resin adhesive with a diameter of 5.5 μm of alumina balls, the rubbing direction in each liquid crystal alignment film was reversed. In a parallel manner, the two substrates A and B are arranged facing each other with a gap therebetween, and the outer edge portions are brought into contact with each other and pressure-bonded to harden the adhesive. Next, a nematic liquid crystal (MLC-2042, manufactured by Merck & Co., Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an acrylic light-curing adhesive to manufacture a transverse electric field type liquid crystal. unit.

<Evaluation of afterimage characteristics (burn-in characteristics)>

The liquid crystal cell manufactured above was placed in an environment of 25° C. and 1 atmosphere, and no voltage was applied to electrode B, but a composite voltage of AC voltage 3.5 V and DC voltage 5 V was applied to electrode A for 2 hours. Immediately thereafter, a voltage of AC 4 V was applied to both the electrode A and the electrode B. The time from when the voltage of AC 4V was started to be applied to both electrodes until the difference in light transmittance between electrode A and electrode B could not be visually recognized was measured. The case where the above time was within 50 seconds was evaluated as "very good (⊚)" in the AC afterimage characteristic, the case where it was more than 50 seconds and less than 100 seconds was evaluated as "good (◯)", and the case where it was more than 100 seconds and less than The case of 150 seconds was evaluated as "possible (Δ)", and the case of exceeding 150 seconds was evaluated as "poor (x)". As a result, it was evaluated as "very good (⊚)" in the above-mentioned Examples.

<Evaluation of voltage retention ratio>

After applying a voltage of 5 V for 60 microseconds to the liquid crystal cell manufactured above in a step of 167 milliseconds, the voltage retention rate after 167 milliseconds after the release of the application was measured. The voltage retention rate was 99.5% or more as "very good (◎)", 99.0% or more and less than 99.5% was "good (○)", and 98.0% or more and less than 99.0% was "possible ( △)", less than 98.0% was regarded as "poor (×)", and as a result, the voltage retention rate in the above-mentioned examples was judged as "very good (⊚)". In addition, the model name "VHR-1" manufactured by Toyo Technica Co., Ltd. was used as the measuring apparatus of the voltage holding ratio.

<Evaluation by low-temperature calcination>

Except for changing the post-baking temperature from 230° C. to 150° C., the amount of foreign matter generated by the rubbing treatment was evaluated in the same manner as described above, and a liquid crystal cell for rubbing alignment was manufactured, and afterimage characteristics and voltage retention were evaluated. Evaluation. As a result, in Examples, evaluations equivalent to those obtained when the post-baking temperature was set to 230° C. were obtained, and the rubbing resistance, voltage retention, and AC afterimage characteristics were also favorable even when low-temperature firing was performed.

[Example 2 to Example 9, Comparative Example 1, Comparative Example 2]

The liquid crystal aligning agent was prepared by the method similar to the said Example 1 except having changed the kind and composition of the polymer used, respectively, as described in following Table 2. Moreover, about each liquid crystal aligning agent, evaluation of the amount of the foreign material by a rubbing process was performed similarly to the said Example 1, and the liquid crystal cell of a transverse electric field type was manufactured, and the afterimage characteristic and the evaluation of the voltage holding rate were performed. About Examples 2-9, Comparative Example 1, and Comparative Example 2, various evaluations were performed about two types of post-baking temperatures (230° C., 150° C.) in the same manner as in Example 1. These results are shown in Table 2 below.

[Table 2]

As shown in Table 2, the evaluations of AC afterimage characteristics and voltage retention of the liquid crystal aligning agents (Examples 1 to 18) containing the polymer [P] were "very good (⊚)" or "good (◯)". , and the evaluations of the friction resistance were all "◯", and various characteristics were balanced. On the other hand, Comparative Examples 1 to 4 not containing the polymer [P] were inferior to Examples 1 to 9 in at least any one of rubbing resistance, AC afterimage characteristics, and voltage retention. In addition, in the examples, even when the post-baking temperature was lowered to 150° C., good results were shown in various evaluations. In contrast, in the comparative example, the post-baking temperature was lowered , resulting in performance degradation. Thus, according to the liquid crystal aligning agent of this indication containing a polymer [P], it turns out that the rubbing resistance of a coating film is favorable, and the liquid crystal element with favorable AC afterimage characteristics and a voltage retention rate can be obtained.

<Synthesis of Polymer>

[Polymerization Example 12 to Polymerization Example 15 and Comparative Polymerization Example 3]

Except having changed the kind and quantity of the tetracarboxylic dianhydride and diamine used like following Table 3, it carried out similarly to the said polymerization example 1, and synthesize|combined polyamic acid, respectively. Moreover, chemical imidation was performed similarly to the polymerization example 9 about the obtained polyamic-acid solution, and polyimide was synthesize|combined, respectively.

[table 3]

In Table 3, the numerical value of a monomer composition shows the usage ratio [mol part] of each compound with respect to 100 mol parts of total amounts of the tetracarboxylic dianhydride used for superposition|polymerization. The abbreviations of the compounds are as follows.

A-2: 2,3,5-Tricarboxycyclopentylacetic dianhydride

D-5: Cholesteryloxy-2,4-diaminobenzene

[Polymerization Example 16]

100 mol parts of p-phenylenediamine as a diamine and 220 mol parts of pyridine as a base were added and dissolved in NMP. Next, stirring the said diamine solution, 100 mol parts of compounds represented by the following formula (ta-1) which are tetracarboxylic-acid derivatives were added, and it was made to react at 15 degreeC for 24 hours. After stirring for 24 hours, 30 mol parts of acryloyl chloride was added, and it was made to react at 15 degreeC for 4 hours. The solution of the obtained polyamic acid ester was poured into 2-propanol, stirring, and the white precipitate which precipitated was filtered. Then, the white polyamic acid ester resin powder (this is made into polymer (PAE1)) was obtained by washing|cleaning five times with 2-propanol, and drying. The solution viscosity of the polymer (PAE1) was 96 mPa·s.

[chem 30]

[Polymerization Example 17]

In the reaction vessel equipped with agitator, thermometer, dropping funnel and reflux cooling pipe, 100.0 g of 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine was mixed at room temperature. Then, after dripping 100 g of deionized water from the dropping funnel over 30 minutes, it mixed under reflux, and was made to react at 80 degreeC for 6 hours. After the reaction, the organic layer was taken out, washed with a 0.2 mass % ammonium nitrate aqueous solution until the washed water became neutral, and the solvent and water were distilled off under reduced pressure to obtain a viscous transparent liquid is obtained as epoxy-containing polyorganosiloxane polymer (EPS1). As a result of ¹ H-NMR analysis of the polymer (EPS1), it was confirmed that a peak due to the oxirane group corresponding to the theoretical intensity was obtained near the chemical shift (δ) = 3.2 ppm, and no epoxy was induced in the reaction. base side reactions. The polymer (EPS1) had a weight average molecular weight of 2,200 and an epoxy equivalent of 186 g/mole.

Then, 9.3 g of the obtained polymer (EPS1), 26 g of methyl isobutyl ketone, and 5.6 g of a compound represented by the following formula (CA-1) (equivalent to the polymer (EPS1)) were charged into a 100 mL three-necked flask. 20 mol% of the silicon atoms contained in EPS1) and 0.10 g of the product name "UCAT 18X" (a quaternary amine salt manufactured by San-Apro Co., Ltd.) were reacted at 80°C with stirring for 12 hours. After the reaction, the reaction mixture was put into methanol and the resulting precipitate was recovered, dissolved in ethyl acetate to make a solution, the solution was washed three times with water and the solvent was distilled off, thereby obtaining a white powder 14.7 g of polymer (ESSQ1) were obtained as polyorganosiloxane. The weight average molecular weight Mw of the polymer (ESSQ1) was 8000.

[chem 31]

[Example 19]

<Preparation of liquid crystal aligning agent>

Add NMP and butyl cellosolve (BC) as an organic solvent to 100 parts by mass of the polymer (PI-2) obtained in the above-mentioned polymerization example 12 as a polymer, and make a solvent composition of NMP: BC=50: 50 (mass ratio), and a solution having a solid content concentration of 4.0% by mass. The liquid crystal aligning agent (G-19) was prepared by filtering the said solution using the filter of 1 micrometer of pore diameters.

<Evaluation of Adhesion to Substrate>

The prepared liquid crystal aligning agent (G-19) is coated on the transparent electrode surface of a glass substrate with a transparent electrode comprising an ITO film by spin coating, and heated (pre-baked) on a hot plate at 80° C. for 1 minute After removing the solvent, it was heated (post-baked) for 15 minutes in a clean oven at 230° C. under nitrogen gas to form a coating film with an average film thickness of 100 nm. Using a rubbing machine with a roller wrapped with cotton cloth, rubbing the coating film 5 times at a roller speed of 1000 rpm, a platform moving speed of 2 cm/sec, and a fluff indentation length of 0.4 mm, and applying a load to the film to obtain Substrate for adhesion evaluation. The foreign matter on the obtained board|substrate for adhesion evaluation was observed with the optical microscope, the number of foreign matter in the area|region of 500 micrometers x 500 micrometers was counted, and adhesiveness was judged by the following reference|standard. In addition, the better the adhesion of the film to the substrate, the better the number of foreign substances is, even if a load is applied to the film.

Amount of foreign matter ×: The number of foreign matter in the area of 500 μm × 500 μm is 10 or more

Amount of foreign matter △: The number of foreign matter in the area of 500μm×500μm is 5 to 10

Amount of foreign matter ○: The number of foreign matter in the area of 500 μm × 500 μm is 4 or less

As a result, in Example 19, foreign matter was not confirmed, and the adhesiveness of the said coating film was favorable.

<Manufacture of VA-type liquid crystal cell>

Two glass substrates with transparent electrodes containing ITO films were prepared, and the prepared liquid crystal aligning agent (G-19) was coated on each transparent electrode surface using a spin coater. Subsequently, after prebaking for 1 minute on a hot plate at 80° C., heating (post-baking) at 230° C. for 30 minutes in an oven in which the interior of the chamber was replaced with nitrogen was performed to form a coating film with a film thickness of about 80 nm. Then, after the outer edge of the surface with the liquid crystal alignment film of one of the substrates in the pair of substrates is coated with an epoxy resin adhesive that has a diameter of 5.5 μm alumina balls, the liquid crystal alignment film faces are opposite to each other. A pair of substrates are laminated and pressure-bonded to harden the adhesive. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an acrylic photocurable adhesive to manufacture a liquid crystal cell.

<Evaluation of voltage retention ratio>

As a result of evaluating the voltage holding ratio of the VA-type liquid crystal cell produced above in the same manner as in Example 1, the evaluation of the voltage holding ratio in the above-mentioned Example was "very good (⊚)".

[Example 20-Example 26 and Comparative Example 5, Comparative Example 6]

The liquid crystal aligning agent was prepared by the method similar to the said Example 19 except having changed the kind and composition of the polymer used, respectively, as described in following Table 4. Moreover, about each liquid crystal aligning agent, the evaluation of the adhesiveness to a board|substrate was performed similarly to the said Example 19, the VA type liquid crystal cell was manufactured, and the voltage retention was measured. These results are shown in Table 4 below.

[Example 27]

<Preparation of liquid crystal aligning agent>

Add NMP and Butyl cellosolve (BC) was prepared as a solution having a solvent composition of NMP:BC=50:50 (mass ratio) and a solid content concentration of 4.0% by mass. The liquid crystal aligning agent (G-27) was prepared by filtering the said solution using the filter whose pore diameter was 1 micrometer.

<Evaluation of Adhesion to Substrate>

Except having used the liquid crystal aligning agent (G-27), it carried out similarly to the said Example 19, and performed the adhesive evaluation with respect to a board|substrate. As a result, foreign matter was not confirmed in the above-described examples, and the film adhesion was good.

<Manufacture of liquid crystal cell by photo-alignment treatment>

A glass substrate having a metal electrode patterned into a comb-shaped chromium, and an opposite glass substrate not provided with an electrode are set as a pair, and the prepared polymer composition (G- 27) Coating on the surface of the glass substrate having the electrode and the surface facing the glass substrate. Next, prebaking was performed for 1 minute on an 80° C. hot plate, and heating (post-baking) was performed at 230° C. for 1 hour in an oven that replaced the interior of the chamber with nitrogen. Then, use a Hg-Xe lamp and a Glan-Taylor Prism (Glan-Taylor Prism) to coat the substrate surface on the side of the liquid crystal aligning agent (G-27) from the vertical direction of the substrate surface with an irradiation amount of ^2,000J /m2. Irradiate polarized ultraviolet rays including bright lines of 254 nm. In addition, the said irradiation amount is the value measured using the light meter which measured based on wavelength 254nm. Then, heating was performed on a 230° C. hot plate for 10 minutes. Thereby, a pair of board|substrates which have a liquid crystal aligning film with a film thickness of about 0.1 micrometer were obtained.

Then, after utilizing screen printing to add the epoxy resin adhesive agent that is added with the alumina ball that diameter is 3.5 μ m to be coated on the outer periphery of the face that has liquid crystal aligning film of a substrate in a pair of substrates, make a pair of substrates The liquid crystal aligning film was faced, and the direction opposite to that of each substrate when irradiated with polarized ultraviolet rays was overlapped and pressure-bonded, and the adhesive was thermally cured at 150° C. for 1 hour. Next, after the liquid crystal "MLC-7028" manufactured by Merck was filled into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow orientation at the time of liquid crystal injection, after heating at 150 degreeC, it cooled gradually to room temperature, and obtained the liquid crystal cell.

<Evaluation of voltage retention ratio>

The liquid crystal cell produced by the photo-alignment method was evaluated in the same manner as in Example 1. As a result, the voltage retention was evaluated as "very good (⊚)" in the above-mentioned Example.

[Example 28 to Example 30 and Comparative Example 7]

The liquid crystal aligning agent was prepared by the method similar to the said Example 27 except having changed the kind and composition of the polymer used, respectively, as described in following Table 4. Moreover, about each liquid crystal aligning agent, the evaluation of the adhesiveness to a board|substrate was performed similarly to the said Example 19, and the same as the said Example 27, the liquid crystal cell of the transverse electric field type was manufactured by the photo-alignment method, and the voltage holding rate was measured. . These results are shown in Table 4 below.

[Table 4]

As shown in Table 4, according to the liquid crystal aligning agent containing a polymer [P], it turned out that the liquid crystal aligning film with favorable adhesiveness to a board|substrate was obtained, and the VA type liquid crystal display element which showed high voltage holding ratio was obtained. Moreover, about the liquid crystal display element manufactured by the photo-alignment method, the result which showed the high voltage retention rate was obtained.

Claims (7)

1. a kind of aligning agent for liquid crystal, it is characterised in that：Containing selected from being made up of polyamic acid, poly amic acid ester and polyimides At least one of group and with the polymer [P] of the part-structure represented by following formula (0)；

In formula (0),

R¹For with cyclic group and-NR³- at least one of base and alkane diyl bilvalent radical or-X²⁰-R²⁰-*¹, wherein R³For hydrogen Atom or any monovalent organic radical, X²⁰For singly-bound, ehter bond, thioether bond or ester bond, R²⁰For alkane diyl, *¹Represent the nitrogen being bonded in urea bond The associative key of atom；R²For divalent organic base；R⁶For cyclic group；Wherein, in R¹For-X²⁰-R²⁰-*¹In the case of, R²For with urea Divalent organic base, divalence chain alkyl or the divalence alicyclic type hydrocarbon of key；* associative key is represented.

2. aligning agent for liquid crystal according to claim 1, it is characterised in that：The polymer [P], which has, is derived from following formula (1) The construction unit of represented diamines；

In formula (1), R¹And R²It is respectively identical meanings with the formula (0).

3. aligning agent for liquid crystal according to claim 1 or 2, it is characterised in that：The R¹For the base represented by following formula (2), The base represented by base or following formula (4) represented by following formula (3)；

In formula (2), A¹For the divalent organic base with cyclic group, singly-bound, methylene, ethylidene, ehter bond, thioether bond or ester bond, a For 1~6 integer；Wherein, in A¹In the case of for singly-bound, methylene, ethylidene, ehter bond, thioether bond or ester bond, the R²For Divalence chain alkyl or alicyclic type hydrocarbon；In formula (3), B¹For singly-bound or bivalence linking base, A²For singly-bound or cyclic group, R³For hydrogen Atom or any monovalent organic radical, b are 1~6 integer；In formula (4), A³For the divalent organic base with cyclic group, c for 1~6 it is whole Number；* the associative key with the nitrogen-atoms in urea bond is represented.

4. a kind of liquid crystal orientation film, it is characterised in that：It is taken using liquid crystal according to any one of claim 1 to 3 To liquid crystal orientation film formed by agent.

5. a kind of liquid crystal cell, it is characterised in that：Including liquid crystal orientation film according to claim 4.

6. a kind of polymer, it is characterised in that：It is selected from the group being made up of polyamic acid, poly amic acid ester and polyimides Group at least one of and be derived from following formula (1) represented by compound construction unit；

In formula (1), R¹For with cyclic group and-NR³- at least one of base and alkane diyl bilvalent radical or-X²⁰-R²⁰-*¹, its Middle R³For hydrogen atom or any monovalent organic radical, X²⁰For singly-bound, ehter bond, thioether bond or ester bond, R²⁰For alkane diyl, *¹Expression is bonded to urea The associative key of nitrogen-atoms in key；R²For divalent organic base；Wherein, in R¹For-X²⁰-R²⁰-*¹In the case of, R²For with urea bond Divalent organic base, divalence chain alkyl or divalence alicyclic type hydrocarbon.

7. a kind of diamines, it is characterised in that：It is represented by following formula (1)；

In formula (1), R¹For with cyclic group and-NR³- at least one of base and alkane diyl bilvalent radical or-X²⁰-R²⁰-*¹, its Middle R³For hydrogen atom or any monovalent organic radical, X²⁰For singly-bound, ehter bond, thioether bond or ester bond, R²⁰For alkane diyl, *¹Expression is bonded to urea The associative key of nitrogen-atoms in key；R²For divalent organic base；Wherein, in R¹For-X²⁰-R²⁰-*¹In the case of, R²For with urea bond Divalent organic base, divalence chain alkyl or divalence alicyclic type hydrocarbon.