CN107022358B

CN107022358B - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer, and diamine

Info

Publication number: CN107022358B
Application number: CN201611221886.8A
Authority: CN
Inventors: 秋池利之; 中岛彰男
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2016-01-29
Filing date: 2016-12-26
Publication date: 2021-09-07
Anticipated expiration: 2036-12-26
Also published as: JP2017138575A; TW201726810A; CN107022358A; JP6852347B2; KR20170091011A

Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal element, a polymer and diamine, which can obtain a liquid crystal element with good AC afterimage characteristic and voltage holding ratio. The liquid crystal aligning agent contains: and a polymer having a partial structure represented by the following formula (0) and selected from at least one of the group consisting of polyamic acids, polyamic acid esters, and polyimides.

(R¹Is a cyclic group and "-NR³- "divalent radical of at least one radical of formula (I) with alkanediyl, or" -X²⁰‑R²⁰‑*¹”(X²⁰Is a single bond, an ether bond, etc., R²⁰Is alkanediyl), R²Is a divalent organic radical, R⁶Is a cyclic group. At R¹is-X²⁰‑R²⁰‑*¹In the case of²A divalent organic group, a divalent chain hydrocarbon group, or a divalent alicyclic hydrocarbon group having a urea bond).

Description

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

Technical Field

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

Background

The liquid crystal element includes a liquid crystal alignment film to control the alignment of liquid crystal molecules in the liquid crystal cell. Polyamic acid or polyimide is generally used as a material of the liquid crystal alignment film in terms of its excellent properties such as heat resistance, mechanical strength, and affinity for liquid crystal.

In recent years, various liquid crystal aligning agents have been proposed to further improve the display performance of liquid crystal panels (see, for example, patent documents 1 and 2). Patent document 1 proposes that a polyamic acid or polyimide obtained by using 4,4' -diaminodiphenylamine be contained in a liquid crystal alignment agent, thereby improving voltage holding characteristics and reducing burning. Patent document 2 discloses that a polyimide precursor or a polyimide obtained by using a diamine having a urea bond is contained in a liquid crystal aligning agent, whereby a liquid crystal alignment film having good liquid crystal alignment properties and rubbing resistance, a small ion density, and a small amount of accumulated charges in a Fringe Field Switching (FFS) mode liquid crystal display device can be obtained.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent No. 4052307 publication

[ patent document 2] International publication No. 2013/008906

Disclosure of Invention

[ problems to be solved by the invention ]

A rubbing method, which is one of methods for developing anisotropy in a liquid crystal alignment film, is generally used because it is simple and has good alignment properties of liquid crystal molecules. However, in many cases, conventional liquid crystal alignment agents having good rubbing resistance tend to cause image sticking or a decrease in voltage holding ratio due to charge accumulation associated with application of an AC voltage, that is, the AC image sticking characteristics and the voltage holding ratio are in a trade-off.

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal aligning agent which can obtain a liquid crystal element having excellent AC image sticking characteristics and voltage holding ratio.

[ means for solving the problems ]

The present inventors have conducted intensive studies to achieve the above object and as a result, have found that the above object can be achieved by incorporating a polymer having a specific structure into a liquid crystal aligning agent, and have completed the present invention. Specifically, the following means are provided.

< 1 > a liquid crystal aligning agent comprising at least one polymer [ P ] selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, and having a partial structure represented by the following formula (0);

[ solution 1]

(in the formula (0), R¹Is a cyclic group and "-NR³- "(wherein, R is³Hydrogen atom or monovalent organic group) and an alkanediyl group, or "-X²⁰-R²⁰-*¹"(wherein, X²⁰Is a single bond, ether bond, thioether bond, ester bond or-CONR^b-(R^bIs a hydrogen atom or a monovalent organic group), R²⁰Is alkanediyl; "*¹"represents a bond to a nitrogen atom in a urea bond), R²Is a divalent organic radical, R⁶Is a cyclic group; wherein, in R¹is-X²⁰-R²⁰-*¹In the case of²Is a divalent organic group, a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group having a urea bond; ") represents a bond.

< 2 > a liquid crystal alignment film formed using the liquid crystal aligning agent < 1 >.

< 3 > a liquid crystal cell comprising the liquid crystal alignment film < 2 >.

< 4 > a polymer which is at least one selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, and has a structural unit derived from a compound represented by the following formula (1);

[ solution 2]

(in the formula (1), R¹Is a cyclic group and "-NR³- "(wherein, R is³Is a hydrogen atom or a monovalent radicalOrganic group) and alkanediyl, or "-X²⁰-R²⁰-*¹"(wherein, X²⁰Is a single bond, ether bond, thioether bond or ester bond, R²⁰Is alkanediyl; "*¹"represents a bond to a nitrogen atom in a urea bond), R²Is a divalent organic radical; wherein, in R¹is-X²⁰-R²⁰-*¹In the case of²A divalent organic group, a divalent chain hydrocarbon group, or a divalent alicyclic hydrocarbon group having a urea bond).

< 5 > a diamine represented by said formula (1).

[ Effect of the invention ]

According to the present disclosure, a liquid crystal element having good voltage holding ratio and good image sticking characteristics can be obtained. The above-mentioned effect is obtained even when heating for forming a liquid crystal alignment film is performed at a relatively low temperature, and low-temperature baking is possible, which is preferable.

Detailed Description

Hereinafter, each component contained in the liquid crystal aligning agent of the present disclosure and other components optionally blended as necessary will be described.

< liquid Crystal Aligning agent >

The liquid crystal aligning agent disclosed by the invention contains at least one polymer [ P ] selected from the group consisting of polyamic acid, polyamic acid ester and polyimide and having a partial structure represented by the formula (0).

In the formula (0), R¹The alkanediyl group in (1) is preferably a carbon number of 1 to 6, and examples thereof include: methylene, ethylene, propylene, butylene, pentylene, hexylene, and the like. These alkanediyl groups may be linear or branched, and are preferably linear.

The cyclic group is a group obtained by removing 2 hydrogen atoms from a substituted or unsubstituted ring. Examples of the ring include an aromatic ring, an aliphatic ring, and a heterocyclic ring, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a cyclohexane ring, a pyridine ring, a piperidine ring, a piperazine ring, and a pyrimidine ring. Examples of the substituent that these rings may have include: alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, halogen atom, etc. In the liquid crystal element obtained, R is high in the effect of improving the electrical characteristics and the rubbing resistance of the coating film¹The cyclic group of (a) is preferably a substituted or unsubstituted phenylene group or a piperidyl group.

“-NR³- "(wherein, R is³Is a hydrogen atom or a monovalent organic group) of³The monovalent organic group (C) is preferably a monovalent hydrocarbon group having 1 to 5 carbon atoms or a protecting group. Examples of the protective group include a carbamate (carbamate) protective group, an amide protective group, an imide protective group, and a sulfonamide protective group, and among these, a tert-butoxycarbonyl group is preferable. Further, "-NR³- "may also form part of an amide, urea or urethane bond.

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

[ solution 3]

(in the formula (2), A¹A divalent organic group having a cyclic group, a single bond, a methylene group, an ethylene group, an ether bond, a thioether bond or an ester bond, and a is an integer of 1 to 6. Wherein, in A¹In the case of a single bond, methylene, ethylene, ether bond, thioether bond or ester bond, R is²Is a divalent chain hydrocarbon group or an alicyclic hydrocarbon group. In the formula (3), B¹Is a single bond or a divalent linking group, A²Is a single bond or a cyclic group, R³Is a hydrogen atom or a monovalent organic group, and b is an integer of 1 to 6. In the formula (4), A³Is a divalent organic group having a cyclic group, and c is an integer of 1 to 6. ") represents a bond to a nitrogen atom in a urea bond).

In the formula (2), A is¹Preferable examples of (3) include, for example, a group represented by the following formula (2-1). Further, A in the following formula (2-1)¹¹Cyclic group of (5), said R being applicable¹Description of the cyclic group contained therein.

[ solution 4]

(in the formula (2-1), A¹¹Is a cyclic radical, X¹Is a single bond, methylene, ethylene, ether bond, thioether bond, ester bond or-CONR^b-(R^bHydrogen atom, C1-C6 monovalent hydrocarbon group or protective group, the same applies hereinafter), Y1 is single bond, ether bond, ester bond, thioether bond, -CONR^b-or-NR^b-. p is 0 or 1, ") represents a bond to an alkanediyl group.

In the above formula (3), B¹The divalent linking group(s) is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms. A with respect to said formula (3)²And A of the formula (4)³Having a cyclic group, said R being applicable¹Description of the cyclic group contained therein. Further, having A³The divalent organic group of the cyclic group (b) may have only one cyclic group, or may have two or more cyclic groups.

As R²Examples of the organic group of (3) 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, a group in which the hydrocarbon group is bonded to the heteroatom-containing group, and the like. 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. Wherein, in R¹is-X²⁰-R²⁰In the case of²Is a divalent organic group, a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group having a urea bond.

As R⁶Examples of the cyclic group of (1) include the group R¹Examples of the cyclic group in (1) are as shown in the description. Preferably R⁶Is phenylene or pyridyl, more preferably phenylene.

Here, the "chain hydrocarbon group" in the present specification means a straight-chain or branched hydrocarbon group having no cyclic structure and consisting of only a chain structure. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure.In this case, it is not necessary to constitute only the alicyclic hydrocarbon structure, and a part thereof may have a chain structure. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. In this case, it is not necessary to constitute only an aromatic ring structure, and a part thereof may contain a chain structure or an alicyclic hydrocarbon structure. By "organyl" is meant a group that contains a hydrocarbon group and may also contain heteroatoms in the structure. The "heteroatom-containing group" refers to a divalent or higher group having a heteroatom, and examples thereof include: -O-, -CO-, -COO-, -CONR^b-、-NR^b-、-NR^bCONR^b-、-OCONR^b-、-S-、-COS-、-OCOO-、-SO₂-and the like.

Polymer [ P ]]As long as it has a partial structure represented by the formula (0), it is particularly preferable to have a structural unit derived from a diamine represented by the formula (1) (hereinafter, simply referred to as "specific diamine"). R in the formula (1)¹In the case of the group represented by the above formula (2), preferable specific examples of the specific diamine include a compound represented by the following formula (11) and a compound represented by the following formula (12).

[ solution 5]

(in the formula (12), R⁴Is a divalent chain hydrocarbon group or alicyclic hydrocarbon group having 1 to 10 carbon atoms, and p is 0 or 1. In the formulas (11) and (12), a is an integer of 1 to 6. A. the¹¹、X¹And Y¹Are each as defined for the formula (2-1). Plural A in formula (11)¹¹A plurality of X¹A plurality of Y¹And a may be the same or different).

With respect to said formula (11), A¹¹The cyclic group of (A) is preferably a 1, 4-phenylene group, a 1, 4-pyridylene group, a 1, 4-cyclohexylene group, a 1, 4-piperidyl group or a 1, 4-piperazinyl group, and these cyclic groups may be substituted with a methyl group or a fluorine atom. Particularly preferred are 1, 4-phenylene and 1, 4-piperidyl. a is preferably 2 to 4.

Preferable specific examples of the compound represented by the formula (11) include compounds represented by the following formulae (1-1) to (1-5).

[ solution 6]

(formula (1-1) to formula (1-5) wherein R⁸Is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a tert-butoxycarbonyl group. R⁹Is a hydrogen atom or a methyl group. a is an integer of 1 to 6. A and R in the formula⁸A plurality of R⁹Respectively may be the same or different).

With respect to said formula (12), X¹Preferably an ethylene group, an ester bond or-CONR^b-。Y¹Preferably a single bond or an ether bond. A. the¹¹The cyclic group of (A) is preferably a 1, 4-phenylene group, a 1, 4-pyridylene group, a 1, 4-cyclohexylene group, a 1, 4-piperidyl group or a 1, 4-piperazinyl group, and these cyclic groups may be substituted with a methyl group or a fluorine atom. R⁴Preferably an alkanediyl group having 2 to 6 carbon atoms or a group represented by the following formula (6).

[ solution 7]

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

Preferable specific examples of the compound represented by the formula (12) include compounds represented by the following formulae (2-1) to (2-7). Among these compounds, preferred are compounds represented by the following formula (2-1) and compounds represented by the following formula (2-3).

[ solution 8]

In (formulae (2-1) to (2-7), R¹⁰Is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a tert-butoxycarbonyl group. a is an integer of 1 to 6, and e is an integer of 1 to 10).

R in the formula (1)¹In the case of the group represented by the above formula (3), preferable specific examples of the specific diamine include a compound represented by the following formula (13) and a compound represented by the following formula (14).

[ solution 9]

(in the formulae (13) and (14), R⁵Is a divalent organic group, and g and k are each independently an integer of 1 to 6 carbon atoms. R³And b is the same as the formula (3). A plurality of R in the formula³And b may be the same or different).

In the formula (13), R³Preferably a hydrogen atom, a methyl group or a tert-butoxycarbonyl group. b is preferably 1 to 4.

As R⁵Examples of the divalent organic group of (3) 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, a group in which the hydrocarbon group is bonded to the heteroatom-containing group, and the like. 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. As R⁵Preferable examples of (3) include a group represented by the following formula (7).

[ solution 10]

(in the formula (7), A¹³Is a cyclic radical, X³Is a single bond, methylene, ethylene, ether bond, thioether bond, ester bond or-CONR^b-，Y³Is a single bond, ether bond, ester bond, thioether bond, -CONR^b-or-NR^b-. "" denotes a bond to a primary amino group. h. r, q and s are each independently an integer of 0 to 6).

Preferable specific examples of the compound represented by the formula (13) include compounds represented by the following formulae (3-1) and (3-2), respectively. In the following formulae (3-1) and (3-2), h is preferably 1 or 2.

[ solution 11]

(in the formulae (3-1) and (3-2), b is an integer of 1 to 6, and h is an integer of 0 to 6).

In the formula (14), R³Preferably a hydrogen atom, a methyl group or a tert-butoxycarbonyl group. b. g and k are preferably 1 to 3, respectively. Preferable specific examples of the compound represented by the formula (14) include compounds represented by the following formulae (4-1) and (4-2), respectively.

[ solution 12]

(in the formulae (4-1) and (4-2), b, g and k are each independently an integer of 1 to 6 carbon atoms).

R in the formula (1)¹In the case of the group represented by the above formula (4), preferable specific examples of the specific diamine include a compound represented by the following formula (15).

[ solution 13]

(in the formula (15), R¹¹Is 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)¹¹Preferably, the hydrocarbon group is a divalent chain hydrocarbon group having 1 to 10 carbon atoms, a group containing a heteroatom-containing group between carbon-carbon bonds of the chain hydrocarbon group, or a group in which the hydrocarbon group is bonded to the heteroatom-containing group. c is preferably 1 to 3. Preferable specific examples of the compound represented by the formula (15) include compounds represented by the following formulae (5-1) and (5-2).

[ solution 14]

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

The specific diamine can be synthesized by appropriately combining known methods. Examples thereof include: a method of synthesizing a nitro intermediate having a nitro group instead of the primary amino group in the formula (1), followed by amination of the nitro of the obtained nitro intermediate using an appropriate reducing agent; a method of synthesizing an intermediate in which the primary amino group in the formula (1) is protected with a tert-butoxycarbonyl group or the like, and then deprotecting the obtained intermediate, and the like.

The method for synthesizing the nitro intermediate may be appropriately selected depending on the target compound. For example, there may be mentioned: having R in the presence of bis (4-nitrophenyl) carbonate¹A method for reacting a nitrobenzene derivative of (1); to have a radical derived from R¹And R²A method of reacting the ureido group-containing compound having the partial structure of (1) with a halide such as nitrobenzoyl chloride; to have R¹Or R²With an isocyanate compound having R²Or R¹A method of reacting the amine compound of (1). The method for synthesizing the specific diamine is not limited to the above 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, reacting a tetracarboxylic dianhydride with a diamine containing the specific diamine.

Examples of tetracarboxylic acid dianhydride used for synthesis of polyamic acid include: aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, and the like. Specific examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride.

Examples of the alicyclic tetracarboxylic dianhydride include: 1,2,3, 4-cyclobutanetetracarboxylic acid tetracarboxylateAcid dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-c ]]Furan-1, 3-dione, 1,3,3a,4,5,9 b-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-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 3,5, 6-tricarboxyl-2-carboxymethylnorbornane-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-tetraone, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, and in addition, tetracarboxylic dianhydrides described in Japanese patent application laid-open No. 2010-97188 can be used. Further, the tetracarboxylic dianhydrides may be used singly or in combination of two or more.

The tetracarboxylic dianhydride used for the synthesis is preferably one containing an alicyclic tetracarboxylic dianhydride in combination with a specific diamine in order to improve the electrical characteristics of the liquid crystal device. The proportion of the alicyclic tetracarboxylic dianhydride used is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 30 mol% to 100 mol% based on the total amount of the tetracarboxylic dianhydride used for synthesizing the polyamic acid.

In the synthesis of polyamic acid [ P ], a specific diamine may be used alone, or a diamine other than the specific diamine (hereinafter, simply referred to as "other diamine") may be used.

Examples of the other diamine include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these other diamines include m-xylylenediamine, 1, 3-propylenediamine, pentamethylenediamine, hexamethylenediamine, and the like; examples of the alicyclic diamine include 1, 4-diaminocyclohexane and 4,4' -methylenebis (cyclohexylamine).

Examples of the aromatic diamine include diamines having an orientation group, such as dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholestanyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryl diaminobenzoate, lanostanyl diaminobenzoate, 3, 6-bis (4-aminobenzoyloxy) cholestane, 3, 6-bis (4-aminophenoxy) cholestane, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, and compounds represented by the following formula (E-1).

[ solution 15]

(in the formula (E-1), X¹And X¹¹Each independently is a single bond, -O-, -COO-or-OCO-, R¹Is C1-3 alkanediyl, R¹¹Is a single bond or C1-3 alkanediyl, a is 0 or 1, b is an integer of 0-2, c is an integer of 1-20, and d is 0 or 1. Where a and b are not both 0).

P-phenylenediamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfide, 4-aminophenyl-4 '-aminobenzoate, 4' -diaminoazobenzene, 1, 5-bis (4-aminophenoxy) pentane, bis [2- (4-aminophenyl) ethyl ] adipic acid, N-bis (4-aminophenyl) methylamine, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 4' -diaminobenzanilide, 4'- (p-phenylenediisopropylidene) dianiline, 4' - (m-phenylenediisopropylidene) dianiline, 4 '-diaminodiphenylsulfide, 4' -diaminodiphenylether, and the like, Non-side-chain diamines such as 1, 4-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, N' -bis (4-aminophenyl) -benzidine, 1, 4-bis- (4-aminophenyl) -piperazine, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, 4'- [4,4' -propane-1, 3-diylbis (piperidine-1, 4-diyl) ] diphenylamine and 3, 5-diaminobenzoic acid.

Examples of the diaminoorganosiloxanes include: 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, and the like, diamines described in Japanese patent application laid-open No. 2010-97188 can be used.

Specific examples of the compound represented by the above formula (E-1) include a compound represented by the following formula (E-1-1), a compound represented by the following formula (E-1-2), and the like.

[ solution 16]

In synthesizing the polyamic acid [ P ], the ratio of the specific diamine to be used is preferably 5 mol% or more relative to the total amount of the diamines used in the synthesis of the polyamic acid [ P ], from the viewpoint of sufficiently obtaining the effect of improving the rubbing resistance of the coating film and the electrical characteristics and image sticking characteristics of the liquid crystal element. More preferably 10 to 70 mol%, and still more preferably 10 to 50 mol%. Further, each of the specific diamine and the other diamines may be used alone or two or more thereof may be used as appropriate.

(Synthesis of Polyamic acid)

The polyamic acid [ P ] can be obtained by reacting the tetracarboxylic dianhydride with a diamine, optionally together with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less with respect to 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine used.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature in this case is preferably-20 ℃ to 150 ℃. The reaction time is preferably 0.1 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. As a particularly preferable organic solvent, it is preferable to use one or more solvents selected from the group consisting of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol, and halogenated phenol, or a mixture of one or more of these solvents and another organic solvent (for example, butyl cellosolve, diethylene glycol diethyl ether, or the like). The amount (a) of the organic solvent used is preferably 0.1 to 50% by mass of the total amount (b) of the tetracarboxylic dianhydride and the diamine relative to the total amount (a + b) of the reaction solution.

In this manner, a reaction solution in which polyamic acid is dissolved can be obtained. The reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after the polyamic acid contained in the reaction solution is separated.

(polyamic acid ester)

The polyamic acid ester as the polymer [ P ] can be obtained, for example, by a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

The tetracarboxylic acid diester dihalide to be used can be obtained by reacting a tetracarboxylic acid diester with an appropriate chlorinating agent such as thionyl chloride. The tetracarboxylic acid diester can be obtained by, for example, reacting tetracarboxylic dianhydride exemplified in the synthesis of polyamic acid with an alcohol such as methanol or ethanol. The diamine may be a specific diamine alone or other diamines may be used in combination. Specific examples of the diamine to be used include the specific diamines exemplified in the description of the synthesis of the polyamic acid and other diamines.

The ratio of the tetracarboxylic acid diester dihalide to the diamine used in the synthesis reaction of the polymer [ P ] is preferably such that the amount of the group "-COX- (X is a halogen atom)" of the tetracarboxylic acid diester dihalide becomes 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine. The reaction of the tetracarboxylic acid diester dihalide with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature in this case is preferably-30 to 150 ℃ and the reaction time is preferably 0.1 to 48 hours. As the organic solvent used in the reaction, the organic solvent used in the synthesis reaction of polyamic acid can be used. As the base used in the reaction, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine, etc.; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium. The amount of the base used is preferably 2 to 4 moles based on 1 mole of the diamine.

The reaction solution in which the polyamic acid ester is dissolved can be obtained in the above manner. The reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after the polyamic acid ester contained in the reaction solution is separated. The polyamic acid ester may have only the amic acid ester structure or may be a partially esterified product in which the amic acid structure and the amic acid ester structure coexist. The polyamic acid ester as the polymer [ P ] is not limited to the above-mentioned synthesis method, and can be obtained by, for example, a method of reacting polyamic acid [ P ], an alcohol or a halogenated alkyl group, a method of reacting a tetracarboxylic acid diester with a diamine, or the like.

(polyimide)

The polyimide as the polymer [ P ] can be obtained, for example, by subjecting the polyamic acid [ P ] synthesized as described above to dehydrative ring closure and imidization. In the case where the polyamic acid is subjected to dehydration ring-closure to prepare the polyimide, the reaction solution of the polyamic acid may be directly subjected to dehydration ring-closure reaction, or may be subjected to dehydration ring-closure reaction after the polyamic acid contained in the reaction solution is separated.

The polyimide may be a complete imide compound obtained by dehydration ring closure of all the amic acid structures of the polyamic acid as a precursor thereof, or may be a partial imide compound obtained by dehydration ring closure of only a part of the amic acid structures to allow coexistence of the amic acid structures and the imide ring structures. The imidization ratio of the polyimide used in the reaction is preferably 20% or more, and more preferably 30% to 99%. The imidization ratio is a percentage representing a ratio of the number of imide ring structures to a total of the number of amic acid structures and the number of imide ring structures of the polyimide. Here, a part of the imide ring may be an imide ring.

The dehydration ring-closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or a method of dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closure catalyst to the solution, and optionally heating the solution. Among them, the latter method is preferably used. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride may be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles based on 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, there can be used: tertiary amines such as pyridine, collidine, lutidine and triethylamine. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as organic solvents used for synthesis of polyamic acid. The reaction temperature of the dehydration ring-closure reaction is preferably 0 ℃ to 180 ℃. The reaction time is preferably 1.0 to 120 hours.

In this manner, a reaction solution containing polyimide can be obtained. The reaction solution can be directly used for preparing the liquid crystal aligning agent, can also be used for preparing the liquid crystal aligning agent after the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, and can also be used for preparing the liquid crystal aligning agent after the polyimide is separated.

The solution viscosity of the polymer [ P ] is preferably 10 to 800 mPas, more preferably 15 to 500 mPas when the polymer [ P ] is prepared into a solution having a concentration of 10% by mass. The solution viscosity (mPas) of the polymer [ P ] is a value measured at 25 ℃ using an E-type rotational viscometer on a 10 mass% polymer solution prepared using a good solvent for the polymer [ P ] (e.g., γ -butyrolactone, N-methyl-2-pyrrolidone, etc.).

The weight average molecular weight (Mw) of the polymer [ P ] in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less.

(other Components)

The liquid crystal aligning agent of the present disclosure may contain other components than the polymer [ P ]. Examples of such other components include: a polymer other than the polymer [ P ] (hereinafter, simply referred to as "other polymer"), a compound having at least one epoxy group in the molecule (hereinafter, also referred to as "epoxy group-containing compound"), and the like.

The other polymer can be used for the purpose of improving various properties such as electrical properties of residual images and transparency, or for the purpose of cost reduction. Examples of such other polymers include: a polymer having no structural unit derived from the compound represented by the formula (1), which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, a polyorganosiloxane, a polyester, a polyamide, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly (styrene-phenylmaleimide) derivative, and the like. The blending ratio of the other polymer to the total amount of the polymer components contained in the liquid crystal aligning agent is preferably 95% by mass or less, and more preferably 10% by mass to 90% by mass.

The epoxy group-containing compound is used for improving the adhesiveness of the liquid crystal alignment film to the substrate surface and the electrical characteristics. 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, trimethylolpropane triglycidyl ether, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl [4,4' -methylenedianiline ], N, N-diglycidylbenzylamine, N, N-diglycidylaminomethylcyclohexane, N, N-diglycidylcyclohexylamine and the like. In addition, the epoxy group-containing polyorganosiloxane described in the international publication No. 2009/096598 can be used. When the epoxy-containing compound is blended in the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by mass or less, and more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the polymers contained in the liquid crystal aligning agent.

In addition to the above, other components include a functional silane compound, a compound having at least one oxetanyl group in the molecule, an antioxidant, a metal chelate compound, a curing accelerator, a surfactant, a filler, a dispersant, a photosensitizer and the like. The blending ratio of these other components may be appropriately selected depending on each compound within a range not impairing the effects of the present disclosure.

In the liquid crystal aligning agent of the present disclosure, the blending ratio of the polymer [ p ] to the total amount of the polymer components contained in the liquid crystal aligning agent is preferably 5% by mass or more, and more preferably 10% by mass or more, in order to improve the electrical characteristics and the image sticking characteristics of the liquid crystal element. When the liquid crystal aligning agent contains another polymer, the blending ratio of the polymer [ p ] is preferably 5 to 99 parts by mass, more preferably 10 to 95 parts by mass, and still more preferably 10 to 80 parts by mass, based on 100 parts by mass of the total amount of the polymer [ p ] and the other polymer contained in the liquid crystal aligning agent.

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

[ solution 17]

(in the formulae (p-1) and (p-2), R⁵¹Is a tetravalent organic radical, R⁵²Is a hydrogen atom or a monovalent organic radical, R⁵³The remaining group is a group obtained by removing 2 primary amino groups from the specific diamine. Plural R⁵²May be the same or different).

As R in said formula (p-1)⁵²Examples of the monovalent organic group(s) include monovalent hydrocarbon groups having 1 to 10 carbon atoms and groups having a cinnamic acid structure. R⁵¹The tetravalent organic group (2) is a residual group obtained by removing 2 acid anhydride groups from tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include the above-mentioned tetracarboxylic dianhydrides.

(solvent)

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

Examples of the organic solvent to be used include: n-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 2-dimethyl-2-imidazolidinone, gamma-butyrolactone, gamma-butyrolactam, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol N-propyl ether, ethylene glycol isopropyl ether, ethylene glycol N-butyl ether (butylcellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These organic solvents may be used alone or in combination of two or more.

The concentration of the solid component in the liquid crystal aligning agent (the ratio of the total mass of the 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, and the like, and is preferably in the range of 1 to 10 mass%. That is, as described later, a liquid crystal alignment agent is applied to the surface of a substrate, and preferably heated, thereby forming a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. In this case, when the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10 mass%, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent tends to increase to lower the coatability.

< liquid crystal element >

The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal aligning agent described in the above. The operation mode of the liquid crystal In the liquid crystal element is not particularly limited, and can be applied to various operation modes such as a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, a Vertical Alignment (VA) type (including a Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, a Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), an In-Plane Switching (IPS) type, an FFS type, and an Optically Compensated Bend (OCB) type. When the method is applied to a mode in which a treatment for imparting liquid crystal aligning ability to a coating film formed using a liquid crystal aligning agent is required, such as a TN-type, STN-type, IPS-type, FFS-type, or OCB-type liquid crystal cell, it is preferable that a liquid crystal cell exhibiting good voltage holding ratio and image sticking characteristics can be obtained even by using a rubbing method. The liquid crystal element of the present disclosure can be manufactured by a method including, for example, steps 1 to 3 below. Step 1 uses different substrates depending on the desired mode of operation. Step 2 and step 3 are common in each operation mode.

[ step 1: formation of coating film ]

A liquid crystal aligning agent is first applied to a substrate, and then the coated surface is heated to form a coating film on the substrate. As the substrate, for example: glass such as float glass (float glass) and soda glass (soda glass); transparent substrates comprising plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly (alicyclic olefin). As the transparent conductive film provided on one surface of the substrate, a transparent conductive film containing tin oxide (SnO) can be used₂) Nessel (NESA) film (PPG Male USA)Registered trademark), contains indium oxide-tin oxide (In)₂O₃-SnO₂) Indium Tin Oxide (ITO) film, and the like. In the case of manufacturing a TN-type, STN-type, or VA-type liquid crystal cell, two substrates provided with a patterned transparent conductive film are used. In the case of manufacturing an IPS-type or FFS-type liquid crystal device, a substrate provided with an electrode including a transparent conductive film or a metal film patterned into a comb-tooth shape and a counter substrate provided with no electrode are used. As the metal film, for example, a film containing a metal such as chromium can be used. The coating of the substrate on the electrode-forming surface is preferably performed by an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method.

After the liquid crystal aligning agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing sagging of the applied liquid crystal aligning agent and the like. The pre-baking temperature is preferably 30-200 ℃. The pre-baking time is preferably 0.25 to 10 minutes. Then, the solvent is completely removed, and a calcination (post-baking) step is carried out, if necessary, for the purpose of thermally imidizing the amic acid structure present in the polymer. The calcination temperature (post-baking temperature) in this case is preferably 80 to 300 ℃, and the post-baking time is preferably 5 to 200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm. After a liquid crystal aligning agent is applied to a substrate, an organic solvent is removed to form a liquid crystal alignment film or a coating film to be the liquid crystal alignment film.

[ step 2: orientation treatment ]

In the case of producing a TN-type, STN-type, IPS-type, FFS-type, or OCB-type liquid crystal cell, the coating film formed in the above-described step 1 is subjected to a treatment (alignment treatment) for imparting liquid crystal alignment ability. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the orientation treatment, there can be mentioned: rubbing treatment for rubbing the coating film in a fixed direction by a roller around which a cloth containing fibers such as nylon, rayon, and cotton is wound to impart liquid crystal alignment ability to the coating film; and photo-alignment treatment for applying light to the coating film formed on the substrate to impart liquid crystal alignment capability to the coating film. 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 may be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment treatment.

[ step 3: construction of liquid Crystal cell

A liquid crystal cell is manufactured by preparing two substrates on which liquid crystal alignment films are formed in this manner, and disposing liquid crystal between the two substrates disposed in opposition to each other. Examples of a method for manufacturing a liquid crystal cell include: (1) a method of arranging two substrates in an opposing manner with a gap (cell gap) therebetween so that the liquid crystal alignment films face each other, bonding peripheral portions of the two substrates with a sealant, injecting a filling liquid crystal into a surface of the substrate and the cell gap defined by the sealant, and then sealing the injection hole; (2) a method of applying, for example, an ultraviolet curable sealant to a predetermined portion of one of the two substrates, dropping liquid crystal to a predetermined plurality of portions on the liquid crystal alignment film surface, bonding the other substrate so that the liquid crystal alignment film faces the other substrate, spreading the liquid crystal over the entire surface of the substrate, and curing the sealant.

As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. Examples of the liquid crystal include nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal), and among them, nematic liquid crystal is preferable, and for example: schiff base (Schiff base) liquid crystals, azoxy (azo) liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl (terphenyl) liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane (cubane) liquid crystals, and the like. For example, a cholesteric liquid crystal (cholesteric liquid crystal), a chiral agent, a ferroelectric liquid crystal (ferroelectric liquid crystal), or the like may be added to the liquid crystal.

Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell as necessary, whereby a liquid crystal element can be obtained. Examples of the polarizing plate include: a polarizing plate formed by sandwiching a polarizing film called "H film" which is a film obtained by absorbing iodine while stretching and orienting polyvinyl alcohol, or a polarizing plate including the H film itself, with a cellulose acetate protective film.

Here, in a liquid crystal cell of a transverse electric field type such as FFS, when anisotropy is found in a liquid crystal alignment film by rubbing treatment, strong rubbing is started in order to improve the display quality by improving the contrast and reducing the residual image. Therefore, the liquid crystal alignment film is thinned during the rubbing treatment, and there is a problem that alignment defects are easily generated. On the other hand, in many cases, conventional liquid crystal alignment agents having good rubbing resistance tend to cause image sticking or a decrease in voltage holding ratio due to charge accumulation associated with application of an AC voltage, and thus the AC image sticking characteristics and the voltage holding ratio are in a trade-off. In this respect, according to the liquid crystal aligning agent containing the polymer [ P ], a liquid crystal element having a coating film with good rubbing resistance, few alignment defects caused by rubbing treatment, and good AC afterimage characteristics and voltage holding ratio can be obtained.

In addition, for example, in a color liquid crystal display element, it is considered that a defect such as discoloration of fuel contained in a color filter occurs due to heat generated when a liquid crystal alignment film is formed. Further, it is considered that if high-temperature heat treatment is required for forming the liquid crystal alignment film, application of a substrate having insufficient heat resistance, such as a plastic substrate, to the production of a liquid crystal device is limited. In this respect, the liquid crystal aligning agent of the present disclosure containing the polymer [ P ] is preferable in that a high voltage holding ratio and a low afterimage can be obtained even when heating at a relatively low temperature at the time of post-baking.

The reason why the above-mentioned effects can be obtained by the liquid crystal aligning agent containing the polymer [ P ] is not clear, and the following is considered, for example. The monomer having the partial structure represented by the above formula (0) has a large monomer size, and when compared with the same molecular weight, the carboxylic acid concentration in the polymer [ P ] is low. From this, one of: the influence of the decrease in voltage holding ratio due to the low imidization accompanying the low-temperature calcination is suppressed, and the AC afterimage is reduced by the urea bond in the formula (0), whereby a liquid crystal device exhibiting good voltage holding ratio and AC afterimage characteristics can be obtained. In addition, when the polymer [ P ] is doped with another polymer, it is considered that the polymer [ P ] due to the low carboxylic acid concentration is likely to be distributed in an upper layer, thereby exhibiting a good voltage holding ratio and AC afterimage characteristics. This is only a presumption and does not limit the disclosure.

The liquid crystal element of the present disclosure can be effectively applied to various devices, for example, can be used for: a clock, a portable game machine (portable game), a word processor (word processor), a notebook Personal computer (note type Personal computer), a car navigation system (car navigation system), a camcorder (camcorder), a Personal Digital Assistant (PDA), a Digital camera (Digital camera), a mobile phone, a smart phone, various monitors, various display devices such as a liquid crystal television, or a light adjusting film. In addition, a liquid crystal element formed using the liquid crystal aligning agent of the present disclosure can also be applied to a retardation film.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

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

[ imidization ratio of Polymer]Adding a solution containing polyimide to pure water, drying the obtained precipitate at room temperature under sufficiently reduced pressure, dissolving in deuterated dimethyl sulfoxide, and measuring at room temperature using tetramethylsilane as a reference substance¹H-NMR. According to the obtained¹The percentage of imidization was determined by using the following equation (1) for H-NMR spectrum.

Imidization rate (%) - (1-A)¹/A²×α)×100···(1)

(in the numerical formula (1), A¹Is the peak area of the proton originating from the NH group present in the vicinity of a chemical shift of 10ppm, A²The peak area derived from other protons, and α is the number of other protons relative to NH in the precursor (polyamic acid) of the polymerThe ratio of one proton of the radicals. )

[ solution viscosity (mPas) of the polymer solution ] was measured at 25 ℃ using a rotational viscometer of the E type.

[ weight average molecular weight Mw of Polymer ]: using the following apparatus, the results of measurement by gel permeation chromatography under the following conditions were obtained as polystyrene equivalent values using monodisperse polystyrene as a standard substance.

A measuring device: tosoh (stock), model 8120-GPC "

Pipe column: manufactured by Tosoh, Strand, "TSK gel (TSKgel) GRCXLII"

Solvent: tetrahydrofuran (THF)

Sample concentration: 5% by weight

Sample injection amount: 100 μ L

Temperature of the pipe column: 40 deg.C

Pipe column pressure: 68kgf/cm²

[ epoxy monomer amount ]: measured according to JIS C2105 "hydrochloric acid-methyl ethyl ketone method".

< Synthesis of Compound >

Synthetic example 1: synthesis of Compound (1-1-1)

Compound (1-1-1) was synthesized as in scheme 1 below.

[ solution 18]

Scheme 1

Synthesis of Compound (1-1-1A)

A200 mL three-necked flask equipped with a nitrogen inlet tube, a thermometer and a reflux tube was charged with 12.2g of hydroxybenzaldehyde, 18.1g of nitrophenylacetic acid and 17.0g of piperidine, and reacted at 140 ℃ for 4 hours. After the reaction was completed, 100mL of ethanol was added, and the precipitate was filtered, washed with ethanol, and then recrystallized from a mixed solvent of tetrahydrofuran and ethanol and dried, thereby obtaining 19.3g of crystals of the compound (1-1-1A).

Synthesis of Compound (1-1-1C)

19.3g of the compound (1-1-1A), 24.4g of the compound (1-1-1B), 13.2g of potassium carbonate and 400mL of N, N-dimethylformamide were placed in a 1000mL three-necked flask equipped with a nitrogen inlet tube, a thermometer and a reflux tube, and stirred at room temperature for 12 hours. After the reaction was completed, the precipitate produced by pouring the reaction solution into 2L of water was filtered and dried. Then, 39.8g of the precipitate, 200mL of tetrahydrofuran, 200mL of ethanol, and 9.61g of hydrazine monohydrate were put into a 1000mL three-necked flask equipped with a nitrogen inlet, a thermometer, and a reflux tube, and refluxed for 5 hours. After the reaction was completed, 1L of tetrahydrofuran and 500mL of toluene were added, followed by liquid separation and washing with water, drying with magnesium sulfate, concentration under reduced pressure, and filtration and drying of the resulting precipitate, whereby 19.2g of compound (1-1-1C) was obtained.

Synthesis of Compound (1-1-1D)

19.2g of the compound (1-1-1C), 9.58g of bis (4-nitrophenyl) carbonate, 1200mL of tetrahydrofuran, 40.6g of triethylamine and 1.63g of N, N-dimethylaminopyridine were put into a 2L three-necked flask equipped with a nitrogen inlet and a thermometer, and stirred at room temperature for 12 hours. After the reaction was completed, the precipitate was filtered, washed with water and methanol, and further recrystallized from a mixed solvent of tetrahydrofuran and ethanol, followed by filtration and drying, whereby 12.0g of the compound (1-1-1D) was obtained.

Synthesis of Compound (1-1-1)

To a 500mL three-necked flask equipped with a reflux tube, a nitrogen inlet tube and a thermometer, 12.0g of compound (1-1-1D), 6.03g of 5% palladium on carbon, 240mL of tetrahydrofuran, 120mL of ethanol and 6.03g of hydrazine monohydrate were added, and the mixture was refluxed for 4 hours. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated to 120mL under reduced pressure, and the resulting precipitate was poured into 1.2L of water, filtered, washed with methanol, and vacuum-dried to obtain 9.74g 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. The synthesis was carried out in the same manner as in the case of the compound (1-1-1) except that 4-nitrodiphenol was used as a starting material in place of the compound (1-1-1A) in the following scheme 2.

[ solution 19]

Scheme 2

[ Synthesis example 3: synthesis of Compound (1-3-1)

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

[ solution 20]

Scheme 3

Synthesis of Compound (1-3-1B)

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

Synthesis of Compound (1-3-1C)

To a 500mL three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube, 11.4g of the compound (1-3-1B), 300mL of tetrahydrofuran, 14.0g of 4-fluoronitrobenzene and 10.0g of triethylamine were added, and the mixture was reacted at 40 ℃ for a whole day and night. After completion of the reaction, 300mL of ethyl acetate was added, followed by three liquid-separation washes with water, followed by drying of the organic layer over magnesium sulfate, concentration under reduced pressure, and filtration and drying of the precipitated crystals, whereby 19.9g of compound (1-3-1C) was obtained.

Synthesis of Compound (1-3-1)

19.9g of the compound (1-3-1C), 1.0g of 5% palladium on carbon, 200mL of tetrahydrofuran, 100mL of ethanol, and 12g of hydrazine monohydrate were put into a 500mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, and refluxed for 2 hours. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated to 200mL under reduced pressure, and the obtained precipitate was poured into 1L of water, filtered, washed with ethanol, and vacuum-dried, whereby 15.7g of compound (1-3-1) was obtained.

[ Synthesis example 4: synthesis of Compound (1-4-1) ]

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

[ solution 21]

Scheme 4

Synthesis of Compound (1-4-1A)

14.9g of the compound (R-1) and 300mL of pyridine were put in a 500mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen inlet, and 20.4g of 4-nitrobenzoyl chloride was added thereto and the mixture was refluxed for 6 hours. After the reaction was completed, the resulting precipitate was poured into 3L of water, filtered, dried under vacuum, recrystallized from N, N-dimethylacetamide, filtered, and dried under vacuum, whereby compound (1-4-1A) was obtained.

Synthesis of Compound (1-4-1B)

26.8g of the compound (1-4-1A), 2.20g of N, N-dimethylaminopyridine, 300mL of dimethyl sulfoxide and 29.4g of tert-butyl dicarbonate were put into a 1L three-necked flask equipped with a thermometer and a nitrogen inlet tube and reacted at 40 ℃ overnight. After the reaction was completed, the resulting precipitate was filtered by pouring into 3L of water, washed with methanol, and dried under vacuum to obtain 34.1g of compound (1-4-1B).

Synthesis of Compound (1-4-1)

A1L autoclave was charged with 34.1g of the compound (1-4-1B), 1.70g of 5% palladium on carbon, 300mL of tetrahydrofuran and 200mL of ethanol, and then reacted at room temperature for 4 hours while blowing hydrogen gas to 0.4 MPa. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated to 200mL under reduced pressure, 1000mL of ethyl acetate was added and three times of liquid-separation washing with water was performed, the organic layer was concentrated under reduced pressure, and the precipitated solid was filtered and dried under vacuum, whereby 29.5g of compound (1-4-1) was obtained.

[ Synthesis example 5: synthesis of Compound (2-1-1-1) ]

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

[ solution 22]

Scheme 5

Synthesis of Compound (2-1-1-1A)

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

Synthesis of Compound (2-1-1-1)

33.5g of the compound (2-1-1-1A), 1.68g of 5% palladium on carbon, 300mL of tetrahydrofuran and 150mL of ethanol were placed in a 500mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, followed by slow addition of 28.5g of hydrazine monohydrate and reflux for 2 hours. After completion of the reaction, the solution obtained by filtration through celite was concentrated to 300mL under reduced pressure, 300mL of ethyl acetate was added, followed by three times of liquid-separation washing with water, and then the organic layer was concentrated under reduced pressure, and the resulting precipitate was filtered and dried under vacuum, whereby 16.9g of compound (2-1-1-1) was obtained.

[ Synthesis example 6: synthesis of Compound (2-1-2)

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

[ solution 23]

Scheme 6

Compound (2-1-2A)

17.6g of the compound (2-1-1-1A), 0.88g of 5% palladium on carbon, 200mL of tetrahydrofuran and 100mL of ethanol were placed in a 1L autoclave, and hydrogen gas was blown into the autoclave until the pressure became 0.4MPa, followed by reaction at room temperature for 4 hours. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated to 150mL under reduced pressure, 300mL of ethyl acetate was added thereto, followed by three times of liquid-separation washing with water, and the organic layer was concentrated under reduced pressure, dried and dried under vacuum to obtain 14.5g of compound (2-1-2A).

Compound (2-1-2B)

14.5g of compound (2-1-2A), 10.7g of 4- (tert-butoxycarbonylamino) benzoic acid, and 400mL of methylene chloride were added to a 1L three-necked flask equipped with a nitrogen inlet and a thermometer, and the mixture was cooled to 5 ℃ or lower in an ice bath. Next, 9.49g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1.10g of N, N-dimethylaminopyridine were added thereto, and the mixture was reacted at 5 ℃ for 2 hours and at room temperature overnight. After the reaction was completed, ethyl acetate 1L was added, followed by three times of liquid separation and washing with water, the organic layer was dried over magnesium sulfate, concentrated and dried to a solid, and then dissolved again in tetrahydrofuran, and the resulting solution was separated by an alumina column (developing solvent; chloroform: ethanol ═ 9: 1), concentrated and dried to a solid, whereby 14.6g of the compound (2-1-2B) was obtained.

Compound (2-1-2)

14.6g of compound (2-1-2B), 200mL of methylene chloride and 100mL of trifluoroacetic acid were placed in a 500mL round bottom flask equipped with a nitrogen inlet tube, and reacted at room temperature for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and dried, 300mL of ethyl acetate and 300mL of tetrahydrofuran were added, followed by liquid-separation washing with saturated aqueous sodium carbonate solution once and three times with water, and then the organic layer was concentrated, dried and dried under vacuum to obtain 9.24g of compound (2-1-2).

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

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

[ solution 24]

Scheme 7

Compound (3-1-1A)

A500 mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen inlet tube was charged with 16.0g of N- (tert-butoxycarbonyl) -1, 2-diaminoethane, 300mL of acetonitrile, 12.1g of triethylamine and 14.1g of 4-fluoronitrobenzene, and reacted at 50 ℃ for a whole day and night. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to 50mL, and the target product was fractionated by an alumina column (developing solvent; chloroform: ethanol: 8: 2), concentrated under reduced pressure, and dried. Next, 300mL of methylene chloride and 150mL of trifluoroacetic acid were added to the mixture, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain a solid, and 200mL of ethyl acetate and 200mL of tetrahydrofuran were added to the mixture, followed by washing with a saturated aqueous solution of sodium carbonate once and three times with water, followed by drying with magnesium sulfate, concentration under reduced pressure, drying to obtain a solid, and drying in vacuum to obtain 14.5g of compound (3-1-1A).

Compound (3-1-1B)

To a 1L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen inlet tube, 15.4g of 4-nitrophenylethyl isocyanate and 200mL of tetrahydrofuran were charged. The dropping funnel was charged with 14.5g of the compound (3-1-1A) and 200mL of tetrahydrofuran, and after dropping over 1 hour, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and the precipitate was filtered, washed with ethanol, and vacuum-dried to obtain 28.4g of compound (3-1-1B).

Compound (3-1-1)

A500 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube was charged with 28.4g of compound (3-1-1B), 1.42g of 5% palladium on carbon, 300mL of tetrahydrofuran, and 150mL of ethanol, followed by slow addition of 20.4g of hydrazine monohydrate and reflux for 2 hours. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated to 300mL under reduced pressure, 300mL of ethyl acetate was added, followed by three times of liquid-separation washing with water, and then the organic layer was concentrated under reduced pressure, and the resulting precipitate was filtered and dried under vacuum, whereby 20.4g of compound (3-1-1) was obtained.

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

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

[ solution 25]

Scheme 8

Compound (4-1-1A)

14.9g of the compound (R-1), 300mL of tetrahydrofuran and 24.0g of tert-butyl dicarbonate were put in a 500mL eggplant type flask equipped with a nitrogen inlet tube, and stirred at room temperature for a whole day and night. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to 200mL, poured into 2L of methanol, and the resulting precipitate was filtered, washed with methanol, and dried under vacuum to obtain 22.4g of compound (4-1-1A).

Compound (4-1-1B)

22.4g of the compound (4-1-1A) was charged into a 1L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen gas inlet tube, vacuum/nitrogen substitution was repeated to dehydrate the inside of the system, and then 200mL of tetrahydrofuran and 70mL of a 1.3M solution of lithium bis (trimethylsilyl) amide in tetrahydrofuran were added, and the mixture was cooled to 5 ℃ or lower in an ice bath. Next, a solution of 41.4g of 4-nitrophenylethyl bromide in 400mL of tetrahydrofuran was slowly added dropwise, and then 70mL of methanol was slowly added to stop the reaction. Next, 400mL of water and 600mL of ethyl acetate were added to remove the aqueous layer, and then three liquid-separation washes were performed with water. Next, the organic layer was dried over magnesium sulfate, then concentrated under reduced pressure, and the precipitated precipitate was filtered and dried, whereby 28.7g of compound (4-1-1B) was obtained.

Compound (4-1-1)

28.7g of the compound (4-1-1B), 1.44g of 5% palladium on carbon, 300mL of tetrahydrofuran and 150mL of ethanol were placed in a 1L autoclave, and hydrogen gas was blown into the autoclave until the pressure became 0.4MPa, followed by reaction at room temperature for 4 hours. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated to 200mL under reduced pressure, and the filtrate was poured into 2L of methanol to filter the resulting precipitate, followed by washing with methanol and vacuum drying, whereby 23.9g of compound (4-1-1) was obtained.

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

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

[ solution 26]

Scheme 9

Compound (1-5-1A)

24.9g of the compound (4-1-1A) was charged into a 1L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen gas inlet tube, vacuum/nitrogen substitution was repeated to dehydrate the inside of the system, 250mL of tetrahydrofuran and 77mL of a 1.3M solution of lithium bis (trimethylsilyl) amide in tetrahydrofuran were then added, and the mixture was cooled to 5 ℃ or lower in an ice bath. Next, a solution of 37.1g of 4-nitrobenzoyl chloride dissolved in 400mL of tetrahydrofuran was slowly added dropwise, and then 80mL of methanol was slowly added thereto to stop the reaction. Next, 500mL of water and 600mL of ethyl acetate were added to remove the aqueous layer, and then three liquid-separation washes were performed with water. Then, the organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the precipitated precipitate was filtered and dried, whereby 31.9g of compound (1-5-1A) was obtained.

Compound (1-5-1)

39.1g of the compound (1-5-1A), 1.60g of 5% palladium on carbon, 300mL of tetrahydrofuran and 150mL of ethanol were placed in a 1L autoclave, and hydrogen gas was blown into the autoclave until the pressure became 0.4MPa, followed by reaction at room temperature for 4 hours. After completion of the reaction, the filtrate obtained by filtration through celite was concentrated to 200mL under reduced pressure, and the filtrate was poured into 2L of methanol to filter the resulting precipitate, followed by washing with methanol and vacuum drying, whereby 26.5g of compound (1-5-1) was obtained.

< Synthesis of Polymer >

[ polymerization example 1]

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

[ solution 27]

Polymerization examples 2 to 11, comparative polymerization example 1 and comparative polymerization example 2

Polyamic acids were each synthesized in the same manner as in polymerization example 1, except that the kinds and amounts of tetracarboxylic dianhydride and diamine used were changed as in table 1 below. In polymerization example 9, 100 parts by mole of pyridine and 100 parts by mole of acetic anhydride were added to the obtained polyamic acid solution, and chemical imidization was performed at 90 ℃ for 8 hours. The reaction solution after chemical imidization was concentrated and prepared using NMP so that the concentration became 10 mass%.

[ Table 1]

In table 1, the numerical values of the monomer compositions indicate the usage ratios [ molar parts ] of the respective compounds with respect to 100 molar parts of the total amount of tetracarboxylic dianhydride used in the polymerization. The compounds are briefly described below.

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

[ solution 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, 80 parts by mass of the polymer (BPA) obtained in the polymerization example 10, and 5 parts by mass (in an amount of 100 parts by mass in total of the polymers) of N, N '-tetraglycidyl [4,4' -methylenedianiline ] (compound represented by the following formula (e-1)) of an epoxy additive, NMP and Butyl Cellosolve (BC) were added as organic solvents to prepare a polymer having a solvent composition of NMP: BC 50: 50 (mass ratio) and a solid content concentration of 4.0 mass%. The solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal aligning agent (G-1).

[ solution 29]

< evaluation of amount of foreign matter produced by Friction treatment >

The liquid crystal aligning agent (G-1) thus prepared was applied to the transparent electrode surface of a glass substrate having a transparent electrode comprising an ITO film by spin coating, heated (pre-baked) on a hot plate at 80 ℃ for 1 minute to remove the solvent, and then heated (post-baked) in a clean oven at 230 ℃ for 15 minutes under nitrogen to form a coating film having an average film thickness of 100 nm. The coating film was rubbed 5 times with a rubbing machine having a roller wrapped with cotton cloth at a roller rotation speed of 1000rpm, a table moving speed of 2 cm/sec and a pile penetration length of 0.4mm to obtain a substrate for evaluation of the amount of foreign matter. The foreign matter on the obtained substrate for evaluation of the amount of foreign matter was observed by an optical microscope, the number of foreign matters in a region of 500 μm × 500 μm was calculated, and the abrasion resistance was determined by the following criteria.

Foreign matter amount x: the number of foreign matters in the 500 μm × 500 μm region is 10 or more

Foreign matter amount Δ: the number of foreign matters in the 500. mu. m.times.500. mu.m region is 5 to 10

Foreign matter amount ≈: the number of foreign matters in the 500 μm × 500 μm region is 4 or less

As a result, no foreign matter was observed in example 1, and the abrasion resistance of the coating film was good.

< production of liquid Crystal cell for rubbing alignment >

The prepared liquid crystal aligning agent (G-1) was applied to a glass substrate having two-system metal electrodes (electrode a and electrode B) containing chromium patterned in a comb-tooth shape on one surface of the substrate by a spinner, prebaked at 80 ℃ for one minute, and then baked at 230 ℃ for 10 minutes to form a coating film having a thickness of about 80 nm. The resulting coating film surface was rubbed using a rubbing machine having a roller wrapped with a nylon cloth at a roller rotation speed of 1000rpm, a table moving speed of 25 mm/sec and a pile penetration length of 0.4mm to impart liquid crystal alignment ability. Further, the substrate was subjected to ultrasonic cleaning in ultrapure water for one minute and dried in a clean oven at 100 ℃ for 10 minutes, thereby producing a substrate having a liquid crystal alignment film on the surface having a comb-teeth-shaped chromium electrode. The substrate having the liquid crystal alignment film was referred to as "substrate a".

In addition, a coating film of a liquid crystal alignment agent was formed on one surface of a glass substrate having a thickness of 1mm and no electrode, and rubbing treatment was performed in the same manner as described above, followed by washing and drying to produce a substrate having a liquid crystal alignment film on one surface. The substrate having the liquid crystal alignment film was referred to as "substrate B".

Then, after an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm was applied to the outer edge of the surface of the substrate having the liquid crystal alignment film subjected to rubbing treatment, the two substrates a and B were arranged to face each other with a gap therebetween so that the rubbing directions in the respective liquid crystal alignment films were antiparallel to each other, and the outer edge portions were brought into contact with each other and pressure-bonded to cure the adhesive. Then, nematic liquid crystal (MLC-2042, manufactured by merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive, thereby manufacturing a lateral electric field type liquid crystal cell.

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

The manufactured liquid crystal cell was placed in an environment of 1 atmosphere at 25 ℃, and a combined voltage of 3.5V ac voltage and 5V dc voltage was applied to the electrode a for 2 hours without applying a voltage to the electrode B. Immediately thereafter, a voltage of 4V was applied to both electrodes a and B. The time from the time point when the ac 4V voltage was applied to both electrodes was measured until the difference in light transmittance between the electrode a and the electrode B could not be visually confirmed. The AC image retention characteristic "very good" (. circleincircle) "was evaluated when the time was within 50 seconds, the" good "(. circleincircle)" was evaluated when the time was more than 50 seconds and less than 100 seconds, the "ok" (. DELTA) "was evaluated when the time was 100 seconds or more and less than 150 seconds, and the" bad "(. times)", was evaluated when the time was more than 150 seconds. As a result, the evaluation was "very good (excellent)" in the examples.

< evaluation of Voltage holding ratio >

After a voltage of 5V was applied for 60 microseconds at a span of 167 milliseconds to the manufactured liquid crystal cell, a voltage holding ratio was measured after 167 milliseconds from the release of the application. The voltage holding ratio was defined as "very good (. circleincircle)" when 99.5% or more and less than 99.5% were defined as "good (. largecircle)", 98.0% or more and less than 99.0% were defined as "acceptable (. DELTA)", and less than 98.0% as "poor (. times)", and as a result, the voltage holding ratio was determined as "very good (. circleircle)" in the examples. Further, as a device for measuring the voltage holding ratio, a model name "VHR-1" manufactured by Toyo Technica, Inc. was used.

< evaluation by Low-temperature calcination >

The amount of foreign materials generated by rubbing treatment was evaluated in the same manner as described above, and a liquid crystal cell for rubbing alignment was produced and evaluated for image retention characteristics and voltage holding ratio, except that the post-baking temperature was changed from 230 ℃ to 150 ℃. As a result, in the examples, evaluation equivalent to that when the post-baking temperature was set to 230 ℃ was obtained, and the rubbing resistance, the voltage holding ratio, and the AC image sticking characteristics were good even when the low-temperature baking was performed.

Examples 2 to 9, comparative examples 1 and 2

Liquid crystal aligning agents were prepared in the same manner as in example 1, except that the kind and composition of the polymer used were changed as described in table 2 below. In addition, with respect to each liquid crystal aligning agent, the amount of foreign matter generated by rubbing treatment was evaluated in the same manner as in example 1, and a liquid crystal cell of a transverse electric field type was manufactured and evaluated for image sticking characteristics and voltage holding ratio. In examples 2 to 9, comparative examples 1 and 2, various evaluations were made for two 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 liquid crystal aligning agents (examples 1 to 18) containing the polymer [ P ] had AC image retention characteristics and voltage holding ratios evaluated as "very good (. circleincircle.) or" good (. largecircle) ", and had rubbing resistance evaluated as" good ", and the various characteristics were balanced. In contrast, comparative examples 1 to 4 containing no polymer [ P ] were inferior to examples 1 to 9 in at least any one of the abrasion resistance, the AC image sticking characteristic and the voltage holding ratio. In the examples, even when the post-baking temperature was lowered to 150 ℃, favorable results were shown in various evaluations, whereas in the comparative examples, the performance was lowered as a result of lowering the post-baking temperature. Thus, the liquid crystal aligning agent of the present disclosure containing the polymer [ P ] can provide a liquid crystal device having a coating film with good rubbing resistance and good AC image sticking characteristics and voltage holding ratio.

< Synthesis of Polymer >

[ polymerization examples 12 to 15 and comparative polymerization example 3]

Polyamic acids were each synthesized in the same manner as in polymerization example 1, except that the kinds and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in table 3 below. In addition, the obtained polyamic acid solution was chemically imidized in the same manner as in polymerization example 9 to synthesize a polyimide.

[ Table 3]

In table 3, the numerical values of the monomer compositions indicate the usage ratios [ molar parts ] of the respective compounds with respect to 100 molar parts of the total amount of tetracarboxylic dianhydride used in the polymerization. The compounds are briefly described below.

A-2: 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride

D-5: cholestanyloxy-2, 4-diaminobenzene

[ polymerization example 16]

100 parts by mole of p-phenylenediamine as a diamine and 220 parts by mole of pyridine as a base were added and dissolved in NMP. Then, 100 parts by mole of a compound represented by the following formula (ta-1) as a tetracarboxylic acid derivative was added while stirring the diamine solution, and the mixture was reacted at 15 ℃ for 24 hours. After stirring for 24 hours, 30 parts by mole of acryloyl chloride was added and reacted at 15 ℃ for 4 hours. The obtained polyamic acid ester solution was poured into 2-propanol with stirring, and the precipitated white precipitate was filtered. Subsequently, the resin was washed 5 times with 2-propanol and dried to obtain a white polyamic acid ester resin powder (referred to as polymer (PAE 1)). The solution viscosity of the polymer (PAE1) was 96 mPas.

[ solution 30]

[ polymerization example 17]

100.0g of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 500g of methyl isobutyl ketone and 10.0g of triethylamine were charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and mixed at room temperature. Then, 100g of deionized water was added dropwise from the dropping funnel over 30 minutes, followed by mixing under reflux and reaction at 80 ℃ for 6 hours. After the reaction was completed, the organic layer was taken out, washed with a 0.2 mass% ammonium nitrate aqueous solution until the water after washing became neutral, and the solvent and water were distilled off under reduced pressure, whereby a polymer (EPS1) which was an epoxy group-containing polyorganosiloxane was obtained as a viscous transparent liquid. Subjecting said polymer (EPS1)¹As a result of H-NMR analysis, it was confirmed that an oxetanyl group-based peak having a theoretical intensity was obtained in the vicinity of a chemical shift (δ) of 3.2ppm, and that no side reaction of an epoxy group occurred during the reaction. The polymer (EPS1) had a weight average molecular weight of 2,200 and an epoxy equivalent of 186 g/mole.

Then, 9.3g of the obtained polymer (EPS1), 26g of methyl isobutyl ketone, 5.6g of a compound represented by the following formula (CA-1) (corresponding to 20 mol% of a silicon atom contained in the polymer (EPS 1)) and 0.10g of a product name "UCAT 18X" (quaternary amine salt manufactured by Santo Apro corporation) were charged in a 100mL three-necked flask, and the reaction was carried out at 80 ℃ with stirring for 12 hours. After the reaction was completed, the reaction mixture was put into methanol to recover the formed precipitate, which was dissolved in ethyl acetate to prepare a solution, and the solution was washed with water three times and then the solvent was distilled off, whereby 14.7g of a polymer as polyorganosiloxane was obtained as a white powder (ESSQ 1). The weight average molecular weight Mw of the polymer (ESSQ1) was 8000.

[ solution 31]

[ example 19]

< preparation of liquid Crystal Aligning agent >

NMP and Butyl Cellosolve (BC) as organic solvents were added to 100 parts by mass of the polymer (PI-2) obtained in polymerization example 12 as a polymer to prepare a solution having a solvent composition of NMP: BC 50: 50 (mass ratio) and a solid content concentration of 4.0 mass%. The solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal aligning agent (G-19).

< evaluation of adhesion to substrate >

The liquid crystal aligning agent (G-19) thus prepared was applied to the transparent electrode surface of a glass substrate having a transparent electrode comprising an ITO film by spin coating, heated (pre-baked) on a hot plate at 80 ℃ for 1 minute to remove the solvent, and then heated (post-baked) in a clean oven at 230 ℃ for 15 minutes under nitrogen to form a coating film having an average film thickness of 100 nm. The coating film was subjected to rubbing treatment 5 times at a roll rotation speed of 1000rpm, a table moving speed of 2 cm/sec and a pile penetration length of 0.4mm by a rubbing machine having a roll around which cotton cloth was wound, and a load was applied to the film, thereby obtaining a substrate for adhesion evaluation. The foreign matter on the obtained substrate for adhesion evaluation was observed by an optical microscope, the number of foreign matters in a 500 μm × 500 μm region was counted, and the adhesion was determined by the following criteria. Further, the more excellent the adhesion of the film to the substrate, the less the number of foreign substances is, and the better the film is, even if a load is applied to the film.

As a result, no foreign matter was observed in example 19, and the adhesion of the coating film was good.

< manufacture of VA type liquid crystal cell >

Two glass substrates having transparent electrodes comprising an ITO film were prepared, and the prepared liquid crystal aligning agent (G-19) was coated on each transparent electrode surface using a spin coater. Subsequently, the film was prebaked on a hot plate at 80 ℃ for 1 minute, and then heated at 230 ℃ for 30 minutes in an oven with a nitrogen gas substitution in the oven (postbaking), to form a coating film having a film thickness of about 80 nm. Then, an epoxy adhesive containing alumina balls having a diameter of 5.5 μm was applied to the outer edge of the surface of one of the pair of substrates having the liquid crystal alignment film, and then the pair of substrates were stacked and pressed so that the liquid crystal alignment films were opposed to each other, thereby curing the adhesive. Then, nematic liquid crystal (MLC-6608, manufactured by merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a liquid crystal cell.

< evaluation of Voltage holding ratio >

The VA liquid crystal cell thus produced was evaluated for the voltage holding ratio in the same manner as in example 1, and as a result, the voltage holding ratio in the example was evaluated as "very good (very excellent)".

Examples 20 to 26 and comparative examples 5 and 6

Liquid crystal aligning agents were prepared in the same manner as in example 19, except that the kind and composition of the polymer used were changed as described in table 4 below. Further, for each liquid crystal aligning agent, adhesion to a substrate was evaluated in the same manner as in example 19, and a VA-type liquid crystal cell was produced and a voltage holding ratio was measured. These results are shown in table 4 below.

[ example 27]

< preparation of liquid Crystal Aligning agent >

NMP and Butyl Cellosolve (BC) as organic solvents were added to 60 parts by mass of the polymer (PAA-1) obtained in polymerization example 1 and 40 parts by mass of the polymer (PAE1) obtained in polymerization example 16 as polymers to prepare a mixture having a solvent composition of NMP: BC 50: 50 (mass ratio) and a solid content concentration of 4.0 mass%. The solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal aligning agent (G-27).

< evaluation of adhesion to substrate >

Adhesion to the substrate was evaluated in the same manner as in example 19, except that the liquid crystal aligning agent (G-27) was used. As a result, foreign matter was not observed in the above examples, and the adhesion of the film was good.

< manufacture of liquid Crystal cell Using photo-alignment treatment >

A pair of a glass substrate having a metal electrode containing chromium patterned in a comb-like shape and an opposing glass substrate having no electrode was prepared, and the prepared polymer composition (G-27) was applied to the surface of the glass substrate having the electrode and the surface of the opposing glass substrate using a spin coater. Subsequently, the resultant was prebaked at 80 ℃ for 1 minute on a hot plate, and heated at 230 ℃ for 1 hour in an oven with a nitrogen gas substitution in the oven. Then, at 2,000J/m using Hg-Xe lamp and Glan-Taylor Prism (Glan-Taylor Prism)²The substrate surface coated with the liquid crystal alignment agent (G-27) was irradiated with polarized ultraviolet rays containing 254nm bright lines in a direction perpendicular to the substrate surface. The irradiation dose is a value measured by using a light amount meter measured with respect to a wavelength of 254 nm. Subsequently, heating was performed on a hot plate at 230 ℃ for 10 minutes. Thus, a pair of substrates having liquid crystal alignment films with a film thickness of about 0.1 μm was obtained.

Then, an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of one of the pair of substrates by screen printing, the liquid crystal alignment films of the pair of substrates were faced to each other, superimposed and pressure-bonded so as to oppose the direction of each substrate when polarized ultraviolet light was irradiated, and the adhesive was heat-cured at 150 ℃ for 1 hour. Then, after filling a gap between the substrates with liquid crystal "MLC-7028" manufactured by merck corporation from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal cell was obtained by heating the liquid crystal at 150 ℃ and then gradually cooling the liquid crystal to room temperature.

< evaluation of Voltage holding ratio >

As a result of evaluating the voltage holding ratio of the liquid crystal cell produced by the photo-alignment method in the same manner as in example 1, the voltage holding ratio in the example was evaluated as "very good (excellent)".

Examples 28 to 30 and comparative example 7

Liquid crystal aligning agents were prepared in the same manner as in example 27, except that the kind and composition of the polymer used were changed as described in table 4 below. Further, for each liquid crystal aligning agent, adhesion to a substrate was evaluated in the same manner as in example 19, and a lateral electric field type liquid crystal cell was produced by a photo-alignment method and a voltage holding ratio was measured in the same manner as in example 27. These results are shown in table 4 below.

[ Table 4]

As shown in table 4, it was found that a VA liquid crystal display device exhibiting high voltage holding ratio could be obtained by obtaining a liquid crystal alignment film having good adhesion to a substrate from a liquid crystal alignment agent containing the polymer [ P ]. In addition, the liquid crystal display element manufactured by the photo-alignment method can obtain a result of showing a high voltage holding ratio.

Claims

1. A liquid crystal aligning agent characterized in that: a polymer [ P ] containing at least one member selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, wherein the polymer [ P ] has a structural unit derived from a diamine represented by the following formula (1-3), formula (1-4), formula (2-3), or formula (14);

in the formulae (1-3) to (1-4), R⁸Is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a tert-butoxy groupA is an integer of 1 to 6, wherein a and R are⁸Each of which may be the same or different,

in the formula (2-3), R¹⁰A hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a tert-butoxycarbonyl group, a is an integer of 1 to 6, e is an integer of 1 to 10,

in the formula (14), g and k are each independently an integer of 1 to 6 carbon atoms, R³Is a hydrogen atom or a monovalent organic group, b is an integer of 1 to 6, wherein R is a plurality of R³And b may be the same or different.

2. A liquid crystal alignment film characterized in that: which is a liquid crystal alignment film formed using the liquid crystal aligning agent according to claim 1.

3. A liquid crystal cell, characterized by: comprising the liquid crystal alignment film according to claim 2.

4. A polymer characterized by: which is at least one selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, and has a structural unit derived from a compound represented by the following formula (1-3), formula (1-4), formula (2-3), or formula (14);

in the formulae (1-3) to (1-4), R⁸A is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a t-butoxycarbonyl group, a is an integer of 1 to 6, wherein a and R are in the formula⁸Each of which may be the same or different,

5. A diamine characterized by: which is represented by the following formula (1-3), formula (1-4), formula (2-3) or formula (14);