WO2020175539A1 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal alignment agent that contains polymers (A) and (B). Polymer A: At least one polymer selected from among polyimide precursors that are the reaction product of a tetracarboxylic acid derivative component and a diamine component that contains a diamine having a skeleton represented by formula (1), and polyimides obtained by the imidization of the polyimide precursors. The definitions of the symbols in the formulas are as presented in the description.

Description

\¥0 2020/175539 1 卩 (: 17 2020 /007694 Clarification

Title of Invention: Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element Technical Field

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, a liquid crystal display device having the liquid crystal aligning film, and novel diamines and polymers suitable for them.

Background technology

Liquid crystal display elements are known as lightweight, thin, and low power consumption display devices. A liquid crystal display element is constructed by sandwiching a liquid crystal layer between a pair of transparent substrates having electrodes. In a liquid crystal display device, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal has a desired alignment state between the substrates. In recent years, high-definition liquid crystal display devices for smartphones and tablet-type terminals are required to have high display quality, and liquid crystal alignment films require various characteristics in addition to liquid crystal alignment. Has been done.

[0003] In order to achieve those requirements, a method of adding a low molecular weight compound having various properties to a liquid crystal aligning agent for producing a liquid crystal aligning film is widely used. For example, in order to improve the mechanical strength of the obtained liquid crystal alignment film, a liquid crystal alignment agent containing a low molecular weight compound that improves the hardness of the liquid crystal alignment film has been proposed (see Patent Documents 1 and 2). This low-molecular compound contains a group that undergoes a crosslinking reaction in the heating step performed in the liquid crystal alignment film preparation process, and the polymers are linked by crosslinking, so that the mechanical properties of the resulting liquid crystal alignment film are increased. The strength is improved.

Prior art documents

Patent literature

[0004] Patent Document 1: Japanese Unexamined Patent Publication No. 2 0 1 0-5 4 4 1 8 5

Patent Document 2: Patent 6 1 7 9 1 1

Summary of the invention 〇 2020/175539 2 卩(：171? 2020/007694 Issues to be solved by the invention

However, in the recent manufacture of liquid crystal displays, there is a demand for a liquid crystal alignment film that satisfies not only the mechanical strength of the liquid crystal alignment film but also other properties at the same time. The problem to be solved by the present invention is to provide a liquid crystal alignment film excellent in mechanical strength of the film, and particularly in a liquid crystal display device for lateral electrolysis, it is excellent in afterimage characteristics by long-term AC drive. Another object is to provide a liquid crystal alignment film, and a liquid crystal aligning agent capable of obtaining this liquid crystal alignment film.

Means for solving the problem

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems, and the present invention has the following aspects.

1. A liquid crystal aligning agent containing the following polymer () and ⑻.

Polymer (8): At least one selected from a polyimide precursor which is a reaction product of a diamine component containing a diamine having a skeleton represented by the following formula (1) and a tetracarboxylic acid derivative component and a polyimide which is an imidized product thereof. One polymer.

[0007] [Chemical 1]

Represents a site that binds to the group.

Polymer (M): Polyimide precursor and its reaction product of a tetracarboxylic acid derivative component and a diamine component containing at least one diamine selected from the following formulas (3) and (4): At least one polymer selected from the imidized polyimides.

[0009] \¥0 2020/175539 卩(: 17 2020 /007694

[Chemical 2]

(3) (4)

During [0010] Formula (3) and (4), eight ₁ is a single bond, an ether bond, an ester bond, amino de bond, a thioether bond, thioester bond, alkylene down group of carbon number 2-2 0 (provided that the alkylene Any of the groups

^1-1 ₂ -, an ether group, an ester group, may be substituted with cyclohexylene group, or a phenylene group. ), or a phenylene group. Eighty _two is a halogen atom, a hydroxy group, or an alkyl group or an alkoxy group having 1 to 5 carbon atoms (provided that any hydrogen atom of the alkyl group or the alkoxy group may be substituted with a halogen atom). Is. 3 is an integer from 0 to 4, and when 3 is 2 or more, 8 ₂ may be the same or different. Swallow and ◯ are each independently an integer of 1 to 2. Effect of the invention

[001 1] According to the present invention, a liquid crystal alignment film having excellent mechanical strength can be obtained. In other words, by using a polymer having an oxazoline skeleton as a component of the liquid crystal aligning agent, it is possible to obtain a liquid crystal aligning film in which peeling or scratching of the film does not easily occur during rubbing. In addition, by using the polymer composed of the diamine of the above formula (3) or (4), which has excellent liquid crystal orientation, the afterimage characteristics after long-term AC driving are excellent especially in the liquid crystal display device for lateral electrolysis. A liquid crystal alignment film can be obtained.

A liquid crystal display device comprising a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is a liquid crystal display which has few display defects due to abrasion and scratches of the liquid crystal alignment film and has excellent afterimage characteristics after long-term AC drive. It becomes an element.

MODE FOR CARRYING OUT THE INVENTION

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing the polymers () and (M) \¥0 2020/175539 4 卩 (: 17 2020 /007694

It is an agent. Hereinafter, each constituent element will be described in detail.

<Polymer ()>

The polymer (8) contained in the liquid crystal aligning agent of the present invention means a polyimide precursor which is a reaction product of a diamine component containing a diamine having a skeleton of the following formula (1) and a tetracarboxylic acid derivative component, and It is at least one polymer selected from its imide, the polyimide.

[0015] [Chemical Formula 3]

[0016] In the above formula (1),

Represents hydrogen or a monovalent organic group, and * represents a site bonded to another group. The specific polymer in the present invention is preferably a polymer obtained from a diamine having the structure of the above formula (1).

[0017] When the amount of the diamine having the skeleton of the formula (1) is too small with respect to the total amount of the diamine component for producing the polymer (8), the mechanical strength of the film is weak, and when the amount is large, it is long-term. It is 1 to 80 mol%, more preferably 3 to 65 mol%, and further preferably 5 to 50 mol% because the afterimage characteristics due to AC driving deteriorate.

[0018] <Specific diamine>

The diamine having an oxazoline skeleton represented by the above formula (1) (hereinafter, also referred to as a specific diamine) is a diamine selected from the group represented by the following formulas (2-1) to (2-3). Can be mentioned.

[0019] \¥02020/175539 5 卩 (: 17 2020 /007694

[Chemical 4]

(2-3)

[0020] In the above formula (2-1) to formula (2-3),

The definition of is the same as in the above equation (1). ^ ² is a single bond, ^_ 〇 ^_ , 100 001, — 000— _% — (01 ^~ 1 2) ,-, -0 (〇 1 ^~ 1 ₂ ), 〇 1, 100 000 [¾ ^{1 1} -,

1 ¹ — is a bond selected from or a divalent organic group consisting of a combination thereof,

Is a structure selected from the following group (3_1), ² is a structure selected from the following group (3-2), ³ is a structure selected from the following group (3_3), ⁴ is a structure selected from the following group (3_4) Represents. here,

Represents hydrogen or a monovalent organic group, 丨 represents an integer of 1 to 12 and 3 represents an integer of 0 or 1.

[0021] [Chemical 5]

[0022] [Chemical 6]

[0023] 〇 2020/175539 6 卩(：171? 2020/007694

[Chemical 7]

[0025] In the above group (3-1),

(2-1) from (2-3) represents the site of amino group and binding in,氺₂ represents a binding site for the oxazoline ring. In the group (3-2), Yi! Represents a site that is bonded to the amino group in formulas (2-1) to (2-3),

Represents the position to combine with. In the group (3 -4), ₂ represents a site that binds to the oxazoline ring. X represents a substituent, hydrogen atom; halogen atom; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; halogenated alkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; dimethyl Substituted amino group such as amino group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; 1\11 ^to 1○○○ 1 ^to 1 ₃ and 1\11 ^to 1○○○ 1 ^to 1 ₂ 〇 1 ^to 1 _3,

Represents an amide group such as Minori. Minori represents a 6 1^ 1:-butyl group.

Specific examples of the diamines of the above formulas (2-1) to (2-3) include the following.

[0027] 〇 2020/175539 7 卩(：171? 2020/007694

[Chemical 9]

[0028] [Chemical 10]

[0029] [Chemical 1 1]

[0030] In the above formula,

Is the same as in the above formula (1), and particularly, a hydrogen atom, a methyl group

Alternatively, an ethyl group (Mimi) is preferred. Definition of \¥0 2020/175539 8 卩 (: 17 2020 /007694

Is the same as in the above formula (1), and in particular, a hydrogen atom, IV! 6 group or

<Method for synthesizing specific diamine>

Examples of the method of synthesizing the specific diamine in the present invention include a method of synthesizing a dinitro compound represented by the following formulas (4 — 1) to (4-3) and further reducing the nitro group to convert it into an amino group. be able to.

[0032] [Chemical 12]

[0033] In the above formulas (4 _ 1) to (4 _ 3),

[¾ The definitions of ² , ¹ , ² , ³ , ^4, and 3 are the same as those in the above formulas (2-1) to (2-3).

[0034] The catalyst used for the reduction reaction of the nitro group is preferably a commercially available activated carbon-supported metal, and examples thereof include palladium-activated carbon, platinum-activated carbon, and sponge-activated carbon. Further, it is not always necessary to use an activated carbon-supporting metal catalyst such as palladium hydroxide, platinum oxide or Raney nickel. Of these, palladium-activated carbon is preferable.

[0035] In order to allow the above reduction reaction to proceed more effectively, the reaction may be carried out in the presence of activated carbon. At this time, the amount of activated carbon used is preferably 1 to 30% by mass, and more preferably 10 to 20% by mass, based on the dinitro compound. For similar reasons, the reaction may be carried out under pressure. In this case, in order to avoid the reduction of benzene nuclei, the reaction is preferably carried out at a pressure of 20 atm or less, more preferably up to 10 atm.

The solvent in the above reduction reaction can be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvent (!\1 ,!\1 _ di 〇 2020/175539 9 卩(：171? 2020/007694

Methylformamide (01\/1), dimethylsulfoxide (01\/13〇), 1\1,

^ 9), etc.); ethers (diethyl ether (Snake 1: ₂ 〇), diisopropyl ether

Methyl ㊀ I ether (! Chomi IV snake), cyclopentyl methyl ether (〇 1 \ / 1 snake), tetrahydrofuran (Ding ^1-1), 1, 4-dioxane), aliphatic hydrocarbons (pentane, hexane, Heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); Halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, etc.) Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitryls (acetonitrile, propionitrile, ptyronitrile, etc.); and the like can be used. These solvents can be appropriately selected in consideration of the easiness of reaction and the like, and two or more kinds can be mixed and used. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent. The amount of solvent used (reaction concentration) is 0.1 to 100 times by mass, preferably 0.5 to 30 times by mass, and more preferably 1 to 10 times by mass that of the dinitro compound. Is.

[0037] The reaction temperature is in the range from _100 °O to the boiling point of the solvent used, preferably 50 to 150 °O. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

[0038] [Method for producing dinitro compound represented by formula (4-1) or formula (4-3)]

The method of synthesizing the compounds of formulas (4_1) and (4_3) is, for example, as shown in the following reaction formula, a compound represented by formula (5_1) or (5_2) and halonitrobenzene are combined with a base. By reacting in the presence of, (4-1-1) or (4-3-1) can be obtained.

[0039] 〇 2020/175539 10 ¥^1^2020/007694

[Chemical 13]

..

[0040] The above reaction is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, and phosphorus. Use of 1 to 4 equivalents of potassium acid, 1,8-diazabicyclo [5,4,0]-7-undecene, organic bases such as triethylamine, etc., with respect to (5-1) or (5-2) You can

[0041] As the reaction solvent, an aprotic polar organic solvent (mouth 1\/1, 01\/13○,

80, 1\/1?, etc.) is preferable. The amount of the solvent used (reaction concentration) is preferably 0.1 to 100 times by mass, more preferably 0.5 to 30 times by mass, relative to (5-1) or (5-2). ..

[0042] The reaction temperature is preferably in the range from _100 ^° to the boiling point of the solvent used, and more preferably from 0 to 150 ^° . The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

[0043] As another method for producing the above dinitro compound, (5 _ 1 _ 1) or (5

5-2- 1) Introducing a leaving group (!_◦) into the alcohol compound to give (5 _ 1 _ 18) or (5 — 2 — 1 3) and then the presence of a base. By reacting with a phenol compound or an amine compound below, the formula (4-1-2) or (4-3-2) can be obtained.

[0044] [Chemical 14]

The leaving group (!_◦) can be introduced by reacting with methanesulfonyl chloride, ethanesulfonyl chloride, toluene sulfonyl chloride or the like in the presence of a base such as triethylamine or pyridine. ..

The reaction of (5-1-1 3) or (5-2-1 3) with the phenol compound or amine compound is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate (5-1-1-13) or (5-2-1-3). ) To 1 to 4 equivalents can be used.

By reacting the compound represented by (5-1) or (5-2) with an acid chloride in the presence of a base such as triethylamine or pyridine, (4-1-2) or (4-1 4—3—3) can be obtained.

[0048] [Chemical 15]

[0049] [Production method of formula (4-2)]

The method for synthesizing the compound of formula (4-2) is not particularly limited. For example, as shown in the following reaction formula, by reacting a compound represented by the formula (5-1) with an acid chloride in the presence of a base such as triethylamine or pyridine (4-2- 〇 2020/175539 12 卩(: 171? 2020/007694

1) or (4-2-2) can be obtained.

[0050] [Chemical 16]

[0051] [Production Method of Formulas (5-1) and (5-2)]

There is no particular limitation on the method of synthesizing formula (5-1) and formula (5-2). For example, by reacting a cyano compound and an aminoethanol compound in the presence of a base, as shown in the following reaction formula with reference to the literature (“6. 6111. 2014, 79, 8668-8677)” (5— 1 — 1) or (5 — 2-1) can be obtained.

[0052] [Chemical 17]

[0053] The above reaction is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, inorganic compounds such as sodium phosphate and potassium phosphate, 1, 8— An organic base such as diazabicyclo[5,4,0]-7-undecene can be used in an amount of 1 to 4 equivalents based on the cyano compound. Of these, alkali metal carbonates such as sodium carbonate and potassium carbonate are preferable.

[0054] As the reaction solvent, an aprotic polar organic solvent (mouth 1\/1,

Eighty,

Etc.); ethers (Snake 1: ₂ 〇,

Tingmi 1\/1M, 09 1\/1M, Ding! ^~ 1, 1, 4,-dioxane, etc.); Aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, 〇 2020/175539 13 卩(: 171? 2020/007694

Toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.; Halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate) , Methyl propionate, etc.); dinitriles (acetonitrile, propionitrile, ptyronitrile, etc.); alcohols (methanol, ethanol, 2-propanol, etc.), etc. can be used. These solvents can be appropriately selected in consideration of the easiness of reaction and the like, and can be used alone or in combination of two or more. If necessary, the solvent can be dried using an appropriate dehydrating agent or desiccant and used as a non-aqueous solvent. Alcohols (methanol, ethanol, 2-propanol, etc.) are particularly preferable.

[0055] Potassium phthalimide was reacted with the following (5-1-1-13) or (5-2-1-3) to give (5-1-1 匕) or (5-2-1 匕) Then, by deprotecting with hydrazine hydrate, (5-1-2) or (5_2_2) can be obtained. Further, by reacting an excess amount of the secondary amine compound with (5 — 1 — 1 3) or (5 — 2 — 1 3), (5 — 1 — 3) or (5 — 2 — 3) can be obtained. Obtainable.

[0056] [Chemical 18]

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[0057] In the formulas in the production schemes up to this point,

\^/ ¹ , ² , ³ , the definition is the same as in the above formulas (2-1) to (2-3),

Is preferably a hydrogen atom, IV! ₆ groups, or M 1: group. 〇 is 1 ^to 1,

丫¹ represents 〇, 1\1 1 ^to 1 or [¾ ^{11 1} ,

The definition of is the same as in the case of the above formula (1), and a hydrogen atom, a group IV! _{6 and a} group I are preferable. Represents, 〇 1, 跳 “, I,

Represents the integer of

Represents the integer.

[0058] <Polymer>

The polymer () of the present invention has a structure represented by the above formula (1). Specific examples thereof include polyamic acid, polyamic acid ester, polyimide, polyurea, and polyamide. From the viewpoint of a liquid crystal aligning agent, at least one selected from a polyimide precursor containing a structural unit represented by the following formula (6) and a polyimide which is an imide thereof is more preferable. More preferably, it is a polyamic acid.

[0059] [Chemical 19]

In the above formula (6), X _! is a tetravalent organic group derived from the tetracarboxylic acid derivative, ₁ is a divalent organic group derived from the diamine containing the structure of the formula (1), and is a hydrogen atom. An atom or an alkyl group having 1 to 5 carbon atoms.

Is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of easy imidization by heating.

[0060] <Tetracarboxylic acid derivative>

X _I in the polyimide precursor of the above formula (6) is a tetravalent organic group derived from the tetracarboxylic acid derivative. Examples of the tetracarboxylic acid derivative include not only tetracarboxylic acid dianhydride but also its derivative: tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester, tet \\02020/175539 15 (: 2020/007694 dicarboxylic acid dialkyl ester dihalide). Among them, those represented by the following formula (7) are preferable.

[0061] [Chemical 20]

In the formula (7), X _! is the same as the definition of X _{! in} the formula (6), and its structure is not particularly limited. Preferred specific examples include the following formulas (X1_1) to (X1-44).

[0062] [Chemical 21]

[0063] [Chemical 22]

(1-15) (1-16) (1-17)

[0064] \¥02020/175539 16 卩(: 17 2020 /007694

[Chemical 23]

[0065] [Chemical 24]

[0066] [Chemical 25]

[0067] [Chemical 26]

[0068] In the formulas (1 to 1) to (XI-4), [¾ ₃ to [¾ ₂₃ are independently 〇 2020/175539 17 卩(：171? 2020/007694

, Hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 6 carbon atoms, monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom Or a phenyl group. From the viewpoint of liquid crystal alignment,

_{2 3} is a hydrogen atom, a halogen atom, preferably a methyl group or an ethyl group, a hydrogen atom, or a methyl group is preferable.

[0069] Specific examples of the formula (X1-1) include the following formulas (X1-1-1) to (X1-1-6). From the viewpoints of liquid crystal alignment and photosensitivity, (X 1 -1-1) is particularly preferable.

[0070] [Chemical 27]

[0071] The tetracarboxylic acid derivative used in the polymer () includes: solubility of the polymer in a solvent, coatability of a liquid crystal aligning agent, liquid crystal alignment when used as a liquid crystal alignment film, voltage holding ratio, accumulated charge Etc. are selected appropriately according to the required degree of properties, and one kind may be contained in the same polymer, or two or more kinds may be mixed, but a tetravalent compound containing an aromatic structure may be used. It is preferable to contain a carboxylic acid dianhydride component from the viewpoint of rapidly relaxing accumulated charges.

[0072] <Diamine>

In the above formula (6), as a specific example of the _first example, there may be mentioned a structure obtained by removing two amino groups from the diamine of the above formula (2-1), (2-2) or (2-3).

<Other structural units of polymer ()>

The polyimide precursor containing a structural unit represented by the formula (6) may contain a structural unit represented by the following formula (7) as long as the effect of the present invention is not impaired. \¥0 2020/175539 18 20201007694

good.

[0074] [Chemical 28]

In formula (7), ₂ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and ₂ is a divalent organic group derived from a diamine not containing the structure of formula (1),

Is the same as the definition of the above formula (6),

Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, 2

It is preferable that at least one of them is a hydrogen atom.

[0075] As specific examples of Example _2, the same structures as those exemplified for XI of the formula (6) can be mentioned including preferable examples. Further, the hindrance ₂ in the polyimide precursor is a divalent organic group derived from a diamine not containing the structure of the formula (1) (hereinafter also referred to as other diamine), and its structure is not particularly limited.

Other diamines used in the production of the polyimide precursor are represented by the following formula (8).

[0076] [Chemical 29] 丫21-⑻

Eight one eight _two

[0077] In the above formula (8),!

Are each independently a hydrogen atom and a carbon number of 1 to

And an alkyl group having 5 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms.

In addition, the _second factor is the solubility of the polymer in the solvent, the coating property of the liquid crystal alignment agent, and the liquid crystal alignment film. \\0 2020/175539 19 卩 (: 17 2020 /007694

In such a case, it may be appropriately selected according to the degree of required properties such as the orientation of the liquid crystal, the voltage holding ratio and the accumulated charge, and two or more kinds may be mixed in the same polymer.

A specific example of the _second item is as follows.

[0078] [Chemical 30]

(丫-13> (丫-14) (丫-15)

[0079] [Chemical 31]

(丫-27) (¥-28)

[0080] [Chemical 32]

[0081] [<b33]

[0082] [<b34]

[0083] [<b35]

[0084] [^36]

[0085] [b37]

[0086] [fb38]

[0087] [<b39]

[0088] u

[0089] Dfb41]

[0090] UW\

[0091] [1b43]

[0092] [1b44]

[0093] [1b45]

[0094] [fb46]

[0095] [-fb47]

[0096]

〇 2020/175539 25 卩 (：171? 2020 /007694

[Chemical 48]

(丫-167)

[0097] [Chemical 49]

<Polymer (Mimi)>

The polymer (Mi) contained in the liquid crystal aligning agent of the present invention means the following formulas (3), (4)

At least one polymer selected from a polyimide precursor which is a reaction product of a diamine component containing at least one diamine selected from the following) and a tetracarboxylic acid derivative component, and a polyimide which is an imidized product thereof. ..

[0099] 〇 2020/175539 26 2020/007694

[Chemical 50]

[01 00] In the formula (3) and (4), eight ₁ is a single bond, an ether bond, an ester bond, amino de bond, a thioether bond, thioester bond, alkylene down group of carbon number 2-2 0 (provided that the Any alkylene group

^1-1 ₂ -, an ether group, an ester group, may be substituted with cyclohexylene group, or a phenylene group. ), or a phenylene group. Eighty- _two is a halogen atom, a hydroxy group, or an alkyl group or an alkoxy group having 1 to 5 carbon atoms (however, any hydrogen atom of the alkyl group or the alkoxy group may be substituted with a halogen atom. ) Is. 3 is an integer from 0 to 4, and when 3 is 2 or more, 8 ₂ may be the same or different. Swallow and ◯ are each independently an integer of 1 to 2.

[01 01] (Diamine component for producing polymer (Mitsumi))

The diamine component for producing the polymer (Mitsumi) contains at least one diamine selected from the group consisting of diamines represented by the above formulas (3) to (4).

[01 02] In formula (3) to formula (4), eight! Is a single bond, an alkylene group having 1 to 8 carbon atoms (provided that at least one of ten 1 ^to the alkylene group 1 ₂ -. Is substituted with an ether group or an Es ether group), or a phenylene group , eight ₂ is 〇 1 ^to 1 _3, 3 is an integer of 〇_～ 1, spoon is 1, it is preferable 〇 is an integer from 1 to 2.

The following are mentioned as an example of the diamine represented by Formula (3)-Formula (4).

[0103] \¥0 2020/175539 27 卩 (: 17 2020 /007694

[Chemical 51]

[0104] [Chemical 52]

[0105] [Chemical 53]

[0106]

[fb54]

[0107]

[ib55]

[0108]

\\0 2020/175539 32 卩 (: 17 2020 /007694

[Chemical 56]

[0109] As the diamine component for producing the polymer (Mitsumi) contained in the liquid crystal aligning agent of the present invention, any diamine other than the diamines represented by the formulas (3) and (4) can be used. Can be used. Specific examples thereof include those excluding the diamines having the skeleton of the formula (1) and the diamines represented by the formulas (3) and (4) from the examples of the other diamines described above.

[0110] The diamine component for producing the polymer (Mi) of the present invention includes the solubility of the polymer (Mi) in a solvent, the coating property of the liquid crystal aligning agent, and the liquid crystal aligning property when used as a liquid crystal alignment film. Depending on characteristics such as voltage holding ratio and accumulated charge, one kind or a mixture of two or more kinds may be used.

As the tetracarboxylic acid derivative component for producing the polymer (Mitsumi) of the present invention, the same tetracarboxylic acid derivative as that used in the polymer (8) can be used. Among them, from the viewpoint of good mechanical strength of the film, \¥0 2020/175539 33 卩(: 17 2020 /007694

It is preferable to use tetracarboxylic dianhydride having a structure.

[01 12] [C57]

[01 13] <Liquid crystal aligning agent>

The liquid crystal aligning agent of the present invention contains the above-mentioned specific polymer, but may contain two or more kinds of the specific polymers having different structures. Further, in addition to the specific polymer, other polymer, that is, a polymer having no divalent group represented by the formula (1) may be contained. Examples of the polymer form are polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or its derivative, and poly(styrene-phenylmaleimide). Examples thereof include derivatives and poly(meth)acrylates. When the liquid crystal aligning agent of the present invention contains another polymer, the ratio of the specific polymer to all polymer components is preferably 5% by mass or more, and for example, 5 to 95% by mass.

[0114] The preferable abundance ratio (mass ratio) of the polymer () and the polymer (M) is 1:99-

9:9, and more preferably 1:9 9 to 50:50.

[0115] The liquid crystal aligning agent generally takes the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing the above polymer component and an organic solvent in which the polymer component is dissolved. At that time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed depending on the setting of the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film,

1 mass% or more is preferable, and from the viewpoint of storage stability of the solution, 10 mass% or less is preferable. A particularly preferable polymer concentration is 2 to 8% by mass. 〇 2020/175539 34 卩 (：171? 2020 /007694

[0116] The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved therein. Specific examples are 1\1, 1\1-dimethylformamide, 1\1, 1\1-dimethylacetamide, 1\1-methyl-2-pyrrolidone, -ethyl-2-pyrrolidone, Examples include dimethyl sulfoxide, arbutyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone and cyclopentanone. Of these, 1\!-methyl-2-pyrrolidone, 1\1-ethyl-2-pyrrolidone, or ^^-butyrolactone is preferably used.

[0117] Further, as the organic solvent contained in the liquid crystal aligning agent of the present invention, in addition to the above-mentioned solvent, a solvent that improves the coating property when applying the liquid crystal aligning agent and the surface smoothness of the coating film is used. You can also Specific examples of such organic solvents are given below.

[01 18] For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isoptyl alcohol, ㊀ "1:-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methylol. 1-butanol, isopentyl alcohol, ㊀

1: _ Pentyl alcohol, 3-methyl 2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl 1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol , 2-heptanol, 3-heptanol,

1-Octanol, 2-Octanol, 2-Ethyl 1-Hexanol, Cyclohexanol, 1-Methylcyclohexanol, 2-Methylcyclohexanol, 3-Methylcyclohexanol, 2,6-Dimethyl-4-heptanol, 1 ,2-Ethanediol, 1,2-Propanediol, 1,3-Propandiol, 1,2-Butanediol, 1,3-Butanediol, 1,

4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropylether, dipropylether, Dibutyl ether, Dihexyl ether, Dioxane, Ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, Ethylene glycol dibutyl ether

77, 4, 6 -77 7k- 2 -^7 ^° 777, 3 -xh 7 ^ykZ-tr 7-h ,1 -7 7^7 ^7-7-k 2 -x5 ^L ykT5 ^L yk5 77— k 2-X5 ¹ yu^dr^yuz-tr^- ki b7^ ^l J P-yki777-k If b7^ ^l J

-yk, 7x5 ¹ 777 ^l J -y 7°P 77775 P-yk, 7°P 77775 R— yify ^fyn- yk 1-(7 f7i hf7) 7°p Ay-yk, 7°P 77 775 -yk" E7757kX- yk:P7-k 7 ^' 7 °P 77775 -y 7 if 777' -yu^y ^yki-f^yl・, 7xf 777 u p-yk^y 7f yu x-fyk 7 ^' 7 °P 7777 ^" 5 R— yki 77 -^ykx— f^y 7^Ptf77^'J ^-y iyifyn- yk 7 ^' 7 °P 77775 I-yl77fyn- y K 57 °P 77775 p-yu^yy^yux -f^yl·, if 77^u p-yk^y 7f yux— yuz-fe^— k if 77^'j P— ybiyifyn- 5^7-7 — k ,if 77^'j P— yi ΐ y ^^yux— yu7i 7— h, if 777'U i-yl· ΐ777 — k x5^775 P— yk7:P7 — k 7xf 777 ^' 5 R— yk ΐ7 c5^c-5^77-h, 7xf 77^'j p-yk^7 y^ykx- yk 777— k 2- (2 -x hf7x hf7) x 5^77 — k 7xf 77 7 ^* 5 P— yk77 — k K 5 if 77^'JP— yk, h 5 if 777 ^' 5 P— yk ΐ77 ^ykx— yk, K 5 if 77^'jp— yk^yx ^kx— 7yk, ?LIt7 ^yk, fLlt'yk M y'yk, M c5^ M n -75^ Mt 7°p 7 777 ^” U p— yki 7 x^ykx— f^yk, ^77ϋ75^ 7yk 77^x5^ \¥0 2020/175539 36 卩 (: 17 2020 /007694

, Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate,

3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, lactate propyl ester, lactate butyl ester, isoamyl lactate Examples thereof include esters and solvents represented by the following formulas [0-1] to [l3].

[01 19] [Chemical 58]

[○ _ 1] 10 -2 ^~ \ [0-3] represents an alkyl group having 1 to 4 carbon atoms. )

[0120] Among them, the organic solvent is 1-hexanol, cyclohexanol, 1,2-ethane diol, 1,2-propanediol, propylene glycol monobutyl ether, propylene glycol benzyl ether, 4-hydroxy _. It is preferable to use 4-methyl-2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether. The type and content of such a solvent are appropriately selected according to the coating apparatus for the liquid crystal aligning agent, the coating conditions, the coating environment, and the like.

[0121] The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent. Examples of such additional components include an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealant, a cross-linking agent for increasing the strength of the liquid crystal alignment film, and a liquid crystal. Examples thereof include a dielectric material and a conductive material for adjusting the dielectric constant and electric resistance of the alignment film. Specific examples of these additional components are disclosed in paragraphs [0 1 0 4] to 60 0 pages [0 1 1 6] of page 203 of International Publication No. 20 15/0 6 0 3 5 7. Poor solvents and crosslinkable compounds.

[0122] As a compound for improving the adhesion between the liquid crystal alignment film and the substrate, a functional silane is used. 〇 2020/175539 37 卩 (：171? 2020 /007694

Examples of compounds containing compounds and compounds containing an epoxy group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane. Sidoxypropylmethyl ethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, -(2-aminoethyl)-1 3-aminopropyltrimethoxysilane, 1\1—(2-aminoethyl)-1 3-amino Propylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 1\1-ethoxycarbonyl-3-aminopropyltrimethoxysilane,

1\1—Ethoxycarbonyl-3-aminopropyltrietoxysilane, 1\1—Triethyloxysilylpropyltriethylenetriamine, 1\1_ Trimethoxysilylpropyltriethylenetriamine, 1 0—Trimethoxysilyl-1,4,

7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethyloxysilyl-3,6-diazanonyl acetate, 1 \1—Benzyl-3-aminopropyltrimethoxysilane, —Benzyl-3-aminopropyltrioxysilane, 1\1—Phenyl-3-aminopropyltrimethoxysilane, 1\1—Phenyl-3-aminopropyltrioxysilane, 1\1—Bis ( Oxy-Cetylene) 1-Aminopropyltrimethoxysilane, 1\1-bis(oxyethylene) 1-Aminopropyltriethoxysilane, Ethylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, Propylene Glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2— Dibromoneopentyl glycol diglycidyl ether, 1, 3, 5, 5 6-tetraglycidyl 2,4-hexanediol, 1\1, 1\1, 1\1, 1, 1\1, tetraglycidyl xylylenediamine, 1, 3—bis (!\1 ,!\1—diglycidyl amino acid 〇 2020/175539 38 卩 (：171? 2020 /007694

Chill) cyclohexane or 1\1, 1\1, 1\1, 1\1, tetraglycidyl 4,4'-diaminodiphenylmethane and the like.

[0123] Further, the liquid crystal aligning agent of the present invention may contain the following additives in order to increase the mechanical strength of the liquid crystal aligning film.

[0124] [Chemical 59]

[0125] The above-mentioned additive is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. If the amount is less than 0.1 part by mass, the effect cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal is deteriorated. Therefore, the amount is more preferably 0.5 to 20 parts by mass.

[0126] In addition to the above, the liquid crystal aligning agent of the present invention includes a polymer other than the specific polymer described in the present invention. 〇 2020/175539 39 卩(：171? 2020/007694

Coupling, dielectric for the purpose of changing the electrical properties such as dielectric constant and conductivity of the liquid crystal alignment film, silane coupling agent for improving the adhesion between the liquid crystal alignment film and the substrate, film when the liquid crystal alignment film is formed A crosslinking compound for the purpose of increasing the hardness and compactness of the film, and an imidization accelerator for the purpose of efficiently promoting imidization by heating the polyimide precursor when baking the coating film. Good.

[0127] <Liquid crystal alignment film>

The liquid crystal alignment film of the present invention is obtained from the liquid crystal alignment agent. To give an example of a method for obtaining a liquid crystal alignment film from a liquid crystal alignment agent, a liquid crystal alignment agent in the form of a coating liquid is applied to a substrate, dried and baked, and then a film obtained by rubbing treatment or optical alignment is applied. A method of performing orientation treatment by a treatment method can be mentioned.

[0128] The substrate to which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used. it can. At this time, it is preferable to use a substrate on which electrodes for driving the liquid crystal are formed in order to simplify the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used only for the substrate on one side, and in this case, a material that reflects light such as aluminum can also be used for the electrode.

[0129] The liquid crystal aligning agent is generally applied industrially by screen printing, offset printing, flexographic printing, ink jet method and the like. Other coating methods include a dip method, a mouth coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.

[0130] After applying the liquid crystal aligning agent on the substrate, the solvent is evaporated and baked by a heating means such as a hot plate, a heat circulation type oven, and a 8 (infrared) type oven. Any temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent. The drying step is not always necessary, but it is preferable to perform the drying step when the time from coating to baking is not constant for each substrate, or when baking is not performed immediately after coating. For this drying, it is sufficient that the solvent is removed to the extent that the shape of the coating film is not deformed due to the transportation of the substrate. 〇 2020/175539 40 卩(：171? 2020/007694

For, example, temperature 4 0 ^° 〇 ~ 1 5 0 ^° 〇, preferably 6 0 ^° 〇 ~ 1 0 0 ^° 〇 of hot plates, 0.5 minutes to 3 0 minutes, preferably 1 minute 5 Examples include a method of drying for minutes.

[0131] The baking temperature of the coating film formed by applying the liquid crystal aligning agent is, for example, 1

It is from 0 to 350°, preferably from 120 to 300°, and more preferably from 150° to 250°. The firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 90 minutes. The heating can be performed by a generally known method, for example, a hot plate, a hot air circulating furnace, an infrared furnace, or the like.

[0132] If the thickness of the liquid crystal alignment film after firing is too thin, it is preferable that the reliability of the liquid crystal display device is deteriorated.

[0133] In case of manufacturing 1-inch type, 3-inch type, 1-inch type, 3-inch type or 3-inch type liquid crystal display device

Then, a treatment for imparting a liquid crystal alignment ability to the coating film formed in the above step is carried out. The orientation ability imparting treatment is performed by rubbing the coating film in a certain direction by rubbing it with a mouth around which a cloth made of fibers such as nylon, rayon, and cotton is wrapped, and irradiating the coating film with polarized or unpolarized radiation. The photo-alignment treatment is performed.

[0134] In the photo-alignment treatment, the radiation applied to the coating film is, for example, 150 to 8

Ultraviolet and visible light containing light of wavelength 0 0 n can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized radiation, the irradiation direction shall be oblique.

[0135] Examples of light sources used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers,

A lamp or the like can be used. For ultraviolet rays in the preferred wavelength range, means for using a light source together with, for example, a filter, a diffraction grating, etc. 〇 2020/175539 41 卩 (：171? 2020 /007694

Can be obtained by The radiation dose is preferably 100 to 50,000 J/m2, more preferably 300 to 20,000 J/m2.

[0136] Further, the coating film may be irradiated with light while heating the coating film in order to increase the reactivity. The temperature during heating is usually 30 to 250 ^° C, preferably 40 to 200°C, and more preferably 50 to 150°C.

[0137] The photo-alignment treatment may be a heat treatment at the time of light irradiation, or a heat treatment after the photo-alignment treatment. The heating temperature at this time is preferably 80 to 300 ^° C, more preferably 120 to 250 ^° C. The heating time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Further, instead of the heat treatment, a cleaning treatment with an organic solvent or water may be performed, or the cleaning treatment and the heat treatment may be combined.

[0138] The liquid crystal alignment film after the rubbing treatment is further subjected to a treatment of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays, After forming a resist film on a part of the film, a rubbing process is performed in a direction different from the previous rubbing process, and then the resist film is removed to make the liquid crystal alignment film have different liquid crystal alignment ability in each region. May be. In this case, it is possible to improve the visual field characteristics of the obtained liquid crystal display element.

[0139] The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a horizontal electric field type liquid crystal display element such as a PPS type or a FFS (Fringe Field Switching) type.

[0140] <Liquid crystal display element>

The liquid crystal display device of the present invention is a device in which a liquid crystal cell is prepared by a known method after a substrate having a liquid crystal alignment film obtained from the above liquid crystal alignment agent is obtained. As a specific example of a liquid crystal display element that can be manufactured, two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal of the present invention provided between the substrate and the liquid crystal layer A liquid crystal display device comprising a liquid crystal cell having the above liquid crystal alignment film formed of an aligning agent. More specifically, the liquid crystal alignment agent of the present invention is applied onto two substrates and baked to form a liquid crystal alignment film, and the two substrates are arranged so that the liquid crystal alignment films face each other. , These two 〇 2020/175539 42 卩 (：171? 2020 /007694

A liquid crystal display element in which a liquid crystal layer composed of liquid crystal is sandwiched between substrates, that is, a liquid crystal layer is provided in contact with a liquid crystal alignment film.

[0141] As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Specifically, a transparent substrate is prepared, and then a liquid crystal alignment film is formed on each substrate under the conditions as described above. As described above, the substrate is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Examples of the material include the same materials as the substrates described for the liquid crystal alignment film.

[0142] — Provide a common electrode on one substrate and a segment electrode on the other substrate. These electrodes can be, for example, custom electrodes, and are patterned so that a desired image can be displayed. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. Insulating film, for example, be a film made of 3丨〇 ₂ _ Ding丨〇 ₂ formed by the sol-gel method.

[0143] In the case of manufacturing an I 3 type or 3 type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape and an electrode are provided. A liquid crystal aligning agent is applied to one surface of the counter substrate which is not applied, and then each applied surface is heated to form a coating film. As the metal film, for example, a film made of a metal such as chromium can be used.

[0144] Further, in a high-performance element such as a tabular element, an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.

[0145] In the case of a transmissive liquid crystal display element, the substrate as described above is generally used. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer is used. Can also be used. At that time, a material such as aluminum that reflects light can be used for the electrodes formed on the substrate.

[0146] On the other hand, the liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the horizontal alignment method such as 3 or 3 is the liquid crystal material conventionally used in the horizontal alignment method, for example, IV! 〇 1 2 0 3 or !\/1 1_ 〇 1 2 0 4 1 or other negative-positive type liquid crystal or !\/1 !_ 〇 〇 2020/175539 43 卩(：171? 2020/007694

-Negative type liquid crystal such as 660 can also be used.

[0147] As a method of sandwiching the liquid crystal layer between the two substrates, a known method can be mentioned. For example, prepare a pair of substrates on which the liquid crystal alignment film is formed, sprinkle spacers such as beads on the liquid crystal alignment film on one substrate, and place the surface on the side where the liquid crystal alignment film is formed on the inside. In this way, the other substrate is attached, and the liquid crystal is injected under reduced pressure to seal it. In addition, a pair of substrates on which a liquid crystal alignment film was formed was prepared, and spacers such as beads were sprinkled on the liquid crystal alignment film on one of the substrates, then liquid crystal was dropped, and then a liquid crystal alignment film was formed. A liquid crystal cell can also be produced by a method in which the other substrate is attached and sealed so that the side surface faces the inside. The thickness of the spacer is preferably 1 to 30 and more preferably 2 to 10.

[0148] After the above steps are completed, a polarizing plate is installed in the liquid crystal cell. In particular,

It is preferable to attach a pair of polarizing plates to the surfaces of the two substrates opposite to the liquid crystal layer.

[0149] The liquid crystal alignment film and liquid crystal display element of the present invention are not limited as long as the liquid crystal aligning agent of the present invention is used, and may be produced by other known methods. .. The process from obtaining the liquid crystal display device from the liquid crystal aligning agent is described, for example, in JP-A No. 20 1 5-1 3 5 3 9 3 page 17 [0 0 7 4] to page 19 [0 0 8 1 ] Is disclosed.

[0150] The liquid crystal display device of the present invention can be effectively applied to various devices, for example, a watch, a portable game machine, a word processor, a notebook computer, a power/navigation system, a camcorder, and Eight, it can be used for various display devices such as digital cameras, mobile phones, smart phones, various monitors, LCD TVs, and information displays.

Example

[0151] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The abbreviations of the compounds and the measuring methods for each property below are as follows. 〇 2020/175539 44 卩 (：171? 2020 /007694

(solvent)

1\/1?: 1\1-methyl-2-pyrrolidone

Arbutyrolactone

603: Petit Cerrosolve

(Diamine)

0-81 1: Phenylenediamine

0 Eight _2: 1, 2, 2-bis (4-aminophenoxy) ethane

0 8 _ 3: Refer to the following formula (0 8 _ 3)

0 8 1 4 :1\1- 6 1^ 1-Butoxycarbonyl- 1\1-(2-(4-aminophenyl)ethyl)_1\1_ (4-aminobenzyl)amine

〇81 1 5:4,4′-diaminodiphenylamine

0 8 _ 6: 1, 3,-bis (4-aminophenethyl) urea

0 81 0 1: Refer to the following formula (0 81 0 1)

0 8102: Refer to the following formula (081 02)

0 8103: See the following formula (081 03)

0 81 04: See the following formula (0 81 04)

(Acid dianhydride)

Chohachi _ 1 :1, 3,-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride

D. 8-1 :3,3,3,4,4,-biphenyltetracarboxylic dianhydride

[0152]

〇 2020/175539 45 2020/007694

[Chemical 60]

[0153] [Viscosity]

The viscosity of the solution was measured using an E-type viscometer TVE—22H (manufactured by Toki Sangyo Co., Ltd.), sample volume 11 mL, cone rotor TE—1 (1°34', R24), temperature 25°C. It was measured at.

[Preparation of liquid crystal cell]

A liquid crystal cell having a configuration of a fringe field switching (FFS) mode liquid crystal display element is manufactured.

[0155] First, a substrate with electrodes was prepared. The substrate is a glass substrate with a size of 30 mm x 35 mm and a thickness of 0.7 mm. On the substrate, the first layer is the TO electrode with a solid pattern that forms the counter electrode. As the second layer, a SiN (silicon nitride) film formed by the CVD method is formed on the counter electrode of the first layer. The second S i N film has a film thickness of 50 nm and functions as an interlayer insulating film. On the second layer S i N film, 〇 2020/175539 46 卩(：171? 2020/007694

As the third layer, a comb-teeth-shaped pixel electrode formed by patterning an I-layer film is arranged to form two pixels, a first pixel and a second pixel. The size of each pixel is

Sideways

Is. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the 3rd layer of the second layer.

[0156] The pixel electrode of the third layer has a comb-tooth shape formed by arranging a plurality of "dogleg"-shaped electrode elements in which the central portion is bent at an inner angle of 160°. The width of each electrode element in the lateral direction is 3, and the distance between the electrode elements is 6. Since the pixel electrode that forms each pixel is composed of multiple arrayed electrode elements in the shape of a "dogleg" with a bent central portion, the shape of each pixel is not rectangular but is similar to that of the electrode element. It has a shape that resembles a bold "dogleg" that bends in the center. Then, each pixel is divided into upper and lower parts with a central bent portion as a boundary, and has a first region on the upper side and a second region on the lower side of the bent portion.

[0157] Next, the liquid crystal aligning agent was filtered through a 1.0 filter, and then the prepared substrate with electrodes and the back surface were prepared. It was applied by spin coating to a glass substrate having. After drying for 2 minutes on a hot plate of 80 ^° 〇, it is baked for 30 minutes with a hot air circulation type oven of 230 ° 〇 to obtain a film thickness of 100 〇.

Was formed. This coating film surface was irradiated with linearly polarized UV light having a wavelength of 254 _n with an extinction ratio of 10:1 or more through a polarizing plate.

The liquid crystal alignment film formed on the first glass substrate was subjected to the alignment treatment so that the direction that evenly divides the interior angle of the bent portion of the pixel and the alignment direction of the liquid crystal were orthogonal to each other, and the liquid crystal alignment film formed on the second glass substrate was aligned. The film is oriented so that the alignment direction of the liquid crystal on the first substrate and the alignment direction of the liquid crystal on the second substrate coincide with each other when the liquid crystal cell is manufactured. This substrate was further baked for 30 minutes in a hot air circulation type oven at 230 ^° to obtain a substrate with a liquid crystal alignment film. Set the above two substrates as a set, print the sealant on the substrate, and bond the other substrate so that the liquid crystal alignment film faces face each other and the alignment direction is 〇 ^° , then apply the sealant. An empty cell was prepared by curing. 〇 2020/175539 47 卩(：171? 2020/007694

Liquid crystal 1\/1 1_(3-3 0 1 9 (manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and the inlet was sealed to obtain a 3-driving liquid crystal cell. The obtained liquid crystal cell was heated at 110 ^° 〇 for 1 hour, left for a while and used for each evaluation.

[0158] [Afterimage evaluation by long-term AC drive]

Using the above liquid crystal cell, an AC voltage of ±5 V was applied for 120 hours at a frequency of 60 1 ^to 1 under a constant temperature environment of 600°. Thereafter, the pixel electrode of the liquid crystal cell and the counter electrode were brought into a state of being short-circuited and left at room temperature for one day.

[0159] After leaving it for a while, the liquid crystal cell was placed between two polarizing plates arranged so that the polarization axes thereof were orthogonal to each other, and the backlight was turned on with no voltage applied. The arrangement angle of the liquid crystal cell was adjusted to be the smallest. Then, the rotation angle when the liquid crystal cell was rotated from the angle where the second region of the first pixel was darkest to the angle where the first region was darkest was calculated as an angle Δ. Similarly, for the second pixel, the same angle Δ was calculated by comparing the second area and the first area. When the calculated value of the angle Δ was 0.3 degrees or less, it was evaluated as “good”, and when it exceeded 0.3 degrees, it was evaluated as “poor”.

[0160] [Rubbing resistance evaluation]

A liquid crystal aligning agent was applied to the prepared substrate by spin coating, dried on a hot plate at 80 ° for 2 minutes, and then heated with a hot air circulation oven at 230. Firing was performed for 0 minutes to form a coating film having a film thickness of 100 nm. This coating film surface was irradiated with linearly polarized UV light having a wavelength of 254 4 n with an extinction ratio of 10:1 or more through a polarizing plate. This substrate was further baked in a hot air circulation type oven at 230 ^{° for} 30 minutes to obtain a substrate with a liquid crystal alignment film. This liquid crystal alignment film was rubbed with rayon cloth (rotor rotation speed: 1 0 0 0 "01, stage moving speed: 2 0 01 111/3 60, pushing length: 0. 4 01 01). Observation was performed with a microscope. When no streak was observed on the film surface due to rubbing, it was evaluated as “good”, and when streak was observed, it was evaluated as “poor”.

[0161] Compound Kuchihachi__ 1

8_04 is a new compound and was synthesized as follows. 〇 2020/175539 48 products (:171? 2020/007694) The products of Synthesis Examples 1 to 4 of the following monomers were identified by 11 ^to 1_1\/|[¾ analysis. The analysis conditions are as follows.

Measuring solvent: dimethyl sulfoxide (mouth 1\/13〇) _〇16

Reference substance: Tetramethylsilane (Ding IV! 3) (50.0 0.01 ¹ 〇 “ ¹

[0162] «Synthesis Example 1: Synthesis of 0-8_01 1»

[0163] [Chemical 61]

[0164] <Synthesis of Compound [1]>

Methanol (3209), -Nitrobenzonitrile (40.09, 27 0 0 1 0 10 丨), 2-Amino-2-methyl-1, 3 -propanediol (1 4 2. 3 ₉ ), Sodium carbonate (28 . were charged 6 ₉₎ in a flask and allowed to react for 22 hours at nitrogen atmosphere under reflux conditions. After completion of the reaction, the reaction solution to precipitate crystals was poured into pure water (960 _9), filtered, and conducted washed with methanol. Subsequently, the resulting crude product with ethyl acetate (2609) hexane (40 ₉₎ performs a slurry washed with mixed-solvent, filtration, compound by drying [1] as white crystals (Yield: 46 . 89, yield: 73%).

36— 3.47 ○ 1 (111, 2 l·\), 1.25 ○ 1 (3, 31-1)

[0165] <Synthesis of Compound [2]> 〇 2020/175539 49 卩 (：171? 2020 /007694

1\]-Methyl-2-pyrrolidone (3809), Compound [1] (44. 7 ₉ ,

4-Fluoronitrobenzene (45. 9) and sodium hydroxide (1 2. 6 ₉ ) were charged into a flask and reacted at room temperature for about 5 days. After the reaction was completed, the reaction solution was poured into pure water (1 1 249) to precipitate crystals, and the crystals were filtered to recover crude crystals. Subsequently, carried out at room temperature slurry washed with methanol (1 79 _9), a slurry wash was performed followed by ethyl acetate (5609). The compound [2] was obtained as pale yellow crystals by washing the slurry, filtering and drying (yield: 5 1.49, yield: 76%).

2 ○ 1 (111, 2 l·\), 8. 1 5 — 8. 1 9 ○ 1 (111, 2 l·\), 8.

09— 8. 1 2 ○ 1 (111, 2 l·\), 7. 1 3 — 7. 1 8 ○ 1 (111, 2)

1-1), 4.56 〇 1 (〇 1,) = 8.8 1-1 å, 11-1), 4. 27 〇 1

(¢1, "= 8. 41-1 å, 11-1), 4.26 〇 1 (○ 1," = 9.6 61-1 å,

1 1-1), 4. 2 1 ○ 1 (○ 1,) = 1 ○ 0.01-1 å, 11-1) 1. 25 ○ 1

(3, 31 ^~ 1)

[0166] <Synthesis of 0_8_1>

Tetrahydrofuran (3979) and methanol (99 _9), the compound [2] (49.7 _9, 1 39_Rei_1_rei_1_rei 1), 5% palladium-carbon (50% water humid product) (3.46 ₉₎ Was charged into a flask and reacted under a hydrogen atmosphere room temperature condition for 24 hours. After the reaction was completed, 5% palladium-carbon was removed by filtration, and the internal mass was adjusted to 73.49 by concentration under reduced pressure. Then, 2-propanol (2509) was added and dissolved by heating at 50° 〇, crystals were precipitated under ice-cooling conditions, filtered, and dried to obtain mouth 8101 as white crystals (yield: 30.

29, yield: 73%).

○ 1 (111, 21-1), 6. 62— 6. 66 ○ 1 (111, 21-1), 6.5

3 — 6. 56 ○ 1 (01, 21-1), 6. 45 — 6. 49 ○ 1 (○ 1, 21-1 ), 5. A, 21-1), 4. 6 1 ○ 1 (3 , 2 l·\) ,4 \¥02020/175539 50 卩(: 17 2020 /007694

3 1 〇 1 (〇 1, )=8.4 1-1-1, 1 1-1 ), 4.00 〇 1 (〇 1, )=8

.401·^, 1 1 ^~ 1), 3. 74-3. 79 ○ 1 (○ 1, 21 ^~ 1), 1. 3

0 〇 1, 31-1)

[0167] «Synthesis Example 2: Synthesis of 0-8_02»

[0168] [Chemical 62]

[0169] <Synthesis of Compound [3]>

Methanol (2409), _ nitrobenzonitrile (30.09, 20 3_Rei_1111_rei丨), 2-amino-1, 3-propanediol (55.6), the flask及beauty sodium carbonate (2 1.6 ₉₎ The solution was charged into a flask and allowed to react for 23 hours under a nitrogen atmosphere reflux condition. After the reaction was completed, the reaction solution was poured into pure water (7209) to precipitate crystals, which was filtered and washed with methanol. Subsequently, the slurry and the resulting et crude product with ethyl acetate (1 50 ₉₎ hexane (30 ₉₎ mixed solvent - was washed, filtered to obtain the compound [3] as a pale yellow crystals followed by drying ( Yield = 30.99, Yield: 69%).

, 4. 33 — 4. 4 1 ○ 1 (01, 2 l·\), 3. 36 — 3. 64 ○ 1 (○ 1, 21 ^~ 1)

[0170] <Synthesis of Compound [4]>

1 \ 1 - methyl-2 - pyrrolidone (1 38 _9), Compound [3] (27.8 _9,

4 - fluoronitrobenzene (28.8) were charged hydroxide of sodium (7.6 ₉₎ in a flask and allowed to reaction for about 4 days at room temperature conditions. After the reaction was completed, ethyl acetate (5049) and pure water (2249) were added to the reaction solution, whereby crystals were precipitated. Crystals are collected by filtration, 〇 2020/175539 51 卩(：171? 2020/007694

The obtained crystals were washed at room temperature with a mixed solvent of methanol (1 409) and pure water (1 409). After the slurry was washed, the compound [4] was obtained as pale yellow crystals by filtering, washing with methanol, and drying (yield = 3 1.39, yield: 72%).

〇 1 (111, 21-1) 8. 1 7 — 8. 2 1 〇 1 (111, 21-1 ), 8. 1 1 —

8.1 4 ○ 1 (111, 21-1 ), 7. 1 5— 7. 1 9 ○ 1 (111, 21-1 ), 4 .76 — 4. 83 ○ 1 (01, 1 1-1) , 4. 66 — 4. 70 ○ 1 (○ 1, 1 1-1 ), 4. 42 — 4. 46 ○ 1 (, 1 1-1 ), 4. 32 — 4. 38 ○ 1 (01, 1 1-1)

[0171] <Synthesis of 0__2>

Tetrahydrofuran (2 1 79) and methanol (62. 69 ), compound [4] (3 1. 3 ₉ , 9 1.

And 5% palladium-carbon (approx.

They were charged 50% water wet product) and (2.34 ₉₎ in a flask and allowed to react for 4 days in a hydrogen atmosphere 40 ° 〇 conditions. After completion of the reaction, 5% palladium-carbon was removed by filtration, and the solvent was removed by concentration under reduced pressure to obtain a crude product. Subsequently, carried out at room temperature slurry washed with methanol (2439), filtered to give the mouth eight _〇_2 as pale pink crystals by drying (Yield: 1 7.5 _9, yield: 68%).

〇 1 (111, 21-1 ), 6. 64 — 6. 68 〇 1 (111, 21-1 ), 6. 54 —

6.57 〇 1 (111, 21-1 ), 6. 47 — 6. 5 1 〇 1 (111, 21-1 ), 5 .73 〇 1, 21-1 ), 4. 62 〇 1, 21- 1 ), 4. 4 1 — 4.47 〇 1 (111, 21-1 ), 4. 1 5 — 4. 1 8 〇 1 (111, 1 1-1 ), 3.9

[0172] «Synthesis Example 3: Synthesis of 0-8_3»

[0173] [Chemical 63]

[0174] <Synthesis of Compound [5]>

Methanol (4009), terephthalonitrile (5_Rei. 2 _9, 392_Rei_1_rei_1 〇 I), 2-amino-2-methyl-1, 3-propanediol (1 659),及Beauty sodium carbonate (83.9 ₉ ) Was charged in a flask and reacted under a nitrogen atmosphere reflux condition for 20 hours. After the reaction was completed, the reaction solution was poured into pure water (1 2009) to precipitate crystals, and a crude product was collected by filtration. The resulting crude product purified water (3009 X6 times), then give methanol (2009 X2 times) compound by washing the [5] as white crystals (crude yield: 1 09.6 _9, crude yield: 1 0 〇%) 〇

), 3.36— 3.44 ○ 1 (, 41-1), 1. 23 ○ 1, 61-1) [0175] <Synthesis of compound [6]>

1\1-methyl-2-pyrrolidone (3279), compound [5] (40. 89,

And viewed charged potassium hydroxide (2 1. 29) into the flask, a nitrogen atmosphere cooled conditions 1 \ 1_-methyl-2-pyrrolidone (1 9.9 ₉₎ was dissolve 4-fluoronitrobenzene (45. 7 ₉₎ was added dropwise. After completion of dropping, the mixture was washed with applying port one Bok 1 \ 1-methyl-2-pyrrolidone (2 1.4 _9), was reacted for 2 hours at Atsushi Muro conditions. After the reaction was completed, the reaction solution 〇 2020/175539 53 卩 (：171? 2020 /007694

Was poured to precipitate crystals, and filtration, washing with pure water and washing with methanol were carried out. Subsequently, the obtained crude crystals were slurry washed with methanol (3009) at room temperature. Subsequently, the crude crystals were dissolved in chloroform (10099) by heating, methanol (466 ₉ ) was added to precipitate the crystals, and the crystals were filtered and dried to obtain compound [6] as pale yellow crystals (yield. : 63.29, yield: 79%).

〇 1 (111, 41-1 ), 7. 95 〇 1 (3, 41-1 ), 7. 1 3 — 7. 1 6 〇 1 (111, 41-1 ), 4.52 〇 1 (〇 1 ,) = 8. 41-1 å, 21-1 ), 4. 1 9— 4. 22 ○ 1 (01, 61-1 ), 1. 42 ○ 1, 61-1)

[0176] <Synthesis of Kuchihachi_03>

Tetrahydrofuran (5099), Methanol (62.3), Compound [

% Water wet product) (3.669) was charged into a flask and reacted for 4 days under a hydrogen atmosphere of 40 ^° ◦. After the reaction was completed, 5% palladium-carbon was removed by filtration. Subsequently, the filter cake was washed with an excess amount of 1\1, 1\1-dimethylformamide. The obtained filtrate was concentrated under reduced pressure, methanol (6609) was added to precipitate crystals, and the crystals were filtered to obtain __8_3 as light pink crystals (yield: 2 0.99, yield: 38%).

01 (01, 41-1 ), 4.61 〇 1, 41-1 ), 4.47 〇 1 (¢1,)

= 8. 41-1 å, 21-1 ), 4.1 6 〇 1 (〇 1, )= 8.4 1-1 å ,21-1 ),

3.87 〇 1 (¢1, )=9.21-1 å ,21-1 ), 3.60 〇 1 (〇 1, ,) = 9.2 Hz, 21 ^~ 1), 1.36 〇 1 , 61 ^~ 1)

[0177] «Synthesis Example 4: Synthesis of 0-8__4»

[0178] 〇 2020/175539 54 卩 (: 171-1? 2020 /007694

[Chemical 64]

<Synthesis of Compound [7]>

1 \ 1 - methyl-2 - pyrrolidone (4009), compound [5] (40.0 _9,

And triethylamine (38.0) to narrow specifications into the flask, in a nitrogen atmosphere cooled conditions of 4-nitro downy Nzoirukurori de (60.7 ₉₎ was divided into four charged. Stirring failure occurred after charging, so 1\1_methyl-2-pyrrolidone (1609) was added to secure stirring property, and the reaction was carried out at room temperature for about 15 hours. After completion of the reaction, the reaction solution was poured into pure water (15009) to precipitate crystals, followed by filtration, washing with pure water and methanol. Subsequently, the obtained crude product was dissolved in tetrahydrofuran (5609) by heating at 50 ^° and methanol (4009) was added to precipitate crystals. The obtained crystals were washed with slurry of tetrahydrofuran (1609), filtered, and dried to obtain Compound [7] as white crystals (yield = 47.49, yield: 55%).

丨门 01\/13 ○ 1 ：8・24-8. 30 ○ 1 (111, 41-1) ,8 06 ― 8. 1 1 ○ 1 (111, 41-1) ,7 93 93 ○ 1, 41-1), 4.58— 4.60 ○ 1 (, 21-1), 4.35— 4.43 ○ 1 (111, 41-1), 4. 1 9— 4. 22 ○ 1 (111 , 21-1), 1.43 ○ 1, 61-1)

[0180] <Synthesis of Kuchihachi_04>

Tetrahydrofuran (4539), methanol (95.6),! \1, !\1— 〇 2020/175539 55 卩 (：171? 2020 /007694

Dimethylformamidine de (4009), compound [7] (47.4 _9, 78.6 〇丨) and 5% palladium-carbon (50% water wet product) (2.90 ₉₎ was charged into a flask, The reaction was carried out in a hydrogen atmosphere at room temperature for about 3 days. The internal mass was set to 1 309 by removing 5% palladium-carbon by filtration and concentrating under reduced pressure. The resulting homogeneous solution was added methanol (3909) to precipitate crystals, filtered to give the mouth eight _〇 4 as white crystals by drying (Yield: 1 7.3 _9, yield: 4 1% ).

丨门01\/13○１: 7.96○1, 41 ^~ 1), 7.52- 7.55○1(○1, 41 ^~ 1), 6.46-6.50○!(01, 41-1), 5.96 〇 1, 41-1), 4. 48 〇 1 (〇 1,) = 8. 81·^, 21 ^~ 1), 4. 1 6-4. 22 〇 1 (〇 1, 61 ^~ 1) ,1.39 ○ 1, 1 ^~ 1)

[0181] <Synthesis example 1 of 88>

2 with stirrer and nitrogen inlet

On four flasks,

1 to 1.089 (1 0.01 111111 0 1), mouth 81 2 to 3.66 (1 5. 〇^^〇I), 0 81 3 to 4.81 9 (1 5.00 1) 〇 101 )and 0 81 1 were weighed out at 3.4 1 9 (15.0 〇 1), 1\/1? was added at 1 32.09, and dissolved by stirring while sending nitrogen. .. While stirring this diamine solution, add 10.54 ₉ (47. 〇 〇 丨) of Chohachi _ 1 and further add IV! so that the solid content concentration is 12% by mass, and add 40° 〇. After stirring for 20 hours, a polyamic acid solution (881-1) was obtained.

[0182] Temperature of this polyamic acid solution

Was 3. This polyamic acid solution (8881 1) 60.09,

The mixture was placed in an Erlenmeyer flask (1), 1\/1? was added in an amount of 20.09, acetic anhydride (4.569) and pyridine (1.189) were added, and the mixture was allowed to react at 55° for 3 hours. The reaction solution was poured into methanol 3009, and the generated precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 80 ^° to obtain a polyimide powder. The imidation ratio of this polyimide was 66%. The obtained polyimide powder 〇 2020/175539 56 卩(：171? 2020/007694

? End 3.1 to 6 ₉ \ / 1 1 3.2 _9, 〇 snake 1_ 1 3. polyimide solution (3 1 by dissolving 70 ° 〇 at and stirred for 20 hours by addition of 2 ₉ - 1 ) Got

[0183] <Synthesis example 2 of 88>

50 with stirrer and nitrogen inlet

On four flasks

5 to 1.59 4 ₉ (8.00 1 0 1 0 1), 0 8 _ 0 1 to 0 .5959 (2.0

〇 〇 丨) Weighed out and added 1\/1? 33.19 and dissolved by stirring while sending nitrogen. While stirring this diamine solution, add 2 824 ₉ (9.60 I) of Choho 12 and add 1\/1? so that the solid content concentration is 12% by mass. The mixture was stirred at 0° for 20 hours to obtain a polyamic acid solution (8881 2).

The viscosity of this polyamic acid solution at a temperature of 25 ^° was 363 ^{° 1} 3-3.

[0184] <Synthesis example 8 of 88>

50 with stirrer and nitrogen inlet

On four flasks

5 to 1.59 4 ₉ (8.00 0 1 0 1 0 1), 0 8 _ 0 3 to 0 9739 (2.0

〇 〇 丨) Weighed out, added 35.49 of 1\/1?, and dissolved by stirring while sending nitrogen. While stirring this diamine solution, add 2 824 ₉ (9.60 I) of Choho 12 and add 1\/1? so that the solid content concentration is 12% by mass. The mixture was stirred at 0° for 20 hours to obtain a polyamic acid solution (8,813).

The viscosity of this polyamic acid solution at a temperature of 25 ^° was 348.0 1 3-3.

[0185] <Synthesis example 4 of 88>

50 with stirrer and nitrogen inlet

On four flasks

5 to 1.59 4 ₉ (8.00 1 0 1 0 1), 0 8 _ 0 4 to 1.0859 (2.0

〇 〇 丨) Weighed out, added 35.99 of 1\/1?, and dissolved by stirring while sending nitrogen. While stirring this diamine solution, add 2.75 1 ₉ (9.35 〇 I) of Choho 12 and further adjust the solid concentration to 12% by mass. 〇 2020/175539 57 卩(:171? 2020/007694 1\/1? was added and stirred at 40° 〇 for 20 hours to obtain a polyamic acid solution (8881-4).

The temperature of this polyamic acid solution

Was 3.

[0186] <Synthesis example 8 of 88>

3. 99 (20. 〇 111111 〇 1) and mouth _ _6 in a 100 x 4 flask equipped with a stirrer and a nitrogen inlet tube. .49 (5.0 ○ 1111 ○ I) Weighed out, 1\/1? was added in 78.09, and dissolved by stirring while feeding nitrogen. While stirring the diamine solution, add D. 8-12 to 6.77 ₉ (23.

0)), IV! was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at 70° 〇 for 20 hours to obtain a polyamic acid solution (8,815).

The temperature of this polyamic acid solution

Was 3.

[0187] <Example 1>

12% by mass of polyimide solution (3 _ 1) 1.889 obtained in Synthesis Example 5 and 12% by mass of polyamic acid solution (88812) obtained in Synthesis Example 6 4.389 Take the 30 I Erlenmeyer flask, 1\/1? 2.08 ₉ , 〇mi 1_3.6

7 _9, the 6033.009 added and stirred for 2 hours at 25 ° 〇 obtain liquid crystal alignment agent (eight 1). No abnormalities such as turbidity or precipitation were observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.

[0188] <Examples 2 and 3>

The procedure of Example 1 was repeated except that the polyamic acid solution (8_8_3) and (PAA-4) were used in place of the polyamic acid solution (8_8_2). Eight two), (eight three) were obtained.

[0189] <Comparative example 1>

12% by mass of polyimide solution obtained in Synthesis Example 5 (3 _ 1) 1. 889 and 12% by mass of polyamic acid solution obtained in Synthesis Example 8 (881-5) 4 〇 2020/175539 58 卩 (：171? 2020 /007694

.

Transfer to an Erlenmeyer flask and add 1\/1? 2. 08 ₉ , 〇mi 1_3.66 7 ₉ and 6033.009, and stir at 25 ° 〇 for 2 hours to obtain a liquid crystal aligning agent (Mimi 1). It was No abnormalities such as turbidity or precipitation were observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.

[0190] [Table 1]

[0191] <Example 4>

After filtering the liquid crystal aligning agent (8 1) obtained in Example 1 with a 1.0 filter, the prepared electrode-attached substrate and a column having a height of 4 on which the I film was formed on the back surface were prepared. A glass substrate having a spacer was applied by spin coating. After drying for 2 minutes on a hot plate of 80 ° 〇, baking was performed for 30 minutes in a hot air circulation type oven of 230 ° 〇 to form a coating film with a film thickness of 100 nm. This coating film surface was irradiated with 0.33"/○ ² of linearly polarized ultraviolet light of wavelength 254 n with an extinction ratio of 26:1 through a polarizing plate. This substrate was baked for 30 minutes in a hot air circulation type oven at 230 °C to obtain a substrate with a liquid crystal alignment film.

The above two substrates obtained above were made into a set, one substrate was coated with a sealant, and the other substrate was laminated so that the liquid crystal alignment film surfaces face each other and the alignment direction was 0 ^° . After that, the sealing agent was cured to prepare an empty cell. By the vacuum injection method in this empty cell,

9 (manufactured by Merck) was injected, and the injection port was sealed to obtain a 3-driving liquid crystal cell.

[0192] [Afterimage evaluation by long-term AC drive]

The liquid crystal cell as described above under 60 ° 〇 constant temperature environment and an AC voltage of ± 5 V with a frequency 601 ^~ 1 Å is applied 1 20 hour. 1 After applying the AC voltage for 20 hours, leave the pixel electrode of the liquid crystal cell and the counter electrode in a short state, and let them stand at room temperature for one day. 〇 2020/175539 59 卩(: 171? 2020/007694

I put it. Then, when the angle Δ in this liquid crystal cell was measured, the value of the angle Δ was 0.08 degrees.

[0193] [Rubbing resistance evaluation]

I 〇 〇 Apply the liquid crystal aligning agent to the substrate by spin coating, dry on a hot plate at 80° 〇 for 2 minutes, and then use a hot air circulation type oven at 230° 〇 for 30 minutes. Firing was performed to form a coating film having a film thickness of 100,000. This coating film surface was irradiated with 0.33"/○ ² of ultraviolet rays having a wavelength of 2 54 4 _n linearly polarized with an extinction ratio of 26: 1 through a polarizing plate. This substrate was baked for 30 minutes in a hot air circulation type oven at 230° to obtain a substrate with a liquid crystal alignment film. The obtained liquid crystal alignment film was evaluated for rubbing resistance according to the above evaluation method. As a result, no rubbing streaks were observed on the film surface, and the rubbing resistance was good.

[0194] <Examples 5 to 6, Comparative Example 2>

Except for using the liquid crystal aligning agents shown in Table 1 instead of the liquid crystal aligning agents (81), the afterimage evaluation and the rubbing resistance evaluation by the long-term AC drive were performed in the same manner as in Example 4. did. Table 2 shows the evaluation results of the afterimage and rubbing resistance by long-term AC drive in each case.

[0195] [Table 2]

Industrial availability

[0196] By using the liquid crystal aligning agent of the present invention,

In a liquid crystal display element of a driving system, a liquid crystal alignment film in which afterimage caused by AC driving is suppressed and which has high mechanical strength can be obtained. Therefore, it can be expected to be used in liquid crystal display devices that require high display quality.

Claims

\¥0 2020/175539 60 60 (: 17 2020 /007694

The scope of the claims

[Claim 1] A liquid crystal aligning agent containing the following polymers () and (M).

Polymer (8): selected from a polyimide precursor which is a reaction product of a diamine component containing a diamine having a skeleton represented by the following formula (1) and a tetracarboxylic acid derivative component and a polyimide which is an imide thereof. At least one polymer.

[Chemical 1]

You

Polymer (M): Polyimide precursor and its imide that are the reaction products of a diamine component containing at least one diamine selected from the following formulas (3) and (4) and a tetracarboxylic acid derivative component. At least one polymer selected from certain polyimides.

[Chemical 2]

In formulas (3) and (4), ₁ is a single bond, an ether bond, an ester bond, an amide bond, a thioether bond, a thioester bond, an alkylene group having 2 to 20 carbon atoms (provided that any alkylene group

Is an ether group, an ester group, a cyclohexylene group, or a phenylene group. 〇 2020/175539 61 卩(：171? 2020/007694

It may be replaced. ), or a phenylene group. 8 ₂ is a halogen atom, a hydroxy group, or an alkyl group or an alkoxy group having 1 to 5 carbon atoms (provided that any hydrogen atom of the alkyl group or alkoxy group may be substituted with a halogen atom). It is. 3 is an integer of 〇_～ 4, the case of 3 is equal to or greater than 2, eight ₂ may be the same or different. Swallow and ◯ are each independently an integer of 1 to 2.

[Claim 2] The liquid crystal aligning agent according to claim 1, wherein the polymer (8) is a polyamic acid.

[Claim 3] The liquid crystal aligning agent according to claim 1 or 2, wherein the mass ratio of the polymer (8) and the polymer (M) is 95:5 to 50:50.

[Claim 4] The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the tetracarboxylic acid derivative component of the polymer () contains an aromatic tetracarboxylic acid dianhydride.

[Claim 5] The diamine having a skeleton represented by the formula (1) is represented by the following formulas (2 — 1) to (2—

The liquid crystal aligning agent according to any one of claims 1 to 4, which is at least one selected from 3).

[Chemical 3]

Formula (2 _ 1) ~ Formula (2 _ 3)

Represents hydrogen or a monovalent organic group, 8 ² is a single bond, ^_ 〇 ^{_, _} thousand ^{_{one, 000 s (0 1 ~ 1}} 2) | -, - 0 ( Rei_1 ^~ 1 ₂₎ 〇 1, 100 [¾ ^{11 1-} ,

〇 consisting of one and one or a combination thereof

, A structure selected from the group (3 _ 1), \\02020/175539 62 卩(: 17 2020/007694 2 is a structure selected from the following group (3_2), ³ is a structure selected from the following group (3_3), ⁴ is a structure selected from the following group (3_4) Represents, where

Or, it represents a monovalent organic group, 丨 is an integer of 1 to 12, and 3 is an integer of 0 or 1.

[Chemical 4]

In the above group (3-1), Yi! Represents the site that binds to the amino group in formulas (2-1) to (2-3), and * ₂ represents the site that binds to the oxazoline ring. 〇 2020/175539 63 卩 (：171? 2020 /007694

You Group (3-2) Middle, Yi! Represents a site that binds to an amino group in (2-3) from equation (2 1), representing the binding site for the氺₃ ^2. Group (3 _ 3)

Represents the site of binding to. In group (3-4), ₂ represents a site that binds to the oxazoline ring. X represents a substituent, hydrogen atom; halogen atom; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; halogenated alkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; dimethyl substituted amino group such as an amino group; main butoxy group, an alkoxy group of from 1 to 6 carbon atoms such as ethoxy alkoxy group; 1 \ 11 ^~ 1_Rei_rei_rei_1 ^~ 1 ₃ and 1 \ 11 ^~ 1_Rei_rei Rei_1 ^~ 1 ₂ ○ 1 ^to 1 ₃ ,

Represents an amide group such as Minori. Minori represents a 6-butyl group.

[Claim 6] The diamine having a skeleton represented by the formula (1) is represented by the following formulas (2_1_1) to (

The liquid crystal aligning agent according to claim 1, which is at least one selected from 2-3-4).

[Chemical 8]

〇 2020/175539 64 卩(：171? 2020/007694

[Chemical 10]

[Claim 7] The tetracarboxylic acid derivative component of the polymer (Mitsumi) contains a tetracarboxylic acid derivative having a structure represented by the following formula: Liquid crystal aligning agent.

[Chemical 1 1]

[Claim 8] Any one of claims 1 to 7, wherein the polymer (M) is a polyimide.

The liquid crystal aligning agent according to item 1.

[Claim 9] The amount of the diamine having the skeleton of the formula (1) used is 5 to 50 mol% based on the total amount of the diamine component for producing the polymer (8). The liquid crystal aligning agent according to any one of claims 1 to 8.

[Claim 10] A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 9.

[Claim 11] A liquid crystal display device comprising the liquid crystal alignment film according to claim 10.