Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device using the same.
• liquid crystal display devices various driving methods having different electrode structures, physical properties of liquid crystal molecules to be used, manufacturing processes, etc. have been developed.
• a TN (twisted nematic) type for example, a TN (twisted nematic) type, an STN (super-twisted nematic) type, a VA (vertical alignment) type, an MVA (multi-domain vertical alignment) type, an IPS (in-plane fringe switching) type, and an IPS (in-plane fringe switching) type.
• Liquid crystal display elements of the type, PSA (polymer-sustained alignment) type, and the like are known.
• These liquid crystal display devices have a liquid crystal alignment film for aligning liquid crystal molecules.
• a material for the liquid crystal alignment film a film made of a polymer such as polyamic acid, polyimide, or polysiloxane is generally used because it has various properties such as heat resistance, mechanical strength, and affinity with liquid crystal. ing.
• a liquid crystal alignment film and a liquid crystal aligning agent that provide a liquid crystal display element excellent in reducing an afterimage are known (Patent Documents 1, 2, and 3).
• the liquid crystal display device for the above-mentioned application is required to have a property capable of withstanding long-term use in a severe use environment, and in Patent Document 4, a liquid crystal aligning agent containing a specific compound was exposed to a backlight for a long time. It is disclosed that a liquid crystal alignment film with a small decrease in voltage holding ratio can be obtained even after that and a highly reliable liquid crystal display device can be obtained.
• the liquid crystal aligning agents proposed so far have not always been able to achieve all the above-mentioned problems.
• the present invention has been made based on the above circumstances, and an object thereof is to reduce the occurrence of an afterimage and to minimize the bright spot even when physical friction such as rubbing by a spacer occurs, which is reliable. It is to provide a high liquid crystal display device, and to provide a liquid crystal alignment film and a liquid crystal aligning agent thereof suitable for such a liquid crystal display device.
• the gist of the present invention is as follows.
• a liquid crystal aligning agent comprising the following component (A) and component (B).
• Component (A) A polymer (A) having at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1) and repeating units represented by the following formula (2).
• Component (B) Compound (B) represented by the following formula (B).
• (X 1 is a tetravalent organic group
• Y 1 is a divalent organic group
• R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• Z 11 and Z 12 are each independently.
• 10 represents an alkynyl group, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group.)
• R represents an alkanediyl group having 1 to 4 carbon atoms.
• m and n each independently represent an integer of 1 or 2.
• a 1 represents a single bond, —O—, —CO—, —OCO.
• divalent organic group (L) two oxygen atoms are not adjacent to each other, and -OCO-, -COO-, -CONR- (R represents a hydrogen atom or a methyl group), and Two groups selected from —NRCONR— (R represents a hydrogen atom or a methyl group) are not adjacent to each other, and any hydrogen atom on the phenylene or biphenylene ring is substituted with a monovalent organic group. You may.)
• liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal display element and a liquid crystal aligning film which can minimize the bright spot even when physical friction such as rubbing by a spacer occurs, with less afterimage.
• the liquid crystal aligning agent of the present invention is a polymer (A) having at least one repeating unit selected from the group consisting of repeating units represented by the above formula (1) and repeating units represented by the above formula (2). Contains.
• alkyl group having 1 to 5 carbon atoms of R 1 in the above formula (2) include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group. Group, t-butyl group, n-pentyl group and the like. From the viewpoint of easiness of imidization by heating, R 1 is preferably a hydrogen atom or a methyl group.
• alkyl group having 1 to 10 carbon atoms of Z 11 and Z 12 in the above formula (2) include hexyl group in addition to the specific examples of the alkyl group having 1 to 5 carbon atoms exemplified for R 1 .
• examples thereof include a heptyl group, an octyl group, a nonyl group and a decyl group.
• Specific examples of the alkenyl group having 2 to 10 carbon atoms of Z 11 and Z 12 include a vinyl group, a propenyl group, a butynyl group and the like, which may be linear or branched.
• alkynyl group having 2 to 10 carbon atoms of Z 11 and Z 12 include ethynyl group, 1-propynyl group, 2-propynyl group and the like.
• the above Z 11 and Z 12 may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a cyano group, an alkoxy group and the like. Can be mentioned. From the viewpoint of less afterimage, it is preferable that Z 11 and Z 12 are each independently a hydrogen atom or a methyl group.
• X 1 and Y 1 are as defined above.
• X 1 of the formula (1) is at least one selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide (hereinafter collectively referred to as tetracarboxylic acid derivative And a tetravalent organic group derived from Specific examples include aromatic tetracarboxylic acid dianhydrides, aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, or tetracarboxylic acid diesters thereof, or tetracarboxylic acid diester dihalides. Examples thereof include a tetravalent organic group derived from.
• Y 1 in the formula (1) is a divalent organic group derived from diamine.
• the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring.
• the aliphatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure.
• it does not have to be composed only of a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure.
• the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups is bonded to the aromatic ring. Further, it is not necessary to be composed only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.
• X 1 is a tetravalent organic compound selected from the group consisting of the following formulas (4a) to (4n), formula (5a) and formula (6a), from the viewpoint that the resulting liquid crystal alignment film has a small afterimage and can suppress bright spots. It is preferably a group.
• X and y are each independently a single bond, —O—, —CO—, —COO—, an alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, a sulfonyl or an amide group.
• Z 1 To Z 6 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, j and k are integers of 0 or 1, and m is an integer of 1 to 5.
• (* represents a bond.)
• a preferable specific example of the formula (4a) is a structure represented by any of the following formulas (4a-1) to (4a-4).
• alkanediyl group having 1 to 5 carbon atoms in the formulas (5a) and (6a) examples include methylene, ethylene, 1,3-propanediyl, 1,4-butanediyl and 1,5-pentanediyl.
• X 1 of the formula (1) is selected from the formulas (4a) to (4h), (4j), (4l), and (4m) to (4n). It is preferably a tetravalent organic group.
• X 1 in the formula (1) is a tetravalent organic group selected from the formulas (4a) to (4h), (4j), (4l), and (4m) to (4n).
• X 1 is a tetravalent organic group selected from the group consisting of the formulas (4a) to (4n), (5a) and the formula (6a)
• Y 1 is a divalent organic group.
• One or more repeating units selected from the group consisting of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) hereinafter, also referred to as the repeating unit (t)).
• the total content is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, based on all repeating units.
• Examples of Y 1 in the formula (1) include a divalent organic group derived from a diamine, and examples thereof include a divalent organic group derived from an aliphatic diamine, an alicyclic diamine, or an aromatic diamine. Specific examples include aliphatic diamines such as metaxylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine; and alicyclic diamines such as p-cyclohexanediamine, 4, 4'-methylenebis(cyclohexylamine) and the like can be mentioned.
• aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 4,4′-diaminoazobenzene and 1-(4-aminophenyl )-1,3,3-Trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 3 ,5-diaminobenzoic acid, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 1,4-bis(4-aminophenyl)-piperazine, N,N′-bis (4-Aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 2,
• a diamine having a photopolymerizable group at the terminal such as 2-(2,4-diaminophenoxy)ethyl methacrylate, and 2,4-diamino-N,N-diallylaniline.
• a diamine having an azobenzene skeleton Diamine having an azobenzene skeleton.
• R 3 represents —NRCO—, —COO—, —NRCONR—, or —(CH 2 ) n — (where n is an integer of 2 to 20), and any —CH 2 — is — It may be replaced with O-, -COO-, -ND-, -NRCO-, -NRCONR-, -NRCOO- or -OCOO-, D represents a heat leaving group and R represents a hydrogen atom or a monovalent group.
• R 4 is a single bond or a benzene ring, and any hydrogen atom on the benzene ring may be replaced with a monovalent organic group.
• X 1 is —CO—, —O—, —COO—, —L 1 —RL 2 —(L 1 and L 2 are each independently a single bond, an oxygen atom, or —COO— , R represents —(CH 2 ) n — (n is an integer of 1 to 12), or —NRCO— (R represents a hydrogen atom or a methyl group.)
• X 2 represents a single bond, NRCO- (R represents a hydrogen atom or a methyl group) or -COO-, n represents an integer of 1 or 2. Any hydrogen atom on the benzene ring may be replaced with a monovalent organic group. Good.)
• (Two Xs each independently represent —O—, —COO—, —NHCO—, —C( ⁇ O)—, or —(CH 2 ) n — (n is an integer of 1 to 12).
• L 1 and L 2 are each independently a single bond, —O—, or —COO—, and R is —CH 2 —, —(CH 2 ) n — (n is an integer of 2 to 12). or the - (CH 2) n -.
• optional hydrogen atoms on the benzene ring to represent any CH 2 is replaced by an oxygen atom groups may be replaced by a monovalent organic group).
• (X is a single bond, —O—, —C(CH 3 ) 2 —, —NH—, —CO—, —NHCO—, —COO—, —(CH 2 ) m —, —SO 2 —, — O- (CH 2) m -O - , - O-C (CH 3) 2 -, - CO- (CH 2) m -, - NH- (CH 2) m -, - SO 2 - (CH 2) m -, - CONH- (CH 2 ) m -, - CONH- (CH 2) m -NHCO-, or -COO- (CH 2) represents an m -OCO-.
• X 1 and X 2 are each independently a single bond, —(CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CON(CH 3 )—, — Represents NH-, -O-, -COO-, -OCO- or -((CH 2 ) a1- A 1 ) m1- .
• plural a1 are each independently an integer of 1 to 15
• plural A 1 are independently oxygen atoms or —COO—
• m 1 is an integer of 1 or 2.
• X 3 represents a single bond, —CONH—, —NHCO—, —CON(CH 3 )—, —NH—, —O—, —CH 2 O—, —COO— or —OCO—.
• X 4 represents —CONH—, —NHCO—, —O—, —COO— or —OCO—.
• G 1 and G 2 are each independently a divalent aromatic group having 6 to 12 carbon atoms such as phenylene, biphenylene and naphthalene, or a divalent alicyclic group having 3 to 8 carbon atoms such as cyclopropylene and cyclohexylene. It represents a divalent cyclic group selected from formula groups.
• Any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.
• k represents an integer of 0 or 1
• m and n are each independently an integer of 0 to 3, and the sum of m and n is 1 to 4.
• R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms.
• R 1 Any hydrogen forming R 1 may be replaced by fluorine.
• R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, and arbitrary hydrogen forming R 2 may be substituted with fluorine.
• R 3 represents a structure having a steroid skeleton. )
• N represents an integer of 2 to 10.
• the hydrogen atom on the benzene ring is an alkyl group having 1 to 5 carbon atoms such as methyl group and ethyl group, and an alkoxy group having 1 to 5 carbon atoms such as methoxy group.
• a halogen atom such as a fluorine atom, a halogenated alkyl group having 1 to 5 carbon atoms such as a trifluoromethyl group, —NR 1 R 2 (R 1 and R 2 are each independently a hydrogen atom, a methyl group, or Boc)), a cyano group, a hydroxy group, or other monovalent organic group.
• Boc represents a tert-butoxycarbonyl group, and the same applies below.
• diamine represented by the formula (H) include diamines represented by any of the following formulas (H-1) to (H-14).
• R represents a hydrogen atom, a methyl group, or a Boc group.
• diamine represented by the formula (H2) include diamines represented by any of the following formulas (H2-1) to (H2-17).
• diamine represented by the formula (H3) include diamines represented by any of the following formulas (H3-1) to (H3-4).
• diamines represented by (V-1) to (V-3) include the diamines represented by any of the following formulas (V2-1) to (V2-13).
• (X v1 to X v4 and X p1 to X p8 are each independently -(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON( CH 3) -, - NH - , - O -, - CH 2 O -, - CH 2 OCO -, - COO-, or -OCO- shows the .
• X v5 is -O -, - CH 2 O - , - CH 2 OCO -, - COO-, or -OCO- shown .
• X V6 ⁇ X V7, X s1 ⁇ X s4 are each independently, -O -, - COO- or -OCO- shown .
• X 1 is a tetravalent organic group
• Y 1 is the above formula (V1).
• the total content is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more, based on all the repeating units of the polymer (A).
• the content of the repeating unit (a) is preferably 99 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, based on all the repeating units of the polymer (A).
• X 1 is a tetravalent organic group
• Y 1 is the diamine having the radical initiation function and the photopolymerizable compound.
• the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) which is a divalent organic group derived from a diamine selected from the group consisting of diamines having a terminal group. It is preferable to include one or more selected repeating units (hereinafter, also referred to as repeating unit (b)).
• the total content is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more, based on all the repeating units of the polymer (A).
• the polymer (A) may be used in combination with one or more repeating units (a).
• the total content of the repeating unit (a) and the repeating unit (b) is preferably 99 mol% or less, more preferably 97 mol% or less, and more preferably 95 mol% or less based on all the repeating units of the polymer (A). It is more preferably not more than mol %.
• a repeating unit other than the repeating unit (a) and the repeating unit (b) may be included depending on the purpose.
• X 1 is a tetravalent organic group
• Y 1 is p-phenylenediamine
• the total content is preferably 5 mol% or more, more preferably 10 mol% or more, based on all repeating units of the polymer (A).
• the content of the repeating unit (c) is preferably 99 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, based on all the repeating units contained in the polymer (A).
• X 1 is a tetravalent organic group and Y 1 is the photo-alignable structure in the polymer (A).
• the total content is preferably 20 mol% or more, more preferably 30 mol% or more, and further preferably 80 mol% or less, based on all repeating units of the polymer (A).
• the content of the repeating unit (d) is preferably 99 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, based on all the repeating units contained in the polymer (A).
• X 1 is represented by the formulas (4a) to (4c) and (4f) to (4g).
• a repeating unit selected from the group consisting of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) in which Y 1 is a divalent organic group (hereinafter, the repeating unit (e Also referred to as )) is preferable.
• the total content is preferably 5 mol% or more, more preferably 10 mol% or more, based on all repeating units of the polymer (A).
• the polymer (A) may be composed of one kind, or may be composed of two or more kinds. Specific examples of two or more polymers (A) include one of the repeating units (t) and (a) to (e) from the viewpoint that afterimages are less likely to occur and bright spots can be suppressed. An embodiment in which at least one kind of polymer having one repeating unit is contained is included.
• the polymer (A) is composed of two types, the blending ratio of the first polymer and the second polymer (first polymer/second polymer) has a small afterimage and a bright spot. From the viewpoint of suppression, the weight ratio is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and even more preferably 20/80 to 80/20.
• the liquid crystal aligning agent of the present invention contains the compound (B) represented by the formula (B). Since the compound (B) has a structure with less steric hindrance, the liquid crystal alignment property of the liquid crystal alignment film containing the polymer (A) is not significantly impaired, and the obtained liquid crystal alignment film has a high liquid crystal alignment property. Further, since it has a methylol group in the molecule, a cross-linking reaction occurs between the polymer (A) and the compound (B) or between the compounds (B), so that the film strength of the obtained liquid crystal alignment film is improved. Can be increased.
• the liquid crystal display device including the liquid crystal alignment film of the present invention has less afterimage, and the bright spot can be minimized even when physical friction such as rubbing by a spacer occurs. Further, since the compound (B) has an effect of increasing the crosslink density of the liquid crystal alignment film, it has an excellent ability to capture the impurity component derived from the substrate, and thus the obtained liquid crystal alignment film exhibits a high voltage holding ratio, A highly reliable liquid crystal display device can be obtained.
• examples of the alkanediyl group having 1 to 4 carbon atoms for R include a methylene group, an ethylene group, a propanediyl group, a butanediyl group and the like. Of these, a methylene group is preferable from the viewpoint of high crosslinking effect.
• divalent organic group (L) which are preferable from the viewpoint of less afterimage, include the following formulas (L-1) to (L-25) and (L2-1) to (L2-3).
• L 1 and L 2 are a single bond, —O—, —CO—, —OCO—, —COO—, —CONR— (R represents a hydrogen atom or a methyl group), —NRCONR— (R is hydrogen.
• L 3 Is —(CH 2 ) n — (n is an integer of 1 to 18), the formula (L-2), (L-4), (L-7), (L-8), (L-10) To (L-11), (L-13), (L-15), (L-17) to (L-18), (L-20) or (L-25), provided that L 3 is , (L-2), (L-15) and (L-17), —(CH 2 ) n —) in L 3 is bonded to —NHCO—.
• Specific preferred examples of the compound (B) include compounds represented by the following formulas (B-1) to (B-34) and (B2-1) to (B2-20).
• the content of the compound (B) is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 25 parts by weight, and still more preferably 100 parts by weight of the component (A). 0.5 to 20 parts by weight.
• the polymer (A) in the present invention is obtained by reacting, for example, a tetracarboxylic acid derivative having the structure of X 1 with a diamine having the structure of Y 1 by a known method as described in WO2013/157586. Can be obtained.
• the polymer (A) in the present invention may be a terminal-modified polymer by using an end-capping agent together with the above-mentioned tetracarboxylic acid derivative and diamine.
• terminal modifier examples include acid monoanhydride, diester dicarbonate compound, chlorocarbonyl compound, monocarboxylic acid chloride, monoamine compound, monoisocyanate compound and the like.
• acid monoanhydride examples include maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimetic anhydride, and the following formula (m- 1) to (m-6), n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydridenickic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,
• dicarbonic acid diester compound examples include compounds represented by the following formula (D). (R represents a monovalent organic group having 1 to 30 carbon atoms.)
• chlorocarbonyl compound examples include compounds represented by the following formula (Mc).
• A represents a single bond, —O—, —S—, or —NR 1 —
• R and R 1 each independently represent a monovalent organic group having 1 to 30 carbon atoms, and R and R 1 may combine with each other to form a ring structure.
• Examples of the monocarboxylic acid chloride include the compounds described in paragraphs [0069] to [0082] of WO2011/115076.
• Examples of the above monoamine compound include aniline, 2-aminophenol, 3-aminophenol, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-o-cresol, 4-amino-m-cresol, 5-amino-o-cresol, 6-amino-m-cresol, 4-amino-2,3-xylenol, 4-amino-3,5-xylenol, 6-amino-2, 4-xylenol, 2-amino-4-ethylphenol, 3-amino-4-ethylphenol, 2-amino-4-tert-butylphenol, 2-amino-4-phenylphenol, 4-amino-2,6-diphenyl Phenol, 4-aminosalicylic acid, 5-aminosalicylic
• Specific examples of the monovalent organic group having 1 to 30 carbon atoms in R of the formulas (D) and (Mc) include methyl group, ethyl group, propyl group, tert-butyl group, cyclobutyl group, 1- Alkyl group such as methylcyclobutyl group or 1-adamantyl group, alkenyl group such as vinyl group, allyl group, alkynyl group such as 1,1-dimethylpropynyl group, 2,2,2-trichloroethyl group or 1,1- Halogenoalkyl group such as dimethyl-2-chloroethyl group, silylalkyl group such as 2-trimethylsilylethyl group, cyanated alkyl group such as 1,1-dimethyl-2-cyanoethyl group, phenyl group, naphthyl group or anthranyl group
• Aryl group such as aryl group, benzyl group, 1-methyl-1-phenylethyl
• Any —CH 2 — of the alkyl group is replaced with a divalent group such as —O—, —COO—, —NHCO—, —N(CH 3 )CO—, —CO—, —NHCONH—. You may be asked.
• the proportion of the terminal modifier used is preferably 20 parts by mole or less, and more preferably 10 parts by mole or less, with respect to 100 parts by mole in total of the diamines used.
• the liquid crystal aligning agent of the present invention may contain other polymers in addition to the polymer (A).
• Other types of polymers include polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene or its derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like.
• the polyorganosiloxane preferably has at least one of an oxetanyl group and an oxiranyl group from the viewpoint of easy synthesis.
• the liquid crystal aligning agent is used for producing a liquid crystal aligning film, and 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-mentioned polymer component and an organic solvent.
• the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed.
• the concentration of the polymer is preferably 1% by weight or more, and from the viewpoint of storage stability of the solution, 10% by weight or less is more preferable, and 2 to 8% by weight is preferable. Particularly preferred.
• the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component can be uniformly dissolved therein.
• Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -valerolactone, 1,3-Dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, N,N-dimethyl lactamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide ( These may be collectively referred to as “good solvent”) and the like.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or ⁇ -butyrolactone can be used.
• the good solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99% by weight, more preferably 20 to 90% by weight, and particularly preferably 30 to 80% by weight based on the whole solvent contained in the liquid crystal aligning agent. Is.
• a solvent also referred to as a poor solvent
• the organic solvent contained in the liquid crystal aligning agent a solvent (also referred to as a poor solvent) is used in addition to the solvent as described above, which improves the coating property when applying the liquid crystal aligning agent and the surface smoothness of the coating film. It is preferable to use the mixed solvent described above. Specific examples of the organic solvent used in combination are shown below, but the invention is not limited to these examples.
• diisobutyl carbinol propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene It is preferable to use glycol monobutyl ether acetate or diisobutyl ketone.
• Preferred solvent combinations of a good solvent and a poor solvent are N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2-.
• the amount of the poor solvent is preferably 1 to 80% by weight, more preferably 10 to 80% by weight, and particularly preferably 20 to 70% by weight, based on the whole solvent contained in the liquid crystal aligning agent.
• the type and content of such a solvent are appropriately selected according to the liquid crystal alignment agent coating device, coating conditions, coating environment, and the like.
• the liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component, the component (B) and the organic solvent.
• additional component 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 sealing material, and a compound for increasing the strength of the liquid crystal alignment film (hereinafter referred to as a cross-linking agent). (Also referred to as a polar compound)), a dielectric material or a conductive material for adjusting the dielectric constant or electric resistance of the liquid crystal alignment film.
• a compound selected from the following compounds (hereinafter collectively referred to as compound (C)) is preferable.
• R 1, R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or “*—CH 2 —OH”. * represents a bond.)
• the compound having an oxiranyl group include two or more compounds such as the compound described in paragraph [0037] of JP-A-10-338880 and the compound having a triazine ring as a skeleton described in WO2017/170483. And a compound having an oxiranyl group.
• the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of WO2011/132751.
• the compound having a protected isocyanate group include compounds having two or more protected isocyanate groups described in JP-A-2014-224978, paragraphs [0046] to [0047], and paragraphs [WO2015/141598]. Examples thereof include the compounds having three or more protected isocyanate groups described in [0119] to [0120]. Of these, compounds represented by the following formulas (bi-1) to (bi-3) are preferable.
• Specific examples of the compound having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in JP-A-2016-200798.
• Specific examples of the compound having a group having an oxazoline ring structure include the compounds having two or more oxazoline structures described in paragraph [0115] of JP-A-2007-286597.
• Specific examples of the compound having a group containing a Meldrum's acid structure include the compounds described in WO 2012/091088, which have two or more Meldrum's acid structures.
• Specific examples of the compound having a cyclocarbonate group include the compounds described in WO2011/155577.
• Examples of the R 1 , R 2 , and R 3 alkyl groups having 1 to 3 carbon atoms in the group represented by the formula (d) include the groups exemplified in the above formulas (1) and (n).
• the compound having a group represented by the formula (d) include compounds represented by the formula (d) described in WO2015/072554 and paragraph [0058] of JP-A-2016-118753. Examples thereof include compounds having two or more groups, compounds described in Japanese Patent Publication No. 2016-200798, and the like. Of these, compounds represented by any of the following formulas (hd-1) to (hd-8) are preferable.
• crosslinkable compounds are examples of crosslinkable compounds and are not limited to these.
• components other than the above disclosed in paragraphs [0105] to [0116] of WO2015/060357 may be mentioned.
• two or more kinds of crosslinkable compounds contained in the liquid crystal aligning agent may be combined.
• the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymer component contained in the liquid crystal aligning agent, and the crosslinking reaction proceeds to obtain the desired effect. Is more preferable and the AC afterimage characteristic is small, the amount is more preferably 1 to 15 parts by weight.
• adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri
• Examples include pulling agents.
• a silane coupling agent When a silane coupling agent is used, it is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer component contained in the liquid crystal aligning agent, from the viewpoint of less AC afterimage. It is 1 to 20 parts by weight.
• a liquid crystal alignment film can be manufactured by using the above liquid crystal aligning agent. Further, the liquid crystal display element according to the present invention comprises a liquid crystal alignment film formed using the above liquid crystal aligning agent.
• the operation mode of the liquid crystal display element according to the present invention is not particularly limited, and includes, for example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS type). , FFS type, optical compensation bend type (OCB type), and the like.
• the liquid crystal display element according to the present invention can be manufactured, for example, by steps including the following steps (1-1) to (1-3).
• step (1-1 the substrate used differs depending on the desired operation mode.
• Steps (1-2) and (1-3) are common to each operation mode.
• Step (1-1): Formation of coating film First, the liquid crystal aligning agent of the present invention is applied onto a substrate, and then the applied surface is heated to form a coating film on the substrate.
• (1-1A) For example, when manufacturing a TN-type, STN-type or VA-type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are set as a pair, and on each transparent conductive film formation surface thereof, The liquid crystal aligning agent prepared above is preferably applied by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method, respectively.
• a glass such as float glass or soda glass
• a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly (alicyclic olefin)
• a transparent conductive film provided on one surface of the substrate
• a NESA film made of tin oxide (SnO 2 ) (trade name of PPG Co., USA), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ) and the like are used. Can be used.
• a patterned transparent conductive film for example, a method of forming a pattern-free transparent conductive film and then forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming the transparent conductive film; You can When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or a functional titanium compound is formed on the surface of the substrate on which the coating film is formed. You may perform the pre-processing which applies in advance.
• preheating is preferably performed for the purpose of preventing the liquid crystal aligning agent applied from dripping.
• the prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C.
• the prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.
• a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermal imidization of the amic acid structure present in the polymer.
• the baking temperature (post-baking temperature) at this time is preferably 80 to 300°C, more preferably 120 to 250°C.
• the post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
• the liquid crystal alignment film thus formed has a thickness of preferably 0.001 to 1 ⁇ m, more preferably 0.005 to 0.5 ⁇ m.
• an electrode formation surface of a substrate provided with an electrode formed of a comb-shaped patterned transparent conductive film or a metal film, and a counter substrate not provided with an electrode A liquid crystal aligning agent is applied to each of the surfaces, and then each applied surface is heated to form a coating film.
• the materials of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferable film thickness of the coating film formed are as described above.
• the metal film a film made of a metal such as chromium can be used.
• the organic solvent is removed to form a liquid crystal aligning film or a coating film to be the liquid crystal aligning film. It At this time, by further heating after forming the coating film, the dehydration ring-closing reaction of the polyamic acid, polyamic acid ester and polyimide compounded in the liquid crystal aligning agent according to the present invention may proceed to give a more imidized coating film. ..
• a treatment for imparting a liquid crystal aligning ability to the coating film formed in the step (1-1) is carried out. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.
• the orientation ability imparting treatment for example, a rubbing treatment of rubbing the coating film in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, photo-alignment of irradiating the coating film with polarized or unpolarized radiation Examples include processing.
• the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film, but the coating film is subjected to an alignment ability imparting treatment. May be.
• the radiation applied to the coating film for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used.
• the radiation when the radiation is polarized light, it may be 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.
• the irradiation direction is an oblique direction.
• a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used.
• Ultraviolet rays in a preferable wavelength range can be obtained by means of using a light source in combination with a filter, a diffraction grating, or the like.
• the irradiation dose of radiation is preferably 10 to 5,000 mJ/cm 2 , and more preferably 30 to 2,000 mJ/cm 2 .
• the light irradiation to the coating film may be performed 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.
• the light irradiation film obtained in the above step can be used as it is as a liquid crystal alignment film. Washing with an organic solvent, or a combination thereof may be performed.
• the firing temperature at this time is preferably 80 to 300°C, more preferably 80 to 250°C.
• the firing time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
• the firing may be performed twice or more.
• the photo-alignment process here corresponds to the process of light irradiation in a state where the photo-alignment process is not in contact with the liquid crystal layer.
• the organic solvent used for the washing is not particularly limited, but specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy- Examples thereof include 2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate or cyclohexyl acetate.
• liquid crystal alignment film after the rubbing treatment is further irradiated with ultraviolet light on a part of the liquid crystal alignment film to change the pretilt angle of a part of the liquid crystal alignment film
• a resist film may be formed on each part and then a rubbing process may be performed in a different direction from the previous rubbing process, and then the resist film may be removed so that the liquid crystal alignment film has different liquid crystal alignment ability in each region. ..
• the liquid crystal alignment film suitable for a VA type liquid crystal display element can be also suitably used for a PSA type liquid crystal display element.
• Step (1-3): Construction of liquid crystal cell (1-3A) A liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed as described above, and disposing the liquid crystal between the two substrates that are opposed to each other.
• the first method is a conventionally known method. First, two substrates are arranged so as to face each other with a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded with a sealant, and the substrates are separated by the sealant.
• a liquid crystal cell is manufactured by injecting and filling liquid crystal into the formed cell gap and then sealing the injection hole.
• the second method is a method called an ODF (One Drop Fill) method.
• ODF One Drop Fill
• an ultraviolet light curable sealant is applied to a predetermined place on one of the two substrates having the liquid crystal alignment film formed thereon, and then liquid crystal is dripped at predetermined places on the surface of the liquid crystal alignment film.
• the other substrate is bonded so that the liquid crystal alignment films face each other, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. ..
• the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature, so that the flow orientation at the time of filling the liquid crystal is improved. It is desirable to remove it.
• sealant for example, a curing agent and an epoxy resin containing aluminum oxide spheres as spacers can be used.
• liquid crystal examples include nematic liquid crystal and smectic liquid crystal.
• nematic liquid crystals are preferable, and for example, Schiff-based, azoxy, biphenyl, phenylcyclohexane, ester, terphenyl, biphenylcyclohexane, pyrimidine, dioxane, bicyclooctane, and cubane liquid crystals are used. ..
• liquid crystals for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate; chiral agents sold as C-15 and CB-15 (trade name of Merck), p-decyloxybenzylidene- Ferroelectric liquid crystal such as p-amino-2-methylbutyl cinnamate may be added.
• the liquid crystal may additionally contain an anisotropic dye.
• “Dye” means a substance capable of intensively absorbing or deforming light in at least a part or the whole range in the visible light region, for example, 400 nm to 700 nm wavelength range.
• the "anisotropic dye” means a substance capable of anisotropically absorbing light in at least a part or the whole range of the visible light region.
• the color appearance of the liquid crystal cell can be adjusted by using the dye.
• the type of anisotropic dye is not particularly limited, and for example, a black dye or a color dye can be used.
• the ratio of the anisotropic dye to the liquid crystal is appropriately selected.
• the anisotropic dye can be contained in an amount of preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal compound.
• the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
• the voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
• the irradiation light for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable.
• the light source of the irradiation light for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used.
• the ultraviolet rays in the above preferable wavelength range can be obtained by means of using a light source in combination with, for example, a filter diffraction grating.
• the irradiation dose of light preferably less than 100 mJ / cm 2 or more 30,000mJ / cm 2, more preferably 100 ⁇ 20,000mJ / cm 2.
• a liquid crystal cell is constructed in the same manner as in (1-3A) above, and then A method of manufacturing a liquid crystal display element may be adopted by subjecting a liquid crystal cell to light irradiation while a voltage is applied between the conductive films of the pair of substrates. According to this method, the merit of the PSA mode can be realized with a small light irradiation amount.
• the light irradiation to the liquid crystal cell may be performed in a state where the liquid crystal is driven by applying a voltage, or in a state in which a voltage low enough to not drive the liquid crystal is applied.
• the applied voltage can be DC or AC of 0.1 to 30 V, for example.
• the description of (1-3B) above can be applied to the conditions of the irradiation light.
• the light irradiation processing here corresponds to the light irradiation processing in the state of being in contact with the liquid crystal layer.
• a liquid crystal display device can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell.
• a polarizing plate to be attached to the outer surface of a liquid crystal cell a polarizing film in which a polarizing film called "H film” in which polyvinyl alcohol is stretched and oriented to absorb iodine and sandwiched between cellulose acetate protective films or the H film itself is used.
• the liquid crystal display device can be effectively applied to various devices, for example, watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors. , A liquid crystal television, an information display, and various other display devices.
• liquid crystal aligning agent of the present invention by using the liquid crystal aligning agent of the present invention, a liquid crystal aligning film having less afterimage and capable of minimizing a bright spot even when physical friction such as rubbing by a spacer occurs and the liquid crystal aligning film are provided. A highly reliable liquid crystal display element can be obtained.
• GPC device Shodex (GPC-101), column: Shodex (KD803, KD805 in series), column temperature: 50°C, eluent: N,N-dimethylformamide (lithium bromide-water as an additive) 30 mmol/L of solvate (LiBr.H 2 O), 30 mmol/L of phosphoric acid/anhydrous crystal (o-phosphoric acid), 10 ml/L of tetrahydrofuran (THF), flow rate: 1.0 ml/min
• This solution was measured for proton NMR at 500 MHz with an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum).
• NMP (18.0 g) was added to the obtained polyimide powder (2.0 g), and M-1 was added so as to be 1% by weight with respect to the polyimide solid content, and dissolved by stirring at 70° C. for 12 hours.
• a solution of polyimide (PI-V-1) having a solid content concentration of 10% was obtained.
• the polyamic acid had Mn of 12,400 and Mw of 33,000.
• NMP NMP
• acetic anhydride 17.1 g
• pyridine 3.54 g
• the deposit obtained by throwing in this reaction liquid in methanol (1111g) was separated by filtration. Methanol wash
• the imidation ratio of this polyimide powder was 66%, Mn was 11,000, and Mw was 28,000.
• NMP was added to the obtained polyimide powder so that the solid content concentration was 15% by weight, and the mixture was stirred and dissolved at 70° C. for 24 hours to obtain a solution of polyimide (PI-I-3).
• ⁇ Synthesis example 4> 5.73 g (20.0 mmol) of DA-5 was weighed into a 5 L four-necked flask equipped with a stirrer and a nitrogen introducing tube, NMP was added so that the solid content concentration was 7%, and stirring was performed while sending nitrogen. And dissolved. While stirring this diamine solution under water cooling, 2.94 g (15.0 mmol) of CA-3 was added, NMP was added so that the solid content concentration became 6%, and the mixture was stirred under a nitrogen atmosphere at 23° C. for 1 hour. .. Then, 11.9 g (40.0 mmol) of DA-3 and 6.01 g (40.0 mmol) of DA-11 were weighed and dissolved by feeding nitrogen while stirring.
• the solution of the obtained polyamic acid ester was poured into 1230 g of water while stirring, and the white precipitate thus deposited was collected by filtration, followed by washing with 1230 g of IPA 5 times and drying to obtain a white polyamic acid ester. 10.2 g of resin powder was obtained. The yield was 83.0%. Moreover, this polyamic acid ester had Mn of 20,786 and Mw of 40,973. GBL was added to the obtained polyamic acid ester so that the solid content concentration was 10% by weight, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a solution of polyamic acid ester (PAE-I-5).
• the values in parentheses represent the compounding ratio (mol part) of each compound with respect to the total amount of 100 mol parts of the tetracarboxylic acid derivative used in the synthesis for the tetracarboxylic acid component, and for the diamine acid component,
• the compounding ratio (mol part) of each compound to 100 mol parts of the total amount of diamine used for the synthesis is shown.
• the compounding ratio (mol part) is shown with respect to 100 mol parts of the total amount of diamine used in the synthesis.
• the organic solvent the compounding ratio (parts by weight) of each organic solvent to 100 parts by weight of the total amount of the organic solvent used in the synthesis is shown.
• ⁇ Synthesis example 13> A reactive polyorganosiloxane polymer was obtained using 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS) according to the method described in paragraph [0091] of JP-A-2018-54761. Then, a polymer of polyorganosiloxane represented by the following formula (P-S2) was obtained according to the method described in paragraph [0093] of JP-A-2018-54761. The numerical value in the formula (P-S2) shows the ratio of each compound used to the total of each silane compound used in the synthesis.
• EETS 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane
• the polymer solid content concentration is 4.5%
• the compounding ratio of the compound (B-3) is 5 parts by weight (V1. )
• V1. was obtained (see Tables 2-1 to 2-3 below). No abnormalities such as turbidity and precipitation were observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Liquid crystal aligning agents (V2) to (V11) and (I12-P) were prepared in the same manner as in Example 1 except that the polymers and additives shown in Tables 2-1 to 2-3 below were used. ⁇ (I29-P), (I30-U) ⁇ (I37-U), (V38) ⁇ (V43), (I44-P) ⁇ (I47-P), (R-V1) ⁇ (R-V2) , (R-I3-P) to (R-I4-P) were obtained.
• the values in parentheses refer to the amount of each polymer component or additive with respect to 100 parts by weight of the total amount of the polymer components used for the preparation of the liquid crystal compound for the polymer and the additive. Represents a blending ratio (parts by weight). Regarding the organic solvent, the compounding ratio (parts by weight) of each organic solvent to 100 parts by weight of the total amount of the organic solvent used for preparing the liquid crystal alignment agent is shown.
• liquid crystal aligning agents (V1) to (V11), (V38) to (V43), and (R-V1) to (R-V2) filtered with a filter having a pore size of 1.0 ⁇ m were spun on each ITO surface.
• the coated substrate was heat-treated at 70° C. for 90 seconds on a hot plate and at 230° C. for 30 minutes in a heat cycle type clean oven to obtain an ITO substrate having a liquid crystal alignment film with a thickness of 100 nm.
• the ITO electrode substrate on which this ITO electrode pattern is formed is divided into four in a checkered (checkered) pattern so that the four areas can be driven separately.
• the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals).
• a sealant XN-1500T manufactured by Mitsui Chemicals.
• the surface of the other substrate, on which the liquid crystal alignment film was formed was set to the inside, and the substrate was bonded to the previous substrate, and then the sealing material was cured to prepare an empty cell.
• Liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
• the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals).
• a sealant XN-1500T manufactured by Mitsui Chemicals.
• the surface of the other substrate, on which the liquid crystal alignment film was formed was set to the inside, and the substrate was bonded to the previous substrate, and then the sealing material was cured to prepare an empty cell.
• Liquid crystal MLC-3023 (trade name of Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
• an ultraviolet ray irradiating device using a high pressure mercury lamp as a light source was used to irradiate 15 J/cm 2 of ultraviolet rays passing through a bandpass filter having a wavelength of 365 nm.
• a vertical alignment type liquid crystal display device was obtained.
• a UV-35 light receiver was used for the UV-M03A manufactured by ORC for the measurement of the ultraviolet irradiation dose.
• this liquid crystal display element was left standing still in an oven at 80° C. under irradiation of an LED lamp for 200 hours, then left at room temperature and naturally cooled to room temperature. After that, a voltage of 1 V was applied at 60° C. for an application time of 60 microseconds and a span of 1667 milliseconds, and the voltage holding ratio was measured 1,000 milliseconds after the application was released.
• a measuring device a product manufactured by Toyo Technica was used.
• the movement direction of the tip of the scratch portion was reciprocating in the lateral direction, and the moving speed was 5.0 mm/sec.
• the scratch area was moved in the vertical direction by moving the substrate with the liquid crystal alignment film in the vertical direction at 20 ⁇ m/sec.
• liquid crystal MLC-3019
• another substrate having a liquid crystal alignment film and spacers having a diameter of 4 ⁇ m was sprinkled on it so that the surfaces of the liquid crystal alignment films face each other, and the dropped liquid crystal was sandwiched.
• ECLIPSE E600WPOL polarization microscope
• the location where the scratch test is performed is observed to see whether the light is transmitted. I observed.
• Table 6 shows that no scratches or light leakage was observed at the scratched portion, and that all scratched portions were defective.
• a substrate with electrodes was prepared.
• the substrate is a glass substrate having a size of 30 mm length ⁇ 50 mm width and a thickness of 0.7 mm.
• an ITO electrode having a solid pattern, which constitutes a counter electrode as a first layer, is formed.
• a SiN (silicon nitride) film formed by the CVD method is formed on the counter electrode of the first layer.
• the film thickness of the second-layer SiN film is 500 nm and functions as an interlayer insulating film.
• a comb-teeth-shaped pixel electrode formed by patterning an ITO film is arranged as a third layer on the second-layer SiN film to form two pixels, a first pixel and a second pixel. ing.
• the size of each pixel is 10 mm in length and about 5 mm in width.
• the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.
• the pixel electrode of the third layer has a comb-tooth shape formed by arranging a plurality of "dogleg"-shaped electrode elements whose central portion is bent at an internal angle of 160°.
• the width of each electrode element in the lateral direction is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m.
• the pixel electrode that forms each pixel is configured by arranging a plurality of bent V-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but is similar to the electrode element in the central portion. It has a shape that bends and resembles a bold "dogleg".
• 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.
• liquid crystal aligning agents (I12-P) to (I29-P), (I44-P) to (I47-P), (R-I3-P) to (R-I4-P) were added to have a pore diameter of 1.0 ⁇ m.
• the glass substrate having the electrode-attached substrate and the columnar spacer having a height of 4 ⁇ m and having the ITO film formed on the back surface was applied by spin coating.
• the coating films obtained from the liquid crystal aligning agents (I44-P) to (I47-P) were dried on a hot plate at 80° C. for 5 minutes, and then the extinction ratio was applied to the coating film surface through a polarizing plate.
• a 26:1 linearly polarized ultraviolet ray having a wavelength of 254 nm was irradiated at 500 mJ/cm 2 , and then baked in a hot air circulation oven at 230° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film having a thickness of 100 nm.
• a sealant was printed on one of the pair of glass substrates with a liquid crystal alignment film, the other substrate was attached so that the liquid crystal alignment film surfaces face each other, and the sealant was cured to prepare an empty cell.
• Liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
• the injection port was sealed to obtain an FFS driven liquid crystal display element.
• the obtained liquid crystal cell was heated at 120° C. for 1 hour and left overnight, and then the afterimage characteristics were evaluated.
• a liquid crystal alignment film having a thickness of 100 nm was prepared.
• a bead spacer having a diameter of 4 ⁇ m (manufactured by JGC Catalysts & Chemicals Co., Ltd., Masagosphere, SW-D1) was applied to the liquid crystal alignment film surface of one of the substrates.
• the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.).
• the surface of the other substrate, on which the liquid crystal alignment film was formed was set to the inside, and the substrate was bonded to the previous substrate, and then the sealing material was cured to prepare an empty cell.
• Liquid crystal MLC-3019 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal display element. Next, this liquid crystal display element was left standing still in an oven at 80° C. under irradiation of an LED lamp for 200 hours, then left at room temperature and naturally cooled to room temperature. After that, the evaluation was performed in the same procedure as in (ii) of 1-2. (Iii) Scratch resistance evaluation The procedure was the same as in (iii) of 1-2 above, except that the same liquid crystal alignment film as in 2-1 was used and the liquid crystal was MLC-3019.
• liquid crystal aligning agents (I30-U) to (I37-U) filtered through a filter having a pore diameter of 1.0 ⁇ m on each surface of a pair of glass substrates similar to the above 2-1. ) was applied using an inkjet coating device (HIS-200, manufactured by Hitachi Plant Technology). The coating was performed under the conditions that the coating area was 70 ⁇ 70 mm, the nozzle pitch was 0.423 mm, the scan pitch was 0.5 mm, the coating speed was 40 mm/sec, and the coating was allowed to stand for 60 seconds between drying. Then, after drying on a hot plate at 80° C.
• a set of these two substrates with a liquid crystal alignment film is set, a sealant is printed on the substrate with the liquid crystal injection port left, and the other substrate has the liquid crystal alignment film surfaces facing each other and the rubbing directions are antiparallel. And pasted together. Then, the sealant was cured to prepare an empty cell having a cell gap of 4 ⁇ m. Liquid crystal MLC-7026-100 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS type liquid crystal display element. Thereafter, the obtained liquid crystal display device was heated at 120° C. for 1 hour, left at 23° C. overnight, and then used for evaluation of afterimage.
• Liquid crystal MLC-7026-100 manufactured by Merck & Co., Inc.
• the liquid crystal aligning agent of the present invention is useful for forming a liquid crystal aligning film in various liquid crystal display devices such as vertical alignment type and FFS driving type.
• the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2019-018889 filed on Feb. 5, 2019 are cited herein as disclosure of the specification of the present invention. , Take in.

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