WO2019013339A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides mettant en œuvre celui-ci - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides mettant en œuvre celui-ci Download PDF

Info

Publication number
WO2019013339A1
WO2019013339A1 PCT/JP2018/026579 JP2018026579W WO2019013339A1 WO 2019013339 A1 WO2019013339 A1 WO 2019013339A1 JP 2018026579 W JP2018026579 W JP 2018026579W WO 2019013339 A1 WO2019013339 A1 WO 2019013339A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
formula
group
diamine
reaction
Prior art date
Application number
PCT/JP2018/026579
Other languages
English (en)
Japanese (ja)
Inventor
里枝 軍司
政太郎 大田
司 藤枝
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to JP2019529810A priority Critical patent/JP7093059B2/ja
Priority to KR1020207003211A priority patent/KR102572922B1/ko
Priority to CN201880046891.0A priority patent/CN110869842B/zh
Publication of WO2019013339A1 publication Critical patent/WO2019013339A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display device using the same.
  • the present invention relates to a liquid crystal aligning agent suitable for a liquid crystal display element of a VA system in which liquid crystal molecules aligned vertically to a substrate are responded to by an electric field, a liquid crystal alignment film, and the liquid crystal display element using the same.
  • Liquid crystal display devices are widely used as display units for personal computers, mobile phones, smart phones, televisions and the like.
  • the liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, and an alignment film for controlling the alignment of liquid crystal molecules of the liquid crystal layer.
  • a thin film transistor (TFT) or the like that switches an electrical signal supplied to the pixel electrode is provided.
  • One of the driving methods of such a liquid crystal display element is a method (also referred to as a vertical alignment (VA) method) in which liquid crystal molecules aligned vertically to the substrate are made to respond by an electric field.
  • a liquid crystal display element of vertical alignment type a liquid crystal composition is previously added with a photopolymerizable compound, and a liquid crystal cell is irradiated with ultraviolet light while applying a voltage to a liquid crystal cell using a vertical alignment film such as polyimide type.
  • PSA Polymer Sustained Alignment
  • the present inventors have found that the above problems can be solved by using a diamine having a specific structure as a liquid crystal aligning agent in which a polymer is incorporated, and completed the present invention.
  • the present invention is based on such findings and has the following gist.
  • the aspect of the present invention for solving the above problems is a diamine having a structure of the following formula (1) and at least one diamine having a side chain structure selected from the group represented by the following formulas [S1] to [S3] Characterized by containing a polyimide precursor obtained from the diamine component to be contained, a tetracarboxylic acid component (including a tetracarboxylic acid derivative component), and / or a polyimide polymer which is an imidized product of the polyimide precursor.
  • Liquid crystal alignment agent characterized by containing a polyimide precursor obtained from the diamine component to be contained, a tetracarboxylic acid component (including a tetracarboxylic acid derivative component), and / or a polyimide polymer which is an imidized product of the polyimide precursor.
  • R 1 represents hydrogen, an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group, a tert-butoxycarbonyl group or a monovalent organic group. * Represents a site to be bonded to another group Any hydrogen atom forming a benzene ring may be substituted by a monovalent organic group.
  • 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 )-, -NH-, -O-, -COO-, -OCO- or-((CH 2 ) a1 -A 1 ) m1- , wherein a plurality of a1's are each independently 1 And A 1 represents an oxygen atom or -COO-, and m 1 represents 1 to 2. G 1 and G 2 each independently have 6 to 12 carbon atoms.
  • a divalent cyclic group selected from a divalent aromatic group of 3 to 8 carbon atoms or a divalent alicyclic group of 3 to 8 carbon atoms Any hydrogen atom on the cyclic group is an alkyl of 1 to 3 carbon atoms.
  • R 1 represents alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxyalkyl having 2 to 20 carbons, and any hydrogen which forms R 1 may be substituted by fluorine.
  • X 3 is a single bond, -CONH-, -NHCO-, -CON (CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO-
  • R 2 represents alkyl having 1 to 20 carbons or alkoxyalkyl having 2 to 20 carbons, and any hydrogen forming R 2 may be substituted with fluorine.
  • X 4 represents -CONH-, -NHCO-, -O-, -COO- or -OCO-.
  • R 3 represents a structure having a steroid skeleton.
  • the diamine which has a structure of said Formula (1) has a structure of following formula (1-1).
  • R 1 is the same as in the case of formula (1). * Represents a site to be bonded to another group. Any hydrogen atom forming a benzene ring is a monovalent organic compound It may be substituted by a group.
  • the diamine having the structure of the formula (1) have a structure of the following formula (1-4).
  • R 1 is the same as in the case of the above-mentioned formula (1)
  • Two Q 2 each independently represent a single bond or a divalent organic group to form a benzene ring Any hydrogen atom may be substituted by a monovalent organic group.
  • the said diamine component contains the diamine which has a side chain structure represented by said Formula [S1].
  • side chain structure represented by the formula [S1] is preferably at least one selected from the group consisting of the following formulas [S1-x1] to [S1-x7].
  • R 1 represents an alkyl group having a carbon number of 1 to 20.
  • X p is-(CH 2 ) a- (a is an integer of 1 to 15 ), - CONH -, - NHCO -, - CON (CH 3) -, - NH -, - O -, - CH 2 O -, - COO- or -OCO- .
  • a 1 representing a represents an oxygen atom or a - COO - * (However, bond marked with "*" is (CH 2) binds to a2) .
  • a 2 representing a represents an oxygen atom or * -COO- (provided that the bond marked with "*" (CH 2) .a3 representing the a2 binds to) is an integer of 0 or 1, the a1 and a2 each independently an integer of 2 ⁇ 10 .Cy xylene group or 1,4-cyclohexylene Re
  • X 3 is -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO-
  • R 2 is preferably alkyl having 3 to 20 carbons or alkoxyalkyl having 2 to 20 carbons.
  • the side chain structure represented by the formula [S3] have a structure represented by the following formula [S3-x].
  • X represents Formula [X1] or Formula [X2]
  • Col represents at least one selected from the group consisting of Formula [Col1] to [Col3].
  • G represents Formula [G1 ] To [G4] In these formulas, * represents a bonding position.
  • the diamine component which has the said specific side chain structure contains at least 1 sort (s) chosen from the diamine represented by following formula [1] and [2].
  • X is a single bond, -O -, - C (CH 3) 2 -, - NH -, - CO -, - (CH 2) m -, - SO 2 - , or any And m represents an integer of 1 to 8.
  • Two Y represent at least one selected from the side chain structures represented by the above formulas [S1] to [S3], respectively. Represent)
  • the other aspect of this invention which solves the said subject is a liquid crystal aligning film characterized by being formed using the liquid crystal aligning agent as described in any one said.
  • liquid crystal display element characterized by comprising the liquid crystal aligning film obtained by said liquid crystal aligning film.
  • liquid crystal aligning agent of the present invention it is possible to provide a liquid crystal alignment film having excellent voltage holding ratio, quick relaxation of stored charges, and excellent residual image characteristics, and a liquid crystal display device excellent in display characteristics. That is, according to the liquid crystal alignment film and the liquid crystal display element of the present invention, it is possible to meet the expectation for the properties of the liquid crystal alignment film and the liquid crystal display element along with the recent increase in performance.
  • the liquid crystal aligning agent of the present invention is a diamine containing a diamine having a structure of the following formula (1) and at least one diamine having a side chain structure selected from the group represented by the following formulas [S1] to [S3]. And a polymer of a polyimide precursor which is obtained from the component, a tetracarboxylic acid component, and / or a polyimide which is an imidized product of the polyimide precursor.
  • the diamine which has a structure of Formula (1) may be called “the diamine which has a specific structure", or a “specific diamine.”
  • the diamine which has a specific structure or a “specific diamine.”
  • at least one diamine having a side chain structure selected from the group represented by the formulas [S1] to [S3] may be referred to as "a diamine having a specific side chain structure”.
  • the polymer containing the specific diamine of this invention and the diamine which has a specific side chain structure may be called a "specific polymer.”
  • the specific diamine has a structure of the following formula (1).
  • R 1 represents hydrogen, an alkyl group of 1 to 5 carbon atoms or a fluoroalkyl group, a tert-butoxycarbonyl group or a monovalent organic group.
  • * represents a site bound to another group. Any hydrogen atom forming a benzene ring may be substituted by a monovalent organic group.
  • the monovalent organic group mentioned here includes an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group or a fluoroalkoxy group having a carbon number of 1 to 10, preferably 1 to 3.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • the bonding position of the benzene ring to the pyrrole ring is preferably a carbon atom next to the nitrogen atom on the pyrrole ring as represented by the following formula (1-1) from the viewpoint of charge transfer .
  • diamines represented are more preferred.
  • R 1 is the same as that of the formula (1).
  • Each of Q 1 and Q 2 independently represents a single bond or a divalent organic group. That is, Q 1 and Q 2 may have different structures. Also, in the formula (1-4), two Q 2 may have different structures. Furthermore, any hydrogen atom that forms a benzene ring may be substituted by a monovalent organic group, as in the case of formula (1).
  • the diamine represented by following formula (2) can be mentioned, More preferably, it is a diamine represented by following formula (2-1).
  • R 1 is the same as in the case of formula (1).
  • Each of two R 2 independently represents a single bond or a structure of the following formula (3).
  • any hydrogen atom forming the benzene ring may be substituted by a monovalent organic group.
  • R 3 is a single bond, -O-, -COO-, -OCO-,-(CH 2 ) p- , -O (CH 2 ) m O-, -CONH-, -NHCO-, It represents a divalent organic group selected from the group consisting of -CON (CH 3 )-and -N (CH 3 ) CO- and -NR 1- .
  • p and m are each independently an integer of 1 to 14, and R 1 is the same as in the case of formula (1).
  • R 3 is preferably a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO— or —N (CH 3 ) — from the viewpoint of relieving the accumulated charge.
  • * 1 represents the site
  • * 2 represents a site to be bonded to the amino group in formula (2).
  • N in the formula (2) and the formula (2-1) is an integer of 1 to 3, preferably 1 or 2.
  • formula (2) examples include the following formulas (2-1-1) to (2-1-16), but are not limited thereto.
  • Formula (2-1-1), Formula (2-1-2), Formula (2-1-3), Formula (2-1-5), Formula (2) -1), formula (2-1-9), formula (2-1-10), formula (2-1-11), formula (2-1-12), formula (2-1-13) Formula (2-1-1), Formula (2-1-15) or Formula (2-1-16) is preferable, Formula (2-1-1), Formula (2-1-2), Formula 2-1-3), the formula (2-1-1), or the formula (2-1-12), the formula (2-1-13), the formula (2-1-14), the formula (2-1-1) 15) or the formula (2-1-16) is particularly preferred.
  • n is an integer of 1 to 14.
  • the synthesis method of the specific diamine is not particularly limited. For example, there is a method of using a dinitro compound represented by the following formula (4) and converting the nitro group into an amino group by a reduction reaction.
  • R 1 is the same as in the case of Formula (1).
  • the catalyst used for the reduction reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon and the like.
  • palladium hydroxide, platinum oxide, Raney nickel and the like can also be used, and they do not necessarily have to be activated carbon-supported metal catalysts.
  • palladium-activated carbon is preferable because good results are easily obtained.
  • the reaction may be carried out in the presence of activated carbon.
  • the amount of activated carbon to be used is not particularly limited, but it is preferably 1 to 30% by mass, more preferably 10 to 20% by mass with respect to the dinitro compound of the above formula (4).
  • the reaction may be carried out under pressure. In this case, in order to avoid reduction of the benzene ring and the pyrrole ring, the pressure is applied in the range of atmospheric pressure to 20 atm. The reaction is preferably carried out in the range from atmospheric pressure to 10 atmospheres.
  • the solvent used for the synthesis of the specific diamine can be used without limitation as long as it does not react with each raw material.
  • aprotic polar organic solvents dimethyl formamide, dimethyl sulfoxide, dimethyl acetate, N-methyl-2-pyrrolidone, etc.
  • ethers diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, Aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); Halogenated carbon Hydrogens (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); Lower fatty acid esters (
  • the amount of the solvent used is not particularly limited, but it is 0.1 to 100 times by mass the dinitro compound of the above formula (4).
  • the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
  • the reaction temperature is not particularly limited, but is in the range of -100 ° C to the boiling point of the solvent used, preferably -50 to 150 ° C.
  • the reaction time is generally 0.05 to 350 hours, preferably 0.5 to 100 hours.
  • the method for synthesizing the dinitro compound of the above formula (4) is not particularly limited.
  • a compound (dinitro form) represented by the following formula (5) is synthesized, and the NH group of the dinitro form is protected with R 4 There is a way to introduce
  • any compound capable of reacting with the NH site of the pyrrole ring of the formula (5) may be used.
  • acid halides, acid anhydrides, isocyanates, epoxy compounds, oxetanes, halogenated aryls, halogenated alkyls and the like can be mentioned.
  • alcohols etc. which substituted the hydroxyl group of alcohol by leaving groups such as OMs (mesyl group), OTf (triflate group), OTs (tosyl group), etc. can be used.
  • an acid halide to introduce the R 4 is preferably carried out in the presence of a base.
  • acid halides include acetyl chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-butyl chloroformate, t- chloroformate
  • acid halides include acetyl chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-butyl chloroformate, t- chloroformate
  • examples include butyl, benzyl chloroformate, chloroformic acid-9-fluorenyl and the like.
  • the base is not particularly limited as long as it can be synthesized, but potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium hydride and other inorganic bases, pyridine, dimethylamino Organic bases such as pyridine, trimethylamine, triethylamine and tributylamine can be used.
  • the reaction solvent and the reaction temperature are the same as in the reduction reaction when synthesizing the dinitro compound of the formula (4).
  • R 4 When R 4 is introduced by reacting with an acid anhydride, examples of the acid anhydride include acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, di-tert-butyl dicarbonate, dibenzyl dicarbonate etc. Can be mentioned. Pyridine, collidine, N, N-dimethyl-4-aminopyridine or the like may be used as a catalyst to accelerate the reaction. The catalytic amount is 0.0001 mol to 1 mol with respect to the compound of the above formula (5).
  • the reaction solvent and reaction temperature are the same as in the case of the above acid halide.
  • isocyanates When isocyanates are reacted to introduce R 4 , examples of isocyanates include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, phenyl isocyanate and the like.
  • the reaction solvent and reaction temperature are the same as in the case of the above acid halide.
  • R 4 is introduced by reacting an epoxy compound or an oxetane compound
  • examples of the epoxy compound or an oxetane include ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene oxide and the like.
  • the reaction solvent and reaction temperature are the same as in the case of the above acid halide.
  • OMs the hydroxyl group of alcohol, OTf if by reacting substituted alcohols to a leaving group such as OTs introducing R 4, is preferably carried out in the presence of a base.
  • the alcohols include methanol, ethanol, 1-propanol and the like, and these alcohols are reacted with methanesulfonyl chloride, trifluoromethanesulfonyl chloride, p-toluenesulfonic acid chloride and the like to obtain OMs and OTf. , OTs, etc., can be obtained.
  • Examples of the base, reaction solvent and reaction temperature are the same as in the case of the above-mentioned acid halide.
  • the alkyl halide When the alkyl halide is reacted to introduce R 4 , it is preferably carried out in the presence of a base.
  • a base examples include methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, ethyl bromide, n-propyl bromide and the like.
  • bases metal alkoxides such as potassium-tert-butoxide and sodium-tert-butoxide can be used in addition to the above-mentioned bases.
  • the reaction solvent and reaction temperature are the same as in the case of the above acid halide.
  • the base illustrated in the above-mentioned acid halide can be used.
  • the reaction solvent and reaction temperature are the same as in the case of the above acid halide.
  • zinc chloride, sodium iodide, potassium iodide, tetrabutylammonium iodide or the like can be used as a promoter.
  • the cross coupling reaction (also referred to as “Suzuki-Miyaura reaction”) of the above reaction formula 2 preferably uses a metal complex and a ligand as a catalyst, but the reaction proceeds even without a catalyst.
  • metal complexes include palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzo) Nitrile) dichloro palladium, CuCl, CuBr, CuI, CuCN etc. are mentioned.
  • Examples of the ligand include triphenyl phosphine, tri-o-tolyl phosphine, diphenylmethyl phosphine, phenyldimethyl phosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane And 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri-tert-butyl phosphine and the like.
  • the amount of the metal complex used may be a so-called catalytic amount, and it is sufficient that it is 20 mol% or less, preferably 10 mol% or less, with respect to the substrate.
  • a diamine having a specific side chain structure is represented, for example, by the following formulas [1] and [2].
  • X is a single bond, -O-, -C- (CH 3 ) 2- , -NH-, -CO-, -NHCO-, -COO-,-(CH 2 ) m -,- SO 2 -or a divalent organic group consisting of any combination thereof.
  • X is preferably a single bond, -O-, -NH- or -O- (CH 2 ) m -O-.
  • m is an integer of 1 to 8;
  • Y each independently represents at least one selected from the side chain structures represented by the formulas [S1] to [S3]. Details of the side chain structures represented by the formulas [S1] to [S3] will be described later.
  • Y may be a meta position or an ortho position from the position of X, preferably an ortho position. That is, it is preferable that said Formula [2] is following formula [2 '].
  • the two amino groups may be located on any position on the benzene ring, but in the following formulas [2] -a1 to [2] -a3
  • the position represented is preferable, and the following Formula [2] -a1 is more preferable.
  • X is the same as in the above formula [2].
  • the following formulas [2] -a1 to [2] -a3 explain the positions of two amino groups, and the notation of Y represented in the above formula [2] is omitted.
  • the above formula [2] is selected from the following formulas [2] -a1-1 to [2] -a3-2
  • the structure represented by the following formula [2] -a1-1 is more preferable.
  • X and Y are each the same as in the formula [2].
  • the two side chain diamine represented by these above-mentioned formula [2] can be used individually by 1 type or in mixture of 2 or more types. Depending on the characteristics required for the liquid crystal alignment film or the liquid crystal display element, it may be used singly or in combination of two or more types, and when two or more types are mixed and used, the ratio etc. may be appropriately adjusted. .
  • Y represents a specific side chain structure selected from the group represented by the following formulas [S1] to [S3].
  • the specific side chain structure will be described in the order of formulas [S1] to [S3].
  • 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 )-, -NH-, -O-, -COO-, -OCO- or-((CH 2 ) a1 -A 1 ) m1- .
  • the plurality of a1 each independently represent an integer of 1 to 15, each independently plurality of A 1 represents an oxygen atom or -COO-, m 1 is 1 or 2.
  • X 1 and X 2 are each independently a single bond or — (CH 2 ) a- (a is an integer of 1 to 15) from the viewpoint of availability of raw materials and easiness of synthesis. ), -O-, -CH 2 O- or -COO- is preferable. More preferably, X 1 and X 2 are each independently a single bond,-(CH 2 ) a- (a is an integer of 1 to 10), -O-, -CH 2 O- or -COO -
  • G 1 and G 2 are each independently selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms. Represents a substituted cyclic group.
  • the optional hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms Or may be substituted by a fluorine atom.
  • 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 alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxyalkyl having 2 to 20 carbons, and any hydrogen forming R 1 is fluorine It may be substituted.
  • examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, biphenylene, naphthalene and the like.
  • examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropylene and cyclohexylene.
  • R 1 is the same as that of the above formula [S1].
  • X p is-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 )-, -NH-, -O-, -CH 2 Represents O-, -COO- or -OCO-.
  • a 1 represents an oxygen atom or -COO - represents * (bond marked with "*" is (CH 2) binding to a2) a.
  • a 2 is an oxygen atom or * -COO - represents (bond marked with "*" is (CH 2) binding to a2) a.
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10.
  • X 3 is a single bond, -CONH-, -NHCO-, -CON (CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO- Represents Among them, from the viewpoint of liquid crystal alignment, X 3 is preferably -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO-.
  • R 2 represents alkyl having 1 to 20 carbons or alkoxyalkyl having 2 to 20 carbons, and any hydrogen which forms R 2 may be substituted by fluorine. Among them, from the viewpoint of liquid crystal alignment, R 2 is preferably alkyl having 3 to 20 carbon atoms or alkoxyalkyl having 2 to 20 carbon atoms.
  • X 4 represents -CONH-, -NHCO-, -O-, -COO- or -OCO-.
  • R 3 represents a structure having a steroid skeleton.
  • the steroid skeleton here has a skeleton represented by the following formula (st) to which three six-membered rings and one five-membered ring are linked.
  • Examples of the formula [S3] include the following formula [S3-x], but not limited thereto.
  • X represents the above formula [X1] or [X2].
  • Col represents at least one selected from the group consisting of the above formulas [Col1] to [Col3]
  • G represents at least one selected from the group consisting of the above formulas [G1] to [G4]. * Represents a site bound to another group.
  • Examples of preferable combinations of X, Col and G in the above formula [S3-x] include combinations of the formulas [X1] and the formulas [Col1] and [G2], the formulas [X1] and the formulas [Col2] and [G2] , A combination of Formula [X2] and Formula [Col1] and [G2], a combination of Formula [X2] and Formula [Col2] and [G2], a combination of Formula [X1] and Formula [Col3] and [G1] Can be mentioned.
  • diamines having specific side chain structures represented by the above formulas [S1] to [S3] can be used singly or in combination of two or more. Depending on the characteristics required for the liquid crystal alignment film or the liquid crystal display element, it may be used singly or in combination of two or more types, and when two or more types are mixed and used, the ratio etc. may be appropriately adjusted. .
  • the diamine component of the present invention is at least at least a diamine having a structure represented by the above formula (1) and a specific side chain structure selected from the group represented by the above formulas [S1] to [S3].
  • diamine having a side chain structure selected from the group represented by the above formulas [S1] to [S3] for example, the following formulas [1-S1] to [1-S3], [2-S1] And [2-S3].
  • Examples of diamines represented by the above formulas [2-S1] to [2-S3] include, but are not limited to, the specific structures shown below.
  • the diamine component of this embodiment may contain, as another diamine, a diamine having a photoreactive side chain.
  • the photoreactive side chain can be introduced into the specific polymer or the other polymer.
  • diamine having a photoreactive side chain examples include, but not limited to, those represented by the following formula [VIII] or [IX].
  • the positions of the two amino groups (—NH 2 ) may be any position on the benzene ring, for example, on the benzene ring with respect to the side chain linking group. 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions or 3, 5 positions. From the viewpoint of reactivity when synthesizing a polyamic acid, the positions of 2, 4, 2, 5 or 3, 5 are preferable. The positions of 2, 4 and 3, 5 are more preferable in consideration of the ease of synthesis of the diamine.
  • R 8 is a single bond, -CH 2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N (CH 3) -, - CON (CH 3) - or -N (CH 3) represents a CO-.
  • R 8 is preferably a single bond, -O-, -COO-, -NHCO- or -CONH-.
  • R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted by a fluorine atom.
  • this bivalent carbocyclic ring or heterocyclic ring can specifically illustrate the thing of following formula (1a), it is not limited to this.
  • R 9 can be formed by a general organic synthetic method, but a single bond or an alkylene group having 1 to 12 carbon atoms is preferable from the viewpoint of easiness of synthesis.
  • R 10 represents a photoreactive group selected from the group consisting of the following formula (1b). Among them, R 10 is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.
  • Y 1 represents -CH 2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-.
  • Y 2 represents an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring.
  • One or more hydrogen atoms in the alkylene group, divalent carbon ring or heterocycle here may be substituted with a fluorine atom or an organic group.
  • -CH 2- when the following groups are not adjacent to each other, -CH 2- may be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.
  • Y 3 represents -CH 2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO- or a single bond.
  • Y 4 represents a cinnamoyl group.
  • Y 5 represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring.
  • One or more hydrogen atoms in the alkylene group, divalent carbon ring or heterocycle here may be substituted with a fluorine atom or an organic group.
  • Y 5 when the following groups are not adjacent to each other, -CH 2- may be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.
  • Y 6 represents a photopolymerizable group such as an acryl group or a methacryl group.
  • X 9 and X 10 each independently represent a single bond, -O-, -COO-, -NHCO- or -NH-.
  • Y represents an alkylene group having 1 to 20 carbon atoms which may be substituted by a fluorine atom.
  • the diamine of following formula [VII] As a diamine which has a photoreactive side chain, the diamine of following formula [VII] is also mentioned.
  • the diamine of the formula [VII] has a site having a radical generating structure in the side chain.
  • radicals are generated by decomposition upon irradiation with ultraviolet light.
  • Ar represents at least one aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, and the hydrogen atom of their ring may be substituted by a halogen atom. Since Ar to which a carbonyl is bound is involved in the absorption wavelength of ultraviolet light, when the wavelength is increased, a structure with a long conjugate length such as naphthylene or biphenylene is preferable. On the other hand, when Ar has a structure such as naphthylene or biphenylene, the solubility may be deteriorated, and in this case, the degree of difficulty of synthesis becomes high. If the wavelength of ultraviolet light is in the range of 250 nm to 380 nm, sufficient characteristics can be obtained even with a phenyl group, so Ar is most preferably a phenyl group.
  • the aromatic hydrocarbon group may be provided with a substituent.
  • a substituent an electron donative organic group such as an alkyl group, a hydroxyl group, an alkoxy group, an amino group and the like is preferable.
  • R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group. In the case of an alkyl group or an alkoxy group, a ring may be formed by R 1 and R 2 .
  • T 1 and T 2 each independently represent a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O -, - N (CH 3) -, - CON (CH 3) - or an -N (CH 3) CO- linking group.
  • S represents a single bond or an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted by a fluorine atom.
  • Q represents a structure selected from the following formula (1d).
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents —CH 2 —, —NR—, —O— or —S—.
  • Q is preferably an electron-donating organic group, and is preferably an alkyl group, a hydroxyl group, an alkoxy group, an amino group or the like as mentioned in the example of Ar above.
  • Q is an amino derivative, a problem such as a carboxylic acid group generated and an amino group forming a salt may occur during polymerization of a polyamic acid which is a precursor of polyimide, so a hydroxyl group or an alkoxy group is generated. Is more preferred.
  • the positions of the two amino groups (-NH 2 ) may be either o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, but the reactivity with acid dianhydride M-phenylenediamine or p-phenylenediamine is preferred from the viewpoint of
  • n is an integer of 2 to 8.
  • diamines having photoreactive side chains represented by the above formulas [VII], [VIII] or [IX] can be used singly or in combination of two or more.
  • pretilt angle, voltage holding characteristics, accumulated charge, etc. when used as a liquid crystal alignment film, and the response speed of the liquid crystal when used as a liquid crystal display element one type alone or a mixture of two or more types What is necessary is just to adjust suitably, such as the ratio, when using it, and also using 2 or more types in mixture.
  • the photoreactive side chain diamine is preferably 10 to 70% by mole, and more preferably 10 to 60% by mole, of the total diamine component.
  • Diamines other than the above> The other diamine which may be contained in the diamine component for obtaining a specific polymer is not limited to the diamine etc. which have the said photoreactive side chain.
  • diamine other than the diamine which has the said photoreactive side chain what is represented by following formula [2] is mentioned.
  • a 1 and A 2 each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5 carbon atoms or an alkynyl group of 2 to 5 carbon atoms .
  • a 1 and A 2 are preferably a hydrogen atom or a methyl group.
  • n is an integer of 1 to 6 in particular, unless otherwise specified.
  • Me represents a methyl group.
  • Boc represents a tert-butoxycarbonyl group.
  • the other diamines including the diamine having a photoreactive side chain described above can be used alone or in combination of two or more.
  • the specified diamine relative to other diamines in the specified polymer is 5 mol% to 80 mol%, preferably 10 mol% to 70 mol%, more preferably 20 mol% to 70 mol% of the specified diamine. Amount is good.
  • tetracarboxylic acid component examples include tetracarboxylic acid, tetracarboxylic acid dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dihalide In the invention, these are also collectively referred to as a tetracarboxylic acid component.
  • tetracarboxylic acid component examples include tetracarboxylic acid dianhydride, and derivatives thereof, such as tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide (these are collectively referred to as The first tetracarboxylic acid component may also be used).
  • tetracarboxylic acid dianhydrides include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides. Specific examples thereof include those in the following groups [1] to [5].
  • aliphatic tetracarboxylic acid dianhydride for example, 1,2,3,4-butanetetracarboxylic acid dianhydride;
  • alicyclic tetracarboxylic acid dianhydride for example, acid dianhydrides such as the following formulas (X1-1) to (X1-13),
  • R 3 to R 23 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, It represents an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group.
  • R M represents a hydrogen atom or a methyl group.
  • Xa represents a tetravalent organic group represented by the following formulas (Xa-1) to (Xa-7).
  • aromatic tetracarboxylic acid dianhydride for example, pyromellitic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid Acid dianhydride, acid dianhydride represented by the following formulas (Xb-1) to (Xb-10), etc., and
  • the tetracarboxylic acid components described above can be used singly or in combination of two or more. Depending on the characteristics required for the liquid crystal alignment film or the liquid crystal display element, it may be used singly or in combination of two or more types, and when two or more types are mixed and used, the ratio etc. may be appropriately adjusted. .
  • the specific polymer is obtained by a method of reacting the diamine component (the diamine component consisting of a plurality of types of diamines) of the embodiment described above with a tetracarboxylic acid component.
  • the method of making it react and obtaining polyamic acid is mentioned. Specifically, a method of polycondensing a primary or secondary diamine and a tetracarboxylic acid dianhydride to obtain a polyamic acid is used.
  • a method of polycondensing a tetracarboxylic acid in which a carboxylic acid group is dialkylated with a primary or secondary diamine, a tetracarboxylic acid dihalide in which a carboxylic acid group is halogenated, and a primary a method of polycondensation with a secondary diamine or a method of converting a carboxy group of a polyamic acid into an ester is used.
  • the method of ring-closing the above-mentioned polyamic acid or polyamic acid alkyl ester to make a polyimide is used.
  • the reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent. It will not specifically limit, if the produced
  • solvents here are N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-sulfoxide Dimethyl-imidazolidinone and the like can be mentioned.
  • the solvent solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D-1] to [D-3].
  • a solvent etc. can be used.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms.
  • D 2 represents an alkyl group having 1 to 3 carbon atoms.
  • D 3 represents an alkyl group having 1 to 4 carbon atoms.
  • solvents can be used singly or in combination of two or more. Even if the solvent does not dissolve the polyimide precursor, it may be used by mixing with the above-mentioned solvent as long as the produced polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and causes hydrolysis of the produced polyimide precursor, it is preferable to use the solvent which has been dehydrated and dried.
  • the temperature at which the diamine component and the tetracarboxylic acid component are polycondensed may be any temperature from -20 to 150 ° C, preferably from -5 to 100 ° C.
  • the reaction can be carried out at any concentration, but when the concentration is too low, it becomes difficult to obtain a polymer of high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult . Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction may be performed at high concentration, and then solvent may be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2.
  • the molecular weight of the resulting polyimide precursor increases as the molar ratio approaches 1.0.
  • the polyimide is a polyimide obtained by ring-closing the above-mentioned polyimide precursor, and in this polyimide, the ring-closing rate (also referred to as imidation rate) of the amic acid group does not necessarily have to be 100%. It can be adjusted arbitrarily.
  • the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which the catalyst is added to the solution of the polyimide precursor.
  • the temperature for thermally imidizing the polyimide precursor in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and the method is preferably performed while removing water generated by the imidization reaction out of the system.
  • the catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 times by mole, preferably 2 to 20 times by mole of the amic acid group, and the amount of acid anhydride is 1 to 50 times by mole, preferably 3 to 3 times the amic acid group. It is 30 molar times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has a suitable basicity to allow the reaction to proceed.
  • As an acid anhydride acetic anhydride, trimellitic anhydride, pyromellitic anhydride etc. are mentioned. In particular, it is preferable to use acetic anhydride because purification after completion of the reaction becomes easy.
  • the imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.
  • the reaction solution may be introduced into a solvent and precipitated.
  • a solvent used for precipitation methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like can be mentioned.
  • the polymer precipitated by charging in a solvent can be recovered by filtration and then dried at normal pressure or under reduced pressure, or at normal temperature or by heating.
  • a solvent for example, alcohols, ketones, hydrocarbons and the like can be mentioned.
  • the use of three or more solvents selected from these is preferable because the efficiency of purification is further increased.
  • this method produces a polyamic acid from a diamine component and a tetracarboxylic acid component, and chemically reacts the carboxy group (COOH group), that is, an esterification reaction.
  • a method of producing a polyamic acid alkyl ester is carried out by reacting the polyamide acid and the esterifying agent in the presence of a solvent at -20 to 150 ° C (preferably 0 to 50 ° C) for 30 minutes to 24 hours (preferably 1 to 4 hours). is there.
  • esterification agent those which can be easily removed after the esterification reaction are preferable, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl -3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the amount of the esterifying agent used is preferably 2 to 6 molar equivalents relative to 1 mole of the repeating unit of the polyamic acid. Among them, 2 to 4 molar equivalents are prefer
  • the solvent used for reaction of the said diamine component and a tetracarboxylic acid component is mentioned from the soluble point to the solvent of polyamic acid.
  • N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable.
  • These solvents can be used alone or in combination of two or more.
  • the concentration of the polyamic acid in the solvent in the esterification reaction is preferably 1 to 30% by mass from the viewpoint that precipitation of the polyamic acid hardly occurs. Among these, 5 to 20% by mass is preferable.
  • the solvent examples include the solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of the solubility of the resulting polymer, that is, the polyamic acid alkyl ester in the solvent.
  • the solvent include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable.
  • These solvents may be used alone or in combination of two or more.
  • the concentration of the polyamic acid alkyl ester in the solvent in the reaction is preferably 1 to 30% by mass from the viewpoint that precipitation of the polyamic acid alkyl ester is unlikely to occur. Among these, 5 to 20% by mass is preferable.
  • the solvent used for preparation of a polyamic-acid alkylester is dehydrated as much as possible. Furthermore, it is preferable to carry out the reaction in a nitrogen atmosphere to prevent the entry of outside air.
  • Method of producing by reaction of diamine component and tetracarboxylic acid diester This method is carried out, for example, at 0 to 150 ° C. (preferably using a diamine component and tetracarboxylic acid diester in the presence of a condensing agent, a base and a solvent) Is a method of carrying out a polycondensation reaction at 0 to 100 ° C. for 30 minutes to 24 hours (preferably 3 to 15 hours).
  • the condensing agent includes triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinyl Methylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate and the like can be used.
  • the amount of the condensing agent to be used is preferably 2 to 3 moles, particularly preferably 2 to 2.5 moles, per mo
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base used is preferably an amount that can be easily removed after the polycondensation reaction, and is preferably 2 to 4 moles, more preferably 2 to 3 moles, per mole of the diamine component.
  • the solvent used for the polycondensation reaction includes the solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of the solubility of the polymer obtained, ie, the polyamic acid alkyl ester in the solvent.
  • N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable.
  • These solvents may be used alone or in combination of two or more.
  • the reaction proceeds efficiently by adding a Lewis acid as an additive.
  • a Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the amount of Lewis acid used is preferably 0.1 to 10 moles per mole of the diamine component. Among them, 2.0 to 3.0 times mol is preferable.
  • the reaction solution may be poured into a solvent and precipitated.
  • the solvent used for the precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like.
  • the polymer precipitated by being introduced into a solvent is preferably subjected to a washing operation several times with the above solvent for the purpose of removing the additives and catalysts used above. After washing and filtration and recovery, the polymer can be dried under normal pressure or reduced pressure, or at normal temperature or by heating.
  • the polymer in the polymer can be reduced in impurities by repeating the operation of re-dissolving the polymer collected in the solvent and re-precipitating it for 2 to 10 times.
  • the polyamic acid alkyl ester is preferably the production method of the above (2) or (3).
  • liquid crystal aligning agent of this invention contains said specific polymer, you may contain 2 or more types of specific polymers of a different structure. In addition to the specific polymer, it is obtained without containing other polymers, that is, a polymer having no divalent group represented by the formula (1) (specific diamine represented by the formula (1) (Polymer) may be contained.
  • the type of polymer includes polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or derivative thereof, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate Etc.
  • the ratio of the specific polymer to the total polymer component is preferably 5% by mass or more, and for example, 5 to 95% by mass can be mentioned.
  • the liquid crystal aligning agent is generally in the form of a coating solution in terms of forming a uniform thin film. It is preferable that the liquid crystal aligning agent of this invention is also a coating liquid containing the said polymer component and the organic solvent in which this polymer component is dissolved. At that time, 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. From the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is preferable, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable. The particularly preferred concentration of the polymer is 2 to 8% by mass.
  • the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component dissolves uniformly.
  • Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl- And imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone and the like.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone.
  • the organic solvent contained in the liquid crystal aligning agent of this invention can also use the solvent which improves the coating property at the time of apply
  • Specific examples of such organic solvents are listed below, but these are not.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-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- Dimethi -4-Heptanol, 1,2-ethanedi
  • organic solvents are 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene It is preferred to use glycol monobutyl ether or dipropylene glycol dimethyl ether.
  • the kind and content of such a solvent are suitably selected according to the coating apparatus of a liquid crystal aligning agent, coating conditions, coating environment, etc.
  • the liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent.
  • additional components adhesion assistants for enhancing the adhesion between the liquid crystal alignment film and the substrate, and the adhesion between the liquid crystal alignment film and the sealing material, a crosslinking agent for enhancing the strength of the liquid crystal alignment film, and liquid crystals Examples thereof include dielectrics and conductive substances for adjusting the dielectric constant and the electrical resistance of the alignment film.
  • these additional components include the poor solvents and crosslinkable compounds disclosed in page 53, paragraph [0104] to page 60, paragraph [0116] of WO 2015/060357.
  • the liquid crystal aligning agent of the present invention includes, in addition to the above, a polymer other than the specific polymer described in the present invention, a dielectric for changing electric properties such as dielectric constant and conductivity of liquid crystal alignment film, liquid crystal alignment film Silane coupling agent for the purpose of improving the adhesion between the film and the substrate, a crosslinkable compound for the purpose of enhancing the hardness and density of the film when it is made into a liquid crystal alignment film, and furthermore, a polyimide precursor An imidization promoter for the purpose of efficiently advancing imidation by heating may be contained.
  • a functional silane containing compound and an epoxy group containing compound are mentioned, for example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl- 3-
  • liquid crystal aligning agent of this invention in order to raise the mechanical strength of a liquid crystal aligning film, you may add the following additives to the liquid crystal aligning agent of this invention.
  • the above 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, no effect can be expected. If the amount is more than 30 parts by mass, the orientation of the liquid crystal is reduced, so the amount is more preferably 0.5 to 20 parts by mass.
  • the liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent.
  • the liquid crystal aligning agent according to the present invention is particularly suitable for the VA mode, particularly PSA mode, in which liquid crystal molecules aligned vertically to the substrate are made to respond by an electric field. It is possible to provide a liquid crystal alignment film and a liquid crystal display element having excellent afterimage characteristics quickly.
  • a liquid crystal alignment agent of the present invention is applied to a substrate, dried as necessary, and then a cured film obtained by baking is used as it is as a liquid crystal alignment film It can also be done.
  • this cured film is rubbed, polarized light or irradiated with light of specific wavelength, etc., treated with ion beam, etc., a state in which a voltage is applied to the liquid crystal display element after liquid crystal filling as an alignment film for PSA. It is also possible to irradiate UV. In particular, it is useful to use as an alignment film for PSA.
  • 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 plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed, from the viewpoint of simplification of the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is only for one substrate, and in this case, a material that reflects light such as aluminum can also be used for the electrode.
  • the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, screen printing, offset printing, flexographic printing, the inkjet method etc. are common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method and the like, and these may be used according to the purpose.
  • the solvent is evaporated and fired by a heating means such as a hot plate, a thermal circulation type oven, an IR (infrared) type oven or the like.
  • the drying and baking steps after the application of the liquid crystal alignment agent can be performed at any temperature and time.
  • the step of drying is not necessarily required, but it is preferable to perform the drying step if the time from application to baking is not constant for each substrate, or if it is not immediately fired after application.
  • the drying is not particularly limited as long as the solvent is removed to such an extent that the coating film shape is not deformed by the transport of the substrate and the like.
  • a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C. for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes can be mentioned.
  • the baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and is, for example, 100 to 350 ° C., preferably 120 to 300 ° C., and more preferably 150 ° C. to 250 ° C.
  • the baking 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 carried out by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace and the like.
  • the thickness of the liquid crystal alignment film after firing is preferably 5 to 300 nm, and more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may decrease.
  • the liquid crystal alignment film of the present invention is useful as a liquid crystal alignment film of a liquid crystal display element of a VA system, particularly a PSA mode.
  • the liquid crystal display element can produce a liquid crystal cell by a well-known method, after forming a liquid crystal aligning film in a board
  • the liquid crystal display element the above-mentioned two substrates disposed to face each other, a liquid crystal layer provided between the substrates, and the liquid crystal alignment agent provided between the substrate and the liquid crystal layer
  • a liquid crystal layer composed of liquid crystal is held between substrates, that is, it is produced by providing a liquid crystal layer in contact with a liquid crystal alignment film and irradiating ultraviolet light while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. It is a liquid crystal display element of the vertical alignment system which comprises a liquid crystal cell.
  • the substrate of the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but in general, it is a substrate on which a transparent electrode for driving liquid crystal is formed on the substrate. As a specific example, the same one as the substrate described for the liquid crystal alignment film can be mentioned. Although a substrate provided with a conventional electrode pattern or protrusion pattern may be used, in the liquid crystal display element, a liquid crystal aligning agent containing the polyimide polymer of the present invention is used, so It is possible to operate even in a structure in which a 10 ⁇ m line / slit electrode pattern is formed and a slit pattern or a protrusion pattern is not formed on the opposite substrate, and the liquid crystal display element of this structure can simplify the manufacturing process. High transmittance can be obtained.
  • a highly functional element such as a TFT type element, one in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
  • a transmission type liquid crystal display element it is general to use the above-mentioned substrate, but in the reflection type liquid crystal display element, it is also possible to use an opaque substrate such as a silicon wafer if it is only one side of the substrate. It is possible. At that time, a material such as aluminum that reflects light can also be used for the electrode formed on the substrate.
  • the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element is not particularly limited, and a liquid crystal material used in the conventional vertical alignment method, for example, negative type such as MLC-6608, MLC-6609, MLC-3023 manufactured by Merck, etc. Liquid crystal can be used.
  • a liquid crystal containing a polymerizable compound represented by the following formula can be used.
  • a known method can be mentioned.
  • a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one of the substrates so that the surface on which the liquid crystal alignment film is formed is inside.
  • the other substrate is attached and the liquid crystal is injected under reduced pressure to seal it.
  • a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one of the substrates and then liquid crystal is dropped, and then the surface on the side where the liquid crystal alignment film is formed.
  • the liquid crystal cell can also be manufactured by a method in which the other substrate is attached and sealed so that the inner side is inside.
  • the thickness of the spacer is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the process of producing a liquid crystal cell by irradiating an ultraviolet-ray, applying a voltage to a liquid crystal aligning film and a liquid crystal layer for example applies an electric voltage between the electrodes currently installed on the board
  • the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
  • the irradiation dose of ultraviolet radiation is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation dose of ultraviolet radiation, the reduction in reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed and the irradiation time is reduced. This is preferable because the production efficiency is increased.
  • the polymerizable compound when ultraviolet light is irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is stored by this polymer.
  • the response speed of the obtained liquid crystal display can be increased.
  • a polyimide precursor having side chains for aligning liquid crystals vertically and light reactive side chains, and this polyimide precursor as an imide
  • the polarizing plate is installed. Specifically, it is preferable to attach a pair of polarizing plates to the surface of the two substrates opposite to the liquid crystal layer.
  • the liquid crystal alignment film and the liquid crystal display device of the present invention are not limited to the above configuration and manufacturing method as long as the liquid crystal alignment agent of the present invention is used, and they are manufactured by other known methods. It may be.
  • the steps for obtaining a liquid crystal display element from a liquid crystal aligning agent are disclosed, for example, in paragraph [0074] to page 19 in page 17 of JP-A-2015-135393, and the like.
  • the polymerizing compound is polymerized, and by reacting the photoreactive side chains with each other, or by reacting the photoreactive side chain of the polymer with the polymerizable compound, more The alignment of the liquid crystal is efficiently fixed, and the liquid crystal display device has excellent response speed.
  • A2 and A5 are novel compounds which have not been published in the literature or the like, and the synthesis method will be described in detail below.
  • the imidation ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid appearing around 9.5 to 10.0 ppm It calculated
  • required by the following formula using the integral value. Imidation ratio (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is the proton peak integrated value derived from the NH group of amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is the NH group proton 1 of the amic acid in the case of polyamic acid (imidation ratio is 0%) It represents the proportion of the number of reference protons to one.
  • the viscosity of the polyimide polymer was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), using a sample volume of 1.1 mL and a cone rotor TE-1 (1 ° 34 ′). , R24), measured at a temperature of 25 ° C.
  • NMP is added to the obtained polyamic acid solution (20.0 g), and after diluting to 6.5 mass%, acetic anhydride (3.59 g) and pyridine (1.11 g) are added as an imidation catalyst, and 80 The reaction was allowed to proceed for 3 hours.
  • the reaction solution was poured into methanol (232 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain polyimide powder (10).
  • the imidation ratio of this polyimide was 75.2%.
  • Example 1 NMP (27.0 g) was added to the polyimide powder (1) (3.00 g) obtained in Synthesis Example 1 and stirred at 70 ° C. for 24 hours for dissolution. BCS (20.0 g) was added to this solution to obtain a liquid crystal aligning agent (V-1) of Example 1.
  • Example 2 to [Example 9]
  • the liquid crystal aligning agents (V-2) to (V-) of Examples 2 to 9 are the same as in Example 1 except that polyimide powders (2) to (9) are used instead of polyimide powder (1). I got 9).
  • Example 10 NMP (27.0 g) was added to the polyimide powder (10) (3.00 g) obtained in Synthesis Example 10 and stirred at 70 ° C. for 24 hours for dissolution. BCS (20.0 g) was added to this solution to obtain a liquid crystal aligning agent (V-10). The liquid crystal aligning agent of Example 10 was mixed with the liquid crystal aligning agent (V-10) (5.00 g) and the liquid crystal aligning agent (R-V2) (5.00 g) obtained in Comparative Example 2 (B-10). Got).
  • Example 11 NMP (15.0 g) and BCS (20.0 g) were added to the polyamic acid solution (10A) (15.0 g) obtained in Synthesis Example 10 to obtain a liquid crystal aligning agent (V-10A).
  • This liquid crystal aligning agent (V-10A) 5.00 g and the liquid crystal aligning agent (R-V2) obtained in Comparative Example 2 were mixed to obtain a liquid crystal aligning agent (B-11) of Example 11. .
  • Example 12 NMP (15.0 g) and BCS (20.0 g) were added to the polyamic acid solution (11A) (15.0 g) obtained in Synthesis Example 11 to obtain a liquid crystal aligning agent (V-11A).
  • liquid crystal aligning agents (V-1) to (V-9) and (B-10) to (B-12) obtained as described above no abnormality such as turbidity or precipitation is observed, and a uniform solution is obtained. It was confirmed that there is.
  • a liquid crystal display device using the obtained liquid crystal aligning agents (V-1) to (V-9) and (B-10) to (B-12) and (V-13) to (V-14) described later The evaluation of the vertical orientation, the evaluation of the pretilt angle, the evaluation of the voltage holding ratio, and the evaluation of the afterimage characteristics were performed.
  • Liquid crystal aligning agents (V-13) to (V-14) were obtained in the same manner as in Example 1 except that polyimide powders (12) to (13) were used instead of polyimide powder (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.
  • Comparative Example 2 A liquid crystal aligning agent (R-V2) was obtained in the same manner as in Comparative Example 1 except that the polyimide powder (R2) was used instead of the polyimide powder (R1) obtained in Comparative Synthesis Example 1.
  • Comparative Example 3 A liquid crystal aligning agent (R-V3) was obtained in the same manner as in Comparative Example 1 except that the polyimide powder (R3) was used instead of the polyimide powder (R1) obtained in Comparative Synthesis Example 1.
  • liquid crystal aligning agents (R-V1) to (R-V3) obtained as described above no abnormality such as turbidity or precipitation was observed, and it was confirmed that they were homogeneous solutions.
  • liquid crystal aligning agents (R-V1) to (R-V2) liquid crystal display devices are manufactured, evaluation of vertical alignment, evaluation of pretilt angle, evaluation of voltage holding ratio, evaluation of afterimage characteristics are performed.
  • Liquid crystal aligning agents (V-1) to (V-9), (B-10) to (B-12), (V-13) to (V-14) obtained in Examples and Comparative Examples
  • the liquid crystal aligning agents (R-V1) to (R-V2) were pressure-filtered with a membrane filter having a pore size of 1 ⁇ m.
  • the resulting solution is spin-coated on the ITO surface of a 40 mm ⁇ 30 mm ITO electrode-attached glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) washed with pure water and IPA (isopropyl alcohol), Heat treatment was performed at 70 ° C.
  • ITO substrate with a liquid crystal alignment film having a thickness of 100 nm Two ITO substrates with a liquid crystal alignment film thus obtained were prepared, and a bead spacer (with Jiro Catalyst Chemicals Co., Ltd., spherical sphere, SW-D1) having a diameter of 4 ⁇ m was coated on the liquid crystal alignment film surface of one of the substrates.
  • a bead spacer with Jiro Catalyst Chemicals Co., Ltd., spherical sphere, SW-D1 having a diameter of 4 ⁇ m was coated on the liquid crystal alignment film surface of one of the substrates.
  • the periphery was coated with a sealing material (Mitsui Chemicals XN-1500T).
  • a sealing material Mitsubishi Chemicals XN-1500T.
  • the sealing material was cured to form an empty cell.
  • a liquid crystal MLC-3023 (trade name of Merck & Co., Inc.) was injected into this empty cell by a pressure reduction injection method to prepare a liquid crystal cell. While applying a DC voltage of 15 V to this liquid crystal cell, UV light of a high pressure mercury lamp passed through a cut filter of 325 nm or less from the outside of this liquid crystal cell was irradiated with 10 J / cm 2 (1st-UV).
  • UV-35 light receiver was connected to UV-M03A manufactured by ORC and used for measurement of the ultraviolet irradiation amount.
  • Liquid crystal aligning agents (V-1) to (V-9), (B-10) to (B-12), (V-13) to (V-14) obtained in Examples and Comparative Examples
  • the liquid crystal aligning agents (R-V1) to (R-V2) were pressure-filtered with a membrane filter having a pore size of 1 ⁇ m.
  • An ITO electrode substrate (vertical: 35 mm, horizontal: 30 mm) on which an ITO electrode pattern of 200 ⁇ m ⁇ 600 ⁇ m in pixel size and 3 ⁇ m in line / space is formed by washing the obtained solution with pure water and IPA (isopropyl alcohol) , Thickness: 0.7 mm) and a photo spacer with a height of 3.2 ⁇ m are patterned on the ITO surface of the ITO electroded glass substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) It was spin-coated and heat-treated at 70 ° C. for 90 seconds on a hot plate at 230 ° C.
  • IPA isopropyl alcohol
  • the ITO electrode substrate on which this ITO electrode pattern is formed is divided into four in a cross checker (checkered) pattern, and can be separately driven in each of four areas.
  • the periphery was coated with a sealing material (Mitsui Chemicals XN-1500T).
  • a sealing material Mitsubishi Chemicals XN-1500T.
  • the sealing material was cured to form an empty cell.
  • a liquid crystal MLC-3023 (trade name of Merck & Co., Inc.) was injected into this empty cell by a pressure reduction injection method to prepare a liquid crystal cell. While applying a DC voltage of 15 V to this liquid crystal cell, UV light of a high pressure mercury lamp passed through a cut filter of 325 nm or less from the outside of this liquid crystal cell was irradiated with 10 J / cm 2 (1st-UV).
  • irradiation with a fluorescent UV lamp (FLR40SUV32 / A-1) for 30 minutes (2nd-UV) with no voltage applied to the liquid crystal cell deactivates the unreacted polymerizable compound present in the liquid crystal cell.
  • the A UV-35 light receiver was connected to a UV-M03A manufactured by ORC for measurement of the ultraviolet radiation dose.
  • residual DC voltage A 30 Hz, 7.8 Vpp rectangular wave superimposed with 2 V DC is applied for 100 hours at 23 ° C. to the liquid crystal display element for voltage holding ratio evaluation manufactured above, and the liquid crystal cell in one hour after the DC voltage is cut.
  • the residual voltage was determined by the flicker elimination method. This value is an index of an afterimage generated by DC accumulation, and when this value is approximately 50 mV or less, it was judged that the afterimage characteristic is excellent.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)

Abstract

L'agent d'alignement de cristaux liquides de l'invention comprend un polymère d'un précurseur de polyimide ou d'un polyimide consistant en un produit imidisé de ce précurseur de polyimide, qui est obtenu à partir d'un composant acide tétracarboxylique et d'un composant diamine comprenant une diamine ayant une structure de formule ［１］ et une diamine ayant une structure de chaîne latérale prédéfinie. (Dans la formule (1), Ｒ１ représente un hydrogène, un groupe alkyle ou un groupe fluoroalkyle de 1 à 5 atomes de carbone, un groupe ｔｅｒｔ－butoxycarbonyle ou un groupe organique monovalent. * représente un site de liaison à un autre groupe. Un atome d'hydrogène quelconque formant un cycle benzène peut être substitué par un groupe organique monovalent.)
PCT/JP2018/026579 2017-07-14 2018-07-13 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides mettant en œuvre celui-ci WO2019013339A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2019529810A JP7093059B2 (ja) 2017-07-14 2018-07-13 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子
KR1020207003211A KR102572922B1 (ko) 2017-07-14 2018-07-13 액정 배향제, 액정 배향막 및 그것을 사용한 액정 표시 소자
CN201880046891.0A CN110869842B (zh) 2017-07-14 2018-07-13 液晶取向剂、液晶取向膜及使用其的液晶表示元件

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-138259 2017-07-14
JP2017138259 2017-07-14

Publications (1)

Publication Number Publication Date
WO2019013339A1 true WO2019013339A1 (fr) 2019-01-17

Family

ID=65001359

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/026579 WO2019013339A1 (fr) 2017-07-14 2018-07-13 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides mettant en œuvre celui-ci

Country Status (5)

Country Link
JP (1) JP7093059B2 (fr)
KR (1) KR102572922B1 (fr)
CN (1) CN110869842B (fr)
TW (1) TWI758513B (fr)
WO (1) WO2019013339A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220159955A (ko) 2020-03-30 2022-12-05 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
KR20230038504A (ko) 2020-07-14 2023-03-20 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7311047B2 (ja) * 2020-07-17 2023-07-19 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
CN113249130B (zh) * 2021-05-17 2023-06-02 Tcl华星光电技术有限公司 液晶介质组合物、显示面板及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005351924A (ja) * 2004-06-08 2005-12-22 Hitachi Displays Ltd 液晶表示装置
WO2014189128A1 (fr) * 2013-05-23 2014-11-27 日産化学工業株式会社 Agent de traitement pour orientation de cristaux liquides, film d'orientation de cristaux liquides et dispositif d'affichage à cristaux liquides
WO2017047596A1 (fr) * 2015-09-16 2017-03-23 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2018097155A1 (fr) * 2016-11-22 2018-05-31 日産化学工業株式会社 Procédé de fabrication d'élément d'affichage à cristaux liquides, substrat pour élément d'affichage à cristaux liquides et ensemble d'éléments d'affichage à cristaux liquides

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3289271B2 (ja) * 1995-02-13 2002-06-04 日産化学工業株式会社 液晶配向処理剤及びこれを用いた液晶素子
TWI291065B (en) * 2000-12-26 2007-12-11 Nissan Chemical Ind Ltd Diamines, polyimide precursors and polyimides produced by using the diamines, and liquid crystal aligning agents
JP4175826B2 (ja) 2002-04-16 2008-11-05 シャープ株式会社 液晶表示装置
JP4788896B2 (ja) * 2006-02-22 2011-10-05 Ｊｓｒ株式会社 垂直配向型液晶配向剤および垂直配向型液晶表示素子
TWI406838B (zh) * 2006-08-04 2013-09-01 Jnc Corp 二胺、液晶配向劑、液晶配向膜和液晶顯示裝置
JP5062109B2 (ja) * 2007-10-09 2012-10-31 Ｊｎｃ株式会社 液晶配向剤、液晶配向膜および液晶表示素子
KR101806351B1 (ko) * 2011-02-01 2018-01-11 삼성디스플레이 주식회사 액정 표시 장치
WO2014133042A1 (fr) * 2013-02-28 2014-09-04 日産化学工業株式会社 Polymère, agent de traitement servant à l'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2014208609A1 (fr) * 2013-06-25 2014-12-31 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP6520716B2 (ja) * 2013-11-15 2019-05-29 日産化学株式会社 液晶配向剤及びそれを用いた液晶表示素子
CN103922989B (zh) * 2014-04-29 2016-08-17 苏州海泰原新材料有限公司 含邻苯二甲腈结构的吡咯基芳香二胺及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005351924A (ja) * 2004-06-08 2005-12-22 Hitachi Displays Ltd 液晶表示装置
WO2014189128A1 (fr) * 2013-05-23 2014-11-27 日産化学工業株式会社 Agent de traitement pour orientation de cristaux liquides, film d'orientation de cristaux liquides et dispositif d'affichage à cristaux liquides
WO2017047596A1 (fr) * 2015-09-16 2017-03-23 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2018097155A1 (fr) * 2016-11-22 2018-05-31 日産化学工業株式会社 Procédé de fabrication d'élément d'affichage à cristaux liquides, substrat pour élément d'affichage à cristaux liquides et ensemble d'éléments d'affichage à cristaux liquides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220159955A (ko) 2020-03-30 2022-12-05 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
KR20230038504A (ko) 2020-07-14 2023-03-20 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자

Also Published As

Publication number Publication date
KR102572922B1 (ko) 2023-08-30
CN110869842B (zh) 2022-06-03
CN110869842A (zh) 2020-03-06
TWI758513B (zh) 2022-03-21
JPWO2019013339A1 (ja) 2020-05-21
KR20200027967A (ko) 2020-03-13
JP7093059B2 (ja) 2022-06-29
TW201920362A (zh) 2019-06-01

Similar Documents

Publication Publication Date Title
JP7096534B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
KR102572922B1 (ko) 액정 배향제, 액정 배향막 및 그것을 사용한 액정 표시 소자
JP7108241B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
TWI814803B (zh) 液晶配向劑、液晶配向膜及液晶顯示元件
CN115968453A (zh) 液晶取向剂、液晶取向膜以及液晶显示元件
CN111936923B (zh) 液晶取向剂、液晶取向膜和液晶表示元件
CN110651221B (zh) 液晶取向剂、液晶取向膜及液晶表示元件
WO2020158819A1 (fr) Agent d'alignment de cristaux liquides, film d'alignment de cristaux liquides et élément d'affichage à cristaux liquides
CN113474725A (zh) 液晶取向剂、液晶取向膜以及液晶显示元件
JP7161147B2 (ja) 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子並びに該液晶配向膜の製造方法
CN116940888A (zh) 液晶取向剂、液晶取向膜以及液晶显示元件
CN115398325A (zh) 新型二胺、聚合物、液晶取向剂、液晶取向膜以及使用其的液晶显示元件
JPWO2020085450A1 (ja) 液晶配向剤、液晶配向膜、及び液晶表示素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18831161

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019529810

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207003211

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18831161

Country of ref document: EP

Kind code of ref document: A1