WO2014092170A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Download PDF

Info

Publication number
WO2014092170A1
WO2014092170A1 PCT/JP2013/083388 JP2013083388W WO2014092170A1 WO 2014092170 A1 WO2014092170 A1 WO 2014092170A1 JP 2013083388 W JP2013083388 W JP 2013083388W WO 2014092170 A1 WO2014092170 A1 WO 2014092170A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
liquid crystal
diamine
mass
polymer
Prior art date
Application number
PCT/JP2013/083388
Other languages
English (en)
Japanese (ja)
Inventor
アルム 金
Original Assignee
日産化学工業株式会社
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 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to CN201380072402.6A priority Critical patent/CN104969123B/zh
Priority to KR1020157018331A priority patent/KR102222790B1/ko
Priority to JP2014552096A priority patent/JPWO2014092170A1/ja
Publication of WO2014092170A1 publication Critical patent/WO2014092170A1/fr

Links

Classifications

    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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

Definitions

  • the present invention relates to a liquid crystal aligning agent used for producing a liquid crystal aligning film, a liquid crystal aligning film using the same, and a liquid crystal display element.
  • a liquid crystal alignment film which is a constituent member of a liquid crystal display element, is a film for uniformly arranging liquid crystals.
  • the alignment uniformity of liquid crystals but also various characteristics are required.
  • the liquid crystal alignment film In the manufacturing process of the liquid crystal alignment film, it is common to perform an alignment process called rubbing by rubbing the surface of the polymer film with a cloth. However, if the rubbing resistance of the liquid crystal alignment film is insufficient, the film is scraped to generate scratches and dust, or the film itself is peeled off, thereby degrading the display quality of the liquid crystal display element.
  • the liquid crystal display element is driven by applying a voltage to the liquid crystal. For this reason, when the voltage holding ratio (VHR) of the liquid crystal alignment film is low, a sufficient voltage is not applied to the liquid crystal, and the display contrast is lowered.
  • VHR voltage holding ratio
  • a phenomenon such as afterimage or display burn-in occurs.
  • Patent Document 1 proposes a method for obtaining a liquid crystal alignment film having excellent rubbing resistance and less afterimage and image sticking.
  • Patent Document 2 proposes a method for obtaining a liquid crystal alignment film having excellent liquid crystal alignment properties, alignment regulating power, and rubbing resistance, a high voltage holding ratio, and reduced charge accumulation.
  • An object of the present invention is to solve the above-mentioned problems of the prior art, and a liquid crystal capable of obtaining a liquid crystal alignment film having a high voltage holding ratio and a very small charge accumulation while maintaining rubbing resistance.
  • An object is to provide an alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
  • the inventor has conducted research to achieve the above object, and has arrived at the present invention having the following summary.
  • the liquid crystal aligning agent characterized by containing the following (A) component and the following (B) component.
  • (A) component at least one polymer selected from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing this polyimide precursor,
  • the tetracarboxylic acid component is 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- And at least one selected from naphthalene succinic diester and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic diester dichloride, and the diamine component is represented by the following formula (1): Polymer comprising a diamine having a side chain represented
  • P 1 represents a single bond or a divalent organic group
  • Q 1 , Q 2 , and Q 3 each independently represent a divalent benzene ring or a cyclohexane ring
  • p, q, r Each independently represents an integer of 0 or 1
  • P 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton.
  • component at least one polymer selected from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing this polyimide precursor,
  • the tetracarboxylic acid component is 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- At least one selected from
  • the diamine component consists only of a diamine represented by the following formula (2).
  • the liquid crystal aligning agent of description is not limited to:
  • two X's each independently represents an oxygen atom or a single bond
  • n represents an integer of 1 to 10
  • two R 22's each independently represent a hydrogen atom, an alkyl having 1 to 5 carbon atoms.
  • the diamine having a side chain represented by the formula (1) is a diamine represented by the following formula (3).
  • Liquid crystal aligning agent as described in.
  • P 1 represents a single bond or a divalent organic group
  • Q 1 , Q 2 , and Q 3 each independently represent a divalent benzene ring or a cyclohexane ring
  • p, q, r Each independently represents an integer of 0 or 1
  • P 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton.
  • a liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of the above to a substrate and baking it.
  • a liquid crystal display element comprising the liquid crystal alignment film described in 1.
  • the liquid crystal aligning agent of the present invention contains the specific component (A) and component (B), the voltage holding ratio is high while maintaining the rubbing resistance, which has been a conventionally required characteristic, and in the present age. It is possible to form a liquid crystal alignment film that has a very small charge accumulation to meet even strict requirements.
  • the present invention is described in detail below.
  • the liquid crystal aligning agent of this invention contains the said (A) component and the said (B) component.
  • the liquid crystal alignment agent is a solution for producing a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction.
  • Each component contained in the liquid crystal aligning agent of this invention is explained in full detail below.
  • the component (A) contained in the liquid crystal aligning agent of the present invention is selected from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and a polyimide obtained by imidizing this polyimide precursor. At least one polymer.
  • the polyimide precursor include polyamic acid (also referred to as polyamic acid), polyamic acid ester, and the like.
  • the tetracarboxylic acid component is 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (hereinafter also referred to as “TDA”).
  • TDA diester 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid diester
  • TDA diester dichloride 4-tetrahydro-1-naphthalene succinic diester dichloride
  • the polymer of the component (A) is a polymer having a tetravalent structure represented by the following formula (4) derived from TDA, TDA diester or TDA diester dichloride.
  • the total content of TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component is, for example, 20 to 100 mol%, preferably 40 to 100 mol%.
  • the diamine component to be polymerized with the tetracarboxylic acid component includes a diamine having a side chain represented by the above formula (1).
  • the main chain of diamine is a structure connecting two amino groups of diamine
  • the side chain of diamine is a structure branched from a structure connecting two amino groups of diamine.
  • the polymer of the component (A) includes a diamine having a side chain represented by the formula (1) as a raw material diamine component
  • the polymer of the component (A) is, for example, This structure has a benzene ring in the main chain and -P 1- (Q 1 ) p- (Q 2 ) q- (Q 3 ) r -P 2 bonded to the benzene ring as a side chain.
  • a TN (Twisted Nematic) mode in which a relatively low pretilt angle of 3 to 5 ° is required, or an OCB (Optically Compensated Bend) in which a pretilt of 8 to 20 ° is required.
  • a side chain (-P 1- (Q 1 ) p- (Q 2 ) q- (Q 3 ) r -P 2 ) having a relatively low tilting ability is preferable.
  • P 1 is preferably —O—, —NHCO— or —CONH—
  • p is 0 to 1
  • q is 0 to 1
  • r is 0.
  • P 2 is preferably a linear alkyl having 1 to 12 carbon atoms
  • P 2 is a linear alkyl having 10 to 22 carbon atoms.
  • a divalent organic group selected from a C 12-25 organic group having a group or a steroid skeleton is preferred.
  • Specific examples of the structure of the side chain having a small tilting ability are shown in Table 1, but are not limited thereto. Note that in this specification, an organic group is, for example, —O—, —NHCO—, —CONH—, —COO—, or a hydrocarbon group which may have N or O.
  • a diamine having a long-chain alkyl side chain as shown in [1-1] of Table 1 is preferable, and is represented by [1-9] of Table 1 from the viewpoint of liquid crystal alignment and pretilt stability.
  • Diamines having side chains are preferred.
  • VA Vertical Alignment
  • P 1 is preferably —O—, —COO—, or —CH 2 O—
  • p is 0 to 1
  • q is 0 to 1
  • r is 0 to 1
  • P 2 is preferably 2 to 22.
  • P 2 is preferably a linear alkyl group having 18 to 22 carbon atoms or a divalent organic group that is an organic group having 12 to 25 carbon atoms having a steroid skeleton.
  • Specific structures of side chains having a large tilting ability are shown in Tables 2-1 and 2-2.
  • side chains have a high tilting ability and are preferable when used in the VA mode.
  • diamines having side chains such as [1-15] and [1-31] are preferable because they have a high tilting ability and exhibit vertical alignment with a relatively small amount of side chains.
  • the diamine having a side chain of 1-34] is preferable in terms of the printability of the liquid crystal aligning agent because it has a very high ability to develop tilt and can achieve vertical alignment with a very small amount of side chain.
  • P 1 is preferably —NHCO—
  • P 2 is preferably an alkyl group having 1 to 16 carbon atoms, preferably 3 to 10 carbon atoms.
  • Q 1 , Q 2 , Q 3 and p, q, r are appropriately combined.
  • such a diamine has a benzene ring in the main chain, and a structure having -P 1- (Q 1 ) P- (Q 2 ) q- (Q 3 ) r -P 2 bonded to the benzene ring as a side chain.
  • the position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amino groups is preferably meta or para.
  • Examples of the diamine having a side chain represented by the above formula (1) include the following [DA-1] to [DA-26].
  • R 6 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • S 5 s may be the same or different from each other, and —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—, wherein R 6 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • S 6 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • R 7 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
  • S 7 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or —CH 2 —, wherein R 8 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
  • S 8 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—, wherein R 9 is fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy Group or hydroxyl group.
  • R 10 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • the content of the diamine having a side chain represented by the above formula (1) is preferably 5 to 50 mol% with respect to the total amount of the diamine component, and 5 to 30 mol% from the viewpoint of pretilt uniformity and printability. Is particularly preferred.
  • the diamine having a side chain represented by the formula (1) is a diamine represented by the above formula (3), that is, the main chain has a benzene ring, and is bonded to the benzene ring.
  • a diamine having a structure having -P 1- (Q 1 ) p- (Q 2 ) q- (Q 3 ) r -P 2 as a side chain is preferable from the viewpoint of availability.
  • the position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amino groups is preferably meta or para.
  • the tetracarboxylic acid component which is a raw material of the component may include other tetracarboxylic acid derivatives other than the above-mentioned TDA, TDA diester and TDA diester dichloride.
  • examples of other tetracarboxylic acid derivatives in the component (A) include the following tetracarboxylic dianhydrides.
  • Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane.
  • Tetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, bicyclo [3.3.0] octane-2,4 6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydr
  • Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid And dianhydrides and 2,3,6,7-naphthalenetetracarboxylic dianhydride.
  • the above-mentioned tetracarboxylic dianhydrides can be used alone or in combination of two or more according to the properties of the liquid crystal alignment film to be formed, such as liquid crystal alignment properties, voltage holding properties, and accumulated charges.
  • examples of other tetracarboxylic acid derivatives that may be contained in the tetracarboxylic acid component that is the raw material of the component (A) include tetracarboxylic acid dialkyl esters and tetracarboxylic acid dialkyl diester dichlorides.
  • the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester that is a polyimide precursor.
  • the tetracarboxylic acid dialkyl ester that can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters. Specific examples are given below.
  • aliphatic tetracarboxylic acid diester examples include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2 , 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy- 1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy 1,2,3,4-tetrahydro-1-naphthalene
  • aromatic tetracarboxylic acid dialkyl ester examples include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4′-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid dialkyl ester Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6, Dialkyl 7-naphthalenetetracar
  • examples of the tetracarboxylic acid dialkyl diester dichloride as other tetracarboxylic acid derivatives that may be contained in the tetracarboxylic acid component that is the raw material of the component (A) include the dichlorides of the above tetracarboxylic acid diesters.
  • the content of the total amount of other tetracarboxylic acid derivatives other than TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component is preferably 0 to 80 mol%, more preferably 0 to 40 mol. %.
  • the diamine component that is a raw material of the component (A) may include other diamines other than the diamine having a side chain represented by the above formula (1).
  • examples of such other diamines in the component (A) include the following alicyclic diamines, aromatic diamines, heterocyclic diamines, aliphatic diamines and urea bond-containing diamines.
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone diamine Etc.
  • aromatic diamines examples include o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino- 2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 ′ -Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3
  • aromatic-aliphatic diamines examples include diamines represented by the following formula [DAM].
  • Ar represents a benzene ring or a naphthalene ring
  • R 1 represents an alkylene group having 1 to 5 carbon atoms
  • R 2 represents a hydrogen atom or a methyl group.
  • aromatic-aliphatic diamine examples include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4 -Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) ) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4- Methylaminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopen) L) aniline, 3- (5-methylaminopenty
  • heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole and the like.
  • aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, Examples thereof include 1,18-diaminooc
  • urea bond-containing diamines examples include N, N′-bis (4-aminophenethyl) urea.
  • the diamine component in the component (A) may contain the following diamine.
  • n is an integer of 1 to 5.
  • examples of the diamine component in the component (A) include diaminosiloxanes represented by the following formula [DA-35].
  • n is an integer of 1 to 10.
  • diamine components in the component (A) can be used singly or in combination of two or more depending on the properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when the liquid crystal alignment film is formed.
  • the mixing ratio is not limited.
  • the molecular weight of the polymer (polyimide precursor, polyimide) of the component (A) is determined by considering the strength of the obtained liquid crystal alignment film, the workability when forming the liquid crystal alignment film, and the uniformity of the liquid crystal alignment film.
  • the weight average molecular weight measured by Gel Permeation Chromatography is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the polymer of component (A) is preferably polyimide.
  • the component (A) tends to be present on the surface of the liquid crystal alignment film (that is, on the side opposite to the substrate) when the liquid crystal alignment film is formed. This is because it is better to have many imide groups that do not cause a reversible reaction in order to contribute.
  • the imidation ratio of this polyimide is preferably 60 to 90%.
  • the component (B) contained in the liquid crystal aligning agent of the present invention is selected from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and a polyimide obtained by imidizing this polyimide precursor. At least one polymer.
  • the polyimide precursor include polyamic acid (also referred to as polyamic acid), polyamic acid ester, and the like.
  • the tetracarboxylic acid component is 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1 , 2,3,4-tetrahydro-1-naphthalene succinic acid diester and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid diester dichloride. Therefore, as will be described in detail later, the polymer of component (B) is also a polymer having a tetravalent structure represented by the above formula (4) derived from TDA, TDA diester or TDA diester dichloride.
  • the total content of TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component is 20 to 100 mol%, preferably 40 to 100 mol%.
  • the diamine component to be polymerized with the tetracarboxylic acid component is a —CR 21 2 — group in the main chain (wherein two R 21 each independently represents a hydrogen atom or an organic group). It consists only of a diamine having two R 21 together (which may form a cyclic structure) (hereinafter also referred to as “diamine having —CR 21 2 — group in the main chain”). As long as the diamine has a —CR 21 2 — group in the main chain, one type or two or more types may be used in combination.
  • the polymer of component (B) is only a diamine having a —CR 21 2 — group in the main chain as the starting diamine component, and will be described in detail later. However, the polymer of component (B) is —CR in the main chain.
  • the structure has 21 2- .
  • the main chain of diamine is a structure that connects two amino groups of diamine. Examples of the organic group R 21 of the —CR 21 2 — group include an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, and a fluorine atom. Further, two R 21 may be combined to form, for example, an alkylene group having 2 to 7 carbon atoms to form a cyclic structure.
  • Examples of the diamine having a —CR 21 2 — group in the main chain include the following alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, aliphatic diamines, urea bond-containing diamines, and the like.
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone diamine Etc.
  • aromatic diamines examples include 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3 ' -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4 -(4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis (4-aminophenyl) cyclohexane, ⁇ , ⁇ '-bis (4-aminophenyl) -1,4-diisopropylbenzene, 2,2-bis (3-a
  • aromatic-aliphatic diamines examples include diamines represented by the following formula [DAM].
  • Ar represents a benzene ring or a naphthalene ring
  • R 1 represents an alkylene group having 1 to 5 carbon atoms
  • R 2 represents a hydrogen atom or a methyl group.
  • aromatic-aliphatic diamine examples include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4 -Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) ) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4- Methylaminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopen) L) aniline, 3- (5-methylaminopenty
  • aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, Examples thereof include 1,18-diaminooc
  • urea bond-containing diamines examples include N, N′-bis (4-aminophenethyl) urea.
  • a diamine represented by the above formula (2) is preferable from the viewpoint of availability.
  • examples of such a diamine include diamines exemplified as aromatic diamines in the description of the component (B).
  • TDA etc. a liquid crystal alignment film having a very high resistance can be obtained by including a polyimide precursor or polyimide in the liquid crystal aligning agent together with the component (A).
  • This liquid crystal alignment film having a very high resistance is less likely to cause a current to flow when a voltage is applied than a liquid crystal alignment agent having a low resistance. It is presumed that a liquid crystal alignment film having a very small value was obtained. Note that since the accumulated charge itself is very small, it takes a long time for the accumulated charge to escape, and there is no conventional problem that an afterimage or display burn-in occurs.
  • the tetracarboxylic acid component which is a raw material of the component (B) may contain other tetracarboxylic acid derivatives other than the TDA, TDA diester and TDA diester dichloride.
  • Such other tetracarboxylic acid derivatives in the component (B) include other tetracarboxylic acid derivatives in the component (A).
  • the content of the total amount of other tetracarboxylic acid derivatives other than TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component is preferably 0 to 80 mol%, more preferably 0 to 60 mol. %.
  • the tetracarboxylic acid component in the component (B) may be the same as or different from the tetracarboxylic acid component in the component (A).
  • the molecular weight of the polymer (polyimide precursor, polyimide) of the component (A) is determined by considering the strength of the obtained liquid crystal alignment film, the workability when forming the liquid crystal alignment film, and the uniformity of the liquid crystal alignment film.
  • the weight average molecular weight measured by Gel Permeation Chromatography is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the polymer of component (B) is preferably a polyimide precursor. This is because the component (B) tends to exist on the side of the substrate on which the liquid crystal aligning agent is applied (that is, the side opposite to the surface of the liquid crystal alignment film) when the liquid crystal alignment film is formed. This is because having a large number of polar groups provides good adhesion to the substrate and excellent printability.
  • the ratio of the component (A) and the component (B) contained in the liquid crystal aligning agent of the present invention is not particularly limited.
  • the liquid crystal aligning agent of this invention is a polymer obtained by making the tetracarboxylic-acid component containing TDA etc. react with the diamine component containing the diamine which has a side chain represented by the said Formula (1).
  • the display screen can be suitably used for mobile phones and tablet terminals.
  • Such an effect of the present invention is a specific polymer obtained by reacting a tetracarboxylic acid component containing TDA or the like and a diamine component containing a diamine having a side chain represented by the above formula (1) (
  • a specific component (B) which is a polymer obtained by reacting the component A) with a tetracarboxylic acid component containing TDA or the like and a diamine component consisting only of a diamine having a —CR 21 2 — group in the main chain.
  • the RDC when a polymer that does not use TDA or the like as a raw material is used, the RDC is large, that is, the charge accumulation is large, and the rubbing resistance is not good, and the effect of the liquid crystal aligning agent of the present invention cannot be exhibited.
  • the component (B) when a polymer not using TDA or the like is used, RDC is large. Even when TDA or the like is used as a raw material, if a diamine having no —CR 21 2 — in the main chain is used as the diamine component of the raw material, the RDC is large.
  • a well-known synthesis method can be used.
  • the tetracarboxylic acid component and the diamine component are reacted in an organic solvent.
  • the reaction between the tetracarboxylic acid component and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent used for the reaction between the tetracarboxylic acid component and the diamine component is not particularly limited as long as the generated polyamic acid dissolves. Specific examples are given below.
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is.
  • a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. Any method may be used.
  • tetracarboxylic acid component or diamine component when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be mixed with individually reacted low molecular weight substances. It is good also as a high molecular weight body by making it react.
  • the polymerization temperature at that time can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic acid component and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the ratio of the total number of moles of the tetracarboxylic acid component to the total number of moles of the diamine component is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
  • Polyimide can be obtained by dehydrating and ring-closing the polyimide precursor such as the polyamic acid or polyamic acid ester.
  • the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted in the range of 0% to 100% depending on the application and purpose.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which a solution of polyamic acid or polyamic acid ester is heated as it is, and catalyst imidization in which a catalyst is added to a solution of polyamic acid or polyamic acid ester.
  • the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is performed while removing water generated by the imidation reaction from the system Is preferred.
  • a basic catalyst and an acid anhydride are added to a solution of polyamic acid or polyamic acid ester and stirred at ⁇ 20 to 250 ° C., preferably 0 to 180 ° C. Can be performed.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like.
  • pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.
  • use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • a tetracarboxylic acid diester dichloride obtained by reacting the tetracarboxylic acid diester with a halogenating agent such as thionyl chloride, sulfuryl chloride, oxalyl chloride, phosphorus oxychloride and the like and And a method of reacting a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent and a base.
  • a suitable condensing agent and a base can also be obtained by polymerizing a polyamic acid in advance and esterifying the carboxylic acid in the amic acid using a polymer reaction.
  • tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
  • pyridine triethylamine, 4-dimethylaminopyridine can be used, but pyridine is preferable because the reaction proceeds gently.
  • the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the amount of Lewis acid added is preferably 0.1 to 1.0 times the molar amount of the tetracarboxylic acid diester.
  • the solvent used in the above reaction can be the solvent used when polymerizing the polyamic acid shown above, but N-methyl-2-pyrrolidone and ⁇ -butyrolactone are preferred from the solubility of the monomer and polymer. These may be used alone or in combination of two or more.
  • the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
  • the reaction solution is poured into a poor solvent. It can be precipitated.
  • the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
  • the polymer precipitated in a poor solvent and collected by filtration can be dried at normal temperature or under reduced pressure at room temperature or by heating.
  • the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the polyimide precursor obtained by polymerizing such a tetracarboxylic acid component and a diamine component is, for example, a polymer having a repeating unit represented by the following formula [a].
  • a polyimide obtained by dehydrating and ring-closing a polyimide precursor having such a repeating unit is polyimide.
  • R 11 is a tetravalent organic group derived from a raw material tetracarboxylic acid component (eg, the following formula (c)), and R 12 is a raw material diamine component (eg, the following formula (b )) Is a divalent organic group
  • a 11 and A 12 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and j is a positive integer Is shown.
  • each of R 11 and R 12 may be one type and a polymer having the same repeating unit, or R 11 and R 12 may be a plurality of types and a polymer having a repeating unit having a different structure. But you can.
  • R 11 is a group derived from a tetracarboxylic acid component as a raw material
  • the polyimide precursor of the component (A) and the component (B) is represented by R 11 in the above formula (4).
  • R 12 is a group derived from a diamine component as a raw material
  • the polyimide precursor of the component (A) is R 12 is -P 1- (Q 1 ) p- (Q 2 ) q- (Q 3 ) having a side chain represented by r -P 2
  • (B) a polyimide precursor component R 12 is -CR 21 2 in the main chain - having.
  • the liquid crystal aligning agent of the present invention contains an organic solvent in addition to the components (A) and (B) described above. And the liquid crystal aligning agent of this invention is a form of the solution which said (A) component and (B) component melt
  • the liquid crystal aligning agent of the present invention may be produced as long as it has the form of a solution in which the component (A) and the component (B) are dissolved in an organic solvent.
  • a method of mixing the powder of the component (A) and the component (B) and dissolving in an organic solvent a method of mixing the powder of the component (A) and the solution of the component (B), and a solution of the component (A) ( There are a method of mixing the powder of component B) and a method of mixing the solution of component (A) and the solution of component (B).
  • the solution of the component (A) or the solution of the component (B) may be the reaction solution obtained when the component (A) or the component (B) is synthesized in an organic solvent,
  • the reaction solution may be diluted with an appropriate solvent.
  • (A) component and (B) component are obtained as a powder, this may be dissolved in an organic solvent to form a solution.
  • the organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the component (A) and the component (B) are uniformly dissolved.
  • Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like.
  • the liquid crystal aligning agent of the present invention contains, in addition to the above, other polymers other than the component (A) and the component (B) as the polymer component as long as the effects of the present invention are not impaired. May be.
  • other polymers include polyamic acid, polyamic acid ester, polyimide, and polyamide that do not use any of TDA, TDA diester, and TDA diester dichloride as raw materials.
  • the content (concentration) of the polymer component contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the liquid crystal alignment film (polyimide film) to be formed.
  • the content of the polymer component with respect to the organic solvent is preferably 0.5% by mass or more, and preferably 15% by mass or less, more preferably from the viewpoint of storage stability of the solution. 1 to 10% by mass.
  • a concentrated solution of the polymer component may be prepared in advance and diluted when the liquid crystal aligning agent is prepared from the concentrated solution.
  • the concentration of the concentrated solution of the polymer component is preferably 10 to 30% by mass, and more preferably 10 to 15% by mass.
  • the polymer component powder may be heated when the solution is prepared by dissolving the powder in an organic solvent.
  • the heating temperature is preferably 20 ° C to 150 ° C, particularly preferably 20 ° C to 80 ° C.
  • content of polymers other than (A) component and (B) component in a polymer component is 0. It is 5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.
  • liquid crystal aligning agent of the present invention may contain components other than the polymer component. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
  • solvents that improve film thickness uniformity and surface smoothness include the following.
  • These poor solvents may be used alone or in combination.
  • the above solvent it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • F-top EF301, EF303, EF352 manufactured by Tochem Products
  • MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
  • Florard FC430, FC431 manufactured by Sumitomo 3M
  • Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.
  • Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • the following phenoplast type additives may be introduced into the liquid crystal aligning agent for the purpose of further preventing deterioration of electrical characteristics due to the backlight.
  • Specific phenoplast additives are shown below, but are not limited to this structure.
  • the amount used 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.
  • the amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the liquid crystal orientation may be deteriorated.
  • the liquid crystal aligning agent of the present invention has a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired.
  • a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
  • the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation or the like, or without alignment treatment in vertical alignment applications.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
  • a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed from the viewpoint of simplifying the process.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose. In this invention, it is estimated that it is isolate
  • the baking after applying the liquid crystal aligning agent on the substrate can be carried out by heating means such as a hot plate at 50 to 300 ° C., preferably 80 to 250 ° C., and the solvent can be evaporated to form a coating film. If the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. The thickness is preferably 10 to 100 nm.
  • the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal alignment film thus obtained is presumed to be separated into two layers, a layer derived from the component (A) and a layer derived from the component (B).
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then producing a liquid crystal cell by a known method.
  • the two substrates disposed so as to face each other, the liquid crystal layer provided between the substrates, and the liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer.
  • a liquid crystal display device comprising a liquid crystal cell having a liquid crystal alignment film.
  • a liquid crystal display device of the present invention a twisted nematic (TN) method, a vertical alignment (VA) method, a horizontal alignment (IPS) method, an OCB alignment (OCB: There are various types such as Optically (Compensated Bend).
  • a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside
  • Examples include a method of bonding substrates and injecting liquid crystal under reduced pressure, or a method of sealing by bonding a substrate after dropping the liquid crystal on the liquid crystal alignment film surface on which spacers are dispersed.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • liquid crystal examples include a positive liquid crystal having a positive dielectric anisotropy and a negative liquid crystal having a negative dielectric anisotropy.
  • a positive liquid crystal having a positive dielectric anisotropy examples include MLC-2003, MLC-6608, MLC-6609 manufactured by Merck & Co., Inc. Etc. can be used.
  • the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has a high voltage holding ratio while maintaining the rubbing resistance, which has been a conventionally required characteristic, and is modern. As the strict requirements are satisfied, the charge accumulation becomes very small, and it can be suitably used for, for example, a mobile phone or a tablet terminal.
  • DBA 3,5-diaminobenzoic acid
  • p-PDA p-phenylenediamine
  • DDM 4,4′-diaminodiphenylmethane
  • BAPU 1,3-bis (4-aminophenethyl) urea
  • APC16 1,3-diamino-4- Hexadecyloxybenzene
  • APC18 1,3-diamino-4-octadecyloxybenzene
  • DADPA 4,4′-diaminodiphenylamine
  • DA-5MG 1,5-bis (4-aminophenoxy) pentane
  • LS-2450 3-aminopropyldiethoxymethylsilane
  • LS-3150 3-aminopropyltriethoxysilane
  • TM-BIP 2,2′-bis [4-hydroxy-3,5-bis (hydroxymethyl) phenyl] propane LS-2450 and LS-3150 are trade names of Shin-Etsu Chemical Co., Ltd.
  • GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 mL / L) Flow rate: 1.0 mL / standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30000) manufactured by Tosoh Corporation, and polyethylene glycol (peak top molecular weight manufactured by Polymer Laboratories) (Mp) about 12000, 4000, 1000). In order to avoid the overlapping of peaks, the measurement was performed separately on two samples: a sample in which 4 types of
  • the imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube, and 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixed product) was added and completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNM-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of polyamic acid appearing in the vicinity of 9.5 to 10.0 ppm.
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is the proton peak integrated value derived from the NH group of the polyamic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is one NH group proton of the polyamic acid in the case of the polyamic acid (imidation rate is 0%).
  • a liquid crystal aligning agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 60 seconds, and then fired in a nitrogen atmosphere using a 220 ° C. IR (infrared) oven for 20 minutes.
  • a coating film having a thickness of 100 nm was formed.
  • This coating surface was rubbed with a cotton cloth (YA-25C, manufactured by Yoshikawa) using a rubbing machine with a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.4 mm, and liquid crystal alignment A substrate with a film was obtained.
  • VHR voltage holding ratio
  • Each composition [AL-1] to [AL-10] was filtered through a 0.2 ⁇ m filter, and then applied by spin coating on a glass substrate with an ITO transparent electrode, and placed on a hot plate at 80 ° C. for 1 minute. After drying, baking was performed at 220 ° C. for 20 minutes to form a film having a thickness of 220 nm.
  • Aluminum is deposited on the surface of the coating film by a vacuum deposition method through a mask at a vacuum degree of 1.0 ⁇ 10 ⁇ 3 Pa and a deposition rate of 1 nm / s to form a 1.0 mm ⁇ upper electrode and measure volume resistivity.
  • a sample was prepared.
  • a voltage of 10 V is applied between the ITO electrode and the aluminum electrode of this sample, the current value 180 seconds after the voltage application is measured, and the volume resistivity is calculated from this value and the measured values of the electrode area and film thickness. did.
  • the resistance value was measured under the condition that an LED backlight was installed under the sample substrate.
  • the apparatus used for the measurement was a 6517A ELECTROMETER manufactured by KEITHLEY, and measurement was performed in a nitrogen atmosphere using a shield box SM-1 with a positioner manufactured by MEASURE Jig. The results are shown in Table 4.
  • the RDC was estimated by comparing with a calibration curve prepared in advance. This RDC estimation method is called a flicker reference method. Moreover, when RDC is small, it can be said that charge accumulation is small. The results are shown in Table 3. ⁇ : Less than 0.05 ⁇ : 0.05 or more and less than 0.08 ⁇ : 0.08 or more and less than 0.20 ⁇ : 0.20 or more
  • the resulting polyamic acid [PAA-3] had a number average molecular weight of 11,000 and a weight average molecular weight of 41,000.
  • the polymer was slowly poured into 580 g of methanol to precipitate the polymer, stirred for 30 minutes, and then the solid was collected by filtration. The obtained solid was sufficiently washed with methanol and then vacuum-dried at 100 ° C. to obtain a polyimide powder.
  • the imidation ratio of the obtained polyimide [SPI-2] was 82%.
  • Synthesis Example 12 Preparation of polyimide [SPI-3: TDA (100) / p-PDA (90) APC16 (10)]
  • a solution of polyamic acid [PAA-7] obtained in Synthesis Example 11 was added to a 100 ml Erlenmeyer flask equipped with a stirrer. 20.00 g, NMP 30.67 g, acetic anhydride 7.18 g, and pyridine 3.33 g were added, and the mixture was stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours for reaction.
  • the polymer was slowly poured into 214 g of methanol to precipitate a polymer, stirred for 30 minutes, and then a solid was collected by filtration. The obtained solid was sufficiently washed with methanol and then vacuum dried at 100 ° C. to obtain a polyimide powder.
  • the imidation ratio of the obtained polyimide [SPI-3] was 88%.
  • the polymer was slowly poured into 250 g of methanol to precipitate a polymer, stirred for 30 minutes, and then a solid was collected by filtration. The obtained solid was sufficiently washed with methanol and then vacuum dried at 100 ° C. to obtain a polyimide powder.
  • the imidation ratio of the obtained polyimide [SPI-4] was 88%.
  • GBL 97.2 g, BCS 48.6 g, and LS-3150 0.15 g were added to the obtained 15% by mass polyamic acid [PAA-9] solution, and the mixture was stirred at room temperature for 2 hours.
  • a composition [AL-7] containing 0% by mass, 59% by mass of GBL, 20% by mass of NMP and 15% by mass of BCS was obtained.
  • GBL 97.2 g, BCS 48.6 g, and LS-3150 0.15 g were added to the resulting polyamic acid [PAA-10] solution, and the mixture was stirred at room temperature for 2 hours.
  • the solid content concentration was 6.0% by mass
  • a composition [AL-8] having 59% by mass of GBL, 20% by mass of NMP and 15% by mass of BCS was obtained.
  • Comparative Example 2 using a polymer not using TDA as a raw material Comparative Examples 1 and 3 using a polymer in which the diamine component of the raw material also contains a diamine having no —CR 21 2 — in the main chain as component (B) 4 and 4 and Comparative Example 5 in which the diamine having the side chain represented by the formula (1) was not used as the component (A), the RDC was remarkably larger than those in Examples 1 to 8.
  • compositions [AL-7] to [AL-10] using a polymer including a diamine having no —CR 21 2 — in the main chain have a low volume resistivity.
  • Comparative Examples 1 and 3 to 5 using [AL-7] to [AL-10] as the component (B) it is presumed that RDC was large.

Landscapes

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

Abstract

La présente invention concerne un agent d'alignement de cristaux liquides contenant le composant (A) et le composant (B) ci-dessous, ledit agent d'alignement de cristaux liquides étant au moins un type de polymère choisi parmi des polyimides et des précurseurs de polyimide obtenus par une réaction de polymérisation entre un composant acide tétracarboxylique et un composant diamine. Composant (A) : un polymère contenant au moins un type de composant acide tétracarboxylique choisi parmi le dianhydride de 3,4-dicarboxy-1,2,3,4-tétrahydro-1-naphtalène succinique ou similaire, et un composant diamine ayant une chaîne latérale représentée par la formule (1). (Dans la formule (1) : P1 représente une liaison simple ou similaire ; Q1, Q2 et Q3 représentent chacun un noyau benzène divalent ou similaire ; p, q et r représentent 0 ou 1 ; et P2 représente un atome d'hydrogène ou similaire). Composant (B) : un polymère comprenant seulement le composant acide tétracarboxylique mentionné ci-dessus et un composant diamine ayant un groupe -CR21 2- (ici, chacun des deux R21 représente un atome d'hydrogène ou similaire) dans la chaîne principale.
PCT/JP2013/083388 2012-12-13 2013-12-12 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2014092170A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201380072402.6A CN104969123B (zh) 2012-12-13 2013-12-12 液晶取向剂、液晶取向膜和液晶显示元件
KR1020157018331A KR102222790B1 (ko) 2012-12-13 2013-12-12 액정 배향제, 액정 배향막 및 액정 표시 소자
JP2014552096A JPWO2014092170A1 (ja) 2012-12-13 2013-12-12 液晶配向剤、液晶配向膜及び液晶表示素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012272551 2012-12-13
JP2012-272551 2012-12-13

Publications (1)

Publication Number Publication Date
WO2014092170A1 true WO2014092170A1 (fr) 2014-06-19

Family

ID=50934452

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/083388 WO2014092170A1 (fr) 2012-12-13 2013-12-12 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

Country Status (5)

Country Link
JP (1) JPWO2014092170A1 (fr)
KR (1) KR102222790B1 (fr)
CN (1) CN104969123B (fr)
TW (1) TWI596201B (fr)
WO (1) WO2014092170A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018066607A1 (fr) * 2016-10-06 2018-04-12 日産化学工業株式会社 Diamine, polymère, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7089229B2 (ja) * 2016-09-29 2022-06-22 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
KR102117392B1 (ko) 2019-06-17 2020-06-03 한경건설(주) 흙막이 벽체 시공방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009185283A (ja) * 2008-02-01 2009-08-20 Daxin Material Corp 液晶配向溶液
JP2010250307A (ja) * 2009-03-31 2010-11-04 Daxin Material Corp 液晶配向溶液
US20120289633A1 (en) * 2011-05-13 2012-11-15 Chi Mei Corporation Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display element formed from the liquid crystal alignment agent

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010024326A (ko) * 1998-07-29 2001-03-26 고토 기치 신규한 디아미노 화합물, 폴리암산, 폴리이미드, 당해폴리이미드 막으로부터 제조된 액정 배향막 및 당해배향막을 함유하는 액정 표시소자
WO2000061684A1 (fr) * 1999-04-09 2000-10-19 Chisso Corporation Composition de vernis et element d'affichage a cristaux liquides
TW556029B (en) 2000-10-16 2003-10-01 Nissan Chemical Ind Ltd Aligning agent for liquid crystal for in-plane switching, liquid-crystal alignment film, and liquid-crystal display element
AU2003289307A1 (en) 2002-12-11 2004-06-30 Nissan Chemical Industries, Ltd. Liquid crystl orientating agent and liquid crystal display element using it
KR100851787B1 (ko) * 2007-04-11 2008-08-13 제일모직주식회사 3,4-디카르복시-1,2,3,4-테트라하이드로-6-터셔리부틸-1-나프탈렌숙신산이무수물 및 그를 이용하여 제조한 폴리이미드중합체를 포함하는 액정 배향제
JP5663876B2 (ja) * 2008-01-25 2015-02-04 日産化学工業株式会社 液晶配向処理剤、及びそれを用いた液晶表示素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009185283A (ja) * 2008-02-01 2009-08-20 Daxin Material Corp 液晶配向溶液
JP2010250307A (ja) * 2009-03-31 2010-11-04 Daxin Material Corp 液晶配向溶液
US20120289633A1 (en) * 2011-05-13 2012-11-15 Chi Mei Corporation Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display element formed from the liquid crystal alignment agent

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018066607A1 (fr) * 2016-10-06 2018-04-12 日産化学工業株式会社 Diamine, polymère, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
CN110049971A (zh) * 2016-10-06 2019-07-23 日产化学株式会社 二胺、聚合物、液晶取向剂、液晶取向膜及液晶表示元件
JPWO2018066607A1 (ja) * 2016-10-06 2019-08-08 日産化学株式会社 ジアミン、重合体、液晶配向剤、液晶配向膜及び液晶表示素子
CN110049971B (zh) * 2016-10-06 2023-01-13 日产化学株式会社 二胺、聚合物、液晶取向剂、液晶取向膜及液晶表示元件

Also Published As

Publication number Publication date
TW201439288A (zh) 2014-10-16
TWI596201B (zh) 2017-08-21
CN104969123B (zh) 2019-03-15
JPWO2014092170A1 (ja) 2017-01-12
CN104969123A (zh) 2015-10-07
KR102222790B1 (ko) 2021-03-03
KR20150094711A (ko) 2015-08-19

Similar Documents

Publication Publication Date Title
JP6070958B2 (ja) 新規ジアミン、重合体、液晶配向剤、液晶配向膜、及びそれを用いた液晶表示素子
JP6593603B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP6447815B2 (ja) 新規ジアミン、重合体、液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子
JP6249182B2 (ja) ポリイミド前駆体、ポリイミド、液晶配向剤、液晶配向膜及び液晶表示素子
JP5831712B2 (ja) ポリイミド膜形成用塗布液、液晶配向剤、ポリイミド膜、液晶配向膜及び液晶表示素子
JP6083388B2 (ja) 液晶配向剤の製造方法
JP6314827B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
WO2015152174A1 (fr) Agent d'alignement de cristaux liquides contenant un copolymère ester d'acide polyamique - acide polyamique, et film d'alignement de cristaux liquides utilisant l'agent d'alignement de cristaux liquides contenant un copolymère ester d'acide polyamique - acide polyamique
JP5900328B2 (ja) 液晶配向剤、それを用いた液晶配向膜及び液晶表示素子
WO2017111117A1 (fr) Agent et film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JP6217937B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
WO2018043326A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JPWO2018043325A1 (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
KR102222790B1 (ko) 액정 배향제, 액정 배향막 및 액정 표시 소자
WO2012161329A1 (fr) Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

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: 13862326

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014552096

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: 20157018331

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 13862326

Country of ref document: EP

Kind code of ref document: A1