WO2018186055A1 - 液晶配向剤、液晶配向膜及びその製造方法、液晶素子、重合体、並びに化合物 - Google Patents

液晶配向剤、液晶配向膜及びその製造方法、液晶素子、重合体、並びに化合物 Download PDF

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WO2018186055A1
WO2018186055A1 PCT/JP2018/007185 JP2018007185W WO2018186055A1 WO 2018186055 A1 WO2018186055 A1 WO 2018186055A1 JP 2018007185 W JP2018007185 W JP 2018007185W WO 2018186055 A1 WO2018186055 A1 WO 2018186055A1
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liquid crystal
formula
group
ring
organic group
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PCT/JP2018/007185
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English (en)
French (fr)
Japanese (ja)
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拓也 村上
伸夫 安池
遼 須原
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Jsr株式会社
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Priority to CN201880015630.2A priority Critical patent/CN110383156B/zh
Priority to JP2019511094A priority patent/JP7028241B2/ja
Priority to KR1020197023941A priority patent/KR102269265B1/ko
Publication of WO2018186055A1 publication Critical patent/WO2018186055A1/ja

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    • 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

Definitions

  • the present disclosure relates to a liquid crystal aligning agent, a liquid crystal aligning film and a manufacturing method thereof, a liquid crystal element, a polymer, and a compound.
  • Liquid crystal elements are widely used in TVs, mobile devices, various monitors, and so on.
  • a liquid crystal alignment film is used to control the alignment of liquid crystal molecules in the liquid crystal cell.
  • Conventional methods for obtaining an organic film having a liquid crystal alignment regulating force include a method of rubbing an organic film, a method of obliquely depositing silicon oxide, a method of forming a monomolecular film having a long chain alkyl group, and a photosensitive organic film.
  • a method of irradiating a film with light photo-alignment method
  • Patent Document 1 discloses forming a liquid crystal alignment film by irradiating a film obtained by applying and baking a liquid crystal aligning agent containing a polyamic acid having a cyclobutane ring structure in the main chain on a substrate and baking it. Has been.
  • the alignment regulating force of liquid crystal molecules is not sufficient as compared with a rubbing process, and image sticking called an AC afterimage tends to occur.
  • the AC afterimage is an afterimage that is generated due to the initial alignment direction deviating from the original direction of the liquid crystal device due to the liquid crystal device being driven for a long time.
  • improving the degree of alignment of the liquid crystal alignment film is one effective means.
  • As a liquid crystal element it is desired that the AC afterimage is sufficiently reduced in order to satisfy the recent demand for higher performance.
  • liquid crystal elements have been applied to a wide range of devices and applications from large-screen liquid crystal televisions to small display devices such as smartphones and tablet PCs. With such versatility, liquid crystal elements are placed or installed in places where they can be hot, such as in the car or outdoors, or they can be driven for a longer time than before, and are used under more severe temperature conditions. It is assumed that Therefore, the liquid crystal element is required to have high reliability with respect to heat resistance.
  • a liquid crystal alignment film is obtained by photo-alignment treatment using a liquid crystal aligning agent containing a polyimide polymer having a cyclobutane ring structure in the main chain, it can be obtained due to decomposition products generated by light irradiation on the coating film.
  • a liquid crystal element is exposed to a high temperature environment for a long time, a fine bright spot is likely to be generated, and there is a concern that the heat resistance (particularly long-term heat resistance) is inferior in reliability.
  • the present disclosure has been made in view of the above circumstances, and provides a liquid crystal aligning agent capable of obtaining a liquid crystal element excellent in AC afterimage characteristics and long-term heat resistance when a liquid crystal alignment film is obtained by a photo-alignment method.
  • a liquid crystal aligning agent capable of obtaining a liquid crystal element excellent in AC afterimage characteristics and long-term heat resistance when a liquid crystal alignment film is obtained by a photo-alignment method.
  • This disclosure employs the following means in order to solve the above problems.
  • X 1 is a tetravalent organic group having a cyclobutane ring structure
  • X 2 having at least one substituent in the ring portion of the cyclobutane ring, the following formula (4) or a divalent organic group represented by the following formula (5):
  • R 5 and R 6 are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.
  • a 1 and A 2 are divalent aromatic ring groups, which may have a substituent in the ring portion. However, A 1 and A 2 are the same. Y 1 and Y 2 are each independently a single bond, an oxygen atom, a sulfur atom, or “—NR 7 —” (R 7 is a hydrogen atom or a monovalent organic group). However, Y 1 and Y 2 are different from each other, B 1 is a divalent heterocyclic group represented by the following formula (7) or formula (8), Y 3 is an oxygen atom or “ ⁇ NR 9 — ”(R 9 is a hydrogen atom or a monovalent organic group).
  • Z 1 has 1 to 15 carbon atoms having at least one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure. a divalent organic group
  • Z 2 is a single bond, or a linear C 1 - having at least one hydrocarbon structures and alicyclic hydrocarbon structure 5 is a divalent organic group.
  • the carbon number of Z 1 is 2 or more.
  • “*” Indicates a bond.)
  • R 8 is a substituent
  • r is an integer of 0 to 3
  • m is an integer of 0 to (r + 2)
  • “*” represents a bond.
  • ⁇ 2> A liquid crystal alignment film formed using the liquid crystal aligning agent of ⁇ 1> above.
  • ⁇ 3> A method for producing a liquid crystal alignment film, comprising a photo-alignment step of forming a coating film using the liquid crystal aligning agent of ⁇ 1> and applying a light irradiation treatment to the coating film to impart liquid crystal alignment ability.
  • ⁇ 4> A liquid crystal element comprising the liquid crystal alignment film of ⁇ 2> above.
  • ⁇ 5> A polymer having at least one selected from the group consisting of a partial structure represented by the above formula (1) and a partial structure represented by the above formula (2).
  • ⁇ 6> A compound represented by the following formula (16).
  • a 3 and A 4 are divalent groups in which two hydrogen atoms have been removed from the ring part of the benzene ring, pyridine ring or pyrimidine ring, and have a substituent in the ring part.
  • R 13 is a hydrogen atom or a monovalent organic group
  • Y 8 is an oxygen atom or a sulfur atom
  • n is 1-5. (It is an integer.)
  • liquid crystal aligning agent of the present disclosure when a liquid crystal alignment film is obtained by a photo-alignment method, a liquid crystal element having excellent long-term heat resistance and reduced AC afterimage can be obtained.
  • FIG. 1 is a 1 H-NMR spectrum of diamine (DA-1).
  • FIG. 2 is a 1 H-NMR spectrum of diamine (DA-4).
  • FIG. 3 is a 1 H-NMR spectrum of diamine (DA-10).
  • the liquid crystal aligning agent of this indication contains the polymer (P) which has at least 1 type chosen from the group which consists of the partial structure represented by the said Formula (1), and the partial structure represented by the said Formula (2).
  • X 1 is a tetravalent organic group having a cyclobutane ring structure, and has at least one substituent in the ring portion of the cyclobutane ring.
  • substituents that the cyclobutane ring has include a halogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, an alkenyl group, and an alkynyl group.
  • the number of substituents is not particularly limited, but 1 to 4 is preferable.
  • X 1 is preferably a group represented by the following formula (3).
  • R 1 to R 3 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • the above formula (1) is represented by the following formula (1-A) or (1-B)
  • the above formula (2) is represented by the following formula (2-A).
  • X 2 , R 5 and R 6 are each synonymous with X 2, R 5 and R 6 in the formula (1) .
  • R 1 ⁇ R 4 has the same meaning as R 1 to R 4 in the above formula (3).
  • X 2 is .R 1 ⁇ R 4 are the same meaning as X 2 in the formula (1) are synonymous with R 1 ⁇ R 4 in each of the above formula (3) is there.
  • X 2 in the above formulas (1) and (2) is a divalent organic group represented by the above formula (4) or formula (5).
  • a 1 and A 2 are groups in which two hydrogen atoms have been removed from the ring portion of the aromatic ring, and the ring portion may have a substituent.
  • the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring and biphenyl ring; nitrogen-containing heterocycles such as pyridine ring, pyrazine ring, pyrimidine ring and pyridazine ring.
  • the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms.
  • a 1 and A 2 are identical, the monomer used in obtaining the polymer (P) can be easily synthesized, but has a high effect of reducing AC afterimage and improving long-term heat resistance. This is preferable.
  • a 1 and A 2 are benzene rings, biphenyl rings, pyridine rings or pyrimidines which may have a substituent among them because a liquid crystal element excellent in liquid crystal alignment and AC afterimage characteristics can be obtained.
  • a group obtained by removing two hydrogen atoms from the ring portion of the ring is preferable.
  • Y 1 and Y 2 in the formula (4) are each independently a single bond, an oxygen atom, a sulfur atom, or “—NR 7 —” (R 7 is a hydrogen atom or a monovalent organic group. .)
  • R 7 is a hydrogen atom or a monovalent organic group. .
  • Y 1 and Y 2 are different from each other. Among these, the sensitivity of the polymer (P) to light can be enhanced, and the effect of improving the liquid crystal orientation and AC afterimage characteristics of the obtained liquid crystal element is higher.
  • X 2 in the above formula (1) has an asymmetric structure, so that the solubility of the polymer can be improved and the crystallinity of the photodegradation product is lowered. Therefore, it is considered that the generation of minute bright spots can be reduced.
  • the monovalent organic group for R 7 include an alkyl group having 1 to 6 carbon atoms and a protecting group.
  • the protecting group is preferably a group capable of leaving by heat, and examples thereof include a carbamate protecting group, an amide protecting group, an imide protecting group, and a sulfonamide protecting group.
  • R 7 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a protecting group. From the viewpoint that generation of fine luminescent spots can be further reduced and transparency of the liquid crystal alignment film can be increased, R 7 has 1 to 3 carbon atoms.
  • the alkyl group is more preferable.
  • Y 3 in the above formula (5) is an oxygen atom or “—NR 9 —”. For the specific examples and preferred examples of R 9 , the description of R 7 in “—NR 7 —” described above applies.
  • Z 1 is a divalent organic group having 1 to 15 carbon atoms having at least one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure
  • Z 2 is a single bond or a chain hydrocarbon structure and A divalent organic group having 1 to 15 carbon atoms and having at least one of alicyclic hydrocarbon structures.
  • the carbon number of Z 1 is an integer of 2 to 15.
  • the “chain hydrocarbon structure” means a linear hydrocarbon structure and a branched hydrocarbon structure composed of only a chain structure without including a cyclic structure.
  • the chain hydrocarbon structure may be saturated or unsaturated.
  • the “alicyclic hydrocarbon structure” means a hydrocarbon structure that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, the alicyclic hydrocarbon structure does not need to be constituted only by the structure of the alicyclic hydrocarbon, and includes a part having a chain structure.
  • Z 1 represents a divalent chain hydrocarbon group or a carbon-carbon bond between the chain hydrocarbon group, an oxygen atom, a sulfur atom or “—NR 12 —” (R 12 represents a hydrogen atom or a monovalent organic group). It is preferably a group having a group.
  • Z 2 may be a single bond, a divalent chain hydrocarbon group, or a group having an oxygen atom, a sulfur atom or “—NR 12 —” between carbon-carbon bonds of the chain hydrocarbon group. preferable.
  • the divalent organic group of Z 1 and Z 2 is preferably a divalent organic group represented by the following formula (6) from the viewpoint that the generation of fine bright spots caused by the photodecomposed product can be further reduced.
  • R 10 and R 11 are each independently an alkanediyl group, and the total carbon number of R 10 and R 11 is 1 to 15.
  • Y 4 represents an oxygen atom, a sulfur atom Or “—NR 12 —” (R 12 is a hydrogen atom or a monovalent organic group.)
  • P is an integer of 0 to 4.
  • a plurality of R 10 , Y 4 may be the same as or different from each other, provided that when one of Y 1 and Y 2 in the formula (4) is a sulfur atom and the other is a single bond, R 10 and R 11 The total number of carbon atoms is 2 or more.
  • R 10 and R 11 may be linear or branched, but are preferably linear in that the effect of suppressing the formation of fine luminescent spots in the liquid crystal element can be enhanced.
  • the group represented by the above formula (6) (that is, Z 1 and Z 2 ) is an alkanediyl group or an oxygen atom, a sulfur atom, or a carbon-carbon bond of the alkanediyl group.
  • a group having “—NR 8 —” is preferable, and an alkanediyl group or a group having an oxygen atom between carbon-carbon bonds of the alkanediyl group is more preferable, and an alkanediyl group is preferable. Further preferred.
  • the description of R 7 in “—NR 7 —” described above applies to specific examples and preferred examples of R 12 .
  • p is preferably 0-2.
  • the total number of carbon atoms of R 10 and R 11 (when p is 2 or more, a plurality of R 10 And the total number of carbon atoms of R 11 ) is that the number of carbon atoms is 2 or more in terms of accelerating realignment of molecular chains by heating in the production of a liquid crystal alignment film and reducing the occurrence of minute bright spots in a liquid crystal element.
  • it has 3 or more carbon atoms.
  • Y 4 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
  • Z 2 in the above formula (5) is a divalent group represented by the above formula (6)
  • Z 2 is preferably a single bond or a methylene group.
  • B 1 in the above formula (5) is a nitrogen-containing heterocyclic group represented by the above formula (7) or formula (8).
  • substituent for R 8 include an alkyl group having 1 to 6 carbon atoms.
  • r is preferably 1 or 2, and more preferably 2.
  • B 1 is a substituted or unsubstituted piperidine-1,4-diyl group, or a substituted or unsubstituted piperazine-1,4-diyl group. From the viewpoint of liquid crystal alignment and AC afterimage characteristics The substituted or unsubstituted piperidine-1,4-diyl group is particularly preferable.
  • the above formula (4) is particularly preferably a group represented by the following formula (4A) in that the effect of improving liquid crystal orientation, AC afterimage characteristics and long-term heat resistance is high.
  • a 3 and A 4 are divalent groups obtained by removing two hydrogen atoms from the ring part of the benzene ring, pyridine ring or pyrimidine ring, and have a substituent in the ring part.
  • Y 5 and Y 6 each independently represent a single bond, an oxygen atom, a sulfur atom, or “—NR 13 —” (R 13 is A hydrogen atom or a monovalent organic group, provided that Y 5 and Y 6 are different from each other, n is an integer of 1 to 5, provided that one of Y 5 and Y 6 is a sulfur atom. When the other is a single bond, n is 2 or more. “*” Indicates a bond.)
  • Examples of the substituent that A 3 and A 4 may have include an alkyl group having 1 to 6 carbon atoms.
  • R 13 With respect to specific examples and preferred examples of the monovalent organic group of R 13 , the description of R 7 described above is applied.
  • Y 5 and Y 6 of the group represented by the above formula (4A) are a single bond, an oxygen atom or a sulfur atom (however, Y 5 and Y 6 are different from each other), they are highly sensitive to light. However, it is preferable in that the yield can be increased in the synthesis of the polyamic acid ester.
  • X 2 is represented by the following formula (4C).
  • one of Y 51 and Y 61 is an oxygen atom and the other is a single bond.
  • Y 51 and Y 61 are each independently a single bond, an oxygen atom, or a sulfur atom, provided that Y 51 and Y 61 are different from each other, n is an integer of 1 to 5)
  • n is 2 or more
  • a 3 and A 4 have the same meanings as in the above formula (4A).
  • the bonding site on the benzene ring, pyridine ring or pyrimidine ring of A 3 and A 4 in Y 5 and Y 6 in the above formula (4A) is the above formula (1). and is preferably para to the nitrogen atom attached to X 2 in the formula (2).
  • the group represented by the above formula (4A) is particularly preferably a group represented by the following formula (4A-1).
  • Q 1 and Q 2 are each independently “CH” or a nitrogen atom.
  • R 13 , Y 5 , Y 6 and n have the same meanings as in Formula (4A) above). “*” Indicates a bond.
  • the above formula (5) is preferably a divalent organic group represented by the following formula (5A).
  • K in the formula (5) is preferably 0 to 3, more preferably 0 or 1.
  • a 5 and A 6 are divalent groups in which two hydrogen atoms have been removed from the ring part of the benzene ring, pyridine ring or pyrimidine ring, and have a substituent in the ring part.
  • B 2 is a substituted or unsubstituted piperidine-1,4-diyl group, or a substituted or unsubstituted piperazine-1,4-diyl group.
  • Y 7 is an oxygen atom or “—NR 9 —” (R 9 is a hydrogen atom or a monovalent organic group), k is an integer of 0 to 5. “*” is a bond Showing hand.)
  • the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.
  • the polymer (P) has a partial structure derived from a tetracarboxylic acid derivative having a cyclobutane ring structure having at least one substituent in the ring portion, and a divalent compound represented by the above formula (4) or formula (5). And a partial structure derived from a diamine compound having an organic group.
  • the synthesis method of such a polymer (P) is not particularly limited, and can be obtained by appropriately combining organic chemistry methods.
  • tetracarboxylic acid derivative is meant to include tetracarboxylic dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide.
  • polyamic acid When the polymer (P) is a polyamic acid, the polyamic acid (hereinafter also referred to as “polyamic acid (P)”) is, for example, a tetrabutane having a cyclobutane ring structure having at least one substituent in the ring portion.
  • a tetracarboxylic dianhydride including a carboxylic dianhydride hereinafter also referred to as “specific acid dianhydride”
  • specific acid dianhydride a divalent organic group represented by the above formula (4) or formula (5). It can be obtained by reacting a diamine compound containing a diamine compound (hereinafter also referred to as “specific diamine”).
  • Specific acid dianhydrides include tetracarboxylic dianhydrides having a partial structure represented by the above formula (3).
  • Specific examples of the specific acid dianhydride include compounds represented by the following formulas (TA-1-1) to (TA-1-15).
  • the specific acid dianhydride is preferably a compound represented by any of the above formulas (TA-1-1) to (TA-1-12), and 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride (a compound represented by the above formula (TA-1-2)) is particularly preferred.
  • specific acid dianhydride can be used individually by 1 type or in combination of 2 or more types.
  • tetracarboxylic dianhydrides other than the specific acid dianhydride may be used as the tetracarboxylic dianhydride together with the specific acid dianhydride.
  • Other tetracarboxylic dianhydrides are not particularly limited as long as they do not have a cyclobutane ring structure having at least one substituent in the ring portion.
  • Specific examples of other tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides such as ethylenediaminetetraacetic acid dianhydride;
  • Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-di Oxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8 -Methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3- Cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride,
  • tetracarboxylic dianhydrides include ethylenediaminetetraacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, among them, in terms of increasing the effect of reducing the fine bright spot. , 2,3,5-tricarboxycyclopentylacetic dianhydride, pyromellitic dianhydride and at least one selected from the group consisting of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride It can be preferably used as a component.
  • combination of a polymer (P), as another tetracarboxylic dianhydride 1 type can be used individually or in combination of 2 or more types.
  • the use ratio of the specific acid dianhydride is 30 mol% with respect to the total amount of tetracarboxylic dianhydrides used for the synthesis from the viewpoint of sufficiently obtaining the effects of the present disclosure.
  • the above is preferable. More preferably, it is 50 mol% or more, More preferably, it is 80 mol% or more.
  • the proportions used are preferably 5 to 70 mol% with respect to the total amount of tetracarboxylic dianhydrides used in the synthesis, and 10 to 50 mol. % Is more preferable.
  • the specific diamine is a compound represented by the following formula (14) or the following formula (15).
  • a 1, A 2, B 1, Y 1, Y 2, Y 3, Z 1 and Z 1 are the above formula (4), with defined for formula (5) is there.
  • the compound represented by the above formula (14) is preferably a compound represented by the following formula (4B), and the compound represented by the above formula (15) is represented by the following formula (5B). It is preferable that it is a compound represented.
  • the primary amino group in the above formula (4B) and formula (5B) is relative to other groups bonded to the ring of A 3 , A 4 , A 5 and A 6 (benzene ring, pyridine ring or pyrimidine ring).
  • the para position is preferred.
  • Specific examples and preferred examples of A 3 , A 4 , Y 5 , Y 6 and n in the above formula (4B) and A 5 , A 6 , B 2 , Y 7 and k in the above formula (5B) The above description applies.
  • specific diamine examples include, for example, compounds represented by the following formulas (d-1) to (d-54).
  • the specific diamine can be synthesized by appropriately combining organic chemistry methods.
  • a specific diamine may be used individually by 1 type, or may be used in combination of 2 or more type.
  • “Boc” in the following formula represents a tert-butoxycarbonyl group.
  • diamine compound In the synthesis of polyamic acid (P), only a specific diamine may be used as the diamine compound, but other diamines other than the specific diamine may be used together with the specific diamine.
  • Other diamines are not particularly limited as long as they do not correspond to specific diamines, and examples thereof include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes.
  • aliphatic diamines such as metaxylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine and the like
  • alicyclic diamines such as p-cyclohexanediamine, 4 , 4'-methylenebis (cyclohexylamine) and the like;
  • aromatic diamines examples include dodecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate, and diaminobenzoic acid.
  • R II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b are not 0 at the same time.
  • Side-chain diamines such as compounds represented by: Paraphenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-ethylenedianiline, 4,4′-diaminodiphenylamine, 4,4′-diaminodiphenyl sulfide, 4-aminophenyl-4′-aminobenzoate, 4 , 4′-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,2-bis (4-aminophenoxy) ethane, 1,5-bis (4-aminophenoxy) pentane, N, N′-di (4- Aminophenyl) -N
  • diamines used for the synthesis of the polyamic acid (P) include O, O′-di (4-aminophenyl) -ethylene glycol, and N, because they have a high effect of reducing the fine bright spots generated in the liquid crystal element.
  • N′-di (4-aminophenyl) -N, N′-dimethylethylenediamine is preferable, and a liquid crystal element having favorable liquid crystal alignment and AC afterimage characteristics can be obtained.
  • it preferably contains at least one selected from the group consisting of paraphenylenediamine, 1,4-bis (4-aminophenyl) -piperazine, and 2,2′-dimethyl-4,4′-diaminobiphenyl.
  • other diamines can be used alone or in combination of two or more.
  • the proportion of the specific diamine used is preferably 20 mol% or more based on the total amount of diamine compounds used in the synthesis of the polyamic acid (P) from the viewpoint of sufficiently obtaining the effects of the present disclosure. More preferably, it is 40 mol% or more, More preferably, it is 60 mol% or more. When other diamines are used, the proportions used are preferably 5 to 80 mol%, more preferably 10 to 60 mol%, based on the total amount of diamine compounds used in the synthesis.
  • the polyamic acid (P) is obtained by reacting the tetracarboxylic dianhydride and the diamine compound as described above with a molecular weight adjusting agent (for example, acid monoanhydride, monoamine compound, monoisocyanate compound, etc.) as necessary. Obtainable.
  • a molecular weight adjusting agent for example, acid monoanhydride, monoamine compound, monoisocyanate compound, etc.
  • the ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid (P) synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is equivalent to 1 equivalent of the amino group of the diamine compound. A ratio of 0.2 to 2 equivalents is preferred.
  • the synthesis reaction of polyamic acid (P) is preferably performed in an organic solvent.
  • the reaction temperature at this time is preferably ⁇ 20 ° C. to 150 ° C., and the reaction time is preferably 0.1 to 24 hours.
  • the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like.
  • organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And one or more selected from the group consisting of halogenated phenols, or a mixture of one or more of these and another organic solvent (for example, butyl cellosolve, diethylene glycol diethyl ether, etc.).
  • the amount of the organic solvent used is preferably such that the total amount of tetracarboxylic dianhydride and diamine compound is 0.1 to 50% by mass relative to the total amount of the reaction solution.
  • the reaction solution obtained by dissolving the polyamic acid (P) may be used as it is for the preparation of the liquid crystal aligning agent, and the polyamic acid (P) contained in the reaction solution is isolated and then used for the preparation of the liquid crystal aligning agent. May be.
  • the polyamic acid ester as the polymer (P) has a structural unit in which at least one of R 5 and R 6 is a monovalent organic group having 1 to 6 carbon atoms in the partial structure represented by the above formula (1). It is a polymer having.
  • R 5 and R 6 include, for example, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, a cyclohexyl group, a phenyl group, and the like. Is mentioned.
  • the polyamic acid ester is, for example, [I] a method of reacting the polyamic acid (P) obtained above with an esterifying agent (for example, methanol, ethanol, N, N-dimethylformamide diethyl acetal, etc.), [II] A tetracarboxylic acid diester containing a tetracarboxylic acid diester having a partial structure represented by the above formula (3) and a diamine compound containing a specific diamine are preferably mixed in a suitable dehydration catalyst (for example, 4- (4 , 6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, phosphorus condensing agent, etc.], [III] the above formula (3 Tetracarboxylic acid diester dihalogen containing a tetracarboxylic acid diester dihalide having a partial structure represented by And a diamine compound containing a specific diamine, preferably in an
  • the tetracarboxylic acid diester used in the above [II] can be obtained by ring-opening a specific acid dianhydride or other tetracarboxylic acid dianhydride with an alcohol or the like.
  • the tetracarboxylic acid diester dihalide used in the above [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride.
  • the polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.
  • the solution may be used as it is for the preparation of the liquid crystal aligning agent.
  • the liquid crystal aligning agent is prepared. May be provided.
  • the polyimide as the polymer (P) is a polymer having a partial structure represented by the above formula (2).
  • the polyimide can be obtained, for example, by dehydrating and ring-closing and imidizing the polyamic acid (P) synthesized as described above.
  • the polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure of the polyamic acid (P) that is a precursor thereof, and only a part of the amic acid structure is dehydrated and cyclized.
  • a partially imidized product in which a structure and an imide ring structure coexist may be used.
  • the polyimide preferably has an imidation ratio of 40 to 100%, more preferably 60 to 90%.
  • This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage.
  • a part of the imide ring may be an isoimide ring.
  • the dehydration ring closure of the polyamic acid (P) is preferably carried out by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary.
  • a dehydrating agent for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used.
  • the amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the amic acid structure of the polyamic acid.
  • the dehydration ring closure catalyst for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used.
  • the amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used.
  • an organic solvent to be used the organic solvent illustrated as what is used for the synthesis
  • the reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., and the reaction time is preferably 1.0 to 120 hours.
  • the reaction solution containing the polyimide thus obtained may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after the polyimide is isolated.
  • a polyimide can also be obtained by imidation by the dehydration ring closure reaction of polyamic acid ester.
  • the solution viscosity of the polymer (P) preferably has a solution viscosity of 10 to 800 mPa ⁇ s, and a solution viscosity of 15 to 500 mPa ⁇ s when the solution is 10% by mass. It is more preferable.
  • the solution viscosity (mPa ⁇ s) is E for a polymer solution having a concentration of 10% by mass prepared using a good solvent for the polymer (P) (for example, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polymer (P) is preferably 1,000 to 500,000, more preferably 5,000 to 100,000. It is.
  • the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
  • the polymer (P) contained in a liquid crystal aligning agent may be only 1 type, or may combine 2 or more types.
  • the liquid crystal aligning agent of this indication may contain other components other than a polymer (P).
  • the other component include a polymer having neither the partial structure represented by the above formula (1) nor the partial structure represented by the above formula (2) (hereinafter referred to as “other polymer”). ), Compounds having at least one epoxy group in the molecule, functional silane compounds, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers, acid generators Agents, base generators, radical generators and the like. These compounding ratios can be appropriately selected according to each compound within a range not impairing the effects of the present disclosure.
  • the liquid crystal aligning agent is preferable in that it can enhance the effect of suppressing the formation of minute bright spots by containing other polymer.
  • the main skeleton of the other polymer is not particularly limited.
  • the other polymer is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide from the viewpoint that generation of fine bright spots can be suitably suppressed.
  • the blending ratio is preferably 1 to 90% by weight, more preferably 10 to 80% by weight, more preferably 20 to 20% by weight based on the total amount of the polymer in the liquid crystal aligning agent. 70 mass% is still more preferable.
  • the liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which the polymer (P) and components used as necessary are preferably dispersed or dissolved in an appropriate solvent.
  • the organic solvent used include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, ⁇ -butyrolactone, ⁇ -butyrolactam, and N, N-dimethylformamide.
  • the solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is in the range of 1 to 10% by mass. That is, the liquid crystal aligning agent is applied to the substrate surface as will be described later, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases and the applicability decreases. There is a tendency.
  • the content ratio of the polymer (P) in the liquid crystal aligning agent is preferably 10 parts by mass or more, more preferably 20 parts by mass with respect to a total of 100 parts by mass of the solid components (components other than the solvent) in the liquid crystal aligning agent. As mentioned above, More preferably, it is 30 mass parts or more.
  • the liquid crystal alignment film of the present disclosure is formed by the liquid crystal aligning agent prepared as described above.
  • the liquid crystal alignment film of the present disclosure can be manufactured by a method including a photo-alignment step of forming a coating film using the liquid crystal aligning agent and applying a light irradiation treatment to the coating film to impart liquid crystal alignment ability.
  • the liquid crystal element of this indication comprises the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above.
  • the operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and includes, for example, a TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type (VA-MVA type, VA-PVA type, etc.). It can be applied to various modes such as an IPS (In-Plane Switching) type, an FFS (Fringe Field Switching) type, and an OCB (Optically Compensated Bend) type.
  • the liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate to be used varies depending on the desired operation mode. Step 2 and step 3 are common to each operation mode.
  • a liquid crystal aligning agent is apply
  • the substrate for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used.
  • an NESA film registered trademark of PPG, USA
  • tin oxide SnO 2
  • ITO film indium oxide-tin oxide
  • a TN type, STN type, or VA type liquid crystal element two substrates provided with a patterned transparent conductive film are used.
  • an IPS type or FFS type liquid crystal element a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and a counter substrate provided with no electrode Is used.
  • the metal film for example, a film made of a metal such as chromium can be used.
  • Application of the liquid crystal aligning agent to the substrate is preferably performed on the electrode forming surface by an offset printing method, a flexographic printing method, a spin coating method, a roll coater method or an ink jet method.
  • preheating is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent.
  • the pre-bake temperature is preferably 30 to 200 ° C., and the pre-bake time is preferably 0.25 to 10 minutes.
  • a baking (post-baking) step is performed for the purpose of thermally imidizing the amic acid structure present in the polymer.
  • the firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C., and the post-bake time is preferably 5 to 200 minutes.
  • the thickness of the film thus formed is preferably 0.001 to 1 ⁇ m.
  • Step 2 Orientation treatment
  • a treatment for imparting liquid crystal alignment ability to the coating film formed in Step 1 is performed.
  • the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.
  • the alignment treatment a rubbing treatment in which a roll wound with a cloth is rubbed in a certain direction may be used.
  • the polymer (P) has high photosensitivity, and can develop anisotropy in the coating film even with a small exposure amount.
  • a photo-alignment treatment in which the coating film formed on the substrate is irradiated with light to impart liquid crystal alignment ability to the coating film can be preferably used.
  • the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment treatment.
  • the light irradiation in the photo-alignment treatment is a method of irradiating the coating film after the post-baking process, a method of irradiating the coating film after the pre-baking process and before the post-baking process, at least the pre-baking process and the post-baking process. In any case, it can be performed by a method of irradiating the coating film while the coating film is heated.
  • ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as radiation applied to the coating film, for example.
  • it is an ultraviolet ray containing light having a wavelength of 200 to 400 nm.
  • the radiation When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When non-polarized radiation is irradiated, the irradiation direction is an oblique direction.
  • a light source to be used for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.
  • the radiation dose is preferably 400 to 20,000 J / m 2 , more preferably 1,000 to 5,000 J / m 2 . You may perform light irradiation with respect to a coating film, heating a coating film, in order to improve the reactivity.
  • the liquid crystal alignment film may further include a contact step of bringing the coating film that has been subjected to the light irradiation treatment into contact with water, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent.
  • a contact step of bringing the coating film that has been subjected to the light irradiation treatment into contact with water, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent.
  • examples of the water-soluble organic solvent include methanol, ethanol, 1-propanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone.
  • the solvent used in the contacting step is preferably water, isopropanol, or a mixture thereof.
  • Examples of the contact method between the coating film and the solvent include, but are not limited to, spraying, showering, dipping, and liquid filling.
  • the contact time between the coating film and the solvent is not particularly limited, but is, for example, 5 seconds to 15 minutes.
  • a heating step of heating the coating film subjected to the light irradiation treatment within a temperature range of 120 ° C. or higher and 280 ° C. or lower before at least one of the contact step and after the contact step. May be further performed.
  • the heating temperature is preferably 140 ° C. or higher, and more preferably 150 ° C. to 250 ° C., from the viewpoint of promoting reorientation of molecular chains by heating.
  • the heating time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 60 minutes.
  • a method of sealing the injection hole after injecting and filling liquid crystal into the cell gap defined by bonding, the substrate surface and the sealing agent, and (2) sealing at a predetermined place on one substrate on which the liquid crystal alignment film is formed A method of applying an agent and dropping liquid crystal to a predetermined number of locations on the surface of the liquid crystal alignment film, and then bonding the other substrate so that the liquid crystal alignment film faces each other and spreading the liquid crystal over the entire surface of the substrate (ODF method) ) And the like.
  • the manufactured liquid crystal cell is preferably heated to a temperature at which the used liquid crystal takes an isotropic phase, and then slowly cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal.
  • an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
  • a photo spacer, a bead spacer, or the like can be used.
  • the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl.
  • Cyclohexane liquid crystals pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, for example, a cholesteric liquid crystal, a chiral agent, or a ferroelectric liquid crystal may be added to these liquid crystals.
  • a polarizing plate is bonded to the outer surface of the liquid crystal cell as necessary.
  • the polarizing plate include a polarizing plate comprising a polarizing film called an “H film” in which iodine is absorbed while stretching and orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself. Thereby, a liquid crystal element is obtained.
  • the reason why the liquid crystal alignment agent containing the polymer (P) can provide a liquid crystal element excellent in AC afterimage characteristics and long-term heat resistance is not clear, but the following may be considered.
  • the polymer (P) has a structural unit having an asymmetric structure as a structural unit derived from diamine. For this reason, it is surmised that the crystallinity of the photodegradation product generated when the coating film containing the polymer (P) is irradiated with light is low, and the generation of fine bright spots is suppressed. In addition, the crystallinity of the photodegradation product is lowered due to the chain hydrocarbon structure and alicyclic hydrocarbon structure of X 2 , which is one reason why a liquid crystal element with few generation of fine bright spots was obtained.
  • the liquid crystal element of the present disclosure can be effectively applied to various applications, for example, watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors. It can be used for various display devices such as liquid crystal televisions and information displays, and light control films. Moreover, the liquid crystal element formed using the liquid crystal aligning agent of this indication can also be applied to retardation film.
  • FIG. 1 shows the measurement result of 1 H-NMR spectrum (DMSO-d 6 , 400 MHz) of diamine (DA-1).
  • FIG. 2 shows the measurement result of 1 H-NMR spectrum (DMSO-d 6 , 400 MHz) of diamine (DA-4).
  • a diamine (DA-7) was obtained in the same manner as in Synthesis Example 1 except that N-methylethanolamine was changed to 2-aminoethanethiol.
  • a diamine (DA-8) was obtained in the same manner as in Synthesis Example 1 except that 4-fluoronitrobenzene was changed to 2-fluoro-5-nitropyridine.
  • a diamine (DA-9) was obtained in the same manner as in Synthesis Example 4 except that 4-fluoronitrobenzene was changed to 2-fluoro-5-nitropyridine.
  • Example 1 Photo-alignment FFS type liquid crystal display element
  • a liquid crystal aligning agent (R-1) was prepared by filtering this solution through a filter having a pore diameter of 0.2 ⁇ m.
  • the surface of the coating film was irradiated with ultraviolet rays of 3,000 J / m 2 containing a linearly polarized 254 nm emission line from the normal direction of the substrate to perform photo-alignment treatment.
  • the coating film that had been subjected to the photo-alignment treatment was heated in a clean oven at 230 ° C. for 30 minutes for heat treatment to form a liquid crystal alignment film.
  • liquid crystal display element About the pair of substrates having the liquid crystal alignment film prepared in (2) above, containing aluminum oxide spheres having a diameter of 5.5 ⁇ m leaving the liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film is formed
  • the substrates are stacked and pressure-bonded so that the projection direction of the polarization axis on the substrate surface during light irradiation is antiparallel, and the adhesive is heated at 150 ° C. for 1 hour. Cured.
  • a nematic liquid crystal (MLC-7028, manufactured by Merck & Co., Inc.) was filled between the pair of substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment during liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature. Next, a polarizing plate was bonded to both sides of the substrate to manufacture an FFS type liquid crystal display element.
  • B 100 is the transmission amount of light under a blank and paranicols.
  • ⁇ is a polarizer under crossed Nicols. (This is the minimum light transmission amount with the liquid crystal cell sandwiched between the analyzers.)
  • the black level in the dark state is represented by the minimum relative transmittance of the liquid crystal cell. In the FFS type liquid crystal cell, the smaller the black level in the dark state, the better the contrast. “Excellent” if the minimum relative transmittance is less than 0.2%, “Good” if the minimum relative transmittance is 0.2% or more and less than 0.5%, 1.0% or more was regarded as “bad”. As a result, this example was evaluated as “excellent”.
  • the observation area was 680 ⁇ m ⁇ 680 ⁇ m, and the microscope magnification was 100 times.
  • the evaluation is “excellent” when no fine luminescent spots are observed, “good” when the number of fine luminescent spots is 1 or more and 5 or less, and the number of fine luminescent spots is 6 or more and 10 or less.
  • the case was “OK”, and the case where the number of fine luminescent spots was 11 points or more was “bad”. As a result, in this example, the evaluation was “good”.
  • Example 2 Comparative Examples 1 to 6
  • a liquid crystal aligning agent was prepared to form a liquid crystal aligning film in the same manner as in Example 1, and FFS A liquid crystal display element and a liquid crystal cell were manufactured and various evaluations were performed. The evaluation results are shown in Table 2 below.
  • Example 13 Example 1 in Example 1 except that “(1) Preparation of liquid crystal aligning agent” and “(2) Formation of liquid crystal alignment film by photo-alignment method” were changed as described in (1a) and (2a) below. In the same manner as described above, an FFS type liquid crystal display element and a liquid crystal cell were manufactured and various evaluations were performed. The evaluation results are shown in Table 2 below.
  • the surface of the coating film was irradiated with ultraviolet rays of 3,000 J / m 2 containing a linearly polarized 254 nm emission line from the normal direction of the substrate to perform photo-alignment treatment.
  • the coating film subjected to the photo-alignment treatment was heated for 30 minutes in an oven at 230 ° C. in which the inside of the chamber was replaced with nitrogen to perform heat treatment (post-bake), thereby forming a liquid crystal alignment film.
  • Example 14 In Example 13, except that the polymer contained in the liquid crystal aligning agent was changed as shown in Table 2 below, a liquid crystal aligning agent was prepared in the same manner as in Example 13 to form a liquid crystal aligning film, and the FFS type A liquid crystal display element and a liquid crystal cell were manufactured and subjected to various evaluations. The evaluation results are shown in Table 2 below.
  • liquid crystal alignment was “good” in Examples 1 to 16. Further, the AC afterimage characteristics were “excellent” or “good” in Examples 1 to 16. These are considered due to the improvement of the photoreactivity of the liquid crystal alignment film. That is, the liquid crystal aligning agents of Examples 1 to 16 contain a polymer of substituted cyclobutanetetracarboxylic dianhydride and diamine. In addition, the diamine used for the synthesis of the polymer has an aromatic ring to which a polymerization bond group (—NH 2 ) is bonded, an alkylamino group, a piperidinediyl group, an oxyalkylene group (—C n H 2n —O—).
  • Examples 1 to 16 were “excellent” or “good”.
  • the liquid crystal aligning agents of Examples 1 to 16 contain a polymer having a structural unit derived from a diamine having an asymmetric structure as a polymer component.
  • the mechanism of long-term heat resistance improvement is not clear, but in the case of diamines having an asymmetric structure, the photolysis product generated by the photo-alignment treatment process becomes an asymmetric structure, which lowers the crystallinity of the photolysis product and generates fine bright spots. Is presumed to be suppressed.
  • the polymer (P) contained in the liquid crystal aligning agents of Examples 8 to 10, 14, and 16 is composed of a compound of plural kinds of acid dianhydride components or diamine components. Therefore, it is presumed that the photodegradation product has various chemical structures, inhibits crystallization of the photodegradation product, and suppresses the generation of fine bright spots. Furthermore, in Examples 11, 12, 15, and 16 (blend system), since the content ratio of the polymer (polymer 1) that undergoes photodegradation is small, the amount of photodegradation product that is generated is small. It is presumed that generation was suppressed.
  • Comparative Examples 1 to 5 using polymers having no partial structure derived from a substituted cyclobutane ring and a specific diamine, the long-term heat resistance of the liquid crystal cell was “poor”.
  • These liquid crystal aligning agents of Comparative Examples 1 to 5 contain a polymer using only a diamine having a symmetric structure as a diamine component. In this case, it is presumed that the photolysis product generated by the photo-alignment treatment has a symmetric structure, and the crystallinity of the photolysis product becomes high, so that fine bright spots are easily generated.
  • Comparative Example 6 the liquid crystal orientation and AC afterimage characteristics of the liquid crystal cell were “bad”. The long-term heat resistance could not be evaluated because the liquid crystal alignment of the liquid crystal cell was “bad”.
  • FIG. 3 shows the measurement result of 1 H-NMR spectrum (DMSO-d 6 , 400 MHz) of diamine (DA-10).
  • the numerical value in Table 3 represents the usage rate (mole part) of each compound with respect to 100 mol part of total amount of the tetracarboxylic dianhydride used for the synthesis about tetracarboxylic dianhydride. Represents the use ratio (mole parts) of each compound with respect to 100 mol parts of the total amount of diamine compounds used in the synthesis.
  • the obtained powder was dissolved in ⁇ BL to obtain a 15% by mass solution of polyamic acid ester (PAE-1) having a structural unit represented by the following formula (PAE-1).
  • the liquid crystal orientation and AC afterimage characteristics were “excellent” or “good” in Examples 17 to 24. These results indicate that, as in Examples 1 to 16, the aromatic ring to which the polymerization bonding group (—NH 2 ) is bonded is formed by the electron donating group (“—O—CH 2 —” of the diamine (DA-10)). It is considered that the photoreactivity of the liquid crystal alignment film was improved by including a polymer having a structural unit derived from a substituted diamine. Further, in terms of long-term heat resistance (reduction of fine bright spot defects), all of Examples 17 to 24 were “excellent”.

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