WO2013065755A1 - 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

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WO2013065755A1
WO2013065755A1 PCT/JP2012/078214 JP2012078214W WO2013065755A1 WO 2013065755 A1 WO2013065755 A1 WO 2013065755A1 JP 2012078214 W JP2012078214 W JP 2012078214W WO 2013065755 A1 WO2013065755 A1 WO 2013065755A1
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liquid crystal
carbon atoms
formula
group
integer
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PCT/JP2012/078214
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English (en)
Japanese (ja)
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雅章 片山
祐樹 高山
勇太 川野
耕平 後藤
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日産化学工業株式会社
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Priority to KR1020147014018A priority Critical patent/KR101938923B1/ko
Priority to CN201280065416.0A priority patent/CN104081268B/zh
Priority to JP2013541826A priority patent/JP6183212B2/ja
Publication of WO2013065755A1 publication Critical patent/WO2013065755A1/fr

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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
    • 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
    • C08G73/1042—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
    • C08G73/1075—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 novel diamine compound, a polyimide precursor obtained by reacting the compound as a part of the raw material, a polyimide obtained by imidizing the polyimide precursor, and a liquid crystal alignment comprising these polymers.
  • the present invention relates to a treatment agent, a liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film.
  • Liquid crystal display elements are now widely used as display devices that are thin and light.
  • a liquid crystal alignment film is used to determine the alignment state of the liquid crystal.
  • a polyimide film is used as the liquid crystal alignment film.
  • a method of applying a polyamic acid solution or a solvent-soluble polyimide solution, which is a polyimide precursor, to a substrate and baking it is employed.
  • This polyamic acid or solvent-soluble polyimide is generally formed by a reaction between a tetracarboxylic acid derivative such as tetracarboxylic dianhydride and a diamine component.
  • the pretilt angle of the liquid crystal As one of the characteristics required for the liquid crystal alignment film, there is control of the so-called pretilt angle of the liquid crystal, which maintains the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.
  • the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle according to the proportion of the diamine used. It is relatively easy to obtain and is useful as means for increasing the pretilt angle (see, for example, Patent Document 1).
  • a liquid crystal dropping method (also referred to as an ODF method) has been developed.
  • a liquid crystal is dropped on a substrate on which a liquid crystal alignment film is formed, bonded to the other substrate in a vacuum, and then the sealing material is UV cured to fill the liquid crystal.
  • the ODF method has been solved by optimizing the manufacturing process so as to reduce the influence of adsorbed water and impurities, such as reducing the dripping amount of liquid crystal and improving the degree of vacuum at the time of bonding.
  • the liquid crystal display element production line becomes larger, it has become impossible to suppress display unevenness by optimizing the manufacturing process so far, and a liquid crystal alignment film that can reduce alignment unevenness more than before has been demanded.
  • the liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal.
  • the pretilt angle of the liquid crystal As the liquid crystal display element becomes more sophisticated and its use range is expanding year by year, Not only can a predetermined pretilt angle be obtained, but also the stability of the pretilt angle has become increasingly important.
  • the liquid crystal In the manufacturing process of the liquid crystal display element, in order to improve the alignment uniformity of the liquid crystal, the liquid crystal is encapsulated and then heat-treated to temporarily make the liquid crystal isotropic.
  • the stability of the pretilt angle is low, there arises a problem that a pretilt angle having a target size cannot be obtained after this isotropic processing or the pretilt angle varies.
  • a liquid crystal display element using a backlight that generates a large amount of heat and has a large amount of light to obtain high brightness, such as a car navigation system or a large television is exposed to high temperature and light irradiation for a long time. There are cases where it is used or left in a dark environment. Under such severe conditions, when the pretilt angle is gradually changed, problems such as inability to obtain initial display characteristics or occurrence of unevenness in display occur.
  • liquid crystal is dropped directly on the alignment film, so that physical stress is applied to the liquid crystal and the liquid crystal alignment film when the liquid crystal is dropped or the substrate is bonded.
  • the ODF method which is a liquid crystal filling process when manufacturing a liquid crystal display element
  • liquid crystal is dropped directly on the alignment film, so that physical stress is applied to the liquid crystal and the liquid crystal alignment film when the liquid crystal is dropped or the substrate is bonded.
  • it is necessary to increase the dropping point of the liquid crystal. For this reason, liquid crystal drops and liquid crystal droplets are in contact with adjacent liquid droplets, so that so-called alignment unevenness such as drop marks and lattice unevenness is likely to occur. There was a problem of unevenness.
  • This alignment unevenness is caused by adsorbed water and impurities adhering to the interface of the liquid crystal alignment film formed on the substrate being swept away by the liquid crystal dropped by the ODF method, so that the liquid crystal dropping part and the liquid crystal droplets are in contact with each other. It is thought to be generated by the amount of adsorbed water and impurities.
  • an object of the present invention is to provide a liquid crystal alignment film whose pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and a liquid crystal alignment film that can reduce liquid crystal alignment unevenness generated by the ODF method. It is to provide. Furthermore, an object of the present invention is to provide a liquid crystal display device having the above liquid crystal alignment film, a liquid crystal alignment treatment agent capable of providing the above liquid crystal alignment film, a polymer for obtaining the liquid crystal alignment treatment agent, and a weight thereof. The object is to provide a diamine compound for obtaining a coalescence.
  • the present inventor has found that a liquid crystal aligning agent containing a polymer having a side chain having a specific structure is extremely effective for achieving the above object, and completes the present invention. It came to. That is, the present invention has the following gist. (1) Containing at least one polymer selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1A] or formula [1B] and a polyimide obtained by imidizing the polyimide precursor. Liquid crystal aligning agent characterized by the above.
  • X 1 is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 1 ) — (R 1 is the number of carbon atoms)
  • X 2 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring.
  • Optional hydrogen atoms on these cyclic groups are alkyl groups having 1 to 3 carbon atoms, alkoxyl groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine having 1 to 3 carbon atoms
  • X 3 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups may have a carbon number.
  • X 4 be substituted with a fluorine atom is an alkyl group having 1 to 18 carbon atoms having 1 to 3 carbon atoms, fluorine having 1 to 18 carbon atoms An alkyl group-containing, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, and p is 0 to 3 is an integer, and n + p is an integer of 1 to 6.)
  • X 5 represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 2 ) — (R 2 represents the number of carbon atoms)
  • X 1 is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 1 ) — (R 1 is the number of carbon atoms) or —S—
  • X 2 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring; Arbitrary hydrogen atoms on these cyclic groups are alkyl groups having 1 to 3 carbon atoms, alkoxyl groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine having 1 to 3 carbon atoms
  • X 3 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring,
  • X 4 be substituted with a fluorine atom is an alkyl group having 1 to 18 carbon atoms having 1 to 3 carbon atoms, fluorine having 1 to 18 carbon atoms An alkyl group-containing, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, and p is 0 to 3 is an integer, and n + p is an integer of 1 to 6.
  • R 2 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • M2 is an integer from 2 to 15
  • p2 is an integer from 0 to 3.
  • R 3 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • M3 is an integer from 2 to 15, n1 is an integer from 1 to 3, p3 is an integer from 0 to 3, and n1 + p3 is an integer from 1 to 6.
  • R 4 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • M4 is an integer from 2 to 15, n2 is an integer from 1 to 3, p4 is an integer from 0 to 3, and n2 + p4 is an integer from 1 to 6.
  • Z 6 and Z 7 are hydrogen atoms or methyl groups, which may be the same or different.
  • a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • a liquid crystal display device having the liquid crystal alignment film according to (15).
  • a polymerizable compound that includes a liquid crystal layer between a pair of substrates including an electrode and the liquid crystal alignment film and that is polymerized by at least one of active energy rays and heat between the pair of substrates.
  • the liquid crystal display element according to the above (16) which is produced through a step of polymerizing the polymerizable compound while disposing a liquid crystal composition and applying a voltage between the electrodes.
  • a liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • a liquid crystal display element comprising the liquid crystal alignment film according to (18).
  • a liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • the liquid crystal display device which is produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.
  • (21) A diamine compound represented by the formula [2A].
  • (22) A diamine compound represented by the formulas [2a] to [2d].
  • (23) Polyamic acid obtained by reacting a diamine component containing the diamine compound represented by the above formula [2A] or formula [2B] with a tetracarboxylic acid component or a polyimide obtained by dehydrating and ring-closing the polyamic acid.
  • the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and in addition, it is generated by the ODF method.
  • a liquid crystal alignment film capable of reducing liquid crystal alignment unevenness can be provided. Accordingly, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.
  • the present invention is described in detail below.
  • the present invention is at least selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1A] or formula [1B] (also referred to as a specific side chain structure) and a polyimide obtained by imidizing the polyimide precursor. It is a liquid crystal aligning agent having one type of polymer (also referred to as a specific polymer).
  • X 1 is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 1 ) — (R 1 is the number of carbon atoms)
  • X 2 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring.
  • Optional hydrogen atoms on these cyclic groups are alkyl groups having 1 to 3 carbon atoms, alkoxyl groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine having 1 to 3 carbon atoms
  • X 3 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups may have a carbon number.
  • X 4 be substituted with a fluorine atom is an alkyl group having 1 to 18 carbon atoms having 1 to 3 carbon atoms, fluorine having 1 to 18 carbon atoms An alkyl group-containing, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, and p is 0 to 3 is an integer, and n + p is an integer of 1 to 6.)
  • X 5 represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 2 ) — (R 2 represents the number of carbon atoms)
  • the specific side chain structure of the present invention is a structure represented by the formula [1A] or the formula [1B].
  • the structure represented by the formula [1A] has a benzene ring, a cyclohexyl ring, or a heterocyclic ring. Thereby, the stability with respect to the heat
  • the structure represented by the formula [1B] has a cyclic group composed of a steroid skeleton.
  • the structure represented by the formula [1A] has a benzene ring, a cyclohexyl ring, or a heterocyclic ring.
  • the structure represented by the formula [1B] has a cyclic group composed of a steroid skeleton.
  • the liquid crystal of the liquid crystal dropped by the ODF method is used.
  • the wet spreading property on the alignment film is increased. Thereby, physical stress on the liquid crystal and the liquid crystal alignment film generated when the substrates are bonded can be reduced. From these points, the liquid crystal alignment film having the structure of the formula [1A] or the formula [1B] which is the specific side chain structure of the present invention can reduce liquid crystal alignment unevenness generated in the ODF method.
  • the structure represented by the formula [1A] is between the polymer main chain and the moiety of — (CH 2 ) m —X 1 — (X 2 ) n — (X 3 ) p —X 4 in the formula [1A].
  • the hydrophobicity of the liquid crystal alignment film can be increased. Thereby, adsorption
  • a benzene ring similar to liquid crystal A cyclohexyl ring or a heterocyclic ring can be efficiently formed at the alignment film interface. Therefore, the wet spread property on the liquid crystal alignment film of the liquid crystal dropped by the ODF method is increased.
  • the specific side chain structure in the formula [1B] has the same function as the specific side chain structure in the formula [1A].
  • X 1 represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 1 ) — (R 1 represents 1 carbon atom)
  • R 1 represents 1 carbon atom
  • a single bond —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH— or —N (R 1 ) — (where R 1 is a straight chain having 1 to 5 carbon atoms)
  • R 1 is a straight chain having 1 to 5 carbon atoms
  • An alkyl group or a branched alkyl group having 1 to 5 carbon atoms is preferred. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
  • X 2 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • X 2 may be the same or different.
  • X 2 is preferably a benzene ring or a cyclohexyl ring.
  • X 3 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. At that time, X 3 may be the same or different.
  • X 3 is preferably a benzene ring or a cyclohexyl ring.
  • X 4 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • n is an integer of 1 to 3. Among these, an integer of 1 or 2 is preferable.
  • p is an integer of 0 to 3. Of these, an integer of 0 to 2 is preferable.
  • n + p is an integer of 1 to 6. Among these, an integer of 1 to 4 is preferable.
  • Preferred combinations of X 1 , X 2 , X 3 , X 4 , m, n and p in the formula [1A] are as shown in Tables 1 to 36.
  • the specific polymer of the present invention is a polyimide precursor and at least one selected from the group consisting of polyimides obtained by imidizing the polyimide precursor has a specific side chain structure represented by the following formula [1B].
  • X 5 is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 2 ) — (R 2 has 1 carbon atom)
  • a single bond —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, or —N (R 2 ) — (R 2 is a straight chain having 1 to 5 carbon atoms) And a branched alkyl group having 1 to 5 carbon atoms is preferred. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
  • X 6 is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and more preferably an organic group having 15 to 25 carbon atoms having a steroid skeleton.
  • q is an integer of 2 to 15. Among these, an integer of 2 to 10 is preferable. More preferred is an integer of 2 to 7.
  • Specific side chain diamine compound that is, at least one selected from the group consisting of a polyimide precursor obtained by reaction of a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyimide precursor
  • a diamine compound represented by the following formula [2A] (also referred to as a specific side chain diamine compound) is preferably used as a part of the raw material.
  • X 1 represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 1 ) — (R 1 represents 1 carbon atom) A linear alkyl group having 5 to 5 or a branched alkyl group having 1 to 5 carbon atoms) or —S—.
  • a single bond —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH— or —N (R 1 ) — (where R 1 is a straight chain having 1 to 5 carbon atoms)
  • R 1 is a straight chain having 1 to 5 carbon atoms
  • An alkyl group or a branched alkyl group having 1 to 5 carbon atoms is preferred. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
  • X 2 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • X 2 may be the same or different.
  • X 2 is preferably a benzene ring or a cyclohexyl ring.
  • X 3 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • n + p is an integer of 1 to 6.
  • the bonding position of the two amino groups (—NH 2 ) in the formula [2A] is not limited. Specifically, with respect to the side chain linking group (— (CH 2 ) m —), the 2,3 position, 2,4 position, 2,5 position, and 2,6 position on the benzene ring. , 3, 4 or 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing the polyimide precursor, positions 2, 4, 2, 5, or 3, 5 are preferable. More preferably, the position is 2, 4 or 3, 5 taking into account the ease of synthesis of the diamine compound. Preferred combinations of X 1 , X 2 , X 3 , m, n and p in the formula [2A] are as shown in Table 1 to Table 30 as in the formula [1A].
  • R 1 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • R 1 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • m1 is an integer of 2 to 15. Among these, an integer of 2 to 10 is preferable. More preferred is an integer of 2 to 7.
  • p1 is an integer of 0 to 3. Of these, an integer of 0 to 2 is preferable.
  • R 2 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • m2 is an integer of 2 to 15. Among these, an integer of 2 to 10 is preferable. More preferred is an integer of 2 to 7.
  • p2 is an integer of 0 to 3. Of these, an integer of 0 to 2 is preferable.
  • R 3 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • n1 is an integer of 1 to 3.
  • p3 is an integer of 0 to 3.
  • an integer of 0 to 2 is preferable.
  • n1 + p3 is an integer of 1 to 6.
  • an integer of 1 to 4 is preferable.
  • R 4 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. .
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • n2 + p4 is an integer of 1 to 6. Among these, an integer of 1 to 4 is preferable.
  • the bonding positions of the two amino groups (—NH 2 ) in the formulas [2a] to [2d] are not limited. Specifically, with respect to the side chain linking group (— (CH 2 ) m1 to m4 —), 2, 3 positions, 2, 4 positions, 2, 5 positions on the benzene ring, 2, 6 Position, 3, 4 position or 3, 5 position. Among these, from the viewpoint of reactivity when synthesizing the polyimide precursor, positions 2, 4, 2, 5, or 3, 5 are preferable. More preferably, the position is 2, 4 or 3, 5 taking into account the ease of synthesis of the diamine compound. More specifically, for example, the structures are represented by the following formulas [2-1] to [2-40].
  • R 5 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms
  • m 5 represents Independently, an integer of 2 to 7).
  • [2-1] to [2-5], [2-8], [2-11], [2-12], formulas [2-14], [2-15], [2-15], 2-17] to [2-20], [2-25], [2-26], [2-29], and [2-30] are more preferable
  • [2-1] to [2-5], [2-8], [2-11], [2-12], [2-14], [2-15], [2-17] to [2 ⁇ 20] is more preferable.
  • the specific polymer of the present invention uses a diamine compound represented by the following formula [2B] (also referred to as a specific side chain type diamine compound in the same manner as the diamine compound represented by the formula [2A]) as a part of the raw material. You can also.
  • X 5 is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R 2 ) — (R 2 has 1 carbon atom)
  • R 2 has 1 carbon atom
  • a single bond —O—, —COO—, —OCO—, —CONH—, —NHCO—, NH— or —N (R 2 ) — (R 2 is a linear alkyl having 1 to 5 carbon atoms) Group or a branched alkyl group having 1 to 5 carbon atoms) is preferred. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
  • X 6 is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and more preferably an organic group having 15 to 25 carbon atoms having a steroid skeleton.
  • q is an integer of 2 to 15. Among these, an integer of 2 to 10 is preferable. More preferred is an integer of 2 to 7.
  • the method for producing the specific side chain diamine compound represented by the formula [2A] or the formula [2B] of the present invention is not particularly limited, for example, it can be produced by the following method.
  • the specific diamine compound represented by the formula [2A] of the present invention can be obtained by synthesizing a dinitro compound represented by the formula [2-I] and further reducing the nitro group to convert it to an amino group.
  • the method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc.
  • X 1 , X 2 , X 3 , X 4 , m, n and p in the formula [2-I] have the same definitions as in the formula [2A].
  • — (CH 2 ) m — moiety of the dinitro compound is bonded to — (X 2 ) n — (X 3 ) p —X 4 via the linking moiety X 1 . It can be obtained by a method.
  • X 1 is a single bond, —O— (ether bond), —COO— (ester bond), —OCO— (reverse ester bond), —CONH— (amide bond), —NHCO— (reverse amide bond), —NH -(Amino bond), -N (R 1 )-(R 1 is an alkylated amino bond which is a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms) or -S-
  • These linking groups are selected from (S bonds), and these linking groups can be formed by appropriately selecting and using known methods in organic synthesis.
  • the halogen of the dinitro group-containing halogen derivative is preferably Cl (chlorine) or Br (bromine).
  • a dinitro group-containing halogen derivative can be obtained by halogenation of a corresponding dinitrobenzyl alcohol.
  • halogenating agent used at that time examples include BBr 3 , BCl 3 , PBr 3 , PCl 3 , PPh 3 / CBr 4 , PPh 3 / CCl 4 , SOBr 2 , and SOCl 2 .
  • X 1 is —COO— (ester bond)
  • Xa in the formula [2-II] is an acid chloride
  • Xb in the formula [2-III] are a hydroxyl group (OH group)
  • a method of reacting with a hydroxyl group derivative in the presence of an alkali a method of reacting with a hydroxyl group derivative in the presence of an alkali.
  • diamine compounds represented by the following formulas [DA-1] to [DA-31] can be used as long as the effects of the present invention are not impaired.
  • R 1 is —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
  • R 2 Is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or (It is a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms.
  • R 3 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —
  • R 5 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 — or —O—
  • R 6 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
  • R 7 is a linear or branched alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is Each is a trans isomer.
  • R 8 is a linear or branched alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is Each is a trans isomer.
  • a 4 represents a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • a 3 represents 1,4-cyclohexylene.
  • a 2 is —O— or —COO— * (where a bond marked with “*” is bonded to A 3 )
  • a 1 is —O— -Or -COO- * (where a bond marked with "*" is bonded to (CH 2 ) a 2 )).
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10
  • a 3 is an integer of 0 or 1.
  • a diamine compound represented by the following formula [DA-32] can be used.
  • a 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON ( A divalent organic group selected from CH 3 ) — or —N (CH 3 ) CO—
  • a 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon.
  • a 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, — CON (CH 3 ) —, —N (CH 3 ) CO—, or —O (CH 2 ) m — (m is an integer of 1 to 5), and A 4 is a nitrogen-containing aromatic heterocycle N is an integer from 1 to 4.) Moreover, as long as the effect of this invention is not impaired, the diamine compound which has an alkyl group or a fluorine-containing alkyl group in a diamine side chain can be used.
  • diamines represented by the following formulas [DA-33] to [DA-44] can be exemplified.
  • a 1 contains a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms. An alkyl group.
  • a 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or — NH— and
  • a 3 is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.
  • p is an integer of 1 to 10.
  • diamine compounds represented by the following formulas [DA-45] to [DA-52] can also be used.
  • m is an integer of 0 to 3.
  • n is an integer of 1 to 5.
  • a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA-53] to [DA-57] can also be used.
  • m 1 is an integer of 1 to 4.
  • a 4 represents a single bond, —CH 2 —, —C 2 H 4 —, —C ( CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — or —N (CH 3 ) CO—, each of m 2 and m 3 independently represents 0 to And m 2 + m 3 is an integer of 1 to 4.
  • m 4 and m 5 are each independently an integer of 1 to 5.
  • a 5 is a linear or branched alkyl group having 1 to 5 carbon atoms, and m 6 is an integer of 1 to 5.
  • diamine compounds represented by the following formulas [DA-58] and [DA-59] can also be used.
  • Said other diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as liquid crystal orientation at the time of setting it as a liquid crystal aligning film, a voltage holding ratio, and an accumulation charge.
  • tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [3] as a part of the raw material.
  • Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.
  • Z 1 is a tetravalent group represented by, for example, the following formulas [3a] to [3j].
  • Z 2 to Z 5 are groups selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
  • Z 6 and Z 7 are a hydrogen atom or a methyl group, and may be the same or different.
  • particularly preferred structure of Z 1 is the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula from the viewpoint of polymerization reactivity and ease of synthesis. [3 g].
  • the formula [3a], the formula [3e], the formula [3f], or the formula [3g] is preferable.
  • tetracarboxylic dianhydrides other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydrides) can be used as long as the effects of the present invention are not impaired.
  • examples of other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides of the following tetracarboxylic acids.
  • the above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides may be used alone or in combination of two or more depending on the properties such as liquid crystal alignment, voltage holding ratio and accumulated charge when used as a liquid crystal alignment film. It can also be used as a mixture.
  • the specific polymer of the present invention is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyamic acid.
  • the polyimide precursor has a structure represented by the following formula [A].
  • R 1 is a tetravalent organic group
  • R 2 is a divalent organic group
  • a 1 and A 2 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Each may be the same or different
  • n represents a positive integer.
  • the specific polymer of the present invention is relatively easily obtained by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as raw materials. For this reason, a polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferable.
  • R 1 and R 2 have the same meaning as defined in Formula [A].
  • R 1 and R 2 may be one kind each, but each may have different R 1 and R 2 and a combination of different kinds as repeating units. But you can.
  • the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid.
  • a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and a diamine component a method of obtaining polyamic acid by dehydration polycondensation reaction of tetracarboxylic acid and a diamine component, or tetracarboxylic acid
  • a method of polycondensation of a dihalide and a diamine component to obtain a polyamic acid is used.
  • polyamic acid alkyl ester a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a diamine component, and a polycondensation of a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a diamine component.
  • the method or the method of converting the carboxyl group of a polyamic acid into ester is used.
  • polyimide a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
  • the liquid crystal alignment film obtained by using the specific polymer of the present invention is a liquid crystal alignment film as the content ratio of the specific side chain structure represented by the formula [1A] or the formula [1B] in the diamine component increases.
  • the hydrophobicity of the liquid crystal and the pretilt angle of the liquid crystal can be increased.
  • a specific side chain diamine compound represented by the formula [2A] is used.
  • 5 mol% or more and 80 mol% or less of the diamine component is the specific side chain diamine compound.
  • a diamine component is a specific side chain type diamine compound from the viewpoint of the applicability
  • the specific polymer of this invention it is preferable to use the specific tetracarboxylic dianhydride shown by said Formula [3] as a tetracarboxylic acid component.
  • a tetracarboxylic dianhydride in which Z 1 in the formula [3] is a structure represented by the formulas [3a] to [3j].
  • a tetracarboxylic acid component is a specific tetracarboxylic dianhydride, More preferably, it is 5 mol% or more, More preferably, it is 10 mol% or more. Further, 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic dianhydride.
  • the reaction of the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent.
  • the organic solvent used in that case is not particularly limited as long as the generated polyimide precursor is dissolved. Specific examples are given below.
  • These may be used alone or in combination.
  • moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.
  • the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, 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 obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent a method of alternately adding a tetracarboxylic acid component and a diamine component, etc. Any of these methods may be used.
  • a plurality of types of diamine components or tetracarboxylic acid components are used for the reaction, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a specific polymer.
  • the polymerization temperature at that time can be selected from an arbitrary temperature of -20 to 150 ° C, preferably in the range of -5 to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a specific polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. It becomes difficult. Therefore, the content is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. It is possible to carry out at a high concentration in the initial stage of the reaction, and then add an organic solvent.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor formed increases as the molar ratio approaches 1.0.
  • the polyimide of the present invention is a polyimide obtained by ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
  • the cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction from the system.
  • the catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, 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. Among them, 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.
  • the reaction solution may be poured into a solvent and precipitated.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or 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 solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the specific polymer of the present invention was measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the polymer film obtained therefrom, workability at the time of forming the polymer film, and uniformity of the polymer film.
  • the weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a coating liquid for forming the resin film containing a specific polymer and an organic solvent.
  • all the polymer components may be all specific polymers used in the present invention, and other polymers are mixed with the specific polymer of the present invention. May be. In that case, the content of the other polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
  • Other polymers include polyimide precursors or polyimides that do not contain a specific side chain structure.
  • the organic solvent in the liquid crystal alignment treatment agent of the present invention forms a uniform film by coating.
  • the content of the organic solvent is preferably 70 to 99% by mass, and more preferably 80 to 99% by mass. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
  • the organic solvent at that time is not particularly limited as long as it is an organic solvent capable of dissolving the specific polymer. Specific examples are given below.
  • N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4 -Hydroxy-4-methyl-2-pentanone and the like.
  • the liquid crystal aligning agent of the present invention includes a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, etc., a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.
  • a crosslinkable compound having at least one substituent selected from the group, a crosslinkable compound having a polymerizable unsaturated bond, and the like can also be introduced. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound. Examples of the crosslinkable compound having an epoxy group, an isocyanate group, etc.
  • the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4]. Specifically, it is a crosslinkable compound represented by the following formulas [4-1] to [4-11].
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5]. Specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-37].
  • n is an integer of 1 to 5. In the formula [5-25], n is an integer of 1 to 5. In the formula [5-36], n is 1 to 100. (In the formula [5-37], n is an integer of 1 to 10.)
  • polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40] can also be mentioned.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represents a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which is a structure represented by the formula [5]. More specifically, compounds of the following formulas [5-41] and [5-42] can be mentioned. (In the formula [5-42], n is an integer of 1 to 10)
  • Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycol.
  • Examples include uril-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene urea-formaldehyde resin.
  • a melamine derivative, a benzoguanamine derivative, glycoluril, or the like in which a hydrogen atom of an amino group is substituted with a methylol group and / or an alkoxymethyl group can be used.
  • the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.
  • Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
  • benzene or phenolic compounds having a hydroxyl group or an alkoxyl group examples include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like. More specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].
  • crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
  • Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane and glycerin polyglycidyl ether poly (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (me ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) ) Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol digly
  • E 1 is a group selected from the group consisting of a cyclohexyl ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring and a phenanthrene ring
  • 2 is a group selected from the following formulas [7a] and [7b]
  • n is an integer of 1 to 4.
  • the said compound is an example of a crosslinkable compound, It is not limited to these.
  • the crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.
  • the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
  • the amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 1 part by weight based on 100 parts by weight of all polymer components. 50 parts by mass is preferred.
  • the compound for promoting charge transfer in the liquid crystal aligning film and promoting charge release of the liquid crystal cell using the liquid crystal aligning film is represented by the following formula: It is preferable to add a nitrogen-containing heterocyclic amine compound represented by [M1] to [M156].
  • This amine compound may be added directly to the solution of the specific polymer, but may be added after making the solution 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. preferable.
  • the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.
  • the liquid-crystal aligning agent of this invention is the organic solvent (poor solvent) which improves the film thickness uniformity and surface smoothness at the time of apply
  • organic solvent poor solvent
  • compounds may be used.
  • a compound that improves the adhesion between the liquid crystal alignment film and the substrate can also be used.
  • Specific examples of the poor solvent that improves the uniformity of the film thickness and the surface smoothness include the following.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propaned
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, 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 (Asahi Glass Co., Ltd.) and the like.
  • 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 all the polymer components contained in the liquid crystal aligning agent. It is.
  • 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 liquid crystal alignment treatment agent of the present invention includes the above-mentioned crosslinkable compound, poor solvent, compound for improving film thickness uniformity and surface smoothness, and compound for improving adhesion to the substrate, and the effects of the present invention. As long as the thickness of the liquid crystal alignment film is not impaired, a dielectric material or conductive material for changing the electrical properties such as the dielectric constant or conductivity of the liquid crystal alignment film may be added.
  • the liquid crystal alignment treatment 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 or light irradiation. Moreover, in the case of vertical alignment use etc., it can be used as a liquid crystal alignment film without alignment treatment.
  • the substrate used at this time is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed.
  • an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, inkjet method, and the like are common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
  • the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C.
  • 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 alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
  • the liquid crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
  • the liquid crystal composition is also preferably used for a liquid crystal display element produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes.
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
  • the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
  • the liquid crystal display element controls a pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
  • the PSA method a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer,
  • the pretilt of liquid crystal molecules is controlled by the polymer produced by irradiation with ultraviolet rays. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.
  • the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.
  • the liquid crystal display element of the present invention is prepared by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and then preparing a liquid crystal cell and polymerizing by at least one of ultraviolet irradiation and heating. By polymerizing the compound, the alignment of the liquid crystal molecules can be controlled.
  • a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
  • the liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation.
  • the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
  • the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
  • the polymerizable compound When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. When the polymerizable compound exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the liquid crystal display The burn-in characteristic of the element is deteriorated. After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates.
  • positioning the liquid crystal aligning film containing this, and applying a voltage between electrodes is used preferably.
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.
  • liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. .
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
  • Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, and a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed.
  • the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
  • the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • Ether form (e) 1 H-NMR (CDCl 3 , ⁇ ppm): 7.11 (d, 2H), 6.83 (d, 2H), 4.04 (t, 2H), 2.45-2.36 (m, 1H) , 2.40 (dt, 2H), 2.03-1.95 (m, 2H), 1.96 (t, 1H), 1.89-1.79 (m, 4H), 1.44-1 .17 (m, 15H), 1.08-0.94 (m, 2H), 0.89 (t, 3H).
  • the molecular weight and imidation rate were measured as follows.
  • the molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as described above.
  • GPC gel permeation chromatography
  • 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 amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from NH group of amic acid
  • y is a peak integrated value of reference proton
  • ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
  • Example 4 CBDA (4.50 g, 22.9 mmol), A-1 (1.94 g, 4.6 mmol), and p-PDA (1.99 g, 18.4 mmol) were mixed in NMP (25.3 g). The reaction was carried out at ° C for 5.5 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25.0% by mass. The number average molecular weight of this polyamic acid was 25,900, and the weight average molecular weight was 78,100.
  • Example 7 After adding NMP to the polyamic acid solution (3) (20.0 g) obtained in Example 6 and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.25 g) were used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. This deposit was wash
  • Example 10 ⁇ Example 10> TCA (4.48 g, 20.0 mmol), A-1 (1.70 g, 4.0 mmol), and DBA (2.44 g, 16.0 mmol) were mixed in NMP (25.8 g) at 40 ° C. The reaction was performed for 6 hours to obtain a polyamic acid solution (7) having a resin solid content concentration of 25.0% by mass. The number average molecular weight of this polyamic acid was 24,200, and the weight average molecular weight was 75,800.
  • Example 11 After adding NMP to the polyamic acid solution (7) (20.5 g) obtained in Example 11 and diluting to 6% by mass, acetic anhydride (1.91 g) and pyridine (1.50 g) were used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was put into methanol (350 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • TCA (4.48 g, 20.0 mmol), A-3 (2.72 g, 6.0 mmol), p-PDA (0.65 g, 6.0 mmol), and DBA (1.22 g, 8.0 mmol) were added to NMP. (27.2 g) and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%. After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (1.90 g) and pyridine (1.45 g) were added as an imidization catalyst, Reacted for hours.
  • This reaction solution was put into methanol (350 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • the imidation ratio of this polyimide was 55%, the number average molecular weight was 21,400, and the weight average molecular weight was 56,900.
  • Example 13 TDA (1.77 g, 5.9 mmol), A-2 (2.66 g, 5.9 mmol), and DBA (2.09 g, 13.7 mmol) were mixed in NMP (15.2 g) at 80 ° C. After reacting for 5.5 hours, CBDA (2.68 g, 13.7 mmol) and NMP (12.5 g) were added and reacted at 40 ° C. for 6 hours, and the polyamic acid having a resin solid content concentration of 25.0 mass% A solution was obtained.
  • Example 14 TDA (4.06 g, 13.5 mmol), A-3 (3.65 g, 8.1 mmol), and p-PDA (2.05 g, 19.0 mmol) were mixed in NMP (20.5 g). After reacting at 5.5 ° C. for 5.5 hours, CBDA (2.65 g, 13.5 mmol) and NMP (16.8 g) were added, and reacted at 40 ° C. for 6 hours. The resin solid content concentration was 25.0% by mass. A polyamic acid solution was obtained.
  • a liquid crystal alignment treatment agent is spin-coated on the ITO surface of a 30 mm ⁇ 40 mm ITO electrode substrate, and heat-treated at 80 ° C. for 5 minutes on a hot plate and at 230 ° C. for 30 minutes in a heat-circulating clean oven.
  • a substrate with a 100 nm-thick polyimide liquid crystal alignment film was obtained.
  • a liquid crystal alignment treatment agent is spin-coated on the ITO surface of a substrate with an ITO electrode of 30 mm ⁇ 40 mm, and heat-treated on a hot plate at 80 ° C. for 5 minutes and in a heat-circulating clean oven at 230 ° C. for 45 minutes.
  • an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.
  • the coated surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having 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 0.1 mm.
  • a liquid crystal alignment treatment agent is spin-coated on the ITO surface of a 10 mm ⁇ 10 mm ITO electrode substrate with a pattern spacing of 20 ⁇ m and a 10 mm ⁇ 40 mm ITO electrode substrate, and heat-circulating on a hot plate at 80 ° C. for 5 minutes. Heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to obtain a polyimide coating film having a thickness of 100 nm. The coating surface was washed with pure water, and then heat-treated at 100 ° C. for 15 minutes in a heat-circulating clean oven to obtain a substrate with a liquid crystal alignment film.
  • This substrate with a liquid crystal alignment film was combined with a liquid crystal alignment film surface inside, with a 6 ⁇ m spacer in between, and the periphery was adhered with a sealant to produce an empty cell.
  • a polymerizable compound (1) represented by the following formula was added to MLC-6608 (manufactured by Merck Japan Co., Ltd.) by a reduced pressure injection method into this empty cell, and 0% of the polymerizable compound was 100% by mass of MLC-6608. .3 mass% mixed and injected, and then the injection port was sealed to obtain a liquid crystal cell.
  • the PSA cells obtained in Examples and Comparative Examples have confirmed that the alignment direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before ultraviolet irradiation. did. In any liquid crystal cell, it was confirmed that the liquid crystal was uniformly aligned by observation with a polarizing microscope.
  • the pretilt angle of the liquid crystal cell obtained in [Preparation of liquid crystal cell (normal cell)] and [Preparation of liquid crystal cell (PSA cell)] was measured.
  • the pretilt angle was measured after the liquid crystal injection and after heat treatment at 95 ° C. for 5 minutes and after heat treatment at 120 ° C. for 5 hours. Furthermore, after the liquid crystal injection, the measurement was performed after the liquid crystal cell after the heat treatment at 95 ° C. for 5 minutes was irradiated with ultraviolet rays of 10 J / cm 2 in terms of 365 nm.
  • the pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Furthermore, ultraviolet irradiation was performed using a tabletop UV curing apparatus (HCT3B28HEX-1) (manufactured by Senlite).
  • Example 15 NMP (12.9 g) and BCS (18.8 g) were added to the polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25.0 mass% obtained in Example 4, and the mixture was added at 25 ° C. It stirred for 3 hours and obtained the liquid-crystal aligning agent (1).
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (1), production of cells and various evaluations were performed under the above-described conditions.
  • Example 16 NMP (18.8 g) and BCS (23.0 g) were added to the polyimide powder (2) (2.51 g) obtained in Example 5, and the mixture was stirred at 25 ° C. for 8 hours. 2) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (2), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 17 NMP (11.4 g) and BCS (21.9 g) were added to the polyamic acid solution (3) (10.5 g) having a resin solid content concentration of 25.0% by mass obtained in Example 6, and at 25 ° C. By stirring for 3 hours, a liquid crystal aligning agent (3) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (3), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 18 NMP (22.9 g) and BCS (18.8 g) were added to the polyimide powder (4) (2.50 g) obtained in Example 7, and the mixture was stirred at 25 ° C. for 8 hours. 4) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (4), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 19 NMP (21.0 g) and BCS (21.0 g) were added to the polyimide powder (5) (2.52 g) obtained in Example 8, and the mixture was stirred at 25 ° C. for 8 hours. 5) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (5), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 20 NMP (25.0 g) and BCS (16.7 g) were added to the polyimide powder (6) (2.50 g) obtained in Example 9, and the mixture was stirred at 25 ° C. for 8 hours. 6) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (6), production of cells and various evaluations were performed under the above-described conditions.
  • Example 21 NMP (15.0 g) and BCS (16.7 g) were added to the polyamic acid solution (7) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Example 10, and at 25 ° C.
  • the liquid crystal aligning agent (7) was obtained by stirring for 3 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (7), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 22 NMP (27.1 g) and BCS (14.6 g) were added to the polyimide powder (8) (2.50 g) obtained in Example 11, and the mixture was stirred at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent ( 8) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • cell preparation and various evaluations were performed under the above-described conditions.
  • Example 23 NMP (22.9 g) and BCS (18.8 g) were added to the polyimide powder (9) obtained in Example 12 (2.50 g), and the mixture was stirred at 25 ° C. for 8 hours. 9) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (9), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 24 NMP (25.0 g) and BCS (16.7 g) were added to the polyimide powder (10) (2.50 g) obtained in Example 13, and the mixture was stirred at 25 ° C. for 8 hours. 10) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (10), cell preparation and various evaluations were performed under the above-described conditions.
  • Example 25 NMP (23.1 g) and BCS (18.9 g) were added to the polyimide powder (11) (2.52 g) obtained in Example 14, and the mixture was stirred at 25 ° C. for 8 hours. 11) was obtained.
  • This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (11), production of cells and various evaluations were performed under the above-described conditions.
  • the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention has a longer temperature and light than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. Even when exposed to ultraviolet (UV) radiation, the change in the pretilt angle is small. The same result was obtained for both the normal cell and the PSA cell.
  • Comparative Example 3 and Comparative Example 4 which do not contain a specific side chain type diamine compound have a large change in pretilt angle after being exposed to high temperature for a long time, and in particular, after being exposed to light (ultraviolet rays) irradiation. The change in the pretilt angle was large.
  • the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention has a larger water contact angle of the liquid crystal alignment film than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. That is, the hydrophobicity of the liquid crystal alignment film is high.
  • Comparative Example 3 and Comparative Example 4 that do not contain a specific side chain diamine compound have a small water contact angle of the liquid crystal alignment film and poor liquid crystal wettability on the liquid crystal alignment film (the liquid crystal contact angle is low). large).
  • the contact angle of water of a liquid crystal aligning film is large, and the hydrophobicity of a liquid crystal aligning film is high.
  • the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and liquid crystal generated by the ODF method
  • a liquid crystal alignment film that can reduce alignment unevenness can be provided.
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful in the production of a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui contient au moins un polymère qui est choisi dans le groupe consistant en les précurseurs de polyimide ayant une chaîne latérale représentée par la formule [1A] ou la formule [1B] et les polyimides obtenus par imidation des précurseurs de polyimide. (Dans la formule [1A] ou [1B], X1 et X5 représentent chacun une simple liaison, -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -N(R1)- (où R1 représente un groupe alkyle linéaire ou ramifié ayant 1-5 atomes de carbone) ou -S- ; X2 et X3 représentent chacun un groupe cyclique divalent choisi parmi un noyau benzénique, un noyau cyclohexyle ou un noyau hétérocyclique, et un atome d'hydrogène arbitraire sur ces groupes cycliques peut être substitué par un groupe alkyle ayant 1-3 atomes de carbone ou similaire ; X4 représente un groupe alkyle, un groupe alkyle à teneur en fluor, un groupe alcoxyle ou un groupe alcoxyle à teneur en fluor ayant 1-18 atomes de carbone ; X6 représente un groupe organique ayant un squelette stéroïde et 12-25 atomes de carbone ; m représente un nombre de 2-15 ; n représente un nombre de 1-3 et p représente un nombre de 0-3, n + p étant un nombre de 1-6 ; et q représente un nombre de 2-15).
PCT/JP2012/078214 2011-11-01 2012-10-31 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2013065755A1 (fr)

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CN201280065416.0A CN104081268B (zh) 2011-11-01 2012-10-31 液晶取向处理剂、液晶取向膜及液晶显示元件
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CN111936922B (zh) * 2018-03-28 2023-05-26 日产化学株式会社 液晶取向剂、液晶取向膜和液晶表示元件
CN112424259B (zh) 2018-07-05 2022-11-08 本州化学工业株式会社 末端(甲基)丙烯酸酯聚碳酸酯寡聚物
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