WO2009088046A1 - Agent d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides l'utilisant - Google Patents

Agent d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides l'utilisant Download PDF

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WO2009088046A1
WO2009088046A1 PCT/JP2009/050154 JP2009050154W WO2009088046A1 WO 2009088046 A1 WO2009088046 A1 WO 2009088046A1 JP 2009050154 W JP2009050154 W JP 2009050154W WO 2009088046 A1 WO2009088046 A1 WO 2009088046A1
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ring
liquid crystal
group
formula
carbon atoms
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Japanese (ja)
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Kohei Goto
Noritoshi Miki
Kenzo Yada
Kazuyoshi Hosaka
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to KR1020107014926A priority Critical patent/KR101536028B1/ko
Priority to CN2009801021322A priority patent/CN101910931B/zh
Priority to JP2009548952A priority patent/JP5229236B2/ja
Publication of WO2009088046A1 publication Critical patent/WO2009088046A1/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
    • C08G73/1042—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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/139—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
    • G02F1/1393—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent the birefringence of the liquid crystal being electrically controlled, e.g. ECB-, DAP-, HAN-, PI-LC cells

Definitions

  • the present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.
  • a so-called polyimide type liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution is applied and baked.
  • a liquid crystal alignment film is mainly used.
  • One of the characteristics required for the liquid crystal alignment film is so-called pre-tilt angle control of the liquid crystal in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained 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 increases the pretilt angle depending on the proportion of the diamine used, so the target pretilt angle is controlled. This is relatively easy and is useful as a means for increasing the pretilt angle.
  • a side chain structure of a diamine that increases the pretilt angle of liquid crystal a structure containing a steroid skeleton (see, for example, Patent Document 1) and a ring structure such as a phenyl group or a cyclohexyl group has been proposed (see, for example, Patent Document 2).
  • a diamine having 3 to 4 such ring structures in the side chain has also been proposed (see, for example, Patent Document 3).
  • liquid crystal alignment films used in the liquid crystal alignment films used in the liquid crystal display elements have a high voltage holding ratio and a direct current voltage from the viewpoint of suppressing contrast reduction and afterimage phenomenon.
  • the characteristics that the accumulated charge when applied is small and the residual charge accumulated by the DC voltage is quickly relaxed are becoming increasingly important.
  • a liquid crystal aligning agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid was used as a short time until the afterimage generated by direct current voltage disappears.
  • a liquid crystal aligning agent containing a soluble polyimide using a specific diamine having a pyridine skeleton or the like as a raw material for example, see Patent Document 6.
  • a compound containing one carboxylic acid group in the molecule In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short
  • a liquid crystal aligning agent using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule For example, see Patent Document 7).
  • liquid crystal display elements in such applications are more effective against afterimages than conventional displays that mainly display characters and still images.
  • the requirements are becoming stricter, and characteristics that can withstand long-term use in harsh usage environments are required. Therefore, the liquid crystal alignment film used there is required to have a higher reliability than before, and the electrical characteristics of the liquid crystal alignment film not only have good initial characteristics, but also, for example, at high temperatures. There is a demand for maintaining good characteristics even after long exposure to the ultraviolet light of the backlight.
  • the object of the present invention is to have a property of increasing the pretilt angle of the liquid crystal when it is used as a liquid crystal alignment film, so that the liquid crystal can be vertically aligned even at a small usage rate, and the liquid crystal alignment treatment agent can be applied.
  • An object of the present invention is to provide a liquid crystal aligning agent that hardly causes precipitation even when a poor solvent is mixed with the liquid. In addition to these characteristics, the voltage holding ratio is high, and even after being exposed to a high temperature for a long time, the residual charge accumulated by the DC voltage is quickly relaxed and exposed to the ultraviolet light of the backlight for a long time.
  • An object of the present invention is to provide a liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio even afterward. It is another object of the present invention to provide a highly reliable liquid crystal display device that can withstand long-term use in harsh usage environments.
  • a liquid crystal aligning agent comprising the following component (A) and the following component (B).
  • Component (A) a polymer obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the following formula [1], and a polyimide having a carboxyl group in the molecule of the polymer.
  • R 1 is a tetravalent organic group
  • R 2 is a divalent organic group including the following formula [2].
  • X 1 is phenylene
  • X 2 is cyclohexylene or phenylene
  • X 3 is cyclohexylene
  • X 4 is an alkyl group having 3 to 12 carbon atoms and 3 to 12 carbon atoms.
  • X 2 in the formula [2] is cyclohexylene or phenylene
  • X 4 is an alkyl group having 3 to 6 carbon atoms, an alkoxy group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or
  • type liquid crystal alignment treating agent according to the above [1] R 2 in is a divalent organic group containing the formula [3] (1).
  • the component (A) is a polymer obtained by imidizing polyamic acid having the structural formula of the repeating unit represented by the formula [1], and the amount of the carboxyl group of the polymer is The liquid crystal aligning agent according to any one of the above (1) to (4), wherein the average value with respect to the repeating unit is 0.1 to 3.
  • the component (A) has a structural formula in which a part or all of the repeating units have a unit represented by the following formula [5].
  • the polymer has an imidized polyamic acid, and the amount of carboxyl groups of the polymer is 0.1 to 3 on average with respect to the repeating unit of the polymer.
  • the liquid-crystal aligning agent in any one of.
  • R 3 is a tetravalent organic group
  • R 4 is a divalent organic group
  • at least one of R 3 and R 4 has a carboxyl group.
  • Y 1 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y 2 is a nitrogen-containing aromatic heterocycle)
  • component (B) is an amine compound represented by the following formula [7].
  • Y 3 is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group
  • Y 4 is a single bond, or —O—, —NH —, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms, and the total number of carbon atoms of Y 3 and Y 4 is 1 to 20.
  • Y 5 contains nitrogen.
  • Aromatic heterocycle. (9)
  • the component (B) is an amine compound comprising a combination in which Y 3 , Y 4 , and Y 5 in the formula [7] are each selected from the following groups or rings: Liquid crystal aligning agent.
  • Y 3 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane Ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricyclo One selected from the group consisting of an eico
  • the liquid crystal aligning agent of the present invention can be obtained by a relatively simple method. Moreover, the liquid crystal aligning agent of this invention has the characteristic which enlarges the pretilt angle of a liquid crystal, when it makes it a liquid crystal aligning film, and can align a liquid crystal vertically even with a small usage rate. In addition, precipitation is unlikely to occur when a poor solvent is mixed in the liquid crystal aligning agent coating solution. Furthermore, it is possible to obtain a liquid crystal alignment film that has a high voltage holding ratio and can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. Moreover, the liquid crystal display element which has the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes the thing excellent in reliability, and can be suitably utilized for a high-definition liquid crystal television etc. with a large screen.
  • the liquid-crystal aligning agent of this invention is a polymer which imidated the polyamic acid which has structural formula of the repeating unit represented by said Formula [1] which is (A) component, and is a molecule
  • the amino group (—NH 2 ) is synonymous with a primary amino group, and is hereinafter also referred to as a primary amino group.
  • the specific polyimide in the liquid crystal alignment treatment agent of the present invention uses, as a raw material, a specific diamine having a substituent having a characteristic of increasing the pretilt angle in the side chain (hereinafter also referred to as a specific diamine). Therefore, when this specific diamine is used, the obtained liquid crystal aligning agent can align a liquid crystal perpendicularly even if it is a small usage rate. Further, by reducing the use ratio, the solubility of the polymer in the organic solvent increases, and precipitation hardly occurs even when a poor solvent is mixed in the coating liquid for the liquid crystal alignment treatment agent.
  • the amino group in the specific amine compound forms a salt with the carboxyl group in the specific polyimide, or water or alcohol is removed from the carboxyl group or carboxy ester group in the specific polyimide. It is thought that it has an amide bond accompanied by separation or a bonding reaction involving ring opening of the imide group with respect to the imide group in the specific polyimide. Furthermore, it is considered that the amino group that forms a salt with the carboxyl group in the specific polyimide forms an amide bond by elimination of water in the baking step in producing the liquid crystal alignment film. As a result, the liquid crystal aligning agent of the present invention is efficiently combined with the specific amine compound and the specific polyimide in the obtained liquid crystal alignment film despite the simple means of mixing in an organic solvent. Think.
  • the nitrogen-containing aromatic heterocycle in the specific amine compound functions as an electron hopping site due to its conjugated structure, it promotes the movement of charges in the obtained liquid crystal alignment film.
  • the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide are linked by an electrostatic interaction such as salt formation or hydrogen bond, so that the specific carboxyl group in the specific polyimide is identified. Charge transfer occurs between the nitrogen-containing aromatic heterocycle in the amine compound.
  • the specific amine compound is chemically bonded to the specific polyimide, the charge transferred to the nitrogen-containing aromatic heterocyclic moiety can efficiently move within and between the polyimide molecules.
  • the liquid crystal aligning agent of the present invention has the property of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal alignment film, and can align the liquid crystal vertically even with a small use ratio.
  • precipitation is unlikely to occur when a poor solvent is mixed in the liquid crystal aligning agent coating solution.
  • the specific polyimide as the component (A) is a polymer obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the formula [1], and a carboxyl group is present in the molecule of the polymer. If it is a polyimide which has, the structure will not be specifically limited. Since this polyimide can be obtained relatively easily by using tetracarboxylic dianhydride and diamine as raw materials, a polyamic acid having a structural formula of a repeating unit represented by the formula [1] is imidized. Polymers are preferred.
  • R 1 is a tetravalent organic group
  • R 2 is a divalent organic group including the following formula [2].
  • X 1 is phenylene
  • X 2 is cyclohexylene or phenylene
  • X 3 is cyclohexylene.
  • the phenylene or cyclohexylene may have a substituent as necessary.
  • X 4 is an alkyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, or A fluoroalkoxy group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms.
  • the alkyl group, fluoroalkyl group, alkoxy group, and fluoroalkoxy group may be linear or branched, but are preferably linear and may have an appropriate substituent.
  • the bonding position of the amino group in the benzene ring of the main chain in the formula [2] is not limited.
  • positions 2, 3; positions 2, 4; positions 2, 5; positions 2, 6; positions 3, 4; 5 positions are preferable.
  • the positions 2, 4 or 2, 5 are preferred.
  • X 1 is preferably 1,4-phenylene.
  • X 2 is preferably 1,4-phenylene or 1,4-cyclohexylene, more preferably 1,4-phenylene or 1,4-trans-cyclohexylene. 4-trans-cyclohexylene is preferred.
  • X 3 is preferably 1,4-cyclohexylene, particularly 1,4-trans-cyclohexylene.
  • n in the following formulas [9] to [12] is each independently preferably an integer of 2 to 11, particularly preferably an integer of 2 to 6.
  • the cis-trans isomerism of 1,4-cyclohexylene in the formula is a trans isomer.
  • the specific polyimide including the structure of the formula [2] can be obtained by using a specific diamine represented by the following formula [13] as a raw material.
  • X 1 , X 2 , X 3 and X 4 have the same definitions as those defined in Formula [2].) It is obtained by synthesizing a dinitro compound of the formula [14] and reducing the nitro group to convert it to an amino group by a usual method.
  • the dinitro compound of the formula [14] can be obtained by reacting a hydroxyl group-containing compound represented by the following formula [15] with dinitrochlorobenzene or the like.
  • the specific polyimide containing the structures of the formulas [3], [4], and [9] to [12] can be obtained by the same method as described above.
  • R 1 and R 2 may be one type or may have different R 1 and R 2 and a combination of different types as repeating units.
  • For the purpose of increasing the pretilt angle of the liquid crystal it is preferable to use 1 mol% or more of the structure of the formula [2].
  • the specific polyimide can be obtained by controlling the imidization ratio when imidating the polyamic acid to usually less than 100%.
  • the specific polyimide can also be obtained by imidizing a polyamic acid containing a structural unit represented by the following formula [5] in the repeating unit in the structural formula of the repeating unit represented by the formula [1]. it can.
  • R 3 is a tetravalent organic group
  • R 4 is a divalent organic group
  • at least one of R 3 or R 4 has a carboxyl group.
  • the imidization ratio may be 100%.
  • the imidation ratio of the specific polyimide is preferably 20% or more, and more preferably 40% or more, because a high voltage holding ratio can be obtained.
  • the amount of the carboxyl group in the specific polyimide is preferably 0.1 to 3, more preferably an average value with respect to the repeating unit of the structural formula as polyimide, because the effect of the present invention can be obtained efficiently.
  • the repeating unit in this case is a combination of units containing a non-imidized amic acid group.
  • a polyimide obtained by imidizing a polyamic acid composed of a repeating unit represented by the formula [1] when the imidization rate is less than 100%, the polyimide is composed of a combination of the structures of the following formulas [16a] to [16d].
  • the repeating unit for calculating the amount of carboxyl group as described above includes all of the formulas [16a] to [16d].
  • the amount of the carboxyl group in the specific polyimide (hereinafter also referred to as the average value of the carboxyl group) is determined as the sum of P in (i) below and Q in (ii).
  • the imidation rate (z) is calculated
  • Q in the above (ii) is an average value of the carboxyl group contained in R 3 of the formula [5] with respect to the repeating unit of the structural formula as polyimide:
  • Q 1 and the polyimide of the carboxyl group contained in R 4 mean values for structural formula repeating units as: determined by the sum of the Q 2.
  • Said R ⁇ 3 >, R ⁇ 4 > is the tetracarboxylic dianhydride residue (R ⁇ 3 >) and the diamine residue (R ⁇ 4 >) which are 1 part or all of the raw material used in order to obtain a specific polyimide, respectively.
  • the above Q 1 uses the molar fraction of the tetracarboxylic dianhydride represented by the following formula [V1] in the total molar amount of the tetracarboxylic dianhydride used to obtain the specific polyimide, It is calculated from the following equation (2).
  • R 3 is the same as defined in formula [5].)
  • Q 1 ⁇ 1 ⁇ W 1 / W 2 (2)
  • ⁇ 1 represents the number of carboxyl groups contained in R 3
  • W 1 is the molar amount of tetracarboxylic dianhydride of the formula [V1]
  • W 2 is the total of tetracarboxylic dianhydrides. Represents molar amount.
  • the Q 2 are using the molar fraction of the diamine represented by the formula [V2] below in the total molar amount of the diamine used to obtain a specific polyimide, is calculated from the following equation (3).
  • adjustment of the amount of carboxyl group in the specific polyimide (1) Means for adjusting by controlling the imidization rate, (2) Means for adjusting by the number of carboxyl groups contained in R 3 or R 4 of formula [5] and the ratio of formula [5] in the structural formula of the repeating unit represented by formula [1], Any of these may be used. Furthermore, the means (1) and (2) can be used in combination.
  • the means (1) is preferable.
  • the means (2) is preferable.
  • the means (2) is preferred from the viewpoint that the specific amine compound is not likely to be detached or the polyimide chain is cleaved by the imidization reaction in the baking step when the liquid crystal alignment film is produced.
  • R 1 and R 2 in the formula [1] is not particularly limited.
  • R 1 and R 2 may each be one type in the formula [1], or may have a different structure of R 1 and R 2 and a combination of different types as repeating units. Specific examples of R 1 in the formula [1] are as follows.
  • A-6, A-16, A-18 to A-22, A-25, A-37, or A-38 are soluble in organic solvents even if they have a high imidization ratio. It is preferable because it is high.
  • R 1 when 10 mol% or more of R 1 has an alicyclic structure or an aliphatic structure such as A-1 to A-25, the voltage holding ratio is improved, which is preferable.
  • a combination of two R 1 selected from A-1, A-16, and A-19 is preferable because a liquid crystal alignment film with faster charge relaxation can be obtained.
  • R 2 may contain an organic group other than the structure represented by the formula [2]. Specific examples are as follows.
  • Q represents any of —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, —NH—.
  • the structure is not particularly limited as long as it has a carboxyl group in either R 3 or R 4 .
  • the number of carboxyl groups are each 0-2 to R 3 and R 4 (however, one of R 3 or R 4 has at least one carboxyl group.) Are preferable.
  • R 4 has a carboxyl group.
  • R 4 having a carboxyl group examples include B-102 to B-113. At that time, R 4 may also be used in combination of two or more even one having a carboxyl group.
  • the structure of R 3 is not particularly limited, and specific examples include A-1 to A-45.
  • the manufacturing method of the specific polyimide which is (A) component used for this invention is not specifically limited, In general, the tetracarboxylic acid component which consists of 1 type or multiple types chosen from tetracarboxylic acid and its derivative (s), and 1 type Alternatively, a method is used in which a polyamic acid having a structural formula of a repeating unit represented by the formula [1] is synthesized by reacting with a diamine component composed of a plurality of types of diamine compounds, and the polyamic acid is imidized to form a polyimide. It is done.
  • the polyamic acid obtained can be made into a homopolymer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component as raw materials.
  • tetracarboxylic acid and derivatives thereof as used herein refers to tetracarboxylic acid, tetracarboxylic acid dihalide, or tetracarboxylic dianhydride. Of these, tetracarboxylic dianhydrides are preferred because of their high reactivity with diamine compounds.
  • Polyamide acid can be obtained by polycondensation reaction in an organic solvent such as N-methylpyrrolidone, N, N′-dimethylacetamide, N, N′-dimethylformamide, and ⁇ -butyrolactone.
  • R 1 in formula [18] is the same as that defined in formula [1].
  • R 2 in formula [19] is the same as defined in formula [1].
  • the reaction temperature can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° C. to 100 ° C.
  • the ratio of the total number of moles of the compound constituting the tetracarboxylic acid component to the total number of moles of the diamine compound constituting the diamine component is preferably 0.8: 1 to 1.2: 1, particularly preferably 0.9. : 1 to 1.1: 1. The closer this molar ratio is to 1.0, the greater the degree of polymerization of the polymer produced.
  • a carboxyl group is added to R 1.
  • a tetracarboxylic dianhydride having a diamine and / or a diamine having a carboxyl group at R 2 may be used.
  • thermal imidization by heating and catalyst imidization using a catalyst are generally used, but the catalyst imidation in which the imidization reaction proceeds at a relatively low temperature is obtained. It is preferable that the molecular weight does not decrease.
  • the catalytic imidation can be performed by stirring the polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • the reaction temperature at this time is ⁇ 20 to 250 ° C., preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but if it is too high, the molecular weight of the polyimide may decrease.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. If the amount of the basic catalyst or the acid anhydride is small, the reaction does not proceed sufficiently.
  • Examples of the basic catalyst used in this case 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.
  • Examples of 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 organic solvent is not limited as long as it can dissolve polyamic acid, and specific examples thereof include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, Examples thereof include N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide, and ⁇ -butyrolactone.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the produced polyimide can be obtained by collecting the reaction solution into a poor solvent and collecting the produced precipitate.
  • the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like.
  • the polyimide that has been poured into a poor solvent and precipitated is filtered, and then can be powdered by drying at normal temperature or under reduced pressure at normal temperature or under reduced pressure.
  • the polyimide can be purified by repeating the steps of dissolving the polyimide powder in an organic solvent and reprecipitating it 2 to 10 times. When the impurities cannot be removed by a single precipitation recovery operation, it is preferable to perform this purification step.
  • the molecular weight of the specific polyimide used in the present invention is not particularly limited, but is preferably 2,000 to 200,000 in terms of weight average molecular weight, more preferably 4 from the viewpoint of easy handling and stability of characteristics when a film is formed. , 50,000 to 50,000.
  • the molecular weight is determined by GPC (gel permeation chromatography).
  • the specific amine compound as the component (B) used in the present invention has one amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the amino group is a divalent aliphatic hydrocarbon group or a non-valent group. It is an amine compound bonded to an aromatic cyclic hydrocarbon group. Since this specific amine compound has only one amino group in the molecule, problems such as polymer precipitation and gelation may occur when preparing the liquid crystal alignment treatment agent or during storage of the liquid crystal alignment agent. Can be avoided.
  • the primary amino group contained in the specific amine compound contains a divalent aliphatic hydrocarbon group or non-aromatic hydrocarbon in the molecule from the viewpoint of salt formation with a specific polyimide and ease of bonding reaction. It must be bonded to an aromatic cyclic hydrocarbon group.
  • aliphatic hydrocarbon group examples include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • divalent non-aromatic cyclic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, and cyclododecane.
  • the nitrogen-containing aromatic heterocyclic ring contained in the specific amine compound is an aromatic cyclic hydrocarbon containing at least one structure selected from the group consisting of the following formula [20a], formula [20b] and formula [20c]. More preferably, it is 1 to 4.
  • Z 2 is a linear or branched alkyl group having 1 to 5 carbon atoms.
  • Y 1 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group
  • Y 2 is a nitrogen-containing aromatic heterocyclic ring.
  • Y 1 is not particularly limited as long as Y 1 is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
  • Preferred Y 1 in the formula [6] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms.
  • Examples of the non-aromatic cyclic hydrocarbon group include the structures described above.
  • Y 1 is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring. , Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y 1 is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.
  • —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 1 is —O—, —NH—, —CO—O—.
  • —O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, — C (CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O -It may be replaced by a divalent cyclic hydrocarbon group or a heterocyclic ring.
  • a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
  • divalent cyclic hydrocarbon group examples include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring.
  • divalent heterocyclic ring examples include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole.
  • Y 2 in the formula [6] is a nitrogen-containing aromatic heterocycle, and as described above, at least one structure selected from the group consisting of the formula [20a], the formula [20b], and the formula [20c] Is an aromatic cyclic hydrocarbon containing Specific examples thereof include the structure described above.
  • pyrrole ring imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring and a phthalazine ring are preferable.
  • Y 1 is represented by the formula [20a] and formula contained in Y 2. It is preferably bonded to a substituent not adjacent to [20b] and formula [20c]. Furthermore, the carbon atom of the nitrogen-containing aromatic heterocyclic ring that is Y 2 in Formula [6] may have a halogen atom and / or a substituent of an organic group, and the organic group includes an oxygen atom, a sulfur atom, You may contain hetero atoms, such as a nitrogen atom.
  • Y 1 is selected from the group consisting of non-aromatic cyclic hydrocarbon group having an aliphatic hydrocarbon group and having 3 to 20 carbon atoms having 1 to 20 carbon atoms
  • Y 2 is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole A ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring.
  • the carbon atom of the nitrogen-containing aromatic heterocycle of Y 2 may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • a more preferred specific amine compound is an amine compound represented by the following formula [7].
  • Y 3 is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group, and Y 4 is a single bond, or —O—, —NH—, — S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms, and the total number of carbon atoms of Y 3 and Y 4 is 1 to 20.
  • Y 5 is a nitrogen-containing aromatic complex. A ring.
  • Y 3 in the formula [7] is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooct
  • a linear or branched alkylene group having 1 to 10 carbon atoms cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane And a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring.
  • Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.
  • —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y 3 is —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —C ( CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O—, It may be replaced with a divalent cyclic hydrocarbon group or a heterocyclic ring.
  • a hydrogen atom bonded to an arbitrary carbon atom includes a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.
  • the cyclic hydrocarbon group and the heterocyclic ring referred to here have the same meaning as defined for Y 1 in the formula [6].
  • Y 4 in the formula [7] is a single bond, —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms.
  • the divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y 4 are given below.
  • Y 5 in Formula [7] is a nitrogen-containing aromatic heterocycle, and is the same as the definition of Y 2 in Formula [6]. Specific examples thereof include the same structure as Y 2 described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring, or a phthalazine ring is preferable.
  • Y 4 is a formula [20a] or formula included in Y 5. It is preferably bonded to a carbon atom that is not adjacent to [20b] or formula [20c]. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring represented by Y 5 in the formula [7] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom, a sulfur atom, nitrogen You may contain hetero atoms, such as an atom.
  • Y 3 is a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclohexane A heptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring, and Y 4 is a single bond, having 1 to 10 carbon atoms A linear or branched alkylene group, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—,
  • the carbon atom of the nitrogen-containing aromatic heterocycle of Y 5 may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Y 3 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, A cycloheptane ring, a norbornene ring, or an adamantane ring
  • Y 4 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—.
  • the carbon atom of the nitrogen-containing aromatic heterocycle of Y 5 may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Y 3 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring or a cyclohexane ring
  • Y 4 is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, — NH—CO—, —CO—, —CH (OH) —, —NH—CH 2 —, —S—CH 2 —, —O—CH 2 —, —NH—CO—CH 2 —, —CO—CH 2 —, —CO—, —CO—NH—CH 2 —, —NH—CH 2 —CH (CH 3 ) —, —S—
  • the carbon atom of the nitrogen-containing aromatic heterocycle of Y 5 may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • a particularly preferred combination of Y 3 , Y 4 and Y 5 in the formula [7] is that Y 3 is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, and Y 4 is a simple group.
  • Y 5 is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.
  • the carbon atom of the nitrogen-containing aromatic heterocycle of Y 5 may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
  • Specific examples of the specific amine compound used in the present invention include compounds of M1 to M156.
  • More preferable compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, M128 to M137, M139 to M143, and M149 to M156.
  • M6 to M8 M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116 M118 to M121, M125, M134 to M136, M139, M140, M143, M150, and M152 to M156.
  • the liquid-crystal aligning agent of this invention is normally obtained by mixing the above-mentioned specific polyimide which is (A) component, and the specific amine compound which is (B) component in an organic solvent.
  • Each of the specific polyimide and the characteristic amine compound to be mixed may be one kind or a plurality of kinds may be used in combination.
  • a reaction solution (specific polyimide solution) obtained by imidizing polyamic acid which is a precursor of the specific polyimide may be used.
  • the powder of the specific polyimide obtained by purification is used as an organic solvent.
  • the method of adding a specific amine compound to the solution dissolved in (1) is mentioned.
  • the organic solvent used in that case will not be specifically limited if it is a solvent which dissolves specific polyimide. Specific examples of such organic solvents are given below.
  • Examples include propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. Two or more kinds of these solvents may be mixed and used.
  • the specific polyimide When the specific polyimide is dissolved in the organic solvent, the specific polyimide may be heated for the purpose of promoting the dissolution of the specific polyimide. If the heating temperature is too high, the molecular weight of the polyimide may decrease, so a temperature of 30 to 100 ° C. is preferred.
  • the concentration of the specific polyimide solution is not particularly limited. However, since it is easy to mix uniformly with the specific amine compound, the specific polyimide concentration in the solution is preferably 1 to 20% by mass, more preferably 3 to 15% by mass. Preferably, it is 3 to 10% by mass.
  • the specific amine compound may be added directly to the solution of the specific polyimide. However, it is preferable to add the specific amine compound after forming a solution with a suitable solvent, preferably at a concentration of 0.1 to 10% by mass. As this solvent, the solvent of the specific polyimide mentioned above is mentioned.
  • the temperature when heating after mixing is preferably 10 to 100 ° C, more preferably 20 to 80 ° C.
  • the content of the specific amine compound in the liquid crystal aligning agent of the present invention is 1 of the carboxyl group contained in the specific polyimide because the effects of the present invention can be obtained efficiently and the stability of the liquid crystal aligning agent is not impaired.
  • the molar amount is preferably 0.01 to 2 mol times, more preferably 0.05 to 1 mol times, and particularly preferably 0.08 to 0.8 mol times.
  • the liquid crystal alignment treatment agent of the present invention is a solvent or compound that improves the film thickness uniformity and surface smoothness when the liquid crystal alignment treatment agent is applied as other components, a liquid crystal alignment film A compound that improves the adhesion between the substrate and the substrate may be contained.
  • Other components may be added during the mixing of the specific polyimide and the specific amine compound, or may be added later to these mixed solutions.
  • the solvent for improving the film thickness uniformity and surface smoothness include the following.
  • solvents may be used alone or in combination.
  • it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. 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 (manufactured by Asahi Glass Co., Ltd.).
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (A) contained in the liquid crystal aligning agent. It is.
  • Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • the amount of the compound used to improve the adhesion to the substrate is preferably 0.1 to 30 parts by mass, more preferably 1 to 100 parts by mass of the specific polyimide component contained in the liquid crystal aligning agent. ⁇ 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • the liquid crystal alignment treatment agent of the present invention changes the polymer components other than the specific polyimide, and the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired. It is also possible to add a target dielectric material or conductive material, or a crosslinkable compound for the purpose of increasing the hardness or density of the liquid crystal alignment film.
  • concentration of the solid content in the liquid crystal alignment treatment agent of the present invention can be appropriately changed depending on the film thickness of the target liquid crystal alignment film, but a film having no defect is formed, and the film thickness is suitable as a liquid crystal alignment film. Is preferably from 1 to 20% by mass, more preferably from 2 to 10% by mass.
  • the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
  • Firing after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
  • 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.
  • the molecular weight of the polyimide in the synthesis example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Science Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex.
  • GPC room temperature gel permeation chromatography
  • the imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 by Kusano Kagaku Co., Ltd.), add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
  • JNW-ECA500 an NMR measuring instrument manufactured by JEOL Datum.
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of reference protons to.
  • NMP (9.34 g) was added to the polyimide powder (A) (1.65 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours.
  • 10 mass% NMP solution (0.50 g) of 3-AMP (0.050 g as 3-AMP), NMP (3.43 g), and BCS (12.5 g)
  • the mixture was stirred at 50 ° C. for 15 hours.
  • a liquid crystal aligning agent [1] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • the liquid crystal aligning agent [1] obtained above was spin-coated on the ITO surface of the 3 cm ⁇ 4 cm ITO electrode substrate, and baked at 80 ° C. for 5 minutes and in a 210 ° C. hot air circulating oven for 1 hour. A polyimide coating was prepared.
  • This substrate with a liquid crystal alignment film is subjected to a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • pretilt angle of the liquid crystal cell produced as described above was measured at room temperature using a pretilt angle measuring device (ELSICON model: PAS-301). The results are shown in Table 2 described later. Moreover, when the liquid crystal cell produced similarly to the above except having not rubbed was observed with the polarizing microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.
  • ⁇ Evaluation of voltage holding ratio> A voltage of 4V was applied to the liquid crystal cell after the pretilt angle measurement at a temperature of 80 ° C. for 60 ⁇ s, the voltage after 16.67 ms and 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 3 described later.
  • ⁇ Evaluation of residual charge relaxation> A DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charges after 50 seconds and 1000 seconds were measured. For measurement, a 6254 type liquid crystal property evaluation apparatus manufactured by Toyo Technica Co., Ltd. was used. The results are shown in Table 4 described later.
  • the liquid crystal cell was irradiated with ultraviolet rays having a dose of 10 J / cm 2 at 365 nm by a desktop UV curing device (HCT3 B28 HEX-1 (manufactured by Sen Special Light Source)), and the voltage was maintained under the same conditions. The rate was measured. The results are shown in Table 5 described later.
  • NMP (9.46 g) was added to the polyimide powder (B) (1.67 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours.
  • 10 mass% NMP solution (0.50 g) of 3-AMP (0.050 g as 3-AMP), NMP (3.47 g), and BCS (12.5 g)
  • the mixture was stirred at 50 ° C. for 15 hours.
  • a liquid crystal aligning agent [2] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 2 Using the obtained liquid crystal aligning agent [2], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10 wt% 3-MP NMP solution (0.83 g) (0.083 g as 3-AMP), NMP (3.14 g), and BCS (12.4 g), and 15 hours at 50 ° C.
  • the liquid crystal aligning agent [3] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 2 Using the obtained liquid crystal aligning agent [3], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours.
  • 10% by weight NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.84 g), and BCS (12.4 g) was added to this solution.
  • the liquid crystal aligning agent [4] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [4], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.29 g) was added to the polyimide powder (B) (1.64 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours.
  • 10 mass% NMP solution (1.64 g) of 3-AMP (0.164 g as 3-AMP), NMP (2.38 g), and BCS (12.3 g) was added to this solution.
  • the liquid crystal aligning agent [5] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 2 Using the obtained liquid crystal aligning agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10 wt% NMP solution (1.16 g) of 4-AMP (0.116 g as 4-AMP), NMP (2.84 g), and BCS (12.4 g)
  • the mixture was stirred at 50 ° C. for 15 hours.
  • a liquid crystal aligning agent [6] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [6], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.41 g) was added to the polyimide powder (B) (1.66 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10 mass% NMP solution (1.16 g) of AEP (0.116 g as AEP), NMP (2.86 g), and BCS (12.5 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours.
  • a liquid crystal aligning agent [7] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [7], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10% by mass NMP solution (1.16 g) of API (0.116 g as API), NMP (2.84 g), and BCS (12.4 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours.
  • a liquid crystal aligning agent [8] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [8], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10% by mass NMP solution of 2-AMMP (1.16 g) (0.116 g as 2-AMMP), NMP (2.84 g), and BCS (12.4 g) were added, and the mixture was stirred at 50 ° C. for 15 hours.
  • the liquid crystal aligning agent [9] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [9], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.29 g) was added to the polyimide powder (C) (1.64 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 40 hours.
  • 10 mass% NMP solution (1.64 g) of 3-AMP (0.164 g as 3-AMP), NMP (2.38 g), and BCS (12.3 g) was added to this solution.
  • a liquid crystal aligning agent [10] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [10], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (D) (1.65 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10 wt% NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.85 g), and BCS (12.4 g) was added to this solution.
  • a liquid crystal aligning agent [11] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [11], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (E) (1.65 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 40 hours.
  • 10% by weight NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.84 g), and BCS (12.5 g) was added to this solution.
  • NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.84 g), and BCS (12.5 g)
  • a liquid crystal aligning agent [12] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 2 Using the obtained liquid crystal aligning agent [12], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • Example 1 when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • Example 1 when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • Example 1 when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • Example 1 when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • Example 1 when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.23 g) was added to the polyimide powder (B) (1.63 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours.
  • PMP 10 mass% PMP of NMP solution (1.14 g) (0.114 g as Py), NMP (2.80 g), and BCS (12.3 g)
  • a liquid crystal aligning agent [18] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [18], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.33 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours.
  • 10% by mass NMP solution (1.16 g) of AP (0.116 g as AP), NMP (2.83 g), and BCS (12.3 g) was added to this solution and stirring at 50 ° C. for 15 hours.
  • a liquid crystal aligning agent [19] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [19], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.23 g) was added to the polyimide powder (B) (1.63 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10 mass% NMP solution (1.14 g) of HA (0.114 g as HA), NMP (2.78 g), and BCS (12.3 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours.
  • a liquid crystal aligning agent [20] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 2 Using the obtained liquid crystal aligning agent [20], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • NMP (9.34 g) was added to the polyimide powder (F) (1.65 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 40 hours.
  • a 10 wt% NMP solution (0.50 g) of 3-AMP (0.05 g as 3-AMP), NMP (3.43 g), and BCS (12.4 g), and the mixture was stirred at 50 ° C. for 15 hours.
  • the liquid crystal aligning agent [21] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 1 Using the obtained liquid crystal aligning agent [21], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarization microscope except having not rubbed, the liquid crystal was not vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • Example 2 Using the obtained liquid crystal aligning agent [22], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.
  • the liquid crystal aligning agent of the present invention has the effect of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal aligning film, and can align the liquid crystal vertically even with a small use ratio. Precipitation does not easily occur when a poor solvent is mixed with the coating solution.
  • the voltage holding ratio is high, and even after being exposed to a high temperature for a long time, the charge accumulated by the DC voltage is quickly relaxed and after being exposed to the ultraviolet light of the backlight for a long time.
  • the liquid crystal aligning agent from which the liquid crystal aligning film which can suppress the fall of a voltage holding rate is obtained is obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a harsh use environment can be provided.

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Abstract

L'invention porte sur un agent d'alignement de cristaux liquides ayant une caractéristique d'augmentation de l'angle de pré-inclinaison d'un cristal liquide, qui est capable d'aligner verticalement des cristaux liquides, même avec une petite quantité d'utilisation. L'invention porte également sur un dispositif d'affichage à cristaux liquides utilisant un tel agent d'alignement de cristaux liquides. De façon précise, l'invention porte sur un agent d'alignement de cristaux liquides caractérisé par le fait qu'il contient les composants (A) et (B) suivants. Le composant (A) : est un polyimide ayant un groupe carboxyle dans une molécule, qui est un polymère obtenu par l'imidation d'un poly(amide-acide) comportant une unité de répétition représentée par la formule structurelle [1] ci-dessous. Le composant (B) : est un composé d'amine ayant un groupe amino primaire et un noyau hétérocyclique aromatique contenant de l'azote dans une molécule, le groupe amino primaire étant lié à un groupe d'hydrocarbure aliphatique ou à un groupe d'hydrocarbure cyclique non aromatique (Dans la formule [1], R1 représente un groupe organique tétravalent; et R2 représente un groupe organique divalent, comprenant le groupe représenté par la formule [2].) (Dans la formule [2], X1 représente un phénylène; X2 représente un cyclohexylène ou un phénylène; X3 représente un cyclohexylène, et X4 représente un groupe alkyle ayant 3 à 12 atomes de carbone, un groupe alcoxy ayant 3 à 12 atomes de carbone, un groupe fluroroalkyle ayant 3 à 12 atomes de carbone ou un groupe fluoroalcoxy ayant 3 à 12 atomes de carbone.)
PCT/JP2009/050154 2008-01-11 2009-01-08 Agent d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides l'utilisant Ceased WO2009088046A1 (fr)

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CN2009801021322A CN101910931B (zh) 2008-01-11 2009-01-08 液晶取向处理剂及使用了该处理剂的液晶显示元件
JP2009548952A JP5229236B2 (ja) 2008-01-11 2009-01-08 液晶配向処理剤、及びそれを用いた液晶表示素子

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110071595A (ko) * 2009-12-21 2011-06-29 삼성전자주식회사 수직 배향막 및 이를 포함하는 액정 표시 장치
US20140104555A1 (en) * 2011-02-01 2014-04-17 Samsung Display Co., Ltd. Vertical alignment layer and liquid crystal display including the same
JP2017197631A (ja) * 2016-04-26 2017-11-02 宇部興産株式会社 ポリイミド前駆体、ポリイミド、ポリイミドフィルム、ポリイミド積層体、ポリイミド／ハードコート積層体
JP2017226647A (ja) * 2011-11-01 2017-12-28 日産化学工業株式会社 新規なジアミン化合物、ポリイミド前駆体及びポリイミド
JP7512879B2 (ja) 2020-12-21 2024-07-09 Jnc株式会社 液晶配向剤、液晶配向膜、およびこれを用いた液晶表示素子

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0627598Y2 (ja) 1986-07-23 1994-07-27 株式会社柴崎製作所 キャッピングマシン
JP5552894B2 (ja) * 2010-05-14 2014-07-16 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
WO2013147083A1 (fr) * 2012-03-30 2013-10-03 日産化学工業株式会社 Agent d'alignement de cristaux liquides à base de polyimide, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
CN104718492B (zh) * 2012-08-10 2018-09-18 日产化学工业株式会社 液晶取向剂、液晶取向膜及液晶显示元件
TWI597305B (zh) * 2012-11-30 2017-09-01 Nissan Chemical Ind Ltd A method of manufacturing a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element
CN107003566B (zh) * 2014-11-13 2020-12-04 日产化学工业株式会社 液晶取向处理剂、液晶取向膜和液晶表示元件
KR101856727B1 (ko) 2016-06-21 2018-05-10 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 및 이를 이용한 액정 배향막
CN110989247B (zh) * 2019-12-03 2023-03-17 Tcl华星光电技术有限公司 一种液晶显示面板及其制备方法
CN116622083B (zh) * 2023-05-29 2025-07-04 南京晶立得科技有限公司 基于四芳基金刚烷结晶伴侣的共晶材料及其制备方法和在分子共晶与结构鉴定中的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003096034A (ja) * 2001-09-27 2003-04-03 Chisso Corp フェニレンジアミン誘導体、液晶配向膜および液晶表示素子
WO2004052962A1 (fr) * 2002-12-11 2004-06-24 Nissan Chemical Industries, Ltd. Nouveau derive de diaminobenzene, precurseur de polyimide et polyimide obtenu a partir de ce derive, et agent d'alignement pour cristal liquide
WO2004099289A1 (fr) * 2003-05-07 2004-11-18 Nissan Chemical Industries, Ltd. Agent d'alignement pour cristal liquide
JP2007248637A (ja) * 2006-03-14 2007-09-27 National Institute For Materials Science 液晶配向膜、液晶配向剤、及び液晶表示素子

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002020487A (ja) * 2000-07-13 2002-01-23 Jsr Corp アルキルフルオレンジアミン、ポリアミック酸、イミド化重合体、液晶配向剤、液晶配向膜の形成方法および液晶表示素子
JP4013052B2 (ja) * 2002-09-25 2007-11-28 日産化学工業株式会社 液晶配向処理剤および液晶表示素子
AU2003286430A1 (en) * 2002-12-10 2004-06-30 Canon Kabushiki Kaisha Process for producing crystalline thin film
TWI409298B (zh) * 2006-03-24 2013-09-21 Jnc Corp 液晶配向劑、液晶配向膜以及液晶顯示元件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003096034A (ja) * 2001-09-27 2003-04-03 Chisso Corp フェニレンジアミン誘導体、液晶配向膜および液晶表示素子
WO2004052962A1 (fr) * 2002-12-11 2004-06-24 Nissan Chemical Industries, Ltd. Nouveau derive de diaminobenzene, precurseur de polyimide et polyimide obtenu a partir de ce derive, et agent d'alignement pour cristal liquide
WO2004099289A1 (fr) * 2003-05-07 2004-11-18 Nissan Chemical Industries, Ltd. Agent d'alignement pour cristal liquide
JP2007248637A (ja) * 2006-03-14 2007-09-27 National Institute For Materials Science 液晶配向膜、液晶配向剤、及び液晶表示素子

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110071595A (ko) * 2009-12-21 2011-06-29 삼성전자주식회사 수직 배향막 및 이를 포함하는 액정 표시 장치
JP2011127090A (ja) * 2009-12-21 2011-06-30 Samsung Electronics Co Ltd 垂直配向膜及びこれを含む液晶表示装置
KR101626900B1 (ko) 2009-12-21 2016-06-03 삼성디스플레이 주식회사 수직 배향막 및 이를 포함하는 액정 표시 장치
US20140104555A1 (en) * 2011-02-01 2014-04-17 Samsung Display Co., Ltd. Vertical alignment layer and liquid crystal display including the same
US9244309B2 (en) * 2011-02-01 2016-01-26 Samsung Display Co., Ltd. Vertical alignment layer and liquid crystal display including the same
JP2017226647A (ja) * 2011-11-01 2017-12-28 日産化学工業株式会社 新規なジアミン化合物、ポリイミド前駆体及びポリイミド
JP2017197631A (ja) * 2016-04-26 2017-11-02 宇部興産株式会社 ポリイミド前駆体、ポリイミド、ポリイミドフィルム、ポリイミド積層体、ポリイミド／ハードコート積層体
JP7512879B2 (ja) 2020-12-21 2024-07-09 Jnc株式会社 液晶配向剤、液晶配向膜、およびこれを用いた液晶表示素子

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TW200951582A (en) 2009-12-16
CN101910931B (zh) 2012-05-30
JPWO2009088046A1 (ja) 2011-05-26
KR20100103554A (ko) 2010-09-27
CN101910931A (zh) 2010-12-08
KR101536028B1 (ko) 2015-07-10

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