WO2019182071A1 - Agent d'alignement de cristaux liquides, polymère permettant de l'obtenir, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides le comprenant - Google Patents

Agent d'alignement de cristaux liquides, polymère permettant de l'obtenir, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides le comprenant Download PDF

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WO2019182071A1
WO2019182071A1 PCT/JP2019/011907 JP2019011907W WO2019182071A1 WO 2019182071 A1 WO2019182071 A1 WO 2019182071A1 JP 2019011907 W JP2019011907 W JP 2019011907W WO 2019182071 A1 WO2019182071 A1 WO 2019182071A1
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liquid crystal
carbon atoms
group
formula
polymer
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PCT/JP2019/011907
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English (en)
Japanese (ja)
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尚宏 野田
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日産化学株式会社
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Priority to JP2020507906A priority Critical patent/JP7235209B2/ja
Priority to CN201980019479.4A priority patent/CN111868618B/zh
Priority to KR1020207029468A priority patent/KR20200135404A/ko
Publication of WO2019182071A1 publication Critical patent/WO2019182071A1/fr
Priority to JP2023004168A priority patent/JP2023052403A/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • C08G18/3259—Reaction products of polyamines with inorganic or organic acids or derivatives thereof other than metallic salts
    • C08G18/3262—Reaction products of polyamines with inorganic or organic acids or derivatives thereof other than metallic salts with carboxylic acids or derivatives thereof
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal alignment agent, a polymer for obtaining the same, a liquid crystal alignment film, and a liquid crystal display element using the same.
  • a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction.
  • the main liquid crystal alignment film used industrially is a polyimide liquid crystal aligning agent made of polyamic acid (also called polyimide precursor or polyamic acid) or a polyimide solution applied to a substrate and baked. A film is formed.
  • Patent Document 1 Japanese Patent Laid-Open No. 2-287324 proposes to use a polyimide resin having a specific repeating structure in order to obtain a high voltage holding ratio (VHR).
  • Patent Document 2 Japanese Patent Laid-Open No. 10-104633 proposes the use of a soluble polyimide having a nitrogen atom in addition to the imide group in order to shorten the time until the afterimage is erased.
  • the material used for the liquid crystal alignment film examples include polyimide precursors such as polyamide acid and polyamide acid ester, and polyimide obtained by dehydrating them by baking or chemical reaction.
  • polyimide precursors such as polyamide acid and polyamide acid ester
  • polyimide obtained by dehydrating them by baking or chemical reaction since the polyamic acid is easy to synthesize and has excellent solubility in a solvent, it is possible to obtain a liquid crystal aligning agent having excellent coating properties and film forming properties on a substrate.
  • polyamic acid is easily decomposed by hydrolysis or the like due to its structure, it is difficult to ensure reliability over a long period of time with a liquid crystal alignment film obtained using the polyamic acid.
  • soluble polyimide polyimide that is soluble in a solvent obtained by polyamic acid dehydration reaction
  • soluble polyimide polyimide that is soluble in a solvent obtained by polyamic acid dehydration reaction
  • it becomes easy to ensure reliability over a long period of time.
  • soluble polyimide has few choices of solvent that can be dissolved, and therefore, the solvent that can be used is limited.
  • precipitation or the like occurs during coating and film formation. It is easy to be defective.
  • the present inventors have found that a polymer having a specific structure and a liquid crystal aligning agent using the polymer are effective for achieving the above object, and have completed the present invention. It was.
  • the said polymer is novel and the monomer for obtaining the said polymer also contains the novel compound.
  • the present invention provides the following 1. ⁇ 10. Is the gist. 1. A liquid crystal aligning agent using a polymer obtained from a diamine derivative represented by the following formula (1), a diisocyanate derivative, and a monomer selected from diamine or diisocyanate having a specific side chain.
  • A represents a divalent organic group selected from an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • B and C each independently represent a single bond or an aliphatic carbon group having 1 to 5 carbon atoms.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms and may be branched.
  • R 2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an organic group represented by the formula (1-1).
  • Ra and Rb each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms.
  • the monomer containing the specific side chain is represented by the following formula (2): Liquid crystal aligning agent as described in.
  • N represents an amino group or an isocyanate group
  • R 3 represents a single bond or a divalent organic group
  • X 1 , X 2 , and X 3 each independently represent a benzene ring or a cyclohexane ring.
  • P, q and r each independently represents an integer of 0 or 1
  • R 4 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent having 12 to 25 carbon atoms having a steroid skeleton.
  • An organic group is shown.
  • the diamine derivative is a diamino compound represented by the following formula (3). Liquid crystal aligning agent as described in.
  • Ar represents an aryl group
  • D represents a single bond or a hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 , R 2 , Ra and Rb are synonymous with the above R 1 , R 2 , Ra and Rb.
  • the diamine derivative is a diamino compound represented by the following formula (3-a): Liquid crystal aligning agent as described in.
  • D and R 1 have the same meanings as D and R 1 above.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms and may be branched.
  • B represents a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • Ra and Rb each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms.
  • the monomer containing the specific side chain is represented by the following formula (2).
  • N represents an amino group or an isocyanate group
  • R 3 represents a single bond or a divalent organic group
  • X 1 , X 2 , and X 3 each independently represent a benzene ring or a cyclohexane ring.
  • P, q and r each independently represents an integer of 0 or 1
  • R 4 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent having 12 to 25 carbon atoms having a steroid skeleton.
  • An organic group is shown.
  • the diisocyanate derivative is at least one of structures represented by the following formulas (4-1) to (4-13); The polymer described in 1.
  • R 5 and R 6 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
  • the present invention it is possible to provide a liquid crystal aligning agent that can be fired at a low temperature and can obtain a high-quality liquid crystal aligning film and has excellent printability. Moreover, according to this invention, the novel polymer for obtaining the said liquid crystal aligning agent can be provided. In addition, according to the present invention, in addition to realizing a high pretilt angle, a liquid crystal alignment film having a high voltage holding ratio can be provided. Furthermore, according to this invention, the liquid crystal display element using the said liquid crystal aligning film can be provided.
  • the liquid crystal aligning agent which is one embodiment of the present invention includes a diamine derivative represented by formula (1) (hereinafter sometimes referred to as “diamine”), a diisocyanate derivative (hereinafter sometimes referred to as “diisocyanate”), It contains a polymer according to one embodiment of the present invention, which is obtained from a monomer selected from diamine or diisocyanate having a specific side chain (hereinafter sometimes referred to as “side chain-containing monomer”).
  • the diamine used in the present invention is represented by the formula (1).
  • A represents a divalent organic group of an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • B and C each independently represent a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • R1 represents an alkyl group having 1 to 4 carbon atoms and may be branched.
  • R2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an organic group represented by the formula (1-1).
  • Ra and Rb each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms.
  • A is an aromatic hydrocarbon group
  • B is 1 carbon atom. It is preferable that the aliphatic hydrocarbon group of 1 to 3 and C is a single bond.
  • Specific examples of the formula (1) include the following structures.
  • Ar represents an aryl group
  • D represents a single bond or a hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 , R 2 , Ra and Rb are synonymous with the above R 1 , R 2 , Ra and Rb.
  • formula (3) When considering the viewpoint that it is easy to obtain a reagent for synthesizing diamine, the reactivity with diisocyanate is good, the physical properties of the obtained polymer are good, etc., formula (3) Among them, Ar is preferably a phenyl group, and R 2 is preferably a hydrogen atom. Therefore, the formula (3) is preferably a structure represented by the following formula (3-a) ′. Especially, in Formula (3), it is preferable that Ra and Rb are each a hydrogen atom. Therefore, the formula (3) is particularly preferably represented by the formula (3-a).
  • D and R 1 have the same meanings as D and R 1 above.
  • the above formula (3-a) ′ is preferably represented by the following formula (3-1). Is done.
  • Formula (3-1) when B has 1 and 2 carbon atoms, and Ra and Rb are each a hydrogen atom, Formula (3-1) can be represented by Formula (3-1a) and Formula (3-1b) It is represented by
  • R 1 has the same meaning as R 1 described above.
  • a specific example of the diamine represented by the formula (1) is not limited to the diamine represented by the formula (3). If the effect of the present invention (for example, that a high pretilt angle can be realized) is not impaired, a part of the diamine represented by the formula (1) or the formula (3) may be used in synthesizing the polymer. You may substitute with the diamine represented by Formula (5) mentioned later.
  • the diisocyanate used in the present invention is represented by the following formula (4).
  • Formula (4) is preferably represented by Formula (4-1) to Formula (4-13).
  • R 5 and R 6 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
  • aromatic diisocyanates represented by formulas (4-1) to (4-5) When using aliphatic diisocyanates represented by formulas (4-1) to (4-5), compared to using aromatic diisocyanates represented by formulas (4-6) to (4-13) The resulting polymer is well dissolved in the solvent. On the other hand, the aromatic diisocyanate reacts better with diamine than the aliphatic diisocyanate.
  • aromatic diisocyanates such as those represented by formulas (4-6) and (4-7) can react well with diamines and improve the heat resistance of the resulting liquid crystal alignment film.
  • the formula (4) is represented by the formula (4-1), the formula (4- 7), Formula (4-8), Formula (4-9), or Formula (4-10) is preferable.
  • the formula (5) is preferably the formula (4-12) from the viewpoint of improving the electrical characteristics of the obtained liquid crystal alignment film, and from the viewpoint of improving the liquid crystal alignment of the obtained liquid crystal alignment film. Is preferably formula (4-13).
  • formula (4) is not limited to the above as long as it is within the scope of the present invention.
  • a readily available diisocyanate can be suitably used in accordance with target properties such as the obtained polymer, liquid crystal aligning agent, and liquid crystal aligning film. Two or more diisocyanates may be used in combination.
  • the side chain-containing monomer used in the present invention is represented by the formula (2).
  • N represents an amino group or an isocyanate group
  • R 3 represents a single bond or a divalent organic group
  • X 1 , X 2 , and X 3 each independently represent a benzene ring or a cyclohexane ring.
  • P, q and r each independently represents an integer of 0 or 1
  • R 4 is selected from a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a carbon atom having 12 to 25 carbon atoms having a steroid skeleton.
  • a valent organic group is selected from a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a carbon atom having 12 to 25 carbon atoms having a steroid skeleton.
  • the side chain-containing monomer represented by the formula (2) contributes to increasing the pretilt angle of the liquid crystal.
  • the side chain-containing monomer is a diamine
  • the diamine may have a long-chain alkyl group, a perfluoroalkyl group, an aromatic cyclic group, an aliphatic cyclic group, a substituent combining these, a steroid skeleton group, and the like. preferable. Since the preferred size of the pretilt angle varies depending on the display mode of the liquid crystal display, the desired pretilt angle can be obtained by variously selecting the structure and amount of the side chain-containing monomer.
  • the TN mode which requires a pretilt angle of 3 ° to 5 °, which is lower than the VA mode, which will be described later
  • the OCB mode which requires a pretilt of 8 ° to 20 °, etc.
  • pretilt development ability it is preferable to use a relatively small side chain-containing monomer.
  • side chain-containing monomers having long alkyl side chains such as [2-1] to [2-3] in Table 1 are preferred.
  • the side chain-containing monomers represented by [2-25] to [2-27] in Table 1 are used. preferable.
  • R 3 is preferably —O—, —COO—, or —CH 2 O—
  • p is 0 to 1
  • q is 0 to 1
  • r is 0 to 1
  • R 4 preferably has 2 to 22 carbon atoms.
  • R 4 is preferably a linear alkyl group having 18 to 22 carbon atoms or a divalent organic group having a steroid skeleton and having 12 to 25 carbon atoms.
  • Specific structures of the side chain-containing monomers having a large tilting ability are shown in Tables 2-1 and 2-2, but the formula (4) is not limited to the structures of Tables 2-1 and 2-2.
  • the side chain-containing monomers in Table 2-1 and Table 2-2 are preferable when used in the VA mode because of their high tilting ability.
  • [2-43], [2-92] and the like have a large tilting ability and can easily align the liquid crystal vertically even with a relatively small amount of side chains.
  • [2-52] and [2-101] have extremely large tilting ability and can align the liquid crystal vertically even with a very small amount of side chain. Accordingly, these side chain-containing monomers are preferable in terms of improving the printability of the liquid crystal aligning agent.
  • the side chain-containing monomer represented by the formula (2) is selected from diamine or diisocyanate.
  • diisocyanates are derived by causing highly toxic phosgene or the like to act on diamines. Therefore, from the viewpoint of easily obtaining the side chain-containing monomer, it is easier to use diamine as the side chain-containing monomer. Therefore, N in the formula (2) is preferably an amino group.
  • Monomers overlapping in Table 1 and Tables 2-1 and 2-2 may be used for both TN mode and OCB mode, and VA mode. is there.
  • the content of the side chain-containing monomer is arbitrary within the scope of the present invention.
  • the number of moles of the side chain-containing monomer can be 0.05 to 0.5 with respect to the total number of moles of the diamine represented by the formula (1) and the side chain-containing monomer.
  • a part of the diamine represented by the formula (1) is replaced with other diamines (other diamines, that is, the diamines represented by the formula (1), and the side chain. It may be replaced with a diamine that does not correspond to the contained monomer.
  • diamines are abundant in types, and since many compounds have organic groups having various functions, by using other diamines in combination, further effects can be imparted to the polymer, The effect of the diamine may be further improved.
  • the ratio of the number of moles of the other diamine to the number of moles of the diamine represented by the formula (1) is arbitrary as long as the effects of the present invention (for example, a high pretilt angle can be realized) are not impaired.
  • other diamines may not be used in combination. Examples of such other diamines include diamines represented by the following formula (5).
  • Y represents a divalent organic group. Examples of specific structures of Y are listed as in the following formulas (Y-1) to (Y-147), but are not limited thereto.
  • the black point means the bonding site to the nitrogen atom.
  • R 7 each independently represents a hydrogen atom, a methyl group, or an ethyl group.
  • a 1 represents an alkyl group or a fluorine-containing alkyl group having 2 to 24 carbon atoms.
  • a 2 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • a 3 represents An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms is shown.
  • a 4 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O— , —OCH 2 — or —CH 2 —
  • a 5 represents an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms.
  • a 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O— , —OCH 2 —, —CH 2 —, —O—, or —NH—
  • a 7 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 is shown.
  • a 8 represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • a 9 represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • a 12 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH.
  • -And A 13 represents an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.
  • n represents an integer of 1 to 10.
  • the polymer (polyurea and polyurea copolymer) is represented by the formula (6).
  • X represents a divalent organic group derived from diisocyanate
  • Y represents a divalent organic group derived from diamine
  • R 1 represents an alkyl group having 1 to 4 carbon atoms and may be branched
  • R 2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an organic group represented by the following formula (1-1).
  • Ra and Rb each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms.
  • R 1, Ra and Rb are as defined above R 1, Ra and Rb.
  • the resulting film has excellent mechanical strength.
  • the strong hydrogen bonding force causes aggregation of the polymer and may deteriorate the stability of the polymer solution (the viscosity of the polymer solution increases, a part of the polymer precipitates, or the polymer solution gels). ,etc). Therefore, the usable solvent is limited depending on the structure of polyurea, and for example, it is necessary to use a highly polar and high boiling point solvent.
  • the polymer has a structure represented by the formula (6), that is, a structure in which an organic group represented by the formula (1-1) is substituted on the N atom of polyurea.
  • the organic group represented by the formula (1-1) inhibits the formation of hydrogen bonds, thereby preventing the polymers from aggregating. For this reason, the stability of the polymer solution is greatly improved. Accordingly, in obtaining a polymer solution of polyurea, the range of selection of usable solvents can be expanded, and as a result, baking at low temperature and great improvement in printability are possible.
  • the urea bond site may form a hydantoin ring or an intermolecular bridge depending on the firing temperature during film formation.
  • the reaction solution (organic solvent used in the reaction for obtaining the polymer) is not particularly limited as long as it is a solution in which the polymer is dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, eth
  • reaction solution since water in the reaction solution inhibits the polymerization reaction and further causes hydrolysis of the produced polymer, it is preferable to use a dehydrated and dried reaction solution.
  • the reaction solution in which the diamine is dispersed or dissolved is stirred, and the diisocyanate is added as it is or dispersed or dissolved in the reaction solution.
  • the diisocyanate is dispersed.
  • the method of adding diamine to the dissolved reaction solution, the method of adding diisocyanate and diamine to a reaction solution alternately, etc. are mentioned, Any of these methods may be used.
  • the diisocyanate or diamine when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted by individually reacting low molecular weight substances. It may be a body.
  • the polymerization temperature can be selected from -20 ° C. to 150 ° C., but it is preferably in the range of ⁇ 5 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes.
  • the total concentration in the reaction solution of diisocyanate (diisocyanate represented by formula (4)) and diamine (diisocyanate represented by formulas (1) and (5)) is preferably from 1% by mass. 50% by mass, more preferably 5% by mass to 30% by mass.
  • the initial stage of the reaction can be performed at a high concentration, and then a reaction solution can be added.
  • the ratio between the total number of moles of diisocyanate (diisocyanate represented by formula (4)) and the total number of moles of diamine (diamines represented by formula (1) and formula (5)) Is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polymer produced.
  • the reaction solution may be poured into a poor solvent to precipitate the polymer.
  • the poor solvent include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like.
  • the polymer that has been precipitated in a poor solvent and collected can be collected by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • the recovered polymer is redissolved in an organic solvent, and reprecipitation and recollection are repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more poor solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the polymer is GPC (Gel) in consideration of the strength of the coating film obtained from the polymer, the ease of work when forming the coating film, the uniformity of the coating film thickness, and the like.
  • the weight average molecular weight measured by the Permeation Chromatography method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the liquid crystal aligning agent which is 1 aspect of this invention is a coating liquid for forming a liquid crystal aligning film, and the resin component for forming a coating film (resin film) is melt
  • the resin component contains at least one kind of the polymer.
  • the content of the resin component in the liquid crystal aligning agent is preferably 2% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
  • all of the polymers contained in the resin component may be the above polymers (polyurea and polyurea copolymers), and other polymers (within the scope of the present invention) Other polymers) may be included.
  • the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.
  • examples of such other polymers include acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose, polysiloxane and the like.
  • the organic solvent used for the liquid crystal aligning agent is not particularly limited as long as it is an organic solvent that dissolves the resin component.
  • Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, Tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethyl Propanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone,
  • the liquid crystal aligning agent may contain components other than those described above.
  • a coating film formed by applying a liquid crystal aligning agent improves the adhesion between the liquid crystal alignment film and the substrate, or a solvent or compound that improves the film thickness uniformity or surface smoothness. Compounds and the like.
  • Solvents that improve film thickness uniformity and surface smoothness include low surface tension solvents such as isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, Ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene Glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol Diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropy
  • Examples of the compound that improves the uniformity of the film thickness and the smoothness of the coating film surface include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. 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 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the resin component 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 following phenoplast type additives may be added for the purpose of preventing deterioration of electrical characteristics caused by light irradiation by the backlight.
  • Specific phenoplast additives are shown below, but are not limited to this structure.
  • the usage-amount of the compound shall be 0.1 mass part to 30 mass parts with respect to 100 mass parts of the resin component contained in a liquid crystal aligning agent. Is more preferable, and it is 1 to 20 parts by mass. If the amount used is less than the above value, it is difficult to improve the adhesion, and if it is more than the above value, the liquid crystal orientation may be deteriorated.
  • the liquid crystal aligning agent includes dielectric materials for the purpose of changing the electrical properties 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.
  • a predetermined crosslinkable compound may be added for the purpose of increasing the hardness and density of the body, the conductive material, and the liquid crystal alignment film.
  • the liquid crystal aligning agent is applied onto a substrate and baked, and then subjected to an alignment treatment if necessary, and a liquid crystal alignment film according to one embodiment of the present invention is obtained even without an alignment treatment in vertical alignment applications.
  • a substrate a highly transparent glass substrate, a plastic substrate (for example, an acrylic substrate or a polycarbonate substrate), or the like can be used.
  • a substrate on which an ITO electrode or the like for driving the liquid crystal is formed from the viewpoint of simplifying the process for manufacturing the liquid crystal display element.
  • an opaque object such as a silicon wafer can be used on one side of the substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, spin coating printing, screen printing, offset printing, flexographic printing, inkjet printing, and the like are common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these methods may be used depending on the purpose.
  • Calcination can be performed at 50 ° C. to 300 ° C., preferably 80 ° C. to 250 ° C., by a heating means such as a hot plate.
  • a coating film can be formed by evaporating the organic solvent in the liquid crystal aligning agent. If the thickness of the coating film is too thick, the power consumption of the liquid crystal display element tends to increase, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, the thickness is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. .
  • the liquid crystal display element which is one embodiment of the present invention can be obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent by the above-described method and then manufacturing a liquid crystal cell by a known method.
  • a method for manufacturing a liquid crystal cell a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers are dispersed on the liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded, and the liquid crystal is injected under reduced pressure to be sealed.
  • the thickness of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. Since the liquid crystal display element manufactured using the liquid crystal aligning agent is excellent in reliability, it can be suitably used for a large-screen, high-definition liquid crystal television.
  • Second Step To a 500 ml four-necked flask equipped with a nitrogen inlet tube and a stirrer, 45.0 g (0.19 mol) of the nitro body obtained above, 300.0 g of THF, and 4.5 g of iron-doped platinum carbon are added, The inside of the vessel was carefully replaced with a hydrogen atmosphere and reacted at room temperature for 24 hours. When the raw material disappeared, the reaction was completed, platinum carbon was removed with a membrane filter, activated carbon (manufactured by Shirasagi) was added to the filtrate, and the mixture was stirred at 40 ° C. for 30 minutes.
  • activated carbon manufactured by Shirasagi
  • Step 1 To a 1 L four-necked flask equipped with a nitrogen introduction tube and a reflux tube was added 50 g (0.246 mol) of 4-nitrophenethylamine hydrochloride, 500 g of THF, and 62.1 g (0.604 mol) of triethylamine, and a mechanical stirrer was used. The mixture was stirred at room temperature for 1 hour and heated at a temperature at which THF was refluxed (setting 70 ° C.). 25.1 g (0.205 mol) of 2-chloroethyl acetate was dissolved in 300 g of THF, and this was slowly added dropwise. The mixture was further reacted for 24 hours.
  • Second Step 30.0 g of the nitro compound obtained above, 300 g of THF, and 3.0 g of iron-doped platinum carbon are added to a 500 ml four-necked flask equipped with a nitrogen inlet tube and a stirring bar, and the inside of the container is carefully placed under a hydrogen atmosphere. And allowed to react at room temperature for 24 hours. When the raw material disappeared, the reaction was completed, platinum carbon was removed with a membrane filter, activated carbon (manufactured by Shirasagi) was added to the filtrate, and the mixture was stirred at 40 ° C. for 30 minutes.
  • p-PDA paraphenylenediamine
  • NG4ABA ethyl (4-aminobenzyl) glycinate
  • NG4APhA ethyl (4-aminophenethyl) glycinate
  • Me4APhA N-methyl-4-aminophenethylamine
  • DA-3MG 1,3-di (4-amino) Phenoxy) propane
  • APC16 2-hexadecyloxy-1,3-diaminobenzene
  • PCH7 4- (4- (4-heptylcyclohexyl) phenoxy) benzene-1,3-diamine
  • CBDA cyclobutane tetracarboxylic dianhydride
  • the molecular weight measurement conditions of polyimide are as follows. Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Column made by Shodex (KD-803, KD-805) Column temperature: 50 ° C Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, THF is 10ml / L) Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight of about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) (Molecular weight about 12,000, 4,000, 1,000)
  • Example 4 DI-2MG / NG4APhA APC16 DI-2MG 2.00 g (6.75 mmol) was measured in a 50 ml two-necked flask equipped with a nitrogen introduction tube and a stirring bar, NMP 20.12 g was added and dissolved, and APC16 0.24 g (0.68 mmol) was added. Then, it was made to react at room temperature for 1 hour. Further, 1.31 g (5.88 mmol) of NG4APhA was added and reacted at 40 ° C. for 24 hours in a nitrogen atmosphere. As a result, a polymer (polymer solution: P-2) having a concentration of 15% by mass and a viscosity of 280 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 39100.
  • Example 5 DI-2MG / NG4ABA, PCH7
  • 2.00 g (6.75 mmol) of DI-2MG was measured, and 20.57 g of NMP was added and dissolved, and 0.52 g (1.36 mmol) of PCH7 was added. Then, it was made to react at room temperature for 1 hour. Further, 1.11 g (5.34 mmol) of NG4ABA was added and reacted at 40 ° C. for 24 hours under a nitrogen atmosphere.
  • a polymer polymer solution: P-3) having a concentration of 15% by mass and a viscosity of 230 mPas was obtained.
  • the weight average molecular weight of the obtained polymer was Mw: 40200.
  • Example 6 IDI, DI-2MG / NG4ABA, PCH7
  • DI-2MG 1.00 g (3.38 mmol) and NMP 14.05 g were added and dissolved, and then PCH7 0.37 g (0.97 mmol) was added, followed by room temperature. For 1 hour.
  • 0.32 g (1.45 mmol) of IDI and 0.79 g (3.81 mmol) of NG4ABA were added and reacted at 40 ° C. for 24 hours in a nitrogen atmosphere.
  • a polymer polymer solution: P-4) having a concentration of 15% by mass and a viscosity of 300 mPas was obtained.
  • the weight average molecular weight of the obtained polymer was Mw: 44200.
  • Example 7 In a 50 ml Erlenmeyer flask equipped with a stir bar, 10.0 g of the polymer (P-1) obtained in Example 3 was weighed, and NMP 2.5 g, GBL 5.0 g, and BCS 7.5 g were added, and then at room temperature. Stir for 30 minutes. As a result, a liquid crystal aligning agent (AL-1) having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • a liquid crystal aligning agent AL-1 having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • Example 8 In a 50 ml Erlenmeyer flask equipped with a stir bar, 10.0 g of the polymer (P-2) obtained in Example 4 was weighed, NMP 2.5 g, GBL 5.0 g, and BCS 7.5 g were added, and then at room temperature. Stir for 30 minutes. As a result, a liquid crystal aligning agent (AL-2) having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • AL-2 liquid crystal aligning agent having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • Example 9 In a 50 ml Erlenmeyer flask equipped with a stir bar, 10.0 g of the polymer (P-3) obtained in Example 5 was measured, and 2.5 g of NMP, 5.0 g of GBL and 7.5 g of BCS were added, and then at room temperature. Stir for 30 minutes. As a result, a liquid crystal aligning agent (AL-3) having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • A-3 liquid crystal aligning agent having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • Example 10 In a 50 ml Erlenmeyer flask equipped with a stir bar, 10.0 g of the polymer (P-4) obtained in Example 6 was weighed, NMP 2.5 g, GBL 5.0 g, and BCS 7.5 g were added, and then at room temperature. Stir for 30 minutes. As a result, a liquid crystal aligning agent (AL-4) having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • A-4 liquid crystal aligning agent having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • Comparative Example 4 In a 50 ml Erlenmeyer flask equipped with a stirrer, 10.0 g of the polymer (PRef-1) obtained in Comparative Example 1 was measured, and NMP 2.5 g, GBL 5.0 g, and BCS 7.5 g were added, and then at room temperature. Stir for 30 minutes. As a result, a liquid crystal aligning agent (AL-5) having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • A-5 liquid crystal aligning agent having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • Comparative Example 5 In a 50 ml Erlenmeyer flask equipped with a stir bar, 10.0 g of the polymer (PRef-2) obtained in Comparative Example 2 was measured, and NMP 2.5 g, GBL 5.0 g, and BCS 7.5 g were added, and then at room temperature. Stir for 30 minutes. As a result, a liquid crystal aligning agent (AL-6) having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • A-6 liquid crystal aligning agent having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • Comparative Example 6 In a 50 ml Erlenmeyer flask equipped with a stir bar, 10.0 g of the polymer (PRef-3) obtained in Comparative Example 3 was measured, and NMP 2.5 g, GBL 5.0 g, and BCS 7.5 g were added, and then at room temperature. Stir for 30 minutes. As a result, a liquid crystal aligning agent (AL-7) having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • A-7 liquid crystal aligning agent having a solid content of 6.0% by mass, NMP 44% by mass, GBL 20% by mass, and BCS 30% by mass was obtained.
  • liquid crystal aligning agents (AL-1 to AL-4) of Examples 7 to 10 and the liquid crystal aligning agents (AL-5 to AL-7) of Comparative Examples 4 to 6 a liquid crystal aligning film was formed based on the following method. evaluated.
  • the applicability test is performed by performing flexographic printing on the washed Cr plate using an alignment film printing machine (“Nongstromer” manufactured by Nissha Printing Co., Ltd.). went.
  • This membrane is rubbed with a rayon cloth (YA-20R manufactured by Yoshikawa Chemical Industries) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm), and then in pure water for 1 minute.
  • the substrate was washed by irradiating with ultrasonic waves, water droplets were removed by air blow, and then dried at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
  • Table 3 shows the results of the various evaluations described above.
  • the liquid crystal aligning agents of Examples 7 to 10 have excellent whitening resistance and good printability as compared with the comparative examples. Since Comparative Example 6 is a polyamic acid-based material, it is a material system with good whitening resistance and printability. In Examples 7 to 10, it is expected that characteristics equivalent to or higher than those of Comparative Example 5 can be obtained in terms of whitening resistance and printability.
  • the liquid crystal cells obtained using the liquid crystal aligning agents of Examples 7 to 10 have a high pretilt angle and a high voltage holding ratio.
  • the target pretilt angle can be adjusted by variously selecting the structure and amount of the side chain-containing monomer monomer. Expected to be able to get.
  • the liquid crystal alignment film which is one embodiment of the present invention is considered very promising as a liquid crystal alignment film that can be obtained by baking at a low temperature. It should be noted that the liquid crystal alignment film and the liquid crystal display element could be suitably obtained using any of the liquid crystal alignment agents of Examples 7 to 10.
  • the liquid crystal display element produced using the liquid crystal aligning agent of this invention can be made into a highly reliable liquid crystal display device, TN liquid crystal display element, STN liquid crystal display element, TFT liquid crystal display element, VA liquid crystal display element, OCB. It can be suitably used for display elements of various systems such as liquid crystal display elements.

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Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui utilise un polymère obtenu à partir des éléments suivants : un dérivé de diamine représenté par la formule (1) ; un dérivé de diisocyanate ; et un monomère choisi parmi les diamines et les diisocyanates et ayant une chaîne latérale spécifique. Dans la formule, A représente un groupe organique divalent choisi parmi des groupes hydrocarbonés aliphatiques et des groupes hydrocarbonés aromatiques et B et C représentent chacun indépendamment une liaison simple ou un groupe hydrocarboné aliphatique ayant de 1 à 5 atomes de carbone. R1 représente un groupe alkyle qui a de 1 à 4 atomes de carbone et qui peut être ramifié. R2 représente un atome d'hydrogène, un groupe hydrocarboné aliphatique ayant de 1 à 4 atomes de carbone, ou un groupe organique représenté par la formule (1-1). Ra et Rb représentent chacun indépendamment un atome d'hydrogène ou un groupe hydrocarboné aliphatique ayant 1 ou 2 atomes de carbone.
PCT/JP2019/011907 2018-03-23 2019-03-20 Agent d'alignement de cristaux liquides, polymère permettant de l'obtenir, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides le comprenant WO2019182071A1 (fr)

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CN201980019479.4A CN111868618B (zh) 2018-03-23 2019-03-20 液晶取向剂、用于得到该液晶取向剂的聚合物、液晶取向膜、以及使用该液晶取向膜的液晶显示元件
KR1020207029468A KR20200135404A (ko) 2018-03-23 2019-03-20 액정 배향제, 그것을 얻기 위한 중합체, 액정 배향막, 및 그것을 이용한 액정 표시 소자
JP2023004168A JP2023052403A (ja) 2018-03-23 2023-01-13 液晶配向剤、それを得るための重合体、液晶配向膜、及びそれを用いた液晶表示素子

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