WO2023219075A1 - 弱アンカリング配向膜付き基板の製造方法、及び液晶表示素子の製造方法 - Google Patents

弱アンカリング配向膜付き基板の製造方法、及び液晶表示素子の製造方法 Download PDF

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WO2023219075A1
WO2023219075A1 PCT/JP2023/017398 JP2023017398W WO2023219075A1 WO 2023219075 A1 WO2023219075 A1 WO 2023219075A1 JP 2023017398 W JP2023017398 W JP 2023017398W WO 2023219075 A1 WO2023219075 A1 WO 2023219075A1
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group
polymer
bond
carbon atoms
formula
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French (fr)
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一世 三宅
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日産化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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

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  • the present invention provides a method for manufacturing a substrate with a weak anchoring alignment film, which allows manufacturing an organic film exhibiting weak anchoring properties (weak anchoring film) using a method that is inexpensive and does not involve complicated steps, and
  • the present invention relates to a liquid crystal display element that achieves higher brightness and lower voltage driving.
  • liquid crystal display elements have been widely used in displays for mobile phones, computers, televisions, and the like.
  • Liquid crystal display elements have characteristics such as being thin, lightweight, and low power consumption, and are expected to be applied to further content such as VR (Virtual Reality) and ultra-high-definition displays in the future.
  • Various display methods have been proposed for liquid crystal displays, including the TN (Twisted Nematic) method, the IPS (In-Plane Switching) method, and the VA (Vertical Alignment) method.
  • TN Transmission Nematic
  • IPS In-Plane Switching
  • VA Very Alignment
  • the IPS method is preferred because the display is less distorted even when touched, and in recent years FFS (Fringe Field Switching ) liquid crystal display elements using the method and liquid crystal alignment technology using the optical alignment method are used.
  • FFS Ringe Field Switching
  • the FFS method has problems in that the manufacturing cost of the substrate is higher than that in the IPS method, and a unique display defect called Vcom shift occurs.
  • the photo-alignment method has the advantage of being easier to adapt to device enlargement and greatly improving display characteristics, but there are some theoretical issues (when using photodegradable materials, Display defects, and if the photoisomerization type is used, there may be burn-in due to insufficient alignment power, etc.).
  • liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are currently making various efforts.
  • a weak anchoring IPS method that applies weak anchoring technology has been proposed. This can improve the contrast ratio and realize significantly lower voltage driving than the conventional IPS method (see Patent Document 2).
  • the weak anchoring IPS method uses a liquid crystal alignment film that has strong anchoring energy on one substrate, and a process that does not have anchoring energy on the other substrate (which is equipped with an electrode that generates a transverse electric field). It is made using organic thin films.
  • a weak anchoring IPS method has been proposed in which a liquid crystal alignment film capable of generating photoradicals and a compound capable of radical polymerization are used to generate weak anchoring by irradiating UV in the liquid crystal and causing a radical reaction (Patent Document (see 4).
  • Patent Document 3 The method of directly providing a dense polymer brush on a substrate (Patent Document 3) requires a surface treatment step to provide reaction points on the substrate and a step of growing polymer from the reaction points on the substrate surface, which complicates the process, and requires advanced technology. Since it requires deoxidizing conditions and the environment must be strictly controlled, it is technically difficult and impractical from the perspective of mass production. Therefore, a method has been proposed in which a weakly anchored IPS display element is obtained by applying a bottlebrush polymer having an anchoring site onto a substrate.However, when manufacturing a bottlebrush polymer, a macromonomer having a polymerization initiation site is used.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • Patent Document 4 In the method of weakly anchoring using a photoradical polymerization reaction and a radically polymerizable compound (Patent Document 4), the polymerizable additive is volatilized under high vacuum conditions during liquid crystal injection, and ultraviolet rays are removed after the liquid crystal element is fabricated. It is thought that there are problems such as an adverse effect on the liquid crystal composition during the irradiation process.
  • the response speed when the voltage is turned off becomes slow. This is a problem specific to weak anchoring IPS systems. If the response speed becomes slow, it is conceivable that the display quality of video images will deteriorate and the applications to which it can be applied will be greatly limited, so increasing the response speed can be said to be the biggest challenge from the perspective of putting weak anchoring IPS into practical use.
  • an object of the present invention is to provide a substrate with a weak anchoring alignment film that does not generate a pretilt angle and can simultaneously realize low-voltage driving and high-speed response when the voltage is turned off, and a liquid crystal display device using the same. There is.
  • the present inventors conducted intensive studies and found that the above-mentioned problems could be solved, and completed the present invention having the following gist. That is, the present invention includes the following.
  • a method for manufacturing a substrate with a weak anchoring alignment film used for manufacturing a liquid crystal cell having a liquid crystal and a weak anchoring alignment film comprising: A weakly anchoring liquid crystal aligning agent containing a polymer ⁇ , which is a component that exhibits weak anchoring properties, and a polymer ⁇ , which is a component that does not exhibit weak anchoring properties and exhibits a uniaxial alignment regulating force through alignment treatment.
  • a method for manufacturing a substrate with a weak anchoring alignment film comprising: [2] The method for producing a substrate with a weak anchoring alignment film according to [1], wherein the polymer ⁇ is a polymer that has a horizontal alignment regulating force when subjected to an alignment treatment. [3] The method for manufacturing a substrate with a weak anchoring alignment film according to [1] or [2], wherein the weak anchoring alignment film is a liquid crystal alignment film subjected to a uniaxial alignment treatment.
  • the weak anchor according to any one of [1] to [3], wherein the polymer ⁇ contains at least one selected from the group consisting of polymer A, polymer B, and polymer C below.
  • Polymer A A block copolymer having a block segment (A) that is compatible with the liquid crystal and a block segment (B) that is not compatible with the liquid crystal or becomes insolubilized in the liquid crystal upon firing.
  • Polymer B a graft copolymer having a backbone polymer and a branch polymer bonded to the backbone polymer as a side chain of the backbone polymer, wherein the branch polymer is compatible with the liquid crystal and the backbone polymer is not compatible with the liquid crystal or becomes incompatible with the liquid crystal upon firing.
  • Polymer C A polymer that has a polymer unit that is compatible with the liquid crystal and reacts with the polymer ⁇ when heated.
  • the block segment (A) in the polymer A is a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and Containing as a constituent component at least one selected from the group consisting of compounds represented by the following formula (5),
  • the block segment (B) in the polymer A contains a compound represented by the following formula (6) as a constituent component,
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • X represents a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, or thioether bond.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms which may have a bonding group inserted therein, and n is an integer of 1 to 2.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • S represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms which may have a bonding group inserted therein.
  • T represents an organic group represented by the following formula (3-T), and n is an integer of 1 to 2. When n is 2, the two Ts may be the same or different.
  • X is a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R 1 )(R 2 )- (R 1 and R 2 each independently represent an alkyl group bonded to Si.), -Si(R 3 )(R 4 )-O-(R 3 and R 4 each independently bond to Si.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 represents an aliphatic hydrocarbon group having a linear or branched structure having 1 to 10 carbon atoms
  • 3 Each of the three X's independently represents a hydrogen atom or the following formula (4-X).However, at least one of the three X's represents the formula (4-X).
  • Y represents a single bond, -O-, -S-, or -N(R)-(R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms bonded to N.
  • R 2 , R 3 , and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group that may have a substituent.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 to R 3 are each independently a single bond or the number of carbon atoms into which a bonding group may be inserted.
  • R 1 X 1 , R 2 X 2 and R 3 are independently a hydrogen atom, or R 1 X 1 and R 2 X 2 and the carbon atoms bonded to R 1 X 1 and R 2 X 2 may form a ring together.
  • the total number of carbon atoms in R 1 X 1 , R 2 X 2 and R 3 is 1 or more.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • n is an integer of 1 to 2.
  • Z represents a group represented by the following formula (6-Z).
  • L is a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetane group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an aniline group, a protected aniline group) group, hydroxy group, protected hydroxy group, phenol group, protected phenol group, thiol group, protected thiol group, thiophenol group, protected thiophenol group, aldehyde group, carboxy group, maleimide group, N-hydroxysuccinimide ester group, bonding group Aromatic hydrocarbon group having 5 to 18 carbon atoms which may have a bonding group inserted therein, an aromatic heterocyclic group having 5 to 18 carbon atoms which may have a bonding group inserted therein, a cinnamic acid group, a cinn
  • J is a single bond or has 1 to 1 carbon atoms.
  • 6 represents an aliphatic hydrocarbon group.
  • K When K is bonded to an aromatic hydrocarbon group, it represents a linking group selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, and a thioether bond. In other cases, it indicates a single bond.
  • * represents a binding site.
  • m is an integer from 1 to 3. When m is 2 or 3, multiple K and L may be the same.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • X represents a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, or thioether bond
  • R 1 represents an alkyl group having 1 to 20 carbon atoms which may have a bonding group inserted therein
  • n is an integer of 1 to 2.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • S represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms which may have a bonding group inserted therein.
  • T represents an organic group represented by the following formula (3-T)
  • n is an integer of 1 to 2.
  • the two Ts may be the same or different.
  • S represents a saturated hydrocarbon group having 1 to 6 carbon atoms that may have a bonding group inserted.
  • * indicates a bonding site.
  • X is a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R 1 )(R 2 )- (R 1 and R 2 each independently represent an alkyl group bonded to Si.), -Si(R 3 )(R 4 )-O-(R 3 and R 4 each independently bond to Si. represents an alkyl group), and -N(R 5 )-(R 5 represents a hydrogen atom or an alkyl group bonded to N), and Cy is a 6- to 20-membered non-ring group.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 represents an aliphatic hydrocarbon group having a linear or branched structure having 1 to 10 carbon atoms
  • 3 Each of the three X's independently represents a hydrogen atom or the following formula (4-X).However, at least one of the three X's represents the formula (4-X).
  • Y represents a single bond, -O-, -S-, or -N(R)-(R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms bonded to N.
  • * indicates a bonding site.
  • R 2 , R 3 , and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group that may have a substituent.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 to R 3 are each independently a single bond or the number of carbon atoms into which a bonding group may be inserted.
  • Ar represents an aromatic hydrocarbon group that may have a substituent
  • X 1 and X 2 are each independently a hydrogen atom, or R 1 X 1 and R 2 X 2 and the carbon atoms bonded to R 1 X 1 and R 2 X 2 may form a ring together.
  • L is a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetane group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an aniline group, a protected aniline group) group, hydroxy group, protected hydroxy group, phenol group, protected phenol group, thiol group, protected thiol group, thiophenol group, protected thiophenol group, aldehyde group, carboxy group, maleimide group, N-hydroxysuccinimide ester group, bonding group Aromatic hydrocarbon group having 5 to 18 carbon atoms which may have a bonding group inserted therein, an aromatic heterocyclic group having 5 to 18 carbon atoms which may have a bonding group inserted therein, a cinnamic acid group, a cinn
  • J is a single bond or has 1 to 1 carbon atoms.
  • 6 represents an aliphatic hydrocarbon group.
  • K When K is bonded to an aromatic hydrocarbon group, it represents a linking group selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, and a thioether bond. In other cases, it indicates a single bond.
  • * represents a binding site.
  • m is an integer from 1 to 3. When m is 2 or 3, multiple K and L may be the same.
  • R is a monovalent organic group selected from the following formulas (8-R-1) to (8-R-11) and having a molecular weight of 500 or less that does not react with the polymer ⁇ upon heating.
  • n is an integer from 1 to 2. When n is 2, the two Q's and R's may be the same or different.
  • R 1 and R 2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms
  • R 3 and R 4 each independently represents a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms
  • X represents an oxygen atom or a sulfur atom.
  • R 1 and R 2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms
  • R 3 and Each R 4 independently represents a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms.
  • * represents a bonding site.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • X represents a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, or thioether bond.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms which may have a bonding group inserted therein, and n is an integer of 1 to 2.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • S represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms which may have a bonding group inserted therein.
  • T represents an organic group represented by the following formula (3-T), and n is an integer of 1 to 2. When n is 2, the two Ts may be the same or different.
  • X is a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R 1 )(R 2 )- (R 1 and R 2 each independently represent an alkyl group bonded to Si.), -Si(R 3 )(R 4 )-O-(R 3 and R 4 each independently bond to Si.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 represents an aliphatic hydrocarbon group having a linear or branched structure having 1 to 10 carbon atoms
  • 3 Each of the three X's independently represents a hydrogen atom or the following formula (4-X).However, at least one of the three X's represents the formula (4-X).
  • Y represents a single bond, -O-, -S-, or -N(R)-(R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms bonded to N.
  • R 2 , R 3 , and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group that may have a substituent.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 to R 3 are each independently a single bond or the number of carbon atoms into which a bonding group may be inserted.
  • X 1 and X 2 are each independently a hydrogen atom, or R 1 X 1 and R 2 X 2 and the carbon atoms bonded to R 1 X 1 and R 2 X 2 may form a ring together.
  • M in the formula (2) is any of the structures represented below
  • M in the formula (3) is any of the structures represented below
  • M in the formula (4) is any of the structures represented below
  • M in the formula (5) is any of the structures represented below
  • R 1 and R 2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms
  • X, Y, and Z each independently represent an oxygen atom or a sulfur atom.
  • n is Represents an integer from 1 to 5.
  • the polymer ⁇ is at least one kind of polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyamide, polyurea, and poly(meth)acrylate.
  • the tetracarboxylic acid derivative component includes a tetracarboxylic dianhydride represented by the following formula (9).
  • X represents a structure selected from the group consisting of the following formulas (X-1) to (X-17) and (XR-1) to (XR-2).)
  • R 1 to R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, Alkynyl group having 2 to 6 carbon atoms, monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, alkoxy group having 1 to 6 carbon atoms, alkoxyalkyl group having 2 to 6 carbon atoms, 2 to 6 carbon atoms represents an alkyloxycarbonyl group or a phenyl group.
  • R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
  • j and k are integers of 0 or 1
  • a 1 and A 2 each independently represent a single bond, -O-, -CO-, -COO-, represents a phenylene group, a sulfonyl group, or an amide group.
  • the plurality of A2 's may be the same or different. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.
  • Ar 1 and Ar 1' each independently represent a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more of the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group.
  • the present invention it is possible to solve the trade-off between weak anchoring property and high-speed response when the voltage is turned off, which has been a trade-off in weak anchoring IPS. Furthermore, by using the materials and methods of the present invention, we provide a weak anchoring alignment film that does not generate a pretilt angle and can simultaneously achieve low voltage drive and high-speed response when the voltage is turned off, and a liquid crystal display element using the same. can do.
  • FIG. 1 is a schematic cross-sectional view showing an example of a horizontal electric field liquid crystal display element of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another example of the horizontal electric field liquid crystal display element of the present invention.
  • weak anchoring refers to having a force that regulates the alignment of liquid crystal molecules in the azimuthal or polar direction with respect to the substrate, but with anchoring strength (i.e., maintaining the position of the liquid crystal molecules).
  • anchoring strength i.e., maintaining the position of the liquid crystal molecules.
  • the azimuthal anchoring strength (A 2 ) is smaller than 10 ⁇ 5 [J/m 2 ].
  • a polymer capable of forming a completely wet state with the liquid crystal is provided at the base material interface, and when the liquid crystal comes into contact with the polymer, a polymer-liquid crystal mixed layer is formed, resulting in weak anchoring.
  • the condition is known to occur.
  • the term “weak anchoring alignment film” refers to a film that forms a weakly anchored state upon contact with liquid crystal, and is not limited to solid films, but also includes liquid films that cover solid surfaces. Note that the "weak anchoring alignment film” is also referred to as “weak anchoring liquid crystal alignment film”.
  • strong anchoring refers to the ability to regulate the alignment of liquid crystal molecules in a uniaxial alignment and maintain the alignment of the liquid crystal even when energy is applied from the outside, or the ability to maintain the alignment of the liquid crystal even if the alignment of the liquid crystal molecules changes. In the strong anchoring of the present invention, it refers to the case where the azimuthal anchoring strength (A 2 ) is greater than 10 ⁇ 4 [J/m 2 ]. .
  • strongly anchoring alignment film refers to a film that forms a strong anchoring state when it comes into contact with liquid crystal, and is not limited to solid films, but also includes liquid films that cover solid surfaces. Note that the "strong anchoring alignment film” is also referred to as “strong anchoring liquid crystal alignment film.”
  • a weak anchoring liquid crystal display element can be produced by applying the above-defined weak anchoring alignment film and strong anchoring alignment film to a substrate with electrodes, respectively, and pasting them together in a pair.
  • the azimuthal anchoring strength of one liquid crystal alignment film is extremely small, so a weak electric field or external field energy can induce alignment changes in the liquid crystal, and liquid crystal molecules in areas that normally do not move can also be aligned. This makes it possible to drive liquid crystal molecules on electrodes with weak electric field strength, especially in display elements using comb-shaped electrodes such as IPS and FFS.
  • a liquid crystal display element in which both films are composed of strong anchoring alignment films higher transmittance and lower driving voltage can be achieved.
  • the azimuthal anchoring strength is an index representing the strength of interfacial elastic energy between liquid crystal molecules and a liquid crystal alignment film in the azimuthal direction.
  • a torque balance method As a method for calculating the azimuthal anchoring strength, a torque balance method, a strong electric field method, a geometry method (external field application method), a Frederiks transfer method, etc. are used.
  • polymer alloy One embodiment of the "polymer alloy” in the present invention is a polymer (hereinafter sometimes referred to as "polymer ⁇ ") that is a component that exhibits weak anchoring properties and is contained in a weakly anchoring liquid crystal aligning agent. It is a polymer alloy made of a polymer (hereinafter sometimes referred to as "polymer ⁇ ") which is a component that does not exhibit weak anchoring properties and exhibits uniaxial alignment regulating force through alignment treatment.
  • Weak anchoring liquid crystal alignment agents are used to form a film for aligning liquid crystals used in liquid crystal display elements, that is, a liquid crystal alignment film.
  • the polymer alloy of the present invention is characterized in that it is obtained by mixing at least one of each of polymer ⁇ and polymer ⁇ .
  • the polymer ⁇ exhibits excellent weak anchoring properties (also referred to as a “weak anchoring component”), while the polymer ⁇ does not exhibit weak anchoring properties and can be easily stabilized by orientation treatment. Expresses uniaxial alignment regulating force.
  • weak anchoring component also referred to as a “weak anchoring component”
  • we can provide the weak anchoring alignment film with excellent film hardness and excellent seal adhesion strength by adhering to the substrate, cross-linking between polymers, and cross-linking with the sealing component.
  • a weakly anchoring liquid crystal aligning agent having excellent solvent selectivity and coating properties can be obtained.
  • a weakly anchored liquid crystal display element that uses a graft copolymer (called a polymer brush) with a high density of branch polymers using living polymerization.
  • the polymer brush is synthesized using a method of extending branch polymers (grafting from method), and needs to be synthesized using living polymerization.
  • attempts have been made to improve the adhesion between the substrate and the polymer by introducing groups into the branch polymer that contribute to improved adhesion to the substrate, but if the amount introduced is large, the weak anchoring property may be impaired.
  • the method for manufacturing a substrate with a weak anchoring alignment film of the present invention is used for manufacturing a liquid crystal cell having a liquid crystal and a weak anchoring alignment film.
  • the method for manufacturing a substrate with a weak anchoring alignment film of the present invention includes the following steps. ⁇ Process of applying a weak anchoring liquid crystal alignment agent containing polymer ⁇ and polymer ⁇ onto a substrate to form a thin film on the substrate ⁇ Process of applying alignment treatment to the thin film
  • the substrate to which the weak anchoring liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving the liquid crystal is formed is preferable. A specific example will be described later.
  • the method of applying the weak anchoring liquid crystal aligning agent onto the substrate is not particularly limited, and examples thereof include spin coating, printing, inkjet, spraying, and roll coating, but from the viewpoint of productivity, Industrially, transfer printing is preferred.
  • drying and/or baking may be performed. Drying and firing conditions are not particularly limited, and include, for example, the conditions described below.
  • the thickness of the thin film can be selected as necessary, it is preferably 5 nm or more, more preferably 10 nm or more, since this improves the reliability of the liquid crystal display element. Further, it is preferable that the thickness of the thin film is preferably 300 nm or less, more preferably 150 nm or less, since the power consumption of the liquid crystal display element does not become extremely large.
  • the orientation treatment applied to the thin film is preferably uniaxial orientation treatment.
  • methods for performing the uniaxial alignment treatment include a photoalignment method, an oblique evaporation method, rubbing, and a uniaxial alignment treatment using a magnetic field.
  • the alignment treatment can be performed by irradiating the entire surface of the film with polarized UV of a specific wavelength and heating if necessary.
  • the direction is selected depending on the electrical properties of the liquid crystal, but when using a liquid crystal with positive dielectric anisotropy, the rubbing direction is the direction in which the comb-teeth electrodes extend. It is preferable that the direction is approximately the same as that of .
  • an organic film made of a polymer alloy obtained by mixing polymer ⁇ and polymer ⁇ is formed on a substrate, and then an alignment treatment is performed on the organic film. (preferably uniaxial alignment treatment).
  • the polymer ⁇ preferably contains at least one selected from the group consisting of polymer A, polymer B, and polymer C.
  • the polymer ⁇ is preferably at least one type of polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyamide, polyurea, and poly(meth)acrylate.
  • polymer ⁇ is a polymer that exhibits excellent uniaxial alignment regulating force through rubbing alignment treatment and photo alignment treatment, and is a polymer that exhibits excellent uniaxial alignment regulating force through rubbing alignment treatment and photo alignment treatment, and is a polymer that exhibits an excellent uniaxial alignment regulating force through rubbing alignment treatment and photo alignment treatment.
  • alignment treatment preferably uniaxial alignment treatment
  • the weak anchoring alignment film can be given excellent film hardness and excellent seal adhesion strength by adhering to the substrate, cross-linking between polymers, and cross-linking with the sealing component. Moreover, a weakly anchoring liquid crystal aligning agent having excellent solvent selectivity and coating properties can be obtained.
  • polymer A One embodiment of the polymer A is a copolymer having a block segment (A) that is compatible with the liquid crystal and a block segment (B) that is not compatible with the liquid crystal or becomes insolubilized in the liquid crystal upon firing.
  • Polymer A is, for example, a linear copolymer consisting of two or more types of block segments obtained by living polymerization, at least one block segment consisting of a block segment (A) soluble in liquid crystal, and at least one block segment consists of a block segment (B) that does not dissolve in the liquid crystal or becomes insoluble in the liquid crystal upon firing.
  • the block segment (A) in polymer A is a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and the following formula (5). It is preferable that at least one kind selected from the group consisting of the compounds represented by: is included as a constituent component. It is preferable that the block segment (B) in the polymer A contains a compound represented by the following formula (6) as a constituent component.
  • the polymer A is a polymer in which the block segment (A) of the polymer A is synthesized from at least one selected from the group consisting of compounds represented by the following formulas (2) to (5), and It is preferable that the block segment (B) is a polymer synthesized from a compound represented by the following formula (6).
  • the present applicant has proposed a radically polymerizable compound contained in a liquid crystal composition that can stably produce a weakly anchoring horizontal electric field liquid crystal display element without generating a pretilt angle, and which is a radical polymerizable compound that contributes to the occurrence of weak anchoring.
  • a compound represented by the following formula (2), a compound represented by the formula (3), a compound represented by the formula (4), and a compound represented by the formula (5) as chemical compounds.
  • the weakly anchoring liquid crystal aligning agent containing Polymer A can produce weakly anchoring films more easily and stably than conventional methods, and that the weakly anchoring liquid crystal aligning agent containing Polymer A can be used to produce weakly anchored films more easily and stably than conventional methods.
  • Horizontal electric field liquid crystal that can simultaneously achieve stable low-voltage drive without the occurrence of corners and high-speed response when voltage is OFF, reduce burn-in, and achieve both high backlight transmittance and low-voltage drive in low-temperature environments.
  • the company has filed an application to provide a display element (Japanese Patent Application No. 2021-96448 and WO202/2260048. By being cited here, the contents of this application and publication are to the same extent as if they were fully disclosed. (incorporated herein).
  • the copolymer may have three or more types of block segments.
  • the copolymer is preferably a copolymer in which the main chain extends linearly without branching.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • X represents a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, or thioether bond
  • R 1 represents an alkyl group having 1 to 20 carbon atoms which may have a bonding group inserted therein
  • n is an integer of 1 to 2. When n is 2, the two X and R 1 are each the same.
  • Examples of the bonding group in the alkyl group having 1 to 20 carbon atoms into which a bonding group may be inserted include ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R 11 )( R 12 )-(R 11 and R 12 each independently represent an alkyl group bonded to Si.), -Si(R 13 )(R 14 )-O-(R 13 and R 14 each independently represent an alkyl group bonded to Si. (represents an alkyl group bonded to Si), -N(R 15 )-(R 15 represents a hydrogen atom or an alkyl group bonded to N). Examples of the alkyl group for R 11 to R 15 include alkyl groups having 1 to 6 carbon atoms.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • S represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms which may have a bonding group inserted therein.
  • T represents an organic group represented by the following formula (3-T), and n is an integer of 1 to 2. When n is 2, the two Ts may be the same or different. (However, when n is 2, S represents a saturated hydrocarbon group having 1 to 6 carbon atoms that may have a bonding group inserted.)
  • X is a single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R 1 )(R 2 )- (R 1 and R 2 each independently represent an alkyl group bonded to Si.), -Si(R 3 )(R 4 )-O-(R 3 and R 4 each independently bond to Si. represents an alkyl group), and -N(R 5 )-(R 5 represents a hydrogen atom or an alkyl group bonded to N), and Cy is a 6- to 20-membered non-ring group. (Represents an aromatic cyclic group.)
  • the saturated hydrocarbon group in S in formula (3) refers to an n+1-valent group formed by removing n+1 hydrogen atoms from a saturated hydrocarbon (n is the same integer as n in formula (3)). be).
  • n 1, the saturated hydrocarbon group is an alkylene group.
  • a saturated hydrocarbon group having 1 to 6 carbon atoms into which a bonding group is inserted is a saturated hydrocarbon group having a bonding group inserted between carbon atoms in a saturated hydrocarbon group having 2 to 6 carbon atoms. or an n+1-valent group in which a bonding group is inserted between a saturated hydrocarbon group having 1 to 6 carbon atoms and an atom bonded thereto (for example, a carbon atom).
  • Examples of the bonding group for S in formula (3) include a carbon-carbon unsaturated bond, an ether bond (-O-), an ester bond (-COO- or -OCO-), an amide bond (-CONH- or - Examples include NHCO-).
  • Examples of carbon-carbon unsaturated bonds include carbon-carbon double bonds, but a saturated hydrocarbon group having 1 to 6 carbon atoms into which a carbon-carbon double bond is inserted has no It is preferable to have a carbon-carbon double bond inside.
  • examples of the alkylene group having 1 to 6 carbon atoms into which a bonding group may be inserted include alkylene groups having 1 to 6 carbon atoms, oxyalkylene groups having 1 to 6 carbon atoms, etc. .
  • the alkylene group having 1 to 6 carbon atoms may be a straight chain alkylene group, a branched alkylene group, or a cyclic alkylene group.
  • R 1 and R 2 of -Si(R 1 )(R 2 )- in X of formula (3-T) are each independently an alkyl group bonded to Si, for example, an alkyl group having 1 to 6 carbon atoms. It is the basis.
  • R 3 and R 4 of -Si(R 3 )(R 4 )-O- in X of formula (3-T) are each independently an alkyl group bonded to Si, for example, a carbon number of 1 to 6. is an alkyl group.
  • R 5 of -N(R 5 )- in X of formula (3-T) is a hydrogen atom or an alkyl group bonded to N.
  • the alkyl group is, for example, an alkyl group having 1 to 6 carbon atoms.
  • Cy is a 6- to 20-membered non-aromatic cyclic group, preferably an 8- to 18-membered non-aromatic cyclic group. Note that Cy may be a 12- to 20-membered non-aromatic cyclic group.
  • X is bonded to an atom constituting a ring in Cy. Examples of the atoms constituting the ring in the non-aromatic cyclic group include carbon atoms, oxygen atoms, nitrogen atoms, and silicon atoms. The bond between the atoms constituting the ring may be a single bond, a double bond, or a triple bond, but a single bond is preferable.
  • Examples of the ring in the non-aromatic cyclic group include cyclic alkanes, cyclic ethers, and cyclic siloxanes.
  • Examples of the cyclic ether include crown ether.
  • the atoms constituting the ring are carbon atoms and oxygen atoms, and the number of members is 12.
  • the ring may be monocyclic or polycyclic.
  • Examples of the number of rings in the polycycle include 2 to 4. For example, the following three ways are included in how the rings are bonded to each other in a polycyclic ring.
  • ⁇ One-atom sharing For example, spiro ring compounds ⁇ Two-atom sharing: When two rings share two atoms, such as in decalin ⁇ Bridging structure: When two rings share three atoms, such as in norbornane Cases in which more than one atom is considered to be in common In the case of a polycyclic ring, the number of ring members is determined by the number of atoms that make up the ring.
  • norbornane is a 7-membered ring.
  • a halogen atom or an alkyl group having 1 to 6 carbon atoms may be bonded to the atoms constituting the ring instead of a hydrogen atom. Examples of the halogen atom include a fluorine atom and a chlorine atom.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 represents an aliphatic hydrocarbon group having a linear or branched structure having 1 to 10 carbon atoms
  • 3 Each of the three X's independently represents a hydrogen atom or the following formula (4-X).However, at least one of the three X's represents the formula (4-X).
  • Y represents a single bond, -O-, -S-, or -N(R)-(R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms bonded to N. ), and * indicates a bonding site.
  • R 2 , R 3 , and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group that may have a substituent.
  • the aliphatic hydrocarbon group in R 1 in formula (4) has 1 to 10 carbon atoms, may have 1 to 8 carbon atoms, may have 1 to 6 carbon atoms, or may have 1 to 6 carbon atoms. It may be 1 to 4.
  • the alkyl group having 1 to 6 carbon atoms in R 2 , R 3 , and R 4 in formula (4-X) may be, for example, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. 4 may be an alkyl group. These alkyl groups may have a linear structure or a branched structure.
  • the aromatic hydrocarbon groups represented by R 2 , R 3 , and R 4 in formula (4-X) may be unsubstituted, or the hydrogen atoms may be substituted with a substituent.
  • substituent of the aromatic hydrocarbon group which may have a substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen having 1 to 4 carbon atoms. Examples include alkyl groups, halogenated alkoxy groups having 1 to 4 carbon atoms, and the like.
  • the halogenation in the halogenated alkyl group and the halogenated alkoxy group may be complete halogenation or partial halogenation.
  • halogen atom examples include a fluorine atom and a chlorine atom.
  • aromatic hydrocarbon group which may have a substituent include a phenyl group and a naphthyl group. The number of substituents in the aromatic hydrocarbon group is not particularly limited.
  • formula (4-X) is one or more, and may be one, two, or three. In formula (4), the three X's are each independent. Therefore, in formula (4), when there are two or more formulas (4-X), the two or more formulas (4-X) may have the same structure or different structures.
  • R 2 , R 3 and R 4 may be an aromatic hydrocarbon group which may have a substituent. Therefore, in formula (4-X), one of R 2 , R 3 , and R 4 may be an aromatic hydrocarbon group that may have a substituent, and R 2 , R 3 , and Two of R 4 may be an aromatic hydrocarbon group which may have a substituent, or three of R 2 , R 3 and R 4 may be an aromatic hydrocarbon group which may have a substituent. It may be a base.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • R 1 to R 3 are each independently a single bond or the number of carbon atoms into which a bonding group may be inserted.
  • R 1 to R 3 are each independently a single bond or the number of carbon atoms into which a bonding group may be inserted.
  • Ar represents an aromatic hydrocarbon group that may have a substituent
  • X 1 and X 2 are each independently a hydrogen atom, or R 1 X 1 and R 2 X 2 and the carbon atoms bonded to R 1 X 1 and R 2 X 2 may form a ring together.
  • the total number of carbon atoms in R 1 X 1 , R 2 X 2 and R 3 is 1 or more.
  • an alkylene group having 1 to 6 carbon atoms into which a bonding group is inserted is an alkylene group having a bonding group inserted between carbon atoms in the alkylene group having 1 to 6 carbon atoms. or a divalent group in which a bonding group is inserted between an alkylene group having 1 to 6 carbon atoms and a carbon atom bonded thereto.
  • the bonding group include a carbon-carbon unsaturated bond, an ether bond (-O-), an ester bond (-COO- or -OCO-), and an amide bond (-CONH- or -NHCO-).
  • Examples of unsaturated bonds include carbon-carbon double bonds, but alkylene groups with 1 to 6 carbon atoms into which a bonding group is inserted have a carbon-carbon double bond inside, not at the end. It is preferable to have a bond.
  • Examples of the alkylene group having 1 to 6 carbon atoms into which a bonding group may be inserted include alkylene groups having 1 to 6 carbon atoms, oxyalkylene groups having 1 to 6 carbon atoms, and the like.
  • the oxygen atom in the oxyalkylene group having 1 to 6 carbon atoms is bonded to, for example, the carbon atom bonded to M, R 1 , R 2 , and R 3 in formula (5).
  • the alkylene group having 1 to 6 carbon atoms may be a straight chain alkylene group, a branched alkylene group, or a cyclic alkylene group.
  • Examples of the aromatic hydrocarbon group which may have a substituent in X 1 and X 2 of formula (5) include a phenyl group, a naphthyl group, and the like which may have a substituent.
  • Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogenated alkoxy group having 1 to 4 carbon atoms, etc. can be mentioned.
  • the halogenation in the halogenated alkyl group and the halogenated alkoxy group may be complete halogenation or partial halogenation.
  • Examples of the halogen atom include a fluorine atom and a chlorine atom.
  • Examples of R 1 in formula (5) include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, the alkylene group having 1 to 6 carbon atoms includes a straight chain alkylene group having 1 to 6 carbon atoms.
  • Examples of R 2 in formula (5) include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, the alkylene group having 1 to 6 carbon atoms includes a straight chain alkylene group having 1 to 6 carbon atoms.
  • Examples of R 3 in formula (5) include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, the alkylene group having 1 to 6 carbon atoms includes a straight chain alkylene group having 1 to 6 carbon atoms.
  • Examples of X 1 in formula (5) include a hydrogen atom and a phenyl group.
  • Examples of X 2 in formula (5) include a hydrogen atom and a phenyl group.
  • Ar in formula (5) includes, for example, a phenyl group.
  • the total carbon number of R 1 X 1 , R 2 X 2 and R 3 in formula (5) is not particularly limited as long as it is 1 or more, but may be 2 or more. Further, the total carbon number of R 1 , R 2 , and R 3 in formula (5) may be, for example, 18 or less, 15 or less, or 10 or less. . Further, when X 1 and X 2 in formula (5) are hydrogen atoms, the total number of carbon atoms in R 1 , R 2 , and R 3 is not particularly limited as long as it is 1 or more, but even if it is 2 or more, good. In addition, when at least one of X 1 and X 2 in formula (5) is an aromatic hydrocarbon group which may have a substituent, the total carbon number of R 1 , R 2 , and R 3 is 0. It may be.
  • the ring formed by R 1 X 1 , R 2 X 2 , and the carbon atoms bonded to R 1 X 1 and R 2 examples include hydrocarbon rings having 3 to 13 carbon atoms, which may be optional.
  • the binding group is as described above.
  • the block segment (A) is mainly swollen by the liquid crystal in a thin film state and plays the role of forming a weak anchoring film. Since the physical properties of the weak anchoring film vary greatly depending on the molecular weight of the block segment (A), optimization of the molecular weight is not necessary but is important. From the viewpoint of forming a good weak anchoring film, the molecular weight of the block segment (A) is preferably 1,000 to 100,000, more preferably 3,000 to 50,000. Note that this molecular weight is a number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC).
  • Mn number average molecular weight
  • the molecular weight distribution PDI (Mw/Mn), which is expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene measured by GPC, is preferably 3.0 or less, and more preferably is 2.0 or less.
  • the block segment (A) may be a single polymer of the above compounds, or a combination of multiple compounds may be used. When used in combination, random copolymerization or block copolymerization may be used.
  • the ratio is not particularly limited regardless of the combination method.
  • the preferred combination ratio of compound species that becomes insolubilized in liquid crystal is 30 mol% or less, more preferably 20 mol% or less, but there are no limitations. do not. It is preferable to use these combination methods, the types of compounds to be combined, and the combination ratio within a range that allows desired physical properties, display characteristics, electrical characteristics, etc. to be obtained.
  • the block segment (B) contributes to the stability of the film in a thin film state.
  • Block segment (B) is preferably a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetane group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an aniline group, a protected aniline group.
  • the bonding group includes the specific examples of the bonding group listed in the explanation of formula (2).
  • the block segment (B) contains, for example, a polymerizable compound having the above functional group and a polymerizable group having a polymerizable unsaturated hydrocarbon group as a constituent component.
  • M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • n is an integer of 1 to 2.
  • Z represents a group represented by the following formula (6-Z). (If n is 2, the two Zs may be the same or different.)
  • L is a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetane group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an aniline group, a protected aniline group) group, hydroxy group, protected hydroxy group, phenol group, protected phenol group, thiol group, protected thiol group, thiophenol group, protected thiophenol group, aldehyde group, carboxy group, maleimide group, N-hydroxysuccinimide ester group, bonding group Aromatic hydrocarbon group having 5 to 18 carbon atoms which may have a bonding group inserted therein, an aromatic heterocyclic group having 5 to 18 carbon atoms which may have a bonding group inserted therein, a cinnamic acid group, a cinnamic acid aromatic ester group , a cinnamic acid
  • J is a single bond or has 1 to 1 carbon atoms.
  • 6 represents an aliphatic hydrocarbon group.
  • K When K is bonded to an aromatic hydrocarbon group, it represents a linking group selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, and a thioether bond. In other cases, it indicates a single bond.
  • * represents a binding site.
  • m is an integer from 1 to 3. When m is 2 or 3, multiple K and L may be the same. (However, if J is a single bond, m is 1.)
  • the block segment (B) has a side chain structure that is not compatible with the liquid crystal or becomes incompatible with the liquid crystal upon firing.
  • Compounds that are incompatible with the liquid crystal used to form the block segment (B) include highly polar compounds and compounds with a rigid structure. Examples of the compound species that are no longer compatible with the thermosetting compound species include thermosetting compound species.
  • polymerizable compound used to form the block segment (B) is a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a highly polar structure.
  • the above highly polar structure preferably has the following structure. However, it is not limited to these.
  • X and Y each independently represent an oxygen atom or a sulfur atom.
  • R 1 and R 2 each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms.
  • R 3 represents an alkylene group having 1 to 18 carbon atoms. Represents an alkyl group.
  • One of A 1 , A 2 and A 3 represents N, and the remaining two represent CH.
  • One of A 4 and A 5 represents N, and the remaining one represents CH.
  • * represents the binding site, and n represents an integer from 0 to 4.
  • polymerizable compound used to form the block segment (B) is a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a rigid structure.
  • the above rigid structure preferably has the following structure. However, it is not limited to these.
  • X, Y, and Z each independently represent an oxygen atom or a sulfur atom.
  • R 1 and R 2 each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms.
  • R 3 represents a carbon number 1 ⁇ 18 represents an alkyl group. * represents a bonding site, n represents an integer from 1 to 5.
  • thermosetting structure preferably has the following structure. However, it is not limited to these.
  • X, Y and Z each independently represent an oxygen atom or a sulfur atom.
  • R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 18 carbon atoms.
  • R 4 and R 5 are Each independently represents a single bond or an alkylene group having 1 to 18 carbon atoms. * represents a bonding site, and n represents an integer from 0 to 5.
  • the following structures are preferred as the polymerizable group having a polymerizable unsaturated hydrocarbon group.
  • R 1 and R 2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms
  • X, Y, and Z each independently represent an oxygen atom or a sulfur atom.
  • *, * 1 and * 2 represent bonding sites, and either one of * 1 and * 2 may be replaced with a hydrogen atom or a straight chain or branched alkyl group having 1 to 12 carbon atoms.
  • n is Represents an integer from 1 to 5.
  • the block segment (B) is mainly responsible for stabilizing the thin film state and does not significantly affect the physical properties of the weak anchoring film. It is sufficient that the block segment (B) complements the stability of the membrane, and the optimal molecular weight that can complement the stability of the membrane is not particularly limited because it varies depending on the type of compound used. Further, depending on the type of compound used, advantages can be obtained in solvent selectivity and coating properties, so it is preferable to control the type of compound constituting the block segment (B) and its molecular weight depending on the use and purpose.
  • the above polymerizable compounds may be used alone, or a plurality of compounds may be used in combination.
  • the block segment (B) is a block segment that only contributes to the stability of the membrane, and does not significantly contribute to the weak anchoring properties. Therefore, as long as the stabilization of the membrane is complemented, the type of compound to be combined and the method of combination are Not particularly limited.
  • One embodiment of the polymer A is characterized in that it is a copolymer having a block segment (A) that is compatible with the liquid crystal and a block segment (B) that is insoluble or insoluble in the liquid crystal, but the number of blocks is not limited.
  • a configuration having a plurality of block segments, such as (A)-(B)-(A), for example, may be used, and the number and combination of block segments are not particularly limited. It is also possible to introduce block segments that impart electrical properties.
  • the number of block segments is preferably about 2 to 4
  • the terminal block segment of the polymer is preferably block segment (B).
  • the block segment (A) that is compatible with the liquid crystal controls weak anchoring properties, and the molecular weight of the block segment (A) greatly affects the properties.
  • the molecular weight ratio is not limited.
  • Polymer A can be obtained, for example, by living polymerization.
  • Living polymerization is a polymerization reaction in which side reactions such as chain transfer reactions and termination reactions are not accompanied during the polymerization reaction, and it is possible to obtain a polymer with a narrow molecular weight distribution and a highly controlled structure.
  • one method is to suppress the deactivation of the active site by introducing a stable covalent species called a dormant species into the polymerization active site, thereby preventing the occurrence of side reactions such as chain transfer reactions and termination reactions.
  • Living polymerizations include those using radicals, cations, and anions as active species, and it is important to select one depending on the structure and properties of the polymerizable compound used.
  • the polymerization method does not need to be particularly limited, but cationic polymerization and anionic polymerization often use alkali metals, metal complexes, and halogen compounds to generate active species.
  • cationic polymerization and anionic polymerization often use alkali metals, metal complexes, and halogen compounds to generate active species.
  • the incorporation of metal residues and halogen compounds can cause burn-in and display defects, so it is preferable to use radical polymerization that uses as few metals and halogen compounds as possible.
  • living radical polymerization examples include living radical polymerization (NMP) using nitroxide as a dormant species, atom transfer radical polymerization (ATRP) using a metal complex, and reversible addition/elimination chain transfer polymerization (RAFT) using a sulfur compound as a dormant.
  • Polymerization living radical polymerization
  • TRP atom transfer radical polymerization
  • RAFT reversible addition/elimination chain transfer polymerization
  • SERP living radical polymerization
  • RTCP reversible transfer catalytic polymerization
  • Examples of the polymerization method include living radical polymerization such as NMP, RTCP, and RAFT polymerization, and NMP or RAFT polymerization is particularly preferred.
  • examples of the polymerization initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1,1 Examples include '-bis(tert-butylperoxy)cyclohexane and hydrogen peroxide.
  • the proportion of the polymerization initiator used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • examples of the nitroxide include compounds represented by the following formulas (N-1) to (N-12).
  • the proportion of nitroxide used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • the reaction temperature in the above polymerization is preferably 20 to 200°C, more preferably 40 to 150°C, and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.
  • examples of the polymerization initiator used include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1,1 Examples include '-bis(tert-butylperoxy)cyclohexane and hydrogen peroxide.
  • the proportion of the polymerization initiator used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • examples of the iodide catalyst include compounds represented by the following formulas (P-1) to (P-7).
  • the proportion of the iodide catalyst used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • examples of the hydride catalyst include compounds represented by the following formulas (O-1) to (O-6).
  • the proportion of the hydride catalyst used is 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • the reaction temperature in the above polymerization is preferably 20 to 200°C, more preferably 40 to 150°C, and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.
  • examples of the polymerization initiator used include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1, Examples include 1'-bis(tert-butylperoxy)cyclohexane and hydrogen peroxide.
  • the proportion of the polymerization initiator used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • chain transfer agent trithiocarbonate, dithiobenzoate, dithiocarbamate, and xanthate are preferable, and specific examples include compounds represented by the following formulas (R-1) to (R-24). can be mentioned.
  • the proportion of the chain transfer agent used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • the reaction temperature in the above polymerization is preferably 20 to 200°C, more preferably 40 to 150°C, and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.
  • Me represents a methyl group.
  • Living radical properties are expressed in RAFT polymerization because most of the living chains are in the dormant type (dormant type), and there are compounds that can reversibly inactivate the growing radical species. This is because a fast equilibrium exists between the chains.
  • RAFT polymerization By using RAFT polymerization, it is possible to control polymer terminals, advanced molecular weight control, and molecular weight distribution control.
  • polymer terminals can be controlled by thermally and chemically modifying the RAFT terminals present at the growing terminals.
  • thermal modification the terminal can be modified into an unsaturated hydrocarbon group by heating at a temperature higher than the temperature at which the RAFT agent used is thermally decomposed.
  • chemical modification the terminal can be modified into a thiol bond by bringing it into contact with a primary amine, secondary amine, etc., accompanied by aminolysis.
  • Mn the number average molecular weight (Mn) changes linearly with the ratio of the molar concentration of the monomer to the molar concentration of the chain transfer agent, making it possible to control the molecular weight.
  • Mn theor
  • [Monomer] 0 the molar concentration of the monomer
  • [CTA] 0 the molar concentration of the chain transfer agent
  • M monomer the molar concentration of the monomer.
  • conv. represents the polymerization conversion rate
  • MCTA represents the molecular weight of the chain transfer agent.
  • the reaction solution when the copolymer obtained by the above polymerization is dissolved in the reaction solution, the reaction solution may be used as it is for preparing the liquid crystal aligning agent, or the copolymer contained in the reaction solution may be isolated. Then, it may be used for preparing a liquid crystal aligning agent.
  • the organic solvent used in the synthesis of the copolymer (polymer A) may be any solvent as long as it does not chemically react with the compound species constituting the copolymer and does not scavenge radicals.
  • Polymer B is a graft copolymer having branch polymers that are compatible with liquid crystals and trunk polymers that are incompatible with liquid crystals or that become incompatible with liquid crystals upon firing. Note that the graft copolymer does not dissolve in the liquid crystal depending on the backbone polymer, or becomes insoluble in the liquid crystal upon baking.
  • the branch polymer is attached to the trunk polymer as a side chain of the trunk polymer.
  • a weak anchoring liquid crystal aligning agent containing polymer B is a weak anchoring liquid crystal aligning agent that can be easily manufactured, has good coating properties, and has good adhesion to a seal
  • this is a weakly anchoring liquid crystal aligning agent that does not generate a pretilt angle and can provide a weakly anchoring liquid crystal aligning film that simultaneously achieves low voltage drive and high-speed response when voltage is turned off, and has filed a patent application. 2021-156886, WO2023/048278.
  • the contents of this application and publication are incorporated herein to the same extent as if expressly set forth in their entirety.
  • Graft copolymer is a general term for polymers with a branched structure, and refers to a polymer that simultaneously has a polymer corresponding to a "trunk” and a polymer corresponding to a "branch” bonded to the trunk as a side chain of the trunk.
  • a graft copolymer is used as the polymer B, but the graft copolymer is composed of a branch polymer that is compatible with the liquid crystal, and a branch polymer that is not compatible with the liquid crystal, or a liquid crystal that is formed by baking. and a backbone polymer that becomes incompatible with the polymer.
  • the branch polymer that is compatible with the liquid crystal dissolves in the liquid crystal and swells, contributing to the formation of a weak anchoring state, while the graft copolymer does not dissolve in the liquid crystal due to the trunk polymer, or becomes insolubilized in the liquid crystal by baking.
  • a weakly anchored liquid crystal display element with excellent film hardness and seal adhesion strength by preventing elution of the graft copolymer into the liquid crystal, fixing it to the substrate, crosslinking the polymers with each other, and crosslinking with the sealing component. I can do it.
  • the structure of the branch polymer that is compatible with the liquid crystal is not particularly limited as long as it is soluble in the liquid crystal, but for example, the branch polymer can be derived from a macromonomer represented by the following formula (7).
  • P represents a polymerizable group having a polymerizable unsaturated hydrocarbon group
  • Q represents a monomer containing at least one of the compounds represented by formulas (2) to (5) above. It is a structure obtained by polymerization, and n is an integer of 1 to 2. When n is 2, the two Qs may be the same or different.
  • the monomer used in the synthesis of the branched polymer may be a single component, or a combination of multiple monomers may be used. Further, other monomers capable of radical polymerization reaction, which will be described below, may be used in combination.
  • the branched polymers are largely involved in the expression of weak anchoring properties. Optimization of the molecular weight is important because the physical properties of the weak anchoring film change depending on the molecular weight of the branch polymer.
  • the preferred number average molecular weight of the branched polymer is 1,000 to 100,000, more preferably 3,000 to 50,000, and the weight average molecular weight (Mw) and number The molecular weight distribution (PDI) expressed as a ratio to the average molecular weight (Mn) is preferably 3.0 or less, more preferably 2.0 or less. Note that when the graft copolymer is synthesized by a grafting through method using a macromonomer, the molecular weight here corresponds to the molecular weight of the macromonomer.
  • the structure in which the terminal end of the branched polymer is removed may be a single polymer structure using only one type of monomer represented by the above formulas (2) to (5), or a structure in which multiple monomers are used.
  • a copolymer structure consisting of a combination of monomers may also be used. When a plurality of monomers are combined, random copolymerization or block copolymerization may be used.
  • the monomers represented by the above formulas (2) to (5) are combined, the ratio is not particularly limited regardless of the method of combination.
  • the preferred combination ratio of monomers that insolubilize liquid crystals is 30 mol% or less, more preferably 20 mol% or less, from the viewpoint of maintaining properties, but there is no limitation. .
  • These synthesis methods, monomers to be combined, and combination ratios are preferably used within a range that allows desired physical properties, display characteristics, electrical characteristics, etc. to be obtained.
  • the backbone polymer may contain, for example, a compound represented by the above formula (6) as a constituent component.
  • the macromonomer represented by formula (7) which is the raw material for forming the branch polymer of the graft copolymer that is polymer B, can be obtained, for example, by a combination of living polymerization, chain transfer polymerization, and polymer terminal modification reaction. . Furthermore, it has been reported that a polymer having a radically polymerizable unsaturated bond in the terminal group can be obtained by continuous bulk polymerization at a high temperature of 200° C. or higher (Toagosei Research Annual Report TREND 2002 No. 5).
  • cationic polymerization and anionic polymerization may use alkali metals, metal complexes, or halogen compounds to generate active species.
  • the contamination of metal residues and halogen compounds can cause burn-in and display defects, so it is preferable to use radical polymerization that uses as few metals and halogen compounds as possible.
  • living radical polymerization examples include nitroxide-mediated radical polymerization (NMP) using nitroxide as a dormant species, atom transfer radical polymerization (ATRP) using a metal complex, and reversible addition/fragmentation chain transfer (RAFT) using a sulfur compound as a dormant. ) polymerization, living radical polymerization (TERP) using an organic tellurium compound, etc., reversible transfer catalytic polymerization (RTCP) using an alkyl iodide compound as a dormant species, and using a phosphorus compound, alcohol, etc. as a catalyst, etc. are preferred.
  • the polymerization method examples include living radical polymerization such as NMP, RTCP, and RAFT polymerization, and NMP or RAFT polymerization is particularly preferred.
  • the main synthesis methods for graft copolymers include the Grafting-to method, in which a branch polymer is directly introduced into a trunk polymer, and the Grafting-from method, in which a monomer is polymerized from a macroinitiator (a trunk polymer having a polymerization active site) to extend a branch polymer.
  • the synthesis method is not limited, as any method can be used.
  • the method for producing the graft copolymer is not particularly limited, and any commonly used industrial method can be used. Specifically, it can be produced by radical polymerization, cationic polymerization, or anionic polymerization using the above-mentioned monomers. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control.
  • radical polymerization initiators Radical thermal polymerization initiators, radical photopolymerization initiators
  • RAFT reversible addition-fragmentation chain transfer
  • a radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature.
  • radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane) etc.), alkyl peroxy esters (peroxyneodecanoic acid tert-butyl ester, peroxypivalic acid tert-butyl ester, peroxy 2-ethylcyclo
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • Such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(
  • the radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, and the like can be used.
  • the organic solvent used in the radical polymerization reaction is not particularly limited as long as it dissolves the produced polymer. Specific examples include the above-mentioned specific organic solvents, which may be used alone or in combination of two or more.
  • the reaction solution may be used as it is for preparing the liquid crystal aligning agent, or the graft copolymer contained in the reaction solution may be dissolved in the reaction solution. After separation, the liquid crystal aligning agent may be prepared.
  • the polymerization temperature during radical polymerization can be any temperature in the range of 30 to 150°C, but is preferably in the range of 50 to 100°C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will become too high, making it difficult to stir uniformly. Therefore, the monomer concentration is preferably 1 to 50% by weight, more preferably 5 to 40% by weight.
  • the initial stage of the reaction can be carried out at a high concentration, and then an organic solvent can be added.
  • the molecular weight of the obtained polymer will be small, and if it is small, the molecular weight of the obtained polymer will be large.
  • the amount is preferably 0.1 to 10 mol% based on the monomer to be polymerized.
  • various monomer components, solvents, initiators, etc. can be added during polymerization.
  • the polymer produced from the reaction solution obtained by the above reaction can be recovered by pouring the reaction solution into a poor solvent to precipitate it, but this reprecipitation treatment is not essential.
  • the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, and the like.
  • the polymer precipitated in a poor solvent can be collected by filtration and then dried under normal pressure or reduced pressure, at room temperature or by heating.
  • the amount of impurities in the polymer can be reduced.
  • the poor solvent in this case include alcohols, ketones, hydrocarbons, etc. It is preferable to use three or more kinds of poor solvents selected from these, since the efficiency of purification will further increase.
  • the weight average molecular weight of the graft copolymer measured by GPC (Gel Permeation Chromatography) method is 2,000 to 5. ,000,000 is preferred, and 5,000 to 2,000,000 is more preferred.
  • Graft copolymers have branch polymers that are compatible with liquid crystals and trunk polymers that are not compatible with liquid crystals or become incompatible with heat, etc., and are characterized by being linked in a random arrangement by free radical polymerization. ing. This provides high seal adhesion, solvent selectivity, and coating properties.
  • the introduction ratio of the branch polymer and the trunk polymer is also an important factor.
  • branch polymers play an important role in weak anchoring properties, and if their introduction ratio increases, the strength of the film will be impaired and heat curing will be inhibited, so it is necessary to consider the appropriate amount of introduction. be.
  • the introduction amount and molecular weight of the backbone polymer do not affect the weak anchoring properties (they are small), so in order to achieve both of the above-mentioned properties, the monomer expressed by formula (6) used to synthesize the backbone polymer must be It is preferable that the ratio of the number of molecules (introduction ratio) of the macromonomer represented by formula (7) used in the synthesis of the branched polymer to the number of molecules is small.
  • the preferred introduction ratio (macromonomer represented by formula (7)/monomer represented by formula (6)) is 0.1/99.9 to 50/50 (mol/mol), more preferably It is 0.2/99.8 to 30/70 (mol/mol).
  • the polymer C is a polymer that has a polymer unit that is compatible with the liquid crystal and reacts with the polymer ⁇ when heated.
  • Polymer C is a polymer obtained by polymerizing one or more monomers that have a group that reacts with polymer ⁇ when heated and is compatible with liquid crystal, and when it comes into contact with liquid crystal in a thin film state, it becomes liquid crystal. It is characterized by contributing to the formation of a weak anchoring state by being compatible with each other.
  • a weakly anchoring liquid crystal aligning agent containing a polymer such as Polymer C (a polymer that has a polymer unit that is compatible with the liquid crystal and reacts with other polymers that are used in combination) is easy to use. It is a weak anchoring liquid crystal aligning agent that can be manufactured in a number of steps, has good coating properties, has good adhesion to the seal, does not generate pre-tilt angles, and has low voltage drive and high-speed response when the voltage is turned off.
  • One embodiment of the polymer C is a polymer represented by the following formula (8).
  • A is an n-valent organic compound having a molecular weight of 500 or less and having a group that reacts with the polymer ⁇ upon heating, selected from the following formulas (8-A-1) to (8-A-16). represents a group.
  • Q is a divalent polymer unit which is compatible with the liquid crystal and contains as a constituent at least one kind selected from the group consisting of compounds represented by the above formulas (2) to (5).
  • R is a monovalent organic group selected from the following formulas (8-R-1) to (8-R-11) and having a molecular weight of 500 or less that does not react with the polymer ⁇ upon heating.
  • n is an integer from 1 to 2. When n is 2, the two Q's and R's may be the same or different.
  • R 1 and R 2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms
  • R 3 and R 4 each independently represents a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms
  • X represents an oxygen atom or a sulfur atom. * represents a bonding site.
  • R 1 and R 2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms
  • R 3 and Each R 4 independently represents a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms. * represents a bonding site.
  • the preferable range of the carbon number of the straight chain or branched alkyl group having 1 to 12 carbon atoms varies depending on each group, and may be, for example, 1 to 6 or 6 to 12.
  • the straight chain or branched alkylene group having 1 to 12 carbon atoms may have, for example, 1 to 6 carbon atoms or 1 to 3 carbon atoms.
  • the molecular weight of A in formula (8) is 500 or less.
  • the molecular weight of R in formula (8) is 500 or less.
  • a in formula (8) is a group selected from formulas (8-A-1) to (8-A-16) above. These are, for example, partial structures of a RAFT agent in RAFT polymerization and a chain transfer agent in chain transfer polymerization, which will be described later.
  • the straight chain or branched alkyl group having 1 to 12 carbon atoms may have, for example, 1 to 6 carbon atoms or 1 to 3 carbon atoms.
  • the straight chain or branched alkylene group having 1 to 12 carbon atoms may have, for example, 1 to 6 carbon atoms or 1 to 3 carbon atoms.
  • R in formula (8) is a group selected from formulas (8-R-1) to (8-R-11) above. These are, for example, partial structures of RAFT agents in RAFT polymerization described below.
  • Q in formula (8) is a divalent polymer unit that is compatible with the liquid crystal and contains as a constituent component at least one selected from the group consisting of compounds represented by formulas (2) to (5) above. It is.
  • the monomer used in the synthesis of Polymer C may be a single component, or a combination of multiple monomers may be used. Further, other radically polymerizable monomers described below may be used in combination.
  • the polymer C When the polymer C comes into contact with liquid crystal in a thin film state, it forms a polymer-liquid crystal mixed layer and exhibits weak anchoring properties. Optimization of the molecular weight is important because the thickness of the formed polymer-liquid crystal mixed layer changes depending on the molecular weight of the polymer C, and the weak anchoring property changes.
  • the number average molecular weight of the polymer C is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and the weight average molecular weight (Mw)
  • the molecular weight distribution (PDI) expressed as a ratio to the number average molecular weight (Mn) is preferably 3.0 or less, more preferably 2.0 or less.
  • the structure of Q in the polymer represented by formula (8) which is an example of polymer C, may be a single polymer structure using only one compound (monomer) represented by formulas (2) to (5) above.
  • a copolymer structure consisting of a combination of a plurality of monomers may be used.
  • random copolymerization or block copolymerization may be used.
  • the ratio is not particularly limited regardless of the method of combination.
  • the preferred combination ratio of compound species that becomes insolubilized in liquid crystal is 30 mol% or less, more preferably 20 mol% or less, but there are no limitations. do not.
  • These synthesis methods, monomers to be combined, and combination ratios are preferably used within a range that allows desired physical properties, display characteristics, electrical characteristics, etc. to be obtained.
  • Examples of the compound species to be insolubilized in the liquid crystal include the compound represented by the above formula (6), the above-mentioned compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a highly polar structure, and the above-mentioned polymerizable compound.
  • Examples include compounds having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a rigid structure, and compounds having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a thermosetting structure.
  • Polymer C is preferably obtained by living polymerization or chain transfer polymerization.
  • radical polymerization that uses no metals or halogen compounds as much as possible.
  • living radical polymerization include living radical polymerization (NMP) using nitroxide as a dormant species, atom transfer radical polymerization (ATRP) using a metal complex, and reversible addition/elimination chain transfer polymerization (RAFT) using a sulfur compound as a dormant.
  • polymerization living radical polymerization (TERP) using an organic tellurium compound, etc.
  • RTCP reversible transfer catalytic polymerization
  • alkyl iodide compound as a dormant species and using a phosphorus compound, alcohol, etc. as a catalyst, etc.
  • examples of the polymerization method include living radical polymerization such as NMP, RTCP, and RAFT polymerization, and NMP or RAFT polymerization is particularly preferred. It is also preferable to use chain transfer polymerization.
  • examples of the polymerization initiator used include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1 , 1'-bis(tert-butylperoxy)cyclohexane, hydrogen peroxide, and the like.
  • the proportion of the polymerization initiator used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • the chain transfer agent it is preferable to use thiols, and specific examples include compounds represented by the following formulas (S-1) to (S-15).
  • the proportion of the chain transfer agent used is usually 0.000001 to 0.1 part by mole, preferably 0.00001 to 0.01 part by mole, per 1 part by mole of the monomer used.
  • the reaction temperature in the above polymerization is preferably 20 to 200°C, more preferably 40 to 150°C, and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.
  • the organic solvent used in the chain transfer polymerization reaction is not particularly limited as long as it can dissolve the produced polymer. Specific examples include the above-mentioned specific organic solvents, which may be used alone or in combination of two or more. Furthermore, even a solvent that does not dissolve the produced polymer may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate. Note that in chain transfer polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the extent possible.
  • chain transfer polymerization polymers are obtained by competitive reactions between chain transfer and growth reactions.
  • the molecular weight and molecular weight distribution of a polymer obtained by chain transfer polymerization are determined by the chain transfer constant (Cs), which is expressed as the quotient of the chain transfer rate constant (kc) and the growth rate constant (kp).
  • Cs chain transfer constant
  • kc chain transfer rate constant
  • kp growth rate constant
  • a structure in which Cs is in the range of 1 to 60 is preferable, and it is important to use the monomer species and chain transfer agent species and the correct combination of these.
  • the chain transfer constant (Cs) varies greatly depending on the type of monomer used and the type of chain transfer agent, so it is necessary to select it correctly.
  • the polymer C is preferably composed of one or more compound species that are compatible with the liquid crystal from the viewpoint of maintaining properties, but a small amount of compound species that are not compatible with the liquid crystal or become insolubilized in the liquid crystal upon firing may also be introduced. be able to.
  • a preferred combination ratio of monomers that are insolubilized in liquid crystal is 30 mol% or less, more preferably 20 mol% or less, but is not limited. These synthesis methods, monomers to be combined, and combination ratios are preferably used within a range that allows desired physical properties, display characteristics, electrical characteristics, etc. to be obtained.
  • One embodiment of the polymer alloy of the present invention includes a polymer C that is obtained by polymerizing one or more monomers that have a group that reacts with the polymer ⁇ when heated and is compatible with the liquid crystal; It is characterized by containing a polymer ⁇ that suppresses the elution of the polymer C into the liquid crystal by reacting with the polymer C by heating. This provides high seal adhesion, solvent selectivity, and coating properties.
  • the temperature at which the group in polymer C that reacts with polymer ⁇ when heated and the site in polymer ⁇ that reacts with polymer C when heated is not particularly limited, but for example, even if it is 150°C or higher. Alternatively, the temperature may be 200°C or higher.
  • the polymer alloy of the present invention consists of a polymer ⁇ , which is a component that exhibits weak anchoring properties, and a component that does not exhibit weak anchoring properties, but which develops a uniaxial orientation regulating force through orientation treatment (preferably uniaxial orientation treatment). It is characterized by containing a certain polymer ⁇ , and the weak anchoring alignment film obtained using this is subjected to alignment treatment (preferably uniaxial alignment treatment) to improve weak anchoring properties and high-speed response when voltage is turned off. It is possible to achieve both. Furthermore, by selecting an appropriate polymer for the polymer ⁇ , good applicability and good seal adhesion can be obtained.
  • the heating temperature of the polymer alloy of the present invention is not particularly limited, but may be, for example, 150°C or higher, or 200°C or higher.
  • polymer ⁇ which is a component that exhibits weak anchoring properties, plays an important role, and if the proportion of polymer ⁇ that is introduced increases, the strength of the film may be impaired or heat curing may be inhibited. Therefore, it is necessary to consider the appropriate amount to introduce.
  • the mass ratio of polymer ⁇ to polymer ⁇ must be made small.
  • the mass ratio (polymer ⁇ /polymer ⁇ ) is preferably 10/90 to 99.9/0.1 (mass ratio), more preferably 30/70 to 99.5/0.5 (mass ratio). , 50/50 to 99.0/1.0 (mass ratio) is particularly preferred.
  • the polymer ⁇ does not exhibit weak anchoring properties, but exhibits a uniaxial alignment regulating force when subjected to alignment treatment (preferably uniaxial alignment treatment).
  • the polymer ⁇ is preferably a polymer that functions as a strong anchoring alignment film by itself.
  • Suitable uniaxial alignment treatment methods include photo alignment treatment, rubbing alignment treatment, and the like.
  • polymer ⁇ By selecting an appropriate polymer ⁇ , it can be fixed to the substrate, cross-linked between polymers, and cross-linked with the sealing component, resulting in excellent film hardness and seal adhesion strength, excellent solvent selectivity, and excellent coating properties.
  • An anchoring liquid crystal aligning agent and a display element using the same can be obtained.
  • polymer C when polymer C is used as polymer ⁇ , polymer ⁇ reacts with polymer C by heating, thereby suppressing elution of polymer C into the liquid crystal.
  • polymer ⁇ and polymer ⁇ undergo phase separation in a sea-island pattern on the surface of the weakly anchored alignment film to create a segmented surface state.
  • physical properties thermal expansion coefficient and polarity
  • polymer ⁇ is hydrophobic, flexible, and has a low Tg.
  • the polymer ⁇ is preferably a highly polar and rigid polymer.
  • the polymer ⁇ is preferably at least one kind of polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyamide, polyurea, and poly(meth)acrylate, and particularly preferably polyimide, polyamic acid, and polyamic acid ester. It is an acid ester and poly(meth)acrylate.
  • the polymer ⁇ is a polymer (hereinafter referred to as (sometimes referred to as "polyimide polymer”) is preferable.
  • the tetracarboxylic acid derivative component includes at least one compound selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof.
  • the polyimide precursor include polyamic acid and polyamic acid ester.
  • polyamic acid As the polymer ⁇ , it can be obtained, for example, by subjecting a tetracarboxylic acid derivative component to a diamine component to a polymerization (polycondensation) reaction.
  • polyimide is selected as the polymer ⁇ , it can be obtained by imidizing the above-mentioned polyamic acid.
  • a polyamic acid ester is selected as the polymer ⁇ , it can be obtained by the method described below. Note that polyimide can also be obtained by imidizing the polyamic acid ester.
  • tetracarboxylic acid derivative component examples include aromatic tetracarboxylic dianhydride, acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, or derivatives thereof.
  • aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring.
  • Acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure.
  • an alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups is bonded to an aromatic ring. Further, it is not necessary to be composed only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.
  • aromatic tetracarboxylic dianhydride acyclic aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is, among others, a tetracarboxylic dianhydride represented by the following formula (9). is preferred.
  • (X represents a structure selected from the group consisting of the following formulas (X-1) to (X-17) and (XR-1) to (XR-2).)
  • R 1 to R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, Alkynyl group having 2 to 6 carbon atoms, monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, alkoxy group having 1 to 6 carbon atoms, alkoxyalkyl group having 2 to 6 carbon atoms, 2 to 6 carbon atoms represents an alkyloxycarbonyl group or a phenyl group.
  • R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
  • j and k are integers of 0 or 1
  • a 1 and A 2 each independently represent a single bond, -O-, -CO-, -COO-, represents a phenylene group, a sulfonyl group, or an amide group.
  • the plurality of A2 's may be the same or different. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.
  • X is represented by the above formulas (X-1) to (X-8), (X-10) to (X-11). , and those selected from (XR-1) to (XR-2).
  • the above formula (X-1) is preferably selected from the group consisting of the following formulas (X1-1) to (X1-6).
  • Preferred specific examples of the above formulas (XR-1) and (XR-2) include the following formulas (XR-3) to (XR-18).
  • the amount of the tetracarboxylic dianhydride or its derivative represented by the above formula (9) to be used is as follows:
  • the content is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more.
  • the diamine component used in the production of the polyimide polymer is not particularly limited, but a diamine component containing a diamine represented by the following formula (10) is preferred.
  • Ar 1 and Ar 1' each independently represent a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more of the benzene ring, the biphenyl structure, or the naphthalene ring
  • the hydrogen atom of may be substituted with a monovalent group.
  • Ar 1 and Ar 1' in the above formula (10) each represent a benzene ring, a biphenyl structure, or a naphthalene ring.
  • One or more hydrogen atoms on the benzene ring, biphenyl structure, or naphthalene ring may be substituted with a monovalent group, and the monovalent group includes a halogen atom, an alkyl group having 1 to 3 carbon atoms, a carbon Alkenyl group having 2 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, fluoroalkyl group having 1 to 3 carbon atoms, fluoroalkenyl group having 2 to 3 carbon atoms, fluoroalkoxy group having 1 to 3 carbon atoms, 2 carbon atoms -3 alkyloxycarbonyl groups, cyano groups, nitro groups, etc.
  • the bonding position of the amino group and L 1 or L 1' to the benzene ring is preferably the 1,4-position or the 1,3-position. , 1,4-position is more preferred.
  • the binding position of the amino group and L 1 or L 1' to the biphenyl structure is more preferably the 4,4'-position or the 3,3'-position, and even more preferably the 4,4'-position.
  • the bonding position of the amino group and L 1 or L 1' to the naphthalene ring is preferably the 1,5-position or the 2,6-position, and even more preferably the 2,6-position.
  • the alkylene group having 2 to 12 carbon atoms may be linear or branched, but is preferably linear.
  • n is an integer of 1 to 12, more preferably an integer of 2 to 12, even more preferably an integer of 2 to 6.
  • the sum of m1, m2 and n' is an integer of 3 to 12, more preferably an integer of 6 to 12.
  • m1 and m2 are each more preferably an integer of 1 to 4, even more preferably an integer of 2 to 4.
  • n' is more preferably an integer of 2 to 6, even more preferably an integer of 2 to 4.
  • the proportion of the diamine represented by formula (10) is preferably 1 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on 1 mol of the diamine component. preferable.
  • the diamine component constituting the polyimide polymer may contain other diamines than the diamines described above. Examples of other diamines are listed below, but the present invention is not limited thereto.
  • the amount of the diamine represented by the formula (10) relative to the diamine component is preferably 90 mol% or less, and 80 mol% The following are more preferred. Examples of other diamines are listed below, but the other diamines in the present invention are not limited to these.
  • the other diamines mentioned above may be used alone or in combination of two or more.
  • p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1, 4-Diamino-2,5-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 4-(2-(methylamino) ethyl)aniline, 4-(2-aminoethyl)aniline, 2-(6-amino-2-naphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamin
  • 2,4-diaminophenol 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxy biphenyl; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid
  • m and n are each independently an integer of 1 to 3 (provided that 1 ⁇ m+n ⁇ 4 is satisfied), j is an integer of 0 or 1, and X 1 is -(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH 3 )-, -NH-, -O-, -CH 2 O-, -CH 2 -OCO-, -COO-, or -OCO-.
  • R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, or a fluorine atom-containing group having 1 to 10 carbon atoms.
  • X 2 represents -O-, -CH 2 O-, -CH 2 -OCO-, -COO-, or -OCO-
  • R 2 is alkyl having 3 to 30 carbon atoms. group, or a fluorine atom-containing alkyl group having 3 to 20 carbon atoms.
  • D in -N(D)- of the other diamines mentioned above is representative of benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, Boc (tert-butoxycarbonyl group), etc.
  • Preferred are carbamate-based organic groups. Boc is particularly preferred from the viewpoint that it has good thermal desorption efficiency, desorbs at a relatively low temperature, and is discharged as a harmless gas upon desorption.
  • diamines having a thermally releasable group include diamines selected from the following formulas (d-1) to (d-7).
  • R represents a hydrogen atom or Boc.
  • a diamine having a heat-eliminating group as described above is preferably 5 to 40% per mole of the diamine component. It is preferably mol%, more preferably 5 to 35 mol%, even more preferably 5 to 30 mol%.
  • the above polymer ⁇ is a polyimide precursor obtained using a diamine component containing a diamine having a nitrogen atom-containing structure, and a polyimide precursor obtained from the viewpoint of reducing afterimages derived from residual DC or improving electrical properties. It may contain at least one kind of polymer selected from the group consisting of imidides (hereinafter also referred to as polyimide polymer (Q)).
  • polyimide polymer (Q) examples include the above-mentioned tetracarboxylic acid derivative component.
  • the tetracarboxylic dianhydride represented by the above formula (9) or a derivative thereof is preferred.
  • the amount of the tetracarboxylic dianhydride or its derivative represented by the above formula (9) to be used is preferably 10 mol% or more, and 20 mol% based on 1 mol of the total tetracarboxylic acid derivative component to be reacted with the diamine component.
  • the above is more preferable.
  • the diamine component for obtaining the polyimide polymer (Q) the amount of the diamine having the nitrogen atom-containing structure used is 5 to 50% based on the total amount of the diamine component for obtaining the polyimide polymer (Q). It is preferably 100 mol%, more preferably 10 to 95 mol%, even more preferably 20 to 80 mol%.
  • the diamine component for obtaining the polyimide polymer (Q) may further contain a diamine other than the diamine having the nitrogen atom-containing structure.
  • a diamine hereinafter also referred to as diamine (c)
  • the amount of diamine (c) used is preferably 1 to 95 mol%, more preferably 5 to 90 mol%, and 20 to 80 mol% based on the total amount of diamine components to obtain the polyimide polymer (Q). is even more preferable.
  • the polymer ⁇ is selected from the group consisting of a polyimide precursor obtained using the above polyimide polymer (Q) and a diamine component not containing a diamine having a nitrogen atom-containing structure, and an imidized product of the polyimide precursor. It may be a mixture with at least one kind of polymer (hereinafter also referred to as polyimide polymer (H)).
  • the content ratio of polyimide polymer (Q) and polyimide polymer (H) is 10/90 to 90/mass ratio of [polyimide polymer (Q)]/[polyimide polymer (H)].
  • the ratio is preferably 10, more preferably 20/80 to 80/20, even more preferably 30/70 to 70/30.
  • the polymer ⁇ has an amino group, a protected amino group, a hydroxy group, a protected hydroxy group, a thiol group, a protected thiol group, a carboxy group, a protected carboxy group, an isocyanate group, a protected isocyanate group, A polymer containing at least one selected from the group consisting of a maleimide group, a carboxylic anhydride group, a vinyl group, an allyl group, a styryl group, a (meth)acrylic group, and a (meth)acrylamide group as a site that reacts with polymer C.
  • the protecting group for the protected amino group, the protecting group for the protected hydroxy group, the protecting group for the protected thiol group, the protecting group for the protected carboxy group, and the protecting group for the protected isocyanate group are removed by heating, and the amino group, Represents a group that produces a hydroxy group, thiol group, carboxy group, or isocyanate group.
  • Examples of the protecting group for the protected amino group include tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, phthaloyl group, nitrobenzenesulfonyl group, (2-trimethylsilyl)- Examples include ethanesulfonyl group, 2,2,2-trichloroethoxycarbonyl group, and azide group.
  • Examples of the protecting group for the protected hydroxy group include a tetrahydropyranyl group, a methoxymethyl ether group, a trityl group, a tert-butyl group, a trialkylsilyl group, a tert-butoxycarbonyl group, a benzyl group, and an acetyl group.
  • Examples of the protecting group for the protected thiol group include tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, phthaloyl group, nitrobenzenesulfonyl group, (2-trimethylsilyl)- Examples include ethanesulfonyl group, 2,2,2-trichloroethoxycarbonyl group, and azide group.
  • Examples of the protecting group for the protected carboxy group include a methyl ester group, a benzyl ester group, and a tert-butyl ester group.
  • Examples of the protecting group for the protected isocyanate group include a tert-butyl group, a dimethylpyrazole group, a methyl ethyl ketone oxime group, and a lactam group.
  • polyamic acid, polyimide, or polyamic acid ester is used as the polymer ⁇
  • a carboxy group generated from the reaction of a tetracarboxylic dianhydride and a diamine component is present, and the terminal group of the polymer chain is a carboxylic acid (anhydride) or an amino acid. Because of the presence of the group, all polyamic acids and polyimides fall under the polymer ⁇ unless the imidization rate is 100%.
  • Polyamic acid which is one of the polyimide precursors, can be produced by the following method. Specifically, a tetracarboxylic acid derivative component and a diamine component are reacted in the presence of an organic solvent at -20 to 150°C, preferably 0 to 50°C, for 30 minutes to 24 hours, preferably 1 to 12 hours. It can be synthesized by a condensation reaction).
  • organic solvent used in the above reaction examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, Examples include 1,3-dimethyl-2-imidazolidinone.
  • methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used. These may be used in combination of two or more types.
  • the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass. It is also possible to carry out the reaction at a high concentration in the initial stage and then add a solvent.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid derivative component is preferably 0.8 to 1.2. As in normal polycondensation reactions, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.
  • the polyamic acid obtained in the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while thoroughly stirring the reaction solution. Further, purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating.
  • the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.
  • a polyamic acid ester which is one of the polyimide precursors, can be produced by (1) a method of esterifying the above-mentioned polyamic acid, (2) a method of reacting a tetracarboxylic acid derivative component containing a tetracarboxylic acid diester dichloride with a diamine component, ( 3) It can be produced by a known method such as a method of polycondensing a tetracarboxylic acid derivative component containing a tetracarboxylic diester with a diamine.
  • the above-mentioned polyamic acid and polyamic acid ester may be terminal-modified polymers obtained by using an appropriate end-capping agent together with the above-mentioned tetracarboxylic acid derivative component and diamine component.
  • the terminal capping agent include acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and trimellitic anhydride.
  • Acid monoanhydrides such as anhydrides; dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; aniline, 2-aminophenol, 3 -Aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n - Monoamine compounds such as hexylamine
  • Polyimide can be produced by imidizing the above polyimide precursor by a known method.
  • the ring closure rate (also referred to as imidization rate) of functional groups possessed by polyamic acid or polyamic acid ester does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the use and purpose.
  • the method for obtaining polyimide by imidizing the polyamic acid or polyamic acid ester includes thermal imidization in which the solution of the polyamic acid or polyamic acid ester is directly heated, or a catalyst (e.g. Examples include catalytic imidization in which a basic catalyst such as pyridine or an acid anhydride such as acetic anhydride is added.
  • a catalyst e.g. Examples include catalytic imidization in which a basic catalyst such as pyridine or an acid anhydride such as acetic anhydride is added.
  • the polyamic acid, polyamic acid ester, and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1000 mPa ⁇ s when made into a solution with a concentration of 10 to 15% by mass, from the viewpoint of workability. , not particularly limited.
  • the solution viscosity (mPa ⁇ s) of the above polymer is a polymer with a concentration of 10 to 15% by mass prepared using a good solvent for the polymer (for example, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.). This is the value measured for the solution at 25°C using an E-type rotational viscometer.
  • the weight average molecular weight (Mw) of the polyamic acid, polyamic acid ester, and polyimide measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, more preferably 2,000. ⁇ 500,000. Further, the molecular weight distribution (Mw/Mn) expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. By having a molecular weight within such a range, good liquid crystal alignment of the liquid crystal display element can be ensured.
  • the diisocyanate to be reacted with the above-mentioned diamine component is not particularly limited and can be used depending on availability and the like.
  • the specific structure of the diisocyanate is shown below.
  • R 2 and R 3 represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
  • formulas (K-1) to (K-5) are inferior in reactivity, they have the advantage of improving solvent solubility; Aromatic diisocyanates are highly reactive and have the effect of improving heat resistance, but they have the disadvantage of decreasing solvent solubility.
  • formulas (K-1), (K-7), (K-8), (K-9), and (K-10) are preferable, and in terms of electrical characteristics, formula (K-12) is preferable.
  • formula (K-13) is preferred from the viewpoint of liquid crystal orientation.
  • Two or more diisocyanates can be used in combination, and it is preferable to use various diisocyanates depending on the desired properties.
  • diisocyanates can be replaced with the above-mentioned tetracarboxylic dianhydride, and they can also be used in the form of a copolymer of polyamic acid and polyurea, and chemical imidization can be used to create a copolymer of polyimide and polyurea. It may also be used in the form of a copolymer.
  • the structure of the dicarboxylic acid to be reacted is not particularly limited, but specific examples are as follows.
  • aliphatic dicarboxylic acids include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, and 2,2-dimethylglutaric acid. Mention may be made of acids, dicarboxylic acids such as 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.
  • alicyclic dicarboxylic acids examples include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid.
  • Aromatic dicarboxylic acids include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butyl isophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid.
  • dicarboxylic acids containing heterocycles include 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.
  • the various dicarboxylic acids mentioned above may have an acid dihalide or anhydride structure. These dicarboxylic acids are particularly preferably dicarboxylic acids that can provide a polyamide with a linear structure in order to maintain the orientation of liquid crystal molecules.
  • dicarboxylic acids are particularly preferably dicarboxylic acids that can provide a polyamide with a linear structure in order to maintain the orientation of liquid crystal molecules.
  • terephthalic acid isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4''-
  • raw material diamine also described as “diamine component”
  • raw material tetracarboxylic dianhydride also described as “tetracarboxylic dianhydride component”
  • tetracarboxylic acid diester Selected from raw material diamine (also described as “diamine component”)
  • raw material tetracarboxylic dianhydride also described as “tetracarboxylic dianhydride component”
  • tetracarboxylic acid diester also described as “tetracarboxylic dianhydride component”
  • diisocyanate diisocyanate
  • poly(meth)acrylate is selected as the polymer ⁇
  • one preferred embodiment of the poly(meth)acrylate is a polyacrylate other than the polymer ⁇ described above.
  • it is a polymer obtained by polymerizing industrially available monomers capable of radical polymerization using a common radical generator.
  • Specific examples of industrially available monomers capable of radical polymerization include unsaturated carboxylic acids, acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds. It will be done.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
  • acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl acrylate.
  • Acrylate compounds having cyclic ether groups such as glycidyl acrylate, (3-methyl-3-oxetanyl) methyl acrylate, and (3-ethyl-3-oxetanyl) methyl acrylate can also be used.
  • methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and tert-butyl.
  • Methacrylate compounds having a cyclic ether group such as glycidyl methacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, and (3-ethyl-3-oxetanyl) methyl methacrylate can also be used.
  • vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
  • maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • liquid crystal side chain monomers monomers with a liquid crystal side chain structure
  • photosensitive monomers photosensitive monomers
  • a liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and can form a mesogenic group at the side chain site. More specific examples of liquid crystalline side chain monomers include hydrocarbons, radically polymerizable groups such as (meth)acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, and norbornene. It is preferable that the structure has a polymerizable group composed of at least one kind selected from the group consisting of a side chain having at least one kind of mesogenic group included in a liquid crystal side chain.
  • the liquid crystal side chain monomer is preferably a monomer in which a liquid crystal side chain selected from the following formulas (LS-1) to (LS-13) is bonded to a polymerizable group capable of radical polymerization.
  • a liquid crystal side chain selected from the following formulas (LS-1) to (LS-13) is bonded to a polymerizable group capable of radical polymerization.
  • the radically polymerizable polymerizable group include the polymerizable group having a polymerizable unsaturated hydrocarbon group as exemplified in the explanation of the polymer ⁇ .
  • R 12 represents an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms
  • R 12 is a phenyl group, a naphthyl group, a biphenylyl group, a furan-2,5-diyl group, or a monovalent nitrogen-containing heterocycle.
  • a photosensitive side chain is bonded to the main chain, and photoreactive side chain monomers can undergo cross-linking reactions, isomerization reactions, or photo-Fries rearrangement in response to light. It is a monomer with side chains.
  • the structure of the photosensitive side chain is not particularly limited, but a structure that causes a crosslinking reaction or a photo-Fries rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time.
  • the structure of the photosensitive side chain type acrylic polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but preferably has a rigid mesogenic component in the side chain structure.
  • the structure of the photosensitive side chain type acrylic polymer has, for example, a main chain and a side chain bonded to the main chain, and the side chain is a biphenyl group, terphenyl group, phenylcyclohexyl group, phenylbenzoate group, or azobenzene group. It has a structure that has a mesogenic component such as and a photosensitive group that is bonded to the tip of the side chain and undergoes a crosslinking reaction or isomerization reaction in response to light, or a main chain and a side chain that is bonded to it. It can have a structure having a phenylbenzoate group whose side chain also serves as a mesogen component and undergoes a photo-Fries rearrangement reaction.
  • More specific examples of structures of photosensitive side chain type acrylic polymers that can exhibit liquid crystallinity in a predetermined temperature range include hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, ⁇ -methylene- ⁇ -
  • a structure having a chain is preferable.
  • Ar 1 and Ar 2 each independently represent a divalent organic group obtained by removing two hydrogen atoms from a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, or a pyridine ring,
  • S 1 and S 2 each independently represent a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, a phenylene group or a biphenylylene group, or a single bond,
  • R is a hydrogen atom, a hydroxy group, a mercapto group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or a dialkylamino group having 2 to 16 carbon atoms.
  • the benzene ring and/or naphthalene ring in Ar 1 , Ar 2 , S 1 and S 2 are the same or different one or more selected from a halogen atom, a cyano group, a nitro group, a carboxy group, and an alkoxycarbonyl group having 2 to 11 carbon atoms. may be substituted with a substituent.
  • the alkyl group having 1 to 10 carbon atoms in the alkoxycarbonyl group having 2 to 11 carbon atoms may be linear, branched, cyclic, or a combination thereof;
  • the hydrogen atom may be substituted with a halogen atom.
  • the method for producing the polyacrylate is not particularly limited, and any industrially-used general-purpose method can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control.
  • a known radical polymerization initiator such as AIBN (azobisisobutyronitrile) or a known compound such as a reversible addition-fragmentation chain transfer (RAFT) polymerization reagent may be used. I can do it.
  • AIBN azobisisobutyronitrile
  • RAFT reversible addition-fragmentation chain transfer
  • the radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, etc. can be used.
  • the organic solvent used in the polymerization reaction of the photosensitive side chain type acrylic polymer capable of exhibiting liquid crystallinity in a predetermined temperature range is not particularly limited as long as it dissolves the produced polymer. Specific examples are listed below. N,N-dimethylformamide, N,N-diethylformamide, N,N-dibutylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylpropionamide , N,N-diethylpropionamide, 3-methoxy-N,N-dimethylpropanamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3- Dimethyl-2-imidazolidinone, N-methyl- ⁇ -caprolactam, N,N-diethylacetamide, N,N-dipropylacetamide, 3-methoxy
  • organic solvents may be used alone or in combination. Furthermore, even a solvent that does not dissolve the produced polymer may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate. Further, in radical polymerization, oxygen in an organic solvent becomes a cause of inhibiting the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the extent possible.
  • the polymerization temperature during radical polymerization can be any temperature from 30 to 150°C, preferably from 50 to 100°C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will become too high, making it difficult to stir uniformly. Therefore, the monomer concentration is preferably 1 to 50% by weight, more preferably 5 to 30% by weight.
  • the initial stage of the reaction can be carried out at a high concentration, and then an organic solvent can be added.
  • the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer will be small, and if it is small, the molecular weight of the obtained polymer will be large, so the ratio of the radical initiator is The amount is preferably 0.1 to 10 mol % based on the monomer to be polymerized. Furthermore, various monomer components, solvents, initiators, etc. can be added during polymerization.
  • the reaction solution When recovering the produced polymer from the reaction solution of the photosensitive side-chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is poured into a poor solvent and the polymers are removed. All you have to do is precipitate the coalescence.
  • the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, and the like.
  • the polymer precipitated in a poor solvent can be collected by filtration and then dried under normal pressure or reduced pressure, at room temperature or by heating. Further, by repeating the operation of redissolving the precipitated and recovered polymer in an organic solvent and reprecipitating and recovering it 2 to 10 times, the amount of impurities in the polymer can be reduced.
  • the poor solvent in this case include alcohols, ketones, hydrocarbons, etc. It is preferable to use three or more types of poor solvents selected from these, since the efficiency of purification will further increase.
  • the molecular weight of the photosensitive side chain type acrylic polymer that can exhibit liquid crystallinity in a predetermined temperature range is determined by considering the strength of the resulting coating film, the workability during coating film formation, and the uniformity of the coating film.
  • the weight average molecular weight measured by GPC method is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
  • the weak anchoring liquid crystal aligning agent is used for forming the weak anchoring alignment film of a liquid crystal cell having liquid crystal and the weak anchoring alignment film.
  • the composite components other than the polymer ⁇ and the polymer ⁇ , which constitute the alignment film may be monomers or polymers.
  • a polymer as a composite component a mixture of a plurality of polymers can be used.
  • polysiloxane polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) ) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates.
  • poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Cerac Manufacturing Co., Ltd.), and poly(isobutylene-maleic anhydride) copolymers include Specific examples of poly(vinyl ether-maleic anhydride) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether anhydride). maleic acid resin (manufactured by Ashland).
  • the other polymers may be used alone or in combination of two or more.
  • the content ratio of other polymers is more preferably 0.1 to 90 parts by weight, and even more preferably 1 to 90 parts by weight, based on 100 parts by weight of the total of polymer ⁇ and polymer ⁇ . Even when monomers are selected as a composite component, a plurality of monomers can be used in combination.
  • the monomers to be composited are thermally curable such as polyfunctional (meth)acrylates, polyfunctional epoxides, and polyfunctional ethylene, and at the same time thermal acid generators, thermal base generators, thermal radical generators, etc. may be used together.
  • the composite ratio of monomers to be composited with the polymer alloy is not particularly limited, but from the viewpoint of optical properties and processability, a preferred composite ratio is 99% by mass or less, more preferably 70% by mass or less.
  • organic solvent used in the liquid crystal aligning agent examples include the above-mentioned specific organic solvents. These organic solvents may be used alone or in combination.
  • a solvent that improves the uniformity and smoothness of the coating film by mixing it with an organic solvent that has high solubility.
  • Examples include 2-ethylhexyl, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, and 2-ethylhexyl maleate.
  • a plurality of types of these solvents may be mixed. When using these solvents, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass of the total solvent contained in the liquid crystal aligning agent.
  • the weakly anchoring liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the solvent (hereinafter also referred to as additive components).
  • additive components include compounds for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as crosslinking compounds), the adhesion between the liquid crystal alignment film and the substrate, and the adhesion between the liquid crystal alignment film and the sealant. Examples include adhesion aids for increasing the liquid crystal alignment film, dielectrics and conductive substances for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film.
  • crosslinkable compound examples include a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an oxetanyl group, an oxazoline structure, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group.
  • a crosslinkable compound (c-1) and (c-2) include the following compounds.
  • Compounds with epoxy groups include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Bisphenol A type epoxy such as diol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Epicote 828 (manufactured by Mitsubishi Chemical Corporation) resins, bisphenol F type epoxy resins such as Epicote 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), biphenyl skeleton-containing epoxy resins such
  • 10-338880 compounds described in WO2017/170483, etc.
  • Examples of compounds having an oxetanyl group include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene (alonoxetane OXT-121 (XDO)), bis[2-(3-oxetanyl)butyl] Ether (alonoxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl) ) methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), two described in paragraphs [0170] to [0175] of WO2011/132751.
  • Examples of compounds having the above oxetanyl group include 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), and Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.). Polymers and oligomers having an oxazoline group such as, compounds described in paragraph [0115] of Japanese Patent Application Publication No.
  • Examples of compounds having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N' ,-di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine and described in paragraphs [0025] to [0030] and [0032] of WO2011/155577.
  • Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals), two described in paragraphs [0046] to [0047] of Japanese Patent Application Publication No.
  • glycerin mono(meth)acrylate As a crosslinkable compound having a polymerizable unsaturated group, glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-,1,3-body mixture), glycerin tris(meth)acrylate, glycerol 1,3 - diglycerolate di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate ) acrylate, hexaethylene glycol mono(meth)acrylate, etc.
  • crosslinkable compounds are examples of crosslinkable compounds, and are not limited thereto.
  • components other than the above disclosed on page 53 [0105] to page 55 [0116] of WO2015/060357 can be mentioned.
  • two or more types of crosslinkable compounds may be used in combination.
  • the content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. , more preferably 1 to 15 parts by mass.
  • adhesion aids include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N -Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropylprop
  • the content of the adhesion aid in the liquid crystal aligning agent is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and more preferably Preferably it is 0.1 to 20 parts by mass.
  • the strong anchoring horizontal alignment film described here is a liquid crystal alignment film that can uniformly align liquid crystals in the horizontal direction and has a sufficiently strong force to maintain the aligned liquid crystals, that is, interfacial anchoring energy.
  • a strong anchoring horizontal alignment film can be obtained by aligning the polyamic acid, polyimide, polyamic acid ester, polyamide, polyester, polyacrylate, etc. described above in a uniaxial direction by rubbing, photo alignment, or the like.
  • a strong anchoring horizontal alignment film can be obtained by combining the monomers mentioned above.
  • the weakly anchoring alignment film of the present invention can be obtained by using the weakly anchoring liquid crystal alignment agent described above.
  • the cured film obtained by drying and baking is rubbed, irradiated with polarized light or light of a specific wavelength, etc., or irradiated with an ion beam, etc. It can be obtained by performing orientation treatment during processing.
  • a strong anchoring horizontal alignment film can be obtained by applying a strong anchoring liquid crystal aligning agent to a substrate, and then subjecting the cured film obtained by drying and baking to an alignment treatment.
  • the first substrate may be a substrate having comb-teeth electrodes
  • the second substrate may be a counter substrate.
  • the second substrate may be a substrate having comb-teeth electrodes
  • the first substrate may be a counter substrate.
  • the substrate on which each liquid crystal alignment film is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving liquid crystal is formed is preferable.
  • Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyethersulfones, polyarylates, polyurethanes, polysulfones, polyethers, polyetherketones, trimethylpentene, polyolefins, polyethylene terephthalate, (meth)acrylonitrile, and Examples include substrates in which transparent electrodes are formed on plastic plates such as cellulose acetate, cellulose diacetate, and cellulose acetate butyrate.
  • Substrates that can be used for IPS type liquid crystal display elements include electrode patterns such as standard IPS comb electrodes and PSA (Polymer-Stabilized Alignment) fishbone electrodes, as well as protrusion patterns such as MVA (Multi-domain Vertical Alignment). can.
  • electrode patterns such as standard IPS comb electrodes and PSA (Polymer-Stabilized Alignment) fishbone electrodes, as well as protrusion patterns such as MVA (Multi-domain Vertical Alignment). can.
  • an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate.
  • transmissive type liquid crystal display element When a transmissive type liquid crystal display element is intended, it is common to use a substrate like the one described above, but when a reflective type liquid crystal display element is intended, silicon is used for only one side of the substrate. Opaque substrates such as wafers can also be used. In this case, a material such as aluminum that reflects light can also be used for the electrodes formed on the substrate.
  • Application methods for weakly anchoring liquid crystal alignment agents include spin coating, printing, inkjet, spraying, and roll coating, but transfer printing is widely used industrially from the viewpoint of productivity. Therefore, it is suitably used in the present invention.
  • the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to firing is not constant for each substrate, or if the board is not fired immediately after application, a drying process is included. is preferable. This drying may be performed as long as the solvent is removed to such an extent that the shape of the coating film is not deformed due to transportation of the substrate, etc., and the drying means is not particularly limited.
  • Preferred conditions for the drying step include drying on a hot plate at a temperature of 40 to 150°C, more preferably 60 to 100°C, for 0.5 to 30 minutes, more preferably 1 to 5 minutes.
  • Preferred conditions for the baking step include baking on a hot plate or hot air circulation oven at a temperature of 80 to 250°C, more preferably 100 to 230°C, for 1 to 120 minutes, more preferably 5 to 30 minutes.
  • the thickness of this cured film can be selected as required, but it is preferably 5 nm or more, more preferably 10 nm or more, since this improves the reliability of the liquid crystal display element. Further, it is preferable that the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, since the power consumption of the liquid crystal display element does not become extremely large.
  • a first substrate or a second substrate having a weak anchoring alignment film and a second substrate or first substrate having a strong anchoring horizontal alignment film can be obtained.
  • methods for performing the uniaxial alignment treatment include a photoalignment method, an oblique evaporation method, rubbing, and a uniaxial alignment treatment using a magnetic field.
  • the alignment process can be performed by irradiating the entire surface of the film with polarized UV light of a specific wavelength and heating if necessary.
  • the direction is selected depending on the electrical properties of the liquid crystal, but when using a liquid crystal with positive dielectric anisotropy, the rubbing direction is the direction in which the comb-teeth electrodes extend. It is preferable that the direction is approximately the same as that of .
  • the liquid crystal cell of the present invention has a substrate (for example, a first substrate) having a weakly anchoring alignment film obtained by using the liquid crystal aligning agent of the present invention by the above method, and a known strong anchoring liquid crystal aligning film.
  • a substrate for example, a second substrate
  • Arranging a substrate so that a weak anchoring alignment film and a strong anchoring horizontal alignment film face each other, sandwiching a spacer, fixing with a sealant, and sealing by injecting liquid crystal. It is obtained by At this time, the size of the spacer used is usually 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
  • the rubbing direction of the first substrate can be used for the IPS method or FFS method, and if the rubbing directions are arranged orthogonally, it can be used for the TN method. can be used.
  • an IPS substrate which is a comb-teeth electrode substrate used in the IPS method, includes a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-teeth shape, and a plurality of linear electrodes formed on the base material. It has a liquid crystal alignment film formed so as to cover the liquid crystal alignment film.
  • the FFS substrate which is a comb-teeth electrode substrate used in the FFS method, consists of a base material, a surface electrode formed on the base material, an insulating film formed on the surface electrode, and an insulating film formed on the insulating film. , has a plurality of linear electrodes arranged in a comb-teeth shape, and a liquid crystal alignment film formed on an insulating film so as to cover the linear electrodes.
  • the method of manufacturing a liquid crystal display element of the present invention includes the step of manufacturing a substrate with a weak anchoring alignment film by the method of manufacturing a substrate with a weak anchoring alignment film of the present invention.
  • a liquid crystal display element includes, for example, a first substrate, a second substrate disposed opposite to the first substrate, and liquid crystal filled between the first substrate and the second substrate.
  • the liquid crystal display element comprises a first substrate or a second substrate coated with a weak anchoring liquid crystal alignment agent of the present invention and provided with a weak anchoring alignment film, and a second substrate or a second substrate provided with a strong anchoring horizontal alignment film. Fabricated using a first substrate.
  • the liquid crystal display element can be made into a reflective liquid crystal display element by, for example, providing a reflective electrode, a transparent electrode, a ⁇ /4 plate, a polarizing film, a color filter layer, etc. in a liquid crystal cell according to a conventional method as necessary. Furthermore, a transmissive liquid crystal display element can be obtained by providing a backlight, a polarizing plate, a ⁇ /4 plate, a transparent electrode, a polarizing film, a color filter layer, etc. in a conventional manner to the liquid crystal cell as required.
  • FIG. 1 is a schematic cross-sectional view showing an example of a horizontal electric field liquid crystal display element of the present invention, and is an example of an IPS type liquid crystal display element.
  • a liquid crystal 3 is sandwiched between a comb-teeth electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a.
  • the comb-teeth electrode substrate 2 includes a base material 2a, a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-teeth shape, and a plurality of linear electrodes 2b formed on the base material 2a so as to cover the linear electrodes 2b. It has a liquid crystal alignment film 2c.
  • the counter substrate 4 has a base material 4b and a weak anchoring liquid crystal alignment film or a strong anchoring horizontal alignment film (liquid crystal alignment film 4a) formed on the base material 4b.
  • the liquid crystal alignment film 2c is, for example, a weak anchoring alignment film or a strong anchoring horizontal alignment film of the present invention.
  • the liquid crystal alignment films provided on the opposing substrates are each made of a combination of a strong anchoring horizontal alignment film and a weak anchoring liquid crystal alignment film. In this horizontal electric field liquid crystal display element 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as shown by lines of electric force L.
  • FIG. 2 is a schematic cross-sectional view showing another example of the horizontal electric field liquid crystal display element of the present invention, and is an example of an FFS type liquid crystal display element.
  • a liquid crystal 3 is sandwiched between a comb-teeth electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a.
  • the comb-teeth electrode substrate 2 is formed on a base material 2d, a surface electrode 2e formed on the base material 2d, an insulating film 2f formed on the surface electrode 2e, and an insulating film 2f, and has a comb-like shape. It has a plurality of arranged linear electrodes 2g and a liquid crystal alignment film 2h formed on an insulating film 2f so as to cover the linear electrodes 2g.
  • the counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b.
  • the liquid crystal alignment film 4a is similar to the liquid crystal alignment film 4a in FIG. 1 described above.
  • the liquid crystal alignment film 2h is similar to the liquid crystal alignment film 2c in FIG. 1 described above.
  • this horizontal electric field liquid crystal display element 1 when a voltage is applied to the plane electrode 2e and the linear electrode 2g, an electric field is generated between the plane electrode 2e and the linear electrode 2g as shown by lines of electric force L.
  • Me represents a methyl group.
  • Viscosity measurement The viscosity of polyamic acid solutions, etc., was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample volume 1.1 mL (milliliter), cone rotor TE-1 (1° 34', R24), temperature 25 Measured at °C.
  • the molecular weight of the polyimide precursor and the synthesized polymers other than polyimide was measured using a cold gel permeation chromatography (GPC) device (CBM-20A) (manufactured by Shimadzu Corporation) and a series column (Shodex (registered trademark) KF-804L and KF-803L). ) (manufactured by Showa Denko) as follows.
  • GPC cold gel permeation chromatography
  • the molecular weight of the polyimide precursor and polyimide was determined using a room-temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko) and a column (GPC KD-803 and GPC KD-805 in series) (manufactured by Showa Denko). The measurement was performed using the following method.
  • GPC room-temperature gel permeation chromatography
  • N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr.H 2 O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/ L, tetrahydrofuran (THF) 10 mL/L)
  • Flow rate 1.0 mL/min Standard sample for creating a calibration curve: TSK standard polyethylene oxide (molecular weight: approx. 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approx. 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
  • the imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and by calculating the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears around 9.5 to 10.0 ppm. It was calculated using the following formula using the integrated value.
  • X is the integrated value of the proton peak derived from the NH group of the amic acid
  • Y is the integrated value of the reference proton peak
  • A is the integrated value of the proton peak derived from the NH group of the amic acid
  • A is the integrated value of the amic acid in the case of polyamic acid (imidization rate is 0%). This is the ratio of the number of standard protons to one proton of the NH group.
  • Imidization rate (%) (1-A ⁇ X/Y) ⁇ 100
  • N,N-dimethyllaurylamine (2.0 mg) and Xylene (20.0 g) were added, stirred at room temperature to dissolve, and then heated and stirred in an oil bath set at 140° C. for 6 hours. After heating and stirring, the reaction solution was gently poured into the mixture while stirring methanol (50 g) to precipitate a solid, and the mixture was stirred for 30 minutes. This precipitate was collected by filtration, slurry washing was performed twice with methanol (50 g) for 30 minutes, and the solid was vacuum-dried at 50° C. to obtain macromonomer (MA-1). Mn: 6,100, Mw: 9,900.
  • Macromonomer synthesized by the above method (MA-2: 2.00 g, 0.03 mmol), B-2 (0.43 g, 1.76 mmol), A-1 (3.00g, 17.62mmol), ethyl 2-bromoisobutyrate (0.012g, 0.06mmol), CuBr (0.03g, 0.19mmol), N, N, N', N'', N ''-Pentamethyldiethylenetriamine (0.043 g, 0.25 mmol) and Anisole (7.5 g) were added, stirred at room temperature to dissolve, then frozen and degassed three times, and left in an oil bath set at 90°C for 6 hours. The mixture was heated and stirred.
  • polyamic acid (PAA-1) By adding TC-1 (5.63 g, 25.1 mmol) and reacting at room temperature under nitrogen atmosphere for 18 hours, polyamic acid (PAA-1) with a viscosity of about 200 mPa ⁇ s and a solid content concentration of 12% by mass was obtained. ) was obtained.
  • the molecular weights of this polyamic acid were Mn: 12,600 and Mw: 35,200.
  • Table 3 shows the contents of the polyamic acid and polyimide synthesized above.
  • WAS-1 weakly anchoring liquid crystal aligning agent
  • BCP-1 to BCP-6 are components of Polymer A that exhibit weak anchoring properties.
  • GP-1 is a component of Polymer B that exhibits weak anchoring properties.
  • mCTA-7 to mCTA-10, mTT-1, and mTr-1 to mTr-3 are components of polymer C that exhibit weak anchoring properties.
  • BBP-1 is a polymer other than polymers A, B, and C, and is a component that exhibits weak anchoring properties.
  • PAA-1 to PAA-3 and SPI-1 correspond to polymer ⁇ .
  • a substrate with electrodes was prepared.
  • the substrate used was an alkali-free glass substrate measuring 30 mm x 35 mm and having a thickness of 0.7 mm.
  • An ITO (INDIUM-TIN-OXIDE) electrode is formed on the substrate with a comb-shaped pattern with an electrode width of 3 ⁇ m, an electrode spacing of 6 ⁇ m, and an angle of 10° with respect to the long side of the substrate. and formed pixels.
  • the size of each pixel was 10 mm in length and about 5 mm in width.
  • the weak anchoring liquid crystal alignment agents WAS-1 to WAS-263 obtained by the above method and the liquid crystal alignment agents for horizontal alignment (SE-6414, NRB-U973 (manufactured by Nissan Chemical Co., Ltd.) were respectively applied.
  • the prepared IPS substrate and a glass substrate hereinafter referred to as Coating and film formation was performed on the opposite substrate (referred to as the counter substrate) using a spin coating method.
  • Coating and film formation was performed on the opposite substrate (referred to as the counter substrate) using a spin coating method.
  • the coating film on the IPS substrate was oriented in the direction along the comb-toothed direction, and the coating film on the counter substrate was oriented in the direction perpendicular to the comb-teeth electrodes.
  • a rubbing method was used in SE-6414, and a photo alignment method was used in NRB-U973.
  • WAS-1 to WAS-23 the liquid crystal cells shown in Examples were subjected to alignment treatment, while the liquid crystal cells shown in Comparative Examples (Comparative Examples 1 to 5, 7 to 11) were not subjected to alignment treatment.
  • a rubbing device manufactured by Iinuma Gauge Co., Ltd., a rubbing cloth (YA-20R) manufactured by Yoshikawa Kako Co., Ltd., a rubbing roller (diameter 10.0 cm), a stage feed rate of 30 mm/s, a roller rotation speed of 700 rpm, and a pushing pressure of 0.3 mm were used.
  • a UV exposure device manufactured by Ushio Inc. was used to irradiate linearly polarized UV with an extinction ratio of about 26:1 so that the irradiation amount was 300 mJ/cm 2 based on a wavelength of 254 nm.
  • orientation treatment was performed by heating at 230° C. for 30 minutes. Then, using the above two types of substrates, combine them in the combinations shown in Tables 6 and 7 below so that their orientation directions are parallel, and seal the periphery leaving the liquid crystal injection port (sealant: XN -1500T (manufactured by Mitsui Chemicals, Inc.)) at 150° C. for 60 minutes to harden the sealant and produce empty cells with a cell gap of about 3.0 ⁇ m. After liquid crystal (MLC-3019 (manufactured by Merck)) was injected into this empty cell under vacuum at room temperature, the injection port was sealed to obtain an antiparallel-aligned liquid crystal cell. The obtained liquid crystal cell constitutes an IPS liquid crystal display element. Thereafter, the obtained liquid crystal cell was heat-treated at 120° C. for 10 minutes to obtain a liquid crystal display element.
  • VT curve (Measurement of VT curve and evaluation of drive threshold voltage, maximum brightness voltage, and transmittance) Set the white LED backlight and brightness meter so that the optical axes are aligned, set the liquid crystal cell (liquid crystal display element) with a polarizing plate attached so that the brightness is the lowest, and apply a voltage up to 8V at 1V intervals.
  • the VT curve was measured by applying the voltage and measuring the brightness at the voltage. A voltage was applied from a state where no voltage was applied, and the voltage value (Vth) at 10% of the maximum transmitted brightness was estimated. The value of the voltage (Vmax) at which the brightness becomes maximum was estimated from the obtained VT curve.
  • the maximum transmittance (Tmax) was estimated by setting the parallel Nicol transmission brightness as 100% through a liquid crystal cell with no voltage applied, and comparing the maximum transmission brightness in the VT curve.
  • V th,SA represents the drive threshold voltage of the strong anchoring liquid crystal cell
  • V th,WA represents the drive threshold voltage of the weak anchoring liquid crystal cell
  • l is the distance between the comb-teeth electrodes
  • d is the cell gap
  • K 2 is the twist elastic constant of the liquid crystal
  • ⁇ 0 is the dielectric constant of the liquid crystal in vacuum
  • ⁇ is the dielectric constant anisotropy of the liquid crystal.
  • Table 5 shows the details of the examples and the evaluation results. Table 5 also shows the measurement results of the azimuthal anchoring strength (A 2 ) of the liquid crystal alignment film on the IPS substrate side.
  • a 2 azimuthal anchoring strength
  • Example 1 a liquid crystal alignment agent containing the polymer alloy of the present invention was formed on an IPS substrate, a photo-alignment film was formed on an opposing substrate, and both substrates were subjected to photo-alignment treatment.
  • Example 23 a liquid crystal aligning agent containing the polymer alloy of the present invention was formed on an opposing substrate, a photo-alignment film was formed on an IPS substrate, and both substrates were subjected to photo-alignment treatment, and Comparative Examples 1 to 23 In No. 5, a liquid crystal aligning agent containing a polymer alloy was formed on an IPS substrate, a photo-alignment film was formed on a counter substrate, and only the counter substrate was subjected to photo-alignment treatment.
  • the response speed at voltage OFF has become faster by about 20 to 30 ms. This is considered to be because both a weak anchoring region and a strong anchoring region can be formed on the weak anchoring alignment film due to the following two phenomena.
  • the azimuthal anchoring strengths of Examples 1 to 22 are larger than those of Comparative Examples 1 to 5, indicating that strong anchoring regions and weak anchoring regions are segmented on the weak anchoring alignment film. It is suggested that there is.
  • the polymer ⁇ contained in the polymer alloy may be polymer A (Examples 1 to 8), polymer B (Example 17), or polymer C (Examples 9 to 16). Also, even with weak anchoring components other than Polymers A to C (Example 18), the response speed (T off ) when the voltage was turned off was increased by the photoalignment treatment. Due to its molecular design, any weak anchoring component is hydrophobic, flexible, and has a low Tg, so it phase separates well from the rigid and highly polar polymer ⁇ , making it an ideal weak anchoring agent. It is thought that a strong anchoring region and a strong anchoring region can be formed.
  • the polymer ⁇ contained in the polymer alloy of the present invention exhibits weak anchoring properties by forming a phase solution layer with the liquid crystal in the liquid crystal element.
  • the components are not limited to the structure of polymerizable groups or polymerizable monomers as long as they are polymers that are compatible with the liquid crystal.
  • the present applicant has proposed a radically polymerizable monomer that is contained in a liquid crystal composition that can stably produce a weakly anchoring horizontal electric field liquid crystal display element without generating a pretilt angle, and that contributes to the occurrence of weak anchoring.
  • polyamic acids, polyamic acid esters, polyimides, poly(meth)acrylic esters, etc., which have photoalignment properties are preferable as the polymer ⁇ , but polymers ⁇ and the like which have photoalignment properties are preferable.
  • the material is not particularly limited as long as it can induce phase separation.
  • a new polymer may be contained as a third component other than the polymer ⁇ and the polymer ⁇ , and the third component may or may not have photoalignment property. . It is predicted that by containing the third component, the film resistance, seal adhesion, and mechanical strength of the weakly anchored alignment film can be controlled.
  • Table 6 shows the details of the examples and the evaluation results. Table 6 also shows the measurement results of the azimuthal anchoring strength (A 2 ) of the liquid crystal alignment film on the IPS substrate side.
  • a 2 azimuthal anchoring strength
  • a liquid crystal aligning agent containing the polymer alloy of the present invention was formed on an IPS substrate, a rubbing alignment film was formed on a counter substrate, and both substrates were subjected to rubbing alignment treatment.
  • a liquid crystal aligning agent containing the polymer alloy of the present invention was formed on a counter substrate, a rubbing alignment film was formed on an IPS substrate, and both substrates were subjected to rubbing alignment treatment.
  • No. 11 a liquid crystal aligning agent containing a polymer alloy was formed on an IPS substrate, a rubbing alignment film was formed on a counter substrate, and the rubbing alignment treatment was performed only on the counter substrate.
  • the azimuthal anchoring strengths of Examples 24 to 45 are larger than those of Comparative Examples 7 to 10, indicating that strong anchoring regions and weak anchoring regions are segmented on the weak anchoring alignment film. It is suggested that there is.
  • polyamic acid, polyamic acid ester, polyimide, poly(meth)acrylic acid ester, etc. which have rubbing orientation as the polymer ⁇ , are preferable, but have uniaxial orientation due to rubbing orientation treatment,
  • the material is not particularly limited as long as it can induce phase separation with the polymer ⁇ .
  • a new polymer may be contained as a third component other than polymer ⁇ and polymer ⁇ , and the third component may or may not have uniaxial orientation. good.
  • the two obtained substrates were each prepared, and after scattering bead spacers with a diameter of 4 ⁇ m on the liquid crystal alignment film surface of one substrate, a sealing agent (XN-1500T manufactured by Mitsui Chemicals, Inc.) was dropped. At that time, the amount of the sealant dropped was adjusted so that the diameter of the sealant after bonding was about 3 mm.
  • the substrates were bonded with their film surfaces facing each other so that the overlapping width of the substrates was 1 cm. After fixing the bonded substrates together with clips, they were thermally cured at 120° C. for 1 hour to prepare samples for adhesive evaluation.
  • Table 7 lists the presence or absence of alignment treatment and the type of alignment treatment for the substrate coated with the liquid crystal alignment agent produced in the preparation example. Note that the substrate on which NRB-U973 was formed was not subjected to alignment treatment (photoalignment treatment).
  • a stable weak anchoring film can be manufactured using an extremely simple method, the response speed when the voltage is turned off can be increased, and the adhesion with the seal can be improved, so that weak anchoring IPS can be used in a wide range of applications.
  • by using the material and method of the present invention while suppressing the occurrence of pre-tilt angles associated with narrowing cell gaps, compared to conventional technology, faster response when voltage is turned off, less burn-in, and higher backlash in low-temperature environments. Since light transmittance and low voltage driving can be realized, it is possible to provide a material and a horizontal electric field liquid crystal display element that can stably exhibit excellent characteristics.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018028621A (ja) * 2016-08-18 2018-02-22 エルジー ディスプレイ カンパニー リミテッド 液晶表示素子及び液晶表示素子の製造方法
JP2019172997A (ja) * 2018-03-26 2019-10-10 Jnc株式会社 硬化性組成物
WO2022092088A1 (ja) * 2020-10-27 2022-05-05 日産化学株式会社 ラジカル発生膜形成組成物、ラジカル発生膜、液晶表示素子の製造方法、及び液晶表示素子
WO2022260048A1 (ja) * 2021-06-09 2022-12-15 日産化学株式会社 弱アンカリング液晶配向剤、液晶表示素子、及び共重合体
WO2023048278A1 (ja) * 2021-09-27 2023-03-30 日産化学株式会社 弱アンカリング液晶配向剤、液晶表示素子、及び重合体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018028621A (ja) * 2016-08-18 2018-02-22 エルジー ディスプレイ カンパニー リミテッド 液晶表示素子及び液晶表示素子の製造方法
JP2019172997A (ja) * 2018-03-26 2019-10-10 Jnc株式会社 硬化性組成物
WO2022092088A1 (ja) * 2020-10-27 2022-05-05 日産化学株式会社 ラジカル発生膜形成組成物、ラジカル発生膜、液晶表示素子の製造方法、及び液晶表示素子
WO2022260048A1 (ja) * 2021-06-09 2022-12-15 日産化学株式会社 弱アンカリング液晶配向剤、液晶表示素子、及び共重合体
WO2023048278A1 (ja) * 2021-09-27 2023-03-30 日産化学株式会社 弱アンカリング液晶配向剤、液晶表示素子、及び重合体

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