WO2022071286A1 - Composition de cristaux liquides, procédé de production d'élément de cristaux liquides, et élément de cristaux liquides - Google Patents

Composition de cristaux liquides, procédé de production d'élément de cristaux liquides, et élément de cristaux liquides Download PDF

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WO2022071286A1
WO2022071286A1 PCT/JP2021/035557 JP2021035557W WO2022071286A1 WO 2022071286 A1 WO2022071286 A1 WO 2022071286A1 JP 2021035557 W JP2021035557 W JP 2021035557W WO 2022071286 A1 WO2022071286 A1 WO 2022071286A1
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liquid crystal
group
carbon atoms
crystal display
substrate
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正人 森内
尚宏 野田
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日産化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention is a method for manufacturing a liquid crystal display element, which can manufacture a weak anchoring film by an inexpensive method and a method not including a complicated process, and which applies a technique for stabilizing a liquid crystal layer with a polymer.
  • the present invention relates to a liquid crystal display element for realizing a further low voltage drive, a liquid crystal composition that can be used for them, and a radically polymerizable compound.
  • liquid crystal display elements have been widely used in mobile phones, computers, television displays, and the like.
  • Liquid crystal display elements have characteristics such as thinness, light weight, and low power consumption, and are expected to be applied to further contents such as VR (Virtual Reality) and ultra-high-definition displays in the future.
  • Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Indicator) have been proposed as display methods for liquid crystal displays, but the liquid crystal is oriented in a desired orientation in all modes.
  • a film (liquid crystal alignment film) that induces IPS is used.
  • the IPS mode which does not distort the display even when touched, is preferred.
  • Liquid crystal display elements using Field Switching and technologies using non-contact technology using optical orientation have come to be used.
  • FFS has a higher substrate manufacturing cost than IPS, and has a problem that a display defect peculiar to FFS mode called Vcom shift occurs.
  • photo-alignment compared to the rubbing method, there are merits that the size of the element that can be manufactured can be increased and the display characteristics can be greatly improved.
  • seizure due to insufficient alignment force, etc. can be mentioned.
  • liquid crystal display element makers and liquid crystal alignment film makers are making various efforts to solve these problems.
  • a liquid crystal alignment film having strong anchoring energy is used for the substrate on one side, and the substrate side provided with the electrode for generating a transverse electric field on one side has no liquid crystal alignment regulating force.
  • Patent Document 3 As a method for solving this, a method of weakly anchoring only on the pixel electrode has been proposed (see Patent Document 3). It has been reported that this makes it possible to achieve both improvement in brightness and response speed.
  • Japanese Patent No. 40553530 Japanese Unexamined Patent Publication No. 2013-231757 Japanese Unexamined Patent Publication No. 2017-21166
  • the response speed delay during driving is suppressed, while in order to make the weak anchoring state only on the electrode, different materials are used in very small areas. It is necessary to prepare difficult techniques such as painting separately, which may be a big issue for actual industrialization.
  • the present invention has been made to solve the above-mentioned problems, and in narrowing the cell gap, a weak anchoring transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle, and a low drive voltage can be produced.
  • a method for manufacturing a liquid crystal display element that can manufacture a transverse electric field liquid crystal display element with a small decrease in VHR (voltage retention rate) even at high temperatures, and a method for manufacturing a liquid crystal display element, which can simultaneously realize the change in voltage and increase the response speed when the voltage is off. It is an object of the present invention to provide the liquid crystal display element, a liquid crystal composition that can be used for the liquid crystal display element, and a radically polymerizable compound.
  • a liquid crystal comprising a step of polymerizing the radically polymerizable compound in a state where the liquid crystal and the liquid crystal composition containing the radically polymerizable compound represented by the following formula (A) are in contact with a radical generating film.
  • Method of manufacturing display element M represents a radically polymerizable polymerizable group
  • R 1 represents a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • the three Xs are independent of each other.
  • Y represents a single bond, -O-, -S-, or -NR-
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • * represents a bond site.
  • R 2 , R 3 and R 4 each independently represent an aromatic hydrocarbon group which may have an alkyl group or a substituent having 1 to 6 carbon atoms.
  • [2] The method for producing a liquid crystal display element according to [1], wherein the aromatic hydrocarbon group which may have the substituent in the formula (B) is a phenyl group.
  • R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the radical-generating film is coated with a composition containing a compound having an organic group that generates a radical and a polymer, and cured to form a film, whereby the organic group that generates the radical is obtained.
  • the polymer containing an organic group that induces radical polymerization is selected from a polyimide precursor, a polyimide, a polyurea, and a polyamide obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization.
  • the organic group that induces radical polymerization is an organic group represented by the following formulas [X-1] to [X-18], [W], [Y], or [Z], [9]. The method for manufacturing a liquid crystal display element according to the above.
  • S 1 and S 2 independently represent -O-, -NR-, or -S-, respectively, and R is.
  • S2R or NR when a part of the ⁇ CH2 - group of the alkyl group is replaced with an oxygen atom, the oxygen atom is directly bonded to S2 or N. No.).
  • R 1 and R 2 independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)
  • Ar is a group consisting of phenylene, naphthylene, and biphenylylene which may have an organic group and / or a halogen atom as a substituent.
  • R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R 9 and R 10 are alkyl groups. In the case of, they may be bonded to each other at the ends to form a ring structure.
  • Q represents any of the following structures.
  • R 11 represents -CH 2- , -NR-, -O-, or -S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond. The site is indicated.
  • S 3 represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or -S-.
  • R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following formula (6), the following formula (7), or the following formula (7'), [9] or [10]
  • R 6 is a single bond, -CH 2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N. Represents (CH 3 )-, -CON (CH 3 )-, or -N (CH 3 ) CO-.
  • R 8 represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18].
  • S 1 and S 2 independently represent -O-, -NR-, or -S-, respectively, and R is.
  • S2R or NR when a part of the ⁇ CH2 - group of the alkyl group is replaced with an oxygen atom, the oxygen atom is directly bonded to S2 or N. No.).
  • R 1 and R 2 independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.))) (In equations (7) and (7'), T 1 and T 2 are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, respectively. -NH-, -CH 2 O-, -N (CH 3 )-, -CON (CH 3 )-, or -N (CH 3 ) CO-.
  • E is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-, -NHCO-, -COO-,-(CH 2 ) m- , -SO 2- , -O.
  • J is an organic group represented by a formula selected from the following formulas [W], [Y] and [Z].
  • R 9 and R 10 independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is described below. Represents either structure.
  • R 11 represents -CH 2- , -NR-, -O-, or -S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond.
  • S 3 represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or -S-.
  • R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • q is independently 0 or 1
  • at least one q is 1
  • p represents an integer of 1 to 2.
  • a liquid crystal composition comprising a liquid crystal display and a radically polymerizable compound represented by the following formula (A).
  • M represents a radically polymerizable polymerizable group
  • R 1 represents a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • the three Xs are independent of each other.
  • Y represents a single bond, -O-, -S-, or -NR-
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • * represents a bond site.
  • R 2 , R 3 and R 4 each independently represent an aromatic hydrocarbon group which may have an alkyl group or a substituent having 1 to 6 carbon atoms.
  • the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound represented by the following formula (A) is in contact with the radically polymerized film of the first substrate having the radically generated film.
  • a liquid crystal display element characterized by having a polymerization reaction.
  • M represents a radically polymerizable polymerizable group
  • R 1 represents a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • the three Xs are independent of each other.
  • a weak anchoring transverse electric field liquid crystal display element in narrowing the cell gap, can be stably manufactured without generating a pretilt angle, and at the same time, the drive voltage can be lowered and the response speed when the voltage is turned off can be increased at the same time.
  • a method for manufacturing a liquid crystal display element that can be realized and that can produce a transverse electric field liquid crystal display element with a small decrease in VHR even at high temperatures, the liquid crystal display element, a liquid crystal composition that can be used for them, and radical polymerizable. Compounds can be provided.
  • the present invention is an additive (with a specific structure) capable of suppressing the development of a pretilt angle due to the formation of a weak anchoring film and stably producing a highly reliable weak anchoring transverse electric field liquid crystal display element even in a narrow cell gap. It utilizes a radically polymerizable compound). For example, a step of preparing a cell having a liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a specific structure between a first substrate having a radical generating film and a second substrate having a liquid crystal alignment film, and the above-mentioned step.
  • It is a method for manufacturing a weak anchoring transverse electric field liquid crystal display element which comprises a step of imparting sufficient energy to a cell to polymerize the radically polymerizable compound.
  • a method for producing a liquid crystal cell comprising a step of creating a cell and a step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a specific structure between the first substrate and the second substrate.
  • one substrate has an oriented radical generation film
  • the other substrate has a uniaxially oriented liquid crystal alignment film
  • one of the substrates has a comb tooth for driving the liquid crystal.
  • the "weak anchoring film” means that there is no force to regulate the orientation of liquid crystal molecules in the in-plane direction, or even if there is, it is weaker than the intramolecular force between liquid crystals.
  • the weak anchoring film is not limited to the solid film, but also includes a liquid film covering the solid surface.
  • a liquid crystal display element uses a film that regulates the orientation of liquid crystal molecules, that is, a liquid crystal alignment film in pairs to align the liquid crystal, but even when the weak anchoring film and the liquid crystal alignment film are used in pairs, the liquid crystal is oriented. Can be made to.
  • Horizontal orientation refers to a state in which the major axes of liquid crystal molecules are arranged substantially parallel to the liquid crystal alignment film surface, and inclined orientation of about several degrees is also included in the category of horizontal orientation.
  • the applicant of the present application comprises a step of imparting sufficient energy to polymerize the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is in contact with the radical generating film.
  • a method for producing a zero-plane anchoring film is proposed (see claim 1 of International Publication No. 2019/004433). [0077] to [0086] of International Publication No. 2019/004433 exemplify the radically polymerizable compound used in the proposal.
  • the present inventors can stably manufacture a weak anchoring lateral electric field liquid crystal display element without generating a pretilt angle in a narrow cell gap, and can reduce the drive voltage and turn off the voltage.
  • the radically polymerizable compound having a specific structure is represented by the following formula (A).
  • M represents a radically polymerizable polymerizable group
  • R 1 represents a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • the three Xs are independent of each other.
  • Y represents a single bond, -O-, -S-, or -NR-
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • * represents a bond site.
  • R 2 , R 3 and R 4 each independently represent an aromatic hydrocarbon group which may have an alkyl group or a substituent having 1 to 6 carbon atoms.
  • a radically polymerizable compound is polymerized in a state where the liquid crystal and the liquid crystal composition containing the radically polymerizable compound represented by the formula (A) are in contact with the radical generating film.
  • the present inventors have stated that a weak anchoring film is obtained by changing the surface of the radical-generating film by the polymerization reaction of the radically polymerizable compound using the radical generated by the radical-generating film. I'm guessing.
  • a weak anchoring lateral electric field liquid crystal display element can be stably manufactured without generating a pretilt angle in a narrow cell gap, and the drive voltage can be lowered and the response speed when the voltage is turned off.
  • the voltage can be increased, and in addition, a lateral electric field liquid crystal display element with a small decrease in VHR even at a high temperature can be manufactured.
  • the present inventors consider how the radically polymerizable compound represented by the formula (A) contributes to this as follows.
  • the radically polymerizable compound M represented by the formula (A) contributes to the radical polymerization of the radically polymerizable compound.
  • the radically polymerizable compound represented by the formula (A) -SiR 2 R 3 R 4 contributes to the suppression of the generation of pretilt angle, the improvement of the response speed, and the high VHR at high temperature.
  • the inventors are speculating.
  • the narrow cell gap means a cell gap of 3.5 ⁇ m or less.
  • the radical-generating film-forming composition for forming a radical-generating film used in the present invention contains a polymer as a component and contains a group capable of generating radicals. At that time, the composition may contain a polymer to which a group capable of generating radicals is bonded, or a composition of a compound having a group capable of generating radicals and a polymer serving as a base resin. It may be a thing. By applying and curing such a composition to form a film, a radical generation film in which radical-generating groups are immobilized in the film can be obtained.
  • the group capable of generating radicals is preferably an organic group that induces radical polymerization.
  • Examples of such an organic group that induces radical polymerization include organic groups represented by the following formulas [X-1] to [X-18], [W], [Y], and [Z].
  • [X-1] to [X-18] * indicates a binding site
  • S 1 and S 2 independently represent -O-, -NR-, or -S-, respectively, and R is.
  • R 1 and R 2 independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
  • Ar is a group consisting of phenylene, naphthylene, and biphenylylene which may have an organic group and / or a halogen atom as a substituent.
  • R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R 9 and R 10 are alkyl groups. In the case of, they may be bonded to each other at the ends to form a ring structure.
  • Q represents any of the following structures.
  • R 11 represents -CH 2- , -NR-, -O-, or -S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond. The site is shown.).
  • S 3 represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or -S-.
  • R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )
  • the polymer at least one polymer selected from the group consisting of a polyimide precursor, a polyimide, a polyurea, a polyamide, a polyacrylate, a polymethacrylate, and a polyorganosiloxane is preferable.
  • a methacrylic group is used as a monomer component.
  • a monomer having a photoreactive side chain containing at least one selected from an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, and a site that is decomposed by ultraviolet irradiation and generates a radical is a side chain. It is preferable to use the monomer contained in the above.
  • the monomer that generates radicals has a problem that it spontaneously polymerizes, and becomes an unstable compound. Therefore, it has a radical generation site in terms of ease of synthesis.
  • Polymers derived from diamines are preferred, and polyimide precursors such as polyamic acids and polyamic acid esters, polyimides, polyureas, polyamides and the like are more preferred.
  • the polymer containing an organic group that induces radical polymerization is at least one weight selected from a polyimide precursor, a polyimide, a polyurea, and a polyamide obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization. It is preferably coalesced.
  • the diamine containing an organic group that induces such radical polymerization is, specifically, for example, a diamine having a side chain that can generate radicals and can be polymerized, and has a structure represented by the following formula (6). Examples include, but are not limited to, having diamines.
  • R 6 is a single bond, -CH 2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N.
  • R 7 represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH 2- or -CF 2- of the alkylene group is independent of each other.
  • R 8 represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18].
  • [X-1] to [X-18] * indicates a binding site
  • S 1 and S 2 independently represent -O-, -NR-, or -S-, respectively, and R is.
  • R 1 and R 2 independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)
  • the bonding position of the two amino groups (-NH 2 ) in the formula (6) is not limited. Specifically, with respect to the bonding group of the side chain, 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions, 3, on the benzene ring. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid. Considering the ease of synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • diamine having a photoreactive group including at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumaryl group, a styryl group and a cinnamoyl group are as follows. Examples include, but are not limited to, compounds.
  • J 1 is a bonding group selected from a single bond, -O-, -COO-, -NHCO-, and -NH-
  • J 2 is a single bond, or unsubstituted or substituted with a fluorine atom. Represents an alkylene group having 1 to 20 carbon atoms.
  • diamines having a site that is decomposed by ultraviolet irradiation to generate radicals as a side chain have a structure represented by the following formula (7) or formula (7').
  • Diamines having, but are not limited to, may be mentioned.
  • T 1 and T 2 are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, respectively.
  • E is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-, -NHCO-, -COO-,-(CH 2 ) m- , -SO 2- , -O.
  • J is an organic group represented by a formula selected from the following formulas [W], [Y] and [Z].
  • R 9 and R 10 independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is described below. Represents either structure.
  • R 11 represents -CH 2- , -NR-, -O-, or -S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond.
  • S 3 represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or -S-.
  • R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • equation (7') q is independently 0 or 1, at least one q is 1, and p represents an integer of 1 to 2.
  • the bonding position of the two amino groups (-NH 2 ) in the above formula (7) is not limited. Specifically, with respect to the bonding group of the side chain, 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions, 3, on the benzene ring. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid.
  • n is an integer of 2 to 8.
  • the bonding position of the amino group (-NH 2 ) and the bonding group E on the benzene ring in the above formula (7') is not limited.
  • the para position is preferable from the viewpoint of availability of raw materials, orientation quality when used as a liquid crystal display element, and black brightness.
  • n is an integer of 2 to 8
  • E is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-, -NHCO-, -CONH-,-.
  • the above diamine can be used alone or in combination of two or more depending on the liquid crystal orientation when the radical generation film is formed, the sensitivity in the polymerization reaction, the voltage holding characteristic, the accumulated charge and the like.
  • the diamine containing an organic group that induces such radical polymerization it is preferable to use an amount of 5 to 50 mol% of the total diamine component used for synthesizing the polymer contained in the radical generation film forming composition. It is preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%.
  • the polymer used for the radical polymerization film of the present invention is obtained from a diamine
  • other diamines other than the diamine containing an organic group that induces the radical polymerization are used as the diamine component as long as the effect of the present invention is not impaired. Can be used together.
  • p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m- Phenylene diamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4- Diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 , 3'-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'
  • Alicyclic diamines 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, Aliphatic diamines such as 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane; 1,3-bis [2- (p-aminophenyl) ethyl] urea, 1, Diamine having a urea structure such as 3-bis [2- (p-aminophenyl) ethyl] -1-tert-butoxycarbonyl urea; Np-aminophenyl-4-p-aminophenyl (tert-butoxycarbonyl) amino Diamine having a nitrogen-containing unsaturated
  • the above other diamines may be used alone or in combination of two or more depending on the liquid crystal orientation when the radical generation film is formed, the sensitivity in the polymerization reaction, the voltage holding characteristics, the accumulated charge and the like. ..
  • the tetracarboxylic dianhydride that reacts with the above diamine component in the synthesis when the polymer is a polyamic acid is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-Anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl
  • one or two or more types of tetracarboxylic dianhydride may be used in combination depending on the liquid crystal orientation when the radical generating film is formed, the sensitivity in the polymerization reaction, the voltage holding property, the accumulated charge, and the like. ..
  • the structure of the tetracarboxylic acid dialkyl ester to be reacted with the above diamine component in the synthesis when the polymer is a polyamic acid ester is not particularly limited, but specific examples thereof are given below.
  • aliphatic tetracarboxylic acid diester examples include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1.
  • aromatic tetracarboxylic acid dialkyl ester examples include pyromellitic acid dialkyl ester, 3,3', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-biphenyltetracarboxylic acid dialkyl ester, and the like.
  • the diisocyanate to be reacted with the above 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.
  • K-1 to K-5 are inferior in reactivity but have the advantage of improving solvent solubility
  • aromatic diisocyanates shown in K-6 to K-13 are highly reactive and heat resistant.
  • K-1, K-7, K-8, K-9, and K-10 are preferable in terms of versatility and characteristics
  • K-12 is preferable from the viewpoint of electrical characteristics
  • K-13 is preferable from the viewpoint of liquid crystal orientation.
  • Two or more kinds of diisocyanates can be used in combination, and it is preferable to apply various diisocyanates according to the desired characteristics.
  • diisocyanates can be replaced with the tetracarboxylic acid dianhydride described above, and they may be used in the form of a copolymer of polyamic acid and polyurea. It may be used in the form of a copolymer.
  • the structure of the dicarboxylic acid to be reacted in the synthesis when the polymer is polyamide is not particularly limited, but specific examples are as follows.
  • the aliphatic dicarboxylic acid 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-dimethylglutal.
  • dicarboxylic acids such as acids, 3,3-diethylsuccinic acid, adipic acid, sebacic acid and suberic acid.
  • Examples of the alicyclic dicarboxylic acid 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 examples include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, and 2,5-dimethylterephthalic acid.
  • dicarboxylic acid containing a heterocycle examples include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, and the like.
  • 1,2,5-Thiadiazol-3,4-dicarboxylic acid 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples thereof include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.
  • various dicarboxylic acids may have an acid dihalide or an anhydrous structure. It is particularly preferable that these dicarboxylic acids are dicarboxylic acids capable of giving a polyamide having a linear structure from the viewpoint of maintaining the orientation of the 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 '-Diphenylpropandicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propandicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 5-Ppyridinedicarboxylic acid or acid dihalide thereof and the like are preferably used. Some of these compounds have isomers, but they may be mixtures containing them. Further, two or more kinds of compounds may be used in combination.
  • the dicarboxylic acids used in the present invention are not limited to the above-mentioned
  • tetracarboxylic acid diester tetracarboxylic acid diester
  • diamine component raw material diamine
  • tetracarboxylic acid dianhydride component raw material tetracarboxylic acid diester
  • diisocyanate and dicarboxylic acid tetracarboxylic acid diester
  • a diamine component is a method of reacting a diamine component with one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic acid diester, a diisocyanate and a dicarboxylic acid in an organic solvent.
  • the reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent used in the above reaction is not particularly limited as long as it dissolves the produced polymer. Further, even if the organic solvent does not dissolve the polymer, it may be mixed with the above solvent and used as long as the produced polymer does not precipitate. Since the water content in the organic solvent inhibits the polymerization reaction and further causes the produced polymer to be hydrolyzed, it is preferable to use a dehydrated and dried organic solvent.
  • organic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, ⁇ -Butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cell solve, ethyl cell solve, methyl cello
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid dianhydride component is used as it is or is organic.
  • a method of adding a tetracarboxylic acid dianhydride component dispersed or dissolved in a solvent conversely a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method of adding a tetracarboxylic acid dianhydride component and a diamine component.
  • Examples thereof include a method of adding alternately, and any of these methods may be used.
  • the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be reacted individually in sequence, or may be reacted individually, and have a low molecular weight.
  • the bodies may be mixed and reacted to form a high molecular weight compound.
  • the temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted can be selected from any temperature, and is, for example, in the range of -20 to 100 ° C, preferably -5 to 80 ° C.
  • the reaction can be carried out at any concentration, for example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass with respect to the reaction solution. ..
  • the ratio of the total number of moles of the tetracarboxylic acid dianhydride component to the total number of moles of the diamine component in the above polymerization reaction can be arbitrarily selected according to the molecular weight of the polyamic acid to be obtained. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. The preferred range is 0.8 to 1.2.
  • the method for synthesizing the polymer used in the present invention is not limited to the above-mentioned method, and when synthesizing a polyamic acid, the above-mentioned tetracarboxylic acid dianhydride is used in the same manner as a general method for synthesizing a polyamic acid.
  • a tetracarboxylic acid having a corresponding structure or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide can be used and reacted by a known method to obtain the corresponding polyamic acid.
  • diamine and diisocyanate may be reacted.
  • a diamine and a component selected from a tetracarboxylic acid diester and a dicarboxylic acid are induced into an acid halide in the presence of a known condensing agent or by a known method. , Diamine may be reacted.
  • polyimide can be obtained by ring-closing (imidizing) the polyamic acid.
  • the imidization rate as used herein is the ratio of the imide group to the total amount of the imide group and the carboxy group derived from the tetracarboxylic acid dianhydride.
  • the imidization ratio does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
  • the imidization ratio of the polyimide in the present invention is preferably 30% or more because the voltage retention rate can be increased, and on the other hand, from the viewpoint of whitening characteristics, that is, from the viewpoint of suppressing the precipitation of the polymer in the varnish, 80 % Or less is preferable.
  • the temperature at which the polyamic acid is thermally imidized in the solution is usually 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferable to remove the water generated by the imidization reaction from the outside of the system.
  • the catalytic imidization of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyamic acid and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is usually 0.5 to 30 mol times, preferably 2 to 20 mol times the amount of the amic acid group
  • the amount of acid anhydride is usually 1 to 50 mol times, preferably 1 to 50 mol times the amic acid group. It is 3 to 30 mol times.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like, and among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, the reaction time, and the like.
  • the reaction solution When recovering the produced polymer from the reaction solution of the polymer, the reaction solution may be put into a poor solvent and precipitated.
  • the poor solvent used for precipitate formation include methanol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like.
  • the polymer put into a poor solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure.
  • impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the efficiency of purification is further improved.
  • the radical generation film-forming composition used in the present invention is other than a polymer containing an organic group that induces radical polymerization. It may contain other polymers. At that time, the content of the other polymer in all the components of the polymer is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.
  • the molecular weight of the polymer contained in the radical generation film forming composition is GPC (GPC) when the strength of the radical generation film obtained by applying the radical generation film, the workability at the time of forming the coating film, the uniformity of the coating film, etc. are taken into consideration.
  • the weight average molecular weight measured by the Gel Permeation Chromatography method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
  • At least one polymer obtained by using the diamine component in which the diamine to be used is 0 mol% of the total diamine component used for synthesizing the polymer contained in the radical generation film forming composition may be used.
  • Examples of the compound having a group that generates a radical to be added at that time include the following.
  • the compound that generates radicals by heat is a compound that generates radicals by heating to a temperature higher than the decomposition temperature.
  • radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation).
  • the compound that generates radicals with light is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone and 2-hydroxy.
  • the radical generation film is made of a polymer containing an organic group that induces radical polymerization
  • the group that generates the above radical is used for the purpose of promoting radical polymerization when energy is applied.
  • the compound may be contained.
  • the radical generating film forming composition can contain a polymer component, and if necessary, an organic solvent that dissolves or disperses a radical generating agent or other contained components.
  • an organic solvent is not particularly limited, and examples thereof include organic solvents as exemplified in the above-mentioned synthesis of polyamic acid.
  • N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like are soluble. It is preferable from the viewpoint of.
  • N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but two or more kinds of mixed solvents may be used.
  • a solvent that improves the uniformity and smoothness of the coating film by mixing it with an organic solvent having high solubility of the components contained in the radical generation film forming composition.
  • Examples of the solvent for improving the uniformity and smoothness of the coating material include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve (ethylene glycol monobutyl ether), methyl cellosolve acetate, butyl cellosolve acetate, and ethyl cellosolve acetate.
  • the radical generation film forming composition may contain components other than the above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when the radical generation film forming composition is applied, compounds that improve the adhesion between the radical generation film forming composition and the substrate, and radical generation film formation. Examples thereof include compounds that further improve the film strength of the composition.
  • Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (manufactured by 3M), Asahi. Examples thereof include Guard AG710 (manufactured by AGC), Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical). When these surfactants are used, the ratio of their use is preferably 0.01 to 2 parts by mass, more preferably 0, with respect to 100 parts by mass of the total amount of the polymer contained in the radical generation film forming composition. It is 0.01 to 1 part by mass.
  • the compound that improves the adhesion between the radical generation film forming composition and the substrate include a functional silane-containing compound and an epoxy group-containing compound.
  • a functional silane-containing compound and an epoxy group-containing compound For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
  • a phenol compound such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol is added. May be good.
  • the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the radical generation film forming composition. Is.
  • the radical generating film forming composition includes a dielectric or a conductive material for changing the electrical properties such as the dielectric constant and the conductivity of the radical generating film as long as the effect of the present invention is not impaired. Substances may be added.
  • the radical generation film of the present invention can be obtained, for example, by using the above-mentioned radical generation film forming composition.
  • a cured film obtained by applying the radical generation film forming composition used in the present invention to a substrate and then drying and firing it can be used as it is as a radical generation film.
  • this cured film can be subjected to alignment processing by rubbing, polarization, light of a specific wavelength, or the like, and by processing an ion beam or the like, and UV (ultraviolet rays) are applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film. ) Is also possible.
  • the substrate on which the radical generation film forming composition 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 a liquid crystal display is formed is preferable.
  • glass plates polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, and tri.
  • a substrate in which a transparent electrode is formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, acetate butylate cellulose or the like.
  • electrode patterns such as standard IPS comb tooth electrodes and PSA fishbone electrodes and protrusion patterns such as MVA can also be used.
  • an element such as a transistor is used between an electrode for driving a liquid crystal display and a substrate.
  • a transmissive liquid crystal display element When a transmissive liquid crystal display element is intended, it is common to use a substrate as described above, but when a reflective liquid crystal display element is intended, silicon is used only on one side of the substrate. An opaque substrate such as a wafer can also be used. At that time, a material such as aluminum that reflects light can be used for the electrodes formed on the substrate.
  • Examples of the method for applying the radical-generating film-forming composition include a spin coating method, a printing method, an inkjet method, a spray method, a roll coating method, and the like, but the transfer printing method is widely used industrially from the viewpoint of productivity. It is also suitably used in the present invention.
  • the step of drying after applying the radical generation film forming composition is not always necessary, but if the time from application to firing is not constant for each substrate or if it is not fired immediately after coating, it is dried. It is preferable to include the process.
  • the drying is not particularly limited as long as the solvent is removed to the extent that the shape of the coating film is not deformed by transporting the substrate or the like, and the drying means thereof is not particularly limited.
  • a method of drying on a hot plate having a temperature of 40 to 150 ° C., preferably 60 to 100 ° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.
  • the coating film formed by applying the radical generation film forming composition by the above method can be fired to form a cured film.
  • the firing temperature can be usually any temperature of 100 to 350 ° C., but is preferably 140 to 300 ° C., more preferably 150 to 230 ° C., and further preferably 160 to 220 ° C.
  • the firing time is usually any time of 5 to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes.
  • a generally known method for example, a hot plate, a hot air circulation oven, an IR (infrared) type oven, a belt furnace, or the like can be used.
  • the thickness of this cured film can be selected as needed, but preferably 5 nm or more, more preferably 10 nm or more, because the reliability of the liquid crystal display element is improved. Further, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is preferable.
  • the radical generating film can be subjected to uniaxial orientation treatment.
  • the method for performing the uniaxial alignment treatment include a photoalignment method, an orthorhombic vapor deposition method, rubbing, and a uniaxial alignment treatment using a magnetic field.
  • the substrate is moved so that the rubbing cloth and the film come into contact with each other while rotating the rubbing roller around which the rubbing cloth is wound.
  • the alignment process can be performed by irradiating the entire surface of the film with polarized UV having a specific wavelength and heating the film as necessary.
  • the direction is selected by the electrical properties of the liquid crystal, but when a liquid crystal having positive dielectric anisotropy is used, the rubbing direction is the comb tooth electrode. It is preferable that the direction is substantially the same as the extending direction of.
  • a step of creating a weak anchoring part and a strong anchoring part there is a method of irradiating radiation with an arbitrary pattern via a photomask or the like.
  • the radiation used in this step include polarized light or light having a specific wavelength, an ion beam, and the like. It is particularly preferable to irradiate light having a wavelength having the highest absorbance at the portion corresponding to the photoradical generation site.
  • the second substrate of the present invention may or may not have a radical generation film.
  • the second substrate is preferably a substrate having a conventionally known liquid crystal alignment film.
  • the first substrate may be a substrate having a comb tooth electrode
  • the second substrate may be a facing substrate
  • the second substrate may be a substrate having a comb tooth electrode
  • the first substrate may be a facing substrate.
  • the liquid crystal cell of the present invention comprises a substrate having the radical generating film (first substrate) and a substrate having a known liquid crystal alignment film (second substrate) after forming a radical generating film on the substrate by the above method. Is obtained by arranging the radical generating film and the liquid crystal alignment film so as to face each other, sandwiching a spacer, fixing with a sealing agent, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. Be done. At that time, the size of the spacer used is usually 1 to 30 ⁇ m, but preferably 2 to 10 ⁇ m.
  • the method of injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and a vacuum method of injecting a mixture containing the liquid crystal and the polymerizable compound after depressurizing the inside of the produced liquid crystal cell, polymerization with the liquid crystal.
  • a dropping method in which a mixture containing a sex compound is dropped and then sealed.
  • the radically polymerizable compound of the present invention is represented by the following formula (A).
  • M represents a radically polymerizable polymerizable group
  • R 1 represents a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • the three Xs are independent of each other.
  • Y represents a single bond, -O-, -S-, or -NR-
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • * represents a bond site.
  • R 2 , R 3 and R 4 each independently represent an aromatic hydrocarbon group which may have an alkyl group or a substituent having 1 to 6 carbon atoms.
  • the aliphatic hydrocarbon group in R1 has 1 to 10 carbon atoms, may have 1 to 8 carbon atoms, may have 1 to 6 carbon atoms, and may have 1 to 4 carbon atoms. May be good.
  • the alkyl group having 1 to 6 carbon atoms in R 2 , R 3 and R 4 may be, for example, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms. good. These alkyl groups may have a linear structure or a branched structure.
  • the aromatic hydrocarbon groups in R 2 , R 3 and R 4 may be unsubstituted or the hydrogen atom 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 thereof include an alkylated group and an alkoxy halide group having 1 to 4 carbon atoms.
  • the halogenation in the alkyl halide group and the halogenated alkoxy group may be total halogenation or partial halogenation.
  • halogen atom examples include a fluorine atom and a chlorine atom.
  • aromatic hydrocarbon group in the aromatic hydrocarbon group which may have a substituent examples include a phenyl group and a naphthyl group. The number of substituents in the aromatic hydrocarbon group is not particularly limited.
  • the number of groups represented by the formula (B) is one or more, and may be one, two, or three. May be.
  • the three Xs are independent of each other. Therefore, in the radically polymerizable compound represented by the formula (A), when there are two or more groups represented by the formula (B), the groups represented by the two or more formulas (B) have the same structure. It may be present or may have a different structure.
  • R 2 , R 3 , and R 4 may be an aromatic hydrocarbon group which may have a substituent. Therefore, in the formula (B), one of R 2 , R 3 , and R 4 may be an aromatic hydrocarbon group which may have a substituent, or R 2 , R 3 , and R 4 . Two may be aromatic hydrocarbon groups which may have a substituent, and three of R 2 , R 3 and R 4 may be an aromatic hydrocarbon group which may have a substituent. There may be.
  • the radically polymerizable polymerizable group M of the radically polymerizable compound is preferably a polymerizable group selected from the following structures.
  • * indicates a binding site.
  • R b represents a linear alkyl group having 2 to 8 carbon atoms
  • E represents a single bond, -O-, -NR c- , -S-, an ester bond and an amide bond.
  • R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
  • R d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Examples of the radically polymerizable compound represented by the formula (A) include radically polymerizable compounds satisfying the following (1) to (3).
  • M represents the following structure (C) or structure (D)
  • R 1 represents an aliphatic hydrocarbon group having a linear or branched structure having 1 to 10 carbon atoms.
  • Each X independently represents a hydrogen atom or formula (B). However, at least one of the three Xs represents equation (B).
  • R2 , R3 , and R4 each independently represent an aromatic hydrocarbon group which may have an alkyl group or a substituent having 1 to 6 carbon atoms.
  • R 2 , R 3 and R 4 represents an aromatic hydrocarbon group which may have a substituent.
  • Examples of the radically polymerizable compound contained in the formula (A) include the following radically polymerizable compounds.
  • the liquid crystal composition contains at least the liquid crystal and the radically polymerizable compound.
  • the content of the radically polymerizable compound in the liquid crystal composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 1% by mass or more, based on the total mass of the liquid crystal and the radically polymerizable compound. It is 10% by mass or less, more preferably 5% by mass or less.
  • a plurality of compounds having other monofunctional radically polymerizable groups (hereinafter, may be referred to as “other radically polymerizable compounds”) are used in combination. May be.
  • radically polymerizable compounds have unsaturated bonds capable of performing radical polymerization in the presence of organic radicals, and are, for example, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl.
  • Methacrylate monomers such as methacrylate, n-octyl methacrylate; acrylate monomers such as tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, n-octyl acrylate; styrene, styrene derivatives (eg, o- , M-, p-methoxystyrene, o-, m-, p-tert-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, benzoate) Vinyl acid acid, etc.), vinyl ketones (eg, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (eg,
  • Ra and R b each independently represent a linear alkyl group having 2 to 8 carbon atoms, and E is a single bond, —O—, —NR c ⁇ , —S—, an ester bond, And a bonding group selected from an amide bond.
  • R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • At least one of the radically polymerizable compounds contained in the liquid crystal composition has a compound having a polymerizable unsaturated bond in one molecule, which is compatible with the liquid crystal, that is, a monofunctional radically polymerizable group. It is preferably a compound.
  • Those are preferable from the viewpoints of ease of synthesis, compatibility with liquid crystal, and polymerization reactivity, and specifically, compounds represented by the following structures are preferable, but are not particularly limited.
  • the liquid crystal composition contains a radically polymerizable compound in which the Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100 ° C. or lower.
  • the polymer obtained by polymerizing a radically polymerizable compound preferably has a Tg of 100 ° C. or lower, more preferably 0 ° C. or lower.
  • the liquid crystal generally refers to a substance exhibiting both solid and liquid properties, and typical liquid crystal phases include nematic liquid crystal and smectic liquid crystal, but the liquid crystal that can be used in the present invention is not particularly limited.
  • One example is 4-pentyl-4'-cyanobiphenyl.
  • the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radically polymerizable compound is introduced to carry out the polymerization reaction of the radically polymerizable compound.
  • This can be done, for example, by applying heat or UV irradiation, and the radically polymerizable compound is polymerized in situ to exhibit the desired properties.
  • UV irradiation is preferable because it enables oriented patterning and allows the polymerization reaction to occur in a shorter time.
  • heating may be performed during UV irradiation.
  • the heating temperature at the time of UV irradiation is preferably in a temperature range in which the introduced liquid crystal exhibits liquid crystal properties, is usually 40 ° C. or higher, and is preferably heated at a temperature lower than a temperature at which the liquid crystal changes to an isotropic phase.
  • the UV irradiation wavelength in the case of UV irradiation, it is preferable to select the wavelength having the best reaction quantum yield of the reactive polymerizable compound, and the UV irradiation amount is usually 0.01 to 30 J / cm 2 . However, preferably, it is 10 J / cm 2 or less, and the smaller the UV irradiation amount, the more the reliability deterioration due to the destruction of the members constituting the liquid crystal display can be suppressed, and the UV irradiation time can be reduced, so that the manufacturing process can be performed. It is suitable because it improves tact.
  • the heating in the case of polymerizing only by heating instead of UV irradiation is performed in a temperature range in which the temperature at which the polymerizable compound reacts and is lower than the decomposition temperature of the liquid crystal display. Specifically, it is 100 to 150 ° C.
  • a liquid crystal display element can be manufactured using the liquid crystal cell thus obtained.
  • the liquid crystal display element has, for example, a first substrate, a second substrate arranged to face the first substrate, and a liquid crystal filled between the first substrate and the second substrate. Then, the liquid crystal display element is subjected to radical polymerization in a state where the liquid crystal and the liquid crystal composition containing the radically polymerizable compound represented by the formula (A) are brought into contact with the radical generating film of the first substrate having the radical generating film. It is made by polymerizing a sex compound.
  • 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, or the like in the liquid crystal cell according to a conventional method. Further, a transmissive liquid crystal display element can be obtained by providing the liquid crystal cell with a backlight, a polarizing plate, a ⁇ / 4 plate, a transparent electrode, a polarizing film, a color filter layer and the like according to a conventional method, if necessary.
  • FIG. 1 is a schematic cross-sectional view showing an example of a transverse electric field liquid crystal display element of the present invention, and is an example of an IPS mode liquid crystal display element.
  • the liquid crystal 3 is sandwiched between the comb tooth electrode substrate 2 provided with the liquid crystal alignment film 2c and the opposed substrate 4 provided with the liquid crystal alignment film 4a.
  • the comb tooth electrode substrate 2 is formed on the base material 2a and the base material 2a, and is formed so as to cover the plurality of linear electrodes 2b arranged in a comb tooth shape and the linear electrodes 2b on the base material 2a. It also has a liquid crystal alignment film 2c.
  • the facing 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 2c is, for example, a weak anchoring film obtained by chemically changing a radical generation film.
  • the liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radically polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is in contact with a radical generating film.
  • a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as shown by the electric lines of force L.
  • FIG. 2 is a schematic cross-sectional view showing another example of the transverse electric field liquid crystal display element of the present invention, and is an example of an FFS mode liquid crystal display element.
  • the liquid crystal 3 is sandwiched between the comb tooth electrode substrate 2 provided with the liquid crystal alignment film 2h and the opposed substrate 4 provided with the liquid crystal alignment film 4a.
  • the comb tooth electrode substrate 2 is formed on the base material 2d, the surface electrode 2e formed on the base material 2d, the insulating film 2f formed on the surface electrode 2e, and the insulating film 2f, and has a comb tooth shape.
  • the facing 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 2h is, for example, a weak anchoring film obtained by chemically changing a radical generating film.
  • the liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radically polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is in contact with a radical generating film.
  • the lateral electric field liquid crystal display element 1 when a voltage is applied to the surface electrode 2e and the linear electrode 2g, an electric field is generated between the surface electrode 2e and the linear electrode 2g as shown by the electric lines of force L.
  • TC-1 to TC-3 Compounds represented by the following formulas (TC-1) to (TC-3), respectively.
  • Add-1 to Add-11 Compounds represented by the following formulas (Add-1) to (Add-11), respectively.
  • Addd-C1 to Add-C3 The following formulas (Add-C1) to (Add-C3, respectively).
  • AD-1 Compound represented by the following formula (AD-1)
  • N N-dimethylformamide (as an additive, 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) is 10 mL / L)
  • Flow rate 1.0 mL / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (Tosoh) and polyethylene glycol (molecular weight; about) 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
  • FT-NMR Fourier transform type superconducting nuclear magnetic resonance apparatus
  • the chemical 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 the peak integrated value of this proton and the proton derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It was calculated by the following formula using the peak integrated value.
  • x is the integrated proton peak value derived from the NH group of the amic acid
  • y is the integrated peak value of the reference proton
  • ⁇ is the integrated value of the amic acid in the case of a polyamic acid (imidization rate is 0%).
  • Imidization rate (%) (1- ⁇ ⁇ x / y) ⁇ 100
  • TC-1 (1.84 g: 9.40 mmol) and NMP (10.0 g) were added and reacted at room temperature for 18 hours to have a viscosity of about 1120 mPa ⁇ s and a solid content concentration of 20 mass.
  • % Polyamic acid solution (PAA-1) was obtained.
  • the molecular weight of this polyamic acid was a number average molecular weight: 11200 and a weight average molecular weight: 31360.
  • the polyamic acid solution (PAA-1) (40.0 g) obtained above was weighed in a 300 mL eggplant flask equipped with a stirrer and a nitrogen introduction tube, NMP (74.3 g) was added, and the mixture was stirred at room temperature for a while.
  • anhydrous acetic acid (5.61 g: 54.98 mmol) and pyridine (2.90 g, 36.65 mmol) were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere and then reacted at 50 ° C. for 3 hours under a nitrogen atmosphere.
  • the reaction solution was slowly poured into methanol (500 mL) cooled to 10 ° C. or lower to precipitate a solid, and the mixture was stirred for 10 minutes. The precipitate was separated by filtration, and the slurry was washed again with methanol (200 mL) for 30 minutes twice in total, and the solid was vacuum dried at 80 ° C.
  • DA-2 (3.42 g: 14.00 mmol) and DA-4 (4.11 g: 6.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen introduction tube, and NMP (56.8 g) was weighed. ), Stir and dissolve in a nitrogen atmosphere, then add TC-3 (4.26 g: 19.00 mol) and NMP (10.0 g) in an ice bath while keeping the temperature below 10 ° C., and add 24 at room temperature.
  • PAA-2 polyamic acid solution having a viscosity of about 680 mPa ⁇ s and a solid content concentration of 15% by mass was obtained.
  • the molecular weight of this polyamic acid was a number average molecular weight: 17200 and a weight average molecular weight: 48160.
  • DA-2 (3.42 g: 14.00 mmol) and DA-5 (1.55 g: 6.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen introduction tube, and NMP (42.0 g) was weighed. ), Stir and dissolve in a nitrogen atmosphere, then add TC-3 (4.21 g: 18.8 mmol) and NMP (10.0 g) in an ice bath while keeping the temperature below 10 ° C., and add 24 at room temperature.
  • a polyamic acid solution (PAA-3) having a viscosity of about 710 mPa ⁇ s and a solid content concentration of 15% by mass was obtained.
  • the molecular weight of this polyamic acid was a number average molecular weight: 15500 and a weight average molecular weight: 41800.
  • a substrate with electrodes was prepared.
  • the substrate is a non-alkali glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
  • the size of each pixel is 10 mm in length and about 5 mm in width.
  • an IPS board Hereinafter referred to as an IPS board.
  • the radical generation film forming composition AL-1 and AL-2 obtained by the above method, the liquid crystal alignment agent AL-3, and the liquid crystal alignment agent SE-6414 for horizontal alignment (manufactured by Nissan Chemical Industries, Ltd.). ) Is filtered through a filter having a pore size of 1.0 ⁇ m, and then the prepared IPS substrate and a glass substrate having an ITO film formed on the back surface and having a columnar spacer having a height of 3.0 ⁇ m (hereinafter referred to as a facing substrate). It was coated and filmed by the spin coating method. Then, it was dried on a hot plate at 80 ° C. for 80 minutes and then fired at 230 ° C.
  • the rubbing method is used for AL-1 and SE-6414, and a rubbing device manufactured by Iinuma Gauge, a rubbing cloth (YA-20R) manufactured by Yoshikawa Kako, a rubbing roller (diameter 10.0 cm), and a stage.
  • the feed rate was 30 mm / s
  • the roller rotation speed was 700 rpm
  • the pushing pressure was 0.3 mm.
  • a UV exposure device manufactured by Ushio, Inc. is used so that the irradiation amount of linearly polarized UV having an extinction ratio of about 26: 1 is 300 mJ / cm 2 based on the wavelength of 254 nm.
  • a radical generation alignment film is used on the IPS substrate side for the display element to be the target of the embodiment and some display elements to be compared (Comparative Examples 2 to 4, 6 to 8).
  • Comparative Example 1 A part of the display elements to be compared (Comparative Example 1) using a combination of AL-1 or AL-2 and those provided with the liquid crystal alignment film SE-6414 or AL-3 on the facing substrate side.
  • SE-6414 or AL-3 was used for both substrates.
  • the cells were combined so that their orientation directions were parallel to each other, and the periphery was sealed leaving the liquid crystal injection port, to prepare an empty cell having a cell gap of about 3.0 ⁇ m.
  • As the liquid crystal mixture used LC-A (manufactured by DIC Corporation, ⁇ n: 0.130, ⁇ : 4.4) was used.
  • Add-C1 to Add-C2 those purchased from Tokyo Chemical Industry were used.
  • the obtained liquid crystal cell constitutes an IPS mode liquid crystal display element.
  • the obtained liquid crystal cell was heat-treated at 120 ° C. for 10 minutes, and UV (UV lamp: FLR40SUV32 / A-1) was applied using a UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied. Irradiation for 30 minutes was performed to obtain a liquid crystal display element.
  • VT curve and drive threshold voltage, maximum luminance voltage, transmittance evaluation A white LED backlight and a luminance meter are set so that the optical axes are aligned, and a liquid crystal cell (liquid crystal display element) with a polarizing plate is set between them so that the brightness is the smallest, and the voltage is applied to 8V at 1V intervals.
  • the VT curve was measured by applying and measuring the brightness at the voltage. From the obtained VT curve, the value of the voltage (Vmax) at which the brightness was maximized was estimated. Further, the maximum transmittance (Tmax) was estimated by comparing the maximum transmitted luminance in the VT curve with the transmitted luminance at the time of parallel Nicol set to 100% via the liquid crystal cell to which no voltage was applied.
  • VHR voltage retention rate
  • the voltage retention rate at room temperature was measured.
  • a voltage of 4 V for 60 ⁇ s was applied to the prepared liquid crystal display element at a temperature of 23 ° C. and measuring the voltage after 16.7 ms, how much the voltage could be maintained was calculated as the voltage retention rate.
  • the voltage retention rate at high temperature was measured.
  • a voltage of 1 V was applied to the prepared liquid crystal display element at a temperature of 70 ° C. for 60 ⁇ s, and the voltage after 1667 ms was measured to measure how much the voltage could be maintained as the voltage retention rate.
  • a VHR-1 voltage holding rate measuring device manufactured by Toyo Corporation was used for measuring the voltage holding rate.
  • Table 1 shows the compositions of the polymers synthesized in Synthesis Examples 13 to 15.
  • Table 2 shows the compositions of the liquid crystal alignment agent or the radical-generating film-forming composition prepared in Preparation Examples 1 to 3.
  • Table 3 shows the contents of Examples and Comparative Examples of the liquid crystal cells subjected to the alignment treatment by the rubbing method.
  • Tables 4-1 and 4-2 show the characteristics evaluation results of the liquid crystal cells that have been oriented by the rubbing method.
  • the orientation state and the black brightness are good, and the occurrence of the pretilt angle on the weak anchoring side is not confirmed and is 0. It was less than 1 °. It can be seen that Vmax is also significantly reduced as compared with the strong anchoring liquid crystal cell of Comparative Example 1, and the transmittance is greatly improved as compared with Comparative Examples 1 to 4. On the other hand, in Comparative Examples 2 to 3, the liquid crystal display element using Addd-C1 or Addd-C2 as an additive has many rubbing streaks and poor black brightness.
  • the additive of the present invention good weak anchoring IPS characteristics can be obtained even when such a liquid crystal display having a high ⁇ n and a small ⁇ can be used, and the response speed can be improved by narrowing the cell gap. Further, the VHR was also higher than that of Comparative Examples 2 to 4 especially at high temperature, and it was found that the reliability can be improved by using the additive of the present invention.
  • Table 5 shows the contents of Examples and Comparative Examples of the liquid crystal cells subjected to the alignment treatment by the optical alignment method.
  • Table 6 shows the characteristics evaluation results of the liquid crystal cells that have been oriented by the optical alignment method.
  • the anisotropy of the pre-tilt angle does not appear, so if a relatively large pre-tilt angle occurs due to some influence, the direction of the pre-tilt angle is not specified and it becomes a domain. It is presumed that the domain cannot be driven because the domain area is expanded by the electric field when it is tried to be driven. It has been found that the additive of the present invention is very useful because no domain is generated even when photo-orientation is used and good weak anchoring IPS characteristics can be obtained. As for VHR, it was found that VHR was good at high temperature as well as rubbing, and it was found that the use of this polymerizable compound as an additive for weak anchoring IPS was effective in improving reliability.
  • the present invention it is possible to provide a lateral electric field liquid crystal display element capable of realizing high backlight transmittance and fast response speed without generating a pretilt angle or a domain even when a liquid crystal having a high ⁇ n and a low ⁇ is used.
  • a liquid crystal display element with good reliability can be obtained. Therefore, the liquid crystal display element obtained by the method of the present invention is useful as a horizontal electric field drive type liquid crystal display element.

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Abstract

L'invention concerne un procédé de production d'élément d'affichage à cristaux liquides dans lequel une composition de cristaux liquides comprenant un cristal liquide et un composé polymérisable par voie radicalaire représenté par la formule (A) est mis en contact avec un film générateur de radicaux et, dans l'état de contact, le composé polymérisable par voie radicalaire est polymérisé. (Dans la formule (A), M représente un composé polymérisable par voie radicalaire, R1 représente un groupe hydrocarboné aliphatique en C1 à C10 ayant une structure linéaire ou ramifiée, et les trois X représentent chacun indépendamment un atome d'hydrogène ou la formule (B). Au moins l'un des trois X indique la formule (B).) (Dans la formule (B) : Y représente une liaison simple, –O–, –S–, ou –NR– ; R représente un atome d'hydrogène ou un groupe alkyle en C1 à C4 ; et * représente un site de liaison. R2, R3, et R4 représentent chacun indépendamment un groupe alkyle en C1 à C6 ou un groupe hydrocarboné aromatique qui peut avoir un substituant.)
PCT/JP2021/035557 2020-09-29 2021-09-28 Composition de cristaux liquides, procédé de production d'élément de cristaux liquides, et élément de cristaux liquides WO2022071286A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015033921A1 (fr) * 2013-09-03 2015-03-12 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
EP3543263A1 (fr) * 2016-11-16 2019-09-25 Zhejiang University Émulsifiant à base de polyoléfine et son application pour la préparation d'une émulsion à phase interne élevée et d'un matériau polymère poreux
JP2019196480A (ja) * 2018-05-07 2019-11-14 達興材料股▲ふん▼有限公司 液晶組成物及びそれを含む液晶ディスプレイ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015033921A1 (fr) * 2013-09-03 2015-03-12 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
EP3543263A1 (fr) * 2016-11-16 2019-09-25 Zhejiang University Émulsifiant à base de polyoléfine et son application pour la préparation d'une émulsion à phase interne élevée et d'un matériau polymère poreux
JP2019196480A (ja) * 2018-05-07 2019-11-14 達興材料股▲ふん▼有限公司 液晶組成物及びそれを含む液晶ディスプレイ

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