WO2018097155A1 - Method for manufacturing liquid crystal display element, substrate for liquid crystal display element, and liquid crystal display element assembly - Google Patents
Method for manufacturing liquid crystal display element, substrate for liquid crystal display element, and liquid crystal display element assembly Download PDFInfo
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- WO2018097155A1 WO2018097155A1 PCT/JP2017/041921 JP2017041921W WO2018097155A1 WO 2018097155 A1 WO2018097155 A1 WO 2018097155A1 JP 2017041921 W JP2017041921 W JP 2017041921W WO 2018097155 A1 WO2018097155 A1 WO 2018097155A1
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- liquid crystal
- group
- carbon atoms
- display element
- crystal display
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- 0 CN1CC*CC1 Chemical compound CN1CC*CC1 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N C=Cc1ccccc1 Chemical compound C=Cc1ccccc1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- KYLUHLJIAMFYKW-UHFFFAOYSA-N CC(CC1=C)OC1=O Chemical compound CC(CC1=C)OC1=O KYLUHLJIAMFYKW-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N CN(C(C=C1)=O)C1=O Chemical compound CN(C(C=C1)=O)C1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Definitions
- the present invention relates to a method for manufacturing a liquid crystal display element, a substrate for a liquid crystal display element, and a liquid crystal display element assembly, and in particular, a vertical alignment type liquid crystal display produced by irradiating ultraviolet rays with voltage applied to liquid crystal molecules.
- the present invention relates to an element manufacturing method, a liquid crystal display element substrate, and a liquid crystal display element assembly.
- a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to the substrate respond by an electric field also referred to as a vertical alignment (VA) method
- VA vertical alignment
- a photopolymerizable compound is previously added to the liquid crystal composition, and a polyimide-based vertical alignment film is used, and ultraviolet rays are applied while applying a voltage to the liquid crystal cell. Therefore, a technique for increasing the response speed of liquid crystal (PSA (Polymer Sustained Alignment) type element, for example, see Patent Document 1 and Non-Patent Document 1) is known.
- PSA Polymer Sustained Alignment
- the direction in which the liquid crystal molecules incline in response to an electric field is usually controlled by protrusions provided on the substrate or slits provided on the display electrode, but photopolymerization is performed in the liquid crystal composition.
- photopolymerization is performed in the liquid crystal composition.
- the first alignment film is formed on the first substrate using the first alignment liquid containing the first alignment agent
- the second alignment film is formed on the second substrate using the second alignment liquid containing the second alignment agent.
- light irradiation is performed while applying an electric field with a liquid crystal layer sandwiched between these substrates, and the first pretilt angle is expressed in the liquid crystal molecules adjacent to the first alignment film, while adjacent to the second alignment film.
- a method of manufacturing a liquid crystal display element that causes a liquid crystal molecule to exhibit a second pretilt angle has been proposed (see Patent Document 3).
- JP 2003-307720 A WO2015 / 033921 Republic of Korea 10-2016-0002599
- Patent Document 3 it is necessary to use two kinds of liquid crystal aligning agents, and there is a problem that a large capital investment is required due to an increase in the number of processes and an increase in production lines.
- An object of the present invention is to provide a method for producing a liquid crystal display element capable of producing a liquid crystal display element having liquid crystal layers having different alignment states on both sides more easily without involving the above-mentioned problems, and this production method. It is an object to provide a substrate for a liquid crystal display element and a liquid crystal display element assembly using the above.
- the present inventors have used a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation, and before providing a liquid crystal layer, liquid crystal on at least one side in advance. Irradiate light to the alignment film and invalidate at least part of the radical generation structure of the radical generation structure of the liquid crystal alignment film on one side, or perform light irradiation so that the amount of light irradiation differs for both radicals.
- the inventors have found that a liquid crystal layer having different alignment states can be formed on both sides of the liquid crystal layer by making the generation ability different, and the present invention has been completed.
- the present invention has the following gist.
- a liquid crystal alignment film forming step of forming a liquid crystal alignment film with a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation on each of the surfaces of the pair of substrates; and the pair of substrates A liquid crystal alignment film light irradiating step in which at least one of the liquid crystal is irradiated with light to change the amount of light applied to the liquid crystal alignment films in different states, and then a liquid crystal layer containing a liquid crystal compound is formed between the pair of substrates And a liquid crystal layer forming step.
- a substrate for forming a liquid crystal display element comprising a liquid crystal alignment film, wherein the liquid crystal alignment film is formed of a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation.
- a substrate for forming a liquid crystal display element wherein a radical is generated from at least a part of the radical generating structure by light irradiation.
- a liquid crystal display element assembly comprising a liquid crystal display element forming substrate having a pair of liquid crystal alignment films and a liquid crystal layer provided between the pair of liquid crystal display element substrates,
- the liquid crystal alignment film of the formation substrate for a liquid crystal display element is formed of a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals upon light irradiation, and at least one is irradiated with light.
- the liquid crystal display element assembly is characterized in that the light irradiation amounts of the two differ from each other.
- a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation is used, and at least one liquid crystal alignment film is irradiated in advance before providing a liquid crystal layer.
- a liquid crystal layer having different alignment states on both sides of the liquid crystal layer can be formed, and a liquid crystal display element having a liquid crystal layer having different alignment states on both sides can be more easily manufactured.
- a method, a liquid crystal display element substrate and a liquid crystal display element assembly used in the manufacturing method can be provided.
- liquid crystal aligning agent suitable for a vertical alignment type liquid crystal display element, particularly a PSA type liquid crystal display element, which has a high response speed.
- the method for producing a liquid crystal display element according to the present invention includes forming a liquid crystal alignment film on each of the surfaces of a pair of substrates with a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation. Between the forming step, the liquid crystal alignment film light irradiating step in which at least one of the pair of substrates is irradiated with light and the amount of light irradiation to the liquid crystal alignment film is different, and then between the pair of substrates, And a liquid crystal layer forming step of forming a liquid crystal layer containing a liquid crystal compound.
- liquid crystal alignment film forming step of the present invention a substrate on which a liquid crystal alignment film formed with a liquid crystal alignment agent having the same composition is prepared.
- the liquid crystal aligning agent used here is a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation. Details of the liquid crystal aligning agent will be described later.
- a liquid crystal alignment film light irradiation step in which at least one of the pair of substrates is irradiated with light so that the amount of light irradiation to the liquid crystal alignment films is different.
- the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least part of the radical generating ability of the radical generating structure of the liquid crystal alignment film on one side, or both Irradiation is performed so that the amount of light irradiation is different so that the radical generating ability on both sides is different.
- the light irradiation is to invalidate at least a part of the radical generation structure of the provided liquid crystal alignment film, that is, to generate radicals at this point and not to generate radicals thereafter.
- the light irradiation may be performed with light having a wavelength necessary to deactivate the radical generating structure.
- the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least a part of the radical generating structure, thereby invalidating the radical generating ability.
- one is a liquid crystal alignment film having no radical generation ability
- the other is a liquid crystal alignment film having radical generation ability
- one is a liquid crystal alignment film having low radical generation ability
- the other is a liquid crystal alignment film having high radical generation ability.
- the liquid crystal alignment films of the substrates on both sides are irradiated with light, but the amount of light irradiation is different on both sides, and the amount of radical generation structure to be invalidated is different on both sides.
- one is a liquid crystal alignment film having a low radical generation capability and the other is a liquid crystal alignment film having a high radical generation capability so that the radical generation capability on both sides is different.
- a liquid crystal layer forming step of forming a liquid crystal layer containing a polymerizable compound between the pair of substrates is included. Accordingly, since the liquid crystal layer is formed by being sandwiched between a pair of liquid crystal alignment films having different radical generation capabilities, it is possible to form an asymmetric liquid crystal layer having different pretilt angles on both sides.
- the polymer having a radical generating structure used in the present invention has a site where a radical is generated by light irradiation, for example, ultraviolet irradiation, as a side chain.
- a radical is generated by light irradiation, for example, ultraviolet irradiation
- Examples of the specific polymer include a polymer having a side chain structure represented by the following formula (I) as a radical generating structure in which radicals are generated by ultraviolet irradiation.
- Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom.
- R 1 and R 2 are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms
- T1 and T2 are each independently a single bond or —O—, —COO—, —OCO—, — NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ) CO—
- the alkylene group —CH 2 — or —CF 2 — may be optionally replaced with —CH ⁇ CH—, and when any of the following groups is not adjacent to each
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 3 represents —CH 2 —, —NR—, —O—, or —S—).
- Ar to which carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays. Therefore, when the wavelength is increased, a structure having a long conjugate length such as naphthylene or biphenylene is preferable.
- Ar may be substituted with a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.
- R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R 1 and R 2 are May be formed.
- Q is preferably an electron donating organic group, and the above group is preferable.
- Q is an amino derivative
- the side chain structure of the formula (I) can be handled as a raw material. It is preferable from the viewpoint of easy synthesis of the polymer.
- the site where radicals are generated by ultraviolet irradiation in the above formula (I) is preferably as follows.
- (b) or (c) is preferable from the viewpoint of the reliability of the obtained liquid crystal display element.
- —T 1 —ST 2 — serves as a linking group that connects diaminobenzene and a site that generates a radical upon irradiation with ultraviolet rays.
- T 1 and T 2 are each independently a single bond, —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, or —N (CH 3 ) CO—.
- S is a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom (provided that —CH 2 — or —CF 2 — of the alkylene group is optionally substituted with —CH ⁇ CH—). If any of the following groups are not adjacent to each other, these groups may be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, — NH—, a divalent carbocyclic ring or a heterocyclic ring. In particular, T 2 is most preferably —O— in terms of synthesis difficulty.
- S is preferably an alkylene group having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, from the viewpoint of synthesis difficulty or solubility.
- examples of the specific polymer used in the present invention include a polymer having a side chain structure represented by the following formula (II).
- a point means a bond to the main chain of the polymer
- n is an integer selected from 1 to 12
- X is a single bond, —O—, —COO—, —OCO—, — NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, or —N (CH 3 ) CO— is represented.
- Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms having at least one unsaturated bond which is necessarily bonded to the carbonyl carbon of the imide group, and a part of the carbon atoms constituting the cyclic hydrocarbon is heterogeneous. It may be replaced by an atom.
- Such a specific polymer has an organic group represented by the above formula (II) in the side chain. It is considered that this organic group is excited by ultraviolet irradiation to generate a radical, or has a function of chain-transferring a radical generated by another organic group, and functions as a radical generating structure.
- the structure having the function of chain-transferring this radical is also included in the radical generating structure of the present invention.
- Cy that is, a cyclic hydrocarbon group having at least one unsaturated bond
- a structure in which the bonds are directly connected is preferable.
- the greater the number of unsaturated bonds the higher the absorbance in the ultraviolet region and the longer the absorption wavelength, which is preferable when performing long wavelength exposure.
- an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic compound, and the like are more preferable.
- a cyclic hydrocarbon group containing no hetero atom is preferable.
- the two points of Cy each represent a bond to imidocarbonyl carbon.
- the number of carbon atoms forming the ring structure increases, the structure becomes more rigid and the solubility in the solvent becomes poor. Therefore, from the viewpoint of monomer synthesis and the ease of handling of the monomer, the number of carbon atoms is relatively high. Fewer cyclic hydrocarbon groups are preferred, and particularly preferred are cyclohexene, benzene, naphthalene, biphenylene and the like. More preferred is the following structure.
- the hydrogen atom of the cyclic hydrocarbon group directly connected to the imide ring may be replaced with a fluorine atom or the like, or an organic group may be substituted.
- the organic group to be substituted is not particularly limited, but introduction of an organic group having a strong electron donating property or electron accepting property is preferable because an effect of increasing the absorption wavelength is expected.
- a nitro group or an amino group may trap a generated radical
- a monovalent organic group having a molecular weight of 14 to 100 is preferable, for example, an organic group such as a hydroxy group or a hydroxyl group, An alkoxyl group or an alkyl group having a relatively small molecular weight can be mentioned, but since the introduced substituent may trap the generated radical, it is necessary to pay attention to the selection of the substituent. For the above reasons, it is most preferably unsubstituted.
- —X—C n (H 2 ) n — represents a connecting site with a polymer chain.
- the linking site is not particularly limited. A bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, or — N (CH 3 ) CO— and the like can be mentioned.
- the alkylene linked to X is preferably an alkylene having 1 to 12 carbon atoms, and the alkylene may have an unsaturated bond, a branched chain, or a cyclic structure, and the hydrogen atom in the alkylene is replaced with fluorine. It may be done. From the viewpoint of reagent availability and synthesis, X is —O— as the most easily synthesized structure, and alkylene is a straight-chain alkylene having 1 to 6 carbon atoms.
- the means for introducing the side chain into the polymer is not particularly limited. Examples thereof include a method of obtaining a polymer by polymerization using a monomer having a side chain structure represented by the above formula (II), a method of introducing by polymer modification, and the like. Preferably, it is a method of introducing into a polymer using a monomer having an organic group represented by the above formula (I).
- the radical generating structure of the present invention is not limited to those described above, and any other side chain structure having a radical generating structure other than the described side chain structure can be preferably used.
- a polymer containing a radical generating structure containing a reactive mesogen structure (see Patent Document 3, claim 1, etc.) in the side chain can be used.
- the specific polymer contained in the liquid crystal aligning agent used in the present invention contains a liquid crystal in addition to the side chain having a radical generating structure represented by the above formula (I) or (II) (hereinafter also referred to as a specific side chain). It is preferred to have side chains that are oriented vertically.
- the side chain for vertically aligning the liquid crystal is represented by the following formula [III-1] or [III-2]. In addition, you may mix
- X 1 is a single bond, - (CH 2) a - (a is an integer of 1 ⁇ 15), - O - , - CH 2 O -, - COO- or -OCO- .
- X 2 representing a is Represents a single bond or (CH 2 ) b — (b is an integer of 1 to 15.)
- X 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), Represents —O—, —CH 2 O—, —COO—, or —OCO—, wherein X 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring;
- the hydrogen atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon
- X 4 is selected from an organic group having a carbon number of 17 to 51 having a steroid skeleton That may be a divalent organic group .
- X 5 represents a divalent cyclic group selected from benzene ring, cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, C 1 - 3 may be substituted with an alkyl group of 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
- X 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
- X 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O, from the viewpoint of availability of raw materials and ease of synthesis.
- — Or —COO— is preferable, and more preferable is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
- X 2 is preferably a single bond or (CH 2 ) b — (b is an integer of 1 to 10).
- X 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, or —COO—, among these, from the viewpoint of ease of synthesis. And more preferably a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
- X 4 is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis.
- X 5 is preferably a benzene ring or a cyclohexane ring.
- n is preferably 0 to 3 and more preferably 0 to 2 in view of availability of raw materials and ease of synthesis.
- X 6 is preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
- the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton.
- An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.
- (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred.
- Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).
- X 7 represents a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— or —OCO—.
- X 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Among them, X 7 is preferably a single bond, —O—, —CH 2 O—, —CONH—, —CON (CH 3 ) — or —COO—, and more preferably a single bond, —O—, — CONH- or -COO-.
- X 8 is preferably an alkyl group having 8 to 18 carbon atoms.
- the side chain for vertically aligning the liquid crystal it is preferable to use a structure represented by the formula [III-1] from the viewpoint that a high and stable vertical alignment of the liquid crystal can be obtained.
- the ability of a polymer having side chains for vertically aligning liquid crystals to align liquid crystals vertically varies depending on the structure of the side chains for vertically aligning liquid crystals, but in general, the side chains for vertically aligning liquid crystals. As the amount increases, the ability to align the liquid crystal vertically increases, and as the amount decreases, it decreases. Moreover, when it has a cyclic structure, compared with what does not have a cyclic structure, there exists a tendency for the capability to orientate a liquid crystal vertically.
- the specific polymer contained in the liquid crystal aligning agent of the present invention has, for example, a photoreactive side chain in addition to the side chain having a radical generating structure represented by the above formula (I) or (II). May be.
- the photoreactive side chain has a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond.
- UV ultraviolet rays
- the photoreactive side chain may be directly bonded to the main chain of the polymer, or may be bonded via a linking group.
- the photoreactive side chain is represented, for example, by the following formula [IV].
- R 8 is a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) — or —N (CH 3 ) CO— is represented.
- R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and —CH 2 — in the alkylene group is optionally substituted with —CF 2 — or —CH ⁇ CH—.
- R 10 represents a photoreactive group selected from the following formulae.
- R 8 is preferably a single bond, —O—, —COO—, —NHCO—, or —CONH—.
- R 9 can be formed by a common organic synthetic method, but from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable.
- Y 1 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—.
- Y 2 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group.
- Y 2 when the following groups are not adjacent to each other, —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
- Y 3 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
- Y 4 represents a cinnamoyl group.
- Y 5 is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group.
- —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
- Y 6 represents a photopolymerizable group which is an acrylic group or a methacryl group.
- R 10 is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.
- the abundance of the photoreactive side chain is preferably within a range where the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond.
- the polymer having a radical generating structure used in the present invention is not particularly limited, but a polyimide-based, poly (meth) acrylate-based, polysiloxane-based polymer, or the like can be preferably used.
- a polyimide-based, poly (meth) acrylate-based, polysiloxane-based polymer, or the like can be preferably used.
- other polymers can be synthesized using known techniques (radical polymerization, sol-gel method, etc.).
- the method for producing a polyimide precursor having a specific side chain and a polyimide obtained by imidizing the polyimide precursor is not particularly limited.
- Examples include a method of polymerizing a compound, a method of polymerizing a tetracarboxylic dianhydride and a diamine, and then modifying a compound containing a specific side chain into a polymer by some kind of reaction.
- a method of polymerizing a diamine compound containing a specific side chain and tetracarboxylic dianhydride or tetracarboxylic diester is preferable.
- the method similar to the above-mentioned is mentioned also about the method of manufacturing the polyimide precursor which has the side chain which orientates a liquid crystal vertically in addition to a specific side chain, and the polyimide which imidated this polyimide precursor.
- the preferable method is also preferably a method of polymerizing a diamine compound containing a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride or a tetracarboxylic acid diester.
- a polyimide having a radical generating structure in the side chain can be prepared by using one or more of diamines such as the following specific diamines 1 to 3, for example.
- the diamine (hereinafter also referred to as a specific diamine) used in the production of the above-mentioned polymer forming the liquid crystal aligning agent of the present invention has, as a side chain, a site having a radical generating structure that is decomposed by ultraviolet irradiation to generate radicals. And represented by the following formula (1).
- the diaminobenzene in the formula (1) may have any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine. However, in terms of reactivity with acid dianhydride, m-phenylenediamine, or p-Phenylenediamine is preferred.
- n is an integer of 2 to 8.
- the specific diamine 1 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction that is usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.
- n is an integer of 2 to 8.
- the base to be used is not particularly limited, inorganic bases such as potassium carbonate, sodium carbonate and cesium carbonate, and organic bases such as pyridine, dimethylaminopyridine, trimethylamine, triethylamine and tributylamine are preferable.
- the method for reducing the dinitro compound, which is a diamine precursor is not particularly limited. Usually, palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran. There is a method in which reduction is carried out with hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as dioxane or alcohol. You may use an autoclave etc. as needed.
- an unsaturated bond site is included in the structure, if palladium carbon or platinum carbon is used, the unsaturated bond site may be reduced and become a saturated bond. Reduction conditions using a transition metal such as tin chloride, poisoned palladium carbon or platinum carbon, platinum carbon doped with iron or the like as a catalyst are preferable.
- the diamine of the present invention can be obtained by deprotecting the diaminobenzene derivative protected with a benzyl group or the like in the same reduction step.
- the specific diamine 1 is preferably 10 to 80 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid.
- the specific diamine 2 of the present invention can be represented by a diamine having an organic group represented by the formula (II) as a side chain, that is, the following formula (VI).
- Sp is an alkylene group having 1 to 12 carbon atoms, and the alkylene group may have an unsaturated bond, a branched chain, or a cyclic structure.
- X represents a single bond or a linking group.
- Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms having at least one unsaturated bond which is necessarily bonded to the carbonyl carbon of the imide group, and a part of the carbon atoms constituting the cyclic hydrocarbon is heterogeneous. It may be replaced by an atom.
- the diaminobenzene in the formula (VI) may have a structure of any of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine. However, in terms of reactivity with acid dianhydride, m-phenylenediamine, Or p-phenylenediamine is preferred.
- a preferred structure of the formula (VI) is a diamine represented by the following formula (X),
- n is an integer from 1 to 6)
- the structure represented by the following formula (XI) is most preferable from the viewpoints of ease of synthesis, high versatility, characteristics, and the like.
- the specific diamine 2 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.
- a method of obtaining a diamine precursor by reacting an alcohol, alkylamine, alkyl halide or the like having a target imide structure with dinitrobenzene, or by reacting an alkylamine having dinitrobenzene already introduced with an acid anhydride examples thereof include a Mitsunobu reaction between an alcohol already introduced with dinitrobenzene and an N unsubstituted imide, and a method of condensing an alkyl halide already introduced with dinitrobenzene and an N unsubstituted imide in the presence of a base or a metal catalyst.
- the method for reducing the dinitro compound, which is a diamine precursor is not particularly limited. Usually, palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran. There is a method in which reduction is carried out with hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as dioxane or alcohol. You may use an autoclave etc. as needed.
- an unsaturated bond site is included in the structure, if palladium carbon or platinum carbon is used, the unsaturated bond site may be reduced and become a saturated bond. Reduction conditions using a transition metal such as tin chloride, poisoned palladium carbon or platinum carbon, platinum carbon doped with iron or the like as a catalyst are preferable.
- the diamine of the present invention can be obtained by deprotecting the diaminobenzene derivative protected with a benzyl group or the like in the same reduction step.
- the specific diamine 3 of the present invention is represented by the following formula (11).
- the specific diamine 3 has a photoreactive structure in which radicals are generated by ultraviolet irradiation in a single molecular structure and a structure in which liquid crystals are aligned vertically. That is, the photoreactive structure is a 4-chromanone structure bonded to the phenylenediamine skeleton via X 11 , and the structure for vertically aligning the liquid crystal is bonded to 4-chromanone —X 2 —X 3 -X 4 structure.
- each definition of X 11 , X 12 , X 13 and X 14 is as described above.
- X 11 is preferably —O— or —CH 2 O— from the viewpoint of ease of synthesis.
- X 12 and X 13 are preferably cyclohexane rings from the viewpoint of high vertical alignment.
- X 14 is preferably an alkyl group having 3 to 7 carbon atoms from the viewpoint of availability of raw materials.
- Preferred examples of the specific diamine 3 include the following.
- the method for reducing the dinitro compound is not particularly limited, and usually palladium-carbon, platinum-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, platinum carbon sulfide, etc. are used as catalysts. , Ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohol-based solvents, hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, and the like.
- the method for synthesizing the dinitro compound represented by the general formula (12) is not particularly limited and can be synthesized by any method. Specific examples thereof include those shown in the following scheme (13). It can be synthesized by the method.
- X 15 is any one of chlorine, bromine, iodine, fluorine, —OH, —COOH, —COOCl, — (CH 2 ) a OH (a is an integer of 1 to 15).
- X 12 to X 14 in the phenol compound B are the same as those in the formula 1.
- the compound shown here is an example and is not specifically limited.
- the specific diamine is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 60 mol%, particularly preferably 30 mol% to 50 mol% of the diamine component used for the synthesis of the polyamic acid. is there.
- X represents the structure of the above formula [III-1] or [III-2], and n represents an integer of 1 to 4.
- R 8 , R 9 and R 10 are as defined above.
- Y 1 to Y 6 are as described above.
- Specific examples of the specific side chain diamine include structures represented by the following formulas [2a-1] to [2a-31].
- R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
- R 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms, A linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched, fluorine-containing alkyl group or fluorine-containing alkoxyl group having 1 to 22 carbon atoms.
- R 3 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or —CH 2 —
- R 4 is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkyl group. Group or fluorine-containing alkoxyl group.
- R 5 is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O —
- R 6 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
- R 7 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
- R 8 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
- a 4 is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A 3 is a 1,4-cyclohexylene group or a 1,4-phenylene group.
- a 2 is an oxygen atom or COO- * (where a bond with “*” is bonded to A 3 ), and A 1 is an oxygen atom or COO— * (where “*” is a bond)
- the hand binds to (CH 2 ) a 2 ).
- a 1 is an integer of 0 or 1
- a 2 is an integer of 2 to 10
- a 3 is an integer of 0 or 1.
- examples of the diamine having the specific side chain structure represented by the formula [III-2] include diamines represented by the following formulas [2b-1] to [2b-10].
- a 1 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
- a 1 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or —NH.
- a 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.
- the above diamines can be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
- the diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 70 mol% of the diamine component used for the synthesis of the polyamic acid, more preferably 20 mol% to 60 mol% of the diamine component, Particularly preferred is 20 to 50 mol%.
- a diamine having a specific side chain structure As a method for introducing a side chain having photoreactivity into a polyimide polymer, it is preferable to use a diamine having a specific side chain structure as a part of the diamine component.
- the diamine having a photoreactive side chain is a diamine having a side chain represented by Formula [VIII] or Formula [IX].
- the bonding positions of the two amino groups (—NH 2 ) in Formula [VIII] and Formula [IX] are not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
- diamine having a photoreactive side chain examples include, but are not limited to, the following.
- X 9 and X 10 are each independently a single bond, —O—, —COO—, —NHCO—, or —NH—, a linking group, and Y is a carbon atom which may be substituted with a fluorine atom. Represents an alkylene group of ⁇ 20.
- examples of the diamine having a photoreactive side chain include a diamine having a group causing a photodimerization reaction and a group causing a photopolymerization reaction represented by the following formula in the side chain.
- Y 1 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—.
- Y 2 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group.
- Y 2 when the following groups are not adjacent to each other, —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
- Y 3 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
- Y 4 represents a cinnamoyl group.
- Y 5 is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group.
- —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
- Y 6 represents a photopolymerizable group which is an acrylic group or a methacryl group.
- the diamine having a photoreactive side chain depends on the liquid crystal alignment property when it is used as a liquid crystal alignment film, the pretilt angle, the voltage holding property, the characteristics such as accumulated charge, the response speed of the liquid crystal when it is used as a liquid crystal display device, etc. 1 type or 2 types or more can be mixed and used.
- the diamine having a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid. It is.
- the liquid crystal aligning agent of the present invention comprises, as component (A), a polyimide precursor having a side chain for vertically aligning liquid crystals and a side chain having a radical generating structure represented by the above formula (I), and this Contains at least one polymer selected from polyimides obtained by imidizing a polyimide precursor and at least one diamine selected from the following formulas (B-1) to (B-5) as component (B)
- Y 1 represents a secondary amine, tertiary amine, or a monovalent organic group having a heterocyclic structure
- Y 2 represents a secondary amine, tertiary amine, or a divalent organic group having a heterocyclic structure. Represents an organic group.
- tetracarboxylic dianhydride selected from the above formulas (3) and (4) When at least one tetracarboxylic dianhydride selected from the above formulas (3) and (4) is used as a raw material, it may cause an interaction between [liquid crystal-alignment film] by light irradiation, or may improve accumulated charge characteristics. be able to.
- the tetracarboxylic dianhydride represented by the formula selected from the formulas (3) and (4) include, but are not limited to, the following compounds.
- At least one tetracarboxylic dianhydride selected from the above formulas (1-1) to (1-4) is a tetracarboxylic dianhydride component used for the synthesis of the component (B) which is a polyamic acid. It is preferable to use an amount of 10 to 100% of the above. More preferably, 10 to 60% is used.
- a tetracarboxylic dianhydride other than the above formulas (1-1) to (1-4) may be used as a raw material for the component (B) as long as the effects of the present invention are not impaired.
- Specific examples include, but are not limited to, the tetracarboxylic dianhydrides described in the component (A).
- tetracarboxylic dianhydride having an aliphatic group or an alicyclic group is also used as a raw material
- 0 to 90% of the tetracarboxylic dianhydride component used for the synthesis of the component (B), which is a polyamic acid Is preferably used.
- the diamine component to be reacted is not particularly limited, and specific examples thereof Examples of the diamine include the diamines mentioned in the component (A), but at least one diamine selected from the above formulas (B-1) to (B-5) is preferably used from the viewpoint of accumulated charge characteristics.
- the polymer as the component (B) includes a polyimide precursor obtained using a diamine component containing at least one diamine selected from the following formulas (B-1) to (B-5) as a raw material,
- the polymer selected from the polyimide obtained by imidating a polyimide precursor may be sufficient.
- Y 1 represents a secondary amine, tertiary amine, or a monovalent organic group having a heterocyclic structure
- Y 2 represents a secondary amine, tertiary amine, or a divalent organic group having a heterocyclic structure. Represents an organic group.
- a diamine having a specific structure with a high polarity selected from the above formulas (B-1) to (B-5) is used, or a diamine having a carboxyl group and a diamine having a nitrogen-containing aromatic heterocyclic ring.
- charge transfer is promoted by electrostatic interactions such as salt formation and hydrogen bonding, so that accumulated charge characteristics can be improved.
- Examples of at least one diamine selected from the formulas (B-1) to (B-5) include, but are not limited to, the following diamines.
- Alicyclic diamines such as diamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3 -Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Examples thereof include aliphatic diamines such as diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.
- the above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is formed.
- the tetracarboxylic dianhydride component to be reacted with the diamine component 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-biphenyltetra Carboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxy) Phen
- the liquid crystal aligning agent of the present invention may contain a polymerizable compound having a photopolymerizable or photocrosslinkable group at two or more terminals as required.
- a polymerizable compound is a compound having two or more terminals having a group that undergoes photopolymerization or photocrosslinking.
- the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light.
- the compound having a photocrosslinking group is at least one selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor by irradiating light. It is a compound having a functional group capable of reacting with the polymer and crosslinking with these polymers.
- a compound having a photocrosslinkable group also reacts with a compound having a photocrosslinkable group.
- the liquid crystal aligning agent of the present invention containing the polymerizable compound in a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display By using the liquid crystal aligning agent of the present invention containing the polymerizable compound in a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display, the side chain and the photoreactive property for aligning the liquid crystal vertically are used. Compared to the case of using a polymer having a side chain and this polymerizable compound alone, the response speed can be remarkably improved, and the response speed can be sufficiently improved even with a small amount of the polymerizable compound added. Can do.
- Examples of the group that undergoes photopolymerization or photocrosslinking include monovalent groups represented by the following formula (X).
- R 12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- Z 1 is a divalent group optionally substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
- Z 2 represents a monovalent aromatic ring or heterocyclic ring optionally substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
- the polymerizable compound examples include a compound having a photopolymerizable group at each of two terminals represented by the following formula (XI), a terminal having a photopolymerizable group represented by the following formula (XII), and light.
- Examples thereof include a compound having a terminal having a cross-linking group and a compound having a photo-crosslinking group at each of two terminals represented by the following formula (XIII).
- R 12, Z 1 and Z 2 are the same as R 12, Z 1 and Z 2 in the formula (X), Q 1 is a divalent organic group is there.
- Q 1 has a ring structure such as a phenylene group (—C 6 H 4 —), a biphenylene group (—C 6 H 4 —C 6 H 4 —), a cyclohexylene group (—C 6 H 10 —), and the like. Preferably it is. This is because the interaction with the liquid crystal tends to increase.
- polymerizable compound represented by the formula [XI] examples include a polymerizable compound represented by the following formula (4).
- V and W are each represented by a single bond or —R 1 O—, and R 1 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably — R 1 is represented by R 1 O—, and R 1 is a linear or branched alkylene group having 2 to 6 carbon atoms.
- V and W may be the same or different, but synthesis is easy when they are the same.
- the photopolymerization or photocrosslinking group is a polymerizable compound having an acrylate group or a methacrylate group instead of an ⁇ -methylene- ⁇ -butyrolactone group
- the acrylate group or methacrylate group is a spacer such as an oxyalkylene group.
- the polymerizable compound having a structure bonded to a phenylene group via a can significantly improve the response speed particularly like the polymerizable compound having ⁇ -methylene- ⁇ -butyrolactone groups at both ends. .
- a polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group through a spacer such as an oxyalkylene group has improved heat stability, and a high temperature, for example, a firing temperature of 200 ° C. or higher. Can withstand enough.
- ⁇ Synthesis of polyamic acid> In obtaining a polyamic acid by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent. The reaction of the diamine component and tetracarbonic dianhydride 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 the generated polyamic acid is soluble. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt
- organic solvent used in the above reaction examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, and N-ethyl-2.
- -Pyrrolidone 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethyl Sulfoxide, ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, Tilcerosolve acetate, butylcellosolve acetate, ethylcellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol
- the method of reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent is to stir a solution in which the diamine component is dispersed or dissolved in the organic solvent, and the tetracarboxylic dianhydride component as it is or an organic solvent.
- Dispersing or dissolving in a solution adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, alternating tetracarboxylic dianhydride component and diamine component Any of the methods of adding to In addition, when the diamine component or tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. The body may be mixed and reacted to form a high molecular weight body.
- the temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted is, for example, in the range of ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
- the total concentration of the diamine component and the tetracarboxylic dianhydride component is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass with respect to the reaction solution.
- the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the usual polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced, and 0.8 to 1.2 if it shows a preferred range.
- the method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and in the same manner as the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetracarboxylic acid having a corresponding structure is used.
- the corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as acid or tetracarboxylic acid dihalide.
- Examples of the method for imidizing the polyamic acid to obtain a polyimide include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
- the imidation ratio from polyamic acid to polyimide is not necessarily 100%.
- the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably carried out while removing water generated by the imidization reaction from the outside of the system.
- the catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C., preferably 0 to 180 ° C.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
- Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
- the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
- the polyamic acid ester is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid, a suitable condensing agent with a diamine similar to the synthesis of the tetracarboxylic acid diester and the polyamic acid, It can be produced by reacting in the presence of a base or the like. It can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction. Specifically, for example, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C.
- a polyamic acid ester By reacting for ⁇ 4 hours, a polyamic acid ester can be synthesized.
- the polyimide can also be obtained by heating the polyamic acid ester at a high temperature to promote dealcoholization and ring closure.
- the reaction solution may be poured into a poor solvent and precipitated.
- the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
- the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
- the operation of re-dissolving the recovered polymer in an organic solvent and repeating the reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the agent of the present invention contains at least one specific polymer having a radical generating structure in the side chain, and the content of the specific polymer is preferably 0.5 to 20% by mass, more preferably 0.5 to 15%. % By mass, particularly preferably 1 to 10% by mass.
- the liquid crystal aligning agent of the present invention may contain a polymer other than the above polymer.
- the content of such other polymer in all the components of the polymer is preferably 0.5 to 80% by mass, more preferably 20 to 50% by mass.
- the molecular weight of the polymer of the liquid crystal aligning agent is GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal aligning film obtained by applying the liquid crystal aligning agent, workability when forming the coating film, and uniformity of the coating film. )
- the weight average molecular weight measured by the method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
- the solvent contained in the liquid crystal aligning agent is not particularly limited.
- combination of said polyamic acid can be mentioned.
- N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and 3-methoxy-N, N-dimethylpropanamide are soluble.
- two or more kinds of mixed solvents may be used.
- a solvent that improves the uniformity and smoothness of the coating film mixed with a solvent in which the components of the liquid crystal aligning agent are highly soluble examples include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, Ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol,
- the liquid crystal aligning agent may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
- Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like.
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. .
- compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds.
- a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added.
- These compounds are 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 liquid crystal aligning agent.
- liquid crystal aligning agent is added with a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant or conductivity of the liquid crystal aligning film as long as the effects of the present invention are not impaired. May be.
- liquid crystal aligning agent By applying this liquid crystal aligning agent on a substrate and baking it, a liquid crystal alignment film for vertically aligning liquid crystals can be formed.
- the response speed of the liquid crystal display element using the liquid crystal aligning film obtained can be made quick.
- the polymerizable compound that has two or more terminal groups that are photopolymerized or photocrosslinked, which may be contained in the liquid crystal aligning agent of the present invention is not contained in the liquid crystal aligning agent, or the liquid crystal aligning agent.
- the photoreaction becomes highly sensitive even in the so-called PSA mode, and a tilt angle can be imparted even with a small amount of ultraviolet irradiation.
- a cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate and then drying and baking as necessary can be used as a liquid crystal aligning film as it is.
- the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.
- the substrate to be used is not particularly limited as long as it is a highly transparent substrate.
- Glass plate polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone ,
- Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose can be used.
- a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
- an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
- the method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include printing methods such as screen printing, offset printing, flexographic printing, ink jet method, spray method, roll coating method, dip, roll coater, slit coater, and spinner. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.
- the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
- the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable.
- the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.
- the baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and is, for example, 100 to 350 ° C, preferably 120 to 300 ° C, and more preferably 150 ° C to 250 ° C.
- the firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 90 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.
- the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 20 to 200 nm.
- a liquid crystal alignment film forming step for forming a liquid crystal alignment film as described above is performed on each of the surfaces of a pair of substrates.
- a liquid crystal alignment film light irradiation step is performed in which at least one of the pair of substrates is irradiated with light so that the amount of light irradiation to the liquid crystal alignment films is different.
- the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least part of the radical generating ability of the radical generating structure of the liquid crystal alignment film on one side, or both Irradiation is performed so that the amount of light irradiation is different so that the radical generating ability on both sides is different.
- the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least a part of the radical generating structure, thereby invalidating the radical generating ability.
- one is a liquid crystal alignment film having no radical generation ability
- the other is a liquid crystal alignment film having radical generation ability
- one is a liquid crystal alignment film having low radical generation ability
- the other is a liquid crystal alignment film having high radical generation ability.
- the liquid crystal alignment films of the substrates on both sides are irradiated with light, but the amount of light irradiation is different on both sides, and the amount of radical generation structure to be invalidated is different on both sides.
- one is a liquid crystal alignment film having a low radical generation capability and the other is a liquid crystal alignment film having a high radical generation capability so that the radical generation capability on both sides is different.
- the liquid crystal alignment film using the liquid crystal aligning agent of the same composition of the present invention has a predetermined liquid crystal alignment ability based on the functions of various side chains of the polymer described above.
- the amount of radicals generated by the ultraviolet rays during the PSA process differs for each substrate. Therefore, the reaction rate of the polymerizable compound is different at each substrate interface, and the liquid crystal alignment ability is also different.
- a wavelength of about 250 nm to 600 nm can be used, and the wavelength is preferably adjusted appropriately for the radical generating structure.
- the structure shown in the formula (I) since the structure shown in the formula (I) often has absorption up to about 250 nm to 420 nm, it is preferable to irradiate ultraviolet rays of 250 nm to 420 nm in accordance with the absorption wavelength. Although it is necessary to match the desired light irradiation amount with a desired panel characteristic, it is preferable to change the light irradiation suitably because long-time light irradiation leads to an increase in tact time in the element manufacturing process. Generally, it is considered that the radical generating structure can be deactivated more efficiently by performing light irradiation in accordance with the maximum absorption wavelength of the radical generating structure.
- the suitable light irradiation amount is preferably 500 mJ / cm 2 to 100 J / cm 2 , more preferably 1 J / cm 2 to 70 J. / Cm 2 , more preferably 1 J / cm 2 to 40 J / cm 2 .
- the portion close to the surface of the liquid crystal layer is adjacent. Since the alignment state is formed based on the liquid crystal alignment ability of the liquid crystal alignment film, the alignment states on both surfaces are different. Specifically, when the side chain is vertically aligned, an asymmetric liquid crystal layer having different pretilt angles on both sides can be realized.
- the liquid crystal display device manufacturing method of the present invention includes a liquid crystal layer forming step of forming a liquid crystal layer containing a liquid crystal compound between the pair of substrates. Accordingly, since the liquid crystal layer is formed by being sandwiched between a pair of liquid crystal alignment films having different radical generation capabilities, it is possible to form an asymmetric liquid crystal layer having different pretilt angles on both sides.
- Liquid crystal display device substrate> When a liquid crystal alignment film is formed using a liquid crystal aligning agent containing a specific polymer having a radical generating structure, the radical generating structure is used to generate radicals by light irradiation when forming the liquid crystal layer. Is normal.
- the liquid crystal alignment film of the substrate used on at least one side is irradiated with light to invalidate at least a part of the radical generating structure before providing the liquid crystal layer, thereby invalidating the radical generating ability.
- a substrate in which at least a part of the radical generating structure is invalidated is the substrate for a liquid crystal display element of the present invention.
- the liquid crystal display element assembly of the present invention uses the liquid crystal display element substrate of the present invention described above and a substrate in which a liquid crystal alignment film is formed using a liquid crystal aligning agent having the same composition, and a liquid crystal material that forms a liquid crystal layer therebetween. Is sandwiched between them. Moreover, it is a liquid crystal display element substrate according to the present invention, wherein a pair of substrates with different light irradiation amounts irradiated in advance is used, and a liquid crystal material to be a liquid crystal layer is sandwiched therebetween.
- the liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element of the present invention can produce a liquid crystal cell by a known method using the above-described substrate for a liquid crystal display element of the present invention, and thereby a pair of radical generating ability is different. Since the liquid crystal layer is formed between the liquid crystal alignment films, an asymmetric liquid crystal layer having different pretilt angles on both sides can be obtained.
- the liquid crystal display element include two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer.
- a vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film.
- the liquid crystal alignment agent of the present invention is applied to two substrates and baked to form a liquid crystal alignment film, and at least one of the radical generating structures is invalidated by irradiating light to at least one of the substrates.
- Two substrates are arranged so that liquid crystal alignment films having different radical generating capabilities of the radical generating structure face each other, and a liquid crystal layer composed of liquid crystals is sandwiched between the two substrates, that is, the liquid crystal alignment film
- a liquid crystal layer is provided in contact with each other, and is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.
- the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used to irradiate ultraviolet rays while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the photoreactive property of the polymer.
- the alignment of the liquid crystal is more efficiently fixed, and the liquid crystal display device is remarkably excellent in response speed.
- the substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed.
- a substrate on which a transparent electrode for driving liquid crystal As a specific example, the thing similar to the board
- a substrate provided with a conventional electrode pattern or protrusion pattern may be used.
- the liquid crystal aligning agent of the present invention since the liquid crystal aligning agent of the present invention is used, a line of 1 to 10 ⁇ m, for example, is formed on one side substrate. / Slit electrode pattern is formed, and it is possible to operate even in the structure where slit pattern or projection pattern is not formed on the counter substrate.
- the liquid crystal display element of this structure can simplify the process at the time of manufacture and has high transmittance. Can be obtained.
- a high-performance element such as a TFT type element
- an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
- a substrate In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
- the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type such as MLC-6608 or MLC-6609 manufactured by Merck & Co., Inc. Liquid crystal can be used.
- a liquid crystal containing a polymerizable compound represented by the following formula can be used.
- a known method can be used as a method of sandwiching the liquid crystal layer between two substrates. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
- a liquid crystal cell can also be produced by a method in which the other substrate is bonded to each other so as to be inside, and sealing is performed.
- the thickness of the spacer is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
- the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field.
- the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
- the irradiation amount of ultraviolet rays is, for example, 1 to 60 J / cm 2 , preferably 40 J / cm 2 or less, and the smaller the ultraviolet irradiation amount, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed.
- the production efficiency is improved by reducing the ultraviolet irradiation time, which is preferable.
- the polymerizable compound when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is stored by this polymer.
- the response speed of the obtained liquid crystal display element can be increased.
- a polyimide precursor having a side chain for vertically aligning liquid crystal and a photoreactive side chain when irradiated with ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and the polyimide precursor as an imide Since the photoreactive side chains of at least one polymer selected from the polyimide obtained by the reaction or the photoreactive side chains of the polymer react with the polymerizable compound, the liquid crystal display element obtained The response speed can be increased.
- Diamine compounds represented by the following formulas DA-4 to DA-7.
- the molecular weight measurement conditions of polyimide are as follows. Apparatus: Room-temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Columns manufactured by Shodex (KD-803, KD-805) Column temperature: 50 ° C.
- GPC Room-temperature gel permeation chromatography
- the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
- the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
- x is the proton peak integrated value derived from the NH group of the amic acid
- y is the peak integrated value of the reference proton
- ⁇ is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
- Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
- NMP (44.0 g) was added to the obtained polyimide powder (A) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (B) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (C) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
- 3AMP (1 mass% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (D) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours. NMP (10.0g) and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (D1) was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 10 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at room temperature for 5 hours.
- NMP (44.0 g) was added to the obtained polyimide powder (F) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
- 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at room temperature for 5 hours.
- Table 1 shows the compositions of the liquid crystal alignment agents A1, B1, and C1.
- Table 2 shows the compositions of the liquid crystal alignment agents D1, E1, F1, and G1.
- Example 1 Using the liquid crystal aligning agent (A2) obtained in Synthesis Example 4, a liquid crystal cell was prepared according to the procedure shown below.
- the liquid crystal aligning agent (A2) obtained in Synthesis Example 4 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m was formed, After drying for 90 seconds on the hot plate, baking was performed in a hot air circulation oven at 230 ° C. for 30 minutes to form a liquid crystal alignment film (A2-1) having a film thickness of 100 nm.
- a liquid crystal alignment film (A2-2) having a thickness of 100 nm was formed.
- each of the liquid crystal alignment films (A2-1, A2-2) is irradiated with 10 J / cm 2 of UV of a high-pressure mercury lamp with a wavelength of 325 nm or less cut to deactivate the radical generating structure existing in the alignment film.
- Pre-UV For the measurement of the irradiation amount, a UV-35 light receiver was connected to UV-M03A manufactured by ORC.
- a sealant (a thermosetting sealant XN-1500T manufactured by Mitsui Chemicals) was printed thereon.
- the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell.
- a negative type liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc.) containing a polymerizable compound for PSA was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.
- UV of a high pressure mercury lamp passed through a 365 nm band-pass filter was irradiated from the outside of the liquid crystal cell at 10 J / cm 2 (1st-UV). Thereafter, irradiation with a fluorescent UV lamp (FLR40SUV32 / A-1) for 30 minutes without applying a voltage to the liquid crystal cell (2nd-UV) to deactivate unreacted polymerizable compounds present in the liquid crystal cell. It was.
- a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector.
- the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols.
- a rectangular wave having a voltage of ⁇ 7 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained.
- a voltage of 0% and ⁇ 7 V was applied, the value of saturated luminance was taken as 100%, and the time taken for the luminance to change from 10% to 90% was taken as the response speed.
- a liquid crystal cell having an asymmetric pretilt angle was prepared in the same procedure as described above except that the liquid crystal alignment film (A2-1) was not irradiated with Pre-UV, and the response speed was measured. The results are shown in Table 3.
- Examples 2 to 3 A liquid crystal cell was produced in the same manner as in Example 1 except that 20-40 J / cm 2 was irradiated instead of 10 J / cm 2 irradiated as Pre-UV in Example 1, and the pretilt angle of the liquid crystal cell was Was measured.
- Example 4 The same operation as in Example 1 was performed except that 1 J / cm 2 of UV from a high-pressure mercury lamp passed through a band-pass filter with a wavelength of 313 nm was irradiated instead of 10 J / cm 2 irradiated as Pre-UV in Example 1. A liquid crystal cell was prepared, and the pretilt angle of the liquid crystal cell was measured.
- Examples 5 to 8 A liquid crystal cell was prepared in the same manner as in Examples 1 to 4 except that the alignment agent used was changed from the liquid crystal alignment agent (A2) to the liquid crystal alignment agent (B2), and the pretilt angle of the liquid crystal cell was measured. Went.
- An alignment film (B2-1) applied to the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m is formed is formed on the ITO film on which the electrode pattern is not formed.
- the alignment film applied on the surface was designated as (B2-2).
- Example 1 A liquid crystal cell was produced in the same manner as in Example 1 except that Pre-UV was not irradiated in Example 1, and the pretilt angle of the liquid crystal cell was measured.
- Example 2 A liquid crystal cell was prepared in the same manner as in Example 5 except that Pre-UV was not irradiated in Example 5, and the pretilt angle of the liquid crystal cell was measured.
- Example 9 to 12 A liquid crystal cell was produced in the same manner as in Examples 1 to 4 except that the liquid crystal aligning agent (A2) was changed to the liquid crystal aligning agent (D2), and the pretilt angle of the liquid crystal cell was measured.
- An alignment film (D2-1) applied on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m is formed is formed on the ITO film on which the electrode pattern is not formed.
- the alignment film applied to the surface was designated as (D2-2).
- Example 13 to 16 A liquid crystal cell was produced in the same manner as in Examples 1 to 4 except that the liquid crystal aligning agent (A2) was changed to the liquid crystal aligning agent (E2), and the pretilt angle of the liquid crystal cell was measured.
- An alignment film (E2-1) applied on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m is formed is formed on the ITO film on which the electrode pattern is not formed.
- the alignment film applied to the surface was designated as (E2-2).
- Example 3 A liquid crystal cell was prepared in the same manner as in Example 9 except that Pre-UV was not irradiated in Example 9, and the pretilt angle of the liquid crystal cell was measured.
- Example 4 A liquid crystal cell was prepared in the same manner as in Example 13 except that Pre-UV was not irradiated in Example 13, and the pretilt angle of the liquid crystal cell was measured.
- the substrate is irradiated with Pre-UV to deactivate the radical generating structure in the alignment film, and the pretilt angle is less likely to be exhibited during the PSA treatment (1st-UV). It was confirmed that it would be too late.
- Pre-UV irradiation since Pre-UV irradiation is not performed, a radical generating structure remains in the alignment film, and a sufficient pretilt can be obtained even when a wavelength of 365 nm with relatively weak energy is used during PSA treatment (1st-UV). It can be seen that the angle and response speed can be obtained.
- the pretilt angle on the side irradiated with Pre-UV should be the pretilt angle described in the examples in Table 3 and Table 5, but the Pre-UV It is considered that the pretilt angle described in the comparative examples in Table 3 and Table 5 is the non-irradiated side (ITO electrode pattern side in this example).
- a liquid crystal display element having an asymmetric pretilt angle can be obtained using one type of liquid crystal aligning agent without impairing the response speed required for the liquid crystal display element. It becomes possible to create.
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Abstract
Description
一対の基板の表面のそれぞれに、光照射によりラジカルを発生するラジカル発生構造を有する重合体を含有する同一組成の液晶配向剤で液晶配向膜を形成する液晶配向膜形成工程と、前記一対の基板の少なくとも一方に光照射を施して両者の液晶配向膜への光照射量を異なる状態とする液晶配向膜光照射工程と、その後、前記一対の基板の間に、液晶化合物を含む液晶層を形成する液晶層形成工程と、を含むことを特徴とする液晶表示素子の製造方法。 That is, the present invention has the following gist.
A liquid crystal alignment film forming step of forming a liquid crystal alignment film with a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation on each of the surfaces of the pair of substrates; and the pair of substrates A liquid crystal alignment film light irradiating step in which at least one of the liquid crystal is irradiated with light to change the amount of light applied to the liquid crystal alignment films in different states, and then a liquid crystal layer containing a liquid crystal compound is formed between the pair of substrates And a liquid crystal layer forming step.
<液晶表示素子の製造方法>
本発明の液晶表示素子の製造方法は、一対の基板の表面のそれぞれに、光照射によりラジカルを発生するラジカル発生構造を有する重合体を含有する液晶配向剤で液晶配向膜を形成する液晶配向膜形成工程と、前記一対の基板の少なくとも一方に光照射を施して両者の液晶配向膜への光照射量を異なる状態とする液晶配向膜光照射工程と、その後、前記一対の基板の間に、液晶化合物を含む液晶層を形成する液晶層形成工程と、を含むことを特徴とする。 The present invention will be described in detail below.
<Method for manufacturing liquid crystal display element>
The method for producing a liquid crystal display element according to the present invention includes forming a liquid crystal alignment film on each of the surfaces of a pair of substrates with a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation. Between the forming step, the liquid crystal alignment film light irradiating step in which at least one of the pair of substrates is irradiated with light and the amount of light irradiation to the liquid crystal alignment film is different, and then between the pair of substrates, And a liquid crystal layer forming step of forming a liquid crystal layer containing a liquid crystal compound.
本発明で用いる液晶配向剤に含有されるラジカル発生構造を有する重合体について、具体例を挙げて説明するが、以下の具体例に限定されるものではない。
本発明で用いられるラジカル発生構造を有する重合体(以下、特定重合体ともいう)は、光照射、例えば、紫外線照射によりラジカルが発生する部位を側鎖として有している。特定重合体としては、紫外線照射によりラジカルが発生するラジカル発生構造として、例えば、下記式(I)で表す側鎖構造を含む重合体を挙げることができる。 <Polymer having radical generating structure>
Although the polymer which has the radical generating structure contained in the liquid crystal aligning agent used by this invention is demonstrated with a specific example, it is not limited to the following specific examples.
The polymer having a radical generating structure used in the present invention (hereinafter also referred to as a specific polymer) has a site where a radical is generated by light irradiation, for example, ultraviolet irradiation, as a side chain. Examples of the specific polymer include a polymer having a side chain structure represented by the following formula (I) as a radical generating structure in which radicals are generated by ultraviolet irradiation.
Qがアミノ誘導体の場合、ポリイミドの前駆体であるポリアミック酸の重合の際に、発生するカルボン酸基とアミノ基が塩を形成するなどの不具合が生じる可能性があるため、より好ましくはヒドロキシル基又はアルコキシル基である。 In the formula (I), Q is preferably an electron donating organic group, and the above group is preferable.
In the case where Q is an amino derivative, there is a possibility that in the polymerization of polyamic acid which is a precursor of polyimide, there is a possibility that a carboxylic acid group generated and an amino group form a salt. Or it is an alkoxyl group.
本発明で用いる液晶配向剤に含有される特定重合体は、上記式(I)や(II)で表されるラジカル発生構造を有する側鎖(以下、特定側鎖ともいう)以外に、液晶を垂直に配向させる側鎖を有するのが好ましい。液晶を垂直に配向させる側鎖は、下記式[III-1]又は式[III-2]で表される。なお、上述した特定重合体とは別に、液晶を垂直に配向させる側鎖を有する重合体を液晶配向剤に配合してもよい。 <Side chains that align liquid crystal vertically>
The specific polymer contained in the liquid crystal aligning agent used in the present invention contains a liquid crystal in addition to the side chain having a radical generating structure represented by the above formula (I) or (II) (hereinafter also referred to as a specific side chain). It is preferred to have side chains that are oriented vertically. The side chain for vertically aligning the liquid crystal is represented by the following formula [III-1] or [III-2]. In addition, you may mix | blend the polymer which has a side chain which aligns a liquid crystal perpendicularly with a liquid crystal aligning agent separately from the specific polymer mentioned above.
本発明の液晶配向剤に含有される特定重合体は、例えば、上記式(I)や(II)で表されるラジカル発生構造を有する側鎖以外に、光反応性の側鎖を有していてもよい。光反応性の側鎖は、紫外線(UV)等の光の照射によって反応し、共有結合を形成し得る官能基(以下、光反応性基ともいう。)を有する。なお、上述した特定重合体とは別に、光反応性の側鎖を有する重合体を液晶配向剤に配合してもよい。 <Photoreactive side chain>
The specific polymer contained in the liquid crystal aligning agent of the present invention has, for example, a photoreactive side chain in addition to the side chain having a radical generating structure represented by the above formula (I) or (II). May be. The photoreactive side chain has a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond. In addition, you may mix | blend the polymer which has a photoreactive side chain with a liquid crystal aligning agent separately from the specific polymer mentioned above.
本発明で使用される、ラジカル発生構造を有する重合体は特に限定されないが、ポリイミド系、ポリ(メタ)アクリレート系、ポリシロキサン系の重合体などを好適に用いることができる。以下、本明細書ではポリイミド構造に限って詳細に説明するが、その他の重合体に関しても公知の技術(ラジカル重合や、ゾル・ゲル法など)を用いて重合体を合成することができる。 <Polymer forming liquid crystal aligning agent>
The polymer having a radical generating structure used in the present invention is not particularly limited, but a polyimide-based, poly (meth) acrylate-based, polysiloxane-based polymer, or the like can be preferably used. Hereinafter, although only the polyimide structure will be described in detail in the present specification, other polymers can be synthesized using known techniques (radical polymerization, sol-gel method, etc.).
ラジカル発生構造を側鎖に有するポリイミドは例えば下記特定ジアミン1~3のようなジアミンのうち1種類以上を使用することで調製することができる。 The method similar to the above-mentioned is mentioned also about the method of manufacturing the polyimide precursor which has the side chain which orientates a liquid crystal vertically in addition to a specific side chain, and the polyimide which imidated this polyimide precursor. The preferable method is also preferably a method of polymerizing a diamine compound containing a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride or a tetracarboxylic acid diester.
A polyimide having a radical generating structure in the side chain can be prepared by using one or more of diamines such as the following specific diamines 1 to 3, for example.
本発明の液晶配向剤を形成する上記の重合体の製造に使用されるジアミン(以下、特定ジアミンともいう。)は、紫外線照射により分解しラジカルが発生するラジカル発生構造を有する部位を側鎖として有し、下記式(1)で表される。 <Specific diamine 1>
The diamine (hereinafter also referred to as a specific diamine) used in the production of the above-mentioned polymer forming the liquid crystal aligning agent of the present invention has, as a side chain, a site having a radical generating structure that is decomposed by ultraviolet irradiation to generate radicals. And represented by the following formula (1).
本発明において、特定ジアミン1は、各ステップを経てジニトロ体、或いは、還元工程で除去可能な保護基を施したアミノ基を有するモノニトロ体、或いは、ジアミンを合成し、通常用いる還元反応にてニトロ基をアミノ基に変換あるいは保護基を脱保護することにより得ることができる。 <Synthesis of specific diamine 1>
In the present invention, the specific diamine 1 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction that is usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.
本発明の特定ジアミン2は、前記式(II)で表される有機基を側鎖として有するジアミン、すなわち下記式(VI)で表すことができる。 <Specific diamine 2>
The specific diamine 2 of the present invention can be represented by a diamine having an organic group represented by the formula (II) as a side chain, that is, the following formula (VI).
本発明において、特定ジアミン2は、各ステップを経てジニトロ体、或いは、還元工程で除去可能な保護基を施したアミノ基を有するモノニトロ体、或いは、ジアミンを合成し、通常用いる還元反応にてニトロ基をアミノ基に変換あるいは保護基を脱保護することにより得ることができる。 <Synthesis of specific diamine 2>
In the present invention, the specific diamine 2 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.
本発明の特定ジアミン3は、下記の式(11)で表される。 <Specific diamine 3>
The specific diamine 3 of the present invention is represented by the following formula (11).
上記式(11)において、X11、X12、X13、X14のそれぞれの定義は、上記したとおりである。なかでも、X11は、合成の容易性の観点から、-O-又は-CH2O-が好ましい。また、X12 、X13は、高い垂直配向性の観点から、シクロヘキサン環が好ましい。また、X14は、原料の入手性の観点から、炭素数3~7のアルキル基が好ましい。 The specific diamine 3 has a photoreactive structure in which radicals are generated by ultraviolet irradiation in a single molecular structure and a structure in which liquid crystals are aligned vertically. That is, the photoreactive structure is a 4-chromanone structure bonded to the phenylenediamine skeleton via X 11 , and the structure for vertically aligning the liquid crystal is bonded to 4-chromanone —X 2 —X 3 -X 4 structure.
In the above formula (11), each definition of X 11 , X 12 , X 13 and X 14 is as described above. Among these, X 11 is preferably —O— or —CH 2 O— from the viewpoint of ease of synthesis. X 12 and X 13 are preferably cyclohexane rings from the viewpoint of high vertical alignment. X 14 is preferably an alkyl group having 3 to 7 carbon atoms from the viewpoint of availability of raw materials.
本発明における特定ジアミン3の合成方法は特に限定されるものではないが、例えば、以下に示す方法によって合成することができる。
すなわち、特定ジアミン3に対応する下記一般式(12)で表されるジニトロ化合物(上記式中、X11~X14は式(11)と同じ)を合成し、さらにニトロ基を還元しアミノ基に変換することで得られる。 <Production of specific diamine 3>
Although the synthesis | combining method of the specific diamine 3 in this invention is not specifically limited, For example, it is compoundable by the method shown below.
That is, a dinitro compound represented by the following general formula (12) corresponding to the specific diamine 3 (wherein X 11 to X 14 are the same as those in the formula (11)) is synthesized, and the nitro group is further reduced to form an amino group. Obtained by converting to.
一般式(12)で表されるジニトロ化合物の合成方法は特に限定されず、任意の方法により合成することができるが、その具体例としては、例えば、以下のスキーム(13)に示されるような方法で合成することができる。 The method for reducing the dinitro compound is not particularly limited, and usually palladium-carbon, platinum-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, platinum carbon sulfide, etc. are used as catalysts. , Ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohol-based solvents, hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, and the like.
The method for synthesizing the dinitro compound represented by the general formula (12) is not particularly limited and can be synthesized by any method. Specific examples thereof include those shown in the following scheme (13). It can be synthesized by the method.
上記ジニトロベンゼン化合物Aにおいて、X15は、塩素、臭素、ヨウ素、フッ素、-OH、-COOH、-COOCl、-(CH2)aOH(aは1~15の整数である)のいずれかからなり、フェノール化合物BにおけるX12~X14は式1と同様である。なお、ここに示した化合物は一例であり、特に限定されるものではない。 In scheme (13), by reacting dinitro compound A and hydroxyl group-containing compound B in an organic solvent (for example, ethyl acetate, toluene, tetrahydrofuran, dioxane, chloroform, dichloromethane, DMF, DMSO, etc.) in the presence of an alkali. Can be synthesized. As the alkali, for example, an organic amine such as triethylamine, or an inorganic salt such as potassium carbonate or sodium hydroxide can be used.
In the dinitrobenzene compound A, X 15 is any one of chlorine, bromine, iodine, fluorine, —OH, —COOH, —COOCl, — (CH 2 ) a OH (a is an integer of 1 to 15). Thus, X 12 to X 14 in the phenol compound B are the same as those in the formula 1. In addition, the compound shown here is an example and is not specifically limited.
液晶を垂直に配向させる側鎖をポリイミド系重合体に導入する方法は、特定側鎖構造を有するジアミンをジアミン成分の一部に用いることが好ましい。 <Diamines with side chains that align liquid crystals vertically>
In the method of introducing a side chain for vertically aligning liquid crystal into the polyimide polymer, it is preferable to use a diamine having a specific side chain structure as a part of the diamine component.
光反応性を有する側鎖をポリイミド系重合体に導入する方法は、特定側鎖構造を有するジアミンをジアミン成分の一部に用いることが好ましい。光反応性の側鎖を有するジアミンとしては、式[VIII]、又は式[IX]で表される側鎖を有するジアミンである。 <Diamine containing photoreactive side chain>
As a method for introducing a side chain having photoreactivity into a polyimide polymer, it is preferable to use a diamine having a specific side chain structure as a part of the diamine component. The diamine having a photoreactive side chain is a diamine having a side chain represented by Formula [VIII] or Formula [IX].
本発明の液晶配向剤は、(A)成分として、液晶を垂直に配向させる側鎖と、上記式(I)で表されるラジカル発生構造を有する側鎖とを有するポリイミド前駆体、及び、このポリイミド前駆体をイミド化して得られるポリイミドから選択される少なくとも一種の重合体と、(B)成分として、下記式(B-1)~(B-5)から選択される少なくとも一種のジアミンを含有するジアミン成分を原料として得られるポリイミド前駆体、及び、このポリイミド前駆体をイミド化して得られるポリイミドから選択される重合体、または、下記式(3)及び(4)から選択される少なくとも一種のテトラカルボン酸二無水物を含有するテトラカルボン酸二無水物成分と、ジアミンの反応により得られるポリイミド前駆体、及び、このポリイミド前駆体をイミド化して得られるポリイミドから選択される重合体を含有することができる。 <(B) component>
The liquid crystal aligning agent of the present invention comprises, as component (A), a polyimide precursor having a side chain for vertically aligning liquid crystals and a side chain having a radical generating structure represented by the above formula (I), and this Contains at least one polymer selected from polyimides obtained by imidizing a polyimide precursor and at least one diamine selected from the following formulas (B-1) to (B-5) as component (B) A polyimide precursor obtained using a diamine component as a raw material, a polymer selected from a polyimide obtained by imidizing this polyimide precursor, or at least one selected from the following formulas (3) and (4) A polyimide precursor obtained by reaction of a tetracarboxylic dianhydride component containing tetracarboxylic dianhydride and a diamine, and the polyimide precursor The can contain polymer selected from the resulting polyimide by imidization.
なお、ポリイミド前駆体及び/又は、ポリイミドを製造する場合、本発明の効果を損わない限りにおいて、上記したジアミン以外のその他のジアミンをジアミン成分として併用することができる。具体的には、例えば、p-フェニレンジアミン、2,3,5,6-テトラメチル-p-フェニレンジアミン、2,5-ジメチル-p-フェニレンジアミン、m-フェニレンジアミン、2,4-ジメチル-m-フェニレンジアミン、2,5-ジアミノトルエン、2,6-ジアミノトルエン、2,5-ジアミノフェノール、2,4-ジアミノフェノール、3,5-ジアミノフェノール、3,5-ジアミノベンジルアルコール、2,4-ジアミノベンジルアルコール、4,6-ジアミノレゾルシノール、4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、3,3’-ジヒドロキシ-4,4’-ジアミノビフェニル、3,3’-ジカルボキシ-4,4’-ジアミノビフェニル、3,3’-ジフルオロ-4,4’-ビフェニル、3,3’-トリフルオロメチル-4,4’-ジアミノビフェニル、3,4’-ジアミノビフェニル、3,3’-ジアミノビフェニル、2,2’-ジアミノビフェニル、2,3’-ジアミノビフェニル、4,4’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、2,2’-ジアミノジフェニルメタン、2,3’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、2,2’-ジアミノジフェニルエーテル、2,3’-ジアミノジフェニルエーテル、4,4’-スルホニルジアニリン、3,3’-スルホニルジアニリン、ビス(4-アミノフェニル)シラン、ビス(3-アミノフェニル)シラン、ジメチル-ビス(4-アミノフェニル)シラン、ジメチル-ビス(3-アミノフェニル)シラン、4,4’-チオジアニリン、3,3’-チオジアニリン、4,4’-ジアミノジフェニルアミン、3,3’-ジアミノジフェニルアミン、3,4’-ジアミノジフェニルアミン、2,2’-ジアミノジフェニルアミン、2,3’-ジアミノジフェニルアミン、N-メチル(4,4’-ジアミノジフェニル)アミン、N-メチル(3,3’-ジアミノジフェニル)アミン、N-メチル(3,4’-ジアミノジフェニル)アミン、N-メチル(2,2’-ジアミノジフェニル)アミン、N-メチル(2,3’-ジアミノジフェニル)アミン、4,4’-ジアミノベンゾフェノン、3,3’-ジアミノベンゾフェノン、3,4’-ジアミノベンゾフェノン、1,4-ジアミノナフタレン、2,2’-ジアミノベンゾフェノン、2,3’-ジアミノベンゾフェノン、1,5-ジアミノナフタレン、1,6-ジアミノナフタレン、1,7-ジアミノナフタレン、1,8-ジアミノナフタレン、2,5-ジアミノナフタレン、2,6-ジアミノナフタレン、2,7-ジアミノナフタレン、2,8-ジアミノナフタレン、1,2-ビス(4-アミノフェニル)エタン、1,2-ビス(3-アミノフェニル)エタン、1,3-ビス(4-アミノフェニル)プロパン、1,3-ビス(3-アミノフェニル)プロパン、1,4-ビス(4-アミノフェニル)ブタン、1,4-ビス(3-アミノフェニル)ブタン、ビス(3,5-ジエチル-4-アミノフェニル)メタン、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、1,4-ビス(4-アミノベンジル)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、4,4’-[1,4-フェニレンビス(メチレン)]ジアニリン、4,4’-[1,3-フェニレンビス(メチレン)]ジアニリン、3,4’-[1,4-フェニレンビス(メチレン)]ジアニリン、3,4’-[1,3-フェニレンビス(メチレン)]ジアニリン、3,3’-[1,4-フェニレンビス(メチレン)]ジアニリン、3,3’-[1,3-フェニレンビス(メチレン)]ジアニリン、1,4-フェニレンビス[(4-アミノフェニル)メタノン]、1,4-フェニレンビス[(3-アミノフェニル)メタノン]、1,3-フェニレンビス[(4-アミノフェニル)メタノン]、1,3-フェニレンビス[(3-アミノフェニル)メタノン]、1,4-フェニレンビス(4-アミノベンゾエート)、1,4-フェニレンビス(3-アミノベンゾエート)、1,3-フェニレンビス(4-アミノベンゾエート)、1,3-フェニレンビス(3-アミノベンゾエート)、ビス(4-アミノフェニル)テレフタレート、ビス(3-アミノフェニル)テレフタレート、ビス(4-アミノフェニル)イソフタレート、ビス(3-アミノフェニル)イソフタレート、N,N’-(1,4-フェニレン)ビス(4-アミノベンズアミド)、N,N’-(1,3-フェニレン)ビス(4-アミノベンズアミド)、N,N’-(1,4-フェニレン)ビス(3-アミノベンズアミド)、N,N’-(1,3-フェニレン)ビス(3-アミノベンズアミド)、N,N’-ビス(4-アミノフェニル)テレフタルアミド、N,N’-ビス(3-アミノフェニル)テレフタルアミド、N,N’-ビス(4-アミノフェニル)イソフタルアミド、N,N’-ビス(3-アミノフェニル)イソフタルアミド、9,10-ビス(4-アミノフェニル)アントラセン、4,4’-ビス(4-アミノフェノキシ)ジフェニルスルホン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2’-ビス(4-アミノフェニル)ヘキサフルオロプロパン、2,2’-ビス(3-アミノフェニル)ヘキサフルオロプロパン、2,2’-ビス(3-アミノ-4-メチルフェニル)ヘキサフルオロプロパン、2,2’-ビス(4-アミノフェニル)プロパン、2,2’-ビス(3-アミノフェニル)プロパン、2,2’-ビス(3-アミノ-4-メチルフェニル)プロパン、3,5-ジアミノ安息香酸、2,5-ジアミノ安息香酸、1,3-ビス(4-アミノフェノキシ)プロパン、1,3-ビス(3-アミノフェノキシ)プロパン、1,4-ビス(4-アミノフェノキシ)ブタン、1,4-ビス(3-アミノフェノキシ)ブタン、1,5-ビス(4-アミノフェノキシ)ペンタン、1,5-ビス(3-アミノフェノキシ)ペンタン、1,6-ビス(4-アミノフェノキシ)へキサン、1,6-ビス(3-アミノフェノキシ)へキサン、1,7-ビス(4-アミノフェノキシ)ヘプタン、1,7-(3-アミノフェノキシ)ヘプタン、1,8-ビス(4-アミノフェノキシ)オクタン、1,8-ビス(3-アミノフェノキシ)オクタン、1,9-ビス(4-アミノフェノキシ)ノナン、1,9-ビス(3-アミノフェノキシ)ノナン、1,10-(4-アミノフェノキシ)デカン、1,10-(3-アミノフェノキシ)デカン、1,11-(4-アミノフェノキシ)ウンデカン、1,11-(3-アミノフェノキシ)ウンデカン、1,12-(4-アミノフェノキシ)ドデカン、1,12-(3-アミノフェノキシ)ドデカンなどの芳香族ジアミン、ビス(4-アミノシクロヘキシル)メタン、ビス(4-アミノ-3-メチルシクロヘキシル)メタンなどの脂環式ジアミン、1,3-ジアミノプロパン、1,4-ジアミノブタン、1,5-ジアミノペンタン、1,6-ジアミノへキサン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、1,11-ジアミノウンデカン、1,12-ジアミノドデカンなどの脂肪族ジアミンが挙げられる。 <Other diamines>
In addition, when manufacturing a polyimide precursor and / or a polyimide, unless the effect of this invention is impaired, other diamines other than the above-mentioned diamine can be used together. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 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′-diaminobiph Nyl, 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2 , 2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3 '-Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'- Sulfonyl dianiline, 3,3′-sulfonyl dianiline, bis (4-aminophenyl) si Lan, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4 '-Diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine N-methyl (3,3′-diaminodiphenyl) amine, N-methyl (3,4′-diaminodiphenyl) amine, N-methyl (2,2′-diaminodiphenyl) amine, N-methyl (2,3 '-Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4' Diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8 -Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4 -Bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4 -Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylene)] dianiline, 4,4'-[1,3-phenylene Bis (methylene)] dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,3 ′-[1 , 4-phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1 4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4- Phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis ( 4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis ( 4-aminobenzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N , N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) ) Terephthalamide, N, N′-bis (3-aminophenyl) terephthalamide, N, N′-bis (4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9 , 10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenyl sulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 ′ -Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) Nyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-amino) Phenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) ) Pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, , 9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, , 11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, etc. Alicyclic diamines such as diamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3 -Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Examples thereof include aliphatic diamines such as diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.
上記のジアミン成分と反応させるテトラカルボン酸二無水物成分は特に限定されない。具体的には、ピロメリット酸、2,3,6,7-ナフタレンテトラカルボン酸、1,2,5,6-ナフタレンテトラカルボン酸、1,4,5,8-ナフタレンテトラカルボン酸、2,3,6,7-アントラセンテトラカルボン酸、1,2,5,6-アントラセンテトラカルボン酸、3,3’,4,4’-ビフェニルテトラカルボン酸、2,3,3’,4-ビフェニルテトラカルボン酸、ビス(3,4-ジカルボキシフェニル)エーテル、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、ビス(3,4-ジカルボキシフェニル)スルホン、ビス(3,4-ジカルボキシフェニル)メタン、2,2-ビス(3,4-ジカルボキシフェニル)プロパン、1,1,1,3,3,3-ヘキサフルオロ-2,2-ビス(3,4-ジカルボキシフェニル)プロパン、ビス(3,4-ジカルボキシフェニル)ジメチルシラン、ビス(3,4-ジカルボキシフェニル)ジフェニルシラン、2,3,4,5-ピリジンテトラカルボン酸、2,6-ビス(3,4-ジカルボキシフェニル)ピリジン、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸、3,4,9,10-ペリレンテトラカルボン酸、1,3-ジフェニル-1,2,3,4-シクロブタンテトラカルボン酸、オキシジフタルテトラカルボン酸、1,2,3,4-シクロブタンテトラカルボン酸、1,2,3,4-シクロペンタンテトラカルボン酸、1,2,4,5-シクロヘキサンテトラカルボン酸、1,2,3,4-テトラメチル-1,2,3,4-シクロブタンテトラカルボン酸、1,2-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸、1,3-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸、1,2,3,4-シクロヘプタンテトラカルボン酸、2,3,4,5-テトラヒドロフランテトラカルボン酸、3,4-ジカルボキシ-1-シクロへキシルコハク酸、2,3,5-トリカルボキシシクロペンチル酢酸、3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸、ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸、ビシクロ[4,3,0]ノナン-2,4,7,9-テトラカルボン酸、ビシクロ[4,4,0]デカン-2,4,7,9-テトラカルボン酸、ビシクロ[4,4,0]デカン-2,4,8,10-テトラカルボン酸、トリシクロ[6.3.0.0<2,6>]ウンデカン-3,5,9,11-テトラカルボン酸、1,2,3,4-ブタンテトラカルボン酸、4-(2,5-ジオキソテトラヒドロフラン-3-イル)-1,2,3,4-テトラヒドリナフタレン-1,2-ジカルボン酸、ビシクロ[2,2,2]オクト-7-エン-2,3,5,6-テトラカルボン酸、5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロへキサン-1,2-ジカルボン酸、テトラシクロ[6,2,1,1,0,2,7]ドデカ-4,5,9,10-テトラカルボン酸、3,5,6-トリカルボキシノルボルナン-2:3,5:6ジカルボン酸、1,2,4,5-シクロヘキサンテトラカルボン酸等が挙げられる。勿論、テトラカルボン酸二無水物も、液晶配向膜にした際の液晶配向性、電圧保持特性、蓄積電荷などの特性に応じて、1種類又は2種類以上併用してもよい。 <Tetracarboxylic dianhydride>
The tetracarboxylic dianhydride component to be reacted with the diamine component 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-biphenyltetra Carboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxy) Phenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) Lopan, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4) -Dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4- Cyclobutanetetracarboxylic acid, oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic Acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobut Tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0 ] Decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6 >] Undecane 3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetra Hydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3 -Methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5, Examples thereof include 6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid. Of course, tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
本発明の液晶配向剤には、必要に応じ、2つ以上の末端に光重合又は光架橋する基を有する重合性化合物を含有しても良い。かかる重合性化合物は、光重合又は光架橋する基を有する末端を二つ以上持っている化合物である。ここで、光重合する基を有する重合性化合物とは、光を照射することにより重合を生じさせる官能基を有する化合物である。また、光架橋する基を有する化合物とは、光を照射することにより、重合性化合物の重合体や、ポリイミド前駆体、及び、このポリイミド前駆体をイミド化して得られるポリイミドから選択される少なくとも一種の重合体と反応してこれらと架橋することができる官能基を有する化合物である。なお、光架橋する基を有する化合物は、光架橋する基を有する化合物同士でも反応する。 <Polymerizable compound>
The liquid crystal aligning agent of the present invention may contain a polymerizable compound having a photopolymerizable or photocrosslinkable group at two or more terminals as required. Such a polymerizable compound is a compound having two or more terminals having a group that undergoes photopolymerization or photocrosslinking. Here, the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light. The compound having a photocrosslinking group is at least one selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor by irradiating light. It is a compound having a functional group capable of reacting with the polymer and crosslinking with these polymers. A compound having a photocrosslinkable group also reacts with a compound having a photocrosslinkable group.
ジアミン成分とテトラカルボン酸二無水物との反応により、ポリアミック酸を得るにあたっては、公知の合成手法を用いることができる。一般的には、ジアミン成分とテトラカルボン酸二無水物成分とを有機溶媒中で反応させる方法である。ジアミン成分とテトラカボン酸二無水物との反応は、有機溶媒中で比較的容易に進行し、かつ副生成物が発生しない点で有利である。 <Synthesis of polyamic acid>
In obtaining a polyamic acid by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent. The reaction of the diamine component and tetracarbonic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
本発明の剤はラジカル発生構造を側鎖に有する少なくとも1つの特定重合体を含有するが、かかる特定重合体の含有量は0.5~20質量%が好ましく、より好ましくは0.5~15質量%、特に好ましくは1~10質量%である。 <Liquid crystal aligning agent>
The agent of the present invention contains at least one specific polymer having a radical generating structure in the side chain, and the content of the specific polymer is preferably 0.5 to 20% by mass, more preferably 0.5 to 15%. % By mass, particularly preferably 1 to 10% by mass.
本発明液晶表示素子の製造方法は、まず、一対の基板の表面のそれぞれに、上述したように液晶配向膜を形成する液晶配向膜形成工程を実施する。 <Method for manufacturing liquid crystal display element>
In the method for producing a liquid crystal display element of the present invention, first, a liquid crystal alignment film forming step for forming a liquid crystal alignment film as described above is performed on each of the surfaces of a pair of substrates.
このため各基板界面で重合性化合物の反応速度が異なり、液晶配向能も異なるものとなる。 Thus, the liquid crystal alignment film using the liquid crystal aligning agent of the same composition of the present invention has a predetermined liquid crystal alignment ability based on the functions of various side chains of the polymer described above. By performing a process with different generation capacities, the amount of radicals generated by the ultraviolet rays during the PSA process differs for each substrate.
Therefore, the reaction rate of the polymerizable compound is different at each substrate interface, and the liquid crystal alignment ability is also different.
ラジカル発生構造を有する特定重合体を含む液晶配向剤を用いて液晶配向膜を形成した場合、ラジカル発生構造は、液晶層を形成する際に光照射によりラジカルを発生するようにして使用されるのが通常である。 <Liquid crystal display device substrate>
When a liquid crystal alignment film is formed using a liquid crystal aligning agent containing a specific polymer having a radical generating structure, the radical generating structure is used to generate radicals by light irradiation when forming the liquid crystal layer. Is normal.
本発明の液晶表示素子組立体は、上述した本発明の液晶表示素子用基板と、同一組成の液晶配向剤を用いて液晶配向膜を形成した基板とを用い、間に液晶層となる液晶原料を挟持したものである。また、本発明の液晶表示素子用基板であって、予め照射した光照射量が異なる一対の基板を用い、間に液晶層となる液晶原料を挟持したものである。 <Liquid crystal display element assembly>
The liquid crystal display element assembly of the present invention uses the liquid crystal display element substrate of the present invention described above and a substrate in which a liquid crystal alignment film is formed using a liquid crystal aligning agent having the same composition, and a liquid crystal material that forms a liquid crystal layer therebetween. Is sandwiched between them. Moreover, it is a liquid crystal display element substrate according to the present invention, wherein a pair of substrates with different light irradiation amounts irradiated in advance is used, and a liquid crystal material to be a liquid crystal layer is sandwiched therebetween.
本発明の液晶表示素子の製造方法で製造された液晶表示素子は、上述した本発明の液晶表示素子用基板を用い、公知の方法で液晶セルを作製でき、これにより、ラジカル発生能力が異なる一対の液晶配向膜で挟まれて液晶層が形成されるので、両側でプレチルト角が異なる非対称の液晶層とすることができる。 <Liquid crystal display element>
The liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element of the present invention can produce a liquid crystal cell by a known method using the above-described substrate for a liquid crystal display element of the present invention, and thereby a pair of radical generating ability is different. Since the liquid crystal layer is formed between the liquid crystal alignment films, an asymmetric liquid crystal layer having different pretilt angles on both sides can be obtained.
下記液晶配向剤の調製で用いた略号は以下のとおりである。
(酸二無水物)
BODA:ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸二無水物
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
PMDA:ピロメリット酸二無水物 <Synthesis of liquid crystal alignment agent>
The abbreviations used in the preparation of the following liquid crystal aligning agents are as follows.
(Acid dianhydride)
BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride object
DBA:3,5-ジアミノ安息香酸
3AMPDA:3,5-ジアミノ-N-(ピリジン-3-イルメチル)ベンズアミド
TCA:2,3,5‐トリカルボキシシクロペンチル酢酸二無水物
DSDA:3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物 (Diamine)
DBA: 3,5-diaminobenzoic acid 3AMPDA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide TCA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride DSDA: 3,3 ′, 4 , 4'-Diphenylsulfonetetracarboxylic dianhydride
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ <Solvent>
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve
3AMP:3-ピコリルアミン <Additives>
3AMP: 3-picolylamine
装置:センシュー科学社製 常温ゲル浸透クロマトグラフィー(GPC)装置(SSC-7200)、カラム:Shodex社製カラム(KD-803、KD-805)カラム温度:50℃溶離液:N,N’-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)流速:1.0ml/分検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(分子量約9000,000、150,000、100,000、30,000)、および、ポリマーラボラトリー社製 ポリエチレングリコール(分子量 約12,000、4,000、1,000)。 Moreover, the molecular weight measurement conditions of polyimide are as follows.
Apparatus: Room-temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Columns manufactured by Shodex (KD-803, KD-805) Column temperature: 50 ° C. Eluent: N, N′-dimethyl Formamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L) Flow rate: 1.0 ml / standard curve preparation standard sample: Tosoh TSK standard polyethylene oxide (molecular weight about 9,000,150,000, 100,000, 30,000) and polymer laboratory polyethylene glycol ( Molecular weight about 12,000, 4,000, 1,000).
イミド化率(%)=(1-α・x/y)×100 Moreover, the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
Imidization rate (%) = (1−α · x / y) × 100
BODA(3.75g、15.0mmol)、DA-1(4.96g、15.0mmol)、DA-2(5.71g、15.0mmol)をNMP(51.9g)中で溶解し、60℃で5時間反応させたのち、CBDA(2.88g、14.7mmol)とNMP(17.3g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。 (Synthesis Example 1)
BODA (3.75 g, 15.0 mmol), DA-1 (4.96 g, 15.0 mmol), DA-2 (5.71 g, 15.0 mmol) were dissolved in NMP (51.9 g) and dissolved at 60 ° C. Then, CBDA (2.88 g, 14.7 mmol) and NMP (17.3 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
BODA(3.75、15.0mmol)、DA-3(3.91g、9.0mmol)、DBA(0.91g、6.0mmol)、DA-1(4.96g、15.0mmol)をNMP(49.3g)中で溶解し、60℃で5時間反応させたのち、CBDA(2.88g、14.7mmol)とNMP(16.4g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。 (Synthesis Example 2)
BODA (3.75, 15.0 mmol), DA-3 (3.91 g, 9.0 mmol), DBA (0.91 g, 6.0 mmol), DA-1 (4.96 g, 15.0 mmol) were mixed with NMP ( 49.3 g), and after reacting at 60 ° C. for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (16.4 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained.
BODA(1.50g、6.0mmol)、DBA(1.83g、12.0mmol)、3AMPDA(2.18g、9.0mmol)、DA-2(3.43g、9.0mmol)をNMP(41.1g)中で溶解し、60℃で3時間反応させたのち、PMDA(1.31g、6.0mmol)、続いてCBDA(3.47g、17.7mmol)とNMP(13.71g)を加え、25℃で10時間反応させポリアミック酸溶液を得た。 (Synthesis Example 3)
BODA (1.50 g, 6.0 mmol), DBA (1.83 g, 12.0 mmol), 3AMPDA (2.18 g, 9.0 mmol), DA-2 (3.43 g, 9.0 mmol) were added to NMP (41. 1 g), and after reacting at 60 ° C. for 3 hours, PMDA (1.31 g, 6.0 mmol) was added, followed by CBDA (3.47 g, 17.7 mmol) and NMP (13.71 g). The mixture was reacted at 25 ° C. for 10 hours to obtain a polyamic acid solution.
合成例1で得られた液晶配向剤(A1)を第1成分として3.0g、合成例3で得られた液晶配向剤(C1)を第2成分として7.0gを混合し、1時間撹拌することにより液晶配向剤(A2)を調製した。 (Synthesis Example 4)
3.0 g of the liquid crystal aligning agent (A1) obtained in Synthesis Example 1 was mixed as the first component, and 7.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 was mixed as the second component and stirred for 1 hour. By doing so, a liquid crystal aligning agent (A2) was prepared.
実施例1で得られた液晶配向剤(B1)を第1成分として3.0g、合成例3で得られた液晶配向剤(C1)を第2成分として7.0gを混合し、1時間撹拌することにより液晶配向剤(B2)を調製した。 (Synthesis Example 5)
3.0 g of the liquid crystal aligning agent (B1) obtained in Example 1 was mixed as the first component, and 7.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 was mixed as the second component, and stirred for 1 hour. By doing so, a liquid crystal aligning agent (B2) was prepared.
TCA(11.1g、50.0mmol)、DA-1(6.61g、20.0mmol)、DA-4(3.97g、20.0mmol)、DA-8(4.95g、10.0mmol)をNMP(106.5g)中で溶解し、60℃で6時間反応させポリアミック酸溶液を得た。 (Synthesis Example 6) TCA
TCA (11.1 g, 50.0 mmol), DA-1 (6.61 g, 20.0 mmol), DA-4 (3.97 g, 20.0 mmol), DA-8 (4.95 g, 10.0 mmol) It melt | dissolved in NMP (106.5g), it was made to react at 60 degreeC for 6 hours, and the polyamic acid solution was obtained.
BODA(5.00g、20.0mmol)、DA-1(3.96g、12.0mmol)、DA-5(2.11g、8.0mmol)、DA-2(7.61g、20.0mmol)をNMP(67.6.g)中で溶解し、60℃で5時間反応させたのち、CBDA(3.84g、20.0mmol)とNMP(22.5g)を加え、40℃で10時間反応させポリアミック酸溶液を得た。 (Synthesis Example 7) BEMS
BODA (5.00 g, 20.0 mmol), DA-1 (3.96 g, 12.0 mmol), DA-5 (2.11 g, 8.0 mmol), DA-2 (7.61 g, 20.0 mmol) After dissolving in NMP (67.6.g) and reacting at 60 ° C for 5 hours, CBDA (3.84g, 20.0mmol) and NMP (22.5g) were added and reacted at 40 ° C for 10 hours. A polyamic acid solution was obtained.
BODA(5.00g、20.0mmol)、DBA(3.04g、20.0mmol)、DA-7(4.93g、12.0mmol)、DA-2(3.04g、8.0mmol)をNMP(65.2g)中で溶解し、60℃で3時間反応させたのち、CBDA(1.41g、7.0mmol)を加え40℃で1時間反応させた。その後DSDA(4.30g、12.0mmol)、とNMP(21.7g)を加え、25℃で10時間反応させポリアミック酸溶液を得た。 (Synthesis Example 8) DSDA
BODA (5.00 g, 20.0 mmol), DBA (3.04 g, 20.0 mmol), DA-7 (4.93 g, 12.0 mmol), DA-2 (3.04 g, 8.0 mmol) were mixed with NMP ( 65.2 g), the mixture was reacted at 60 ° C. for 3 hours, CBDA (1.41 g, 7.0 mmol) was added, and the mixture was reacted at 40 ° C. for 1 hour. Then, DSDA (4.30 g, 12.0 mmol) and NMP (21.7 g) were added and reacted at 25 ° C. for 10 hours to obtain a polyamic acid solution.
BODA(2.50g,10.0mmol)、DA-6(3.49g,14.0mmol)、DA-2(2.28g,6.00mmol)をNMP(40.2g)中で混合し、50℃で3時間反応させた後、CBDA(1.76g,9.00mmol)を加え、40℃で3時間反応させポリアミック酸溶液を得た。 (Synthesis Example 9) A199
BODA (2.50 g, 10.0 mmol), DA-6 (3.49 g, 14.0 mmol), DA-2 (2.28 g, 6.00 mmol) were mixed in NMP (40.2 g) at 50 ° C. Then, CBDA (1.76 g, 9.00 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution.
合成例6で得られた液晶配向剤(D1)を第1成分として5.0g、合成例8で得られた液晶配向剤(F1)を第2成分として5.0gを混合し、1時間撹拌することにより液晶配向剤(D2)を調製した。 (Synthesis Example 10)
The liquid crystal aligning agent (D1) obtained in Synthesis Example 6 is mixed with 5.0 g as the first component, and the liquid crystal aligning agent (F1) obtained in Synthesis Example 8 is mixed with 5.0 g as the second component and stirred for 1 hour. By doing so, a liquid crystal aligning agent (D2) was prepared.
合成例7で得られた液晶配向剤(E1)を第1成分として5.0g、合成例9で得られた液晶配向剤(G1)を第2成分として5.0gを混合し、1時間撹拌することにより液晶配向剤(E2)を調製した。 (Synthesis Example 11)
The liquid crystal aligning agent (E1) obtained in Synthesis Example 7 is mixed with 5.0 g as the first component, and the liquid crystal aligning agent (G1) obtained in Synthesis Example 9 is mixed with 5.0 g as the second component and stirred for 1 hour. By doing so, a liquid crystal aligning agent (E2) was prepared.
(実施例1)
合成例4で得られた液晶配向剤(A2)を用いて下記に示すような手順で液晶セルの作製を行った。合成例4で得られた液晶配向剤(A2)を、画素サイズが100μm×300μmでライン/スペースがそれぞれ5μmのITO電極パターンが形成されているITO電極基板のITO面にスピンコートし、80℃のホットプレートで90秒間乾燥した後、230℃の熱風循環式オーブンで30分間焼成を行い、膜厚100nmの液晶配向膜(A2-1)を形成した。 <Production of liquid crystal cell>
Example 1
Using the liquid crystal aligning agent (A2) obtained in Synthesis Example 4, a liquid crystal cell was prepared according to the procedure shown below. The liquid crystal aligning agent (A2) obtained in Synthesis Example 4 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed, After drying for 90 seconds on the hot plate, baking was performed in a hot air circulation oven at 230 ° C. for 30 minutes to form a liquid crystal alignment film (A2-1) having a film thickness of 100 nm.
名菱テクニカ製LCDアナライザーLCA-LUV42Aを使用した。 "Measurement of pretilt angle"
An LCD analyzer LCA-LUV42A manufactured by Meiryo Technica was used.
まず、バックライト、クロスニコルの状態にした一組の偏光版、光量検出器の順で構成される測定装置において、一組の偏光版の間に液晶セルを配置した。このときライン/スペースが形成されているITO電極のパターンがクロスニコルに対して45°の角度になるようにした。そして、上記の液晶セルに電圧±7V、周波数1kHzの矩形波を印加し、光量検出器によって観測される輝度が飽和するまでの変化をオシロスコープにて取り込み、電圧を印加していない時の輝度を0%、±7Vの電圧を印加し、飽和した輝度の値を100%として、輝度が10%から90%まで変化するのにかかる時間を応答速度とした。 "Response speed measurement method"
First, a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector. At this time, the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols. Then, a rectangular wave having a voltage of ± 7 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained. A voltage of 0% and ± 7 V was applied, the value of saturated luminance was taken as 100%, and the time taken for the luminance to change from 10% to 90% was taken as the response speed.
実施例1でPre-UVとして照射した10J/cm2のかわりに20~40J/cm2を照射した以外は実施例1と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。 (Examples 2 to 3)
A liquid crystal cell was produced in the same manner as in Example 1 except that 20-40 J / cm 2 was irradiated instead of 10 J / cm 2 irradiated as Pre-UV in Example 1, and the pretilt angle of the liquid crystal cell was Was measured.
実施例1でPre-UVとして照射した10J/cm2のかわりに波長313nmのバンドパスフィルターを通した高圧水銀ランプのUVを1J/cm2を照射した以外は実施例1と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。 Example 4
The same operation as in Example 1 was performed except that 1 J / cm 2 of UV from a high-pressure mercury lamp passed through a band-pass filter with a wavelength of 313 nm was irradiated instead of 10 J / cm 2 irradiated as Pre-UV in Example 1. A liquid crystal cell was prepared, and the pretilt angle of the liquid crystal cell was measured.
用いた配向剤を液晶配向剤(A2)から液晶配向剤(B2)に変更した以外は、実施例1~4と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。
なお、画素サイズが100μm×300μmでライン/スペースがそれぞれ5μmのITO電極パターンが形成されているITO電極基板のITO面に塗布した配向膜を(B2-1)、電極パターンが形成されていないITO面に塗布した配向膜を(B2-2)とした。 (Examples 5 to 8)
A liquid crystal cell was prepared in the same manner as in Examples 1 to 4 except that the alignment agent used was changed from the liquid crystal alignment agent (A2) to the liquid crystal alignment agent (B2), and the pretilt angle of the liquid crystal cell was measured. Went.
An alignment film (B2-1) applied to the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed is formed on the ITO film on which the electrode pattern is not formed. The alignment film applied on the surface was designated as (B2-2).
実施例1でPre-UVを照射しなかった以外は実施例1と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。 (Comparative Example 1)
A liquid crystal cell was produced in the same manner as in Example 1 except that Pre-UV was not irradiated in Example 1, and the pretilt angle of the liquid crystal cell was measured.
実施例5でPre-UVを照射しなかった以外は実施例5と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。 (Comparative Example 2)
A liquid crystal cell was prepared in the same manner as in Example 5 except that Pre-UV was not irradiated in Example 5, and the pretilt angle of the liquid crystal cell was measured.
液晶配向剤(A2)から液晶配向剤(D2)に変更した以外は、実施例1~4と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。
なお、画素サイズが100μm×300μmでライン/スペースがそれぞれ5μmのITO電極パターンが形成されているITO電極基板のITO面に塗布した配向膜を(D2-1)、電極パターンが形成されていないITO面に塗布した配向膜を(D2-2)とした。 (Examples 9 to 12)
A liquid crystal cell was produced in the same manner as in Examples 1 to 4 except that the liquid crystal aligning agent (A2) was changed to the liquid crystal aligning agent (D2), and the pretilt angle of the liquid crystal cell was measured.
An alignment film (D2-1) applied on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed is formed on the ITO film on which the electrode pattern is not formed. The alignment film applied to the surface was designated as (D2-2).
液晶配向剤(A2)から液晶配向剤(E2)に変更した以外は、実施例1~4と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。
なお、画素サイズが100μm×300μmでライン/スペースがそれぞれ5μmのITO電極パターンが形成されているITO電極基板のITO面に塗布した配向膜を(E2-1)、電極パターンが形成されていないITO面に塗布した配向膜を(E2-2)とした。 (Examples 13 to 16)
A liquid crystal cell was produced in the same manner as in Examples 1 to 4 except that the liquid crystal aligning agent (A2) was changed to the liquid crystal aligning agent (E2), and the pretilt angle of the liquid crystal cell was measured.
An alignment film (E2-1) applied on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed is formed on the ITO film on which the electrode pattern is not formed. The alignment film applied to the surface was designated as (E2-2).
実施例9でPre-UVを照射しなかった以外は実施例9と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。 (Comparative Example 3)
A liquid crystal cell was prepared in the same manner as in Example 9 except that Pre-UV was not irradiated in Example 9, and the pretilt angle of the liquid crystal cell was measured.
実施例13でPre-UVを照射しなかった以外は実施例13と同様の操作を行って、液晶セルを作製し、液晶セルのプレチルト角の測定を行った。 (Comparative Example 4)
A liquid crystal cell was prepared in the same manner as in Example 13 except that Pre-UV was not irradiated in Example 13, and the pretilt angle of the liquid crystal cell was measured.
Claims (16)
- 一対の基板の表面のそれぞれに、光照射によりラジカルを発生するラジカル発生構造を有する特定重合体を含有する同一組成の液晶配向剤で液晶配向膜を形成する液晶配向膜形成工程と、前記一対の基板の少なくとも一方に光照射を施して両者の液晶配向膜への光照射量を異なる状態とする液晶配向膜光照射工程と、その後、前記一対の基板の間に、液晶化合物を含む液晶層を形成する液晶層形成工程と、を含むことを特徴とする液晶表示素子の製造方法。 A liquid crystal alignment film forming step of forming a liquid crystal alignment film with a liquid crystal aligning agent of the same composition containing a specific polymer having a radical generating structure that generates radicals by light irradiation on each of the surfaces of the pair of substrates; A liquid crystal alignment film light irradiation step in which at least one of the substrates is irradiated with light to change the amount of light irradiation to the liquid crystal alignment films in different states, and then a liquid crystal layer containing a liquid crystal compound is interposed between the pair of substrates. And a liquid crystal layer forming step of forming a liquid crystal display element.
- 前記液晶層がPSAタイプ液晶層であり、前記液晶層形成工程では、電圧を印加しながら光照射により前記ラジカル発生構造からラジカルを発生させることを特徴とする請求項1に記載の液晶表示素子の製造方法。 2. The liquid crystal display element according to claim 1, wherein the liquid crystal layer is a PSA type liquid crystal layer, and in the liquid crystal layer forming step, radicals are generated from the radical generating structure by light irradiation while applying a voltage. Production method.
- 前記液晶配向膜光照射工程では、一方の基板の液晶配向膜のみに光照射を行い、他方の基板の液晶配向膜へは光照射を行わないことを特徴とする請求項1又は2に記載の液晶表示素子の製造方法。 3. The liquid crystal alignment film light irradiating step performs light irradiation only on the liquid crystal alignment film on one substrate and does not perform light irradiation on the liquid crystal alignment film on the other substrate. A method for manufacturing a liquid crystal display element.
- 前記特定重合体が、下記式(I)で表される側鎖構造を有する重合体を含むことを特徴とする請求項1~3のいずれか1項に記載の液晶表示素子の製造方法。
- 前記式(I)で表される側鎖構造を有する特定重合体が、前記式(I)で表される側鎖構造を有するポリイミド前駆体及びそれをイミド化して得られるポリイミドからなる群から選ばれる少なくとも1つの重合体である請求項4に記載の液晶表示素子の製造方法。 The specific polymer having a side chain structure represented by the formula (I) is selected from the group consisting of a polyimide precursor having a side chain structure represented by the formula (I) and a polyimide obtained by imidizing it. The method for producing a liquid crystal display element according to claim 4, wherein the liquid crystal display element is at least one polymer.
- 前記特定重合体が、下記式(II)で表される側鎖構造を有する重合体を含むことを特徴とする請求項1~3のいずれか1項に記載の液晶表示素子の製造方法。
- 前記式(II)中のnが1~6の整数であり、Cyが以下に示す環状炭化水素基であって、2つの点はそれぞれイミドカルボニル炭素への結合を示す請求項6に記載の液晶表示素子の製造方法。
- 前記式(II)中のnが1~6の整数であり、Xが-O-を表し、Cyがシクロヘキセン、ベンゼン、ナフタレン、ビフェニレンである請求項6又は請求項7に記載の液晶表示素子の製造方法。 8. The liquid crystal display element according to claim 6, wherein n in the formula (II) is an integer of 1 to 6, X represents —O—, and Cy is cyclohexene, benzene, naphthalene, or biphenylene. Production method.
- 上記特定重合体が、液晶を垂直に配向させる側鎖を更に有する請求項4~8のいずれか1項に記載の液晶表示素子の製造方法。 The method for producing a liquid crystal display element according to any one of claims 4 to 8, wherein the specific polymer further has a side chain for vertically aligning the liquid crystal.
- 上記液晶を垂直に配向させる側鎖が、下記式(III-1)及び(III-2)から選ばれる少なくとも1つである請求項9に記載の液晶表示素子の製造方法。
- 上記特定重合体が、下記式(1)で表されるジアミン成分を構成単位として有するポリイミド前駆体及びそれをイミド化して得られるポリイミドのうち少なくとも1つの重合体を含有する請求項1~9のいずれか1項に記載の液晶表示素子の製造方法。
- 上記特定重合体が、さらに下記式(VII)で表されるジアミンを含有するジアミン成分を構成単位として有するポリイミド前駆体及びそれをイミド化して得られるポリイミドのうち少なくとも1つの重合体を含有する請求項11に記載の液晶表示素子の製造方法。
- 上記特定重合体が、さらに下記式(VIII)又は(IX)で表されるジアミンを含有するジアミン成分を構成単位として有するポリイミド前駆体及びそれをイミド化して得られるポリイミドのうち少なくとも1つの重合体を含有する請求項11又は12に記載の液晶配向剤。
- 前記重合体が、下記(A)成分と、下記(B)成分とを含むことを特徴とする請求項1~3のいずれか1項に記載の液晶表示素子の製造方法。
(A)成分:液晶を垂直に配向させる側鎖と、下記式(1)で表される紫外線照射によってラジカルを発生する部位を有する側鎖とを有するポリイミド前駆体、及び、このポリイミド前駆体をイミド化して得られるポリイミドから選択される少なくとも一種の重合体と、
(B)成分:下記式(B-1)~(B-5)から選択される少なくとも一種のジアミンを含有するジアミン成分を原料として得られるポリイミド前駆体、及び、このポリイミド前駆体をイミド化して得られるポリイミドから選択される重合体、または、下記式(3)及び(4)から選択される少なくとも一種のテトラカルボン酸二無水物を含有するテトラカルボン酸二無水物成分を原料として得られるポリイミド前駆体、及び、このポリイミド前駆体をイミド化して得られるポリイミドから選択される重合体。
Component (A): a polyimide precursor having a side chain for vertically aligning liquid crystals and a side chain having a site that generates radicals by ultraviolet irradiation represented by the following formula (1), and this polyimide precursor: At least one polymer selected from polyimides obtained by imidization; and
Component (B): a polyimide precursor obtained by using a diamine component containing at least one diamine selected from the following formulas (B-1) to (B-5) as a raw material, and imidating the polyimide precursor A polyimide selected from a polymer selected from polyimides obtained or a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the following formulas (3) and (4) A polymer selected from a precursor and a polyimide obtained by imidizing the polyimide precursor.
- 液晶配向膜を具備する液晶表示素子形成用基板であって、前記液晶配向膜が、光照射によりラジカルを発生するラジカル発生構造を有する重合体を含有する液晶配向剤で形成されたものであり、且つ光照射により前記ラジカル発生構造の少なくとも一部からラジカルが発生されたものであることを特徴とする液晶表示素子形成用基板。 A substrate for forming a liquid crystal display element comprising a liquid crystal alignment film, wherein the liquid crystal alignment film is formed of a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation, A substrate for forming a liquid crystal display element, wherein radicals are generated from at least a part of the radical generating structure by light irradiation.
- 一対の液晶配向膜を具備する液晶表示素子形成用基板と、前記一対の液晶表示素子用基板の間に設けられた液晶層とを具備する液晶表示素子組立体であって、前記一対の液晶表示素子用形成基板の前記液晶配向膜は、光照射によりラジカルを発生するラジカル発生構造を有する重合体を含有する同一組成の液晶配向剤で形成されたものであり、且つ少なくとも一方に光照射が施されて両者の光照射量が異なる状態となったものであることを特徴とする液晶表示素子組立体。 A liquid crystal display element assembly comprising a liquid crystal display element forming substrate having a pair of liquid crystal alignment films and a liquid crystal layer provided between the pair of liquid crystal display element substrates, wherein the pair of liquid crystal displays The liquid crystal alignment film of the device formation substrate is formed of a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation, and at least one is irradiated with light. Thus, the liquid crystal display element assembly is characterized in that the light irradiation amounts of the two are different.
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