Classifications

• • 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
  • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • 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
  • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
  • G02F1/13347—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals working in reverse mode, i.e. clear in the off-state and scattering in the on-state
• • 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
• • 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
  • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment

Definitions

• the present invention relates to a transmission / scattering type liquid crystal display element that is transparent when no voltage is applied and is in a scattering state when a voltage is applied, a liquid crystal alignment film used therefor, and a liquid crystal alignment treatment agent for forming the liquid crystal alignment film. is there.
• a TN (Twisted Nematic) mode has been put to practical use as a liquid crystal display element using a liquid crystal material.
• this mode light is switched using the optical rotation characteristics of the liquid crystal, and when used as a liquid crystal display element, it is necessary to use a polarizing plate.
• the use efficiency of light becomes low by using a polarizing plate.
• As a liquid crystal display element having a high light utilization efficiency without using a polarizing plate there is a liquid crystal display element that switches between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state.
• PDLC Dispersive liquid crystal
• PNLC Polymer network liquid crystal
• a liquid crystal display element using these includes a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates.
• the liquid crystal composition is disposed, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and is manufactured through a process of forming a cured product composite of liquid crystal and a polymerizable compound It is a liquid crystal display element.
• this liquid crystal display element controls the permeation
• liquid crystal display elements using PDLC and PNLC are in a cloudy (scattering) state because the liquid crystal molecules are in a random direction when no voltage is applied, and the liquid crystal is aligned in the direction of the electric field and transmits light when voltage is applied.
• a transmission state is obtained (a liquid crystal display element that controls such transmission scattering is also referred to as a normal element).
• this normal type element it is necessary to always apply a voltage in order to obtain a transmissive state. Therefore, it is often used in a transparent state, such as a window glass. Electric power is large.
• PDLCs that are in a transmission state when no voltage is applied to a normal type element and in a scattering state when a voltage is applied have been reported (a liquid crystal display element that controls such transmission and scattering is also called a reverse type element) (for example, see Patent Document 1 or 2.)
• a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) that aligns the liquid crystal vertically is used.
• the vertical liquid crystal alignment film is a highly hydrophobic film, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, a large amount of a polymerizable compound (also referred to as a curing agent) for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film must be introduced into the liquid crystal composition used for the reverse type element.
• the liquid crystal alignment film used for the reverse element needs to have a high vertical alignment property of the liquid crystal.
• an object of the present invention is to provide a liquid crystal display element having the above characteristics. That is, the present invention is a liquid crystal display device, which has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, and further has high liquid crystal vertical alignment and good optical characteristics, that is, when no voltage is applied. An object of the present invention is to provide a liquid crystal display device having excellent transparency and scattering characteristics when a voltage is applied. In addition, it aims at providing the liquid crystal aligning film and liquid-crystal aligning agent which are used for the said liquid crystal display element.
• the present inventors have found that a liquid crystal display device using a vertical liquid crystal alignment film obtained from a polymer having a side chain having a specific structure and a liquid crystal alignment treatment agent containing a generator having a specific structure is The present invention has been found to be extremely effective for achieving the above object, and the present invention has been completed. That is, the present invention has the following gist.
• a liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and
• at least one of the substrates has a liquid crystal alignment film that vertically aligns the liquid crystal, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and the liquid crystal and the polymerizable compound are cured.
• (A) component a polymer having at least one structure selected from the group consisting of the structures represented by the following formulas [1-1] and [1-2]
• Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
• Y 3 represents a single bond, — (CH 2 ) c — (c Is an integer of 1 to 15, and represents at least one linking group selected from the group consisting of —O—, —CH 2 O—, —COO— and —OCO—, wherein Y 4 represents a benzene ring or a cyclohexane ring.
• At least one divalent cyclic group selected from the group consisting of a heterocyclic ring or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group is a carbon
• Containing alkyl group, good .Y 5 be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms represents a divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic, Arbitrary hydrogen atoms on these cyclic groups include 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 atoms, and a fluorine-containing alkoxyl having 1 to 3 carbon atoms.
• N is an integer of 0 to 4.
• Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. And at least one selected from the group consisting of an alkoxyl group and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.)
• Y 7 is a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— and —OCO—.
• at least one linking group selected from the group consisting of Y 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.
• the polymer of the component (A) is at least one selected from the group consisting of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane.
• the polymer is at least one selected from the group consisting of a diamine compound having a side chain having the structure of the formula [1-1] and a diamine compound having a side chain having the structure of the formula [1-2].
• the liquid crystal display element according to the above (2) which is at least one selected from the group consisting of a polyimide precursor obtained by using a diamine compound as a part of the raw material and a polyimide.
• the polymer of the component (A) is at least one selected from the group consisting of a polyimide precursor obtained by using a tetracarboxylic acid component represented by the following formula [3] as part of the raw material and a polyimide.
• the polymer of the component (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the following formula [A1], or the formula [A1] and the following formula [A2] and formula
• the liquid crystal display device according to (2) which is a polysiloxane obtained by polycondensation with at least one alkoxysilane selected from the group consisting of alkoxysilanes represented by [A3].
• a 1 represents a structure represented by the above formula [1-1] or [1-2].
• a 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• a 3 represents a carbon number of 1 respectively.
• B 1 represents at least one organic group having 2 to 12 carbon atoms selected from the group consisting of vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacryl group, acrylic group, ureido group, and cinnamoyl group.
• B 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• B 3 represents an alkyl group having 1 to 5 carbon atoms
• m represents an integer of 1 or 2
• n represents 0 to 2
• p represents an integer of 0 to 3
• D 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• D 2 represents an alkyl group having 1 to 5 carbon atoms.
• N represents an integer of 0 to 3)
• the above liquid crystal aligning agent contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and ⁇ -butyrolactone.
• the liquid crystal display element according to any one of the above.
• the liquid crystal aligning agent includes at least one compound selected from the group consisting of compounds having structures represented by formulas [B1] to [B7] to be described later.
• the liquid crystal display element in any one.
• the adhesion between a liquid crystal layer and a vertical liquid crystal alignment film is obtained by using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a specific structure side chain and a specific structure generator.
• a liquid crystal display device that has a high vertical alignment property of the liquid crystal and a good optical characteristic, that is, a transparency when no voltage is applied and a scattering characteristic when a voltage is applied.
• the reverse type element which is the liquid crystal display element of the present invention can be used for a liquid crystal display for display purposes, a light control window for controlling transmission and blocking of light, an optical shutter element, and the like.
• the liquid crystal display element of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and includes a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates.
• At least one of the substrates has a liquid crystal alignment film for vertically aligning the liquid crystal, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and the liquid crystal A liquid crystal display element obtained by forming a cured product composite of a polymerizable compound, wherein the liquid crystal alignment film is a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing the following components (A) and (B): Have.
• Component (A) a polymer having at least one structure selected from the group consisting of the structures represented by the following formulas [1-1] and [1-2] (also referred to as a specific polymer)
• Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , and n are as defined above.
• Y 7 and Y 8 are as defined above.
• the vertical liquid crystal alignment film in the present invention is obtained from a liquid crystal alignment treatment agent containing a specific generator that generates radicals, acids, or bases (also referred to as catalysts) by active energy rays such as ultraviolet rays or heat. Therefore, a catalyst is generated from a specific generator in the vertical liquid crystal alignment film by ultraviolet rays or heating used in the process of forming a liquid crystal layer, that is, a cured product composite of liquid crystal and a polymerizable compound when producing a liquid crystal display element. Thus, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film becomes stronger.
• the specific side chain structure represented by the formula [1-1] contained in the specific polymer used in the liquid crystal display element of the present invention has a benzene ring, a cyclohexyl ring, a heterocyclic ring, or a steroid at the side chain site. It has a C 17-51 divalent organic group having a skeleton. Since the side chain structure of these rings and organic groups shows a rigid structure, a high and stable liquid crystal vertical alignment can be obtained. From the above points, the liquid crystal display element having a vertical liquid crystal alignment film obtained from the liquid crystal alignment treatment agent containing the polymer having the specific side chain structure and the specific generator of the present invention has a high liquid crystal vertical alignment property and is excellent.
• a nematic liquid crystal or a smectic liquid crystal can be used as the liquid crystal in the liquid crystal composition used for manufacturing the liquid crystal display element of the present invention.
• those having negative dielectric anisotropy are preferable.
• those having a large dielectric anisotropy and a large refractive index anisotropy are preferred.
• the liquid crystal display element in order to drive the liquid crystal display element as an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also referred to as VHR).
• a fluorine-based or chlorine-based liquid crystal that has high electrical resistance and does not lower VHR by active energy rays such as ultraviolet rays. Further, it is preferable to use a liquid crystal having a large birefringence ( ⁇ n).
• the liquid crystal display element in the present invention can be made into a guest-host type element by dissolving a dichroic dye in a liquid crystal composition.
• a dichroic dye in a liquid crystal composition.
• an element is obtained that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied.
• the orientation direction of the liquid crystal changes by 90 degrees depending on whether or not voltage is applied. Therefore, in the liquid crystal display element of the present invention, a high contrast can be obtained by utilizing the difference in light absorption characteristics of the dichroic dye as compared with a conventional guest-host type element that switches between random alignment and vertical alignment. .
• a guest-host type element in which a dichroic dye is dissolved is colored when the liquid crystal is aligned in the horizontal direction, and is opaque only in a scattering state. Therefore, as the voltage is applied, it is possible to obtain an element that switches from colorless and transparent when no voltage is applied to a colored opaque and colored transparent state.
• the liquid crystal composition in the present invention contains a polymerizable compound that is polymerized by at least one of active energy rays such as ultraviolet rays and heat.
• the polymerization of the polymerizable compound may be performed in any form of reaction, and a cured product composite of the liquid crystal and the polymerizable compound may be formed.
• Specific reaction modes of polymerization include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction.
• cured material composite means the state as which the liquid crystal exists in the high molecular weight body (polymer) formed with a polymeric compound.
• the polymerizable compound may be any compound as long as it dissolves in the liquid crystal.
• the polymerizable compound when dissolved in the liquid crystal, it is necessary that a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is sufficient that the liquid crystal display element is confirmed with the naked eye and almost uniform transparency and scattering characteristics are obtained throughout the element.
• the reaction form of the polymerizable compound is radical polymerization
• the following radical type polymerizable compound can be used.
• a polyfunctional radical-type polymerizable compound having three or more functional groups for the purpose of enhancing the scattering characteristics when a voltage is applied.
• the radical type polymerizable compound may be used alone or in combination of two or more depending on the optical characteristics of the liquid crystal display element and the adhesion characteristics between the liquid crystal layer and the vertical liquid crystal alignment film. Furthermore, when the reaction form of the polymerizable compound is radical polymerization, a radical initiator that generates radicals by ultraviolet rays can be introduced into the liquid crystal composition.
• tert-butylperoxy-iso-butrate 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [ ⁇ - (tert-butyldioxy) -iso-propoxy Benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, ⁇ - (iso-propylphenyl) -iso-propyl hydroperoxide, 2,5- Dimethylhexane, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) valerate, cyclohexanone Peroxide, 2,2 ', 5,5'-tetra (tert-butylperoxide
• the reaction form of the polymerizable compound is cationic polymerization or anionic polymerization
• the following ionic type polymerizable compounds can be used. Specifically, it is a compound having at least one cross-linking group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.
• a melamine derivative, a benzoguanamine derivative or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group or both can be used.
• the melamine derivative or benzoguanamine derivative may be an oligomer. These preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triazine ring.
• Examples of such melamine derivatives and benzoguanamine derivatives include MX-750, which is an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
• Eight-substituted MW-30 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamine, Cymel 235, Of methoxymethylated butoxymethylated melamine such as 236, 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated be
• Examples of the benzene having a hydroxyl group or an alkoxyl group or a phenolic compound include 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, and 1,4-bis. (Sec-butoxymethoxy) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
• a compound having an epoxy group and an isocyanate group and having a crosslinking group can also be used.
• an ion initiator that generates an acid or a base by ultraviolet rays can be introduced into the liquid crystal composition.
• triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, diaryl iodonium salts, triaryl sulfonium salts, triaryl phosphonium salts, iron arene complexes, and the like can be used. However, it is not limited to these.
• diphenyl iodonium chloride diphenyl iodonium trifluoromethanesulfonate
• diphenyl iodonium mesylate diphenyl iodonium tosylate
• diphenyl iodonium bromide diphenyl iodonium tetrafluoroborate
• diphenyl iodonium hexafluoroantimonate diphenyl iodonium hexafluoroarsenate.
• the content of the polymerizable compound in the liquid crystal composition is not particularly limited, but when the content of the polymerizable compound is large, the temperature at which the polymerizable compound does not dissolve in the liquid crystal or the liquid crystal composition exhibits a liquid crystal phase. Or the change between the transparent state and the scattering state of the element becomes small, and the optical characteristics deteriorate.
• the content of the polymerizable compound is small, the curability of the liquid crystal layer is lowered, and further, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is lowered, and the alignment of the liquid crystal against mechanical external pressure is reduced. Is easily disturbed.
• the content of the polymerizable compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the liquid crystal, and more preferably 5 to 40 parts by mass. Particularly preferred is 11 to 30 parts by mass. Further, the content of the radical initiator and the ionic initiator for promoting the reaction of the polymerizable compound is not particularly limited, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal. However, 0.05 to 5 parts by mass is preferable. Particularly preferred is 0.05 to 3 parts by mass.
• the liquid crystal display element of the present invention is an element having a vertical liquid crystal alignment film that vertically aligns liquid crystal on at least one of the substrates.
• the vertical liquid crystal alignment film is a specific polymer having at least one specific side chain structure selected from the group consisting of specific side chain structures represented by the following formulas [1-1] and [1-2]: It is a liquid crystal aligning film obtained from the liquid-crystal aligning agent containing.
• Y 1 is a single bond, at least one selected from the group consisting of — (CH 2 ) a — (wherein a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— and —OCO—.
• a single bond — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO.
• Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15).
• a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
• Y 3 is a single bond, at least one selected from the group consisting of — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— and —OCO—.
• a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
• Y 4 is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted with 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.
• Y 4 may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton.
• Y 5 represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted with 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.
• a benzene ring or a cyclohexane ring is preferable.
• n represents an integer of 0 to 4. Among these, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
• Y 6 is at least one selected from the group consisting of 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, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Indicates the species.
• 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 is preferable. 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.
• (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).
• Y 7 comprises a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— and —OCO—.
• 1 represents at least one linking group selected from the group.
• a single bond, —O—, —CH 2 O—, —CONH—, —CON (CH 3 ) — or —COO— is preferable. More preferably, they are a single bond, —O—, —CONH— or —COO—.
• Y 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Of these, an alkyl group having 8 to 18 carbon atoms is preferable.
• the specific side chain structure it is preferable to use a structure represented by the formula [1-1] from the viewpoint that a high and stable liquid crystal vertical alignment can be obtained
• the specific polymer having a specific side chain structure is not particularly limited, but is selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane.
• the polymer is at least one polymer.
• a polyimide precursor, polyimide or polysiloxane is preferable.
• a polyimide precursor or polyimide also collectively referred to as a polyimide polymer
• they may be a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component. preferable.
• the polyimide precursor has a structure represented by the following formula [A].
• R 1 represents a tetravalent organic group.
• R 2 represents a divalent organic group.
• a 1 and A 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
• a 3 and A 4 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and may be the same or different, and n represents a positive integer.
• the diamine component is a diamine compound having two primary or secondary amino groups in the molecule
• the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, or tetracarboxylic acid dihalide compound.
• Tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds From the reason that the polyimide-based polymer is relatively easily obtained by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials.
• Polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or polyimide obtained by imidizing the polyamic acid is preferable.
• the specific polyimide polymer it is preferable to use polyimide from the viewpoint of physical and chemical stability of the vertical liquid crystal alignment film.
• R 1 and R 2 have the same meaning as defined in formula [A].
• R 1 and R 2 have the same meaning as defined in formula [A].
• the polymer of the formula [D] obtained above by the usual synthesis method is added to the alkyl group having 1 to 8 carbon atoms of A 1 and A 2 represented by the formula [A] and the formula [A]. It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A 3 and A 4 shown.
• a diamine compound having the specific side chain structure As a method for introducing the specific side chain structure into the polyimide polymer, it is preferable to use a diamine compound having the specific side chain structure as a part of the raw material.
• a diamine compound represented by the following formula [1a] also referred to as a specific side chain diamine compound.
• Y represents a structure represented by the formula [1-1] and the formula [1-2].
• the preferred combinations of Y 1 to Y 6 and n in the formula [1-1] and the preferred combinations of Y 7 and Y 8 in the formula [1-2] are as described above.
• m represents an integer of 1 to 4. Of these, 1 is preferable.
• a diamine compound having a structure represented by the above formula [1-1] is preferably used from the viewpoint that a high and stable liquid crystal vertical alignment can be obtained.
• Specific examples include structures represented by the following formulas [1a-1] to [1a-31].
• R 1 independently represents at least one linking group selected from the group consisting of —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, and —CH 2 OCO—.
• 2 is independently a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms. Represents a containing alkyl group or a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms.
• each R 4 independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched group having 1 to 22 carbon atoms.
• R 5 is each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2
• R 7 independently represents 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 independently represents 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— * (note that “*” is attached).
• Bond is bonded 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.
• specific side chain diamine compounds having particularly preferred structures include those represented by formulas [1a-1] to [1a-6] and [1a-9] to Formula [1a-13] or Formula [1a-22] to Formula [1a-31].
• the specific side chain diamine compound is 10 mol% or more and 80 mol% or less of the total diamine component from the viewpoint of the vertical alignment of the liquid crystal and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable that More preferably, it is 10 mol% or more and 70 mol% or less.
• the above-mentioned specific side chain type diamine compound depends on properties such as solubility of the polyimide polymer in the solvent, vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and optical characteristics of the liquid crystal display element.
• One type or a mixture of two or more types can be used.
• the diamine component for producing the polyimide polymer it is also preferable to use a second diamine compound (also referred to as a second diamine compound) represented by the following formula [2].
• X represents a substituent having a structure selected from the following formula [2a], formula [2b], formula [2c] and formula [2d].
• a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
• b represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
• X 1 and X 2 each independently represents a hydrocarbon group having 1 to 12 carbon atoms.
• X 3 represents an alkyl group having 1 to 5 carbon atoms.
• m represents an integer of 1 to 4. Of these, 1 is preferable.
• examples of the diamine compound represented by the formula [2] include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5- In addition to diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, the following formula [ Examples thereof include diamine compounds having structures represented by 2-1] to [2-6].
• 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid 2, Preference is given to 5-diaminobenzoic acid, 3,5-diaminobenzoic acid, diamine compounds of the formula [2-1], formula [2-2] or formula [2-3].
• the diamine compound represented by the above formula [2] has properties such as the solubility of the polyimide polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the situation, one kind or a mixture of two or more kinds can be used.
• diamine component for producing the polyimide polymer a diamine compound other than the diamine compounds represented by the formulas [1a] and [2] (also referred to as other diamine compounds) can be used. Specific examples of other diamine compounds are shown below, but are not limited to these examples.
• diamine compound examples include those having an alkyl group, a fluorine-containing alkyl group or a heterocyclic ring in the side chain of the diamine compound.
• diamine compounds represented by the following formulas [DA1] to [DA12] can be exemplified as long as the effects of the present invention are not impaired.
• P represents an integer of 1 to 10.
• (A 1 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — and —N ( CH 3 ) CO— represents at least one linking group selected from the group consisting of m 1 and m 2 each representing an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4.
• m 3 and m 4 each represent an integer of 1 to 5.
• a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
• m 5 represents an integer of 1 to 5.
• a 3 represents a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - O -, - CO -, - NH , -N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) - and -N (CH 3)
• This represents at least one linking group selected from the group consisting of CO—
• m 6 represents an integer of 1 to 4.
• a 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — and —N (CH 3 )
• a divalent organic group selected from the group consisting of CO—, wherein A 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group.
• a 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, -CON (CH 3) -, - N (CH 3) CO- and -O (CH 2)
• m - ( m is an integer of 1 to 5) exhibits at least one selected from the group consisting .
• a 4 Represents a nitrogen-containing aromatic heterocycle, and n represents an integer of 1 to 4.
• diamine compounds represented by the following formula [DA13] or [DA14] can also be used.
• One of the other diamine compounds may be selected depending on the solubility of the polyimide polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element.
• two or more types can be mixed and used.
• tetracarboxylic acid component for producing the polyimide polymer examples include tetracarboxylic dianhydride represented by the following formula [3] and tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid derivative thereof, tetra It is preferable to use a carboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all are collectively referred to as a specific tetracarboxylic acid component).
• Z 1 is a group having a structure selected from the following formulas [3a] to [3j].
• Z 2 to Z 5 each represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
• Z 6 and Z 7 represent a hydrogen atom or a methyl group, and may be the same or different.
• Z 1 is represented by formula [3a]
• a structure represented by [3c], formula [3d], formula [3e], formula [3f] or formula [3g] is preferable. More preferred is a structure represented by formula [3a], formula [3e], formula [3f] or formula [3g], and particularly preferred is formula [3e], formula [3f] or formula [3g].
• the specific tetracarboxylic acid component is preferably 1 mol% or more of the total tetracarboxylic acid component. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more. Among these, 10 to 90 mol% is more preferable.
• the usage-amount is made into 20 mol% or more of the whole tetracarboxylic acid component, and it is desired. An effect is obtained. Preferably, it is 30 mol% or more.
• all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f], or the formula [3g].
• tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide polymer.
• examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, and dialkyl ester dihalide compounds.
• tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalene.
• Tetracarboxylic acid 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinet
• the specific tetracarboxylic acid component and other tetracarboxylic acid components include solubility of the polyimide polymer in the solvent, vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and optical characteristics of the liquid crystal display element. Depending on the characteristics, one type or a mixture of two or more types can be used.
• the method for synthesizing the polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid.
• a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound
• a method of obtaining a polyamic acid by polycondensation of a dicarboxylic acid dihalide and a primary or secondary diamine compound is a method of obtaining a polyamic acid by polycondensation of a dicarboxylic acid dihalide and a primary or secondary diamine compound.
• a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group and a primary or secondary diamine compound are polycondensed, and a dicarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a primary grade.
• a method of polycondensation with a secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.
• polyimide a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
• the reaction between the diamine component and the tetracarboxylic acid component is usually performed in a solvent containing the diamine component and the tetracarboxylic acid component.
• the solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.
• These may be used alone or in combination.
• water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydrated and dried solvent.
• the polymerization temperature can be selected from -20 to 150 ° C., but is preferably in the range of ⁇ 5 to 100 ° C.
• the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial reaction can be carried out at a high concentration, and then a solvent can be added.
• the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
• the polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose.
• Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
• the temperature is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction from the system.
• the catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor 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 reaction solution may be poured into a solvent and precipitated.
• the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
• the polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
• the molecular weight of the polyimide-based polymer is a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the vertical liquid crystal alignment film obtained therefrom, workability at the time of forming the vertical film, and coating properties. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
• polysiloxane obtained by polycondensation of alkoxysilane represented by the following formula [A1], or formula [A1], and the following formula [A2] and formula [A3] are preferably polysiloxanes obtained by polycondensation with at least one alkoxysilane selected from the group consisting of alkoxysilanes (collectively also referred to as polysiloxane polymers).
• the alkoxysilane represented by the formula [A1] is represented by the following formula [A1].
• a 1 represents a structure represented by the formula [1-1] or the formula [1-2].
• a 1 is preferably a structure represented by the formula [1-1] from the viewpoint that a high and stable vertical alignment of liquid crystal can be obtained.
• a 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
• a 3 represents an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity.
• m represents an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.
• n represents an integer of 0-2.
• p represents an integer of 0 to 3. Among these, an integer of 1 to 3 is preferable from the viewpoint of polycondensation reactivity. More preferably, it is 2 or 3.
• m + n + p represents 4.
• alkoxysilane represented by the formula [A1] include alkoxysilanes represented by the following formulas [A1-1] to [A1-32].
• R 1 independently represents an alkyl group having 1 to 3 carbon atoms.
• R 2 independently represents an alkyl group having 1 to 3 carbon atoms.
• R 1 independently represents an alkyl group having 1 to 3 carbon atoms
• R 2 independently represents an alkyl group having 1 to 3 carbon atoms
• m independently represents 2 or 3
• Each R 3 independently represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH 3 ) —.
• R 1 independently represents an alkyl group having 1 to 3 carbon atoms.
• R 2 independently represents an alkyl group having 1 to 3 carbon atoms.
• M independently represents 2 or 3; Each independently represents 0 or 1.
• Each R 3 independently represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH 3 ) —. , —N (CH 3 ) CO—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, and —CH 2 OCO—, each independently representing R 4.
• Group At least one selected from
• R 1 independently represents an alkyl group having 1 to 3 carbon atoms.
• R 2 independently represents an alkyl group having 1 to 3 carbon atoms.
• M independently represents 2 or 3; Each independently represents 0 or 1.
• Each R 3 independently represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH 3 ) —.
• R 1 represents an alkyl group having 1 to 3 carbon atoms
• R 2 represents an alkyl group having 1 to 3 carbon atoms
• m represents 2 or 3
• n represents 0 or 1
• B 4 represents An alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
• B 3 represents a 1,4-cyclohexylene group or a 1,4-phenylene group
• B 2 represents an oxygen atom or —COO— * (However, a bond marked with “*” is bonded to B 3. )
• B 1 is an oxygen atom or —COO— * (where a bond marked with “*” is (CH 2 ) a. 2 ).
• the alkoxysilane represented by the above formula [A1] is used for the solubility of the polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the characteristics, one type or a mixture of two or more types can be used.
• the alkoxysilane represented by the formula [A2] is represented by the following formula [A2].
• B 1 is an organic group having 2 to 12 carbon atoms having at least one selected from the group consisting of vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacryl group, acrylic group, ureido group and cinnamoyl group. Show. Of these, a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a ureido group is preferable from the viewpoint of availability. More preferably, they are a methacryl group, an acryl group, or a ureido group.
• B 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
• B 3 represents an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity.
• m represents an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.
• n represents an integer of 0-2.
• p represents an integer of 0 to 3. Among these, an integer of 1 to 3 is preferable from the viewpoint of polycondensation reactivity. More preferably, it is 2 or 3.
• m + n + p represents 4.
• alkoxysilane represented by the above formula [A2] include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxy Ethoxy) silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) Propyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl
• the alkoxysilane represented by the above formula [A2] is used for the solubility of the polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.
• the alkoxysilane represented by the formula [A3] is represented by the following formula [A3].
• D 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be substituted with a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom or the like. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
• D 2 represents an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity.
• n represents an integer of 0 to 3.
• alkoxysilane represented by the above formula [A3] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane.
• examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
• the alkoxysilane represented by the above formula [A3] is used for the solubility of the polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.
• the polysiloxane polymer is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the above formula [A1], or an alkoxysilane represented by the formula [A1] and the above formulas [A2] and [A3].
• polysiloxanes obtained by polycondensation of a plurality of types of alkoxysilanes are preferred in terms of polycondensation reactivity and solubility of polysiloxane polymers in a solvent. That is, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by formula [A1] and formula [A2], and polycondensation of two types of alkoxysilanes represented by formula [A1] and formula [A3]. Or a polysiloxane obtained by polycondensation of three types of alkoxysilanes represented by the formulas [A1], [A2] and [A3].
• the alkoxysilane represented by the formula [A1] is preferably 1 to 40 mol% in all alkoxysilanes, and more Preferably, it is 1 to 30 mol%.
• the alkoxysilane represented by the formula [A2] is preferably 1 to 70 mol%, more preferably 1 to 60 mol% in all alkoxysilanes.
• the alkoxysilane represented by the formula [A3] is preferably 1 to 99 mol%, more preferably 1 to 80 mol% in all alkoxysilanes.
• the method for producing the polysiloxane polymer is not particularly limited.
• the polysiloxane polymer in the present invention is a method obtained by polycondensing an alkoxysilane represented by the formula [A1] in a solvent, and an alkoxysilane represented by the formula [A1] and the formula [A2] in a solvent.
• a method obtained by polycondensation a method obtained by polycondensation of the alkoxysilane represented by the formula [A1] and the formula [A3] in a solvent, and further by the formula [A1], the formula [A2] and the formula [A3] Examples thereof include a method obtained by polycondensation of the indicated alkoxysilane in a solvent.
• the polysiloxane polymer of the present invention can be obtained as a solution obtained by polycondensing these alkoxysilanes and uniformly dissolved in a solvent.
• the method for polycondensing the polysiloxane polymer is not particularly limited.
• a method in which an alkoxysilane is hydrolyzed and polycondensed in an alcohol solvent or a glycol solvent can be mentioned.
• the hydrolysis / polycondensation reaction may be partially hydrolyzed or completely hydrolyzed.
• complete hydrolysis theoretically, it is sufficient to add 0.5 times the molar amount of water of all alkoxy groups in the alkoxysilane, but it is possible to add an excessive amount of water more than 0.5 times the molar amount. preferable.
• the amount of water used in the above hydrolysis / polycondensation reaction can be appropriately selected according to the purpose, but 0.5% of all alkoxy groups in the alkoxysilane can be selected. A molar amount of ⁇ 2.5 times is preferable.
• acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid, and alkaline substances such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc.
• Compounds or metal salts such as hydrochloric acid, nitric acid, and oxalic acid can be used as the catalyst.
• the hydrolysis / polycondensation reaction can be promoted by heating the solution in which the alkoxysilane is dissolved.
• the heating temperature and heating time in that case can be suitably selected according to the objective. For example, conditions such as heating and stirring at 50 ° C. for 24 hours and then stirring for 1 hour under reflux conditions may be mentioned.
• a method for polycondensation a method in which a polycondensation reaction is performed by heating a mixture of an alkoxysilane, a solvent, and oxalic acid. Specifically, after adding oxalic acid to a solvent to prepare a solution of oxalic acid in advance, the alkoxysilane is mixed in a state where the solution is heated. At that time, the amount of oxalic acid used in the above reaction is preferably 0.2 to 2.0 mol with respect to 1 mol of all alkoxy groups in the alkoxysilane.
• This reaction can be carried out at a solution temperature of 50 to 180 ° C., but is preferably carried out under reflux for several tens of minutes to several tens of hours so that the solvent does not evaporate or volatilize.
• a mixture in which a plurality of types of alkoxysilanes are mixed in advance is used. Even if it reacts using, it may react, adding several types of alkoxysilane sequentially.
• the solvent used for the polycondensation reaction of alkoxysilane is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even if it is a solvent in which an alkoxysilane does not melt
• an alcohol is generally generated by the polycondensation reaction of alkoxysilane, and therefore, an alcohol solvent, a glycol solvent, a glycol ether solvent, or a solvent that is compatible with alcohol is used.
• solvent used in such a polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol or diacetone alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4 -Glucol solvents such as pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol or 1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol monopropyl ether, ethylene
• the concentration of silicon atoms contained in all alkoxysilanes charged as a raw material in terms of SiO 2 is 20% by mass or less. It is preferable. In particular, the content is preferably 5 to 15% by mass.
• the polysiloxane polymer solution obtained by the above method may be used as a specific polymer as it is, and if necessary, the polysiloxane polymer solution obtained by the above method. Can be concentrated, diluted by adding a solvent, or substituted with another solvent to be used as a specific polymer.
• the solvent used for dilution by adding the above solvent may be a solvent used for the polycondensation reaction or other solvents.
• the additive solvent is not particularly limited as long as the polysiloxane polymer is uniformly dissolved, and one or two or more types can be arbitrarily selected and used.
• the additive solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvent used in the polycondensation reaction.
• the polysiloxane polymer is subjected to a polycondensation reaction before mixing the other polymers with the polysiloxane polymer.
• the generated alcohol is preferably distilled off at normal pressure or reduced pressure.
• the vertical liquid crystal alignment film in the present invention is obtained from a liquid crystal aligning agent containing at least one specific generator selected from the group consisting of a photoradical generator, a photoacid generator and a photobase generator as component (B).
• the photo radical generator is not particularly limited as long as it generates radicals by ultraviolet rays, and examples thereof include tert-butylperoxy-iso-butrate, 2,5-dimethyl-2,5-bis (benzoyldioxy).
• the photoacid generator and the photobase generator are not particularly limited as long as they generate an acid or a base by ultraviolet rays.
• triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfones are available.
• examples thereof include acid derivative compounds, diaryl iodonium salts, triaryl sulfonium salts, triaryl phosphonium salts, iron arene complexes, and the like.
• diphenyl iodonium chloride diphenyl iodonium trifluoromethanesulfonate
• diphenyl iodonium mesylate diphenyl iodonium tosylate
• diphenyl iodonium bromide diphenyl iodonium tetrafluoroborate
• diphenyl iodonium hexafluoroantimonate diphenyl iodonium hexafluoroarsenate.
• the liquid crystal aligning agent of the present invention is a coating solution for forming a vertical liquid crystal alignment film, and is at least selected from the group consisting of the formula [1-1] and the formula [1-2] as the component (A).
• the specific polymer having the specific side chain structure is not particularly limited, but a group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane. It is preferable that it is at least one selected from. Among these, a polyimide precursor, polyimide or polysiloxane is preferable, and polyimide or polysiloxane is particularly preferable. In addition, one kind or two or more kinds of these polymers can be used as the specific polymer. All the polymer components in the liquid crystal aligning agent may be all specific polymers, or other polymers may be mixed.
• the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the specific polymer.
• the other polymer include the polymer not containing the specific side chain structure represented by the formula [1-1] or the formula [1-2].
• the specific generator in the liquid crystal alignment treatment agent is at least one specific generator selected from the group consisting of a photo radical generator, a photo acid generator and a photo base generator. Especially, it is preferable to use a photoradical generator from the point which can improve the adhesiveness of a liquid crystal layer and a vertical liquid crystal aligning film.
• the content of the specific generator in the liquid crystal alignment treatment agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of all the polymer components. Of these, 0.01 to 30 parts by mass is preferable, and 0.1 to 20 parts by mass is particularly preferable.
• Content of the solvent in a liquid-crystal aligning agent can be suitably selected from a viewpoint of obtaining the coating method of a liquid-crystal aligning agent, and the target film thickness.
• the content of the solvent in the liquid crystal aligning agent is preferably 50 to 99.9% by mass.
• 60 to 99% by mass is preferable, and 65 to 99% by mass is particularly preferable.
• the solvent used for the liquid crystal aligning agent is not particularly limited as long as the solvent dissolves the specific polymer.
• the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility in a solvent such as acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose, polysiloxane is low, It is preferable to use a solvent (also referred to as solvent A) as shown below.
• a solvent also referred to as solvent A
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferably used. These may be used alone or in combination.
• a solvent as shown (also referred to as solvent B) can be used.
• ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propaned
• D 1 represents an alkyl group having 1 to 3 carbon atoms.
• D 2 represents an alkyl group having 1 to 3 carbon atoms.
• D 3 represents an alkyl group having 1 to 4 carbon atoms.
• solvents B can improve the coating properties and surface smoothness of the vertical liquid crystal alignment film when applying the liquid crystal alignment treatment agent.
• a polyimide precursor, polyimide, polyamide or polyester was used as the specific polymer.
• the solvent B is preferably 1 to 70% by mass of the whole solvent contained in the liquid crystal aligning agent. Of these, 10 to 60% by mass is more preferable. More preferred is 20 to 60% by mass. Further, when the solubility in a solvent such as a polyimide precursor, polyimide, polyamide, or polyester is high, only the solvent B can be used.
• the liquid crystal aligning agent comprises a compound having a structure represented by the following formulas [B1] to [B7] (also referred to as an adhesive compound) for the purpose of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable to contain at least one compound selected from the group. In that case, it is preferable that two or more structures represented by the formulas [B1] to [B7] are included in the compound.
• W 1 represents a hydrogen atom or a benzene ring.
• W 2 represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring.
• W 3 is at least selected from the group consisting of 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, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
• One type is shown. More specifically, the following are mentioned.
• trimethylolpropane tri (meth) acrylate pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly (meth) acrylate
• Compounds having three polymerizable unsaturated groups in the molecule further ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide
• E 1 represents a group selected from the group consisting of cyclohexane ring, bicyclohexane ring, benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, fluorene ring, anthracene ring and phenanthrene ring.
• E 2 represents the following formula [7a Or a group selected from formula [7b], n represents an integer of 1 to 4.)
• the adhesive compound is represented by the above formulas [B1] to [B6] because it has a great effect of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable to use a compound having a structure or a compound represented by the formula [7]. Among them, it is preferable to use a compound having a structure represented by the formulas [B1] to [B5] or a compound represented by the formula [7].
• the said adhesive compound is an example of a compound, It is not limited to these. Moreover, one type of adhesive compound may be used, or two or more types may be combined.
• the content of the adhesive compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components. In order for the crosslinking reaction to proceed and to achieve the desired effect, the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight, based on 100 parts by weight of all polymer components.
• the liquid crystal alignment treatment agent is selected from the group consisting of a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, or a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is also possible to introduce a compound having at least one kind of substituent (collectively referred to as a crosslinkable compound). In that case, it is necessary to have two or more of these substituents in the crosslinkable compound.
• crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-amin
• the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4]. Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).
• the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5]. Specifically, the crosslinkable compounds represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication No. WO2012 / 014898 (published on 2012.2.2). It is done.
• Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
• a melamine resin, a urea resin, a guanamine resin, and a glycoluril such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
• a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used.
• the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups
• Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
• Examples of benzene having a hydroxyl group or an alkoxyl group, or phenolic compounds include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, and 1,4-bis. (Sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like. More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48] described on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27). Is mentioned.
• the content of the crosslinkable compound is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. In order for the crosslinking reaction to proceed and to achieve the desired effect, the amount is more preferably 0.1 to 50 parts by weight, and most preferably 1 to 30 parts by weight, based on 100 parts by weight of all polymer components.
• liquid crystal display element of the present invention as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge removal of the element, pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27). It is also possible to add nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156] described in This amine compound may be added directly to the liquid crystal aligning agent, but it is preferably added after a solution having an appropriate solvent concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. .
• the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.
• the liquid crystal aligning agent a compound that improves the uniformity of the thickness of the vertical liquid crystal aligning film and the surface smoothness when the liquid crystal aligning agent is applied can be used as long as the effects of the present invention are not impaired. Furthermore, a compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate can also be used. Examples of the compound that improves the film thickness uniformity and surface smoothness of the vertical liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
• F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
• the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. It is.
• the compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
• the liquid crystal aligning agent When using a compound to be adhered to these substrates, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal aligning agent. 20 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the liquid crystal aligning agent may be deteriorated.
• the liquid crystal aligning agent includes a dielectric material for changing the electrical properties such as dielectric constant and conductivity of the vertical liquid crystal alignment film, as long as the effects of the present invention are not impaired. A conductive substance may be added.
• the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate.
• an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, a plastic substrate such as a film thereof, or the like is used. be able to.
• a plastic substrate is preferable. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving a liquid crystal is formed.
• a substrate on which a metal or dielectric multilayer film such as a silicon wafer or aluminum is formed can be used as long as the substrate is only on one side.
• the substrates has a vertical liquid crystal alignment film that vertically aligns liquid crystal molecules.
• This vertical liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent on a substrate and baking it, followed by alignment treatment by rubbing treatment or light irradiation. Further, the vertical liquid crystal alignment film in the present invention can be used as a vertical liquid crystal alignment film without these alignment treatments.
• the application method of the liquid crystal alignment treatment agent is not particularly limited, but industrially includes screen printing, offset printing, flexographic printing, ink jet method, dipping method, roll coater method, slit coater method, spinner method, spray method, etc. Depending on the kind of the substrate and the desired thickness of the vertical liquid crystal alignment film, it can be appropriately selected.
• the liquid crystal aligning agent After applying the liquid crystal aligning agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven. Can evaporate the solvent at a temperature of 30 to 250 ° C. to obtain a vertical liquid crystal alignment film.
• the thickness of the vertical liquid crystal alignment film after firing is disadvantageous in terms of power consumption of the liquid crystal display element if it is too thick, and if it is too thin, the reliability of this element may be lowered, so it is preferably 5 to 300 nm, more preferably Is 10 to 200 nm.
• the liquid crystal composition used for the liquid crystal display element is a liquid crystal composition having at least a liquid crystal and a polymerizable compound.
• Examples other than the liquid crystal and the polymerizable compound include the initiator and a spacer for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element.
• the injection method of a liquid crystal composition is not specifically limited, For example, the following method is mentioned. That is, when a glass substrate is used as a substrate, a pair of substrates on which a vertical liquid crystal alignment film is formed is prepared, and a sealant is applied to four pieces of one side of the substrate except for a part, and then the vertical liquid crystal alignment film is formed. An empty cell is manufactured by attaching the substrate on the other side so that the surface is on the inside. And the method of obtaining the liquid crystal composition injection cell by injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied can be mentioned.
• a plastic substrate is used as a substrate
• a pair of substrates on which a vertical liquid crystal alignment film is formed is prepared, and a liquid crystal composition is formed on one substrate by an ODF (One Drop Filling) method or an inkjet method.
• ODF One Drop Filling
• a liquid crystal composition injection cell is obtained by dropping and then bonding the other substrate.
• the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, it is not necessary to apply the sealing agent to the four pieces of the substrate.
• the gap of the liquid crystal display element can be controlled with a spaser or the like.
• the method include a method of introducing a spacer having a target size into the liquid crystal composition described above, and a method of using a substrate having a column spacer of a target size.
• the size of the gap is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m. Particularly preferred is 3 to 30 ⁇ m. If the gap is too small, the contrast of the liquid crystal display element is lowered, and if it is too large, the drive voltage of the element is increased.
• the liquid crystal display element of the present invention can be obtained by curing the liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of the liquid crystal and the polymerizable compound.
• the liquid crystal composition is cured by at least one of irradiation with active energy rays and heating the liquid crystal composition injection cell obtained above.
• ultraviolet rays are suitable as the active energy ray.
• the ultraviolet light has a wavelength of 250 to 400 nm, preferably 310 to 370 nm.
• the temperature is 40 to 120 ° C., preferably 60 to 80 ° C.
• both the ultraviolet treatment and the heat treatment may be performed simultaneously, or the heat treatment may be performed after the ultraviolet treatment. Only the ultraviolet treatment is preferable for curing the liquid crystal composition.
• a liquid crystal display element using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a specific polymer has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film as a reverse type element, Liquid crystal display and light control window that controls the transmission and blocking of light, with high vertical alignment of liquid crystal, good optical properties, that is, transparency when no voltage is applied and scattering property when voltage is applied And an optical shutter element. It is also suitable for liquid crystal display elements used in transportation equipment and transportation machinery such as automobiles, railways, and aircraft, specifically, light control elements used for light control windows and room mirrors that control the transmission and blocking of light. Can do.
• the transparency when no voltage is applied and the scattering characteristics when a voltage is applied are good. Incorporation efficiency is high, and the effect of preventing glare from outside light is also enhanced. Therefore, it is possible to further improve the safety when driving a vehicle and the comfort when riding.
• the cause is that the adhesion between the liquid crystal layer and the vertical alignment film is lower than that of a conventional reverse type element. Defects and deterioration are unlikely to occur, and reliability is increased.
• a light guide plate of a display device such as an LCD (Liquid Crystal Display) or an OLED (Organic Light-emitting Diode) display
• a back plate of a transparent display using these displays when used for the back plate of a transparent display, the transparent display and the liquid crystal display element of the present invention are combined, and when a screen is displayed on the transparent display, the light entering from the back surface of the liquid crystal display element is displayed. Can be used for suppression.
• the liquid crystal display element of the present invention is in a scattering state where a voltage is applied when performing screen display on a transparent display, and the screen display can be clarified. Additional transparency.
• A1 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene
• A2 1,3-diamino-4- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene
• A3 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene
• A4 A4] diamine compound
• A5 1,3-diamino-4-octadecyloxybenzene
• Alkoxysilane alkoxysilane represented by the following formula [E1]
• E2 octadecyltriethoxysilane
• E3 3-methacryloxypropyltrimethoxysilane
• E4 3-ureidopropyltriethoxysilane
• E5 tetraethoxysilane
• S1 Photoradical generator represented by the following formula [S1]
• S2 Photoradical generator represented by the following formula [S2]
• NMP N-methyl-2-pyrrolidone
• NEP N-ethyl-2-pyrrolidone
• ⁇ -BL ⁇ -butyrolactone
• PGME propylene glycol monomethyl ether
• ECS ethylene glycol monoethyl ether
• BCS ethylene glycol monobutyl ether
• PB propylene glycol monobutyl ether
• EC Diethylene glycol monoethyl ether
• This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash
• the imidation ratio of this polyimide was 63%, the number average molecular weight was 17,200, and the weight average molecular weight was 49,100.
• This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash
• the imidation ratio of this polyimide was 54%, the number average molecular weight was 17,400, and the weight average molecular weight was 47,800.
• ⁇ Synthesis Example 14> Prepare a solution of alkoxysilane monomer by mixing ECS (29.2 g), E1 (4.10 g) and E5 (38.8 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, ECS (14.6 g), water (10.8 g), and a solution prepared by mixing oxalic acid (0.50 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes. The mixture was further stirred at 25 ° C. for 30 minutes.
• the liquid crystal display element before a process was obtained. Using a metal halide lamp with an illuminance of 60 mW, the obtained liquid crystal display element before treatment was cut at a wavelength of 350 nm or less, and irradiated with ultraviolet rays at 7 J / cm 2 in terms of 365 nm to obtain a liquid crystal display element. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled at 25 ° C.
• the liquid crystal display element was obtained. Using a metal halide lamp with an illuminance of 60 mW, the obtained liquid crystal display element before treatment was cut at a wavelength of 350 nm or less, and irradiated with ultraviolet rays at 7 J / cm 2 in terms of 365 nm to obtain a liquid crystal display element.
• the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled at 25 ° C.
• the evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better the evaluation (the transmittance values are shown in Tables 13 to 17).
• the scattering characteristics at the time of voltage application were performed by applying 40 V to the liquid crystal display element (glass substrate) by AC driving and visually observing the alignment state of the liquid crystal. Specifically, a device in which this element is clouded, that is, a device having a scattering characteristic, is regarded as excellent in this evaluation (good display in Tables 13 to 17).
• the evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better the evaluation (the transmittance values are shown in Tables 13 to 16).
• the scattering characteristics at the time of voltage application were performed by applying 40V to the liquid crystal display element (plastic substrate) by AC driving and visually observing the alignment state of the liquid crystal. Specifically, a device in which the present element is clouded, that is, a device having a scattering characteristic, is considered to be excellent in this evaluation (good display in Tables 13 to 16).
• Example 1 To the polyamic acid solution (1) (10.5 g) having a resin solid concentration of 25% by mass obtained in Synthesis Example 1, NEP (16.8 g), BCS (16.5 g), S1 (0.263 g), M2 (0.263 g) and K1 (0.132 g) were added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (1).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• a liquid crystal aligning agent (1) and a liquid crystal composition (1) production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 2 NMP (16.0 g), BCS (15.7 g) and S2 (0.125 g) were added to the polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2. In addition, the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (2). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (2) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 3 Using the liquid crystal aligning agent (2) and the liquid crystal composition (2) obtained in Example 2, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties ( Glass substrate) and adhesion evaluation (glass substrate) were performed.
• Example 4 NMP (16.0 g) and BCS (10.7 g) were added to the polyimide powder (3) (1.70 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, S2 (0.085 g) was added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (3) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 5 Using the liquid crystal aligning agent (3) and the liquid crystal composition (2) obtained in Example 4, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties ( Glass substrate) and adhesion evaluation (glass substrate) were performed.
• NEP (16.2 g) and PB (10.8 g) were added to the polyimide powder (3) (1.70 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours.
• S2 (0.085 g), M2 (0.51 g) and K1 (0.17 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (4).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 7 ⁇ -BL (4.20 g) and PGME (24.0 g) were added to the polyimide powder (3) (1.80 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, S2 (0.09 g), M2 (0.36 g) and K1 (0.18 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• liquid crystal aligning agent (5) Using liquid crystal aligning agent (5) and liquid crystal composition (1), production of liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• NEP (15.1 g), BCS (2.70 g) and PB (9.60 g) are added to the polyimide powder (4) (1.75 g) obtained in Synthesis Example 4, and the mixture is stirred at 70 ° C. for 24 hours. And dissolved.
• S1 (0.088 g), M2 (0.35 g), and K1 (0.088 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (6).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 9 Using the liquid crystal aligning agent (6) and the liquid crystal composition (2) obtained in Example 8, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties ( Glass substrate) and adhesion evaluation (glass substrate) were performed.
• Example 10 ⁇ -BL (4.20 g), PGME (21.2 g) and ECS (2.80 g) were added to the polyimide powder (4) (1.80 g) obtained in Synthesis Example 4, and the mixture was added at 70 ° C. for 24 hours. Stir to dissolve. To this solution, S2 (0.126 g), M2 (0.27 g) and K1 (0.18 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• liquid crystal aligning agent (7) Using the liquid crystal aligning agent (7) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• Example 11 ⁇ -BL (1.30 g), PGME (22.0 g) and EC (2.60 g) were added to the polyimide powder (4) (1.65 g) obtained in Synthesis Example 4, and the mixture was added at 70 ° C. for 24 hours. Stir to dissolve. To this solution, S2 (0.083 g) and M2 (0.33 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (8) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 12 ⁇ -BL (2.80 g), PGME (24.0 g) and EC (2.60 g) were added to the polyimide powder (5) (1.80 g) obtained in Synthesis Example 5, and the mixture was added at 70 ° C. for 24 hours. Stir to dissolve. S2 (0.27g) and K1 (0.27g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (9). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• liquid crystal aligning agent (9) Using the liquid crystal aligning agent (9) and the liquid crystal composition (2), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• NMP (16.9 g), BCS (5.60 g) and PB (5.60 g) are added to the polyimide powder (5) (1.80 g) obtained in Synthesis Example 5, and the mixture is stirred at 70 ° C. for 24 hours. And dissolved. S2 (0.018g) and M3 (0.09g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (10).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• the liquid crystal aligning agent (10) and the liquid crystal composition (1) production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 14 ⁇ -BL (2.80 g) and PGME (25.4 g) were added to the polyimide powder (5) (1.80 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, S1 (0.09 g), M2 (0.54 g) and K1 (0.09 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (11) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 15 NMP (16.5 g) and PB (11.0 g) were added to the polyimide powder (5) (1.75 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. S1 (0.263g) and M1 (0.70g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (12).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• a liquid crystal aligning agent (12) and a liquid crystal composition (2) production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 16 ⁇ -BL (5.60 g), PGME (19.7 g) and ECS (2.80 g) were added to the polyimide powder (6) obtained in Synthesis Example 6 (1.80 g), and the mixture was added at 70 ° C. for 24 hours. Stir to dissolve. To this solution, S1 (0.126 g), M2 (0.54 g) and K1 (0.09 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (13). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• liquid crystal aligning agent (13) and the liquid crystal composition (2) Using the liquid crystal aligning agent (13) and the liquid crystal composition (2), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• Example 17 ⁇ -BL (2.80 g), PGME (22.6 g), and EC (2.80 g) were added to the polyimide powder (6) (1.80 g) obtained in Synthesis Example 6, and the mixture was added at 70 ° C. for 24 hours. Stir to dissolve. To this solution, S2 (0.09 g), M2 (0.27 g) and K1 (0.09 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (14). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• liquid crystal aligning agent (14) Using the liquid crystal aligning agent (14) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• NEP (16.8 g) and PB (9.00 g) were added to the polyimide powder (6) (1.65 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours.
• S2 (0.017 g) and M3 (0.248 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (15).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 19 ⁇ -BL (6.70 g) and PGME (20.0 g) were added to the polyimide powder (7) (1.70 g) obtained in Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, S1 (0.34 g) and M2 (0.255 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (16). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (16) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• ⁇ -BL (6.70 g) and PGME (20.0 g) were added to the polyimide powder (7) (1.70 g) obtained in Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours.
• S2 (0.051 g), M1 (0.425 g) and K1 (0.085 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (17).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• a liquid crystal aligning agent (17) and a liquid crystal composition (2) production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 22 ⁇ -BL (2.80 g), PGME (22.6 g) and ECS (2.80 g) were added to the polyimide powder (8) (1.80 g) obtained in Synthesis Example 8, and the mixture was added at 70 ° C. for 24 hours. Stir to dissolve. To this solution, S2 (0.126 g), M2 (0.54 g) and K1 (0.18 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (19). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• liquid crystal aligning agent (19) and the liquid crystal composition (1) Using the liquid crystal aligning agent (19) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• NEP (16.5 g), BCS (5.50 g) and PB (5.50 g) are added to the polyimide powder (8) (1.75 g) obtained in Synthesis Example 8, and the mixture is stirred at 70 ° C. for 24 hours. And dissolved.
• S1 (0.088 g), M2 (0.35 g) and K1 (0.088 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (20).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• NEP (14.6 g) and BCS (12.0 g) were added to the polyimide powder (9) (1.70 g) obtained in Synthesis Example 9, and dissolved by stirring at 70 ° C. for 24 hours.
• S2 (0.17 g) was added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (21).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 25 ⁇ -BL (1.30 g), PGME (24.0 g) and EC (1.30 g) were added to the polyimide powder (9) (1.70 g) obtained in Synthesis Example 9, and the mixture was added at 70 ° C. for 24 hours. Stir to dissolve. To this solution, S1 (0.085 g), M2 (0.51 g) and K1 (0.17 g) were added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (22). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (22) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 26 ECS (10.8 g), BCS (4.20 g) and S2 (0.09 g) were added to the polysiloxane solution (1) (15.0 g) obtained in Synthesis Example 12, and the mixture was stirred at 25 ° C. for 5 hours. Thus, a liquid crystal aligning agent (23) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (23) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• Example 27 Using the liquid crystal aligning agent (23) obtained in Example 26 and the liquid crystal composition (2), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties ( Glass substrate) and adhesion evaluation (glass substrate) were performed.
• Example 28 EC (3.70 g), PB (11.3 g) and S2 (0.09 g) were added to the polysiloxane solution (2) (15.0 g) obtained in Synthesis Example 13, and the mixture was stirred at 25 ° C. for 5 hours. Thus, a liquid crystal aligning agent (24) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the liquid crystal aligning agent (24) and the liquid crystal composition (1), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• Example 29 Using the liquid crystal aligning agent (24) obtained in Example 28 and the liquid crystal composition (2), production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties ( Glass substrate) and adhesion evaluation (glass substrate) were performed.
• Example 30 ECS (13.0 g), PB (3.00 g), S2 (0.192 g) and M2 (0.384 g) were added to the polysiloxane solution (3) (16.0 g) obtained in Synthesis Example 14. It stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (25). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• liquid crystal aligning agent (25) and liquid crystal composition (2) production of liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass) Substrate, plastic substrate) and adhesion evaluation (glass substrate, plastic substrate) were performed.
• Example 31 To the polysiloxane solution (3) (15.0 g) obtained in Synthesis Example 14, ECS (6.50 g), PGME (2.80 g), BCS (5.60 g), S1 (0.09 g) and M2 ( 0.54 g) was added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (26).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• the liquid crystal aligning agent (26) and the liquid crystal composition (1) Production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and adhesion Evaluation (glass substrate) was performed.
• the liquid crystal display element of the example (reverse type element) has higher adhesion between the liquid crystal layer and the vertical liquid crystal alignment film than the liquid crystal display element of the comparative example.
• the orientation was high, and good optical characteristics, that is, transparency when no voltage was applied and scattering characteristics when a voltage was applied were good.
• the liquid crystal display element of the comparative example has poor adhesion between the liquid crystal layer and the vertical alignment film, and after storing it in a high temperature bath, the liquid crystal orientation is disturbed or stored in a high temperature and high humidity bath. Bubbles were observed in the device, or peeling occurred between the liquid crystal layer and the vertical alignment film.
• Example 2 and Comparative Example 3 Example 3 and Comparative Example 4
• Example 4 and Comparative Example 5 Example 5 and Comparative Example 6, Example 28 and Comparative Example 7, and Example 29 and Comparative Example 8
• the liquid crystal display element of the present invention has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, and also has high vertical alignment of the liquid crystal and good optical properties, that is, transparency and voltage application when no voltage is applied.
• the scattering characteristics at the time are good, and it can be suitably used as a reverse element.
• it is useful as a liquid crystal display for display, a light control window for controlling the transmission and blocking of light, an optical shutter element, etc., and when the element is made of a plastic substrate such as a film substrate, it is a glass as a support. It is also possible to use it on a window glass.

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