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
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a transmissive/scattering reverse liquid crystal display element that is in a transparent state when no voltage is applied and is in a scattering state when a voltage is applied.
• a TN (Twisted Nematic) mode As a liquid crystal display element, a TN (Twisted Nematic) mode has been put into practical use. In this mode, it is necessary to use a polarizing plate to switch the light by utilizing the optical rotation property of the liquid crystal. If a polarizing plate is used, the light utilization efficiency will be low.
• a liquid crystal display element that does not use a polarizing plate, there is an element that switches between a transparent state (also called a transparent state) and a scattering state of liquid crystal.
• a transparent state also called a transparent state
• a scattering state of liquid crystal In general, those using a high molecular dispersion liquid crystal (also referred to as PD LC (Polymer Dispersed Liquid Crystal)) or a polymer network liquid crystal (PN LC (Polymer Network Liquid Crystal) are known. ing.
• PD LC Polymer Dispersed Liquid Crystal
• PN LC Polymer Network Liquid Crystal
• liquid crystal display elements a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet rays is placed between a pair of substrates equipped with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays. And a cured product of a polymerizable compound (for example, a polymer network) are formed. Then, in this liquid crystal display element, the transmission state and the scattering state of the liquid crystal are controlled by applying a voltage.
• a polymerizable compound for example, a polymer network
• conventional liquid crystal display devices using PD LC or PN LC are in a cloudy (scattering) state because the liquid crystal molecules are oriented in random directions when no voltage is applied, and the liquid crystal is oriented in the electric field direction when voltage is applied.
• It is a normal type liquid crystal display element (also referred to as a normal type element) that is arranged in a matrix and transmits light to enter a transmissive state.
• a normal type element also referred to as a normal type element
• Patent Document 1 Japanese Patent No. 2 8 8 5 1 1 6
• Patent Document 2 Japanese Patent 4 1 3 2 4 2 4 Publication
• the liquid crystal alignment film used for the reverse type element since the liquid crystal must be vertically aligned, a liquid crystal alignment film that vertically aligns the liquid crystal is used. However, since this liquid crystal alignment film has a high water repellency, the adhesion between the liquid crystal layer and the liquid crystal alignment film will be low. Therefore, a large amount of polymerizable compound must be introduced into the liquid crystal composition used for the reverse type device in order to enhance the adhesion between the liquid crystal layer and the liquid crystal alignment film. However, when a large amount of a polymerizable compound is introduced, there is a problem that the vertical alignment of the liquid crystal is hindered, and the transparency when no voltage is applied and the scattering property when a voltage is applied are greatly reduced. Therefore, the liquid crystal alignment film used for the reverse type element needs to have a high vertical alignment property of the liquid crystal.
• the reverse type element is sometimes used by being stuck on the window glass of an automobile or a building, the vertical alignment of the liquid crystal can be maintained even in a harsh environment exposed to high temperature and high humidity or light irradiation for a long time. It is necessary that the liquid crystal layer does not decrease and the adhesion between the liquid crystal layer and the liquid crystal alignment film is high.
• the present invention provides a liquid crystal having a high vertical alignment property and good optical properties, that is, excellent transparency when no voltage is applied and scattering properties when a voltage is applied, and a liquid crystal layer and a liquid crystal alignment film. It is an object of the present invention to provide a reverse type liquid crystal display element which has high adhesiveness and can maintain these characteristics even in an environment exposed to high temperature and high humidity and light irradiation for a long time. ⁇ 2020/175561 3 units (:171? 2020 /007787 Means for solving problems)
• a liquid crystal composition containing a liquid crystal and a polymerizable compound which is disposed between a pair of substrates provided with electrodes, has a liquid crystal layer that is hardened by applying at least one of active energy rays and heat, and A liquid crystal alignment film is provided on at least one of the substrates, and is a transmissive reverse type liquid crystal display element that is in a transparent state when no voltage is applied and is in a scattering state when a voltage is applied.
• a liquid crystal display device wherein the liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent containing the following component (8) and component (M).
• Component a compound having a group of the following formula [1] (also referred to as a specific compound).
• (Mi) Component A polymer having at least one structure (also referred to as a specific structure (1)) selected from the following formula [2 — 1] and formula [2 — 2].
• a symbol represents a binding site with another structure.
• X I represents a single bond, one (Rei_1 ⁇ 1 2) 3 - (3 is an integer from 1 1 5), one hundred and one, - 0 1 - 1 2 ⁇ -, ⁇ 1, 100 ⁇ (01 ⁇ 1 3 ) —, ( ⁇ 1 ⁇ 13 3 ) (30 1, ⁇ 1 and 1 (indicate at least one selected from ⁇ _.) 2 is a single bond or 1 ( ⁇ 1 to 12 )-- (the ⁇ is an integer of 1 to 15)
• X 4 has at least one divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, or has a steroid skeleton. Indicates a divalent organic group having 17 to 51 carbon atoms, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms.
• X 5 is at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle. Shows that any hydrogen atom on these cyclic groups represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. It may be substituted with a contained alkoxyl group or a fluorine atom.
• X 6 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms.
• At least one selected from 18 fluorine-containing alkoxyl groups is shown.
• X 7 is a single bond, 101, One C ⁇ NH—, one 1 ⁇ 1-1 001, one
• 0_Rei (0 1-1 3) - one (0 1 to 3) 0 0 represents at least one selected from a 0 0 0 and 10,001.
• X 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.
• the liquid crystal has a high vertical alignment property and excellent optical properties, that is, excellent transparency when no voltage is applied and scattering properties when a voltage is applied, and further has a liquid crystal layer and a liquid crystal alignment film. It is possible to obtain a reverse type liquid crystal display element which has a high adhesion with and which can maintain these characteristics even in an environment exposed to high temperature and high humidity for a long time and irradiation of light.
• the liquid crystal alignment film of the present invention is obtained from a liquid crystal alignment treatment agent containing a polymer having the specific structure (1) of the formula [2 — 1] or the formula [2 — 2]. Since the specific structure (1) of the formula [2-1] shows a rigid structure, a liquid crystal display device using a liquid crystal alignment film having this structure can obtain high and stable vertical alignment of liquid crystals. it can. Therefore, in particular, when the specific structure (1) of the formula [2-1] is used, it is considered that a reverse type element exhibiting good optical characteristics can be obtained. Thus, the liquid crystal display device using the liquid crystal alignment treatment agent containing the specific compound and the polymer having the specific structure (1) becomes the liquid crystal display device having the above-mentioned characteristics. Therefore, the liquid crystal display device of the present invention can be used for a liquid crystal display for display, a dimming window for controlling blocking and transmission of light, an optical shutter device, and the like.
• the specific compound is the compound of the above formula [1].
• Ding 1 has at least one kind of structure selected from the following formula [1_3] to formula [1_].
• D represents an alkyl group having 1 to 3 carbon atoms.
• Ding 2 represents a single bond or an organic group having 1 to 18 carbon atoms. Of these, a single bond or an organic group having 1 to 6 carbon atoms is preferable.
• Ding 3 shows the structure of the above formula [1].
• the use ratio of the specific compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of all the polymers. More preferably, it is 0.5 to 20 parts by mass. Most preferred is 1 to 15 parts by mass. Further, the specific compound may be used alone or in combination of two or more, depending on each characteristic.
• the specific structure (1) is the structure of the formula [2 — 1] or the formula [2 — 2]. ⁇ 2020/175561 7 ⁇ (:171? 2020/007787
• X l ⁇ X 6 and c n is as defined above, also in the name or, respectively, preferably from below.
• X 1 is for ease of the availability of raw materials and synthetic, single bond, _ ( ⁇ 31-1 2) (
• 3 is an integer from 1 to 15), 101, 0 or 1 or 0,001 is preferred. More preferred is a single bond, one (Rei_1 ⁇ 1 2) 3 -
• X 2 represents a single bond or one (Rei_1 ⁇ 1 2) -(The swallow is an integer from 1 to 10) is preferred.
• X 3 is, for ease of synthesis, a single bond, one (Rei_1 ⁇ 1 2) 3 - (3 is an integer from 1 1 5), one hundred and one, ten 2 ⁇ one or ten 001 is preferred. More preferably Ino is a single bond, one (Rei_1 ⁇ 1 2) 3 - (3 is an integer from 1 1 0), one hundred and one,
• X 4 is preferably a benzene ring, a cyclohexane ring, or an organic group having a carbon number of 17 to 51 having a skeleton skeleton.
• X 5 is preferably a benzene ring or a cyclohexane ring.
• X 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 10 carbon atoms.
• a fluorine-containing alkyl group having 1 to 10 carbon atoms is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
• Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
• the content of O is 3 to 3. More preferred is O to 2.
• a preferable combination of X 1 to X 6 and X n is as follows.
• the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention is shown to be an organic group having 12 25 carbon atoms having a steroid skeleton.
• the organic group having a carbon number of 12 to 25 having a steroid skeleton is to be read as an organic group having a carbon number of 17 to 51 having a steroid skeleton.
• the combination of 2-603) to (2-6 15) is preferable. Particularly preferred are (2 -49) ⁇ (2-96), (2-1 45) ⁇ (2-1 68), (2-
• X 7 is a single bond, one hundred and one, _ ⁇ _1 ⁇ 1 2 ⁇ one, One C_ ⁇ _N H-, one hundred (Rei_1 ⁇ 1 3) - or ten thousand and one is preferred. More preferred is a single bond, 101, 1001 ⁇ 11 ⁇ 1_ or 1001.
• X 8 is preferably an alkyl group having 8 to 18 carbon atoms.
• the specific structure (1) is preferably contained in the repeating unit constituting the polymer.
• the repeating unit containing the specific structure (1) is preferably contained in an amount of 10 to 80 mol%, more preferably 20 to 70 mol%, based on the entire repeating units constituting the polymer.
• polymer having the specific structure (1) may be used alone or in combination of two or more, depending on each property. ⁇ 0 2020/175 5561 9 (: 17 2020/007787
• the polymer in the invention preferably further has at least one structure selected from the following formulas [3-3] to [3-1] (also referred to as a specific structure (2)).
• Eighteen represents a hydrogen atom or a benzene ring.
• the formula [3-8] to the formula [-dry] are preferable. More preferred are formula [3-3] to formula [3-6]. From the viewpoint of the adhesion between the liquid crystal layer and the liquid crystal alignment film, the formula [3-8], the formula [3 _ 10], the formula [3 _ 0 1] or the formula [3-6] is particularly preferable. ..
• the liquid crystal alignment treatment agent in the present invention preferably further contains a polymer having a specific structure (2).
• the specific structure (2) is preferably contained in the repeating unit that constitutes the polymer.
• the repeating unit containing the specific structure (2) is preferably contained in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, based on the entire repeating units constituting the polymer. is there.
• the liquid crystal layer and the liquid crystal alignment film are photoreacted with the reactive group of the polymerizable compound in the liquid crystal composition in the process of irradiation with ultraviolet rays and heating during the production of the liquid crystal display device. It is thought that the adhesion to and becomes stronger.
• the polymer is not particularly limited, but at least one polymer selected from acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses and polysiloxanes. Coalescence is preferred. More preferred are polyimide precursors or polyimides.
• polyimido polymer When a polyimido precursor or polyimido (collectively referred to as polyimido polymer) is used as a polymer, they are a polyimido precursor or a polyimido precursor obtained by reacting a diamine component with a tetracarboxylic acid component. Polyimide is preferred.
• the polyimide precursor has a structure of the following formula [8].
• [0034] represents a tetravalent organic group. Indicates a divalent organic group. 8 1 and 8 2 are respectively hydrogen atom or carbon number
• n is a positive integer.
• the diamine component is a diamine having two primary or secondary amino groups in the molecule
• the tetracarboxylic acid component is a tetracarboxylic acid compound, a tetracarboxylic dianhydride, or a tetracarboxylic acid.
• examples thereof include a dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkylester dihalide compound.
• a polyamic acid having a structural formula of a repeating unit of the formula [or] or a polyimide obtained by imidizing the polyamic acid is preferable. ⁇ 2020/175561 11 ⁇ (: 171-1?2020/007787
• the polymer of the formula [mouth] obtained above is added to the polymer of the formula [8] having an alkyl group of 1 and 2 having 1 to 8 carbon atoms, and 3 and eight 4 alkyl group or an acetyl group with carbon number from 1 to 5 can also be introduced.
• a diamine having the specific structure (1) As a method of introducing the specific structure (1) into the polyimide polymer, it is preferable to use a diamine having the specific structure (1) as a part of the raw material. Among them, it is preferable to use a diamine (also referred to as a specific diamine (1)) having a structure of at least one selected from the above formulas [2_1] and [2_2]. [0042] In particular, it is preferable to use a diamine represented by the following formula [23].
• X represents at least one structure selected from the formula [2-1] and the formula [2-2]. Also, details of X 1 to X 6 and X n in the formula [2-1], and ⁇ 2020/175561 12 boxes (: 171-1?2020/007787
• a preferred combination is as shown in the above formula [2-1], and details of X 7 and X 8 in the formula [2-2] and a preferable combination are as shown in the above formula [2_2].
• the subscript indicates an integer of 1 to 4. Of these, 1 or 2 is preferable.
• the specific diamine (1) of the formula [2-1] specifically, the formulas described on pages 15 to 19 of International Publication No. 0201 3/1 25595 (published 201. 8.29) [ 2-1]-Formula [2-6], Formula [2-9]-Formula [2-36] The diamine compound of this is mentioned.
• preferred diamines are those described in International Publication WO 201 3/1 2559.
• the optical characteristics of the liquid crystal display element points are the diamines of the formula [2 3 _ 3 2] to the formula [23- 4 1].
• [3 ⁇ 4 3 and [3 ⁇ 4 4 each represent an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.
• the optical characteristics of the liquid crystal display element points, the formula [2 3 _3 5] to the formula [23- 37], are diamines of the formula [23- 40] or formula [23- 4 1] ..
• a fluorine-containing alkyl group is shown.
• the use ratio of the specific diamine (1) is preferably 10 to 80 mol% with respect to the entire diamine component. More preferred is 20 to 70 mol %. Further, the specific diamine (1) can be used alone or in combination of two or more, depending on each characteristic.
• the diamine having (2) is preferable to use as a part of the raw material. Especially the following formula
• a diamine having a structure of [3] also referred to as a specific diamine (2).
• [0051] 1 is a single bond, _ _ _ , _ (0 1 to 1 3 ) _ , _ 0 1 to 1 2 ⁇ _ , _ ⁇ ⁇ one one hundred (0 1-1 3) - one (0 1-1 3) hundred one, indicating at least one selected from the ten thousand and one and ten thousand and one.
• single bond
• ⁇ 2 is a single bond, an alkylene group, or a benzene ring, cyclohexane ring and the carbon number of 6-2 4 organic group having a cyclic group selected from the heterocyclic ring 1-1 8 carbon atoms, on those cyclic groups
• An arbitrary hydrogen atom of is 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, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. It may be replaced.
• a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is preferable. From the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film, more preferred is a single bond or an alkylene group having 1 to 12 carbon atoms. ⁇ 2020/175561 15 ⁇ (: 171-1?2020/007787
• Rei_1 ⁇ 1 3 One (Rei_1 ⁇ 1 3) - one Rei_1 ⁇ 1 2 ⁇ one, ten 0 1 ⁇ 1 3 ) —, 1 (0 1 ⁇ 1 3 ) ⁇ ⁇ 1, 1
• Reference 4 shows at least one structure selected from the above formula [3-8] to formula [3__].
• the formula [3-8] to the formula [-dry] are preferable.
• Equations [3-8] to [3-6] are more preferable.
• From the viewpoint of the adhesiveness between the liquid crystal layer and the liquid crystal alignment film particularly preferred are Formula [3-3], Formula [3-Case], Formula [3_] or Formula [3-6].
• Y n represents an integer of 1 to 4. Of these, 1 or 2 is preferable.
• ⁇ means an integer from 1 to 4. Among them, 1 is preferable.
• More specific specific diamines (2) include the following formulas [3 3 -1] to formulas [3
• Door 1 represents an integer of 2 to 12.
• n 2 represents an integer of 0 to 12.
• n 3 represents an integer of 2 to 12.
• the formula [33-1], the formula [38-2], the formula [38-5] to the formula [38-7], the formula [33-1 1] or the formula [33-1 2] are preferable. More preferred are Formula [33-5] to Formula [33-7], Formula [33-11] or Formula [38-12].
• the specific diamine (2) is preferably used in an amount of 10 to 70 mol% based on the whole diamine component. More preferred is 20 to 60 mol %. Also specific ⁇ 0 2020/175561 17 ⁇ (: 17 2020/007787
• the diamine (2) may be used alone or in combination of two or more depending on each characteristic.
• a diamine other than the specific diamine (1) and the specific diamine (2) (also referred to as other diamine) can also be used as the diamine component for producing the polyimide polymer.
• diamine compounds of Further, other diamines may be used alone or in combination of two or more, depending on each characteristic.
• tetracarboxylic acid component for producing the polyimide-based polymer examples include tetracarboxylic acid dianhydride represented by the following formula [4], tetracarboxylic acid which is a tetracarboxylic acid derivative thereof, tetracarboxylic acid dihalide, and tetracarboxylic acid. It is preferable to use a carboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dihalide (all of which are collectively referred to as a specific tetracarboxylic acid component).
• [0064] represents at least one structure selected from the following formulas [43] to [4I].
• Each represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. And each represent a hydrogen atom or a methyl group.
• the formula [48], the formula [40], and the formula [4] are preferable in view of easiness of synthesis and easiness of polyreactivity in producing a polymer.
• 1] the formula [4 ⁇ ], the formula [4 ⁇ ! 1 ], the formula [4], the formula [41 ⁇ ] or the formula [41] are preferable.
• the formula [48], the formula [46], the formula [4 ⁇ ! 1 ], the formula [4] or the formula [4 I] is particularly preferable.
• the ratio of the specific tetracarboxylic acid component used is preferably 1 mol% or more based on all tetracarboxylic acid components. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more. Most preferably, it is 10 to 90 mol% from the viewpoint of optical characteristics of the liquid crystal display device.
• tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used.
• examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds and dialkyl ester dihalide compounds.
• the specific tetracarboxylic acid component and the other tetracarboxylic acid component may be used alone or in combination of two or more, depending on each characteristic.
• 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. Specific examples include the method described on pages 35 to 36 of International Publication No. 201 5/01 2368 (Published May 29, 201).
• 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 it can dissolve the formed polyimide precursor.
• solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or a solvent represented by the following formula [mouth 1] to formula [03] is used. Can be used.
• ⁇ 3 represents an alkyl group having 1 to 4 carbon atoms.
• the generated polyimide precursor will You may mix and use it in the said solvent in the range which does not precipitate. Further, since water in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the formed polyimide precursor, it is preferable to use dehydrated and dried organic solvent.
• the total number of moles of the tetracarboxylic acid component when the total number of moles of the diamine component is 1.0 is preferably 0.8 to 1.2.
• the polymer has an amino group structure at the terminal, and 1
• it is larger than 0.0, that is, when the total number of moles of the tetracarboxylic acid component is larger than the number of moles of the diamine component, the polymer end has a carboxylic acid anhydride or dicarboxylic acid structure.
• the total number of moles of the tetracarboxylic acid component is greater than 1.0, that is, the total number of moles of the tetracarboxylic acid component is greater than the number of moles of the diamine component. Is also preferably large. Specifically, when the total number of moles of the diamine component is 1.0, it is preferable that the total number of moles of the tetracarboxylic acid component is 1.05 to 1.20.
• Polyimide is a polyimide obtained by ring-closing a polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidation rate) of amide acid groups is not necessarily 100%. It does not need to be present, and can be arbitrarily prepared depending on the application and purpose. Among them, 30 to 80% is preferable from the viewpoint of the solubility of the polyimide polymer in a solvent. More preferred is 40 to 70%.
• the molecular weight of the polyimido polymer is GPC (Gel Perm eat i on Chromatog).
• the Mw (weight average molecular weight) measured by the raphy method is preferably 5,000 to 1,100,000. More preferred are 1 0, 0 0 0 to 1 5 0, 0 0 0.
• the liquid crystal alignment treatment agent contains a specific compound and a polymer having a specific structure (1), and is preferably a solution for forming a liquid crystal alignment film, and contains a specific compound and a specific structure (1). It is a solution containing the polymer and a solvent.
• the content of the polymer component in the liquid crystal alignment treatment agent of the present invention can be appropriately changed by setting the thickness of the liquid crystal alignment film to be formed, but a uniform and defect-free liquid crystal alignment film is formed. It is preferably 1% by weight or more from the standpoint of making it possible, and is preferably 10% by weight or less from the viewpoint of storage stability of the solution. Among them, 2 to 8% by weight is preferable, and 3 to 7% by weight is particularly preferable.
• the polymer component contained in the liquid crystal alignment treatment agent may be a polymer having all the specific structure (1), but in the present invention, as described above, the characteristic structure (1) and the specific structure (1) 2) and both are preferable. In that case, even if one kind of polymer having both the specific structure (1) and the specific structure (2) is used, the polymer having the specific structure (1) and the polymer having the specific structure (2) are You may use together.
• the use ratio of the polymer having the specific structure (2) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the polymer having the specific structure (1). .. More preferably, it is 50 to 200 parts by mass.
• the polymer having the specific structure (2) one kind or two or more kinds can be used according to each property.
• the polymer component may be a mixture of a polymer having the specific structure (1) and a polymer other than the polymer having the specific structure (2).
• the usage ratio of the polymer having no specific structure is preferably 10 to 200 parts by mass with respect to 100 parts by mass of all the polymers having a specific structure. More preferably, it is 10 to 100 parts by mass.
• the content of the solvent in the liquid crystal alignment treatment agent can be appropriately selected from the viewpoint of applying the liquid crystal alignment treatment agent and obtaining a target film thickness.
• the content of the solvent in the liquid crystal alignment treatment agent is preferably 50 to 99.9 mass% from the viewpoint of forming a uniform liquid crystal alignment film by coating. More preferably, it is 60 to 99% by mass. Particularly preferred is 65 to 99% by mass. ⁇ 2020/175561 22 ⁇ (:171? 2020 /007787
• the solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent that dissolves the specific compound and the polymer having the specific structure.
• the polymer is a polyimido precursor, polyimido, polyamid or polyester, or the solubility of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in the solvent is low.
• the polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose or polysiloxane, and further, the polymer is a polyimide precursor, polyimide, polyamide or polyester, When the solubility of these polymers in a solvent is high, the following solvent (also referred to as a solvent) can be used.
• solvent methods are described on pages 58 to 60 of International Publication WO 020 1 4/1 7 1 4 9 3 (2 0 1 4 1 0.2 3 published). Solvents such as Among them, 1-hexanol, cyclohexanol, 1,2-ethanedine
• redone or ⁇ ) ⁇ _butyrolactone in combination. More preferably, it is used in combination with arbutyrolactone.
• solvent grades can enhance the coating property and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, and therefore the polymer precursors, polyimides and polyamides are added to the polymer.
• polyester it is preferably used in combination with the above solvent Eight.
• the amount of the solvent is preferably 1 to 99% by mass of the whole solvent contained in the liquid crystal alignment treatment agent. Above all, 10 to 99 mass% is preferable. More preferably, it is 20 to 95% by mass.
• the liquid crystal alignment treatment agent is at least one selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group in order to enhance the film strength of the liquid crystal alignment film. It is preferable to introduce a compound having: (collectively referred to as a specific crosslinkable compound). In that case, it is necessary for the compound to have two or more of these groups.
• crosslinkable compound having an epoxy group or an isocyanate group examples include epoxy groups or isocyanates described on pages 63 to 64 of International Publication WO 201 4/1 7 1 493 (201 4.1 0.23 publication). Examples thereof include crosslinkable compounds having a group.
• crosslinkable compound having an oxetane group are described in International Publication WO ⁇ /0201.
• crosslinkable compound having a cyclocarbonate group examples include compounds represented by the formula [5-1] disclosed on pages 76 to 82 of International Publication No. 0201 2/01 4898 (published on February 2, 2.2). ⁇ Crosslinkable compounds of the formula [5-42] are mentioned.
• crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group are described in International Publication No. WO 201 4/1 7 1 493 (published 2 01 4.1 0.23), pp. 65 to 66. Melamine derivative or benzoguanamine derivative described in page, and International Publication WO 201 1/1 3275 1 ⁇ 2020/175561 24 ⁇ (:171? 2020 /007787
• the proportion of the specific crosslinkable compound used in the liquid crystal alignment treatment agent is preferably 0.1 to 100 parts by mass based on 100 parts by mass of all polymer components. More preferred is 0.1 to 50 parts by mass because the crosslinking reaction proceeds and the desired effect is exhibited. Particularly preferred is 1 to 30 parts by mass.
• At least one kind of generator also referred to as a specific generator selected from a photoradical generator, a photoacid generator and a photobase generator into the liquid crystal alignment treatment agent.
• Specific examples of the specific generator include the specific generators described on pages 54 to 56 of International Publication No. 201 4/1 7 1 493 (published 201 4.10.23).
• the photo-radical generator is preferably used as the specific generator from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film.
• the liquid crystal alignment treatment agent a compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used. Furthermore, a compound or the like that improves the adhesion between the liquid crystal alignment film and the substrate can be used.
• the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specific examples thereof include the surfactants described on page 67 of International Publication WO 201 4/1 7 1 493 (201 4.1 0.23 publication). In addition, the usage ratio is ⁇ .
• ⁇ 1 to 2 parts by mass is preferable. More preferred is 0.01 to 1 part by mass.
• the liquid crystal alignment treatment agent may be added with a dielectric or a conductive substance for the purpose of changing the electrical properties of the liquid crystal alignment film, such as the dielectric constant and conductivity.
• the liquid crystal composition has a liquid crystal and a polymerizable compound.
• liquid crystal nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal can be used. In that case, it is preferable to use a liquid crystal having a negative dielectric anisotropy for the liquid crystal display element in the present invention. At that time, from the viewpoint of low voltage driving and scattering characteristics, those having a large anisotropy of dielectric constant and a large anisotropy of refractive index are preferable. Further, as the liquid crystal, two or more kinds of liquid crystal can be mixed and used according to the physical properties such as the phase transition temperature, the dielectric anisotropy and the refractive index anisotropy.
• liquid crystal display element As an active element such as TFT (Thin Fiber Transistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also referred to as VHR). Therefore, it is preferable to use, for the liquid crystal, a fluorine-based or chlorine-based liquid crystal whose electric resistance is high and whose V H R does not decrease due to active energy rays such as ultraviolet rays.
• the liquid crystal display device can be made into a guest host type device by dissolving a dichroic dye in the liquid crystal composition. At that time, an element that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied is obtained. Moreover, in this liquid crystal display element, the direction of the director (orientation direction) of the liquid crystal changes by 90 degrees depending on whether or not a voltage is applied. Therefore, this device can obtain higher contrast than the conventional guest-host type device that performs switching in the random alignment and the vertical alignment by utilizing the difference in the light absorption characteristics of the dichroic dye. When the dichroic dye is dissolved, it becomes colored when the liquid crystal is aligned in the horizontal direction, and becomes opaque only in the scattering state. Therefore, it is possible to obtain an element that switches from a colorless and transparent state to a colored and opaque state when no voltage is applied, as a voltage is applied.
• the polymerizable compound in the liquid crystal composition undergoes a polymerization reaction by an active energy ray or heat during the production of a liquid crystal display element to form a polymer network (also referred to as a curable resin).
• a polymer network also referred to as a curable resin.
• the polymerization reaction in the present invention is preferably one that proceeds by irradiation with ultraviolet rays.
• a polymer obtained by polymerizing the polymerizable compound may be introduced into the liquid crystal composition in advance.
• a liquid crystal composition containing a polymerizable compound it is preferable to use.
• the polymerizable compound is not particularly limited as long as it is dissolved in the liquid crystal, but it is necessary that a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists when the polymerizable compound is dissolved in the liquid crystal. .. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is sufficient if the liquid crystal display element is visually inspected and almost uniform transparency and scattering characteristics are obtained in the entire element.
• the polymerizable compound may be a compound that is polymerized by ultraviolet rays or heat, and in that case, the polymerization may proceed in any reaction mode to form a curable resin.
• Specific reaction modes include radical polymerization, cationic polymerization, anionic polymerization and polyaddition reaction.
• the reaction mode of the polymerizable compound is preferably radical polymerization from the viewpoint of optical characteristics of the liquid crystal display device.
• the polymerizable compound the following radical-type polymerizable compound or an oligomer thereof can be used. Further, as described above, it is also possible to use a polymer obtained by polymerizing these polymerizable compounds.
• radical-type polymerizable compounds or oligomers thereof are described on pages 69 to 71 of International Publication No. 20 15/1 4 6 9 8 7 (2 0 1 5 .1 0.1 published).
• the radical-type polymerizable compound to be mounted may be mentioned.
• the proportion of the radical-type polymerizable compound or its oligomer used is, from the viewpoint of the adhesiveness between the liquid crystal layer and the liquid crystal alignment film, relative to 100 parts by mass of the liquid crystal in the liquid crystal composition,
• radical-type polymerizable compound may be used alone or in combination of two or more, depending on each characteristic. ⁇ 2020/175561 27 ⁇ (: 171-1?2020/007787
• a radical initiator also referred to as a polymerization initiator
• a radical initiator that generates a radical by ultraviolet rays
• the proportion of the radical initiator used is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition. More preferred is 0.05 to 10 parts by mass. Further, the radical initiator may be used alone or in combination of two or more depending on each characteristic.
• [0097] 3 1 represents at least one structure selected from the following formulas [5-8] to the formula [5_ ". Among them, the formula [5-8], the formula [5_! ⁇ ], the formula [5_ ⁇ ], the formula [5_], the formula [5-6], or the formula [5_dry] is preferable. From the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film, more preferable are the formula [5-8], the formula [5_6], and the formula [5_6].
• [0099] 38 represents a hydrogen atom or a benzene ring.
• Rei_1 ⁇ 1 3 One (Rei_1 ⁇ 1 3) - one Rei_1 ⁇ 1 2 ⁇ one, ten 0 1 ⁇ 1 3 ) —, 1 (0 1 ⁇ 1 3 ) ⁇ ⁇ 1, 1
• 3 3 is a single bond or one (Rei_1 ⁇ 1 2) 3 - shows a (3 is an integer from 1 1 5).
• a single bond or one (Rei_1 ⁇ 1 2) 3 - (3 is an integer from 1 1 0) is favored arbitrary. More preferred are one (Rei_1 ⁇ 1 2) 3 - (3 is an integer from 1 1 0).
• 3 4 is a single bond, one hundred and one, one Rei_rei_1 ⁇ 1 2 -, represents at least one Bareru selected from ten thousand and one and ten thousand and one. Of these, a single bond, _001 or 100001 is preferred. More preferred is Is.
• a benzene ring a divalent organic group having 1 7-5 1 carbon atoms with a divalent cyclic group, or steroid skeleton selected from the cyclohexane ring and heterocyclic, any of the said cyclic group Hydrogen atom is an alkyl group having 1 to 3 carbon atoms, 1 to 3 carbon atoms
• 3 6 is a single bond, _ _ _ , _ 0 ⁇ 2 _ , _ 0 0 1 ⁇ 1 2 _ , _ 0 1 ⁇ 1 2 _ _ , _ _ _ _ _ _ _ and _ _ _ _ _ 1 Indicates at least one Of these, a single bond, 101, 100111 or 100001 is preferable. More preferred is a single bond, Is.
• a benzene ring shows a cyclic group selected from the cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, an alkyl group of from 1 to 3 carbon atoms, an alkoxy group having a carbon number of 1 to 3 It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.
• an alkyl group or an alkoxy group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms is preferable. More preferred is an alkyl group or alkoxy group having 1 to 12 carbon atoms.
• 3 represents an integer from 0 to 4. Among them, 0 to 2 is preferable.
• the specific liquid crystal-added compound has a site having a rigid structure such as a benzene ring or a cyclohexane ring, and a site represented by 31 in the formula [5 3] that undergoes a polymerization reaction by ultraviolet rays or heat. Therefore, when the specific liquid crystal additive compound is included in the liquid crystal composition, the portion having the rigid structure of the specific liquid crystal additive compound enhances the vertical alignment of the liquid crystal and can enhance the transparency when no voltage is applied. Also, the formula [53] It is possible to keep the polymer network in a dense state by reacting the site of with the compound.
• Specific examples of the specific liquid crystal additive compound include compounds represented by the following formulas [5 3 _ 1] to formula [5 3-11], and it is preferable to use these. ⁇ 2020/175 5561 30 (: 17 2020/007787
• 3 & indicates 1- or 100-, respectively. 3 13 each have 1 carbon
• ⁇ 12 shows an alkyl group. Each 1 represents an integer of 1 to 10. Each 2 represents an integer of 1 or 2.
• [0105] indicates 101 or 1001, respectively.
• Each of 3 ⁇ represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms.
• 3 9 show respectively a carbon number 1-1 2 alkyl or alkenyl group of carbon number 2-1 8.
• Each 5 represents an integer of 1 to 10.
• the use ratio of the specific liquid crystal additive compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition. .. More preferably, it is 0.5 to 20 parts by mass. Especially preferred is
• the specific liquid crystal additive compound may be used alone or in combination of two or more types depending on each characteristic.
• the liquid crystal composition may be prepared by mixing the liquid crystal, the polymerizable compound, and the specific liquid crystal additive compound together, or by previously mixing the polymerizable compound and the specific liquid crystal additive compound with the liquid crystal. There is a method of doing.
• a method of mixing a mixture of the polymerizable compound and the specific liquid crystal additive compound in advance with the liquid crystal is preferable.
• liquid crystal composition When the liquid crystal composition is prepared as described above, heating can be performed depending on the solubility of the polymerizable compound and the specific liquid crystal additive compound.
• the temperature at that time is preferably less than 100°.
• the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, and the like. Those films can be used. In particular, when used for a light control window or the like, a plastic substrate or film is preferable.
• a substrate on which an IZO (Indium GaUium Zinc Oxide) electrode, an organic conductive film, or the like is formed.
• a substrate such as a silicon wafer or a metal such as aluminum or a substrate on which a dielectric multilayer film is formed can be used.
• the liquid crystal display element has a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a specific compound and a polymer having a specific structure on at least one side of the substrate.
• a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a specific compound and a polymer having a specific structure on at least one side of the substrate.
• both substrates have a liquid crystal alignment film.
• the method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, screen printing, offset printing, flexo printing ! ⁇ , ink jet method, dip method, mouth coater method, slit coater method.
• a spinner method, a spray method, and the like which can be appropriately selected depending on the type of substrate and the target thickness of the liquid crystal alignment film.
• the type of the substrate and the solvent used for the liquid crystal alignment treatment agent are heated by a heating means such as a hot plate, a heat circulation type oven, or an R (infrared) type oven. Accordingly, the liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 300 ° C., preferably 30 to 250° C. Particularly when a plastic substrate is used as the substrate, it is preferable to perform the treatment at a temperature of 30 to 150 ° C.
• the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the element may be deteriorated.
• the liquid crystal composition used for the liquid crystal display element is the liquid crystal composition as described above, and a spacer for controlling the electrode gap (also referred to as a gap) of the liquid crystal display element is included therein. It can also be introduced.
• the method of injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. That is, when a glass substrate is used as the substrate, prepare a pair of substrates on which the liquid crystal alignment film is formed, apply the sealant on four pieces of the substrate on one side except for a part, and then, on the surface of the liquid crystal alignment film. Make the inside of so that the other side of the substrate is attached to form an empty cell. Then, a method of injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied to obtain a liquid crystal composition injection cell can be mentioned. Furthermore, when using a plastic substrate or film as the substrate, prepare a pair of substrates on which a liquid crystal alignment film is formed, and place one on one substrate.
• the liquid crystal composition may be dropped by a method such as a [strike] method or an inkjet method, and then the other substrate is bonded to obtain a liquid crystal composition injection cell.
• a method such as a [strike] method or an inkjet method
• the adhesiveness between the liquid crystal layer and the liquid crystal alignment film is high, and therefore it is not necessary to apply the sealant to the four pieces of the substrate.
• the gap of the liquid crystal display device can be controlled by the spacer or the like.
• Examples of the method include a method of introducing a spacer having a target size into the liquid crystal composition and a method of using a substrate having a column spacer of a target size, as described above.
• the gap can be controlled without introducing a spacer.
• the size of the gap of the liquid crystal display element is preferably 1 to 100.
• the more preferable range is 1 to 5001. Particularly preferred is 2 to 3001. If the gap is too small, the contrast of the liquid crystal display device will be lowered, and if it is too large, the driving voltage of the liquid crystal display device will be high.
• the liquid crystal display device is obtained by curing the liquid crystal composition to form a liquid crystal layer in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity.
• the liquid crystal composition is cured by irradiating the liquid crystal composition injecting cell with ultraviolet rays or heating.
• ⁇ 2020/175561 34 ⁇ (: 171-1?2020/007787
• irradiation with ultraviolet rays is preferable.
• Examples of the light source of the ultraviolet irradiation device used for ultraviolet irradiation include a metal halide lamp or a high-pressure mercury lamp.
• the wavelength of ultraviolet rays is 2 Is preferred. Of these, 310 to 370 n is preferable. Further, heat treatment may be performed after irradiation with ultraviolet rays.
• the temperature at that time is preferably 40 to 120°. More preferred is 40 to 80°
• a heating means used after applying the liquid crystal alignment treatment agent on a substrate can be mentioned.
• the temperature at that time is appropriately selected depending on the temperature at which the reaction of the polymerizable compound proceeds and the type of substrate. Specifically, preferably 8 0 ° ⁇ _ ⁇ 2 0 0 ° ⁇ .
• Standard sample for making calibration curve Ding 3 ⁇ Standard polyethylene oxide (Molecular weight: about 900,000, 150,000, 100,000 and 30,000) (Tosoh Corporation) and Polyethylene glycol (Molecular weight; Approx. 1 2,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
• This solution 500 IV! 1 to 12 protons IV! were measured with a measuring machine (" ⁇ /_Mitsuhachi 500) (manufactured by JEOL DATAM).
• the imidation rate is determined by using the proton derived from the structure that does not change before and after imidization as the reference proton, and the peak integrated value of this proton and the 1 ⁇ 11% of the amide acid appearing around 9.5 0 to 1 0.0. It was calculated by the following formula using the integrated value of the proton peak derived from ⁇ 1 group.
• ⁇ I) and ⁇ 1 are mixed in 1 ⁇ /1? (1 0.39) and reacted at 80° ⁇ for 4 hours, then 01 (1.20 9, 6.1 2 Rei_1_rei_1_rei ⁇ ) and 1 ⁇ / 1? a (5.1 3 9) was added, reacted at 40 ° ⁇ 6 hours, the resin solid content of 25 mass%
• a polyamic acid solution (1) was obtained.
• the number average molecular weight (also referred to as 1 ⁇ / ⁇ ) of this polyamic acid was 19,800, and the weight average molecular weight (also referred to as IV! was 61,200.
• a polyamic acid solution (2) having a solid content concentration of 25 mass% was obtained.
• the IV! n of this polyamic acid was 21 1, 100 and 1 ⁇ /1 was 63,500.
• a polyamic acid solution (5) having a resin solid content concentration of 25 mass% was obtained.
• the IV! n of this polyamic acid was 14,500 and 1 ⁇ /1 was 45,100.
• a polyamic acid solution (7) having a resin solid content concentration of 25 mass% was obtained.
• the IV! n of this polyamic acid was 12,000 and 1 ⁇ /1 was 40,100.
• a polyamic acid solution (9) having a solid content concentration of 25% by mass was obtained.
• the IV! n of this polyamic acid was 22,900 and 1 ⁇ /1 was 65,700.
• Table 1 shows the polyimide-based polymers obtained in the synthesis examples.
• Tables 2 to 4 show the liquid crystal alignment treatment agents obtained in the examples.
• the liquid crystal alignment treatment agents obtained by the methods of Examples and Comparative Examples were pressure-filtered with a membrane filter having a pore size of 1.
• the resulting solution was washed with pure water and water (isopropyl alcohol) 100X100 Glass substrate with electrodes (vertical: 1 0001111, horizontal: 1 0001111, thickness: 0.7071111) spin coated on the I-plane of the substrate and 100 ° on the hot plate .
• electrodes vertical: 1 0001111, horizontal: 1 0001111, thickness: 0.7071111
• the liquid crystal compositions () to ( ⁇ ) are dropped by the method of ( ⁇ 0 “ ⁇ ⁇ _ _ 1 1 _1 hit), and then the liquid crystal alignment film surfaces of the other substrate are bonded so that they face each other. A liquid crystal display device before the process was obtained.
• liquid crystal display element before this treatment A dramp was used to cut wavelengths of 350 n or less, and UV irradiation was performed for an irradiation time of 60 seconds. As a result, a liquid crystal display element (glass substrate) was obtained.
• the liquid crystal alignment treatment agents obtained by the methods of Examples and Comparative Examples were pressure-filtered with a membrane filter having a pore size of 1.
• the obtained solution was washed with pure water 15 Mingo substrate with electrodes (vertical: 150 1 0 1, horizontal: 1 5 0 Of was applied by a bar coater ⁇ Ding ⁇ surface on, then for 2 minutes heat treatment at 1 2 0 ° ⁇ at Netsu ⁇ ring oven, the film thickness is 1 0 0 n m with a liquid crystal alignment film I got a board of No Ding 0.
• the liquid crystal compositions () to ( ⁇ ) were dropped by the method of ⁇ ( ⁇ ⁇ ⁇ ⁇ 11 1 _1 hit) method, and then the other Bonding was performed so that the liquid crystal alignment film surfaces of the substrates faced each other to obtain an unprocessed liquid crystal display element
• ⁇ ⁇ ⁇ ⁇ ⁇ 11 1 _1 hit
• the other Bonding was performed so that the liquid crystal alignment film surfaces of the substrates faced each other to obtain an unprocessed liquid crystal display element
• liquid crystal display element plastic substrate
• liquid crystal display element glass substrate and plastic substrate
• voltage AC drive:
• Example 6 The measurement results of Example 6 are summarized in Tables 5 to 7.
• the liquid crystal display elements (glass substrate and plastic substrate) were stored for 24 hours in a thermo-hygrostat at a temperature of 80 ° and a humidity of 90% [3 ⁇ 4!! It was performed by confirming the presence or absence of air bubbles (as a stability test of the liquid crystal display element under high temperature and high humidity environment). Specifically, there is no peeling of the device (a state in which the liquid crystal layer and the liquid crystal alignment film, or the liquid crystal alignment film and the electrode are peeled off), and one in which no bubbles are generated in the element. The evaluation was excellent (good display in the table).
• liquid crystal display device is equipped with a desk-top type II V curing device (1 to 10 3 3 2 8 1 to 1 1 1
• liquid crystal display element is obtained by the method.
• the optical characteristics scattering characteristics and transparency
• the adhesion between the liquid crystal layer and the liquid crystal orientation film liquid crystal orientation film and electrode
• Examples 14 to Example 18, Example 26, Comparative Example 5, Comparative Example 6 and Comparative Example 8 were manufactured and each evaluation of a liquid crystal display element using a glass substrate, Example 1 In 9 to Example 25 and Comparative Example 7, a plastic substrate was used.
• the liquid crystal display element of the example using the liquid crystal alignment treatment agent containing the specific compound and the polymer having the specific structure (1) has a higher isothermal temperature than the comparative example not using it.
• the change in !3 3 2 6 after storage in a constant humidity chamber and after irradiation with ultraviolet light became smaller.
• neither peeling of the liquid crystal display element nor generation of bubbles was observed even after storage in a constant temperature and humidity chamber and after irradiation with ultraviolet rays.
• the polymer terminal has a carboxylic acid or dicarboxylic acid structure, that is, when the diamine component and the tetracarboxylic acid component are polymerized, If the total number of moles of the components is greater than the number of moles of the diamine component, one having a structure with an amino group at the polymer end (the total number of moles of the tetracarboxylic acid component during the above-mentioned polymer reaction is The generation of bubbles in the liquid crystal display element during the stress test was suppressed compared to the smaller one). Specifically, in comparison under the same conditions, Example 14 and Example 15 are compared.
• Example 21 is a comparison between Example 21 and Example 22 under the same conditions.
• liquid crystal alignment film obtained from a liquid crystal orientation treatment agent containing a compound having a specific structure and a polymer having a specific structure
• the liquid crystal alignment film can be exposed to high temperature and high humidity and irradiation of light for a long time. It is possible to obtain a liquid crystal display device capable of suppressing peeling of the device, generation of bubbles, and deterioration of optical characteristics even in a severe environment.
• liquid crystal display element of the present invention can be suitably used for a reverse type element which is in a transparent state when no voltage is applied and is in a scattering state when a voltage is applied.
• this device can be used for liquid crystal displays for display purposes, as well as for dimming windows and optical shutter devices that control the blocking and transmission of light.
• a plastic substrate can be used.

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