CN107003567B - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDF

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CN107003567B
CN107003567B CN201580061923.0A CN201580061923A CN107003567B CN 107003567 B CN107003567 B CN 107003567B CN 201580061923 A CN201580061923 A CN 201580061923A CN 107003567 B CN107003567 B CN 107003567B
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CN107003567A (en
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桥本淳
若林晓子
三木德俊
保坂和義
中家直树
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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Abstract

A liquid crystal aligning agent comprising the following components (A) and (B). (A) The components: a heteropoly acid. (B) The components: a polymer.

Description

Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
Technical Field
The present invention relates to a liquid crystal aligning agent used for producing a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film.
Background
Liquid crystal display elements are widely used today as display devices that achieve a thin volume/light weight. In general, in the liquid crystal display element, a liquid crystal alignment film is used to determine the alignment state of liquid crystal.
With the increase in the definition of liquid crystal display elements, the liquid crystal alignment film used for the liquid crystal display elements is required to have a high voltage holding ratio from the viewpoint of suppressing the decrease in contrast and reducing the image sticking phenomenon. In contrast, a liquid crystal aligning agent containing a polyamic acid, an imidized polymer thereof, and the like, and a very small amount of a compound selected from the group consisting of a compound having 1 carboxylic acid group in the molecule, a compound having 1 carboxylic anhydride group in the molecule, and a compound having 1 tertiary amino group in the molecule is used (for example, see patent document 1).
Further, with the increase in definition of liquid crystal display elements, it is required to suppress a decrease in contrast of the liquid crystal display elements and display defects associated with long-term use. On the other hand, as a method for improving the liquid crystal alignment property and preventing the occurrence of defective display in the peripheral portion of the liquid crystal display screen, a liquid crystal alignment film using a liquid crystal alignment treatment agent to which an alkoxysilane compound is added has been proposed (for example, see patent document 2 or patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 8-76128
Patent document 2: japanese laid-open patent publication No. 61-171762
Patent document 3: japanese laid-open patent publication No. 11-119226
Disclosure of Invention
Problems to be solved by the invention
With the recent enhancement of the performance of liquid crystal display elements, liquid crystal display elements have been used in liquid crystal televisions having a large screen and high definition, and in vehicle-mounted applications such as car navigation systems and instrument panel panels. In these applications, a backlight having a large heat radiation amount may be used to obtain high luminance. Therefore, from another viewpoint, the liquid crystal alignment film is required to have high reliability, that is, high stability against light from a backlight. In particular, when the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, is lowered by light irradiation from a backlight, an afterimage defect (also referred to as a line afterimage), which is one of the display defects of the liquid crystal display element, is likely to occur, and a highly reliable liquid crystal display element cannot be obtained. Therefore, the liquid crystal alignment film is required to have good initial characteristics, and is also required to have a voltage holding ratio that is not easily lowered even after long-term exposure to light, for example.
In addition, in mobile applications such as smartphones and cellular phones, the use environment is becoming severer than ever before. That is, the present invention is sometimes used under high temperature and high humidity, in addition to the environment of room temperature and low humidity. When used under such high temperature and high humidity conditions, there are the following problems: water is likely to enter between the sealant of the liquid crystal display element and the liquid crystal alignment film, and display unevenness is likely to occur in the vicinity of the edge of the liquid crystal display element. Therefore, it is required that such a display failure does not occur even under high-temperature and high-humidity conditions.
Accordingly, an object of the present invention is to provide a liquid crystal alignment film having the above-described characteristics. That is, an object of the present invention is to provide a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio even after long-term exposure to light. Further, it is an object of the present invention to provide a liquid crystal alignment film which does not cause display unevenness in the vicinity of the edge of a liquid crystal display element even under high-temperature and high-humidity conditions.
It is another object of the present invention to provide a liquid crystal display element having the liquid crystal alignment film, a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film, and a composition used for the liquid crystal alignment treatment agent.
Means for solving the problems
The inventors of the present invention conducted extensive studies and found that: the liquid crystal aligning agent comprising a compound of a specific structure and a polymer is extremely effective for achieving the above object, and the present invention has been completed.
That is, the present invention has the following gist.
(1) A liquid crystal aligning agent comprising the following components (A) and (B).
(A) The components: a heteropoly acid.
(B) The components: a polymer.
(2) The liquid crystal alignment treatment agent according to the above (1), wherein the heteropoly acid is at least 1 selected from the group consisting of phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid and phosphotungstomolybdic acid.
(3) The liquid crystal aligning agent according to the above (1) or (2), wherein the polymer has a nitrogen-containing aromatic heterocycle.
(4) The liquid crystal alignment treatment agent according to any one of the above (1) to (3), wherein the polymer is at least 1 selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, a polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane.
(5) The liquid crystal aligning agent according to the item (4), wherein the polymer is a polyimide precursor obtained by a reaction between a diamine component and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor.
(6) The liquid crystal aligning agent according to the item (5), wherein the diamine component contains a diamine compound having a structure represented by the following formula [2 ].
-W1-W2-W3-W4 [2]
(W1Represents a group selected from-O-, -NH-, -N (CH)3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3) -and-N (CH)3) At least 1 bonding group of the group consisting of CO-. W2Represents at least 1 selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring. W3Represents a group selected from the group consisting of a single bond, -O-, -NH-, -N (CH)3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、-N(CH3) CO-and-O (CH)2)mAt least 1 kind of- (m represents an integer of 1-5). W4Represents a nitrogen-containing aromatic heterocycle. )
(7) The liquid crystal aligning agent according to the item (6), wherein the diamine component contains a diamine compound represented by the following formula [2a ].
Figure BDA0001294629370000041
(W represents a structure represented by the formula [2], and m1 represents an integer of 1 to 4.)
(8) The liquid crystal alignment treatment agent according to any one of the above (5) to (7), wherein the diamine component contains a diamine compound having a structure represented by the following formula [3-1] or formula [3-2 ].
Figure BDA0001294629370000042
(Y1Is selected from the group consisting of a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from the group consisting of CO-, -COO-and-OCO-. Y is2Represents a single bond or- (CH)2)b- (b is an integer of 1 to 15). Y is3Is selected from the group consisting of a single bond, - (CH)2)c- (c is an integer of 1 to 15), -O-, -CH2At least 1 of the group consisting of O-, -COO-and-OCO-. Y is4At least 1 2-valent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocycle, or a 2-valent organic group having 17 to 51 carbon atoms and having a steroid skeleton, wherein any hydrogen atom on the cyclic group is optionally substituted by 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Y is5Represents at least 1 cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic groups is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom. n represents an integer of 0 to 4. Y is6Represents at least 1 selected from the group consisting of C1-18 alkyl, C2-18 alkenyl, C1-18 fluoroalkyl, C1-18 alkoxy and C1-18 fluoroalkoxy. )
-Y7-Y8 [3-2]
(Y7Represents a group selected from the group consisting of a single bond, -O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from the group consisting of CO-, -COO-and-OCO-. Y is8Represents an alkyl group having 8 to 18 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms. )
(9) The liquid crystal aligning agent according to the item (8), wherein the diamine compound is represented by the following formula [3a ].
Figure BDA0001294629370000051
(Y represents a structure represented by the formula [3-1] or the formula [3-2], and n1 represents an integer of 1 to 4.)
(10) The liquid crystal aligning agent according to any one of the above (5) to (9), wherein the tetracarboxylic acid component comprises a tetracarboxylic dianhydride represented by the following formula [4 ].
Figure BDA0001294629370000052
(Z represents at least 1 structure selected from the group consisting of structures represented by the following formulas [4a ] to [4k ])
Figure BDA0001294629370000061
(Z1～Z4Each independently represents at least 1 selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring. Z5And Z6Each independently represents a hydrogen atom or a methyl group. )
(11) The liquid crystal aligning agent according to any one of the above (1) to (10), wherein the liquid crystal aligning agent contains at least 1 solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ -butyrolactone.
(12) The liquid crystal aligning agent according to any one of the above (1) to (11), wherein the liquid crystal aligning agent contains at least 1 solvent selected from the group consisting of 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and solvents represented by the following formulae [ D1] to [ D3 ].
Figure BDA0001294629370000062
(D1Represents an alkyl group having 1 to 3 carbon atoms. D2Represents an alkyl group having 1 to 3 carbon atoms. D3Represents an alkyl group having 1 to 4 carbon atoms. )
(13) The liquid crystal aligning agent according to any one of the above (1) to (12), wherein the liquid crystal aligning agent contains: a crosslinkable compound having a group selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group and a cyclocarbonate group; a crosslinkable compound having a group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms; or a crosslinkable compound having a polymerizable unsaturated bonding group.
(14) A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of the above (1) to (13).
(15) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of the above (1) to (13) by an ink jet method.
(16) A liquid crystal display element comprising the liquid crystal alignment film according to the above (14) or (15).
(17) The liquid crystal alignment film according to the above (14) or (15), which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes, wherein the liquid crystal display element is manufactured through the following steps: a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the polymerizable compound is polymerized while applying a voltage between the electrodes.
(18) A liquid crystal display element comprising the liquid crystal alignment film according to (17) above.
(19) The liquid crystal alignment film according to the above (14) or (15), which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes, wherein the liquid crystal display element is manufactured through the following steps: a liquid crystal alignment film including a polymerizable group that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the polymerizable group is polymerized while applying a voltage between the electrodes.
(20) A liquid crystal display element comprising the liquid crystal alignment film according to (19) above.
ADVANTAGEOUS EFFECTS OF INVENTION
The liquid crystal alignment treatment agent containing the specific compound and the polymer can obtain a liquid crystal alignment film which can inhibit the reduction of the voltage holding ratio even after long-term exposure to light irradiation. Further, a liquid crystal alignment film which does not cause display unevenness in the vicinity of the edge of the liquid crystal display element even under high-temperature and high-humidity conditions can be formed.
The mechanism by which the liquid crystal display element having the above-described excellent characteristics can be obtained by the present invention is not clear, and can be roughly estimated as follows.
The present invention relates to a liquid crystal aligning agent containing the following component (a) and component (B), a liquid crystal alignment film obtained using the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film.
(A) The components: heteropoly acids (also referred to as specific compounds).
(B) The components: a polymer.
The effects of the specific compound can be considered as follows. As one factor of the decrease in the voltage holding ratio, a large amount of ionic impurity components may be present in the liquid crystal. In contrast, when the liquid crystal display element is exposed to light for a long period of time and the liquid crystal is decomposed, the specific compound adsorbs ionic impurity components generated at that time, and it is considered that the decrease in the voltage holding ratio is suppressed. Further, it can be considered that: when a polymer having a nitrogen-containing aromatic heterocycle is used, the effect of the heterocycle can be further improved.
Further, when a polyimide precursor obtained by the reaction of a diamine component and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor is used as the polymer, and a diamine compound having a structure represented by the above formula [3-1] or formula [3-2] is used as the diamine component in the case of the polymer, and a liquid crystal Alignment treatment agent for a liquid crystal display element of a Vertical Alignment (VA) mode, a PSA (Polymer stabilized Alignment) mode or an SC-PVA mode is used, the structure represented by the formula [3-1] shows a rigid structure in particular, and therefore, a liquid crystal display element using a liquid crystal Alignment film having such a structure is stable against light such as ultraviolet light, and the occurrence of ionic impurities which reduce the voltage holding ratio can be suppressed.
Thus, a liquid crystal display element provided with a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for a large-screen, high-definition liquid crystal television set or the like. In particular, the present invention is useful for a liquid crystal display element obtained using a PSA mode or an SC-PVA mode in which high-energy ultraviolet rays are irradiated when the liquid crystal display element is manufactured.
Detailed Description
< specific Compound >
The specific compound in the present invention is a heteropoly acid.
Heteropolyacids typically refer to: has a structure represented by a Keggin type chemical structure represented by the following formula [1-1] or a Dawson type chemical structure represented by the following formula [1-2] in which a hetero atom is located at the center of a molecule, and is obtained by condensing an isopolyacid, which is an oxyacid of vanadium (V), molybdenum (Mo), tungsten (W), or the like, and an oxyacid of a different element. Examples of the oxyacids of such different elements include oxyacids of silicon (Si), phosphorus (P) and arsenic (As).
Figure BDA0001294629370000091
Specific examples of the heteropoly acid compound include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid, and the like, and in the present invention, these compounds are preferably used. Further, they may be used alone, or 2 or more kinds thereof may be used in combination. The heteropoly acid compound in the present invention can be obtained as a commercially available product, or can be synthesized by a known method.
In quantitative analysis such as elemental analysis, the heteropoly-acid can be used in the present invention as long as it is obtained as a commercially available product or appropriately synthesized according to a known synthesis method, regardless of the number of elements, depending on the structure represented by the general formula.
That is, for example, phosphotungstic acid generally has a structure represented by the following formula [1a ], and phosphomolybdic acid generally has a structure represented by the following formula [1b ].
H3(PW12O40)·nH2O [1a] H3(PMo12O40)·nH2O [1b]
In the quantitative analysis, the compounds of the present invention can be used in the present invention as long as they are obtained as commercially available products or appropriately synthesized according to a known synthesis method, regardless of whether the amount of P (phosphorus), O (oxygen), W (tungsten) or Mo (molybdenum) in the formulae is large or small. In this case, the mass of the heteropoly-acid specified in the present invention is not the pure mass (phosphotungstic acid content) of phosphotungstic acid in the composition and/or commercial product, but means: the total mass of the product in a state of containing water of hydration or other impurities in a form that can be obtained as a commercially available product and in a form that can be separated by a known synthesis method.
< polymers >
The polymer of the present invention is preferably at least 1 polymer selected from the group consisting of acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyimide precursors, polyimide, polyamide, polyester, cellulose, and polysiloxane. More preferably a polyimide precursor, polyimide or polysiloxane. Particularly preferred is a polyimide precursor or polyimide (also collectively referred to as a specific polyimide-based polymer).
In addition, as described above, in order to further enhance the effect of the present invention, these polymers preferably contain a nitrogen-containing aromatic heterocycle.
The nitrogen-containing aromatic heterocycle is a heterocycle having a structure represented by the following formula [ a ], formula [ b ] or formula [ c ].
Figure BDA0001294629370000101
(Wa represents an alkyl group having 1 to 5 carbon atoms.)
More specifically, there may be mentioned a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a Benzimidazole ring (Benzimidazole ring), a cinnoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring and an acridine ring. Among them, preferred is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring or a benzimidazole ring. From the viewpoint of being able to suppress a decrease in voltage holding ratio after long-term exposure to light irradiation, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring is more preferable. Particularly preferred is an imidazole ring or a pyridine ring.
< specific polyimide-based Polymer >
When the specific polyimide-based polymer is used as the polymer of the present invention, it is preferably a polyimide precursor or a polyimide obtained by reacting a diamine component with a tetracarboxylic acid component.
The polyimide precursor has a structure represented by the following formula [ A ].
Figure BDA0001294629370000111
(R1Represents a 4-valent organic group. R2Represents a 2-valent organic group. A. the1And A2Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A. the3And A4Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group. nA represents a positive integer.
The diamine component includes a diamine having 2 primary or secondary amino groups in the molecule. Examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound.
The specific polyimide polymer is preferably a polyamic acid having a structural formula including a repeating unit represented by the following formula [ D ] or a polyimide obtained by imidizing the polyamic acid, because the polyimide can be obtained relatively easily from a tetracarboxylic dianhydride represented by the following formula [ B ] and a diamine represented by the following formula [ C ]. Among them, in the present invention, polyimide obtained by imidizing a polyimide precursor is preferable from the viewpoint of physical stability and chemical stability of the liquid crystal alignment film.
Figure BDA0001294629370000121
(R1And R2And formula [ A]The meanings defined in (1) are the same. )
Figure BDA0001294629370000122
(R1、R2And nA and formula [ A]The meanings defined in (1) are the same. )
Further, the formula [ D ] obtained as described above can also be synthesized by a usual synthesis method]Into the polymer of the formula [ A ]]Shown as A1And A2An alkyl group having 1 to 8 carbon atoms and the formula [ A]Shown as A3And A4An alkyl group or acetyl group having 1 to 5 carbon atoms.
As the diamine component in the present invention, a known component can be used.
Among them, as described above, in order to further improve the effect of the present invention, it is preferable to use a diamine compound having a structure represented by the following formula [2] (also referred to as a specific structure (1)).
-W1-W2-W3-W4 [2]
Formula [2]]In, W1、W2、W3And W4As shown in the above definitionAmong them, the following groups are each preferable.
W1preferably-O-, -NH-, -CONH-, -NHCO-, -CH2O-、-OCO-、-CON(CH3) -or-N (CH)3) CO-. From the viewpoint of ease of synthesis, -O-, -NH-, -CONH-, -NHCO-, -CH are more preferable2O-, -OCO-or-CON (CH)3) -. Particularly preferred is-O-, -CONH-or-CH2O-。
W2Represents at least 1 selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring.
The alkylene group having 1 to 20 carbon atoms may be straight or branched. Further, the resin composition may have an unsaturated bond. Among them, alkylene groups having 1 to 10 carbon atoms are preferable from the viewpoint of ease of synthesis.
Specific examples of the non-aromatic ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, bicycloheptane ring, decalin ring, norbornene ring, and adamantane ring. Among them, preferred is a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring.
Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, and a phenalene ring. Among them, preferred is a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring.
As W2Preferably, the compound is a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring. Among them, from the viewpoint of ease of synthesis and the viewpoint of being able to suppress a decrease in voltage holding ratio after long-term exposure to light, a single bond or carbon is preferableAn alkylene group having a number of 1 to 5, a cyclohexane ring or a benzene ring.
W3Preferably a single bond, -O-, -COO-, -OCO-or-O (CH)2)m- (m represents an integer of 1 to 5). From the viewpoint of ease of synthesis, a single bond, -O-, -OCO-or-O (CH) is more preferable2)m- (m represents an integer of 1 to 5).
W4Represents a nitrogen-containing aromatic heterocycle containing the formula [ a ] as described above]Is of the formula [ b]Or formula [ c]Heterocyclic ring of the structure shown. Specifically, as described above, among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring is preferable. From the viewpoint of being able to suppress a decrease in voltage holding ratio after long-term exposure to light irradiation, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring is more preferable. Particularly preferred is an imidazole ring or a pyridine ring.
Further, formula [2]W in3Preferably with W4Is not related to the formula [ a ] contained in]Is of the formula [ b]And formula [ c]Adjacent substituents are bonded.
Formula [2]]W in1、W2、W3And W4The preferable combinations of (A) are shown in tables 1 to 31 below.
[ Table 1]
W1 W2 W3 W4
a-1 -O- Single bond Single bond Pyrrole ring
a-2 -NH- Single bond Single bond Pyrrole ring
a-3 -CONH- Single bond Single bond Pyrrole ring
a-4 -NHCO- Single bond Single bond Pyrrole ring
a-5 -CH2O- Single bond Single bond Pyrrole ring
a-6 -OCO- Single bond Single bond Pyrrole ring
a-7 -CON(CH3)- Single bond Single bond Pyrrole ring
a-8 -O- Single bond Single bond Imidazole ring
a-9 -NH- Single bond Single bond Imidazole ring
a-10 -CONH- Single bond Single bond Imidazole ring
a-11 -NHCO- Single bond Single bond Imidazole ring
a-12 -CH2O- Single bond Single bond Imidazole ring
a-13 -OCO- Single bond Single bond Imidazole ring
a-14 -CON(CH3)- Single bond Single bond Imidazole ring
a-15 -O- Single bond Single bond Pyrazole ring
[ Table 2]
W1 W2 W3 W4
a-16 -NH- Single bond Single bond Pyrazole ring
a-17 -CONH- Single bond Single bond Pyrazole ring
a-18 -NHCO- Single bond Single bond Pyrazole ring
a-19 -CH2O- Single bond Single bond Pyrazole ring
a-20 -OCO- Single bond Single bond Pyrazole ring
a-21 -CON(CH3)- Single bond Single bond Pyrazole ring
a-22 -O- Single bond Single bond Pyridine ring
a-23 -NH- Single bond Single bond Pyridine ring
a-24 -CONH- Single bond Single bond Pyridine ring
a-25 -NHCO- Single bond Single bond Pyridine ring
a-26 -CH2O- Single bond Single bond Pyridine compoundRing (C)
a-27 -OCO- Single bond Single bond Pyridine ring
a-28 -CON(CH3)- Single bond Single bond Pyridine ring
a-29 -O- Single bond Single bond Pyrimidine ring
a-30 -NH- Single bond Single bond Pyrimidine ring
[ Table 3]
W1 W2 W3 W4
a-31 -CONH- Single bond Single bond Pyrimidine ring
a-32 -NHCO- Single bond Single bond Pyrimidine ring
a-33 -CH2O- Single bond Single bond Pyrimidine ring
a-34 -OCO- Single bond Single bond Pyrimidine ring
a-35 -CON(CH3)- Single bond Single bond Pyrimidine ring
a-36 -O- C1-C5 alkylene Single bond Pyrrole ring
a-37 -NH- C1-C5 alkylene Single bond Pyrrole ring
a-38 -CONH- C1-C5 alkylene Single bond Pyrrole ring
a-39 -NHCO- C1-C5 alkylene Single bond Pyrrole ring
a-40 -CH2O- C1-C5 alkylene Single bond Pyrrole ring
a-41 -OCO- C1-C5 alkylene Single bond Pyrrole ring
a-42 -CON(CH3)- C1-C5 alkylene Single bond Pyrrole ring
a-43 -O- C1-C5 alkylene Single bond Imidazole ring
a-44 -NH- C1-C5 alkylene Single bond Imidazole ring
a-45 -CONH- C1-C5 alkylene Single bond Imidazole ring
[ Table 4]
W1 W2 W3 W4
a-46 -NHCO- C1-C5 alkylene Single bond Imidazole ring
a-47 -CH2O- C1-C5 alkylene Single bond Imidazole ring
a-48 -OCO- C1-C5 alkylene Single bond Imidazole ring
a-49 -CON(CH3)- C1-C5 alkylene Single bond Imidazole ring
a-50 -O- C1-C5 alkylene Single bond Pyrazole ring
a-51 -NH- C1-C5 alkylene Single bond Pyrazole ring
a-52 -CONH- C1-C5 alkylene Single bond Pyrazole ring
a-53 -NHCO- C1-C5 alkylene Single bond Pyrazole ring
a-54 -CH2O- C1-C5 alkylene Single bond Pyrazole ring
a-55 -OCO- C1-C5 alkylene Single bond Pyrazole ring
a-56 -CON(CH3)- C1-C5 alkylene Single bond Pyrazole ring
a-57 -O- C1-C5 alkylene Single bond Pyridine ring
a-58 -NH- C1-C5 alkylene Single bond Pyridine ring
a-59 -CONH- C1-C5 alkylene Single bond Pyridine ring
a-60 -NHCO- C1-C5 alkylene Single bond Pyridine ring
[ Table 5]
W1 W2 W3 W4
a-61 -CH2O- C1-C5 alkylene Single bond Pyridine ring
a-62 -OCO- C1-C5 alkylene Single bond Pyridine ring
a-63 -CON(CH3)- C1-C5 alkylene Single bond Pyridine ring
a-64 -O- C1-C5 alkylene Single bond Pyrimidine ring
a-65 -NH- C1-C5 alkylene Single bond Pyrimidine ring
a-66 -CONH- C1-C5 alkylene Single bond Pyrimidine ring
a-67 -NHCO- C1-C5 alkylene Single bond Pyrimidine ring
a-68 -CH2O- C1-C5 alkylene Single bond Pyrimidine ring
a-69 -OCO- C1-C5 alkylene Single bond Pyrimidine ring
a-70 -CON(CH3)- C1-C5 alkylene Single bond Pyrimidine ring
a-71 -O- Cyclohexane ring Single bond Pyrrole ring
a-72 -NH- Cyclohexane ring Single bond Pyrrole ring
a-73 -CONH- Cyclohexane ring Single bond Pyrrole ring
a-74 -NHCO- Cyclohexane ring Single bond Pyrrole ring
a-75 -CH2O- Cyclohexane ring Single bond Pyrrole ring
[ Table 6]
W1 W2 W3 W4
a-76 -OCO- Cyclohexane ring Single bond Pyrrole ring
a-77 -CON(CH3)- Cyclohexane ring Single bond Pyrrole ring
a-78 -O- Cyclohexane ring Single bond Imidazole ring
a-79 -NH- Cyclohexane ring Single bond Imidazole ring
a-80 -CONH- Cyclohexane ring Single bond Imidazole ring
a-81 -NHCO- Cyclohexane ring Single bond Imidazole ring
a-82 -CH2O- Cyclohexane ring Single bond Imidazole ring
a-83 -OCO- Cyclohexane ring Single bond Imidazole ring
a-84 -CON(CH3)- Cyclohexane ring Single bond Imidazole ring
a-85 -O- Cyclohexane ring Single bond Pyrazole ring
a-86 -NH- Cyclohexane ring Single bond Pyrazole ring
a-87 -CONH- Cyclohexane ring Single bond Pyrazole ring
a-88 -NHCO- Cyclohexane ring Single bond Pyrazole ring
a-89 -CH2O- Cyclohexane ring Single bond Pyrazole ring
a-90 -OCO- Cyclohexane ring Single bond Pyrazole ring
[ Table 7]
W1 W2 W3 W4
a-91 -CON(CH3)- CyclohexaneAlkyl ring Single bond Pyrazole ring
a-92 -O- Cyclohexane ring Single bond Pyridine ring
a-93 -NH- Cyclohexane ring Single bond Pyridine ring
a-94 -CONH- Cyclohexane ring Single bond Pyridine ring
a-95 -NHCO- Cyclohexane ring Single bond Pyridine ring
a-96 -CH2O- Cyclohexane ring Single bond Pyridine ring
a-97 -OCO- Cyclohexane ring Single bond Pyridine ring
a-98 -CON(CH3)- Cyclohexane ring Single bond Pyridine ring
a-99 -O- Cyclohexane ring Single bond Pyrimidine ring
a-100 -NH- Cyclohexane ring Single bond Pyrimidine ring
a-101 -CONH- Cyclohexane ring Single bond Pyrimidine ring
a-102 -NHCO- Cyclohexane ring Single bond Pyrimidine ring
a-103 -CH2O- Cyclohexane ring Single bond Pyrimidine ring
a-104 -OCO- Cyclohexane ring Single bond Pyrimidine ring
a-105 -CON(CH3)- Cyclohexane ring Single bond Pyrimidine ring
[ Table 8]
W1 W2 W3 W4
a-106 -O- Benzene ring Single bond Pyrrole ring
a-107 -NH- Benzene ring Single bond Pyrrole ring
a-108 -CONH- Benzene ring Single bond Pyrrole ring
a-109 -NHCO- Benzene ring Single bond Pyrrole ring
a-110 -CH2O- Benzene ring Single bond Pyrrole ring
a-111 -OCO- Benzene ring Single bond Pyrrole ring
a-112 -CON(CH3)- Benzene ring Single bond Pyrrole ring
a-113 -O- Benzene ring Single bond Imidazole ring
a-114 -NH- Benzene ring Single bond Imidazole ring
a-115 -CONH- Benzene ring Single bond Imidazole ring
a-116 -NHCO- Benzene ring Single bond Imidazole ring
a-117 -CH2O- Benzene ring Single bond Imidazole ring
a-118 -OCO- Benzene ring Single bond Imidazole ring
a-119 -CON(CH3)- Benzene ring Single bond Imidazole ring
a-120 -O- Benzene ring Single bond Pyrazole ring
[ Table 9]
W1 W2 W3 W4
a-121 -NH- Benzene ring Single bond Pyrazole ring
a-122 -CONH- Benzene ring Single bond Pyrazole ring
a-123 -NHCO- Benzene ring Single bond Pyrazole ring
a-124 -CH2O- Benzene ring Single bond Pyrazole ring
a-125 -OCO- Benzene ring Single bond Pyrazole ring
a-126 -CON(CH3)- Benzene ring Single bond Pyrazole ring
a-127 -O- Benzene ring Single bond Pyridine ring
a-128 -NH- Benzene ring Single bond Pyridine ring
a-129 -CONH- Benzene ring Single bond Pyridine ring
a-130 -NHCO- Benzene ring Single bond Pyridine ring
a-131 -CH2O- Benzene ring Single bond Pyridine ring
a-132 -OCO- Benzene ring Single bond Pyridine ring
a-133 -CON(CH3)- Benzene ring Single bond Pyridine ring
a-134 -O- Benzene ring Single bond Pyrimidine ring
a-135 -NH- Benzene ring Single bond Pyrimidine ring
[ Table 10]
W1 W2 W3 W4
a-136 -CONH- Benzene ring Single bond Pyrimidine ring
a-137 -NHCO- Benzene ring Single bond Pyrimidine ring
a-138 -CH2O- Benzene ring Single bond Pyrimidine ring
a-139 -OCO- Benzene ring Single bond Pyrimidine ring
a-140 -CON(CH3)- Benzene ring Single bond Pyrimidine ring
a-141 -O- C1-C5 alkylene -O- Pyrrole ring
a-142 -NH- C1-C5 alkylene -O- Pyrrole ring
a-143 -CONH- C1-C5 alkylene -O- Pyrrole ring
a-144 -NHCO- C1-C5 alkylene -O- Pyrrole ring
a-145 -CH2O- C1-C5 alkylene -O- Pyrrole ring
a-146 -OCO- C1-C5 alkylene -O- Pyrrole ring
a-147 -CON(CH3)- C1-C5 alkylene -O- Pyrrole ring
a-148 -O- C1-C5 alkylene -O- Imidazole ring
a-149 -NH- C1-C5 alkylene -O- Imidazole ring
a-150 -CONH- C1-C5 alkylene -O- Imidazole ring
[ Table 11]
W1 W2 W3 W4
a-151 -NHCO- C1-C5 alkylene -O- Imidazole ring
a-152 -CH2O- C1-C5 alkylene -O- Imidazole ring
a-153 -OCO- C1-C5 alkylene -O- Imidazole ring
a-154 -CON(CH3)- C1-C5 alkylene -O- Imidazole ring
a-155 -O- C1-C5 alkylene -O- Pyrazole ring
a-156 -NH- C1-C5 alkylene -O- Pyrazole ring
a-157 -CONH- C1-C5 alkylene -O- Pyrazole ring
a-158 -NHCO- C1-C5 alkylene -O- Pyrazole ring
a-159 -CH2O- C1-C5 alkylene -O- Pyrazole ring
a-160 -OCO- C1-C5 alkylene -O- Pyrazole ring
a-161 -CON(CH3)- C1-C5 alkylene -O- Pyrazole ring
a-162 -O- C1-C5 alkylene -O- Pyridine ring
a-163 -NH- C1-C5 alkylene -O- Pyridine ring
a-164 -CONH- C1-C5 alkylene -O- Pyridine ring
a-165 -NHCO- C1-C5 alkylene -O- Pyridine ring
[ Table 12]
W1 W2 W3 W4
a-166 -CH2O- C1-C5 alkylene -O- Pyridine ring
a-167 -OCO- C1-C5 alkylene -O- Pyridine ring
a-168 -CON(CH3)- C1-C5 alkylene -O- Pyridine ring
a-169 -O- C1-C5 alkylene -O- Pyrimidine ring
a-170 -NH- C1-C5 alkylene -O- Pyrimidine ring
a-171 -CONH- C1-C5 alkylene -O- Pyrimidine ring
a-172 -NHCO- C1-C5 alkylene -O- Pyrimidine ring
a-173 -CH2O- C1-C5 alkylene -O- Pyrimidine ring
a-174 -OCO- C1-C5 alkylene -O- Pyrimidine ring
a-175 -CON(CH3)- C1-C5 alkylene -O- Pyrimidine ring
a-176 -O- C1-C5 alkylene -OCO- Pyrrole ring
a-177 -NH- C1-C5 alkylene -OCO- Pyrrole ring
a-178 -CONH- C1-C5 alkylene -OCO- Pyrrole ring
a-179 -NHCO- C1-C5 alkylene -OCO- Pyrrole ring
a-180 -CH2O- C1-C5 alkylene -OCO- Pyrrole ring
[ Table 13]
W1 W2 W3 W4
a-181 -OCO- C1-C5 alkylene -OCO- Pyrrole ring
a-182 -CON(CH3)- C1-C5 alkylene -OCO- Pyrrole ring
a-183 -O- C1-C5 alkylene -OCO- Imidazole ring
a-184 -NH- C1-C5 alkylene -OCO- Imidazole ring
a-185 -CONH- C1-C5 alkylene -OCO- Imidazole ring
a-186 -NHCO- C1-C5 alkylene -OCO- Imidazole ring
a-187 -CH2O- C1-5Alkyl radical -OCO- Imidazole ring
a-188 -OCO- C1-C5 alkylene -OCO- Imidazole ring
a-189 -CON(CH3)- C1-C5 alkylene -OCO- Imidazole ring
a-190 -O- C1-C5 alkylene -OCO- Pyrazole ring
a-191 -NH- C1-C5 alkylene -OCO- Pyrazole ring
a-192 -CONH- C1-C5 alkylene -OCO- Pyrazole ring
a-193 -NHCO- C1-C5 alkylene -OCO- Pyrazole ring
a-194 -CH2O- C1-C5 alkylene -OCO- Pyrazole ring
a-195 -OCO- C1-C5 alkylene -OCO- Pyrazole ring
[ Table 14]
W1 W2 W3 W4
a-196 -CON(CH3)- C1-C5 alkylene -OCO- Pyrazole ring
a-197 -O- C1-C5 alkylene -OCO- Pyridine ring
a-198 -NH- C1-C5 alkylene -OCO- Pyridine ring
a-199 -CONH- C1-C5 alkylene -OCO- Pyridine ring
a-200 -NHCO- C1-C5 alkylene -OCO- Pyridine ring
a-201 -CH2O- C1-C5 alkylene -OCO- Pyridine ring
a-202 -OCO- C1-C5 alkylene -OCO- Pyridine ring
a-203 -CON(CH3)- C1-C5 alkylene -OCO- Pyridine ring
a-204 -O- C1-C5 alkylene -OCO- Pyrimidine ring
a-205 -NH- C1-C5 alkylene -OCO- Pyrimidine ring
a-206 -CONH- C1-C5 alkylene -OCO- Pyrimidine ring
a-207 -NHCO- C1-C5 alkylene -OCO- Pyrimidine ring
a-208 -CH2O- C1-C5 alkylene -OCO- Pyrimidine ring
a-209 -OCO- C1-C5 alkylene -OCO- Pyrimidine ring
a-210 -CON(CH3)- C1-C5 alkylene -OCO- Pyrimidine ring
[ Table 15]
W1 W2 W3 W4
a-211 -O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-212 -NH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-213 -CONH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-214 -NHCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-215 -CH2O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-216 -OCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-217 -CON(CH3)- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-218 -O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-219 -NH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-220 -CONH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-221 -NHCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-222 -CH2O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-223 -OCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-224 -CON(CH3)- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-225 -O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
[ Table 16]
W1 W2 W3 W4
a-226 -NH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-227 -CONH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-228 -NHCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-229 -CH2O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-230 -OCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-231 -CON(CH3)- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-232 -O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-233 -NH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-234 -CONH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-235 -NHCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-236 -CH2O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-237 -OCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-238 -CON(CH3)- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-239 -O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-240 -NH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
[ Table 17]
W1 W2 W3 W4
a-241 -CONH- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-242 -NHCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-243 -CH2O- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-244 -OCO- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-245 -CON(CH3)- C1-C5 alkylene -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-246 -O- Cyclohexane ring -O- Pyrrole ring
a-247 -NH- Cyclohexane ring -O- Pyrrole ring
a-248 -CONH- Cyclohexane ring -O- Pyrrole ring
a-249 -NHCO- Cyclohexane ring -O- Pyrrole ring
a-250 -CH2O- Cyclohexane ring -O- Pyrrole ring
a-251 -OCO- Cyclohexane ring -O- Pyrrole ring
a-252 -CON(CH3)- Cyclohexane ring -O- Pyrrole ring
a-253 -O- Cyclohexane ring -O- Imidazole ring
a-254 -NH- Cyclohexane ring -O- Imidazole ring
a-255 -CONH- Cyclohexane ring -O- Imidazole ring
[ Table 18]
W1 W2 W3 W4
a-256 -NHCO- Cyclohexane ring -O- Imidazole ring
a-257 -CH2O- Cyclohexane ring -O- Imidazole ring
a-258 -OCO- Cyclohexane ring -O- Imidazole ring
a-259 -CON(CH3)- Cyclohexane ring -O- Imidazole ring
a-260 -O- Cyclohexane ring -O- Pyrazole ring
a-261 -NH- Cyclohexane ring -O- Pyrazole ring
a-262 -CONH- Cyclohexane ring -O- Pyrazole ring
a-263 -NHCO- Cyclohexane ring -O- Pyrazole ring
a-264 -CH2O- Cyclohexane ring -O- Pyrazole ring
a-265 -OCO- Cyclohexane ring -O- Pyrazole ring
a-266 -CON(CH3)- Cyclohexane ring -O- Pyrazole ring
a-267 -O- Cyclohexane ring -O- Pyridine ring
a-268 -NH- Cyclohexane ring -O- Pyridine ring
a-269 -CONH- Cyclohexane ring -O- Pyridine ring
a-270 -NHCO- Cyclohexane ring -O- Pyridine ring
[ Table 19]
W1 W2 W3 W4
a-271 -CH2O- Cyclohexane ring -O- Pyridine ring
a-272 -OCO- Cyclohexane ring -O- Pyridine ring
a-273 -CON(CH3)- Cyclohexane ring -O- Pyridine ring
a-274 -O- Cyclohexane ring -O- Pyrimidine ring
a-275 -NH- Cyclohexane ring -O- Pyrimidine ring
a-276 -CONH- Cyclohexane ring -O- Pyrimidine ring
a-277 -NHCO- Cyclohexane ring -O- Pyrimidine ring
a-278 -CH2O- Cyclohexane ring -O- Pyrimidine ring
a-279 -OCO- Cyclohexane ring -O- Pyrimidine ring
a-280 -CON(CH3)- Cyclohexane ring -O- Pyrimidine ring
a-281 -O- Cyclohexane ring -OCO- Pyrrole ring
a-282 -NH- Cyclohexane ring -OCO- Pyrrole ring
a-283 -CONH- Cyclohexane ring -OCO- Pyrrole ring
a-284 -NHCO- Cyclohexane ring -OCO- Pyrrole ring
a-285 -CH2O- Cyclohexane ring -OCO- Pyrrole ring
[ Table 20]
W1 W2 W3 W4
a-286 -OCO- Cyclohexane ring -OCO- Pyrrole ring
a-287 -CON(CH3)- Cyclohexane ring -OCO- Pyrrole ring
a-288 -O- Cyclohexane ring -OCO- Imidazole ring
a-289 -NH- Cyclohexane ring -OCO- Imidazole ring
a-290 -CONH- Cyclohexane ring -OCO- Imidazole ring
a-291 -NHCO- Cyclohexane ring -OCO- Imidazole ring
a-292 -CH2O- Cyclohexane ring -OCO- Imidazole ring
a-293 -OCO- Cyclohexane ring -OCO- Imidazole ring
a-294 -CON(CH3)- Cyclohexane ring -OCO- Imidazole ring
a-295 -O- Cyclohexane ring -OCO- Pyrazole ring
a-296 -NH- Cyclohexane ring -OCO- Pyrazole ring
a-297 -CONH- Cyclohexane ring -OCO- Pyrazole ring
a-298 -NHCO- Cyclohexane ring -OCO- Pyrazole ring
a-299 -CH2O- Cyclohexane ring -OCO- Pyrazole ring
a-300 -OCO- Cyclohexane ring -OCO- Pyrazole ring
[ Table 21]
W1 W2 W3 W4
a-301 -CON(CH3)- Cyclohexane ring -OCO- Pyrazole ring
a-302 -O- Cyclohexane ring -OCO- Pyridine ring
a-303 -NH- Cyclohexane ring -OCO- Pyridine ring
a-304 -CONH- Cyclohexane ring -OCO- Pyridine ring
a-305 -NHCO- Cyclohexane ring -OCO- Pyridine ring
a-306 -CH2O- Cyclohexane ring -OCO- Pyridine ring
a-307 -OCO- Cyclohexane ring -OCO- Pyridine ring
a-308 -CON(CH3)- Cyclohexane ring -OCO- Pyridine ring
a-309 -O- Cyclohexane ring -OCO- Pyrimidine ring
a-310 -NH- Cyclohexane ring -OCO- Pyrimidine ring
a-311 -CONH- Cyclohexane ring -OCO- Pyrimidine ring
a-312 -NHCO- Cyclohexane ring -OCO- Pyrimidine ring
a-313 -CH2O- Cyclohexane ring -OCO- Pyrimidine ring
a-314 -OCO- Cyclohexane ring -OCO- Pyrimidine ring
a-315 -CON(CH3)- Cyclohexane ring -OCO- Pyrimidine ring
[ Table 22]
W1 W2 W3 W4
a-316 -O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-317 -NH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-318 -CONH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-319 -NHCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-320 -CH2O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-321 -OCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-322 -CON(CH3)- Cyclohexane ring -O(CH2)m- (m is an integer of 1 to 5) Pyrrole ring
a-323 -O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-324 -NH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-325 -CONH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-326 -NHCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-327 -CH2O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-328 -OCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-329 -CON(CH3)- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-330 -O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
[ Table 23]
W1 W2 W3 W4
a-331 -NH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-332 -CONH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-333 -NHCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-334 -CH2O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-335 -OCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-336 -CON(CH3)- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-337 -O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-338 -NH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-339 -CONH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-340 -NHCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-341 -CH2O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-342 -OCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-343 -CON(CH3)- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-344 -O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-345 -NH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
[ Table 24]
W1 W2 W3 W4
a-346 -CONH- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-347 -NHCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-348 -CH2O- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-349 -OCO- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-350 -CON(CH3)- Cyclohexane ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-351 -O- Benzene ring -O- Pyrrole ring
a-352 -NH- Benzene ring -O- Pyrrole ring
a-353 -CONH- Benzene ring -O- Pyrrole ring
a-354 -NHCO- Benzene ring -O- Pyrrole ring
a-355 -CH2O- Benzene ring -O- Pyrrole ring
a-356 -OCO- Benzene ring -O- Pyrrole ring
a-357 -CON(CH3)- Benzene ring -O- Pyrrole ring
a-358 -O- Benzene ring -O- Imidazole ring
a-359 -NH- Benzene ring -O- Imidazole ring
a-360 -CONH- Benzene ring -O- Imidazole ring
[ Table 25]
W1 W2 W3 W4
a-361 -NHCO- Benzene ring -O- Imidazole ring
a-362 -CH2O- Benzene ring -O- Imidazole ring
a-363 -OCO- Benzene ring -O- Imidazole ring
a-364 -CON(CH3)- Benzene ring -O- Imidazole ring
a-365 -O- Benzene ring -O- Pyrazole ring
a-366 -NH- Benzene ring -O- Pyrazole ring
a-367 -CONH- Benzene ring -O- Pyrazole ring
a-368 -NHCO- Benzene ring -O- Pyrazole ring
a-369 -CH2O- Benzene ring -O- Pyrazole ring
a-370 -OCO- Benzene ring -O- Pyrazole ring
a-371 -CON(CH3)- Benzene ring -O- Pyrazole ring
a-372 -O- Benzene ring -O- Pyridine ring
a-373 -NH- Benzene ring -O- Pyridine ring
a-374 -CONH- Benzene ring -O- Pyridine ring
a-375 -NHCO- Benzene ring -O- Pyridine ring
[ Table 26]
W1 W2 W3 W4
a-376 -CH2O- Benzene ring -O- Pyridine ring
a-377 -OCO- Benzene ring -O- Pyridine ring
a-378 -CON(CH3)- Benzene ring -O- Pyridine ring
a-379 -O- Benzene ring -O- Pyrimidine ring
a-380 -NH- Benzene ring -O- Pyrimidine ring
a-381 -CONH- Benzene ring -O- Pyrimidine ring
a-382 -NHCO- Benzene ring -O- Pyrimidine ring
a-383 -CH2O- Benzene ring -O- Pyrimidine ring
a-384 -OCO- Benzene ring -O- Pyrimidine ring
a-385 -CON(CH3)- Benzene ring -O- Pyrimidine ring
a-386 -O- Benzene ring -OCO- Pyrrole ring
a-387 -NH- Benzene ring -OCO- Pyrrole ring
a-388 -CONH- Benzene ring -OCO- Pyrrole ring
a-389 -NHCO- Benzene ring -OCO- Pyrrole ring
a-390 -CH2O- Benzene ring -OCO- Pyrrole ring
[ Table 27]
W1 W2 W3 W4
a-391 -OCO- Benzene ring -OCO- Pyrrole ring
a-392 -CON(CH3)- Benzene ring -OCO- Pyrrole ring
a-393 -O- Benzene ring -OCO- Imidazole ring
a-394 -NH- Benzene ring -OCO- Imidazole ring
a-395 -CONH- Benzene ring -OCO- Imidazole ring
a-396 -NHCO- Benzene ring -OCO- Imidazole ring
a-397 -CH2O- Benzene ring -OCO- Imidazole ring
a-398 -OCO- Benzene ring -OCO- Imidazole ring
a-399 -CON(CH3)- Benzene ring -OCO- Imidazole ring
a-400 -O- Benzene ring -OCO- Pyrazole ring
a-401 -NH- Benzene ring -OCO- Pyrazole ring
a-402 -CONH- Benzene ring -OCO- Pyrazole ring
a-403 -NHCO- Benzene ring -OCO- Pyrazole ring
a-404 -CH2O- Benzene ring -OCO- Pyrazole ring
a-405 -OCO- Benzene ring -OCO- Pyrazole ring
[ Table 28]
W1 W2 W3 W4
a-406 -CON(CH3)- Benzene ring -OCO- Pyrazole ring
a-407 -O- Benzene ring -OCO- Pyridine ring
a-408 -NH- Benzene ring -OCO- Pyridine ring
a-409 -CONH- Benzene ring -OCO- Pyridine ring
a-410 -NHCO- Benzene ring -OCO- Pyridine ring
a-411 -CH2O- Benzene ring -OCO- Pyridine ring
a-412 -OCO- Benzene ring -OCO- Pyridine ring
a-413 -CON(CH3)- Benzene ring -OCO- Pyridine ring
a-414 -O- Benzene ring -OCO- Pyrimidine ring
a-415 -NH- Benzene ring -OCO- Pyrimidine ring
a-416 -CONH- Benzene ring -OCO- Pyrimidine ring
a-417 -NHCO- Benzene ring -OCO- Pyrimidine ring
a-418 -CH2O- Benzene ring -OCO- Pyrimidine ring
a-419 -OCO- Benzene ring -OCO- Pyrimidine ring
a-420 -CON(CH3)- Benzene ring -OCO- Pyrimidine ring
[ Table 29]
W1 W2 W3 W4
a-421 -O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-422 -NH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-423 -CONH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-424 -NHCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-425 -CH2O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-426 -OCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-427 -CON(CH3)- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrrole ring
a-428 -O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-429 -NH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-430 -CONH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-431 -NHCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-432 -CH2O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-433 -OCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-434 -CON(CH3)- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Imidazole ring
a-435 -O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
[ Table 30]
W1 W2 W3 W4
a-436 -NH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-437 -CONH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-438 -NHCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-439 -CH2O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-440 -OCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-441 -CON(CH3)- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrazole ring
a-442 -O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-443 -NH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-444 -CONH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-445 -NHCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-446 -CH2O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-447 -OCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-448 -CON(CH3)- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyridine ring
a-449 -O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-450 -NH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
[ Table 31]
W1 W2 W3 W4
a-451 -CONH- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-452 -NHCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-453 -CH2O- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-454 -OCO- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
a-455 -CON(CH3)- Benzene ring -O (CH2) m- (m is an integer of 1 to 5) Pyrimidine ring
Among them, preferred is a combination of (a-43) to (a-49), (a-57) to (a-63), (a-218) to (a-224), (a-232) to (a-238), (a-323) to (a-329), (a-337) to (a-343), (a-428) to (a-434), or (a-442) to (a-448). From the viewpoint of being able to suppress a decrease in the voltage holding ratio after long-term exposure to light, a combination of (a-44), (a-45), (a-58), or (a-59) is more preferable.
As the diamine compound having the specific structure (1), a diamine compound represented by the following formula [2a ] (also referred to as a specific diamine compound (1)) is preferably used.
Figure BDA0001294629370000291
In the formula [2a ], W represents a structure represented by the formula [2 ].
Further, formula [2]W in1、W2、W3And W4The details and preferred combinations of (A) are as described in the above formula [2]]As shown.
From the viewpoint of ease of synthesis, m1 is preferably 1.
The proportion of the specific diamine compound (1) used is preferably 1 to 60 mol% based on the whole diamine component, from the viewpoint of suppressing a decrease in the voltage holding ratio after long-term exposure to light. More preferably 1 to 50 mol%, and particularly preferably 5 to 50 mol%.
The specific diamine compound (1) may be used in 1 kind or in combination of 2 or more kinds depending on the solubility of the specific polyimide polymer in a solvent, the liquid crystal alignment property when a liquid crystal alignment film is formed, or the electrical characteristics of a liquid crystal display element.
When the liquid crystal aligning agent of the present invention is used for a liquid crystal display element of VA mode, PSA mode or SC-PVA mode, a diamine compound having a structure represented by the following formula [3-1] or formula [3-2] (also referred to as specific structure (2)) is preferably used as the diamine component.
Figure BDA0001294629370000292
Formula [3-1]In, Y1、Y2、Y3、Y4、Y5、Y6And n is as defined above, wherein the following groups are each preferred.
From the viewpoints of availability of raw materials and ease of synthesis, Y1Preferably a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-or-COO-. More preferably a single bond, - (CH)2)a- (a is an integer of 1 to 10), -O-, -CH2O-or-COO-.
Y2Preferably a single bond or- (CH)2)b- (b is an integer of 1 to 10).
From the viewpoint of ease of synthesis, Y3Preferably a single bond, - (CH)2)c- (c is an integer of 1 to 15), -O-, -CH2O-or-COO-. More preferably a single bond, - (CH)2)c- (c is an integer of 1 to 10), -O-, -CH2O-or-COO-.
From the viewpoint of ease of synthesis, Y4Preferably a benzene ring, a cyclohexane ring, or an organic group having 17 to 51 carbon atoms and having a steroid skeleton.
Y5Preferably a benzene ring or a cyclohexane ring.
Y6Preferably C1-18 alkyl, C2-18 alkenyl, CA 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. More preferably an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferably an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
From the viewpoint of raw material availability and ease of synthesis, n is preferably 0 to 3, more preferably 0 to 2.
Y1、Y2、Y3、Y4、Y5、Y6Preferable combinations with n include combinations similar to (2-1) to (2-629) described in tables 6 to 47 on pages 13 to 34 of International publication WO2011/132751 (published 2011.10.27). In the tables of International publication, Y in the present invention1～Y6Are represented as Y1-Y6, but Y1-Y6 are understood to be Y1～Y6. In addition, (2-605) to (2-629) described in each table of the international publication, the organic group having 17 to 51 carbon atoms of the steroid skeleton of the present invention is represented by an organic group having 12 to 25 carbon atoms of the steroid skeleton, but the organic group having 12 to 25 carbon atoms of the steroid skeleton can be understood as an organic group having 17 to 51 carbon atoms of the steroid skeleton.
Among them, preferred is a combination of (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). 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).
-Y7-Y8 [3-2]
Formula [3-2]In, Y7And Y8As shown in the foregoing definitions, among them, the following groups are each preferred.
Y7Preferably a single bond, -O-, -CH2O-、-CONH-、-CON(CH3) -or-COO-. More preferably a single bond, -O-, -CONH-or-COO-.
Y8Preferably an alkyl group having 8 to 18 carbon atoms.
In the present invention, the specific structure (2) is preferably a structure represented by the formula [3-1] from the viewpoint of obtaining a high and stable vertical alignment property of liquid crystal.
As the diamine compound having the specific structure (2), a diamine compound represented by the following formula [3a ] (also referred to as a specific diamine compound (2)) is preferably used.
Figure BDA0001294629370000311
In the formula [3a ], Y represents a structure represented by the formula [3-1] or the formula [3-2 ].
Further, the formula [3-1]Y in (1)1、Y2、Y3、Y4、Y5、Y6In detail and preferred combinations with n as described for formula [3-1] above]Is of the formula [3-2]Y in (1)7And Y8The details and preferred combinations of (A) are as described in the aforementioned formula [3-2]]。
From the viewpoint of ease of synthesis, n1 is preferably 1.
Specific examples of the specific diamine compound (2) having a specific structure represented by the formula [3-1] include diamine compounds represented by the following formulae [3a-1] to [3a-31 ].
Figure BDA0001294629370000321
(R1Respectively represent a group selected from-O-, -OCH2-、-CH2O-、-COOCH2-and-CH2OCO-, at least 1 bonding group in the group. R2Respectively represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a linear or branched fluoroalkyl group having 1 to 18 carbon atoms, or a linear or branched fluoroalkoxy group having 1 to 18 carbon atoms. )
Figure BDA0001294629370000322
(R3Each represents a group selected from-COO-),-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-and-CH2-at least 1 bonding group of the group. R4Respectively represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a linear or branched fluoroalkyl group having 1 to 18 carbon atoms, or a linear or branched fluoroalkoxy group having 1 to 18 carbon atoms. )
Figure BDA0001294629370000323
(R5Respectively represent a group selected from-COO-, -OCO-, -CONH-, -NHCO-, -COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、-CH2At least 1 bonding group of the group consisting of-O-, and-NH-. R6Each represents at least 1 selected from the group consisting of fluoro, cyano, trifluoromethyl, nitro, azo, formyl, acetyl, acetoxy, and hydroxy. )
Figure BDA0001294629370000331
(R7Each represents a straight-chain or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1, 4-cyclohexylidene is a trans isomer. )
Figure BDA0001294629370000332
(R8Each represents a straight-chain or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1, 4-cyclohexylidene is a trans isomer. )
Figure BDA0001294629370000333
(A4Represents a straight or branched chain of 3 to 18 carbon atoms optionally substituted with a fluorine atomAn alkyl group. A. the3Represents 1, 4-cyclohexylene or 1, 4-phenylene. A. the2Represents an oxygen atom or-COO- ("marked") bond with A3Bonding). A. the1Represents an oxygen atom or-COO- ("marked") bond with (CH)2)a2Bonding). In addition, a1Represents an integer of 0 or 1. a is2Represents an integer of 2 to 10. a is3Represents an integer of 0 or 1. )
Figure BDA0001294629370000341
Figure BDA0001294629370000351
In the above formulas [3a-1] to [3a-31], preferred diamine compounds are those of formulas [3a-1] to [3a-6], formulas [3a-9] to [3a-13] or formulas [3a-22] to [3a-31 ].
Specific examples of the specific diamine compound (2) having the specific structure (2) represented by the above formula [3-2] include diamine compounds represented by the following formulae [3a-32] to [3a-35 ].
Figure BDA0001294629370000352
(A1Each represents an alkyl group having 8 to 18 carbon atoms or a fluoroalkyl group. )
Particularly, in the case of a liquid crystal display element used in a VA mode, PSA mode, or SC-PVA mode, the use ratio of the specific diamine compound (2) is preferably 10 to 70 mol% based on the whole diamine component. More preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol%.
The specific diamine compound (2) may be used in 1 kind or 2 or more kinds in combination depending on the solubility of the specific polyimide polymer in a solvent, the liquid crystal alignment property when a liquid crystal alignment film is formed, or the electrical characteristics of a liquid crystal display element.
In the diamine component of the present invention, the specific diamine compound (1) and the specific diamine compound (2) can be appropriately selected and used according to the display mode of the liquid crystal display element, that is, tn (twisted nematic) mode, IPS (In-plane Switching) mode, VA mode, PSA mode, and SC-PVA mode. These specific diamine compounds may be used in 2 or more kinds, that is, in plural kinds.
As the diamine component for producing the specific polyimide-based polymer, the following diamine compound (also referred to as another diamine compound) may be used.
Specific examples thereof include 2, 4-dimethyl-m-phenylenediamine, 2, 6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 5-diaminobenzoic acid, 4 ' -diaminobiphenyl, 3 ' -dimethyl-4, 4 ' -diaminobiphenyl, 3 ' -dimethoxy-4, 4 ' -diaminobiphenyl, 3 ' -dihydroxy-4, 4 ' -diaminobiphenyl, 3 ' -dicarboxyl-4, 4 ' -diaminobiphenyl, p-phenylenediamine, 3,3 '- ジ F-4, 4' -biphenyl, 3 '-trifluoromethyl-4, 4' -diaminobiphenyl, 3 '-diaminobiphenyl, 2' -diaminobiphenyl, 2,3 '-diaminobiphenyl, 4' -diaminodiphenylmethane, 3 '-diaminodiphenylmethane, 3, 4' -diaminodiphenylmethane, 2 '-diaminodiphenylmethane, 2, 3' -diaminodiphenylmethane, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 2' -diaminodiphenyl ether, 2,3 '-diaminodiphenyl ether, 4' -sulfonyldiphenylamine, 2,3 '-diaminodiphenyl ether, 4' -sulfonyldiphenylether, and mixtures thereof, 3,3 ' -sulfonyldiphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4 ' -thiodiphenylamine, 3 ' -thiodiphenylamine, 4 ' -diaminodiphenylamine, 3 ' -diaminodiphenylamine, 3,4 ' -diaminodiphenylamine, 2 ' -diaminodiphenylamine, 2,3 ' -diaminodiphenylamine, N-methyl (4,4 ' -diaminodiphenyl) amine, N-methyl (3,3 ' -diaminodiphenyl) amine, N-methyl (3,4 ' -diaminodiphenyl) amine, N-methyl (2,2 '-diaminodiphenyl) amine, N-methyl (2, 3' -diaminodiphenyl) amine, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, 3,4 '-diaminobenzophenone, 1, 4-diaminonaphthalene, 2' -diaminobenzophenone, 2,3 '-diaminobenzophenone, 1, 5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1, 7-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2, 8-diaminonaphthalene, 1, 2-bis (4-aminophenyl) ethane, 1, 2-bis (3-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) propane, N-methyl (2, 3' -diaminodiphenyl) amine, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, 1, 5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1, 2-diaminonaphthalene, 1,1, 3-bis (3-aminophenyl) propane, 1, 4-bis (4-aminophenyl) butane, 1, 4-bis (3-aminophenyl) butane, bis (3, 5-diethyl-4-aminophenyl) methane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (4-aminobenzyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4 ' - [1, 4-phenylenebismethylene ] diphenylamine, 4 ' - [1, 3-phenylenebismethylene ] diphenylamine, 3,4 ' - [1, 4-phenylenebismethylene diphenylamine, 3,4 ' - [1, 3-phenylenebismethylene ] diphenylamine, 3 ' - [1, 4-phenylenebismethylene ] diphenylamine, 3 ' - [1, 3-phenylenebismethylene ] diphenylamine, 1, 4-phenylenebis [ (4-aminophenyl) methanone ], 1, 4-phenylenebis [ (3-aminophenyl) methanone ], 1, 3-phenylenebis [ (4-aminophenyl) methanone ], 1, 3-phenylenebis [ (3-aminophenyl) methanone ], 1, 4-phenylenebis (4-aminobenzoate), 1, 4-phenylenebis (3-aminobenzoate), 1, 3-phenylenebis (4-aminobenzoate), 1, 3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N ' - (1, 4-phenylene) bis (4-aminobenzamide), N ' - (1, 3-phenylene) bis (4-aminobenzamide), N ' - (1, 4-phenylene) bis (3-aminobenzamide), N ' - (1, 3-phenylene) bis (3-aminobenzamide), N ' -bis (4-aminophenyl) terephthalamide, N ' -bis (3-aminophenyl) terephthalate, bis (4-aminobenzamide), bis (3-aminobenzamide, N ' -bis (, N, N ' -bis (4-aminophenyl) isophthaloyl, N ' -bis (3-aminophenyl) isophthaloyl, 9, 10-bis (4-aminophenyl) anthracene, 4 ' -bis (4-aminophenoxy) diphenylsulfone, 2 ' -bis [4- (4-aminophenoxy) phenyl ] propane, 2 ' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2 ' -bis (4-aminophenyl) hexafluoropropane, 2 ' -bis (3-amino-4-methylphenyl) hexafluoropropane, 2 ' -bis (4-aminophenyl) propane, 2 ' -bis (3-aminophenyl) propane, 2, 2' -bis (3-amino-4-methylphenyl) propane, 1, 3-bis (4-aminophenoxy) propane, 1, 3-bis (3-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 4-bis (3-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 5-bis (3-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, 1, 6-bis (3-aminophenoxy) hexane, 1, 7-bis (4-aminophenoxy) heptane, 1, 7-bis (3-aminophenoxy) heptane, 1, 8-bis (4-aminophenoxy) octane, 1, 3-bis (4-aminophenoxy) pentane, 1, 5-bis (3-aminophenoxy) pentane, 1, 8-bis (3-aminophenoxy) octane, 1, 9-bis (4-aminophenoxy) nonane, 1, 9-bis (3-aminophenoxy) nonane, 1, 10-bis (4-aminophenoxy) decane, 1, 10-bis (3-aminophenoxy) decane, 1, 11-bis (4-aminophenoxy) undecane, 1, 11-bis (3-aminophenoxy) undecane, 1, 12-bis (4-aminophenoxy) dodecane, 1, 12-bis (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, 1, 12-diaminododecane, or the like.
Further, as the other diamine compound, diamine compounds represented by the following formulae [ D1] to [ DA15] may be used.
Figure BDA0001294629370000381
Figure BDA0001294629370000391
(p represents an integer of 1 to 10.)
Figure BDA0001294629370000392
(L1Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 5. )
Figure BDA0001294629370000401
The other diamine compounds may be used in 1 kind or in combination of 2 or more kinds depending on the solubility of the specific polyimide-based polymer in a solvent, the liquid crystal alignment property when a liquid crystal alignment film is formed, or the electrical characteristics of a liquid crystal display element.
As the tetracarboxylic acid component used for producing the specific polyimide-based polymer, a tetracarboxylic dianhydride represented by the following formula [4] (also referred to as a specific tetracarboxylic acid component) is preferably used.
Figure BDA0001294629370000402
In the formula [4], Z represents at least 1 structure selected from the group consisting of the structures represented by the formulas [4a ] to [4k ].
From the viewpoint of ease of synthesis and ease of polymerization in the production of a polymer, Z in formula [4] is preferably a structure represented by formula [4a ], formula [4c ], formula [4d ], formula [4e ], formula [4f ], formula [4g ] or formula [4k ]. More preferably represented by the formula [4a ], 4e ], 4f, 4g or 4 k. Particularly preferred is a structure represented by the formula [4e ], the formula [4f ], the formula [4g ] or the formula [4k ].
The proportion of the specific tetracarboxylic acid component is preferably 1 mol% or more based on the total tetracarboxylic acid components. More preferably 5 mol% or more. Particularly preferably 10 mol% or more, and most preferably 10 to 90 mol% from the viewpoint of suppressing a decrease in the voltage holding ratio after long-term exposure to light.
When the tetracarboxylic acid component having a structure represented by the above formula [4e ], formula [4f ], formula [4g ] or formula [4k ] is used, a desired effect can be obtained by using the tetracarboxylic acid component in an amount of 20 mol% or more based on the whole tetracarboxylic acid component. Preferably 30 mol% or more. Further, the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure represented by the formula [4e ], the formula [4f ], the formula [4g ] or the formula [4k ].
As the tetracarboxylic acid component in the present invention, other tetracarboxylic acid components than the specific tetracarboxylic acid component may be used within a range not impairing the effects of the present invention.
Specific examples thereof include pyromellitic acid, 2,3,6, 7-naphthalenetetracarboxylic acid, 1,2,5, 6-naphthalenetetracarboxylic acid, 1,4,5, 8-naphthalenetetracarboxylic acid, 2,3,6, 7-anthracenetetracarboxylic acid, 1,2,5, 6-anthracenetetracarboxylic acid, 3,3 ', 4, 4' -biphenyltetracarboxylic acid, 2,3,3 ', 4' -biphenyltetracarboxylic acid, bis (3, 4-dicarboxyphenyl) ether, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid, bis (3, 4-dicarboxyphenyl) sulfone, bis (3, 4-dicarboxyphenyl) methane, 2-bis (3, 4-dicarboxyphenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3, 4-dicarboxyphenyl) propane, 2,3, 4-dicarboxyphenyl, Bis (3, 4-dicarboxyphenyl) dimethylsilane, bis (3, 4-dicarboxyphenyl) diphenylsilane, 2,3,4, 5-pyridinetetracarboxylic acid, 2, 6-bis (3, 4-dicarboxyphenyl) pyridine, 3 ', 4, 4' -diphenylsulfonetetracarboxylic acid, 3,4,9, 10-perylenetetracarboxylic acid, or 1, 3-diphenyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, and the like.
The specific tetracarboxylic acid component and the other tetracarboxylic acid components may be used in 1 kind or in a mixture of 2 or more kinds depending on the solubility of the specific polyimide-based polymer in a solvent, the liquid crystal alignment property when a liquid crystal alignment film is formed, or the electrical characteristics of a liquid crystal display element.
The method for producing the specific polyimide-based polymer is not particularly limited. Usually, the diamine component is reacted with a tetracarboxylic acid component. In general, there is a method of obtaining a polyamic acid by reacting at least 1 tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydrides and derivatives of tetracarboxylic acids thereof with a diamine component containing 1 or more kinds of diamine compounds. Specifically, the following method may be used: a method of obtaining a polyamic acid by polycondensing a tetracarboxylic dianhydride with a primary diamine compound or a secondary diamine compound, a method of obtaining a polyamic acid by subjecting a tetracarboxylic dianhydride and a primary diamine compound or a secondary diamine compound to a dehydration polycondensation reaction, or a method of obtaining a polyamic acid by reacting a tetracarboxylic acid dihalide with a primary diamine compound or a secondary diamine compound.
To obtain polyamic acid alkyl ester, the following method may be used: a method of polycondensing a tetracarboxylic acid having a carboxylic acid group dialkylated with a primary diamine compound or a secondary diamine compound, a method of reacting a tetracarboxylic acid dihalide having a carboxylic acid group dialkylated with a primary diamine compound or a secondary diamine compound, or a method of converting a carboxylic acid group of a polyamic acid into an ester.
In order to obtain polyimide, a method of ring-closing the polyamic acid or polyamic acid alkyl ester to obtain polyimide can be used.
The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent used in this case is not particularly limited as long as it dissolves the polyimide precursor formed. Specific examples of the organic solvent used in the reaction are shown below, but the organic solvent is not limited to these examples.
Examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and 1, 3-dimethyl-imidazolidinone. When the polyimide precursor has high solubility in the solvent, a solvent represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formulae [ D-1] to [ D-3] can be used.
Figure BDA0001294629370000421
(D1Represents an alkyl group having 1 to 3 carbon atoms. D2Represents an alkyl group having 1 to 3 carbon atoms. D3Represents an alkyl group having 1 to 4 carbon atoms. )
They may be used alone or in combination. Further, even if the solvent does not dissolve the polyimide precursor, the solvent may be mixed and used in a range where the produced polyimide precursor does not precipitate. Further, the water content in the organic solvent may inhibit the polymerization reaction and may cause hydrolysis of the polyimide precursor to be produced, and therefore the organic solvent is preferably used after dehydration and drying.
When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the following methods may be mentioned: a method of stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and adding a tetracarboxylic acid component as it is or after dispersing or dissolving in an organic solvent; conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent; a method of alternately adding a diamine component and a tetracarboxylic acid component, and any of these methods can be used. When a plurality of diamine components and tetracarboxylic acid components are used and reacted, they may be reacted in a state of being mixed in advance, or may be reacted in sequence, or low molecular weight materials obtained by the respective reactions may be mixed and reacted to produce a polymer. The polymerization temperature in this case may be any temperature from-20 ℃ to 150 ℃, and preferably from-5 ℃ to 100 ℃. The reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the amount is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The polymerization reaction may be carried out at a high concentration in the initial stage, and then an organic solvent may be added.
In the polymerization reaction of the polyimide precursor, 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. Similarly to the usual polymerization reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor to be produced becomes.
The polyimide is obtained by ring-closing the polyimide precursor, and the ring-closing ratio of the amic acid group (also referred to as imidization ratio) does not necessarily need to be 100%, and can be arbitrarily adjusted depending on the application and purpose. Among these, the specific polyimide-based polymer of the present invention is preferably a polyimide obtained by imidizing a polyimide precursor. The imidization ratio in this case is preferably 40 to 90%. More preferably 50 to 90%.
Examples of the method for imidizing a polyimide precursor include: thermal imidization in which a solution of a polyimide precursor is directly heated, or catalytic imidization in which a catalyst is added to a solution of a polyimide precursor. The temperature at which the polyimide precursor is thermally imidized in a solution is preferably 100 to 400 ℃, more preferably 120 to 250 ℃, and the method is preferably carried out while discharging water generated by the imidization reaction to the outside of the system.
The catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at-20 to 250 ℃, preferably at 0 to 180 ℃. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times, the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times, the amount of the acid amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a basicity suitable for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because purification after completion of the reaction is easy. The imidization rate based on the catalytic imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature and the reaction time.
When the polyimide precursor or polyimide to be produced is recovered from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be put into a solvent to precipitate the polyimide. Examples of the solvent used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by charging the solvent may be recovered by filtration, and then dried at normal temperature or under reduced pressure or dried by heating. Further, when the operation of re-dissolving the polymer recovered by precipitation in the organic solvent and recovering by re-precipitation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent in this case include alcohols, ketones, hydrocarbons, and the like, and the use of 3 or more solvents selected from these is preferable because the purification efficiency is further improved.
The molecular weight of the polyimide-based polymer is preferably 5,000 to 1,000,000 in terms of a weight average molecular weight measured by a Gel Permeation Chromatography (GPC) method in consideration of the strength of a liquid crystal alignment film obtained therefrom, workability in forming the liquid crystal alignment film, and film coatability. Among them, it is preferably 10,000 to 150,000.
The specific polyimide-based polymer in the present invention is preferably a polyimide obtained by catalytically imidizing the polyimide precursor, as described above, from the viewpoint that a decrease in the voltage holding ratio can be suppressed even after exposure to light for a long period of time. The imidization ratio in this case is preferably in the above range.
< liquid Crystal alignment treating agent >
The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin coating film), and preferably contains a specific compound, a polymer, and a solvent.
The ratio of the specific compound used in the liquid crystal aligning agent is preferably as follows. That is, it is preferably 1 to 30 parts by mass per 100 parts by mass of all the polymers. More preferably 1 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass.
The polymer component in the liquid crystal aligning agent is preferably a specific polyimide polymer, and other polymers may be mixed. In this case, the content of the other polymer is preferably 0.5 to 15 parts by mass per 100 parts by mass of the specific polyimide polymer. More preferably 1 to 10 parts by mass. Examples of the other polymers include the above-mentioned acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrene, polyamides, polyesters, cellulose, and polysiloxanes.
The solvent in the liquid crystal aligning agent is preferably contained in an amount of 70 to 99.9% by mass from the viewpoint of forming a uniform liquid crystal alignment film by coating. The content may be appropriately changed depending on the target film thickness of the liquid crystal alignment film.
The solvent used in the liquid crystal alignment treatment agent is not particularly limited as long as it dissolves the polymer (also referred to as a good solvent). Specific examples of the good solvent when a specific polyimide-based polymer is used are shown below, but the solvent is not limited to these examples.
Examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.
Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone is preferably used.
Further, when the specific polyimide-based polymer has high solubility in a solvent, it is preferable to use solvents represented by the formulae [ D-1] to [ D-3 ].
The ratio of the good solvent in the liquid crystal aligning agent is preferably 10 to 100% by mass of the entire solvent contained in the liquid crystal aligning agent. More preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass.
As the liquid crystal alignment treatment agent, a solvent (also referred to as a poor solvent) that improves the film coatability and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used within a range that does not impair the effects of the present invention. Specific examples of the poor solvent are given below, but the poor solvent is not limited to these examples.
Examples thereof include ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentanol, tert-pentanol, 3-methyl-2-butanol, neopentanol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1, 2-ethanediol, 1, 2-propanediol, isobutanol, 2-butanol, 2-pentanol, 2-methyl-1-pentanol, 2-methyl-, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, Ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, propylene glycol monobutyl ether acetate, propylene glycol mono-butyl ether acetate, propylene glycol mono-, Triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl glutarate, ethyl glutarate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, or a solvent represented by the formulae [ D-1] to [ D-3], and the like.
Among them, 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or a solvent represented by the above-mentioned formulae [ D-1] to [ D-3] is preferably used.
The proportion of the poor solvent is preferably 1 to 70% by mass of the entire solvent contained in the liquid crystal aligning agent. More preferably 1 to 60% by mass, and particularly preferably 5 to 60% by mass.
The liquid crystal aligning agent of the present invention is preferably introduced: a crosslinkable compound having a group selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group and a cyclocarbonate group; a crosslinkable compound having a group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms; or a crosslinkable compound having a polymerizable unsaturated bonding group (also collectively referred to as a specific crosslinkable compound). In this case, these groups need to be present in the compound in an amount of 2 or more.
Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminobiphenyl, tetraglycidyl m-xylylenediamine, tetraglycidyl-1, 3-bis (aminoethyl) cyclohexane, tetraphenylglycidylethane, triphenylglycidylethane, bisphenol hexafluoroacetyl diglycidyl ether, 1, 3-bis (1- (2, 3-epoxypropoxy) -1-trifluoromethyl-2, 2, 2-trifluoromethyl) benzene, 4-bis (2, 3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl m-xylylenediamine, and the like, 2- (4- (2, 3-epoxypropoxy) phenyl) -2- (4- (1, 1-bis (4- (2, 3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1, 3-bis (4- (1- (4- (2, 3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol, etc.
The crosslinkable compound having an oxetanyl group is a crosslinkable compound having at least 2 oxetanyl groups represented by the following formula [4A ].
Figure BDA0001294629370000481
Specifically, examples of the crosslinkable compound include crosslinkable compounds represented by the formulae [4a ] to [4k ] described in International patent publication WO2011/132751(2011.10.27 publication) at pages 58 to 59.
The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least 2 cyclocarbonate groups represented by the following formula [5A ].
Figure BDA0001294629370000482
Specifically, examples thereof include crosslinkable compounds represented by the formulae [5-1] to [5-42] described in International patent publication WO2012/014898 (published 2012.2.2) on pages 76 to 82.
Examples of the crosslinkable compound having at least 1 group selected from the group consisting of a hydroxyl group and an alkoxy group include amino resins having a hydroxyl group or an alkoxy group, such as melamine resins, urea resins, guanamine resins, glycoluril-formaldehyde resins, succinamide-formaldehyde resins, and ethyleneurea-formaldehyde resins. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group, an alkoxymethyl group, or both of them can be used. The melamine derivative or benzoguanamine derivative may also be present in the form of a dimer or trimer. They preferably have an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per 1 triazine ring.
Examples of such melamine derivatives or benzoguanamine derivatives include commercially available MX-750 substituted with an average of 3.7 methoxymethyl groups per 1 triazine ring and MW-30 substituted with an average of 5.8 methoxymethyl groups per 1 triazine ring (see above, Sanko chemical Co., Ltd.); methoxymethylated melamines such as CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, and the like; methoxymethylated butoxymethylated melamines such as CYMEL 235, 236, 238, 212, 253, 254; butoxymethylated melamines such as CYMEL 506, 508; carboxy-containing methoxymethylated isobutoxymethylated melamines such as CYMEL 1141; methoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1123; methoxymethylated butoxymethylated benzoguanamine such as CYMEL 1123-10; butoxymethylated benzoguanamine such as CYMEL 1128; carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1125-80 (manufactured by Mitsui サイアナミド Co., Ltd.). Examples of glycolurils include butoxymethylated glycolurils such as CYMEL 1170, hydroxymethylated glycolurils such as CYMEL 1172, and methoxyhydroxymethylated glycolurils such as Powder link 1174.
Examples of the benzene or phenol compound having a hydroxyl group or an alkoxy group include 1,3, 5-tris (methoxymethyl) benzene, 1,2, 4-tris (isopropoxymethyl) benzene, 1, 4-bis (sec-butoxymethyl) benzene, 2, 6-dihydroxymethyl-p-tert-butylphenol, and the like. More specifically, crosslinkable compounds represented by the formulae [6-1] to [6-48] described in International publication WO2011/132751 (published 2011.10.27) at pages 62 to 66 are exemplified.
Examples of the crosslinkable compound having a polymerizable unsaturated bond include crosslinkable compounds having 3 polymerizable unsaturated groups in the molecule, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, and glycerol polyglycidyl ether poly (meth) acrylate; 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, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol a type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, or hydroxypivalyl hydroxypivalate di (meth) acrylate, etc., having a crosslinkable property of 2 polymerizable unsaturated groups in a molecule Compounds, and the like.
The content of the specific crosslinkable compound in the liquid crystal aligning agent is preferably 1 to 50 parts by mass per 100 parts by mass of the total polymer components. In order to promote the crosslinking reaction and to exhibit the desired effect, the amount is more preferably 1 to 30 parts by mass, and particularly preferably 1 to 10 parts by mass.
As the liquid crystal aligning agent, a compound which improves the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film when the liquid crystal aligning agent is applied can be used within a range not impairing the effects of the present invention. Further, a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate can be used.
Examples of the compound for improving the uniformity of the film thickness and the 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 Eftop EF301, EF303, and EF352 (manufactured by Tohkem products Corporation); megafac F171, F173 and R-30 (manufactured by Dainippon ink Co., Ltd.); fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi glass Co., Ltd.). The amount of the surfactant is preferably 0.01 to 2 parts by mass per 100 parts by mass of the total polymer components contained in the liquid crystal aligning agent. More preferably 0.01 to 1 part by mass.
Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy-containing compound. Examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazacyclodecane, 10-triethoxysilyl-1, 4, 7-triazacyclodecane, 9-trimethoxysilyl-3, 6-diazanonylacetate, 9-triethoxysilyl-3, 6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl-triethoxysilane, N-bis (oxyethylene) -3-aminopropyl-trimethoxysilane, N-bis (oxyethylene) -3-aminopropyl-triethoxysilane, N-bis (oxyethylene) -3-, Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N ', -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, or N, N ', -tetraglycidyl-4, 4 ' -diaminodiphenylmethane.
The ratio of the compound to be used in close contact with the substrates is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total polymer components contained in the liquid crystal aligning agent. More preferably 1 to 20 parts by mass. When the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when the amount is more than 30 parts by mass, the storage stability of the liquid crystal aligning agent may be deteriorated.
In addition to the above-mentioned compounds, a dielectric material or a conductive material for changing electrical characteristics such as a dielectric constant and conductivity of the liquid crystal alignment film may be added to the liquid crystal alignment treatment agent within a range not to impair the effects of the present invention.
< liquid Crystal alignment film/liquid Crystal display device >
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film by applying the agent to a substrate, baking the agent, and then performing alignment treatment such as brushing or light irradiation. In the case of a liquid crystal display element for VA mode, the liquid crystal display element can be used as a liquid crystal alignment film without alignment treatment. The substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acryl substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of simplifying the process, a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed is preferably used. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used as a single-sided substrate, and a material that reflects light such as aluminum may be used as an electrode in this case.
The method of applying the liquid crystal aligning agent is not particularly limited, and a method of applying the liquid crystal aligning agent by screen printing, gravure printing, offset printing, inkjet printing, or the like is generally industrially used. Other coating methods include dip coating, roll coating, slit coating, spin coating, and spray coating, and they can be used according to the purpose.
After coating the liquid crystal alignment treatment agent on the substrate, the solvent is evaporated at a temperature of 30 to 300 ℃, preferably 30 to 250 ℃ depending on the solvent used in the liquid crystal alignment treatment agent by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven, thereby forming a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too large, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when the thickness is too small, the reliability of the liquid crystal display element may be lowered, so that it is preferably 5 to 300nm, more preferably 10 to 100 nm. When liquid crystals are aligned in an oblique or horizontal direction as in liquid crystal display devices for TN mode and IPS mode, the liquid crystal alignment film after firing is treated by brushing, polarized ultraviolet irradiation, or the like.
The liquid crystal display element of the present invention is produced by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and then producing a liquid crystal cell by a known method.
As a method for manufacturing a liquid crystal cell, the following method can be exemplified: a method of preparing a pair of substrates on which liquid crystal alignment films are formed, spreading spacers on the liquid crystal alignment films of the individual substrates, attaching the other substrate so that the liquid crystal alignment film faces inward, injecting liquid crystal under reduced pressure, and sealing; or a method of dropping a liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and then attaching and sealing the substrate (also referred to as ODF: One Drop Filling method).
The liquid crystal aligning agent of the present invention is preferably used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes, the liquid crystal display element being produced through the following steps: a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between a pair of substrates, and the polymerizable compound is polymerized by at least one of irradiation with the active energy rays and heating while applying a voltage between electrodes. Here, the active energy ray is preferably ultraviolet ray. The ultraviolet ray has a wavelength of 300 to 400nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ℃, preferably 60 to 80 ℃. Further, ultraviolet rays and heat may be applied simultaneously.
The liquid crystal display element described above controls the pretilt of liquid crystal molecules by means of the PSA mode. In the PSA mode, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed into a liquid crystal material in advance, a liquid crystal cell is assembled, and then the photopolymerizable compound is irradiated with ultraviolet light or the like while a predetermined voltage is applied to the liquid crystal layer, whereby the generated polymer controls the pretilt of liquid crystal molecules. Since the alignment state of the liquid crystal molecules when the polymer is produced is memorized even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling an electric field or the like formed in the liquid crystal layer. In addition, in the PSA mode, since the brushing process is not necessary, it is suitable for formation of a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the brushing process. That is, in the liquid crystal display element of the present invention, after the substrate with the liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent by the above-described method, the liquid crystal cell is produced, and the polymerizable compound is polymerized by at least one of irradiation with ultraviolet rays and heating, whereby the alignment of the liquid crystal molecules can be controlled.
An example of manufacturing a PSA mode liquid crystal cell is as follows. That is, the liquid crystal cell is manufactured by the above manufacturing method. A polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed into the liquid crystal at this time. Examples of the polymerizable compound include compounds having 1 or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. If the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled, and if the polymerizable compound is more than 10 parts by mass, the unreacted polymerizable compound increases and the afterimage characteristics of the liquid crystal display element deteriorate. After the liquid crystal cell is produced, the polymerizable compound is polymerized by applying an ac voltage or a dc voltage to the liquid crystal cell and irradiating the liquid crystal cell with heat or ultraviolet light. Thereby enabling control of the orientation of the liquid crystal molecules.
Further, the liquid crystal aligning agent of the present invention can be used in an SC-PVA mode, which is a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes. Here, the active energy ray is preferably ultraviolet ray. The ultraviolet ray has a wavelength of 300 to 400nm, more preferably 310 to 360 nm. When polymerization is carried out by heating, the heating temperature is 40 to 120 ℃, and more preferably 60 to 80 ℃. Further, ultraviolet rays and heat may be applied simultaneously.
In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat, examples of the liquid crystal alignment film include: a method of adding a compound containing the polymerizable group to a liquid crystal aligning agent; a method of using a polymer component containing a polymerizable group.
An example of producing an SC-PVA mode liquid crystal cell is as follows. That is, the liquid crystal cell is manufactured by the above manufacturing method. Then, the liquid crystal cell is irradiated with heat or ultraviolet rays while applying an ac voltage or a dc voltage thereto, whereby the alignment of the liquid crystal molecules can be controlled.
As described above, by using the liquid crystal alignment treatment agent of the present invention, it is possible to provide a liquid crystal alignment film which can suppress a decrease in voltage holding ratio even after exposure to light for a long period of time and which does not cause display unevenness in the vicinity of the edge of a liquid crystal display element even under high-temperature and high-humidity conditions. Therefore, a liquid crystal display element produced using the liquid crystal aligning agent of the present invention has excellent reliability, and can be suitably used for large-sized liquid crystal televisions, medium-sized and small-sized car navigation systems, smart phones, and the like. In particular, the liquid crystal alignment treatment agent of the present invention is useful for liquid crystal alignment films using liquid crystal display elements of VA mode, PSA mode, and SC-PVA mode.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.
Abbreviations used in the synthesis examples, examples and comparative examples are as follows.
(specific Compound)
S1: phosphotungstic acid (made by Nippon New Metal Co., Ltd.)
S2: phosphomolybdic acid (12 molybdenum (IV) phosphoric acid n-hydrate) (manufactured by Kanto chemical Co., Ltd.)
(specific diamine Compound (1))
A1: a diamine compound represented by the following formula [ A1]
A2: a diamine compound represented by the following formula [ A2]
Figure BDA0001294629370000551
(specific diamine Compound (2))
B1: 1, 3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy ] benzene
B2: 1, 3-diamino-5- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl ] benzene
B3: 1, 3-diamino-4- {4- [ trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl ] phenoxy } benzene
B4: a diamine compound represented by the following formula [ B4]
B5: 1, 3-diamino-4-octadecyloxybenzene
Figure BDA0001294629370000552
Figure BDA0001294629370000561
(other diamine Compound)
C1: p-phenylenediamine
C2: m-phenylenediamine
C3: a diamine compound represented by the following formula [ C3]
C4: 4, 4' -diaminodiphenylamine
C5: 3, 5-diaminobenzoic acid
Figure BDA0001294629370000562
(specific tetracarboxylic dianhydride)
D1: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
D2: bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride
D3: tetracarboxylic dianhydride represented by the following formula [ D3]
D4: tetracarboxylic dianhydride represented by the following formula [ D4]
D5: tetracarboxylic dianhydride represented by the following formula [ D5]
Figure BDA0001294629370000571
(crosslinkable Compound)
M1: a crosslinkable compound represented by the following formula [ M1]
Figure BDA0001294629370000572
(solvent)
NMP: n-methyl-2-pyrrolidone
NEP: n-ethyl-2-pyrrolidone
gamma-BL: gamma-butyrolactone
BCS: ethylene glycol monobutyl ether
PB: propylene glycol monobutyl ether
DME: dipropylene glycol dimethyl ether
"molecular weight measurement of polyimide-based Polymer"
The measurement was carried out by the following procedure using a Gel Permeation Chromatography (GPC) apparatus (GPC-101, manufactured by Showa Denko K.K.) and columns (KD-803, KD-805, manufactured by Shodex).
Column temperature: 50 deg.C
Eluent: n, N' -dimethylformamide (as additive, lithium bromide monohydrate (LiBr. H)2O) 30mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10ml/L)
Flow rate: 1.0 ml/min
Standard sample for standard curve preparation: TSK standard polyethylene oxides (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh corporation) and polyethylene glycols (molecular weight: about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories Ltd.).
"measurement of imidization ratio of polyimide-based Polymer"
20mg of the polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (. phi.5, manufactured by Softweed scientific Co., Ltd.), deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) (0.53ml) was added thereto, and the mixture was completely dissolved by applying ultrasonic waves. The proton NMR of the solution at 500MHz was measured by an NMR spectrometer (JNW-ECA500, JEOL DATUM). The imidization ratio was determined using a proton derived from a structure that did not change before and after imidization as a reference proton, and was obtained by the following equation using the peak integrated value of the proton and the peak integrated value of the proton derived from the NH group of amic acid appearing in the vicinity of 9.5ppm to 10.0 ppm.
Imidization ratio (%) - (1-. alpha.x/y). times.100
(x is the peak accumulation value of the proton derived from the NH group of amic acid, y is the peak accumulation value of the standard proton, and α is the number ratio of the standard proton to 1 NH group proton of amic acid in the case of polyamic acid (imidization ratio of 0%))
Synthesis of polyimide-based Polymer "
< Synthesis example 1>
D4(9.65g, 32.1mmol), B5(1.36g, 3.61mmol) and C1(3.52g, 32.6mmol) were mixed with NMP (30.5g) and reacted at 40 ℃ for 6 hours, and then D1(0.70g, 3.57mmol) and NMP (15.2g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25 mass%.
NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and then acetic anhydride (3.90g) and pyridine (2.40g) were added as an imidization catalyst to react at 70 ℃ for 4 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (1). The polyimide had an imidization rate of 85%, a number average molecular weight of 19,800 and a weight average molecular weight of 51,800.
< Synthesis example 2>
D2(5.95g, 23.8mmol), B3(4.47g, 10.3mmol), C1(1.49g, 13.8mmol) and C3(2.10g, 10.3mmol) were mixed with NEP (32.0g) and reacted at 80 ℃ for 5 hours, and then D1(2.00g, 10.2mmol) and NEP (16.0g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. The polyamic acid had a number-average molecular weight of 20,200 and a weight-average molecular weight of 68,300.
< Synthesis example 3>
To a polyamic acid solution (2) (30.0g) obtained in Synthesis example 2, NEP was added and diluted to 6 mass%, and then acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidization catalyst to conduct a reaction at 80 ℃ for 4 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (3). The polyimide had an imidization rate of 80%, a number average molecular weight of 18,300 and a weight average molecular weight of 46,800.
< Synthesis example 4>
D2(2.98g, 11.9mmol), A1(1.25g, 5.16mmol), B3(2.23g, 5.15mmol) and C1(0.74g, 6.84mmol) were mixed with NEP (16.4g) and reacted at 80 ℃ for 5 hours, and then D1(1.00g, 5.10mmol) and NEP (8.21g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25 mass%.
To the obtained polyamic acid solution (30.0g) was added NEP and diluted to 6% by mass, and acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidization catalyst to conduct a reaction at 80 ℃ for 4 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (4). The polyimide had an imidization rate of 81%, a number average molecular weight of 17,800 and a weight average molecular weight of 44,900.
< Synthesis example 5>
D2(2.17g, 8.67mmol), A1(1.28g, 5.28mmol), B1(2.67g, 7.02mmol) and C1(0.57g, 5.27mmol) were mixed with NMP (16.8g) and reacted at 80 ℃ for 5 hours, and then D1(1.70g, 8.67mmol) and NMP (8.39g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25 mass%.
NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and then acetic anhydride (3.80g) and pyridine (2.40g) were added as an imidization catalyst to react at 60 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (5). The polyimide had an imidization rate of 56%, a number average molecular weight of 17,000, and a weight average molecular weight of 43,200.
< Synthesis example 6>
D2(2.17g, 8.67mmol), A1(1.28g, 5.28mmol), B5(2.65g, 7.04mmol) and C1(0.57g, 5.27mmol) were mixed with NMP (16.7g) and reacted at 80 ℃ for 5 hours, and then D1(1.70g, 8.67mmol) and NMP (8.36g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25 mass%.
NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and then acetic anhydride (3.80g) and pyridine (2.40g) were added as an imidization catalyst to react at 60 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (6). The polyimide had an imidization rate of 55%, a number average molecular weight of 16,300 and a weight average molecular weight of 41,100.
< Synthesis example 7>
D2(1.31g, 5.24mmol), A1(0.86g, 3.55mmol), B2(2.80g, 7.10mmol), C1(0.57g, 5.27mmol) and C4(0.35g, 1.76mmol) were mixed with NMP (16.6g) and reacted at 80 ℃ for 5 hours, then D1(2.40g, 12.2mmol) and NMP (8.29g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid content of 25 mass%.
NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and then acetic anhydride (3.80g) and pyridine (2.40g) were added as an imidization catalyst to react at 60 ℃ for 2.5 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (7). The polyimide had an imidization rate of 60%, a number average molecular weight of 17,500 and a weight average molecular weight of 43,800.
< Synthesis example 8>
D2(2.04g, 8.15mmol), A2(1.07g, 4.13mmol), B2(2.94g, 7.45mmol), C1(0.36g, 3.33mmol) and C5(0.25g, 1.64mmol) were mixed with NEP (16.5g) and reacted at 80 ℃ for 5 hours, then D1(1.60g, 8.16mmol) and NEP (8.26g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25 mass%.
NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidization catalyst to react at 80 ℃ for 3 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (8). The polyimide had an imidization rate of 72%, a number average molecular weight of 16,800 and a weight average molecular weight of 41,900.
< Synthesis example 9>
D2(2.30g, 9.19mmol), A1(0.90g, 3.71mmol), B4(2.29g, 4.65mmol) and C2(1.11g, 10.3mmol) were mixed with NMP (16.8g) and reacted at 80 ℃ for 5 hours, and then D1(1.80g, 9.18mmol) and NMP (8.39g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25 mass%.
NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and then acetic anhydride (3.80g) and pyridine (2.40g) were added as an imidization catalyst to react at 60 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (9). The polyimide had an imidization rate of 52%, a number average molecular weight of 15,300 and a weight average molecular weight of 39,700.
< Synthesis example 10>
D3(7.10g, 31.7mmol), A1(3.11g, 12.8mmol), B2(5.06g, 12.8mmol) and C1(0.69g, 6.38mmol) were mixed with NMP (47.9g) and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.
NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidization catalyst to react at 80 ℃ for 3 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (10). The polyimide had an imidization rate of 73%, a number average molecular weight of 18,600 and a weight average molecular weight of 48,400.
< Synthesis example 11>
D4(3.22g, 10.7mmol), A1(0.38g, 1.57mmol), B1(2.95g, 7.75mmol), C2(0.34g, 3.14mmol) and C4(0.62g, 3.11mmol) were mixed with NMP (16.8g) and reacted at 80 ℃ for 5 hours, then D1(0.90g, 4.59mmol) and NMP (8.39g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid content of 25 mass%.
To the obtained polyamic acid solution (30.0g) was added NEP and diluted to 6% by mass, and acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidization catalyst to conduct a reaction at 80 ℃ for 4 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (11). The polyimide had an imidization rate of 85%, a number average molecular weight of 16,200 and a weight average molecular weight of 41,500.
< Synthesis example 12>
D4(3.67g, 12.2mmol), A2(1.00g, 3.86mmol), B3(2.35g, 5.43mmol), C1(0.50g, 4.62mmol) and C3(0.32g, 1.57mmol) were mixed with NMP (16.9g) and reacted at 80 ℃ for 5 hours, then D1(0.60g, 3.06mmol) and NMP (8.44g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid content of 25 mass%.
To the obtained polyamic acid solution (30.0g) was added NEP and diluted to 6% by mass, and acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidization catalyst to conduct a reaction at 80 ℃ for 3 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (12). The polyimide had an imidization rate of 72%, a number average molecular weight of 17,500 and a weight average molecular weight of 43,100.
< Synthesis example 13>
D2(2.48g, 9.91mmol), A1(1.62g, 6.69mmol), B2(2.64g, 6.69mmol) and C1(0.36g, 3.33mmol) were mixed with NMP (17.0g) and reacted at 80 ℃ for 5 hours, and then D5(1.40g, 6.60mmol) and NMP (8.50g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25 mass%.
To the obtained polyamic acid solution (30.0g) was added NEP and diluted to 6% by mass, and then acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidization catalyst to conduct a reaction at 80 ℃ for 3.5 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (13). The polyimide had an imidization rate of 74%, a number average molecular weight of 16,200 and a weight average molecular weight of 41,500.
The polyimide-based polymers obtained by the synthesis examples are shown in tables 32 and 33.
[ Table 32]
Figure BDA0001294629370000641
*1: a polyamic acid.
[ Table 33]
Figure BDA0001294629370000642
Production of liquid Crystal alignment treatment agent "
Examples of the production of the liquid crystal aligning agent are described in examples and comparative examples below. The liquid crystal aligning agent is also used for production of a liquid crystal display element and evaluation thereof. The liquid crystal aligning agents obtained in examples and comparative examples are shown in tables 34 to 36.
"evaluation of ink-jet coatability of liquid Crystal alignment treatment agent"
The liquid crystal alignment treatment agents obtained in example 7 and example 11 described later were used to evaluate ink jet coatability. Specifically, these liquid crystal aligning agents were pressure-filtered through a membrane filter having a pore diameter of 1 μm, and applied to an ITO surface of an ITO (indium tin oxide) electrode-attached substrate (100 mm in length. times.100 mm in width, 0.7mm in thickness) cleaned with pure water and IPA (isopropyl alcohol) under conditions of a coating area of 70X 70mm, a nozzle pitch of 0.423mm, a scanning pitch of 0.5mm, and a coating speed of 40 mm/sec. In this case, HIS-200 (manufactured by Hitachi Plant Technologies, Ltd.) was used as the ink jet coater. The time from coating to predrying was 60 seconds, and predrying was performed on a hot plate at 70 ℃ for 5 minutes.
The coating properties were evaluated by visually observing the coating surface of the substrate with the liquid crystal alignment film obtained above. Specifically, the film surface was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, no pinhole was observed in the film surface of the liquid crystal alignment film obtained in any of the examples, and a liquid crystal alignment film having excellent film coatability was obtained.
"evaluation of uneven characteristics in the vicinity of the edge of liquid crystal cell (ordinary cell)"
The liquid crystal alignment agents obtained in examples and comparative examples described later were pressure-filtered through a membrane filter having a pore diameter of 1 μm, and spin-coated on the ITO surface of an ITO electrode-equipped substrate (40 mm in length by 30mm in width, 0.7mm in thickness) cleaned with pure water and IPA, and then heated on a hot plate at 100 ℃ for 5 minutes and a thermal cycle type cleaning oven at 230 ℃ for 30 minutes to obtain an ITO substrate equipped with a liquid crystal alignment film having a film thickness of 100 nm. In addition, the liquid crystal aligning agents of examples 7 and 11 were used to prepare substrates (substrates with ITO electrodes (40 mm in length × 30mm in width, 0.7mm in thickness) cleaned with pure water and IPA in the same manner as described above) under the same conditions as in the above "evaluation of the ink jet coatability of the liquid crystal aligning agent", and then the substrates were subjected to heat treatment at 230 ℃ for 30 minutes in a heat cycle type cleaning oven to prepare ITO substrates with liquid crystal alignment films having a film thickness of 100 nm.
Then, the coated surface of the substrate was brushed using rayon cloth at a roller rotation speed of 1000rpm, a roller forward speed of 50mm/sec and a pressing amount of 0.1mm by a brushing device having a roller diameter of 120 mm.
Thereafter, 2 substrates were prepared after the brushing treatment, and the coated surfaces were combined with a 6 μm spacer interposed therebetween, and the periphery was bonded with a sealant to prepare an empty cell. The liquid crystal is injected into the empty cell by a reduced pressure injection method, and the injection port is sealed to obtain a liquid crystal cell. In example 1 and comparative example 1, MLC-3018U (manufactured by MERCK JAPAN) was used as the liquid crystal, and MLC-6608 (manufactured by MERCK JAPAN) was used as the liquid crystal in the other examples and comparative examples.
Using the obtained liquid crystal cell, the characteristic of showing unevenness in the vicinity of the edge of the liquid crystal cell was evaluated. Specifically, the liquid crystal alignment properties near the sealant were evaluated by visual observation using a polarizing plate and a backlight. As a result, all the liquid crystal cells obtained in examples and comparative examples exhibited uniform liquid crystal alignment properties.
Thereafter, the liquid crystal cell was stored in a high-temperature and high-humidity tank at a temperature of 80 ℃ and a humidity of 90% for 96 hours, and the liquid crystal alignment properties in the vicinity of the sealant were evaluated under the same conditions as described above. The evaluation was excellent in the case where no disturbance of the liquid crystal alignment was observed in the vicinity of the sealant after storage in the high-temperature and high-humidity tank (shown as good in tables 37 to 39). Tables 37 to 39 show the results of the uneven characteristics near the edge of the liquid crystal cell after storage in the high-temperature and high-humidity chamber.
"evaluation of Voltage holding ratio (ordinary Unit)"
The liquid crystal cell produced under the same conditions as in the above-described "evaluation of uneven characteristics in the vicinity of the edge of the liquid crystal cell (ordinary cell)" was used to evaluate the voltage holding ratio. Specifically, a voltage of 1V of 60 μ s was applied to the liquid crystal cell obtained by the above method at a temperature of 80 ℃, and the voltage after 50ms was measured, and how much the voltage can be maintained was calculated as a voltage holding ratio (also referred to as VHR). Incidentally, using a Voltage holding ratio measuring apparatus (VHR-1) (manufactured by TOYO Corporation), the Voltage: ± 1V, Pulse Width: 60 μ s, Flame Period (frame Period): the measurement was performed at a setting of 50 ms.
Further, the liquid crystal cell after completion of the measurement of the voltage holding ratio immediately after the production of the liquid crystal cell was irradiated with 50J/cm in terms of 365nm using a desktop UV curing apparatus (HCT3B28HEX-1) (manufactured by SENTLIGHT Co.)2The voltage holding ratio of (2) was measured under the same conditions as described above.
In this evaluation, a case where the value of the voltage holding capacity immediately after the liquid crystal cell was produced was high and the decrease of the value after the ultraviolet irradiation (also referred to as after the ultraviolet irradiation) was small compared to the value of the voltage holding capacity immediately after the liquid crystal cell was produced (also referred to as initial) was regarded as excellent. The values of VHRs are shown in tables 37 to 39.
< example 1>
NMP (7.83g) and gamma-BL (23.5g) were added to the polyimide powder (1) (2.50g) obtained in Synthesis example 1, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP and the gamma-BL. S1(0.25g) and BCS (7.83g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (1). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 2>
S1(0.125g), NEP (14.0g) and PB (17.6g) were added to a polyamic acid solution (2) (10.0g) having a resin solid content concentration of 25.0 mass% obtained in Synthesis example 2, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (2). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 3>
NEP (23.5g) was added to the polyimide powder (3) (2.50g) obtained in Synthesis example 3, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. S1(0.25g), BCS (3.92g) and PB (11.8g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (3). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
As an emphasis test together with the standard test, the "evaluation (normal cell) showing the uneven characteristics in the vicinity of the edge of the liquid crystal cell" was also evaluated when the cell was stored for 144 hours in a high-temperature and high-humidity tank at a temperature of 80 ℃ and a humidity of 90% (other conditions were the same as the above conditions). As a result, in the liquid crystal cell, disturbance of the liquid crystal alignment was observed until the self-sealing agent reached a width region of 0.5 cm.
< example 4>
NEP (23.5g) was added to the polyimide powder (4) (2.50g) obtained in Synthesis example 4, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. S1(0.25g), BCS (3.92g) and PB (11.8g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (4). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
As an emphasis test together with the standard test, the "evaluation (normal cell) showing the uneven characteristics in the vicinity of the edge of the liquid crystal cell" was also evaluated when the cell was stored for 144 hours in a high-temperature and high-humidity tank at a temperature of 80 ℃ and a humidity of 90% (other conditions were the same as the above conditions). As a result, in the liquid crystal cell, no disturbance of the liquid crystal alignment was observed in the vicinity of the sealant.
< example 5>
NEP (23.5g) was added to the polyimide powder (5) (2.50g) obtained in Synthesis example 5, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. S1(0.175g) and PB (15.7g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (5). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
As an emphasis test together with the standard test, the "evaluation (normal cell) showing the uneven characteristics in the vicinity of the edge of the liquid crystal cell" was also evaluated when the cell was stored for 168 hours in a high-temperature and high-humidity tank at a temperature of 80 ℃ and a humidity of 90% (other conditions were the same as the above conditions). As a result, in the liquid crystal cell, no disturbance of the liquid crystal alignment was observed in the vicinity of the sealant.
< example 6>
NEP (23.5g) was added to the polyimide powder (6) (2.50g) obtained in Synthesis example 6, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. S1(0.175g) and PB (15.7g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (6). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
As an emphasis test together with the standard test, the "evaluation (normal cell) showing the uneven characteristics in the vicinity of the edge of the liquid crystal cell" was also evaluated when the cell was stored for 168 hours in a high-temperature and high-humidity tank at a temperature of 80 ℃ and a humidity of 90% (other conditions were the same as the above conditions). As a result, in the liquid crystal cell, disturbance of liquid crystal alignment was observed in the vicinity of the sealant.
< example 7>
NEP (20.7g) was added to the polyimide powder (7) (1.50g) obtained in Synthesis example 7, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. S2(0.105g), PB (16.5g) and DME (4.14g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal alignment treatment agent (7). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 8>
NMP (23.5g) was added to the polyimide powder (8) (2.50g) obtained in synthesis example 8, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. To the solution were added S1(0.075g), M1(0.125g), BCS (7.83g) and PB (7.83g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal alignment treatment agent (8). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 9>
NEP (25.5g) was added to the polyimide powder (9) (2.50g) obtained in Synthesis example 9, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. S1(0.30g), BCS (5.88g) and PB (7.83g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (9). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 10>
NEP (23.5g) was added to the polyimide powder (10) (2.50g) obtained in Synthesis example 10, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. To the solution were added S2(0.125g) and PB (15.7g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (10). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 11>
To the polyimide powder (11) (1.50g) obtained in Synthesis example 11, NEP (16.5g) and γ -BL (4.14g) were added and dissolved by stirring at 70 ℃ for 24 hours. S1(0.105g), BCS (8.27g) and PB (12.4g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (11). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 12>
NMP (19.6g) was added to the polyimide powder (12) (2.50g) obtained in synthesis example 12, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. To the solution were added S1(0.25g), M1(0.175g), BCS (15.7g) and DME (3.92g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal alignment treatment agent (12). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< example 13>
NEP (23.5g) was added to the polyimide powder (13) (2.50g) obtained in Synthesis example 13, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. S2(0.175g), BCS (7.83g) and PB (7.83g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (13). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< comparative example 1>
NMP (7.83g) and gamma-BL (23.5g) were added to the polyimide powder (1) (2.50g) obtained in Synthesis example 1, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP and the gamma-BL. BCS (7.83g) was added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (14). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
< comparative example 2>
NEP (23.5g) was added to the polyimide powder (3) (2.50g) obtained in Synthesis example 3, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. BCS (3.92g) and PB (11.8g) were added to the solution, and the mixture was stirred at 25 ℃ for 6 hours to obtain a liquid crystal aligning agent (15). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
[ Table 34]
Liquid crystal aligning agent Polyimide polymer Specific compounds (ratio): 1 Concentration of solid component 2
Example 1 Liquid Crystal alignment treatment agent (1) Polyimide powder (1) S1(10) 6.0
Example 2 Liquid Crystal alignment treatment agent (2) Polyamic acid solution (2) S1(5) 6.0
Example 3 Liquid Crystal alignment treatment agent (3) Polyimide powder (3) S1(10) 6.0
Example 4 Liquid Crystal alignment treatment agent (4) Polyimide powder (4) S1(10) 6.0
Example 5 Liquid Crystal alignment treatment agent (5) Polyimide powder (5) S1(7) 6.0
Example 6 Liquid Crystal alignment treatment agent (6) Polyimide powder (6) S1(7) 6.0
Example 7 Liquid Crystal alignment treatment agent (7) Polyimide powder (7) S2(7) 3.5
Example 8 Liquid Crystal alignment treatment agent (8) Polyimide powder (8) S1(3) 6.0
Example 9 Liquid Crystal alignment treatment agent (9) Polyimide powder (9) S1(12) 6.0
Example 10 Liquid crystal aligning agent (10) Polyimide powder (10) S2(5) 6.0
[ Table 35]
Liquid crystal aligning agent Polyimide polymer Specific compounds (ratio): 1 Concentration of solid component 2
Example 11 Liquid Crystal alignment treatment agent (11) Polyimide powder (11) S1(7) 3.5
Example 12 Liquid Crystal alignment treatment agent (12) Polyimide powder (12) S1(10) 6.0
Example 13 Liquid Crystal alignment treatment agent (13) Polyimide powder (13) S2(7) 6.0
[ Table 36]
Liquid crystal aligning agent Polyimide polymer Specific compounds (ratio): 1 Concentration of solid component 2
Comparative example 1 Liquid Crystal alignment treatment agent (14) Polyimide powder (1) - 6.0
Comparative example 2 Liquid Crystal alignment treatment agent (15) Polyimide powder (3) - 6.0
*1: the introduction amount (parts by mass) of the specific compound to 100 parts by mass of the polyimide-based polymer is shown.
*2: the ratio of the polyimide-based polymer in the liquid crystal aligning agent is shown.
[ Table 37]
Figure BDA0001294629370000711
[ Table 38]
Figure BDA0001294629370000712
[ Table 39]
Figure BDA0001294629370000721
*1: in the liquid crystal cell, disturbance of liquid crystal alignment was observed in the vicinity of the sealant.
*2: in the liquid crystal cell, disturbance of liquid crystal alignment was observed up to a width region of 0.5cm from the sealing agent (the width of disturbance of liquid crystal alignment was observed to be larger than 1).
From the above results, it can be seen that: the liquid crystal aligning agent of the examples of the present invention can suppress the decrease in the voltage holding ratio even when the liquid crystal cell is irradiated with ultraviolet rays, as compared with the liquid crystal aligning agent of the comparative example. Further, even when the liquid crystal cell was stored in a high-temperature and high-humidity chamber for a long period of time, no disturbance of the liquid crystal alignment was observed in the vicinity of the sealant. That is, the liquid crystal aligning agent of the present invention forms a liquid crystal alignment film which can suppress a decrease in voltage holding ratio even after long-term exposure to light and can suppress the occurrence of display unevenness in the vicinity of the edge of a liquid crystal display element under high-temperature and high-humidity conditions.
Specifically, the following can be found: the liquid crystal aligning agent of the comparative example is inferior in the above-mentioned properties to the examples using the liquid crystal aligning agent of the specific compound of the present invention and the specific polyimide-based polymer and the comparative examples using no liquid crystal aligning agent of the specific compound. More specifically, the results are a comparison between example 1 and comparative example 1, and a comparison between example 3 and comparative example 3.
In addition, in the stress test, the liquid crystal alignment treatment agent using the specific diamine compound (1) having the specific structure (1) of the present invention showed no disturbance in the liquid crystal alignment in the vicinity of the sealant even when the liquid crystal cell was stored in the high-temperature high-humidity tank for a long period of time, as compared with the liquid crystal alignment treatment agent not using the specific diamine compound (1). More specifically, for the comparison under the same conditions in the stress test, it is the comparison of example 3 with example 4.
In addition, in the specific structure (2) of the present invention, the liquid crystal alignment treatment agent using the specific diamine compound (2) having the specific structure represented by the above formula [3-1] did not cause any disturbance in the liquid crystal alignment in the vicinity of the sealant even when the liquid crystal cell was stored in a high-temperature and high-humidity tank for a long period of time in the stress test, as compared with the liquid crystal alignment treatment agent using the diamine compound having the specific structure represented by the above formula [3-2 ]. More specifically, for the comparison under the same conditions in the stress test, it is a comparison of example 5 with example 6.
Industrial applicability
The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film which can suppress a decrease in voltage holding ratio even after long-term exposure to light, can improve the adhesion between a sealing agent and a liquid crystal alignment film, and can suppress display unevenness in the vicinity of the edge of a liquid crystal display element which occurs under high-temperature and high-humidity conditions. Further, a liquid crystal display element having the liquid crystal alignment film and a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film can be provided.
Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is applicable to a large-screen and high-definition liquid crystal television set or the like, and is useful for TN elements, STN elements, TFT liquid crystal elements, and particularly vertical alignment type liquid crystal display elements.
Further, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element to be irradiated with ultraviolet rays when manufacturing a liquid crystal display element. That is, the present invention is particularly useful for a liquid crystal display element which has a liquid crystal layer between a pair of substrates having electrodes and is manufactured through the following steps: disposing a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of an active energy ray and heat between the pair of substrates, and polymerizing the polymerizable compound while applying a voltage between the electrodes; in particular, a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes and manufactured through the following steps: a liquid crystal alignment film containing the polymerizable group that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the polymerizable group is polymerized while applying a voltage between the electrodes.

Claims (19)

1. A liquid crystal aligning agent comprising the following component (A), component (B) and the following crosslinkable compound,
(A) the components: at least 1 heteropolyacid selected from the group consisting of phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid and phosphotungstomolybdic acid;
(B) the components: a polymer of at least 1 selected from the group consisting of acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyimide precursors, polyimide, polyamide, polyester, cellulose and polysiloxane,
crosslinkable compound: a crosslinkable compound having a group selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group and a cyclocarbonate group; or a crosslinkable compound having a group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms; or a crosslinkable compound having a polymerizable unsaturated bonding group.
2. The agent for alignment treatment of liquid crystal according to claim 1, wherein the polymer has a nitrogen-containing aromatic heterocycle.
3. The agent for alignment treatment of liquid crystal according to claim 1, wherein the polymer is a polyimide precursor obtained by a reaction of a diamine component and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor.
4. The liquid crystal aligning agent according to claim 3, wherein the diamine component comprises a diamine compound having a structure represented by the following formula [2],
-W1-W2-W3-W4 [2]
W1represents a group selected from-O-, -NH-, -N (CH)3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3) -and-N (CH)3) At least 1 bonding group of the group consisting of CO-; w2Represents at least 1 selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring; w3Represents a group selected from the group consisting of a single bond, -O-, -NH-, -N (CH)3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、-N(CH3) CO-and-O (CH)2)m-at least 1 of the group consisting of, wherein m represents an integer from 1 to 5; w4Represents a nitrogen-containing aromatic heterocycle.
5. The liquid crystal aligning agent according to claim 4, wherein the diamine component comprises a diamine compound represented by the following formula [2a ],
Figure FDA0002821131910000021
w represents a structure represented by the formula [2 ]; m1 represents an integer of 1 to 4.
6. The liquid crystal aligning agent according to claim 3, wherein the diamine component comprises a diamine compound having a structure represented by the following formula [3-1] or formula [3-2],
Figure FDA0002821131910000022
Y1is selected from the group consisting of a single bond, - (CH)2)a-、-O-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from the group consisting of CO-, -COO-, and-OCO-, wherein a is an integer of 1 to 15; y is2Represents a single bond or- (CH)2)b-, wherein b is an integer of 1 to 15; y is3Is selected from the group consisting of a single bond, - (CH)2)c-、-O-、-CH2At least 1 of the group consisting of O-, -COO-and-OCO-, wherein c is an integer of 1 to 15; y is4Represents at least 1 2-valent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle, or a 2-valent organic group having 17 to 51 carbon atoms and having a steroid skeleton, wherein any hydrogen atom on the cyclic group is optionally substituted by 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; y is5Represents at least 1 cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocycle, any hydrogen atom on the cyclic groups is optionally substituted by C1-3 alkyl, C1-3 alkoxy, C1-3 fluoroalkyl, C1-C E3 or a fluorine atom or a fluorine-containing alkoxy group; n represents an integer of 0 to 4; y is6Represents at least 1 kind selected from the group consisting of C1-18 alkyl, C2-18 alkenyl, C1-18 fluorine-containing alkyl, C1-18 alkoxy and C1-18 fluorine-containing alkoxy,
-Y7-Y8 [3-2]
Y7represents a group selected from-O-, -CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) At least 1 bonding group selected from the group consisting of CO-, -COO-and-OCO-; y is8Represents an alkyl group having 8 to 18 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms.
7. The liquid crystal aligning agent according to claim 6, wherein the diamine compound is represented by the following formula [3a ],
Figure FDA0002821131910000031
y represents a structure represented by the above formula [3-1] or formula [3-2 ]; n1 represents an integer of 1 to 4.
8. The liquid crystal aligning agent according to any one of claims 3 to 7, wherein the tetracarboxylic acid component comprises a tetracarboxylic dianhydride represented by the following formula [4],
Figure FDA0002821131910000032
z represents at least 1 structure selected from the group consisting of structures represented by the following formulas [4a ] to [4k ],
Figure FDA0002821131910000033
Z1～Z4each independently represents a group selected from a hydrogen atom, a methyl group, a chlorine atom and a benzene ringAt least 1 of; z5And Z6Each independently represents a hydrogen atom or a methyl group.
9. The liquid crystal alignment treatment agent according to any one of claims 1 to 7, wherein the liquid crystal alignment treatment agent contains at least 1 solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ -butyrolactone.
10. The liquid crystal alignment treatment agent according to claim 8, wherein the liquid crystal alignment treatment agent contains at least 1 solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ -butyrolactone.
11. The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the agent contains at least 1 solvent selected from the group consisting of 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and solvents represented by the following formulae [ D1] to [ D3],
Figure FDA0002821131910000041
D1represents an alkyl group having 1 to 3 carbon atoms; d2Represents an alkyl group having 1 to 3 carbon atoms; d3Represents an alkyl group having 1 to 4 carbon atoms.
12. The liquid crystal aligning agent according to claim 8, wherein the agent contains at least 1 solvent selected from the group consisting of 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and solvents represented by the following formulae [ D1] to [ D3],
Figure FDA0002821131910000042
D1represents an alkyl group having 1 to 3 carbon atoms; d2Represents an alkyl group having 1 to 3 carbon atoms; d3Represents an alkyl group having 1 to 4 carbon atoms.
13. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 12.
14. A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of claims 1 to 12 by an inkjet method.
15. A liquid crystal display element having the liquid crystal alignment film according to claim 13 or 14.
16. The liquid crystal alignment film according to claim 13 or 14, which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes, the liquid crystal display element being manufactured through the following steps: a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the polymerizable compound is polymerized while applying a voltage between the electrodes.
17. A liquid crystal display element comprising the liquid crystal alignment film according to claim 16.
18. The liquid crystal alignment film according to claim 13 or 14, which is used for a liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes, the liquid crystal display element being manufactured through the following steps: a liquid crystal alignment film including a polymerizable group that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the polymerizable group is polymerized while applying a voltage between the electrodes.
19. A liquid crystal display element comprising the liquid crystal alignment film according to claim 18.
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