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CN119569593A - Diamine, polymer and polyimide for liquid crystal aligning agent - Google Patents

Diamine, polymer and polyimide for liquid crystal aligning agent Download PDF

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Publication number
CN119569593A
CN119569593A CN202411750590.XA CN202411750590A CN119569593A CN 119569593 A CN119569593 A CN 119569593A CN 202411750590 A CN202411750590 A CN 202411750590A CN 119569593 A CN119569593 A CN 119569593A
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liquid crystal
diamine
compound
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大野慎跃
山本雄介
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
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    • C07C217/94—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
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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
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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
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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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
    • C08G73/1075—Partially aromatic polyimides
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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Abstract

The invention provides a diamine, a polymer and a polyimide for a liquid crystal alignment agent for forming a liquid crystal alignment film for Vertical Alignment (VA) which has high refractive index and high light transmittance due to no colorability. A diamine represented by formula (2-1). A polymer derived from the diamine component of the diamine. A polyimide which is a polyimide precursor obtained by a polycondensation reaction of a diamine component containing the diamine and a tetracarboxylic acid component or an imide compound of the polyimide precursor.

Description

Diamine, polymer and polyimide for liquid crystal aligning agent
The application is a divisional application of the following application:
liquid crystal aligning agent for vertical alignment, liquid crystal alignment film, and liquid crystal display element
International application date: 09/23/2020
International application No. PCT/JP2020/035773
National application number 202080066916.0
Technical Field
The present invention relates to a liquid crystal aligning agent for vertical alignment (VA: VERTICAL ALIGNMENT), a liquid crystal alignment film obtained from the liquid crystal aligning agent, a liquid crystal display element having the liquid crystal alignment film, and a novel diamine and polymer suitable for the liquid crystal aligning agent, the liquid crystal alignment film, and the liquid crystal display element.
Background
Liquid crystal display devices are widely used in applications ranging from small-sized applications such as cellular phones and smart phones to larger-sized applications such as televisions and displays. The liquid crystal display device is generally configured such that a pair of electrode substrates are arranged so as to face each other with a predetermined gap (several μm) therebetween, and liquid crystal is sealed between the electrode substrates. Then, a voltage is applied between the transparent conductive films of the electrodes constituting the electrode substrate, so that display in the liquid crystal display element is performed. These liquid crystal display elements have a liquid crystal alignment film which is indispensable for controlling the alignment state of liquid crystal molecules.
On the other hand, as a liquid crystal display element, various driving methods have been developed in which the electrode structure and physical properties of liquid crystal molecules used are different. For example, various modes such as TN (TWISTED NEMATIC: twisted nematic), STN (Super TWISTED NEMATIC: super twisted nematic), VA (VERTICAL ALIGNMENT: vertical alignment), IPS (In-PLANE SWITCHING: in-plane switching) and FFS (FRINGE FIELD SWITCHING: fringe field switching) are known.
Among them, VA (vertical alignment) type liquid crystal display elements have a wide viewing angle, a high response speed, and a high contrast, and are widely used particularly for televisions and displays, which are required to be large in size, because a brushing process is not required in the production process.
Prior art literature
Patent literature
Patent document 1 International publication No. 2008/117615
Patent document 2 Japanese patent application laid-open No. 2008-76950
Disclosure of Invention
Problems to be solved by the invention
The transparent conductive film in the liquid crystal display element is generally formed of a composition (ITO) containing indium oxide as a main component and several% of tin oxide doped thereto, but has a high value, unlike the refractive index of the liquid crystal alignment film. Therefore, when an attempt is made to transmit light from the display light source to the electrode substrates, the light is reflected at the boundary surface between the transparent conductive film and the liquid crystal alignment film in each electrode substrate. As a result, the light transmittance of the electrode substrate cannot be sufficiently obtained, and the display luminance is decreased.
In particular, in recent years, ultra-high definition panels such as 4K and 8K have been developed, but in these panels, the occupancy of Black Matrix (BM) and TFT has been increased, the aperture ratio of the panel has been lowered, and improvement of the transmittance of the display has been emphasized.
Accordingly, the present inventors have made various studies on materials for forming the liquid crystal alignment film in order to increase the refractive index of the liquid crystal alignment film, from the viewpoint that the above-described drawbacks can be eliminated by reducing the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal alignment film. Specifically, in order to increase the refractive index of the liquid crystal alignment film, various types of polymers contained in a liquid crystal alignment agent for forming the liquid crystal alignment film have been searched for.
As a result, it was found that a liquid crystal alignment film having a refractive index similar to that of the transparent conductive film can be obtained by selecting a specific polymer, but on the other hand, in the case where a large number of polymers are used to form a liquid crystal alignment film having a high refractive index, the liquid crystal alignment film has colorability. The liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer having colorability has low light transmittance, and as a result, the display brightness is lowered, and as a result, the above object is not achieved.
In view of the above, an object of the present invention is to provide a liquid crystal aligning agent for forming a liquid crystal alignment film for VA (vertical alignment) having a high refractive index and having high light transmittance due to no colorability, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film.
Solution for solving the problem
The present inventors have conducted intensive studies to achieve the above-mentioned problems, and as a result, have found that a liquid crystal aligning agent containing a part of a novel polymer having a specific structure is effective for achieving the above-mentioned object, and have completed the present invention.
The present invention provides a liquid crystal aligning agent for Vertical Alignment (VA), a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element of vertical alignment system having the liquid crystal alignment film, wherein the liquid crystal aligning agent contains at least one polymer (P) selected from the group consisting of a polyimide precursor obtained by using a diamine component comprising a diamine (0) represented by the following formula (0), and a polyimide which is an imide compound of the polyimide precursor.
H2N-A-L-A′-NH2 (0)
( A and A 'each independently represent a monocyclic group, a condensed cyclic group, or a group formed by bonding two of the monocyclic groups, and at least one of A and A' represents a condensed cyclic group. L represents a single bond or a-X 1－Q－X2 -group. X 1 and X 2 each independently represent a single bond, an oxygen atom or a sulfur atom. Q represents an alkylene group having 1 or 2 carbon atoms. )
Effects of the invention
According to the present invention, a liquid crystal alignment agent for Vertical Alignment (VA) that forms a liquid crystal alignment film having a high refractive index and high light transmittance due to no colorability can be obtained. Since the liquid crystal alignment film formed by the liquid crystal alignment agent has a high refractive index, the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal alignment film in the liquid crystal display element can be reduced, and since the liquid crystal alignment agent does not have colorability, a Vertical Alignment (VA) liquid crystal display element having high light transmittance and high display brightness can be obtained.
Detailed Description
As described above, the liquid crystal aligning agent of the present invention is characterized by containing at least one polymer (P) selected from the group consisting of a polyimide precursor obtained by using a diamine component comprising a diamine (0) represented by the following formula (0), and a polyimide which is an imide compound of the polyimide precursor.
H 2N-A-L-A′-NH2 (0) in the above formula (0), A, A' and L, X 1、X2 are each as defined above.
A. The monocyclic group in A' means a divalent group obtained by removing two hydrogen atoms from a monocyclic ring. Examples of the monocyclic ring include benzene, five-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole, and six-membered heterocyclic rings such as pyran, pyrone, pyridine, pyridazine, pyrimidine, and pyrazine. The monocyclic ring is preferably benzene or pyridine. In the case where the monocyclic ring is benzene, the monocyclic group is phenylene.
A. The condensed ring group in A' is a divalent group obtained by removing two hydrogen atoms from a condensed ring. Examples of the condensed ring include condensed polycyclic aromatic hydrocarbons such as naphthalene, tetrahydronaphthalene, indene, fluorene, anthracene, phenanthrene, and pyrene, and condensed polycyclic heterocyclic rings such as coumarone, thiaindene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, and quinoxaline. The condensed ring is preferably naphthalene, anthracene, pyrene, indole, carbazole, coumarin, benzopyrone, quinoline, or isoquinoline.
The two monocyclic groups are preferably bonded to each other, and the group is preferably a biphenyl structure or a bipyridyl group.
Among them, A, A' is preferably a phenylene group, a pyridyl group, a naphthylene group, an anthryl group, a quinolyl group, a biphenyl structure, or a bipyridyl group from the viewpoint of obtaining the effect of the present invention.
L is preferably a single bond, -O- (CH 2)n - (n is an integer 1 or 2), or-O- (CH 2)n -O- (n is an integer 1 or 2).
Specific examples of the diamine (0) represented by the above formula (0) include the following formulas (d-1) to (d-21).
Preferable specific examples of the diamine (0) represented by the above formula (0) include diamines represented by the following formula (1).
In the above formula (1), A, L, X 1、X2 are each as defined above.
As preferable specific examples of the diamine (1) represented by the above formula (1), those represented by the formulae (d-1) to (d-7), (d-13) to (d-14), (d-17) to (d-18) and (d-21) among the formulae (d-1) to (d-21) are mentioned.
The polymer (P) contained in the liquid crystal aligning agent of the present invention is preferably at least one polymer selected from the group consisting of polyimide precursors obtained by using a diamine component containing a diamine (S) having at least one selected from the group consisting of structures represented by the following formulas (S1) to (S3), and polyimides which are imidized as polyimide precursors, in addition to the diamine represented by the formula (0).
In the formula (S1), X 1 and X 2 each independently represent a single bond, - (CH 2)a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3) -, -NH-, -O-, -COO-, -OCO-, or- ((CH 2)a1－A1)m1 - (a 1 is an integer of 1 to 15, A 1 represents an oxygen atom or-COO-, m 1 is an integer of 1 to 2 in the case that m 1 is 2, a plurality of a1 and A 1 each independently have the definition), G 1 and G 2 each independently represent a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms, a divalent alicyclic group having 3 to 8 carbon atoms, any hydrogen atom on the cyclic group is optionally substituted with 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 fluoroalkoxy group having 1 to 3 carbon atoms, m and n are each independently an integer of 0 to 3, n is an alkyl group having 1 to 3 carbon atoms, and n is preferably an alkoxy group having 1 to 20 carbon atoms, and a total of 1 to 20 carbon atoms is optionally substituted with an alkoxy group having 1 to 20 carbon atoms.
Examples of the divalent cyclic group in G 1、G2 include cyclopropylene, cyclohexylene and phenylene. Any hydrogen atom on these cyclic groups is optionally substituted with 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.
-X3-R2 (S2)
In the formula (S2), X 3 represents a single bond, -CONH-, -NHCO-, -CON (CH 3)－、－NH－、－O－、－CH2 O-, -COO-or-OCO- & lt 2 & gt represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, and any hydrogen atom forming R 2 is optionally substituted with a fluorine atom.
In addition, R 2 is preferably an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms from the viewpoint of improving the alignment of the liquid crystal.
-X4-R3 (S3)
In the formula (S3), the amino acid sequence, X 4 represents-CONH-; -NHCO-, -O-, -CH 2O－、－OCH2 -, -COO-or-OCO-. R 3 represents a structure having a steroid skeleton. In addition, R 3 is preferably a structure comprising cholestanyl, cholestanyl or lanostanyl.
As preferable specific examples of the formula (S1), the following formulas [ S1-x1] [ S1-x7] can be cited.
In the formula, R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. X p is- (CH 2)a - (a is an integer of 1-15), -CONH-, -NHCO-, -CON (CH 3)－、－NH－、－O－、－CH2O－、－CH2 OCO-, -COO-, or-OCO- & A 1 is an oxygen atom or-COO- & A 1 is an oxygen atom with a bonding of ". With a bonding of CH 2)a2, A 2 is an oxygen atom with a bonding of". With a bonding of CH 2)a2, a 3 is 0 or 1, a 1、a2 is an integer of 1-10 independently, and Cy is 1, 4-cyclohexylene or 1, 4-phenylene.
As a preferable specific example of the formula (S2), X 3 is any of-O-, -CH 2 O-, -COO-or-OCO-, preferably R 2 is an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, further, when R 2 is an alkyl group having 3 to 20 carbon atoms, any hydrogen atom forming R 2 is optionally substituted with a fluorine atom.
As a preferable specific example of the above formula (S3), the following formula [ S3-x ] can be given. In the formula [ S3-X ], X is a formula [ X1], a formula [ X2] or a formula [ X3], col is a formula [ Col1], a formula [ Col2] or a formula [ Col3], and G is a formula [ G1], a formula [ G2], a formula [ G3] or a formula [ G4]. Me represents methyl.
Preferable diamines (S) having the structures represented by the above formulas (S1) to (S3) include diamines represented by the following formulas (d 1) and (d 2).
In the formulae (d 1) and (d 2), Y represents a side chain structure represented by the formulae (S1) to (S3), and two Y in the formula (d 2) may be the same or different. In addition, X represents a single bond 、－O－、－C(CH3)2－、－NH－、－CO－、－(CH2)m－、－SO2－、－O－(CH2)m－O－、－O－C(CH3)2－、－CO－(CH2)m－、－NH－(CH2)m－、－SO2－(CH2)m－、－CONH－(CH2)m－、－CONH－(CH2)m－NHCO－、－COO－(CH2)m－OCO－、－COO－、－CONH－、－NH－(CH2)m－NH－、－SO2－(CH2)m－SO2－.m and is an integer of 1 to 8.
As preferable specific examples of the diamine of the above formula (d 1), the following formulas (d 1-1) to (d 1-18) are given.
(N is an integer of 1 to 20.)
The diamine represented by the formula (d 2) may be selected from the group consisting of the following formulas (d 2-1) to (d 2-6).
Wherein X p1～Xp8 is synonymous with X p in the formulae [ S1-X1] to [ S1-X6] independently of each other, X s1～Xs4 each independently represents-O-, -CH 2O－、－OCH2 -, -COO-or-OCO-, X a～Xf represents －O－、－NH－、－O－(CH2)m－O－、－C(CH3)2－、－CO－、－COO－、－CONH－、－(CH2)m－、－SO2－、－O－C(CH3)2－、－CO－(CH2)m－、－NH－(CH2)m－、－NH－(CH2)m－NH－、－SO2－(CH2)m－、－SO2－(CH2)m－SO2－、－CONH－(CH2)m－、－CONH－(CH2)m－NHCO－、 or-COO- (CH 2)m－OCO－,R1a～R1h) independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, and m is 1 to 8.
(Production of Polymer (P))
The polymer (P) contained in the liquid crystal aligning agent of the present invention is a polyimide precursor obtained by using a diamine component containing the diamine (0), preferably a diamine component containing a diamine(s) in addition to the diamine (0), or a polyimide which is an imide of the polyimide precursor. Here, the polyimide precursor is a polymer that can be imidized to obtain polyimide, such as polyamic acid and polyamic acid ester.
The polyamide acid (P) which is a polyimide precursor of the polymer (P) can be obtained by polymerization of a diamine component containing the diamine (0), preferably a diamine component containing a diamine(s) in addition to the diamine (0), and a tetracarboxylic acid component.
In this case, the amount of the diamine (0) to be used is preferably 1 to 100 mol%, more preferably 1 to 99 mol%, and even more preferably 5 to 95 mol% based on the diamine component to be reacted with the tetracarboxylic acid component.
When the diamine(s) is used in addition to the diamine (0), the amount of the diamine(s) to be used is preferably 1 to 99 mol%, more preferably 1 to 95 mol%, based on the diamine component to be reacted with the tetracarboxylic acid component.
The diamine component used in the production of the polyamic acid (P) may contain diamine (0) and diamine other than diamine(s) (hereinafter, these may be referred to as other diamines). Examples of other diamines are listed below, but the present invention is not limited thereto.
Diamines having carboxyl groups such as p-phenylenediamine, m-phenylenediamine, 4- (2- (methylamino) ethyl) aniline, 3, 5-diaminobenzoic acid, 4' -diaminodiphenylmethane, 3' -diaminodiphenylmethane, 4' -diaminodiphenylether 3,3' -diaminodiphenyl ether, 4' -diaminobenzophenone, 3' -diaminobenzophenone, 1, 2-bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) propane, 1, 4-bis (4-aminophenyl) butane, 1, 4-bis (4-aminophenoxy) benzene 1, 3-bis (4-aminophenoxy) benzene, 1, 2-bis (4-aminophenoxy) ethane, 1, 2-bis (4-amino-2-methylphenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, 4- (2- (4-aminophenoxy) ethoxy) -3-fluoroaniline, bis (2- (4-aminophenoxy) ethyl) ether, 4-amino-4 ' - (2- (4-aminophenoxy) ethoxy) biphenyl, diamines having urea bonds such as 2,2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dimethyl-4, 4' -diaminobiphenyl, 1, 4-diaminonaphthalene, 1, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2' -bis (4-aminophenyl) propane, 1, 3-bis (4-aminophenylethyl) urea, diamines represented by the following formulas (a-1) to (a-6), preferably 2- (2, 4-diaminophenoxy) ethyl methacrylate, 2, 4-diamino-N, diamines having a photopolymerizable group at the terminal such as N-diallylaniline, diamines having a radical initiating function such as the following formulae (R1) to (R5), diamines having a heterocyclic ring such as 3, 6-diaminocarbazole, N-methyl-3, 6-diaminocarbazole, diamines having a diphenylamine skeleton such as the following formulae (z-1) to (z-18), diamines having a diphenylamine skeleton such as the following formulae (Dp-1) to (Dp-3), diamines having an organosiloxane such as 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, and the like, diamines having a group "-N (D) -" (D is a protecting group which is detached by heating and substituted with a hydrogen atom, preferably t-butoxycarbonyl group) such as the following formulae (5-1) to (5-11), diamines having an oxazoline structure such as the following formulae (Ox-1) to (Ox-2), diamines described in International publication No. 2016/125870, and the like.
(D 1 represents an integer of 2 to 10.)
(N represents an integer of 2 to 10.)
(Boc represents tert-butoxycarbonyl.)
Among these, p-phenylenediamine, 3, 5-diaminobenzoic acid, 4 '-diaminodiphenylmethane, 4' -diaminobenzophenone, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2- (2, 4-diaminophenoxy) ethyl methacrylate, 2, 4-diamino-N, N-diallylaniline, diamines represented by the above formulae (R1) to (R5), diamines represented by the above formulae (z-1) to (z-18), diamines represented by the above formulae (5-1) to (5-11), and diamines represented by the above formulae (Ox-1) to (Ox-2) are preferable as other diamines from the viewpoint of obtaining the effects of the present invention.
When a diamine other than the diamine (0) is used, the amount of the diamine used is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, based on the total diamine components used.
When a diamine other than the diamine (0) and the diamine(s) is used, the amount of the diamine(s) used is preferably 98 mol% or less, more preferably 94 mol% or less, based on the diamine component that reacts with the tetracarboxylic acid component.
The amount of the other diamine used is preferably 5 to 40 mol%, more preferably 10 to 40 mol%, based on the total diamine components used in the production of the polyamic acid (P).
In a liquid crystal display element using a PSA (Polymer Sustained Alignment: polymer stable alignment) system or an SC-PVA (PATTERNED VERTICAL ALIGNMENT: image homeotropic alignment) mode, from the viewpoint of improving the response speed, the amount of the diamine represented by the formulae (R1) to (R5) and the diamine represented by the formulae (z-1) to (z-18) to be used is preferably 1 to 40 mol%, more preferably 5 to 40 mol%, based on the total amount of the diamine components used in the production of the polyamic acid (P), and the diamine having a photopolymerizable group at the terminal thereof is preferably a diamine represented by the formulae (R1) to (R5).
(Tetracarboxylic acid component)
In the case of producing the polyamide acid (P), the tetracarboxylic acid component to be reacted with the diamine component may be not only a tetracarboxylic dianhydride but also a derivative of a tetracarboxylic dianhydride such as a tetracarboxylic acid, a tetracarboxylic dihalide, a tetraalkyl tetracarboxylic acid ester, or a tetraalkyl tetracarboxylic acid ester dihalide.
Examples of the tetracarboxylic dianhydride or derivative thereof include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and derivatives thereof. Here, the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group of an aromatic ring. The aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. The aromatic hydrocarbon compound may have an alicyclic structure or an aromatic ring structure in a part thereof, without being composed of only a chain hydrocarbon structure.
The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. Wherein none of the four carboxyl groups is bonded to an aromatic ring. Further, the structure need not be composed of only an alicyclic structure, and may have a chain hydrocarbon structure or an aromatic ring structure in a part thereof.
Among them, the tetracarboxylic dianhydride or its derivative is preferably represented by the following formula (T).
Wherein, in the formula (T), X represents a structure selected from the group consisting of the following (X-1) to (X-13).
In the above formula (x-1), R 1～R4 each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a phenyl group. R 5 and R 6 each independently represent a hydrogen atom or a methyl group. j and k each independently represent 0 or 1, A 1 and A 2 each independently represent a single bond, an ether (-O-), a carbonyl (-CO-), an ester (-COO-), a phenylene, a sulfonyl (-SO 2 -) or an amide (-CONH-), and two A 2 are optionally the same or different. *1 is a bond to one anhydride group, and 2 is a bond to the other anhydride group.
As preferable specific examples of the above-mentioned formulae (x-12) and (x-13), the following formulae (x-14) to (x-29) are given. * Representing a bond.
As a preferable specific example of the tetracarboxylic dianhydride represented by the above formula (T) or a derivative thereof, there can be mentioned a tetracarboxylic dianhydride or a derivative thereof selected from the group consisting of the above formulae (X-1) to (X-7) and (X-11) to (X-13).
The ratio of the tetracarboxylic dianhydride represented by the formula (T) or a derivative thereof to be used is preferably 1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, based on 1mol of the total tetracarboxylic acid components to be used.
The tetracarboxylic dianhydride or derivative thereof used for producing the polyamic acid (P) may contain a tetracarboxylic dianhydride or derivative thereof other than the above formula (T).
The polyamide acid (P) is produced by reacting the diamine component and the tetracarboxylic acid component in a solvent (condensation polymerization). The solvent is not particularly limited as long as the polymer formed is dissolved.
Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and 1, 3-dimethyl-2-imidazolidinone. In addition, in the polymer solvent solubility is high, can use methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [ D-1] to formula [ D-3] solvent.
(In the formula [ D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, in the formula [ D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, in the formula [ D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms).
These solvents may be used alone or in combination. Further, even if the solvent does not dissolve the polymer, the solvent may be used in combination within a range where the polymer to be produced does not precipitate.
When the diamine component and the tetracarboxylic acid component are reacted in a solvent, the reaction may be carried out at an arbitrary concentration, and the concentration of the diamine component and the tetracarboxylic acid component relative to the solvent is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration at the beginning of the reaction, and then a solvent may be added.
In the reaction, the ratio of the total mole number of the diamine components to the total mole number of the tetracarboxylic acid components (total mole number of the diamine components/total mole number of the tetracarboxylic acid components) is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the molar ratio becomes closer to 1.0, and the molecular weight of the specific polymer to be produced becomes larger.
The polyamic acid ester as a polyimide precursor can be obtained, for example, by a known method of [ I ] reacting the polyamic acid obtained by the above-described synthesis reaction with an esterifying agent, [ II ] reacting a tetracarboxylic acid diester with a diamine, [ III ] reacting a tetracarboxylic acid diester dihalide with a diamine, and the like.
[ Polyimide ]
The polyimide contained in the liquid crystal aligning agent of the present invention is a polyimide obtained by ring-closing the polyimide precursor. In polyimide, the ring closure rate (also referred to as imidization rate) of the amide group is not necessarily 100%, and may be arbitrarily adjusted according to the application and purpose.
As a method for imidizing a polyimide precursor to obtain a polyimide, there may be mentioned thermal imidization in which a solution of the polyimide precursor is directly heated or catalytic imidization in which a catalyst is added to a solution of the polyimide precursor. The temperature in the case of thermally imidizing the polyimide precursor in a solution is 100 to 400 ℃, preferably 120 to 250 ℃, and is preferably carried out while removing water generated by the imidization reaction to the outside of the system.
The catalyst imidization of the polyimide precursor is performed 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 mol times, preferably 2 to 20 mol times, that of the amide acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times, that of the amide acid group. The basic catalyst includes pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and pyridine is preferable because pyridine has a proper basicity to allow the reaction to proceed. The acid anhydride may be acetic anhydride, trimellitic anhydride, pyromellitic anhydride (pyromellitic anhydride) or the like, and among them, when acetic anhydride is used, purification after completion of the reaction is easy, and is preferable. The imidization rate based on catalyst imidization can be controlled by adjusting the catalyst amount and the reaction temperature, the reaction time.
In the case of recovering the polyimide to be produced from the reaction solution for imidization of the polyimide precursor, the reaction solution may be poured into a solvent to precipitate the polyimide. As the solvent used for precipitation, methanol, ethanol, isopropanol, acetone, hexane, butyl cellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like can be mentioned. The polymer obtained by precipitating the polymer by adding a solvent is recovered by filtration and then dried at normal temperature or under reduced pressure, normal temperature or by heating. In addition, when the polymer recovered by precipitation is redissolved in a solvent and the reprecipitation recovery operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent include alcohols and ketone hydrocarbons, and when three or more solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.
The weight average molecular weight (Mw) of the polyimide precursor and the polyimide in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is preferably 1000 to 500000, more preferably 2000 to 300000. The molecular weight distribution (Mw/Mn) expressed by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. In this molecular weight range, good alignment properties of the liquid crystal display element can be ensured.
(Liquid Crystal alignment agent)
The liquid crystal aligning agent of the present invention is a liquid composition comprising the polymer (P) and, if necessary, other components dispersed or dissolved in an appropriate solvent.
The liquid crystal aligning agent of the present invention may contain a polymer (P) in addition to the polymer (P) for the purpose of improving electric characteristics, homeotropic alignment, solution characteristics, and the like, for example (hereinafter, also referred to as other polymers). As a specific example of the other polymer, in addition to the polymer (P), at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine component containing at least one kind selected from the group consisting of structures represented by the formulae (S1) to (S3), and polyimide which is an imide compound of the polyimide precursor may be contained in view of improving the vertical alignment property.
The content of the other polymer is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and still more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total polymer contained in the liquid crystal aligning agent.
Examples of the other polymer include, but are not particularly limited to, polyimide precursors, polyimides, polysiloxanes, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and other main backbones. Among them, at least one selected from the group consisting of polyimide precursors, polyimides, polyamides, polyorganosiloxanes, poly (meth) acrylates, and polyesters is preferable. Among them, at least one selected from the group consisting of polyimide precursors, polyimides, and polysiloxanes is more preferable. It should be noted that two or more other polymers may be used in combination.
The liquid crystal aligning agent of the present invention may contain other components than those described above as needed. Examples of the component include at least one compound selected from the group consisting of crosslinkable compounds having a substituent selected from at least one of epoxy groups, isocyanate groups, oxetane groups, cyclic carbonate groups, blocked isocyanate groups, hydroxyl groups, and alkoxy groups, functional silane compounds, metal chelating compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds for adjusting the dielectric constant and electric resistance of the liquid crystal alignment film.
As preferable specific examples of the crosslinkable compound, compounds represented by the following formulas (CL-1) to (CL-11) are given. Examples of the compound for adjusting the dielectric constant and the electric resistance of the liquid crystal alignment film include monoamines having nitrogen-containing aromatic heterocycles such as 3-aminomethylpyridine.
Examples of the organic solvent used in the liquid crystal aligning agent of the present invention include: N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, N- (N-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (N-butyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (N-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropane amide, 3-butoxy-N, N-dimethylpropaneamide, gamma-butyrolactone, gamma-butyrolactam, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol N-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), and, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diisobutyl methanol (2, 6-dimethyl-4-heptanol), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used in combination of two or more.
The solid content concentration (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) in the liquid crystal aligning agent is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 10 mass%. In terms of forming a uniform and defect-free coating film, it is preferably 1 mass% or more, and in terms of storage stability of the solution, it is preferably 10 mass% or less. The concentration of the particularly preferable polymer is 2 to 8 mass%.
< Liquid Crystal alignment film >
The liquid crystal alignment film for vertical alignment using the liquid crystal alignment agent of the present invention can be produced by applying the liquid crystal alignment agent to a substrate and sequentially performing the steps of drying and baking. The substrate used in this case is not particularly limited as long as it has high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to a glass substrate. From the viewpoint of process simplification, a substrate formed with an ITO electrode or the like for liquid crystal driving is preferably used. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used only on one side, and a material reflecting light such as aluminum may be used as the electrode in this case.
Examples of the method for applying the liquid crystal alignment agent include screen printing, offset printing, flexography, inkjet method, dipping method, roll coater method, slit coating method, spin coating method, and spray coating method, and from the viewpoint of improving the production efficiency of the liquid crystal alignment film, a method of applying by flexography or inkjet method is preferable.
The liquid crystal alignment agent is coated on a substrate, and then dried at a temperature of preferably 40 to 150 ℃ and then fired at a temperature of preferably 150 to 300 ℃, more preferably 180 to 250 ℃ according to a solvent used for the liquid crystal alignment agent by a heating unit such as a heating plate or a thermal cycle oven IR (infrared ray) type oven, thereby producing a liquid crystal alignment film.
If 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 if it is too small, the reliability of the liquid crystal display element may be lowered, and thus it is preferably 5 to 300nm, more preferably 10 to 100nm.
< Liquid Crystal display element >
The liquid crystal display element of the present invention includes the liquid crystal alignment film.
In the VA mode liquid crystal display device, the coating film formed as described above may be used as a liquid crystal alignment film as it is, or may be subjected to a brushing treatment or PSA treatment described later as necessary.
The liquid crystal aligning agent of the present invention is also preferably used for a liquid crystal display element produced by a process in which a liquid crystal layer is provided between a pair of substrates provided with electrodes, 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, a voltage is applied between the electrodes, and the polymerizable compound is polymerized by at least one of irradiation of active energy rays and heating. The applied voltage may be, for example, 5 to 50v dc or ac. Further, ultraviolet rays are preferable as active energy rays. The ultraviolet ray is an ultraviolet ray containing light having a wavelength of 300 to 400nm, preferably an ultraviolet ray containing light having a wavelength of 310 to 360 nm. The irradiation amount of light is preferably 0.1 to 20J/cm 2, more preferably 1 to 20J/cm 2.
As a method for manufacturing a liquid crystal display element using the liquid crystal aligning agent of the present invention, for example, a method in which the liquid crystal aligning agent is applied to a pair of substrates having a conductive film to form a coating film, the coating film is disposed so as to face each other with a layer of liquid crystal molecules interposed therebetween to form a liquid crystal cell, and the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates is used.
The liquid crystal display element controls the pretilt angle of liquid crystal molecules by PSA (Polymer Sustained Alignment) method. In the PSA method, 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 after that, the photopolymerizable compound is irradiated with ultraviolet rays or the like in a state where a predetermined voltage is applied to a liquid crystal layer, and the pretilt angle of liquid crystal molecules is controlled by the polymer produced. Since the alignment state of the liquid crystal molecules at the time of polymer formation is stored even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. In addition, the PSA method does not require a brushing process, and is therefore suitable for forming a vertically aligned liquid crystal layer in which it is difficult to control the pretilt angle by the brushing process.
In the liquid crystal display element of the present invention, a substrate with a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above-described method, and then a liquid crystal cell is fabricated by a known method to produce a liquid crystal display element.
Examples of the method for producing the liquid crystal cell include a method in which a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are spread on the liquid crystal alignment film of one substrate, the other substrate is bonded so that the liquid crystal alignment film surface is inside, liquid crystal is injected under reduced pressure, and the liquid crystal is packaged, and a method in which liquid crystal is dropped onto the liquid crystal alignment film surface on which the spacers are spread, and then the substrates are bonded and packaged.
The liquid crystal may be mixed with a polymerizable compound which is polymerized by ultraviolet irradiation or heat as described above. The polymerizable compound may be a compound having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule, and examples thereof include polymerizable compounds represented by the following formulae (M-1) to (M-3).
In this case, the content of the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the liquid crystal component. If the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound is not polymerized, and the alignment of the liquid crystal is not controlled, and if the amount of the polymerizable compound is more than 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the residual image characteristics of the liquid crystal display element are lowered. After the liquid crystal cell is produced, an ac/dc voltage is applied to the liquid crystal cell, and the polymerizable compound is polymerized by heat or ultraviolet irradiation. Thereby, the orientation of the liquid crystal molecules can be controlled.
The liquid crystal aligning agent of the present invention can be used for a liquid crystal display element manufactured by a process in which a liquid crystal layer is provided between a pair of substrates provided with electrodes, a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat is arranged between the pair of substrates, and a voltage is applied between the electrodes. Here, ultraviolet rays are preferable as active energy rays. The ultraviolet rays used in the PSA method are preferably applied to the ultraviolet rays. In the case of polymerization by heating, the heating temperature is 40 to 120 ℃, preferably 60 to 80 ℃. In addition, ultraviolet rays and heating may be performed 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, a method of adding a compound containing the polymerizable group to a liquid crystal alignment agent, and a method of using a polymer component containing the polymerizable group are mentioned. Specific examples of the polymer containing a polymerizable group include polymers obtained by using a diamine having a function of polymerization by irradiation with light as described above.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. The following abbreviations of the compounds and the measurement methods of the respective characteristics are as follows. Unless otherwise specified, the numerical values are mass references.
< Specific diamine >
< Diamine(s) >
< Other diamines >
(Boc represents tert-butoxycarbonyl.)
(Tetracarboxylic dianhydride)
(Organic solvent)
NMP, N-methyl-2-pyrrolidone, BCS, butyl cellosolve.
THF, tetrahydrofuran.
[ Viscosity ]
The viscosity of the polyamic acid solution was measured at 25℃using an E-type viscometer TVE-22H (manufactured by east machine industries Co., ltd.) in terms of sample size of 1.1mL (milliliter) and a conical rotor TE-1 (1℃34', R24).
[ Measurement of molecular weight ]
Molecular weights of the polyimide precursor, polyimide and the like were measured using a normal temperature Gel Permeation Chromatography (GPC) apparatus (GPC-101) (manufactured by Showa electric company), and a chromatography column (KD-803, KD-805) (manufactured by Shodex company), as follows.
Column temperature 50 ℃.
The eluent was N, N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr. H 2 O) 30mmol/L, phosphoric acid/anhydrous crystal (O-phosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10 ml/L).
The flow rate was 1.0 ml/min.
The calibration curve was prepared using TSK-standard polyethylene oxide (molecular weight: about 900000, 150000, 100000 and 30000) (manufactured by Tosoh Co.) and polyethylene glycol (molecular weight: about 12000, 4000 and 1000) (manufactured by Polymer Laboratory).
[ Measurement of imidization Rate ]
Polyimide powder (20 mg) was added to an NMR (nuclear magnetic resonance) sample tube (NMR standard sample tube, phi 5 (manufactured by Bruhnum science Co.), deuterated dimethyl sulfoxide (DMSO-d 6,0.05 mass% TMS (tetramethylsilane) mixture) (0.53 ml) was added, and ultrasonic waves were applied to dissolve the mixture completely. The solution was subjected to proton NMR at 500MHz in an NMR measuring machine (JNW-ECA 500) (manufactured by Japanese electric date UM Co., ltd.). The imidization rate is determined by using the peak integrated value of a proton derived from the structure unchanged before and after imidization as a reference proton and the peak integrated value of a proton derived from the NH group of amic acid occurring in the vicinity of 9.5 to 10.0ppm by using the following formula.
Imidization ratio (%) = (1- α·x/y) ×100
In the above formula, x is a proton peak integral value of NH group derived from amic acid, y is a peak integral value of reference proton, and α is a number ratio of reference proton to one NH group proton of amic acid in the case of polyamic acid (imidization ratio is 0%).
< Synthetic example of Compound [ DA-n-2]
The compound [ DA-n-2] was synthesized according to the following scheme.
(Synthesis of Compound [1 ])
To dimethylformamide (1050 g) was added 6-bromonaphthalen-2-ol (150 g,672 mmol) and cooled under ice-cooling. Sodium hydride (60%, 29.6 g) was added in small amounts each time, and after stirring under ice-cooling for 1 hour, benzyl bromide (121 g) was added and stirred at room temperature for 1 hour. Further, pure water (750 g) was added thereto in small amounts each time under water cooling, followed by stirring to precipitate crystals, filtering, washing the filtrate with methanol (750 g), filtering, and drying the filtrate to give compound [1] (yield: 207g, yield: 98%, white crystals).
1H－NMR(400MHz,DMSO－D6,δ(ppm))：8.13(d,1H,J＝2.0Hz),7.85(d,1H,J＝9.2Hz),7.78(d,1H,J＝8.8Hz),7.58(dd,1H,J＝8.8Hz,2.4Hz),7.53－7.48(m,3H),7.44－7.40(m,2H),7.38－7.33(m,1H),7.30(dd,1H,J＝9.0Hz,2.6Hz),5.22(s,2H).
(Synthesis of Compound [2 ])
To tetrahydrofuran (1000 g) were added sodium t-butoxide (82.6 g) and benzophenone imine (126 g), and the mixture was stirred at room temperature for 30 minutes. To this was added compound [1] (207 g, 661mmol), PD 2(dba)3 (tris (dibenzylideneacetone) dipalladium (0), 3.03 g) and BINAP (2, 2 '-bis (diphenylphosphino) -1,1' -binaphthyl, 6.17 g), and stirred under nitrogen at 65℃for 23 hours. After cooling to room temperature, 1-fold hydrochloric acid (1000 g) was added thereto, and the mixture was stirred at room temperature for 15 minutes to separate an aqueous layer. To the organic layer were further added ethyl acetate (200 g), hexane (100 g) and 1-specified hydrochloric acid (500 g), and the separated aqueous layer was added. Sodium hydroxide (80 g) was added under water cooling to make it alkaline. The organic layer was separated, washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the filtrate was concentrated to obtain a crude body (154 g). To the crude material was added ethyl acetate (462 g) which was dissolved by heating at 70 ℃, and after that hexane (770 g) was added and cooled. Then, it was filtered, and the filtrate was dried, whereby compound [2] (yield: 124g, yield: 74%, pale tea crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：7.50－7.43(m,4H),7.42－7.37(m,2H),7.35－7.30(m,1H),7.19(d,1H,J＝2.8Hz),7.04(dd,1H,J＝8.8Hz,2.8Hz),6.90(dd,1H,J＝8.8Hz,2.0Hz),6.80(d,1H,J＝2.0Hz),5.13(br,4H).
(Synthesis of Compound [3 ])
To methylene chloride (1000 g) were added compound [2] (124 g,497 mmol) and di-tert-butyl dicarbonate (130 g), and the mixture was stirred at room temperature for 20 hours. The reaction was not completed, and therefore, di-tert-butyl dicarbonate (10 g) was additionally added thereto, followed by stirring at room temperature for 20 hours. Saturated aqueous sodium hydrogencarbonate (1L) and methylene chloride (300 g) were added to carry out liquid separation. The organic layer was washed successively with pure water (450 mL) and a saturated aqueous sodium chloride solution (300 mL), dried over sodium sulfate, filtered, and the filtrate was concentrated to obtain a crude body (198 g). To the crude body, ethyl acetate (600 g) was added and dissolved by heating at 70 ℃, and then hexane (1000 g) was added and cooled. Then, it was filtered, and the filtrate was dried, whereby compound [3] (yield: 142g, yield: 82%, white crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：9.46(s,1H),8.02(s,1H),7.69(t,2H,J＝8.6Hz),7.52－7.49(m,2H),7.45(dd,1H,J＝9.0Hz,2.2Hz),7.43－7.39(m,2H),7.37－7.32(m,2H),7.17(dd,1H,J＝9.0Hz,2.6Hz),5.18(s,2H),1.50(s,9H).
(Synthesis of Compound [4 ])
To ethanol (976 g) was added compound [3] (122 g,349 mmol) and 5% palladium on carbon (12.2 g), and the mixture was stirred under hydrogen at 40℃for 96 hours. The 5% palladium on carbon was filtered, and the filtrate was concentrated, whereby compound [4] (yield: 89.3g, yield: 99%, white crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：9.52(s,1H),9.37(s,1H),7.94(s,1H),7.62－7.59(m,1H),7.56(d,1H,J＝9.2Hz),7.39(dd,1H,J＝9.0Hz,2.2Hz),7.04－7.00(m,2H),1.50(s,9H).
(Synthesis of Compound [5 ])
To dimethyl sulfoxide (500 g) was added 4-nitrochlorobenzene (100 g,635 mmol), ethylene glycol (551 g) and sodium hydroxide (23.1 g), at 100℃for 19 hours. After cooling to room temperature, ethyl acetate (560 g) and pure water (700 g) were added thereto, and the mixture was separated. After recovering the upper layer, ethyl acetate (300 g) was added to the lower layer to separate the liquid, and the upper layer was combined. Pure water (400 g) and a saturated aqueous sodium chloride solution (200 g) were added to the combined upper layers, and the mixture was separated again, and after drying the ethyl acetate layer with sodium sulfate, the mixture was filtered, and the filtrate was concentrated to obtain a crude body (110 g). To the crude material was added ethyl acetate (330 g) which was dissolved by heating at 60 ℃, and after that, hexane (550 g) was added and cooled. Then, it was filtered, and the filtrate was dried, whereby compound [5] (yield: 64.2g, yield: 55%, pale yellow crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：8.21(d,2H,J＝9.4Hz),7.16(d,2H,J＝9.4Hz),4.97(t,1H,J＝5.6Hz),4.15(t,2H,J＝4.8Hz),3.77－3.73(m,2H).
(Synthesis of Compound [6 ])
To methylene chloride (1264 g) was added compound [5] (63.2 g,345 mmol), and cooled under ice-cooling. To this was added triethylamine (52.4 g), p-toluenesulfonyl chloride (69.0 g) and 4-dimethylaminopyridine (1.26 g), and the mixture was stirred at room temperature for 19 hours. Pure water (632 g) was added thereto, followed by separation to collect a methylene chloride layer, followed by washing with 1-specified hydrochloric acid (300 g), pure water (300 g) and a saturated aqueous sodium chloride solution (300 g) in this order, drying with anhydrous sodium sulfate, filtration, and concentration of the filtrate, whereby compound [6] (yield: 108g, yield: 93%, white crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：8.18(d,2H,J＝9.2Hz),7.80(d,2H,J＝8.6Hz),7.47(d,2H,J＝8.6Hz),7.05(d,2H,J＝9.2Hz),4.40－4.37(m,2H),4.35－4.31(m,2H),2.41(s,3H).
(Synthesis of Compound [7 ])
To dimethylformamide (360 g) were added compound [4] (45.0 g,174 mmol), compound [6] (61.5 g) and potassium carbonate (36.0 g), and the mixture was stirred at 80℃for 21 hours. After cooling to room temperature, pure water (720 g) was added to precipitate crystals. The filtrate was subjected to slurry washing with methanol (360 g), and was filtered, and the filtrate was dried, whereby compound [7] (yield: 67.2g, yield: 91%, pale yellow crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：9.47(s,1H),8.23(d,2H,J＝9.2Hz),8.02(s,1H),7.72－7.69(m,2H),7.46(dd,1H,J＝8.8Hz,2.0Hz),7.31(d,1H,J＝2.4Hz),7.24(d,2H,J＝9.2Hz),7.14(dd,1H,J＝9.0Hz,2.6Hz),4.56－4.53(m,2H),4.46－4.43(m,2H),1.50(s,9H).
(Synthesis of Compound [8 ])
To chloroform (1096 g) was added compound [7] (73.1 g,172 mmol), while stirring under water cooling, trifluoroacetic acid (98.1 g) was added, and stirring was carried out at 50℃for 19 hours. After cooling to room temperature, triethylamine (87.0 g) and pure water (1096 g) were added to precipitate crystals. After the filtrate was washed with methanol (365 g), the filtrate was filtered and dried, whereby a coarse body (49.5 g) was obtained. Dimethylformamide (124 g) was added to the crude body, and after dissolving it by heating at 80 ℃, methanol (248 g) was added and cooled to precipitate crystals. The filtrate was filtered, and the filtrate was dried, whereby compound [8] (yield: 47.3g, yield: 85%, orange crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：8.23(d,2H,J＝9.2Hz),7.51(dd,1H,J＝8.8Hz,2.4Hz),7.45(dd,1H,J＝8.8Hz,2.4Hz),7.24(dd,2H,J＝9.2Hz,2.4Hz),7.27(s,1H),7.01(d,1H,J＝9.2Hz),6.91(d,1H,J＝8.8Hz),6.80(s,1H),5.15(br,2H),4.55－4.51(m,2H),4.41－4.37(m,2H).
(Synthesis of Compound [ DA-n-2 ])
To dimethylformamide (371 g) was added compound [8] (46.4 g,143 mmol) and 5% palladium on carbon (4.6 g), and the mixture was stirred under hydrogen at 60℃for 19 hours. Since the reaction hardly proceeds, stirring was performed in an autoclave at 60℃under a hydrogen atmosphere of 0.4MPa for 8 hours. After nitrogen substitution, 5% palladium on carbon was filtered, and the filtrate was concentrated to a content of 80g. Dimethylformamide (46 g) was added thereto, and after dissolving it by heating at 90 ℃, methanol (210 g) was added thereto and cooled to precipitate crystals. Then, it was filtered, and the filtrate was dried, whereby the compound [ DA-n-2] (yield: 33.4g, yield: 79%, pale purple crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：7.50(d,1H,J＝8.8Hz),7.44(d,1H,J＝8.8Hz),7.13(d,1H,J＝2.8Hz),7.00(dd,1H,J＝8.8Hz,2.8Hz),6.90(dd,1H,J＝8.8Hz,2.4Hz),6.79(d,1H,J＝2.4Hz),6.71(d,2H,J＝8.8Hz),6.52(d,2H,J＝8.8Hz),5.13(br,2H),4.63(br,2H),4.28－4.25(m,2H),4.20－4.17(m,2H).
< Synthesis of Compound [ DA-n-3]
The compound [ DA-n-3] was synthesized according to the following scheme.
(Synthesis of Compound [9 ])
A four-necked flask was charged with 6-bromo-2-naphthylamine (30.0 g,135 mmol), tetrahydrofuran (450 g), 4-nitrophenyl) boric acid (27.2 g,163 mmol), methanol (300 g), cesium carbonate (132 g,405 mmol), and water (150 g), and nitrogen substitution was performed. Here, tetrakis (triphenylphosphine) palladium (0) (3.12 g,2.70 mmol) was added thereto, nitrogen substitution was performed, and stirred at 55℃overnight. After completion of the reaction, the reaction solution was added to water (750 g) to precipitate crystals, which were then collected by filtration. To the obtained crystals, isopropyl alcohol (216 g) was added, and toluene (300 g) was added while stirring under heating at 65℃and cooling to room temperature, to crystallize the crystals. This was filtered, and after washing the cake with toluene and hexane, the crystals were dried to give compound [9] (yield: 28.0g,106mmol, yield 78%).
1H－NMR(500MHz,DMSO－D6,δ(ppm))：8.30(d,J＝8.5Hz,2H),8.13(s,1H),8.03(d,J＝8.6Hz,2H),7.72(d,J＝8.8Hz,2H),7.63(d,J＝8.7Hz,1H),7.00(d,J＝8.5Hz,1H),6.85(s,1H),5.63(s,2H).
(Synthesis of Compound [ DA-n-3 ])
N, N-dimethylformamide (224 g) was added to the compound [9] (28.0 g,106 mmol) and after nitrogen substitution, 5% palladium on carbon (aqueous article, 2.24 g) was added for nitrogen substitution, a hydrogen Tedlar sampling (Tedlar Bag) Bag was fitted, and stirred at room temperature overnight. After the completion of the reaction, palladium on carbon was removed by a membrane filter, and then, a filtrate was added to water (248 g) to precipitate crystals, followed by filtration to recover the crystals (wet). To the obtained crystals, isopropyl alcohol (50 g) was added, and toluene (74 g) was added while stirring under heating at 55℃and cooling to room temperature to crystallize. The crystals (crystal a) were recovered by filtration. The filtrate was concentrated, crystallized again using isopropyl alcohol (55 ℃) and toluene (room temperature), filtered, and crystals (crystals B) were recovered, and the obtained crystals A, B were dried to obtain the compound [ DA-n-3]. (yield: 17.6g,75.1mmol, 71% yield).
1H－NMR(500MHz,DMSO－D6,δ(ppm))：7.76(s,1H),7.60(d,J＝8.7Hz,1H),7.53－7.49(m,2H),7.41(d,J＝8.2Hz,2H),6.92(d,J＝8.7Hz,1H),6.80(s,1H),6.66(d,J＝8.2Hz,2H),5.25(s,4H).
< Synthetic example of Compound [ DA-n-9]
The compound [ DA-n-9] was synthesized according to the following scheme.
(Synthesis of Compound [4 ])
A compound [4] which is a synthetic intermediate in [ DA-n-2] was used.
(Synthesis of Compound [10 ])
To dimethylformamide (607 g) were added ethylene glycol xylene sulfonate (60.7 g,164 mmol), compound [4] (89.3 g) and potassium carbonate (56.7 g), and stirred at 80℃for 22 hours. After cooling to room temperature, pure water (1200 g) was added to precipitate crystals. Then, the filtrate was filtered, and the slurry was washed with methanol (450 g), filtered, and the filtrate was dried, whereby a coarse body (83.9 g) was obtained. Dimethylformamide (839 g) was added to the crude material, and after dissolving it by heating at 90 ℃, methanol (839 g) was added and cooled to precipitate crystals. Then, filtration was carried out, and the filtrate was dried to thereby obtain compound [10] (yield: 71.2g, yield: 80%, orange crystals).
1H－NMR(400MHz,DMSO－D6,δ(ppm))：9.43(s,2H),7.99(br,2H),7.67(d,4H,J＝8.8Hz),7.43(dd,2H,J＝8.8Hz,2.4Hz),7.28(d,2H,J＝2.4Hz),7.12(dd,2H,J＝8.8Hz,2.4Hz),4.42(s,4H),1.47(s,18H).
(Synthesis of Compound [ DA-n-9 ])
To chloroform (1143 g) was added compound [10] (71.2 g,129 mmol), and the mixture was cooled under water cooling. Trifluoroacetic acid (160 g) was added thereto, and stirred at 50℃for 24 hours. After cooling to room temperature, triethylamine (142 g) and pure water (1143 g) were added to precipitate crystals. Then, the filtrate was filtered, and the slurry was washed with methanol (400 g), filtered, and the filtrate was dried, whereby a coarse body (37.5 g) was obtained. Dimethylformamide (225 g) was added to the crude body, and after dissolving it by heating at 90 ℃, methanol (225 g) was added and cooled to precipitate crystals. The filtrate was filtered and dried, whereby Compound DA-n-9 (yield: 33.5g, yield: 75%, pale purple crystals) was obtained.
1H－NMR(400MHz,DMSO－D6,δ(ppm))：7.51(d,2H,J＝8.8Hz),7.45(d,2H,J＝8.8Hz),7.17(d,2H,J＝2.4Hz),7.02(dd,2H,J＝8.8Hz,2.4Hz),6.91(dd,2H,J＝8.8Hz,2.4Hz),6.80(d,2H,J＝2.4Hz),5.14(br,4H),4.37(s,4H).
< Synthetic example of Compound [ DA-n-10]
The compound [ DA-n-10] was synthesized according to the following scheme.
(Synthesis of Compound [11 ])
Tert-butyl (5-hydroxy-1-naphthyl) carbamate (27.0 g,104 mmol) was charged with N, N-dimethylformamide (216 g) and potassium carbonate (33 g,239 mmol) and stirred at 80 ℃. Next, a solution of 1, 2-bis (4-methylbenzenesulfonate) -1, 2-ethanediol (18.0 g,496 mmol) in N, N-dimethylformamide (162 g) was added dropwise thereto via a dropping funnel, and the mixture was heated and stirred at 80℃overnight. After the completion of the reaction, the reaction solution was poured into water (2268 g) to precipitate crystals. The mixture was filtered using a buchner funnel to give dark purple crystals (93 g) with stickiness. N, N-dimethylformamide was added to the obtained crude product, and the mixture was heated at 80℃to dissolve the N, N-dimethylformamide, and crystallized with methanol while cooling to room temperature, followed by filtration and drying to obtain compound [11] (yield: 28.0g,51.4mmol, yield 67%).
1H－NMR(500MHz,DMSO－D6,δ(ppm))：9.14(s,2H),7.98(d,J＝10.0Hz,2H),7.64(d,J＝10.0Hz,2H),7.55(d,J＝10.0Hz,2H),7.46(t,J＝7.5Hz,2H),7.39(t,J＝7.5Hz,2H),7.13(d,J＝10.0Hz,2H),4.65(s,4H),1.49(s,18H).
(Synthesis of Compound [ DA-n-10 ])
Compound [11] (28.0 g,51.4 mmol) was charged with chloroform (374 g) and potassium carbonate (33 g,239 mmol), and stirred at 80 ℃. Then, trifluoroacetic acid (31.0 g,313 mmol) was slowly added dropwise thereto via a dropping funnel, and the mixture was heated and stirred at 50℃for 6 hours, whereby gray crystals were precipitated in the reaction system. After cooling to 25 ℃, the reaction solution was poured into water (374 g) and filtered. To the obtained crystals were added triethylamine and water with stirring, and the diamine was dissociated from trifluoroacetate salt, filtered again, washed with methanol and then hexane, and dried to obtain the compound [ DA-n-10] (yield: 9.30g,27.0mmol, yield 86%).
1H－NMR(500MHz,DMSO－D6,δ(ppm))：7.65(d,J＝7.5Hz,2H),7.41(d,J＝8.0Hz,2H),7.29(t,J＝8.0Hz,2H),7.12(t,J＝8.0Hz,2H),7.00(t,J＝7.5Hz,2H),6.67(d,J＝7.5Hz,2H),5.62(s,4H),4.56(s,4H).
< Synthesis of DA-v-7 >
The compound [ DA-v-7] was synthesized according to the following scheme. "MeO" means methoxy.
(Synthesis of Compound 3 (3 a, 3b mixture))
Magnesium (15.39 g,63.3mmol,1.5 eq.) was added to a four-necked flask, and after vacuum drying was performed in a vacuum pump for 1 hour, THF (100 g) was added by syringe and stirred at room temperature. A solution of Compound 1 (100 g,42.2 mmol) in THF (300 g) was then slowly added dropwise at a rate of about steady reflux. Then, the reaction solution was cooled to 0 ℃, and a THF (200 g) solution of compound 2 (105.60 g,42.2mmol,1.0 eq.) was added dropwise. After the completion of the dropwise addition, the temperature of the reaction solution was returned to room temperature, and stirring was performed at room temperature for 3 hours. Then, toluene (1L) was added to dilute the reaction solution, and the reaction solution was cooled again to 0℃and 10% acetic acid solution (500 g) was slowly added dropwise.
Then, the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with saturated brine (1L), saturated sodium bicarbonate aqueous solution (1L), and saturated brine (1L), and dried over anhydrous magnesium sulfate. Then, the mixture was filtered and distilled off by an evaporator to obtain crude crystals (172 g) of Compound 3. The crude crystals obtained were used directly in the following reaction.
(Synthesis of Compound 4)
A mixture of crude crystals of compound 3 (172 g,422 mmol), p-toluenesulfonic acid monohydrate (4.82 g, and 25.3mmol,0.06 eq.) in dehydrated toluene (MS 4A dehydrated product, 2L) was reacted for 2 hours under reflux while removing water. After completion of the reaction, about half of the amount of toluene used was distilled off in an evaporator, and the solution was stirred at room temperature to precipitate a solid. The obtained solid was filtered to obtain crystals of compound 4 (yield 150g, yield 91%).
(Synthesis of Compound 5 (5 a, 5b mixture))
A mixture of compound 4 (108 g,276 mmol), 5% palladium on carbon (aqueous, 11g,10 wt%), ethyl acetate (1L), and ethanol (1L) was stirred at room temperature in the presence of hydrogen. After completion of the reaction, toluene (2L) was added to dissolve the crystals, and the reaction mixture was filtered through celite (celite), and the celite was washed with toluene 1L. The filtrate was concentrated under reduced pressure, whereby the objective compound 5 was obtained (yield: 103.3g, yield: 95%).
(Synthesis of Compound 6)
To a solution of compound 5 (95.4 g,243 mmol) in dichloromethane (800 mL) was added BBr 3(1.0M－CH2Cl2, 243mL,1.01mol dropwise at 0℃under nitrogen displacement. After the dropwise addition, stirring was carried out at 0℃for 2 hours. After the completion of the reaction, a small amount of the reaction solution was added to distilled water each time. The extract was extracted with ethyl acetate (1L), and the extract was washed twice with 500mL of distilled water. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure. The crude product obtained was recrystallized from ethanol, filtered, and washed with ethanol, whereby the target compound 6 was obtained (yield: 18.6g, yield: 21%).
(Synthesis of Compound 8)
To a mixture of compound 6 (10.0 g,26.4 mmol), potassium carbonate (11.0 g,79.2mmol,3 eq.) and toluene (50 g) was added dropwise a solution of compound 7 (5.35 g,26.4 mmol) in toluene (20 g) under reflux. After the dropping, the mixture was stirred at reflux. After the completion of the reaction, the reaction mixture was cooled to about 60 ℃, ethyl acetate (500 g) was added thereto, and the mixture was washed three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The crude product obtained was recrystallized from acetonitrile/ethanol (2:1) solution, and after filtration, the filtration was washed with ethanol to obtain crude crystals of compound 8. The crude crystals were purified by column chromatography (SiO 2,CHCl3) to give crystals of compound 8 (yield 7.1g, yield 49%).
(Synthesis of DA-v-7)
A mixture of compound 8 (12.2 g,22.4 mmol), 5% palladium on carbon (aqueous, 1.22g,10 wt%), 1, 4-dioxane (120 g) was stirred in the presence of hydrogen at 60℃for 4 hours. After the completion of the reaction, nitrogen substitution was performed, and filtration was performed with celite while maintaining the state at 60 ℃. The filtrate was distilled off under reduced pressure to remove the solvent, whereby a crude product was obtained. The crude product was recrystallized from 2-propanol/ethyl acetate (2:1), whereby DA-v-7 was obtained as a target (yield 8.0g, yield 74%).
1H－NMR(500MHz,CDCl3,δ(ppm))：7.725(1H,d),7.577(2H,m),7.272(2H,m),7.102(1H,s),6.791(1H,d),6.207(1H,d),6.117(1H,dd),3.621(4H,broad),2.553(1H,m),2.067－0.863(31H,m).
[ Synthesis of Polyamic acid ]
Synthesis example 1
DA-4 (1.66 g,7.00 mmol), DA-5 (2.89 g,8.75 mmol), DA-v-6 (5.30 g,7.00 mmol) and DA-13 (2.43 g,12.3 mmol) were weighed into a 100mL four-necked flask equipped with a stirring device, and NMP (49.1 g) was added thereto and dissolved by stirring. DC-3 (7.53 g,33.6 mmol) was added while stirring the diamine solution, and NMP (30.1 g) was further added, and the mixture was stirred at 60℃for 15 hours to obtain a solution of polyamic acid (A-R1, viscosity: 649 mPas, number-average molecular weight: 14231).
< Synthetic examples 2 to 13>
The same procedure as in Synthesis example 1 was repeated except that the diamine component and the acid dianhydride component were changed to those shown in Table 1 below, to obtain polyamic acid solutions (A-R2) to (A-R9) and (A-B1) to (A-B4) shown in Table 1 below. The viscosity and molecular weight of the obtained polyamic acid are also shown in table 1 below.
TABLE 1
[ Preparation of liquid Crystal alignment agent ]
< Example 1>
NMP (6.0 g) and BCS (8.0 g) were added to the solution (6.0 g) of the polyamic acid (A-R1) obtained in the above, and the mixture was stirred at room temperature for 10 hours, to obtain a liquid crystal aligning agent (R1) comprising 6 mass% of the polyamic acid (A-R1), 54 mass% of NMP and 40 mass% of BCS.
< Synthetic examples 2 to 13>
Liquid crystal aligning agents (R2) to (R9) and (B1) to (B4) of examples 2 to 13 shown in Table 2 were obtained in the same manner as in example 1 except that the polyamic acids (A-R2) to (A-R9) and (A-B1) to (A-B4) shown in Table 2 were used instead of the polyamic acids (A-R1).
In examples 1 to 13 in table 2, examples 1 to 3 and 6 to 9 are comparative examples, and examples 4,5 and 10 to 13 are examples of the present invention.
TABLE 2
The solid content ratio in table 2 represents the content ratio of the polymer solid content to 100 parts by mass of the liquid crystal aligning agent, and the solvent composition ratio represents the content ratio (parts by mass) in each organic solvent.
< Examples 14 to 21>
The liquid crystal aligning agent (R1) obtained in example 1 and the liquid crystal aligning agent (R4) obtained in example 4 were mixed so that the mass ratio thereof became 3:7, and stirred at room temperature for 3 hours, to prepare the liquid crystal aligning agent (B5) of example 14.
In addition, in examples 15 to 21, liquid crystal aligning agents (B6 to B8, R10 to R13) in examples 15 to 21 shown in table 3 below were prepared in the same manner as in example 14, except that the combinations of the liquid crystal aligning agents used were changed as shown in table 3 below.
TABLE 3
< Examples 22 to 35>
A liquid crystal alignment film and a liquid crystal cell were produced as described below, and characteristics of each produced liquid crystal cell were evaluated. The results are shown in Table 4 below. In the following examples, examples 22 to 25, 28 to 31 are examples of the present invention, and examples 26, 27, 32 to 35 are comparative examples.
[ Production of liquid Crystal alignment film ]
Using the liquid crystal aligning agents prepared in examples 1 to 21, liquid crystal alignment films were produced as follows. Each liquid crystal alignment agent was spin-coated on a quartz substrate or a silicon wafer, dried on a heating plate at 70 ℃ for 90 seconds, and then baked in a hot air circulation oven (manufactured by Denko corporation, MB1-1G 3030X) at 230 ℃ for 20 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.
[ Measurement of refractive index of liquid Crystal alignment film ]
The refractive index at a wavelength of 250 to 800nm was measured by fitting using a spectroscopic ellipsometer (Spectroscopic Ellipsometry) (manufactured by J.A. Woollam Co., ltd., M-2000) based on a CAUCHY model. The results are shown in Table 4. In Table 4, the refractive index at 550nm is shown. The case where the refractive index is greater than 1.62 is referred to as "good", and the case where the refractive index is 1.62 or less is referred to as "bad".
[ Measurement of transmittance of liquid Crystal alignment film ]
The cartridge was manufactured using two quartz substrates. A liquid crystal alignment film is formed on one of the two sheets, and a quartz substrate on which the liquid crystal alignment film is not formed is bonded with the surface on the side on which the liquid crystal alignment film is formed as the inner side. A refractive fluid (contact fluid, manufactured by Shimadzu equipment Co., ltd.) was inserted between the two fluid transfer tubes (spuit) to prepare a measurement cassette. The refractive liquid is used in accordance with the refractive index of each of 11 kinds of the scale of 0.01 of 1.60 to 1.70.
The transmittance of the measurement cell manufactured by the above was measured at a wavelength of 380 to 800nm using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu corporation). The results are shown in Table 4. The average transmittance at a wavelength of 380 to 800nm is shown in Table 4.
The transmittance was evaluated as "good" when the transmittance was greater than 99.0%, and as "poor" when the transmittance was 99.0% or less.
Production of liquid Crystal alignment film and liquid Crystal Box "
Using the liquid crystal aligning agent prepared in each of the above examples, a liquid crystal cell was prepared as follows.
Each liquid crystal alignment agent was spin-coated on an ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm×300 μm and a line/space (line/space) of 5 μm was formed, dried on a heating plate at 70 ℃ for 90 seconds, and then baked in a hot air circulation oven (manufactured by Denko corporation, MB1-1G 3030X) at 230 ℃ for 30 minutes, to form a liquid crystal alignment film having a film thickness of 100 nm.
The liquid crystal alignment agent was spin-coated on the ITO surface on which no electrode pattern was formed, dried on a heating plate at 70℃for 90 seconds, and then baked in a hot air circulation oven (manufactured by Denko Co., ltd., MB1-1G 3030X) at 230℃for 20 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.
For the two substrates, a bead spacer of 4 μm was spread on a liquid crystal alignment film of one substrate, and then a sealant (solvent-based thermosetting epoxy resin) was printed thereon. Next, the other substrate was bonded to the previous substrate with the surface on the side on which the liquid crystal alignment film was formed as the inner side, and then the sealant was cured to prepare a void box. The liquid crystal cell was prepared by injecting liquid crystal MLC-3023 (trade name manufactured by MERCK Co.) containing a polymerizable compound into the empty cell by vacuum injection.
Then, in a state where a DC voltage of 15V was applied to the liquid crystal cell, UV having passed through a filter for cutting a wavelength of 325nm or less was irradiated from the outside of the liquid crystal cell at a rate of 10J/cm 2. The illuminance of UV was measured using an ultraviolet radiation photometer (UV-MO 3A manufactured by ORC Co.). Then, for the purpose of inactivating unreacted polymerizable compounds remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV 32/A-1) was irradiated for 30 minutes using a UV-FL irradiation apparatus (Toshiba Lighting & Technology Co., ltd.) in a state where no voltage was applied.
Evaluation of liquid Crystal cell "
The characteristics of each liquid crystal cell manufactured as described above were evaluated as follows.
(Evaluation of vertical orientation)
The liquid crystal cell was rotated in a state where the liquid crystal cell was sandwiched by polarizing plates of crossed nicols (cross nicols) and backlit from the rear, and whether or not the liquid crystal was vertically aligned was observed by visual observation through a change in brightness. The evaluation criteria are as follows.
Liquid crystal vertical alignment. Liquid crystal was not vertically aligned.
TABLE 4
All contents of the specification, claims and abstract of japanese patent application No. 2019-173271 of 24 th 9/2019 are incorporated herein by reference as if disclosed in the specification of the present invention.

Claims (3)

1. A diamine represented by the following formula (2-1),
2. A polymer derived from a diamine component comprising the diamine of claim 1.
3. A polyimide which is a polyimide precursor obtained by polycondensation of a diamine component comprising the diamine according to claim 1 with a tetracarboxylic acid component or an imide compound of the polyimide precursor.
CN202411750590.XA 2019-09-24 2020-09-23 Diamine, polymer and polyimide for liquid crystal aligning agent Pending CN119569593A (en)

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