CN114507149A - Diamine compound, polymer, alignment agent, alignment film, and liquid crystal display element - Google Patents
Diamine compound, polymer, alignment agent, alignment film, and liquid crystal display element Download PDFInfo
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- CN114507149A CN114507149A CN202011282222.9A CN202011282222A CN114507149A CN 114507149 A CN114507149 A CN 114507149A CN 202011282222 A CN202011282222 A CN 202011282222A CN 114507149 A CN114507149 A CN 114507149A
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- 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
The invention provides a diamine compound, a polymer, a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element. The invention provides a diamine compound with a specific structure, which is applied to forming a polymer, a liquid crystal alignment agent and a liquid crystal display element, and the liquid crystal display element manufactured by using the liquid crystal alignment agent has good electric field memory effect and environmental resistance. The diamine compound is a diamine compound b1-1 represented by the formula (I). The polymer a-1 is prepared by reacting a first mixture comprising a tetracarboxylic dianhydride compound a1 and a diamine compound b1, wherein the diamine compound b1 comprises a diamine compound b1-1 represented by formula (I). The liquid crystal aligning agent comprises a polymer A-1 and a solvent B.
Description
Technical Field
The present invention relates to a diamine compound, a polymer, a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display device, and more particularly, to a diamine compound, a polymer, a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display device capable of fabricating a liquid crystal display device having an excellent electric field memory effect and environmental resistance.
Background
Conventionally, as an operation mode of a liquid crystal display device, various liquid crystal display devices using liquid crystal molecules having a positive dielectric anisotropy, such as a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, a Vertical Alignment (VA) type, an In-Plane Switching (IPS) type, a Fringe Field Switching (FFS) type, and an Optically Compensated Bend (OCB) type, have been known, and a liquid crystal Alignment film formed of an organic film is mainly used to control the Alignment of each liquid crystal molecule (patent documents 1 to 4).
Since the liquid crystal molecules of the liquid crystal alignment film of the TN mode, the STN mode, or the like respond at a high speed and the tilt direction of the liquid crystal alignment film of the VA mode or the like is constant at the time of liquid crystal driving, each of them needs to have a pretilt angle characteristic. As a method for imparting the pretilt angle characteristic, a rubbing method is generally used in the former case, and a rubbing method is generally used in the latter case, or a method of providing a protrusion on the surface of the substrate is used. The method of providing the projections on the surface of the substrate may deteriorate the brightness of the liquid crystal display element to be obtained, and therefore, these methods have problems.
As a pretilt angle providing method that is an alternative to these methods, a so-called photoalignment method has been proposed in which a photosensitive film is irradiated with ultraviolet light from a direction oblique to the film line (patent document 5). However, the liquid crystal display device manufactured by using the liquid crystal aligning agent described in patent document 5 has a problem that the electric field memory effect and the environmental resistance of the liquid crystal display device are not good, and thus it is not suitable for application.
On the other hand, as a method for imparting liquid crystal aligning ability to a coating film formed of a liquid crystal aligning agent containing polyamic acid or the like, a technique using a photo-alignment method such as photo-isomerization, photo-dimerization, or photo-decomposition as a substitute for a rubbing method has been proposed in recent years. The photoalignment method is a method as follows: the alignment of the liquid crystal molecules is controlled by irradiating a radiation-sensitive organic thin film formed on a substrate with polarized or unpolarized radiation to impart anisotropy to the film. According to this method, generation of dust or static electricity in the step can be suppressed as compared with the conventional rubbing method, and therefore generation of display defects or reduction in yield due to dust or the like can be suppressed. In addition, the method also has the advantages of uniformly endowing the organic thin film formed on the substrate with liquid crystal alignment capability and the like.
Specifically, the technical literature of the photoalignment method is as in patent literature 6. Patent document 6 proposes a liquid crystal aligning agent having a repeating unit of a conjugated enone (conjugated enone) and having an imide structure. However, the liquid crystal display device manufactured by using the liquid crystal aligning agent described in patent document 6 also has a problem that the electric field memory effect and the environmental resistance of the liquid crystal display device are not good.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent application laid-open No. Sho 56-91277
[ patent document 2] Japanese patent application laid-open No. 1-120528
[ patent document 3] Japanese patent application laid-open No. 11-258605
[ patent document 4] Japanese patent application laid-open No. 2002-250924
[ patent document 5] Japanese patent laid-open publication No. 2004-
[ patent document 6] Japanese patent laid-open No. 2005-037654
Therefore, how to improve the problems of poor electric field memory effect and environmental resistance of the liquid crystal display device to meet the requirements of the current industry is a problem that those skilled in the art are demanding to solve.
Disclosure of Invention
In view of the above, the present invention provides a diamine compound capable of forming a polymer, which can be used to produce a liquid crystal alignment agent and a liquid crystal alignment film for a liquid crystal display device, which can improve the problems of poor electric field memory effect and environmental resistance of the liquid crystal display device.
The present invention provides a diamine compound represented by the formula (I) (b 1-1).
In the formula (I), the compound is shown in the specification,
X1and X2Each independently represents a single bond, -O-, or,
Wherein R is14Represents hydrogen or an alkyl group having 1 to 4 carbon atoms;
x represents 0 or 1;
y represents an integer of 0 to 4;
R1represents a methylene group or an alkylene group having 2 to 4 carbon atoms;
R3each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group;
R2represents an organic group represented by the formula (I-A) or a monovalent organic group having a steroid skeleton with a carbon number of 17 to 40;
in the formula (I-A),
R4represents fluorine or methyl;
R5、R6and R7Each independently represents a single bond, -O-, or,
Methylene or alkylene having 2 to 3 carbon atoms;
R8to represent
Wherein R is10And R11Each independently represents fluorine or methyl, and represents a bonding position;
R9represents hydrogen, fluorine, alkyl group having 1 to 12 carbon atoms, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, fluorine-substituted alkoxy group having 1 to 12 carbon atoms, -OCH2F、-OCHF2、-OCF3；
a represents an integer of 0 to 2;
b. c and d each independently represent an integer of 0 to 4;
e. f and g each independently represent an integer of 0 to 3;
i and j each independently represent an integer of 0 to 2;
indicates a bonding site;
when R is4、R5、R6、R7、R8、R10Or R11When plural, each independently represents the same or different groups.
In one embodiment of the present invention, in the diamine compound (b1-1) represented by the above formula (I), when X is 0, X1is-O-),
Wherein R is14Represents hydrogen or an alkyl group having a carbon number of 1 to 4; when X is 1, X1Is a single bond.
In one embodiment of the present invention, in the diamine compound (b1-1) represented by the above formula (I), when X is 0, X is1is-O-),
In one embodiment of the present invention, in the diamine compound (b1-1) represented by the above formula (I), R5、R6And R7Each independently represents a single bond, -O-, or,
Methylene or alkylene having a carbon number of 2 to 3.
In one embodiment of the present invention, in the diamine compound (b1-1) represented by the above formula (I), when e + f + g < 3, f and g are not 0 at the same time; b ≧ 1 when f ≧ 1; when g ≧ 1, c + d ≧ 1.
The present invention provides a polymer (A-1) prepared by reacting a first mixture comprising a tetracarboxylic dianhydride compound (a1) and a diamine compound (b 1). The diamine compound (b1) includes the diamine compound (b1-1) represented by the formula (I) described above.
In an embodiment of the present invention, the diamine compound (b1) further includes a diamine compound (b1-2) represented by formula (II).
In the formula (II), the compound is shown in the specification,
R15and R17Each independently represents-O-, -S-),
R16Represents an alkylene group having 2 to 10 carbon atoms;
R18represents a single bond, a methylene group or an ethylene group;
Y1represents a monovalent organic group having a steroid skeleton with a carbon number of 17 to 40.
In an embodiment of the present invention, the diamine compound (b1) further includes a diamine compound (b1-3) represented by formula (III).
In the formula (III), the compound represented by the formula (III),
Y2each independently represents-O-, -NH-,
-CH2O-、
Y3each independently represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group;
Y4each independently represents a single bond, -O-, -NH-,
wherein m represents an integer of 1 to 5;
Y5each independently represents a nitrogen-containing aromatic heterocyclic group;
k represents an integer of 1 to 4.
In one embodiment of the present invention, the diamine compound (b1-1) represented by the formula (I) is used in an amount of 50 to 100 parts by mole based on 100 parts by mole of the diamine compound (b 1).
In one embodiment of the present invention, the diamine compound (b1-2) represented by the formula (II) is used in an amount of 5 to 30 parts by mole based on 100 parts by mole of the diamine compound (b 1).
In one embodiment of the present invention, the diamine compound (b1-3) represented by the formula (III) is used in an amount of 1 to 20 parts by mole based on 100 parts by mole of the diamine compound (b 1).
The invention also provides a liquid crystal alignment agent which comprises the polymer (A-1) and a solvent (B).
In an embodiment of the invention, the liquid crystal aligning agent further includes a polymer (a-2). The polymer (A-2) is obtained by reacting the second mixture. The second mixture comprises a tetracarboxylic dianhydride compound (a2) and a diamine compound (b 2).
In one embodiment of the present invention, the solvent (B) is used in an amount of 1000 parts by weight to 3500 parts by weight based on 100 parts by weight of the polymer (a-1).
In one embodiment of the present invention, the polymer (A-1) is used in an amount of 30 to 95 parts by weight, based on 100 parts by weight of the total amount of the polymer (A-1) and the polymer (A-2).
In one embodiment of the present invention, the solvent (B) is used in an amount of 1000 parts by weight to 3500 parts by weight, based on 100 parts by weight of the total amount of the polymer (A-1) and the polymer (A-2).
The invention also provides a liquid crystal alignment film which is formed by the liquid crystal alignment agent.
The invention also provides a liquid crystal display element which comprises the liquid crystal alignment film.
Based on the above, when the diamine compound with a specific structure is applied to the formation of a polymer, a liquid crystal aligning agent and a liquid crystal display device, the liquid crystal display device manufactured by using the liquid crystal aligning agent can have good electric field memory effect and environmental resistance, and is further suitable for a liquid crystal alignment film and a liquid crystal display device.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
Fig. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention.
Description of reference numerals 100: liquid crystal display element
110: first unit
112: first substrate
114: first conductive film
116: a first liquid crystal alignment film
120: second unit
122: second substrate
124: second conductive film
126: second liquid crystal alignment film
130: liquid crystal cell
Detailed Description
< diamine Compound >
The diamine compound is a diamine compound (b1-1) represented by formula (I).
In the formula (I), X1And X2Each independently represents a single bond, -O-, or,
Wherein R is14Represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
In the formula (I), x represents 0 or 1. When X is 0, X1Preferably represents-O-,
more preferably-O-),
Wherein R is14Represents hydrogen or an alkyl group having 1 to 4 carbon atoms. When X is 1, X1Preferably represents a single bond.
In the formula (I), y represents an integer of 0 to 4; preferably represents an integer of 0 to 3; more preferably, it represents an integer of 0 to 2.
In the formula (I), R1Represents a methylene group or an alkylene group having 2 to 4 carbon atoms; preferably represents a methylene group or an alkylene group having 2 to 3 carbon atoms; more preferably, it represents a methylene group.
In the formula (I), R3Represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group; preferably represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom or a cyano group.
In the formula (I), R2Represents an organic group represented by the formula (I-A) or a monovalent organic group having a steroid skeleton and having a carbon number of 17 to 40.
In the formula (I-A), R4Represents fluorine or methyl.
In the formula (I-A), R5、R6And R7Each independently represents a single bond, -O-, or,
Methylene or alkylene having 2 to 3 carbon atoms; preferably each independently represents a single bond, -O-, or,
Methylene or alkylene having 2 to 3 carbon atoms.
In the formula (I-A), R8To represent
Wherein R is10And R11Each independently represents fluorine or methyl; denotes a bonding site. i and j each independently represent an integer of 0 to 2.
In the formula (I-A), a represents an integer of 0 to 2; b. c and d each independently represent an integer of 0 to 4, preferably an integer of 0 to 2; e. f and g each independently represent an integer of 0 to 3, preferably an integer of 0 to 2. When e + f + g < 3, f and g cannot be 0 at the same time. When f ≧ 1, b ≧ 1. When g ≧ 1, c + d ≧ 1.
In the formula (I-A), a bond site is represented.
In the formula (I-A), when R is4、R5、R6、R7、R8、R10Or R11When plural, each independently represents the same or different groups.
Specifically, when f and g are not 0, when a represents 2, a plurality of R' s4Each of which may represent the same or different groups; when b, c and d each independently represent an integer of 2 to 4, a plurality of R' s5Each of which may represent the same or different groups, a plurality of R6Each of which may represent the same or different groups, a plurality of R7Each of which may represent the same or different groups; when e represents 2 or 3, a plurality of R8Each of which may represent the same or different groups. In addition, when i represents 2, a plurality of R10Each of which may represent the same or different groups. When j represents 2, a plurality of R11Each of which may represent the same or different groups.
In the formula (I-A), R9Represents hydrogen, fluorine, alkyl group having 1 to 12 carbon atoms, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, fluorine-substituted alkoxy group having 1 to 12 carbon atoms, -OCH2F、-OCHF2、-OCF3。
Specific examples of the organic group represented by the formula (I-A) include at least one of the organic groups represented by the formulae (I-A-1) to (I-A-9).
In the formulae (I-A-1) to (I-A-9), R9The group represented is as defined with R in formula (I-A)9The groups represented are the same and are not described in detail herein.
The steroid skeleton in the monovalent organic group having a steroid skeleton with a carbon number of 17 to 40 means a skeleton in which one or more of cyclopentane-perhydrophenanthrene (cyclopentane-perhydrophenanthrene) skeleton or carbon-carbon bonds contained therein are changed to double bonds. Examples of the monovalent organic group having such a steroid skeleton include groups represented by the following formula (I-B-a), formula (I-B-B), formula (I-B-c) or formula (I-B-d), wherein X represents a bonding site.
In the formula (I-B-a), the formula (I-B-B), the formula (I-B-c) and the formula (I-B-d), AIEach independently represents a group represented by any one of the following structural formulae, wherein denotes a bonding position.
Specific examples of the monovalent organic group having a steroid skeleton with a carbon number of 17 to 40 include organic groups represented by formula (I-B-1), formula (I-B-2), formula (I-B-3) or formula (I-B-4), wherein x represents a bonding position.
Specific examples of the diamine compound (b1-1) represented by the formula (I) preferably include compounds represented by the formulae (I-1) to (I-9), more preferably compounds represented by the formulae (I-1) to (I-3), formula (I-6), formula (I-7) and formula (I-9).
When the diamine compound (b1-1) is not used in the polymer (A-1) of the liquid crystal aligning agent, the liquid crystal aligning film and the liquid crystal display device formed by the liquid crystal aligning agent have the problems of poor electric field memory effect and environmental resistance.
< liquid Crystal alignment agent >
The invention provides a liquid crystal alignment agent, which comprises a polymer (A-1) and a solvent (B). In other embodiments, the liquid crystal aligning agent may further include a polymer (A-2). In addition, the liquid crystal aligning agent may further include an additive (C), if necessary. The respective components of the liquid crystal aligning agent used in the present invention will be described in detail below.
Polymer (A-1)
The polymer (A-1) comprises a polyamic acid polymer, a polyimide block copolymer or a combination of the foregoing polymers, wherein the polyimide block copolymer comprises a polyamic acid block copolymer, a polyimide block copolymer, a polyamic acid-polyimide block copolymer or a combination of the foregoing copolymers.
The polymer (A-1) is obtained by reacting a first mixture comprising a tetracarboxylic dianhydride compound (a1) and a diamine compound (b 1). The tetracarboxylic dianhydride compound (a1), the diamine compound (b1), and the method for producing the polymer (A-1) will be described in detail below.
Tetracarboxylic dianhydride Compound (a1)
The tetracarboxylic dianhydride compound (a1) includes a tetracarboxylic dianhydride compound such as an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, or a tetracarboxylic dianhydride compound represented by the following formulae (1-1) to (1-6).
Specific examples of the aliphatic tetracarboxylic dianhydride compound include aliphatic tetracarboxylic dianhydrides such as ethane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. However, the present invention is not limited thereto, and the aliphatic tetracarboxylic dianhydride compound may further include other suitable aliphatic tetracarboxylic dianhydride compounds.
Specific examples of the alicyclic tetracarboxylic dianhydride compound include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3-dichloro-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3 ', 4, 4' -dicyclohexyltetracarboxylic dianhydride, cis-3, 7-dibutylcycloheptyl-1, 5-diene-1, alicyclic tetracarboxylic dianhydride compounds such as 2,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride, and bicyclo [2.2.2] -oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride. However, the present invention is not limited thereto, and the alicyclic tetracarboxylic dianhydride compound may further include other suitable alicyclic tetracarboxylic dianhydride compounds.
Specific examples of the aromatic tetracarboxylic dianhydride compound include 3, 4-dicarboxyl-1, 2,3, 4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4, 4' -biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 3,3 '-4, 4' -diphenylethanetetracarboxylic dianhydride, 3,3 ', 4, 4' -dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4, 4' -tetraphenylsilanetetracarboxylic dianhydride, 1,2,3, 4-furan tetracarboxylic dianhydride, 2,3,3 ', 4 ' -diphenylether tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylether tetracarboxylic dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 2,3,3 ', 4 ' -diphenyl sulfide tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenyl sulfide tetracarboxylic dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3 ', 4,4 ' -perfluoroisopropylidene diphenyl diacid dianhydride, 2 ', 3,3 ' -diphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 ' -diphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenyl tetracarboxylic dianhydride, Bis (benzenedioic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylbenzenedioic acid) dianhydride, m-phenylene-bis (triphenylbenzenedioic acid) dianhydride, bis (triphenylbenzenedioic acid) -4,4 '-diphenylether dianhydride, bis (triphenylbenzenedioic acid) -4, 4' -diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1, 4-butanediol-bis (anhydrotrimellitate), 1, 6-hexanediol-bis (anhydrotrimellitate), 1, 8-octanediol-bis (anhydrotrimellitate), 2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), 2,3,4, 5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-Hexahydro-5- (tetrahydro-2, 5-bisoxylo-3-furanyl) -naphtho [1,2-c ] -furan-1, 3-dione (1,3,3a,4,5,9b-Hexahydro-5- (tetrahydro-2, 5-diofuro-3-yl) naphto [1,2-c ] furan-1,3-dione), 1,3,3a,4,5,9 b-Hexahydro-5-methyl-5- (tetrahydro-2, 5-bisoxylo-3-furanyl) -naphtho [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-5-ethyl-5- (tetrahydro-2, 5-diphenoxy-3-furyl) -naphtho [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-7-methyl-5- (tetrahydro-2, 5-diphenoxy-3-furyl) -naphtho [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-7-ethyl-5- (tetrahydro-2, 5-diphenoxy-3-furyl) -naphtho [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-methyl-5- (tetrahydro-2, 5-di-acetoxy-3-furanyl) -naphtho [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-ethyl-5- (tetrahydro-2, 5-di-acetoxy-3-furanyl) -naphtho [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9b-hexahydro-5, 8-dimethyl-5- (tetrahydro-2, 5-di-acetoxy-3-furanyl) -naphtho [1, aromatic tetracarboxylic dianhydride compounds such as 2-c-furan-1, 3-dione and 5- (2, 5-bisoxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic dianhydride. However, the present invention is not limited thereto, and the aromatic tetracarboxylic dianhydride compound may further include other suitable aromatic tetracarboxylic dianhydride compounds.
The tetracarboxylic dianhydride compounds represented by the formulae (1-1) to (1-6) are shown below.
In the formula (1-5), A1Represents a divalent group containing an aromatic ring; r represents 1 or 2; a. the2And A3Each independently represents hydrogen or an alkyl group.
In the formula (1-6), A4Represents a divalent group containing an aromatic ring; a. the5And A6Each independently may represent hydrogen or an alkyl group.
Specific examples of the tetracarboxylic dianhydride compound (a1) represented by formula (1-5) include tetracarboxylic dianhydride compounds represented by formulae (1-5-1) to (1-5-3).
Specific examples of the tetracarboxylic dianhydride compound (a1) represented by formula (1-6) include tetracarboxylic dianhydride compounds represented by formula (1-6-1).
The tetracarboxylic dianhydride compound (a1) can be used singly or in combination.
Specific examples of the tetracarboxylic dianhydride compound (a1) preferably include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (1,2,3, 4-cyclobutanetetracarboxylic dianhydride), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride (2,3,5-tricarboxycyclopentylacetic acid dianhydride), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3, 4-dicarboxy-1, 2,3, 4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 3 ', 4, 4' -biphenylsulfone tetracarboxylic dianhydride or a combination thereof, more preferably include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride, pyromellitic dianhydride, or a combination thereof.
Diamine compound (b1)
The diamine compound (b1) includes at least one diamine compound (b1-1) represented by the formula (I). In addition, the diamine compound (b1) may further include at least one of a diamine compound (b1-2) represented by formula (II) and a diamine compound (b1-3) represented by formula (III). The diamine compound (b1) may further include another diamine compound (b 1-4). Hereinafter, the diamine compound (b1-1), the diamine compound (b1-2), the diamine compound (b1-3) and the other diamine compound (b1-4) will be described in detail.
Diamine Compound (b1-1)
The diamine compound (b1-1) is described in the above < diamine compound >, and will not be described in detail. When the diamine compound (b1-1) is not used as the polymer (A-1) in the liquid crystal aligning agent, the liquid crystal aligning film and the liquid crystal display device formed by the liquid crystal aligning agent have the problems of poor electric field memory effect and environmental resistance.
The diamine compound (b1-1) represented by the formula (I) may be used in an amount of 50 to 100 mol parts, preferably 55 to 100 mol parts, more preferably 65 to 100 mol parts, based on 100 mol parts of the diamine compound (b 1).
Diamine Compound (b1-2)
The diamine compound (b1-2) is a diamine compound represented by the formula (II).
In the formula (II), R15And R17Each independently represents an ether group, a thioether group, a thioester group or an ester group. In particular, R15And R17Each independently represents-O-, -S-),
In the formula (II), R16Represents an alkylene group having 2 to 10 carbon atoms; preferably represents an alkylene group having 2 to 4 carbon atoms.
In the formula (II), R18Represents a single bond, a methylene group or an ethylene group; preferably represents a single bond or a methylene group.
In the formula (II), Y1Represents a monovalent organic group having a steroid skeleton with a carbon number of 17 to 40. The steroid skeleton and R in the formula (I)2The steroid skeleton is shown to be the same and will not be described further herein.
Specific examples of the diamine compound (b1-2) include diamine compounds represented by the formulae (II-1) to (II-29), and preferably include at least one of diamine compounds represented by the formulae (II-10), (II-18), (II-24), (II-22) and (II-26).
The diamine compound (b1-2) represented by the formula (II) can be synthesized by a conventional organic synthesis method. For example, the compound represented by the formula (II-1), the formula (II-2), the formula (II-7) or the formula (II-8) is synthesized by performing an addition reaction of anhydrous succinic acid with cholesterol or cholestanol (cholestanol), respectively, forming an acid chloride with, for example, thionyl chloride (thionyl chloride), reacting dinitrophenol (dinitrophenol) with the acid chloride in the presence of a base in a larger equivalent amount based on the acid chloride, and thereafter performing a reduction reaction using an appropriate reducing agent such as tin chloride.
The compound represented by the formula (II-3), (II-4), (II-9) or (II-10) can be synthesized by subjecting anhydrous succinic acid to addition reaction with cholesterol or cholestanol, respectively, then subjecting the above adduct to esterification reaction with dinitrobenzoyl chloride (dinitrobenzoyl chloride) in the presence of potassium carbonate, and then subjecting the product to reduction reaction using an appropriate reducing agent such as tin chloride.
The synthesis of the compound represented by the formula (II-5) or (II-11) can be carried out by subjecting cholesterol or cholestanol to tosylation with tosyl chloride (tosyl chloride) to obtain tosylated cholesterol or tosylated cholestanol, reacting butanediol with an excess of dinitrobenzoyl chloride in the presence of a base to obtain dinitrobenzoyl butanediol monoester, heating the tosylated cholestanol in an appropriate organic solvent to form an ether group, and then subjecting the ether group to a reduction reaction using an appropriate reducing agent such as tin chloride.
The compound represented by the formula (II-6) or (II-12) can be synthesized by subjecting anhydrous succinic acid to addition reaction with cholesterol or cholestanol, respectively, then reducing the carbonyl group of the adduct to methylene with lithium aluminum hydride, esterifying the reduced product with 2,4-dinitrochlorobenzene (2,4-dinitrochlorobenzene) in the presence of a base such as potassium tert-butoxide, and then reducing the esterified product with a suitable reducing agent such as tin chloride; or 1- (4-hydroxybutoxy) -2,4-dinitrobenzene (1- (4-hydroxybutoxy) -2, 4-dinobenzene) obtained by reacting 2,4-dinitrochlorobenzene with an excess of butanediol in the presence of a base such as potassium tert-butoxide, and tosylated cholesterol or tosylated cholestanol obtained by the above-mentioned method, are heated in an appropriate organic solvent to form an ether group, and then subjected to a reduction reaction using an appropriate reducing agent such as tin chloride, thereby completing the above synthesis.
The compound represented by the formula (II-13) can be synthesized by reacting 1- (4-hydroxyethoxy) -2,4-dinitrobenzene (1- (4-hydroxyethoxy) -2,4-dinitro benzene) obtained by reacting 2,4-dinitrochlorobenzene with an excess of ethylene glycol in the presence of a base such as potassium tert-butoxide with tosylated cholestanol obtained by the method described above, heating the resulting product in an appropriate organic solvent to form an ether group, and then subjecting the resulting product to a reduction reaction using an appropriate reducing agent such as tin chloride.
The compound represented by formula (II-14), formula (II-15) or formula (II-16) may be synthesized by the synthesis method of formula (II-6) using lanosterol, lumisterol or ergosterol, respectively, as starting materials.
The compound represented by the formula (II-17) or (II-18) can be synthesized by separately mesylating cholesterol or cholestanol with methanesulfonyl chloride (methylsulfonyl chloride), then performing substitution reaction with an excess amount of ethylene glycol to synthesize a monoether compound, reacting the monoether compound with 3,5-dinitrobenzoyl chloride (3,5-dinitrobenzoyl chloride) in the presence of a base to synthesize a dinitro compound, and then performing reduction reaction using a suitable reducing agent such as palladium carbide (palladium carbide).
The compound represented by the formula (II-19) or (II-20) can be synthesized by reacting cholestanol or cholesterol with potassium hydride to form an alkoxide (alkoxide), respectively, and then with excess dibromopropane to form an ether group to obtain an intermediate, followed by reacting this intermediate with 3,5-dinitrobenzoic acid (3,5-dinitrobenzoic acid) in the presence of potassium carbonate to synthesize a dinitro compound, and then performing a reduction reaction using a suitable reducing agent such as palladium carbide to complete the above synthesis.
The compound represented by the formula (II-21) or (II-22) can be synthesized by subjecting anhydrous succinic acid to addition reaction with cholesterol or cholestanol, respectively, reacting the adduct with 3,5- (N, N-diallyl) aminophenol (3,5- (N, N-diallyl) aminophenylide in the presence of N, N-dicyclohexylcarbodiimide, and then removing allyl groups from 1,3-dimethylbarbituric acid (1,3-dimethylbarbituric acid) and tetratriphenylphosphine palladium (tetrakistriphenylphosphine).
The compound represented by the formula (II-23) or (II-24) can be synthesized by subjecting anhydrous succinic acid to addition reaction with cholesterol or cholestanol, respectively, and then reducing the carbonyl group to alcohol using Borane-tetrahydrofuran complex (Borane-oxolane complex) as an intermediate; the above synthesis is accomplished by reacting the above intermediate with 3,5-dinitrobenzoyl chloride in the presence of a base to synthesize a dinitro compound, followed by reduction using a suitable reducing agent such as palladium carbide.
The compound represented by the formula (II-25) or (II-26) can be synthesized by the method of synthesizing the compound represented by the formula (II-4) or (II-10) by addition reaction of anhydrous glutaric acid-substituted succinic acid with cholesterol or cholestanol, respectively.
The compound represented by formula (II-27), formula (II-28) or formula (II-29) can be synthesized by the method of synthesizing formula (II-14), formula (II-15) or formula (II-16) using, as a starting material, lanosterol, photosterol or ergosterol, which is hydrogenated using a suitable hydrogenation catalyst.
When the diamine compound (b1) in the polymer (A-1) in the liquid crystal aligning agent comprises the diamine compound (b1-2), the liquid crystal aligning film and the liquid crystal display element formed by the liquid crystal aligning agent have better electric field memory effect.
The diamine compound (b1-2) represented by the formula (II) may be used in an amount of 5 to 30 mol parts, preferably 7 to 27 mol parts, more preferably 10 to 25 mol parts, based on 100 mol parts of the diamine compound (b 1).
Diamine Compound (b1-3)
The diamine compound (b1-3) is a diamine compound (b1-3) represented by the formula (III).
In the formula (III), Y2Each independently represents-O-, -NH-,
-CH2O-、
Y3each independently represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group; y is4Each independently represents a single bond, -O-, -NH-,
wherein m represents an integer of 1 to 5; y is5Each independently represents a nitrogen-containing aromatic heterocyclic group; k represents an integer of 1 to 4.
In detail, 2 amino groups (-NH) in the formula (III)2) The bonding position(s) is not particularly limited. Specifically, a bonding group (Y) to the side chain2) The 2 amino groups on the benzene ring are respectively 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position or 3,5 position, etc. From the viewpoint of reactivity in synthesizing the polyamic acid, the bonding position of the 2 amino groups is preferably a2, 4 position, a2, 5 position, or a3, 5 position. In view of easiness in synthesizing the diamine compound, the bonding position of the 2 amino groups is more preferably a2, 4 position or a2, 5 position.
In the formula (III), Y2Each independently represents-O-, -NH-,
-CH2O-、
in terms of easiness in synthesizing the diamine compound, Y2Preferably each independently represents-O-, -NH-, -,
-CH2O-、
in the formula (III), Y3Each independently represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched, may have an unsaturated bond, and is preferably a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the alicyclic ring in the divalent alicyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cycloeicosane ring, a tricycloecosane ring (tricyclocosan ring), a tricycloodocosane ring (tricyclooxane ring), a bicycloheptane ring (bicycloheptane ring), a decahydronaphthalene ring (decahydronaphthalene ring), a norbornene ring (norbomene ring), or an adamantane ring (adamantane ring), and the like.
Specific examples of the aromatic ring in the divalent aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring (azulene ring), an indene ring (indene ring), a fluorene ring (fluorene ring), an anthracene ring, a phenanthrene ring, or a phenalene ring (phenalene ring).
Specifically, in the formula (III), Y3Preferably each independently represents a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, a linear or branched alkenylene group having 2 to 10 carbon atoms, a linear or branched alkynylene group having 2 to 10 carbon atoms, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, wherein the alicyclic group in the divalent alicyclic hydrocarbon group is a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a naphthalene ring, a conjugated diene ring,Norbornene ring or adamantane ring, and the aromatic ring in the divalent aromatic hydrocarbon group is a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring. Y is3More preferably, the aromatic ring in the divalent aromatic hydrocarbon group is a benzene ring, a naphthalene ring, a fluorene ring or an anthracene ring, and the aromatic ring in the divalent aromatic hydrocarbon group is a cyclohexane ring, a norbornene ring or an adamantane ring. Y is3Still more preferably, each independently represents a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, a cyclohexylene group, a phenylene group or a naphthylene group. Y is3Particularly preferred is a straight-chain or branched alkylene group having 2 to 5 carbon atoms or phenylene group, each independently representing a single bond, a methylene group.
In the formula (III), Y4Each independently represents a single bond, -O-, -NH-,
wherein m represents an integer of 1 to 5. Y is4Preferably each independently represents a single bond, -O-, or,
Wherein m represents an integer of 1 to 5.
In the formula (III), Y5Each independently represents a nitrogen-containing aromatic heterocyclic group. Specifically, the nitrogen-containing aromatic heterocyclic group is a nitrogen-containing aromatic heterocyclic group containing at least one structure selected from the group consisting of the formula (III-A), the formula (III-B) and the formula (III-C).
In the formula (III-C), R19Represents a linear or branched alkyl group having 1 to 5 carbon atoms.
Y5Specific examples of the nitrogen-containing aromatic heterocycle in (1) include a pyrrole ring (pyroling ring), an imidazole ring (imidazoring), an oxazole ring (oxazoring), a thiazole ring (thiazoline ring), a pyrazole ring (pyrazoring), a pyridine ring (pyridinine ring), a pyrimidine ring (pyrimidine ring), a quinoline ring (quinolinine ring), a pyrazoline ring (pyrazoline ring), an isoquinoline ring (isoquinoxaline ring), a carbazole ring (carbazoline ring), a purine ring (purine ring), a thiadiazole ring (thiadiazoline ring), a pyridazine ring (pyrazoline ring), a pyrazoline ring (pyrazoline ring), a triazine ring (triazine ring), a pyrazoline ring (pyrolidine ring), a triazole ring (triazoline ring), a pyrazine ring (pyrolidine ring), a thiazine ring (diazophenol ring), a diazoquinone ring (diazoquinone ring), a thiadiazole ring (diazone ring), a thiadiazole ring (diazoquinone ring), a thiazine ring (diazone ring), a thiadiazole ring (quinazoline ring), a thiadiazole ring (diazone ring), a thiadiazole ring (quinazoline ring), a triazine ring (diazone ring), a triazine ring (diazone ring (triazine ring), a triazine ring (triazine ring), a triazine ring (triazine ring), a triazine ring (triazine ring), a triazine ring (triazine ring), a triazine ring (triazine ring), a triazine ring (a triazine ring), a triazine ring (triazine ring), a triazine ring (a triazine ring), a triazine ring (a triazine ring), a triazine ring (triazine ring, a triazine ring (triazine ring), a triazine ring (a triazine ring), a triazine ring (a triazine ring), a triazine ring (a triazine ring), a triazine ring (a triazine ring, a triazine ring (a triazine ring, a triazine ring), a triazine ring (a triazine ring, a triazine, An oxadiazole ring (oxadiazole ring) or an acridine ring (acridine ring). Specifically, Y5Preferably each independently represents pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, triazinyl, triazolyl, pyrazinyl or benzimidazolyl. Y is5More preferably, each independently represents a pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group or pyrimidinyl group.
And Y is4Preferably bonded to a group other than Y5Adjacent substituents of the contained formulae (III-A), (III-B) and (III-C).
In the formula (III), k represents an integer of 1 to 4. In addition, from the viewpoint of reactivity with the tetracarboxylic dianhydride compound, k is preferably an integer of 1 to 3. And when k represents an integer of 2 to 4, a plurality of "-Y2-Y3-Y4-Y5Plural of Y in `2、Y3、Y4、Y5Each of which may represent the same or different groups.
In the formula (III), Y2、Y3、Y4、Y5And k is preferably a combination of: y is2is-O-, -NH-),
-CH2O-or
Y3Is methylene, a straight chain or branched alkylene group with 2 to 10 carbon atoms, a straight chain or branched alkenylene group with 2 to 10 carbon atoms, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, wherein the alicyclic ring in the divalent alicyclic hydrocarbon group is a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring, and the aromatic ring in the divalent aromatic hydrocarbon group is a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring; y is4Is a single bond, -O-, -NH-),
(m is an integer of 1 to 5); y is5The nitrogen-containing aromatic heterocycle in (1) is 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, a diazophenanthrene ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring or an acridine ring; and k is 1 or 2.
In the formula (III), Y2、Y3、Y4、Y5And k is more preferably: y is2is-O-, -NH-),
-CH2O-or
Y3Is methylene, linear or branched alkylene with 2 to 10 carbon atoms, linear or branched alkenylene with 2 to 10 carbon atoms, divalent alicyclic hydrocarbon group or divalent aromatic hydrocarbon group, wherein the alicyclic ring in the divalent alicyclic hydrocarbon group is cyclohexane ring, norbornene ring or adamantane ring, and the aromatic ring in the divalent aromatic hydrocarbon group is benzene ring, naphthalene ring, fluorene ring or anthracene ring; y is4Is a single bond, -O-, -NH-),
(m is an integer of 1 to 5); y is5Is pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazolinyl, carbazolyl, pyridazinyl, pyrazolinyl, triazinyl, pyrazolinyl, triazolyl, pyrazinyl or benzimidazolyl; and k is 1 or 2.
In the formula (III), Y2、Y3、Y4、Y5And k is, more preferably, in combination: y is2is-O-, -NH-),
or-CH2O-；Y3Is methylene, linear or branched alkylene having 2 to 5 carbon atoms, or phenylene; y is4Is a single bond, -O-),
(m is an integer of 1 to 5); y is5Is pyrrolyl, imidazolyl, pyrazolyl, pyridyl or pyrimidyl; and k is 1,2 or 3.
Specific examples of the diamine compound (b1-3) include the following tablesI to Y described in Table VIII2、Y3、Y4、Y5And k, and a diamine compound.
TABLE I
TABLE II
TABLE III
TABLE IV
TABLE V
TABLE VI
TABLE VII
TABLE VIII
The method for producing the diamine compound (b1-3) of the present invention is not particularly limited, and for example, the diamine compound can be produced by the following method: a dinitro compound represented by the formula (III-D) is synthesized, and then the nitro group is reduced to an amino group in the presence of a catalyst, a solvent and a hydride.
In the formula (III-D), Y2、Y3、Y4、Y5And k is independently from Y in formula (III)2、Y3、Y4、Y5And k are synonymous and not described further herein.
Specific examples of the catalyst are not particularly limited but may include palladium-carbon, platinum dioxide, Raney nickel (Raney nickel), platinum black, rhodium-alumina, sulfided platinum-carbon, or a combination of the above catalysts. Specific examples of the solvent are not particularly limited but may include ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohols, or a combination of the above solvents. Specific examples of the hydride are not particularly limited but may include hydrogen, hydrazine (hydrazine), hydrogen chloride (hydrogen chloride), or a combination of the above compounds.
The dinitro compound represented by the formula (III-D) is represented by Y4To make Y3And Y5Bonding; followed by Y3Warp Y2And is bonded with a benzene ring containing dinitro; or by passing a dinitrogen-containing benzene ring over Y2And with Y3Is bonded to, then, Y3Warp Y4And with Y5The method of bonding.
Y2is-O-, -NH-),
-CH2O-、 
And the like, which can be formed by an existing organic synthesis method.
For example, in Y2is-O-or-CH2In the case of O-, the dinitro compound represented by the formula (III-D) can be prepared by reacting a halogen derivative containing dinitro with a halogen containing Y3、Y4And Y5In the presence of alkali to obtain the hydroxyl derivative; or by reacting a hydroxy derivative containing dinitro with a compound containing Y3、Y4And Y5In the presence of a base.
At Y2In the case of-NH-, the dinitro compound represented by the formula (III-D) can be prepared by reacting a halogen derivative containing dinitro with a halogen containing Y3、Y4And Y5In the presence of a base.
At Y2Is composed of
In the case of (2), the dinitro compound represented by the formula (III-D) can be produced by reacting a hydroxyl derivative containing dinitro with a hydroxyl derivative containing Y3、Y4And Y5The acid chloride (acid chloride) compound is obtained by reaction in the presence of alkali.
At Y2Is composed of
In the case of (A), a dinitro group represented by the formula (III-D)The compound can be prepared by reacting a dinitrogen-containing acid chloride compound with a compound containing Y3、Y4And Y5In the presence of a base.
At Y2Is composed of
In the case of (2), the dinitro compound represented by the formula (III-D) can be prepared by reacting an amino-substituted compound with a compound containing Y3、Y4And Y5In the presence of a base.
Specific examples of the dinitro-containing halogen derivative and the dinitro-containing derivative include 3,5-dinitrochlorobenzene (3,5-dinitrochlorobenzene), 2,4-dinitrochlorobenzene (2,4-dinitrochlorobenzene), 2, 4-dinitrofluorobenzene (2, 4-dinitrofluorobenzene), 3,5-dinitrobenzoyl chloride (3,5-dinitrobenzoyl chloride), 3,5-dinitrobenzoic acid (3,5-dinitrobenzoic acid), 2,4-dinitrobenzoyl chloride (2,4-dinitrobenzoyl chloride), 2,4-dinitrobenzoic acid (2,4-dinitrobenzoic acid), 3,5-dinitrobenzyl chloride (3,5-dinitrobenzoic acid), 2,4-dinitrobenzyl chloride (2,4-dinitrobenzyl chloride), 2,4-dinitrobenzyl chloride (2,4-dinitrobenzoic acid), 3,5-dinitrobenzyl chloride (3,5-dinitrobenzyl chloride), 2,4-dinitrobenzyl chloride (2,4-dinitrobenzyl chloride), and 3, 5-dinitrobenzene (3, 5-dinitrobenzene, 5-dinitrophenyl alcohol), 2,4-dinitrobenzyl alcohol (2,4-dinitrophenyl alcohol), 2,4-dinitroaniline (2,4-dinitroaniline), 3,5-dinitroaniline (3,5-dinitroaniline), 2,6-dinitroaniline (2,6-dinitroaniline), 2,4-dinitrophenol (2,4-dinitrophenol), 2,5-dinitrophenol (2,5-dinitrophenol), 2,6-dinitrophenol (2,6-dinitrophenol) or 2,4-dinitrophenylacetic acid (2,4-dinitrophenylacetic acid). The dinitro-containing halogen derivative and the dinitro-containing derivative may be used singly or in combination of two or more in view of availability and reactivity of the raw material.
Specific examples of the diamine compound (b1-3) preferably include at least one of the diamine compounds represented by the formulae (III-1) to (III-6).
When the diamine compound (b1) in the polymer (A-1) in the liquid crystal aligning agent comprises the diamine compound (b1-3), the liquid crystal aligning film and the liquid crystal display element formed by the liquid crystal aligning agent have better environmental resistance.
The diamine compound (b1-3) represented by the formula (III) may be used in an amount of 1 to 20 parts by mole, preferably 3 to 18 parts by mole, more preferably 5 to 15 parts by mole, based on 100 parts by mole of the diamine compound (b 1).
Other diamine Compound (b1-4)
Specific examples of the other diamine compound (b1-4) include 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 4' -diaminoheptane, 1, 3-diamino-2, 2-dimethylpropane, 1, 6-diamino-2, 5-dimethylhexane, 1, 7-diamino-2, 5-dimethylheptane, 1, 7-diamino-4, 4-dimethylheptane, 1, 7-diamino-3-methylheptane, 1, 7-diamino-4-dimethylheptane, 1, 7-diamino-3-methylheptane, 1, 4-diaminoheptane, 1, 3-dimethylheptane, 1, 4-diaminoheptane, 1, 4-diaminoheptane, 1, 3-methylheptane, 1, 4-diaminoheptane, 1-diaminoheptane, 1, 4-diaminoheptane, 1-diaminoheptane, 4, 1, 4-diaminoheptane, 1,4, or the like, 1, 9-diamino-5-methylnonane, 2, 11-diaminododecane, 1, 12-diaminooctadecane, 1, 2-bis (3-aminopropoxy) ethane, 4 ' -diaminodicyclohexylmethane, 4 ' -diamino-3, 3 ' -dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane (1, 4-diaminodicyclohexylamine), isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclo [6.2.1.0 ]2,7]Undecene dimethyldiamine, 4 '-methylenebis (cyclohexylamine) (4, 4' -methylenebisis (cyclohexenylamine)), 4 '-diaminodiphenylmethane, 4' -diaminodiphenylethane, 4 '-diaminodiphenylsulfone, 4' -diaminobenzanilide, 4 '-diaminodiphenylether, 3, 4' -diaminodiphenylether, 1, 5-diaminonaphthalene, 5-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindane, 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindan, hexahydro-4, 7-methanoindenylidenedimethylene diamine, 3 ' -diaminobenzophenone, 3,4 ' -diaminobenzophenone, 4 ' -diaminobenzophenone, 2-bis [4- (4-aminophenoxy) phenyl group]Propane, 2-bis [4- (4-aminophenoxy) phenyl]Hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl]Sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 9-bis (4-aminophenyl) -10-hydroanthracene, 9,10-bis (4-aminophenyl) anthracene (9,10-bis (4-aminophenyl) anthracene), 2, 7-diaminofluorene, 9-bis (4-aminophenyl) fluorene, 4 '-methylene-bis (2-chloroaniline), 4' - (p-phenyleneisopropylene) dianiline, 4 '- (m-phenyleneisopropylene) dianiline, 2' -bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl.]Hexafluoropropane, 4' -bis [ (4-amino-2-trifluoromethyl) phenoxy ] benzene]-octafluorobiphenyl, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl]Phenylmethylene-1, 3-diaminobenzene (5- [4- (4-n-phenylcyclohexyloxy) cyclohexyloxy)]phenyl methyl-1, 3-diaminobezene), 1-bis [4- (4-aminophenoxy) phenyl]-4- (4-ethylphenyl) cyclohexane (1,1-bis [4- (4-aminophenyl) phenyl [)]-4- (4-ethylphenyl) cyclohexane) or other diamine compounds (b1-4) such as diamine compounds represented by the formulae (2-1) to (2-25). However, the present invention is not limited thereto, and the other diamine compound (b1-4) may further include other suitable diamine compounds.
Other diamine compounds represented by the formulae (2-1) to (2-25) are shown below.
In the formula (2-1), B1represents-O-),
B2Represents an alkyl group having 2 to 30 carbon atoms or a derivative thereof and containing a steroid group, a trifluoromethyl group, a fluoro groupAnd a monovalent group having a nitrogen atom-containing cyclic structure selected from pyridine, pyrimidine, triazine, piperidine, piperazine and the like.
Specific examples of the other diamine compound represented by the formula (2-1) include ethyl 2, 4-diaminophenylformate (2, 4-diaminophenylethyl form), ethyl 3, 5-diaminophenylformate (3, 5-diaminophenylethyl form), propyl 2, 4-diaminophenylformate (2, 4-diaminophenylpropyl form), propyl 3, 5-diaminophenylformate (3, 5-diaminophenylpropyl form), 1-dodecyloxy-2, 4-diaminobenzene (1-dodecoxy-2,4-diaminobenzene), 1-hexadecyloxy-2, 4-diaminobenzene (1-hexadecyloxy-2, 4-diaminobenzene), 1-octadecyloxy-2, 4-diaminobenzene (1-octadecoxy-2, 4-diaminobezene) or other diamine compounds represented by the formulae (2-1-1) to (2-1-4).
In the formula (2-2), B3represents-O-),
B4And B5Represents an aliphatic, aromatic or heterocyclic ring group; b is6Represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, a cyano group or a halogen atom.
Specific examples of the other diamine compound represented by the formula (2-2) include diamine compounds represented by the formulae (2-2-1) to (2-2-13).
In the formulae (2-2-10) to (2-2-13), q represents an integer of 3 to 12.
In the formula (2-3), B7Represents hydrogen, an acyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or halogen; s represents an integer of 1 to 3. When s represents an integer of 2 or 3, a plurality of B7May be the same or different.
Specific examples of the diamine compound represented by the formula (2-3) include (1) when s is 1: p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, 2, 5-diaminotoluene, or the like; (2) when s is 2: 4,4 '-diaminobiphenyl, 2' -dimethyl-4,4 '-diaminobiphenyl (2, 2' -dimethyl-4,4 '-diaminodiphenyl), 3' -dimethyl-4,4 '-diaminobiphenyl, 3' -dimethoxy-4, 4 '-diaminobiphenyl, 2' -dichloro-4, 4 '-diaminobiphenyl, 3' -dichloro-4, 4 '-diaminobiphenyl, 2', 5,5 ' -tetrachloro-4, 4 ' -diaminobiphenyl, 2 ' -dichloro-4, 4 ' -diamino-5, 5 ' -dimethoxybiphenyl, 4 ' -diamino-2, 2 ' -bis (trifluoromethyl) biphenyl, or the like; (3) when s is 3: 1, 4-bis (4' -aminophenyl) benzene, or a combination thereof. Specific examples of the diamine compound represented by the formula (2-3) preferably include p-diaminobenzene, 2 '-dimethyl-4, 4' -diaminobiphenyl, or a combination thereof.
In the formula (2-4), t represents an integer of 2 to 12.
In the formula (2-5), v represents an integer of 1 to 5.
Specific examples of the diamine compound represented by the formula (2-5) include 4, 4' -diaminodiphenylsulfide.
In the formula (2-6), B8And B10Each independently represents a divalent organic group, B9Represents a divalent group derived from a nitrogen atom-containing cyclic structure such as pyridine, pyrimidine, triazine, piperidine, and piperazine.
In the formula (2-7), B11、B12、B13And B14Each independently represents a hydrocarbon group having 1 to 12 carbon atoms; w represents an integer of 1 to 3; z represents an integer of 1 to 20.
Formula (2-8)
In the formula (2-8), B15represents-O-or cyclohexylene; b is16Represents a methylene group; b is17Represents phenylene or cyclohexylene; b is18Represents hydrogen or heptalkyl.
Specific examples of the diamine compound represented by the formula (2-8) include diamine compounds represented by the formulae (2-8-1) to (2-8-2).
Other diamine compounds represented by the formulae (2-9) to (2-25) are shown below.
In formulae (2-17) to (2-25), B19Represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; b is20Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
Specific examples of the other diamine compound (b1-4) include diamine compounds having a chalcone (chalcone) structure such as 3,3 '-diaminochalcone (3, 3' -diaminochalcone), 4 '-diaminochalcone (4, 4' -diaminochalcone), 3,4 '-diaminochalcone (3, 4' -diaminochalcone), and 3,4-diaminochalcone (3, 4-diaminochalcone); diamine compounds having a stilbene (stilbene) structure such as 3,3 '-diaminostilbene (3, 3' -diaminostilbene), 4 '-diaminostilbene (4, 4' -diaminostilbene), 4 '-diaminostilbene-2, 2' -sulfonic acid (4,4 '-diaminostilbene-2, 2' -sulfonic acid) or 4,4 '-bis (4-amino-1-naphthylazo) -2, 2' -stilbene sulfonic acid (4,4 '-bis (4-amino-1-naphthylazo) -2, 2' -stilbene sulfonic acid); diamine compounds having an anthraquinone (anthraquinone) structure, such as 1, 2-diaminoanthraquinone (1, 2-diaminoanthraquinone), 1, 4-diaminoanthraquinone (1, 4-diaminoanthraquinone), 1, 5-diaminoanthraquinone (1, 5-diaminoanthraquinone), or 1, 4-diaminoanthraquinone-2, 3-dicyano-9,10-anthraquinone (1, 4-diaminoanthraquinone-2, 3-dicyano-9, 10-anthraquinone); or diamine compounds having a carbazole structure such as 3, 6-diaminocarbazole.
Specific examples of the other diamine compound (b1-4) preferably include 1, 2-diaminoethane, 4 '-diaminodicyclohexylmethane, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylether, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl ] phenylmethylene-1, 3-diaminobenzene, 1-bis [4- (4-aminophenoxy) phenyl ] -4- (4-ethylphenyl) cyclohexane, ethyl 2, 4-diaminophenylcarboxylate, 2' -dimethyl-4,4 '-diaminobiphenyl, 4' -methylenebis (cyclohexylamine), 1,4-diaminocyclohexane, the diamine compound represented by the formula (2-1-1), the diamine compound represented by the formula (b1-4), the diamine compound represented by the formula (b-b) and the like, A diamine compound represented by the formula (2-1-2), a diamine compound represented by the formula (2-2-1), a diamine compound represented by the formula (2-2-11), p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, a diamine compound represented by the formula (2-8-1), 3 '-diaminochalcone, 4' -diaminostilbene, or the like.
Specific examples of the other diamine compound (b1-4) more preferably include p-diaminobenzene, 2 '-dimethyl-4, 4' -diaminobiphenyl, 4 '-methylenebis (cyclohexylamine), 1,4-diaminocyclohexane, 3' -diaminochalcone, or a combination thereof.
The other diamine compound (b1-4) may be used in an amount of 0 to 70 mol parts, preferably 0 to 60 mol parts, more preferably 0 to 50 mol parts, based on 100 mol parts of the diamine compound (b 1).
Process for producing Polymer (A-1)
Method for preparing polyamic acid polymer
The polyamic acid polymer is prepared by dissolving a first mixture comprising a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1) in a solvent, and performing a polycondensation reaction at a temperature of 0 ℃ to 100 ℃. After the reaction for 1 to 24 hours, the reaction solution was distilled under reduced pressure with an evaporator to obtain a polyamic acid polymer. Alternatively, the above reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate was dried under reduced pressure to obtain a polyamic acid polymer. The diamine compound (b1) may be used in an amount of 20 to 200 parts by mole, preferably 30 to 120 parts by mole, based on 100 parts by mole of the tetracarboxylic dianhydride compound (a 1).
The solvent used in the polycondensation reaction may be the same as or different from the solvent used in the liquid crystal aligning agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. Specific examples of the solvent include (1) aprotic polar solvents such as: non-polar solvents such as N-methyl-2-pyrrolidone (NMP), N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, γ -butyrolactone, tetramethylurea, or hexamethylphosphoric triamide; (2) phenolic solvents, for example: phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenols; or combinations of the above solvents. However, the present invention is not limited thereto, and the solvent may further include other suitable solvents. The solvent used in the polycondensation reaction may be used in an amount of 200 to 2000 parts by weight, preferably 300 to 1800 parts by weight, based on 100 parts by weight of the total amount of the first mixture.
In the polycondensation reaction, the solvent may be used in combination with an appropriate amount of a poor solvent, wherein the poor solvent does not cause precipitation of the polyamic acid polymer. Specific examples of the lean solvent include (1) alcohols such as: alcohols such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4-butanediol, and triethylene glycol; (2) ketones, for example: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; (3) esters, for example: esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate; (4) ethers, for example: ethers such as diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether; (5) halogenated hydrocarbons, for example: halogenated hydrocarbons such as dichloromethane, 1, 2-dichloroethane, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, and o-dichlorobenzene; (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene, or xylene, or combinations of the foregoing lean solvents. However, the invention is not so limited and the lean solvent may also include other suitable solvents. The lean solvent may be used in an amount of 0 to 60 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the total amount of the first mixture.
Polyimide polymer
The polyimide polymer is prepared by first dissolving a first mixture comprising a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1) in a solvent and performing a polycondensation reaction to form a polyamic acid polymer. Then, in the presence of a dehydrating agent and a catalyst, further heating and dehydration ring-closure reaction are carried out, so that the amic acid functional group in the polyamic acid polymer is converted into an imide functional group (i.e. imidization) through the dehydration ring-closure reaction, and a polyimide polymer is obtained.
The solvent used in the polycondensation reaction and the dehydration ring-closing reaction may be the same as the solvent used in the liquid crystal aligning agent described below, and therefore, the details thereof are not repeated herein. The solvent used in the dehydration ring-closure reaction may be used in an amount of 200 to 2000 parts by weight, preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid polymer.
In order to obtain a preferable imidization degree of the polyamic acid polymer, the operation temperature of the dehydration ring-closure reaction is preferably 40 to 200 ℃, more preferably 40 to 150 ℃. If the operation temperature of the dehydration ring-closure reaction is lower than 40 ℃, the imidization reaction is not complete, and the imidization degree of the polyamic acid polymer is reduced. However, when the operation temperature of the dehydration ring-closure reaction is higher than 200 ℃, the weight average molecular weight of the resulting polyimide polymer is low.
The imidization ratio of the polymer (A-1) is usually 30% or less, preferably 20% or less, more preferably 10% or less.
The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, wherein specific examples of the acid anhydride compounds include acetic anhydride, propionic anhydride, trifluoroacetic anhydride, or a combination thereof. The dehydrating agent may be used in an amount of 0.01 to 20 parts by mole based on 1 part by mole of the polyamic acid polymer. Specific examples of the catalyst used in the dehydration ring-closure reaction include (1) pyridine compounds such as: pyridine compounds such as pyridine, collidine or lutidine; (2) tertiary amine compounds, for example: tertiary amine compounds such as triethylamine; or combinations thereof. The catalyst may be used in an amount of 0.5 to 10 parts by mole based on 1 part by mole of the dehydrating agent.
Polyimide-based block copolymer
The polyimide-based block copolymer comprises a polyamic acid block copolymer, a polyimide block copolymer, a polyamic acid-polyimide block copolymer, or a combination thereof.
The polyimide-based block copolymer is preferably prepared by dissolving an initiator in a solvent and performing a polycondensation reaction, wherein the initiator comprises the at least one polyamic acid polymer and/or the at least one polyimide polymer, and may further comprise a tetracarboxylic dianhydride compound (a1) and a diamine compound (b 1).
The starting material includes the tetracarboxylic dianhydride compound (a1) and the diamine compound (b1) used in the preparation of the polyamic acid polymer, and the solvent used in the polycondensation reaction may be the same as the solvent in the liquid crystal aligning agent described below, which is not described herein again.
The solvent used in the polycondensation reaction may be used in an amount of 200 to 2000 parts by weight, preferably 300 to 1800 parts by weight, based on 100 parts by weight of the starting material. The polycondensation reaction is preferably carried out at an operating temperature of 0 ℃ to 200 ℃, more preferably 0 ℃ to 100 ℃.
Specific examples of the starting material include (1) two kinds of polyamic acid polymers having different terminal groups and different structures; (2) two polyimide polymers with different end groups and different structures; (3) polyamide acid polymers and polyimide polymers with different terminal groups and different structures; (4) a polyamic acid polymer, a tetracarboxylic dianhydride compound and a diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and the diamine compound is different from the structures of the tetracarboxylic dianhydride compound and the diamine compound used for forming the polyamic acid polymer; (5) a polyimide polymer, a tetracarboxylic dianhydride compound and a diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and the diamine compound is different in structure from the tetracarboxylic dianhydride compound and the diamine compound used for forming the polyimide polymer; (6) a polyamic acid polymer, a polyimide polymer, a tetracarboxylic dianhydride compound and a diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and the diamine compound is different from the structures of the tetracarboxylic dianhydride compound and the diamine compound used for forming the polyamic acid polymer or the polyimide polymer; (7) two polyamide acid polymers, tetracarboxylic dianhydride compounds and diamine compounds with different structures; (8) two polyimide polymers, tetracarboxylic dianhydride compounds and diamine compounds with different structures; (9) two types of polyamic acid polymers and diamine compounds with end groups of anhydride groups and different structures; (10) two types of polyamic acid polymers and tetracarboxylic dianhydride compounds with different structures and amino end groups; (11) two polyimide polymers and diamine compounds with end groups of anhydride groups and different structures; or (12) two kinds of polyimide polymers and tetracarboxylic dianhydride compounds having different structures and amino end groups.
Within the scope of not affecting the efficacy of the present invention, the polyamic acid polymer, the polyimide polymer and the polyimide block copolymer are preferably end-modified polymers with molecular weight adjusted first. By using the end-modified polymer, the coating property of the liquid crystal aligning agent can be improved. The end-modified polymer may be prepared by adding a monofunctional compound while the polyamic acid polymer is subjected to polycondensation. Specific examples of the monofunctional compound include (1) a monobasic acid anhydride such as: monobasic acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, and n-hexadecylsuccinic anhydride; (2) monoamine compounds, for example: monoamine compounds such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine and n-eicosylamine; (3) monoisocyanate compounds, for example: monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate; or combinations of the foregoing monofunctional compounds. However, the present invention is not limited thereto, and the monofunctional compound may further include other suitable monofunctional compounds.
In the liquid crystal aligning agent, the polymer (A-1) may be used in an amount of 30 to 95 parts by weight, preferably 40 to 90 parts by weight, more preferably 50 to 90 parts by weight, based on 100 parts by weight of the total amount of the polymer (A-1) and the polymer (A-2) described later. When the amount of the polymer (A-1) in the liquid crystal aligning agent falls within the above range, the liquid crystal alignment film and the liquid crystal display device formed by the liquid crystal aligning agent can have a better electric field memory effect.
Polymer (A-2)
The liquid crystal aligning agent may also include a polymer (A-2) other than the polymer (A-1). The polymer (A-2) is obtained by reacting a second mixture comprising a tetracarboxylic dianhydride compound (a2) and a diamine compound (b 2).
The tetracarboxylic dianhydride compound (a2) is not particularly limited, and may be the same as or different from the tetracarboxylic dianhydride compound (a1) in the polymer (a-1).
The diamine compound (b2) is not particularly limited, and may be the same as or different from the diamine compound (b1-2), diamine compound (b1-3) or diamine compound (b1-4) in the polymer (A-1).
The method for preparing the polymer (A-2) is not particularly limited, and for example, it can be the same as the method for preparing the polymer (A-1), and thus, the description thereof is omitted.
In the liquid crystal aligning agent, the polymer (A-1) may be used in an amount of 5 to 70 parts by weight, preferably 10 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the polymer (A-1) and the polymer (A-2).
Solvent (B)
Specific examples of the solvent (B) include N-methyl-2-pyrrolidone, γ -butyrolactone, γ -butyrolactam, 4-hydroxy-4-methyl-2-pentanone, Ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, Ethylene glycol methyl ether, Ethylene glycol ethyl ether, Ethylene glycol N-propyl ether, Ethylene glycol isopropyl ether, Ethylene glycol N-butyl ether (Ethylene glycol N-butyl ether), Ethylene glycol dimethyl ether, Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Ethylene glycol N-butyl ether diethylene glycol monoethyl ether acetate, N-dimethylformamide, N-dimethylacetamide (N, n-dimethyl acetamide), or any combination of the foregoing solvents. The solvent (B) is preferably N-methyl-2-pyrrolidone, ethylene glycol N-butyl ether, N-dimethylacetamide, or a combination of the above solvents. However, the present invention is not limited thereto, and the solvent (B) may further include other suitable solvents. The solvent (B) may be used singly or in combination of two or more.
When the liquid crystal alignment agent includes the polymer (a-1) and the solvent (B), the amount of the solvent (B) may be 1000 to 3500 parts by weight, preferably 1000 to 3200 parts by weight, more preferably 1000 to 3000 parts by weight, based on 100 parts by weight of the polymer (a-1).
When the liquid crystal alignment agent includes the polymer (a-1), the polymer (a-2), and the solvent (B), the solvent (B) may be used in an amount of 1000 to 3500 parts by weight, preferably 1000 to 3200 parts by weight, more preferably 1000 to 3000 parts by weight, based on 100 parts by weight of the total amount of the polymer (a-1) and the polymer (a-2).
Additive (C)
The liquid crystal aligning agent may further optionally include an additive (C) within a range not affecting the efficacy of the present invention. The additive (C) may be an epoxy compound, a silane compound having a functional group, or a combination thereof. The additive (C) is used for improving the adhesion between the liquid crystal alignment film and the surface of the substrate. The additive (C) may be used singly or in combination of two or more.
Specific examples of the epoxy compound include 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-tetracyclooxypropyl-2, 4-hexanediol, N, N, N ', N ' -tetracyclooxypropyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', N ' -tetracyclooxypropyl-4, 4 ' -diaminodiphenylmethane, N, N-diglycidyl-p-glycidoxyaniline, 3- (N-allyl-N-epoxypropyl) aminopropyltrimethoxysilane or 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane or a combination thereof. However, the present invention is not limited thereto, and the epoxy compound may further include other suitable epoxy compounds.
The epoxy compound is used in an amount of generally 40 parts by weight or less, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer (A-1).
Specific examples of the silane compound having a functional group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane (3-uredopropyltrimethoxysilane), 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, n-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazodecane, 10-triethoxysilyl-1, 4, 7-triazodecane, 9-trimethoxysilyl-3, 6-diazanone acetate, 9-triethoxysilyl-3, 6-diazanone acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltrimethoxysilane, N-methoxysilylpropyltriethoxysilane, N-methoxysilylpropyltrimethoxysilane, N-silylpropyltrimethoxysilane, N-silylpropyltriethoxysilane, N-silylpropyltrimethoxysilane, N-1-silylpropyltriethoxysilane, N-1-silylpropyltrimethoxysilane, N-1-ester, N-silylpropyltrimethoxysilane, N-ester, N-type ester, N-ester, and ester, N-ester, and ester, N-ester, and, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, or a combination thereof. However, the present invention is not limited thereto, and the silane compound having a functional group may further include other suitable silane compounds having a functional group.
The silane compound is used in an amount of generally 10 parts by weight or less, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A-1).
< preparation method of liquid Crystal alignment agent >
The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited, and it can be prepared by a general mixing method. For example: adding the polymer (A-1) or the mixture of the polymer (A-1) and the polymer (A-2) into the solvent (B) at a temperature of 0 ℃ to 200 ℃, and optionally adding the additive (C); and continuously stirring by a stirring device until the mixture is dissolved. The temperature at which the polymer is added to the solvent (B) is preferably 20 ℃ to 60 ℃.
The viscosity of the liquid crystal aligning agent of the present invention is usually 15cps to 35cps, preferably 17cps to 33cps, more preferably 20cps to 30cps at 25 ℃.
< method for producing liquid Crystal alignment film >
The liquid crystal alignment agent can form a liquid crystal alignment film by a photo-alignment method.
A method of forming a liquid crystal alignment film is, for example, a method of applying a liquid crystal alignment agent to a substrate to form a coating film, and irradiating polarized or unpolarized ultraviolet rays to the coating film from a direction inclined with respect to the surface of the coating film; or a method of applying a liquid crystal alignment property to a coating film by irradiating the coating film with polarized ultraviolet rays from a direction perpendicular to the surface of the coating film.
First, the liquid crystal aligning agent of the present invention is applied to the transparent conductive film side of the substrate provided with the patterned transparent conductive film by an appropriate application method such as a roll coating method, a spin coating method, a printing method, or an ink-jet method (ink-jet). After coating, the coated surface is subjected to a pre-bake treatment (pre-bak treatment) and then a post-bake treatment (post-bak treatment), thereby forming a coating film. The pre-baking treatment described above is intended to volatilize the organic solvent in the pre-coat layer. The conditions of the pre-baking treatment are, for example, 0.1 to 5 minutes at a temperature of 40 to 120 ℃. The post-baking treatment temperature may be 120 ℃ to 300 ℃, preferably 150 ℃ to 250 ℃. The post-baking treatment time may be 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5. mu.m.
As the substrate, for example, a glass such as float glass (float glass) or soda-lime glass; and transparent substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, and polycarbonate.
SnO can be used as the transparent conductive film2Formed film of Nessel (NESA) or In2O3-SnO2An Indium Tin Oxide (ITO) film formed, and the like. For forming these transparent conductive film patterns, photo-etching (photo-etching) technology, a method using a mask (mask) for forming a transparent conductive film, or the like can be used.
When the liquid crystal aligning agent is applied, a functional silane compound, a titanate compound (titanate), or the like may be applied in advance to the substrate or the transparent conductive film in order to improve the adhesion between the substrate or the transparent conductive film and the coating film.
Then, the coating film is irradiated with polarized or unpolarized ultraviolet rays to impart liquid crystal alignment ability, and a liquid crystal alignment film is formed from the coating film. Here, the radiation may use, for example, ultraviolet rays and visible light including light having a wavelength of 150 to 800nm, and preferably ultraviolet rays including light having a wavelength of 300 to 400 nm. When the radiation used is polarized light (linearly polarized light or partially polarized light), the irradiation may be performed from a direction perpendicular to the coating surface, or may be performed from an oblique direction in order to provide a pretilt angle. On the other hand, when non-polarized radiation is irradiated, it is necessary to irradiate the radiation from a direction inclined with respect to the film surface.
As a light source for irradiating radiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet light in the preferred wavelength range can be obtained by a method of using the light source in combination with, for example, a filter, a diffraction grating, or the like.
The irradiation dose of the radiation is preferably 1J/m2More than and less than 10000J/m2More preferably 10J/m2To 3000J/m2. In addition, when a coating film formed of a conventionally known liquid crystal aligning agent is imparted with liquid crystal aligning ability by a photo-alignment method, 10000J/m is required2The above radiation exposure amount. However, if the liquid crystal aligning agent of the present invention is used, the radiation exposure amount is 3000J/m even in the photo-alignment method2Hereinafter, the ratio is further 1000J/m2The lower limit is still further 300J/m2Hereinafter, it is also possible to impart a good liquid crystal aligning ability, which contributes to a reduction in the manufacturing cost of the liquid crystal display element.
< method for producing liquid Crystal display device >
The liquid crystal display element of the invention comprises a liquid crystal alignment film formed by the liquid crystal alignment agent. The liquid crystal display element of the present invention can be manufactured as follows.
Two substrates on which the liquid crystal alignment films are formed as described above are prepared, and liquid crystal is disposed between the two substrates to manufacture a liquid crystal cell. For manufacturing a liquid crystal cell (cell), for example, the following two methods can be cited.
The first method comprises the following steps: first, two substrates are arranged to face each other with a gap (cell gap) therebetween, and the respective liquid crystal alignment films are opposed to each other; attaching the peripheral parts of the two substrates together by using a sealant; filling liquid crystal into a cell gap defined by the surface of the substrate and the sealant; and the injection hole is closed, so that a liquid crystal cell can be manufactured.
The second method comprises the following steps: a method called a Drop On Drop (ODF) method. First, a sealing material curable with ultraviolet rays, for example, is applied to a predetermined portion on one of two substrates on which a liquid crystal alignment film is formed; dripping liquid crystal on the liquid crystal alignment film surface; then, another substrate is attached to make the liquid crystal alignment films opposite; subsequently, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealing agent, thereby manufacturing a liquid crystal cell.
In the case of any of the above methods, it is desirable that the liquid crystal cell is subsequently heated to a temperature at which the liquid crystal used exhibits an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment at the time of filling the liquid crystal.
Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell, whereby the liquid crystal display element of the present invention can be obtained. Here, when the liquid crystal alignment film is horizontally aligned, a liquid crystal display element having a TN-type or STN-type liquid crystal cell can be obtained by adjusting the angle formed by the polarization direction of the linearly polarized radiation irradiated to the two substrates on which the liquid crystal alignment film is formed and the angle between each substrate and the polarizing plate. On the other hand, when the liquid crystal alignment film is vertically aligned, the liquid crystal cell is configured such that the directions of alignment easy axes (easy-to-alignment axes) of the two substrates on which the liquid crystal alignment film is formed are parallel, and a polarizing plate is bonded to the liquid crystal cell such that the polarizing direction thereof makes an angle of 45 ° with respect to the alignment easy axes, whereby a liquid crystal display element having a vertically aligned liquid crystal cell can be formed.
Specific examples of the sealant include an epoxy resin containing alumina balls as spacers and a curing agent.
Specific examples of the liquid crystal include nematic liquid crystal, smectic liquid crystal, and the like.
In the case of TN type or STN type liquid crystal cells, specific examples of nematic liquid crystals having positive dielectric anisotropy preferably include biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenyl-based cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubic-based liquid crystals, and the like. In addition, cholesteric liquid crystals (cholesteric liquid crystals) such as cholesterol chloride (cholesteric chloride), cholesterol nonanoate (cholesteryl nonabenzoate), and cholesterol carbonate (cholesteryl carbonate) may be further added to the liquid crystal; chiral agents sold under the trade names "C-15", "CB-15" (manufactured by Merck); additives such as ferroelectric liquid crystals (ferroelectric liquid crystals) such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate (p-decyloxybenzylidene-p-amino-2-methyl butyl cinnamate) are used.
On the other hand, in the case of a vertical alignment type liquid crystal cell, specific examples of the nematic liquid crystal having a negative dielectric anisotropy preferably include dicyanobenzene-based liquid crystals (dicyanobenzene-based liquid crystals), pyridazine-based liquid crystals (pyridazoxy-based liquid crystals), Schiff-base-based liquid crystals (Schiff-base-based liquid crystals), azo-based liquid crystals (azo-base-based liquid crystals), biphenyl-based liquid crystals (biphenyi-base liquid crystals), phenylcyclohexane-based liquid crystals (phenylcyclohexane-base liquid crystals), or a combination thereof.
Examples of the polarizing plate used outside the liquid crystal cell include a polarizing plate formed by sandwiching a polarizing film called an "H film" obtained by causing polyvinyl alcohol (polyvinyl alcohol) to absorb iodine while being sublevel aligned with a cellulose acetate protective film, or a polarizing plate formed by the H film itself.
The liquid crystal display element of the present invention thus manufactured has excellent display performance, and the display performance does not deteriorate even when used for a long time.
Fig. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention. The liquid crystal display device 100 includes a first unit 110, a second unit 120, and a liquid crystal unit 130, wherein the second unit 120 is disposed apart from the first unit 110, and the liquid crystal unit 130 is disposed between the first unit 110 and the second unit 120.
The first cell 110 includes a first substrate 112, a first conductive film 114, and a first liquid crystal alignment film 116, wherein the first conductive film 114 is located between the first substrate 112 and the first liquid crystal alignment film 116. In addition, the first liquid crystal alignment film 116 in the first cell 110 is located on the side of the first cell 110 close to the liquid crystal cell 130.
The second cell 120 includes a second substrate 122, a second conductive film 124, and a second liquid crystal alignment film 126, wherein the second conductive film 124 is disposed between the second substrate 122 and the second liquid crystal alignment film 126. In addition, the second liquid crystal alignment film 126 in the second cell 120 is located on a side of the second liquid crystal alignment film 126 close to the liquid crystal cell 130. In other words, the liquid crystal cell 130 is located between the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126.
The first substrate 112 and the second substrate 122 are selected from transparent materials, such as alkali-free glass, soda lime glass, hard glass (pyrex glass), quartz glass, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate, which are used for liquid crystal display devices. However, the invention is not limited thereto, and the material of the first substrate 112 and the second substrate 122 may also be selected from other suitable materials.
The material of the first conductive film 114 and the second conductive film 124 is selected from tin oxide (SnO)2) Or indium oxide-tin oxide (In)2O3-SnO2) And the like. However, the invention is not limited thereto, and the materials of the first conductive film 114 and the second conductive film 124 may be selected from other suitable materials.
The first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 are the liquid crystal alignment films, and are used for forming a pre-tilt angle in the liquid crystal cell 130. In addition, when a voltage is applied to the first conductive film 114 and the second conductive film 124, an electric field may be generated between the first conductive film 114 and the second conductive film 124. The electric field drives the liquid crystal cell 130, thereby changing the arrangement of the liquid crystal molecules in the liquid crystal cell 130.
Preparation example of diamine Compound (b1-1)
The following are descriptions of preparation examples 1 to 6 of the diamine compound (b 1-1).
Preparation example 1
A compound represented by the formula (I-1) (hereinafter referred to as "diamine compound (b 1-1-1)") was synthesized according to the following scheme 1.
[ Synthesis route 1]
105 g of hydroquinone and 135 g of potassium carbonate (K)2CO3) Placed in a four-neck flask with a capacity of 3 l together with 700 ml of Acetonitrile (ACN), stirred and warmed to 80 ℃. Then, a mixed solution of 100 g of 4,4,4-trifluorobutyl methanesulfonate (4,4, 4-trifluorobutylmethane sulfonate) and 500 ml of acetonitrile was dropped into the four-neck flask. After the completion of the dropping, the mixture was kept at 80 ℃ for 4 hours. Then, 190 g of a 25 wt% aqueous solution of sodium hydroxide was added, and the mixture was refluxed at 80 ℃ for 30 minutes. Then, 415 ml of water was added and the mixture was kept at 80 ℃ for 1 hour. After the reaction was completed, filtration was performed, and the filtrate after filtration was collected and drained, followed by column chromatography to obtain about 65 g of R1OH as a solid.
Next, 120 grams of R1OH solid, 95 grams of 4-formylcinnamic acid, 12 grams of 4-Dimethylaminopyridine (DMAP), and 1080 milliliters of methylene Chloride (CH)2Cl2) The resulting solution was placed in a 2-liter four-necked flask and stirred. 125 g of 1- (3-Dimethylaminopropyl) -3-ethylcarbodiimide Hydrochloride (1- (3-dimethylamino propyl) -3-ethylcarbodiimide Hydrochloride, EDC. HCl) were added with stirring and after the addition, the temperature was raised to 40 ℃ and the reaction was refluxed at 40 ℃ for 6 hours. After the reaction was completed, the mixture was extracted 2 times with 540 ml of water, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and dried. The solid obtained after suction drying was dissolved by heating with 300 g of isopropyl alcohol, and after cooling, it was left to crystallize, and the crystals were collected by filtration and suction dried to obtain about 130 g of R3A as a solid.
Then, 64 g of R3A solid and 560 ml of Dimethylformamide (DMF) were charged into a three-necked flask having a capacity of 3 liters and dissolved with stirring, and 150 g of Potassium hydrogen persulfate (Oxone) was added and reacted at room temperature for 3 hours. After the reaction was complete, the solution was drained and the solid was washed 3 times with 1300 ml of water. Thereafter, the column was washed with 1300 ml of methanol 1 time. The washed solid was collected and dried in vacuo to yield about 55 g of R3B as a solid.
Next, 67 g of R3B solid, 60 g of 2- (N, N-di-t-butoxycarbonyl-2, 4-diaminophenyl) -1-ethanol (2- (N, N-di-Boc-2,4-diaminophenyl) -1-ethanol, t-Boc DPE) and 2 g of 4-dimethylaminopyridine were placed in a 5-liter four-neck flask with 340 ml of dichloromethane and stirred. 40 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) were added while stirring, and after the addition, the temperature was raised to 40 ℃ and the reaction was refluxed at 40 ℃ for 6 hours. After completion of the reaction, it was extracted 2 times with 2500 ml of water, and the organic layer was collected and dehydrated with anhydrous magnesium sulfate, followed by filtration and suction drying. The solid obtained after suction drying was dissolved by heating with 370 g of isopropyl alcohol, and after cooling, it was left to crystallize, and the crystals were collected by filtration and suction dried to obtain about 100 g of R4B solid.
Then, 100 g of the solid R4B and 1400 ml of methylene chloride were placed in a 5-liter four-neck flask and stirred. 135 g of tin (II) trifluoromethanesulfonate (tin (II) trifluoromethane sulfonate, Sn (OTf))2) And after the addition, the temperature was raised to 40 ℃ in nitrogen and the reaction was refluxed for 1.5 hours. After the reaction was completed, 1600 ml of ethyl acetate was poured into the flask and stirred. Next, 970 ml of 2.5M aqueous sodium hydroxide solution was poured into the flask and stirred for 30 minutes. Then, the solution was poured into a 2-liter separatory flask, allowed to stand and the upper organic layer was collected. Subsequently, the extract was extracted 4 times with 970 ml of 2.5M aqueous sodium hydroxide solution and 10 times with 970 ml of water. The extracted organic layer was dehydrated with anhydrous magnesium sulfate, filtered and dried by suction, washed with 200 g of methanol, filtered and dried by suction to collect a solid. The solid was then dissolved by heating again with 300 g of acetonitrile and left to crystallize after cooling, and the crystals were collected by filtration and suction-dried to obtain about 48 g of RPADA solid (i.e., diamine compound b1-1-1 represented by formula (I-1)).
Preparation example 2
A compound represented by the formula (I-2) (hereinafter referred to as "diamine compound (b 1-1-2)") was synthesized according to the following scheme 2.
[ Synthesis scheme 2]
65 g of 4-formylcinnamic acid, 100 g of 4- (4-heptylcyclohexyl) phenol (4- (4-heptadecylhexyl) phenol, 7CPO) and 4.5 g of 4-dimethylaminopyridine were placed in a2 l four-neck flask. 730 ml of dichloromethane were added to the four-neck flask, and 84 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) were added while stirring. Thereafter, the reaction was carried out at 40 ℃ for 6 hours. After the reaction, water was added for extraction, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and dried. The solid obtained after suction drying was further washed with isopropanol by heating, after which the solid was filtered and collected to obtain about 130 g of R3CHO solid.
Next, 80 g of R3CHO solid and 620 ml of dimethylformamide were put into a three-neck flask having a capacity of 1 liter and stirred. After the R3CHO solid dissolved, 170 grams of Oxone (Oxone) was added and reacted at room temperature for 3 hours. After completion of the reaction, the solvent was drained to obtain a solid, and the solid was washed with pure water and methanol. After washing, vacuum drying was performed to obtain about 75 g of R3COOH solid.
Then, 46.7 g of R3COOH solid and 250 ml of toluene were put into a 0.5L capacity three-necked flask and dissolved with stirring, and then, 0.09 g of Dimethylformamide (DMF) was added thereto and the temperature was raised to 75 ℃. Subsequently, 13.6 g of thionyl chloride (SOCl) was slowly dropped2) And after the dropping, the temperature is raised to 80 ℃ for reaction for 5 minutes. Subsequently, the temperature was reduced to 40 ℃. 26.5 g of 2, 4-dinitrophenylethanol (2,4-dinitrophenyl-ethanol) and 0.6 g of 4-dimethylaminopyridine are dissolved in 12.4 g of Pyridine (Pyridine) and added dropwise to the three-necked flask with stirring for 12 hours. Thereafter, the temperature was raised to 60 ℃ and 20 ml of methanol was added, and the temperature was maintained at 45 ℃ for 1 hour. Finally, the solvent was drained and washed with methanol to obtain about 57 g of precipitated R3DiNO-L as a solid.
Then, 48.4 g of R3DiNO-L solid and 440 ml of anisole were put in a four-necked flask having a capacity of 3L and stirred. Separately, 186 ml of pure water and 7.7 g of Pt/C were placed in a 2-liter beaker and stirred, followed by addition of 0.13 g of ammonium metavanadate (NH)4VO3) With 0.7 g of hypophosphorous acid (H)3PO2) Aqueous solution (A), (B) and (C)50 wt%), to prepare a mixed solution. The mixed solution was poured into a four-necked flask and heated to 65 ℃. Subsequently, 30 g of hydrazine (NH) were added dropwise2NH2) After the whole amount was dropped, the temperature was raised to 80 ℃ and the reaction was carried out for 4 hours. Subsequently, the solution was filtered, and the filtrate was extracted with ethyl acetate and water and then drained to obtain a solid. Next, the solid was washed with ethyl acetate under heating, followed by re-filtration and collection of the solid, to obtain about 30 g of RPADA3 solid (i.e., diamine compound b1-1-2 represented by formula (I-2)).
Preparation example 3
A compound represented by the formula (I-3) (hereinafter referred to as "diamine compound (b 1-1-3)") was synthesized according to the following scheme 3.
[ Synthesis scheme 3]
140 g of Tetrahydropyranyloxy Phenol (Tetrahydropyranyloxy Phenol), 180 g of 4- (4,4,4-trifluorobutoxy) benzoic acid (4- (4,4,4-trifluorobutoxy) benzoic acid) and 8.8 g of 4-dimethylaminopyridine were placed in a four-neck flask having a capacity of 3 l. 1600 grams of methylene chloride were added to a four-neck flask, and 150 grams of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) were added while stirring. After the addition was completed, the reaction was carried out at room temperature for 8 hours. After the reaction, water was added for extraction, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and dried. The solid obtained after draining was washed with isopropanol and heated. After washing, the solid was collected by filtration and dried under vacuum to obtain about 270 g of R5THP as a solid.
Then, 270 g of the R5THP solid, 65 ml of methanol and 1200 ml of methylene chloride were put into a four-necked flask having a capacity of 2L and stirred. While stirring, 170 g of a 12 wt% solution of p-toluenesulfonic acid in acetic acid was added dropwise. After the addition, the reaction was carried out at room temperature for 2 hours. After the reaction was completed, water was added for extraction, and after the extraction, the solvent was drained to obtain about 210 g of R5OH as a solid.
Then, 70 g of R5OH solid, 36 g of 4-formylcinnamic acid and 2.5 g of 4-dimethylaminopyridine were placed in a1 l four-necked flask, and 550 g of dichloromethane was added thereto and stirred. Subsequently, 47.3 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) were added dropwise while stirring. After the addition, the reaction was carried out at 40 ℃ for 8 hours. After the reaction, water was added for extraction, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and dried. The solid obtained after draining was washed with isopropanol and heated. After washing, the solid was collected by filtration and dried under vacuum to obtain about 87 g of R5BCHO solid.
Then, 87 g of R5BCHO solid and 583 ml of dimethylformamide were put into a three-necked flask with a capacity of 1 liter and dissolved with stirring. An additional 160 grams of Oxone (Oxone) was added and the reaction was allowed to proceed at room temperature for 3 hours. After the reaction was complete, the solution was drained and the solid was washed 3 times with 1600 ml of water. Thereafter, the column was washed with 800 ml of methanol 1 time. The washed solid was collected and dried in vacuo to yield about 44 g of R5BCOOH as a solid.
Then, 44 g of R5BCOOH solid, 30 g of 2- (N, N-di-tert-butoxycarbonyl-2, 4-diaminophenyl) -1-ethanol (t-Boc DPE), 2 g of 4-dimethylaminopyridine and 850 ml of dichloromethane were placed in a 1-liter four-necked flask and stirred. During stirring, 20 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) were added and the reaction was refluxed at room temperature for 6 hours. After the reaction, the mixture was extracted with 350 ml of water, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and dried. The solid obtained after suction drying was dissolved by heating with isopropyl alcohol and left to crystallize after cooling, and the crystals were collected by filtration and suction dried to obtain about 70 g of R5BBoc solid.
Subsequently, 50 g of the R5BBoc solid and 1200 ml of methylene chloride were placed in a four-necked flask having a capacity of 5 l and stirred. While stirring, 62 g of tin (II) trifluoromethanesulfonate (Sn (OTf))2). After the addition, the temperature was raised to 40 ℃ under nitrogen and the reaction was refluxed for 1.5 hours. After completion of the reaction, 2000 ml of ethyl acetate was poured into the flask and stirred. Subsequently, 450 ml of 2.5M aqueous sodium hydroxide solution was poured into the flask and stirred for 30 minutes. Then, the solution was poured into a 2-liter separatory flask, allowed to stand and the upper organic layer was collected. Subsequently, the extract was extracted 4 times with 450 ml of 2.5M aqueous sodium hydroxide solution and further extracted 4 times with 200 ml of water. And (3) removing water from the extracted organic layer by using anhydrous magnesium sulfate, filtering, draining, washing by using methanol, filtering, draining and collecting a solid. The solid was then dissolved by heating with acetonitrile again, and left to crystallize after cooling, and the crystals were collected by filtration and suction-dried to obtain about 28 g of RPADA5B solid (i.e., diamine compound b1-1-3 represented by formula (I-3)).
Preparation example 4
A compound represented by the formula (I-6) (hereinafter referred to as "diamine compound (b 1-1-4)") was synthesized according to the following scheme 4.
[ Synthesis route 4]
285 g of 4-hydroxycinnamic acid (4-hydroxycinnamic acid), 293 g of dihydropyran (3,4-Dihydro-2H-pyran, DHP) and 1800 ml of dichloromethane are placed in a four-neck flask with the volume of 3 liters and stirred uniformly, and 20.6 g of Trifluoroacetic acid (2,2,2-Trifluoroacetic acid, TFA) is added dropwise during stirring. Thereafter, the reaction was carried out at 40 ℃ for 6 hours. After the reaction was completed, the solid was collected by suction filtration. The collected solid was further washed with 1300 g of methanol at 50 ℃ and the solid was subsequently dried to obtain about 345 g of R4-COOH solid.
Next, 124 g of R4-COOH solid, 137 g of 4- (4-heptylcyclohexyl) phenol (7CPO) and 6.1 g of 4-dimethylaminopyridine were placed in a3 l four-necked flask. An additional 830 ml of methylene chloride was placed in a four-neck flask, and 105 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) was added while stirring. Thereafter, the reaction was carried out at 40 ℃ for 8 hours. After the reaction, water was added for extraction, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and drained. The solid obtained after draining was washed with isopropanol and heated. After washing, the solid was collected by filtration and dried under vacuum to obtain about 210 g of R4-7CPO as a solid.
Then, 110 g of R4-7CPO solid and 670 ml of methylene chloride were charged into a flask having a capacity of 3L and stirred. 140 g of a 12 wt% p-toluenesulfonic acid acetic acid solution was added dropwise during stirring. Thereafter, the reaction was carried out at room temperature for 2 hours. After the reaction was completed, a small amount of methanol was added. Subsequently, the solvent was again drained and extracted with dichloromethane and saturated aqueous sodium bicarbonate, and finally with water, and the organic layer was collected. The organic layer was filtered off with anhydrous magnesium sulfate to remove water and then dried by suction to obtain about 80 g of R4-OH as a solid.
Subsequently, 20.7 g of 2, 4-dinitrophenylethanol and 96.5 g of toluene were placed in a 0.5 l three-necked flask, 0.1 g of dimethylformamide was added and the temperature was raised to 75 ℃. Subsequently, 12 g of thionyl chloride was slowly added, the temperature was maintained at 80 ℃ after the addition and the reaction was continued, and the temperature was reduced to 30 ℃ after the solution appeared yellow and clear. 46 g of R4-OH solid and 0.56 g of 4-dimethylaminopyridine are dissolved in 22 g of pyridine and subsequently added dropwise to a three-necked flask. After the addition was complete, the mixture was stirred at room temperature for 12 hours, then warmed to 60 ℃ and 80 g of methanol were added. After 1 hour at 45 ℃, the solvent was drained to yield about 44 g of R4-DiNO as a solid.
Then, 80 grams of R4-DiNO solid, 85 grams of reduced iron, and 40 grams of ammonium chloride (NH)4Cl) was placed in a 5-liter four-necked flask, 950 g of water and 1050 g of Ethyl Acetate (EA) were added to the flask, stirred uniformly, heated to 70 ℃, and reacted at 70 ℃ for 2 hours. After completion of the reaction, the mixture was filtered through celite at 70 ℃, an aqueous layer was removed after the filtrate was separated into layers, and an organic layer was collected and dehydrated with anhydrous magnesium sulfate and then filtered and drained to obtain about 35 g of RPADA4 solid (i.e., diamine compound b1-1-4 represented by formula (I-6)).
Preparation example 5
A compound represented by the formula (I-7) (hereinafter referred to as "diamine compound (b 1-1-5)") was synthesized according to the following scheme 5.
[ Synthesis route 5]
65 g of 4-formylcinnamic acid, 100 g of 4- (4-heptylcyclohexyl) phenol (7CPO) and 4.5 g of 4-dimethylaminopyridine were placed in a2 l four-necked flask. 730 ml of dichloromethane were added to the four-neck flask, and 84 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) were added while stirring. Thereafter, the reaction was carried out at 40 ℃ for 6 hours. After the reaction, water was added for extraction, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and dried. The solid obtained after suction drying was further washed with isopropanol by heating. Thereafter, the solid was filtered again and collected to obtain about 130 g of R3CHO solid.
Next, 80 g of R3CHO solid, 620 ml of dimethylformamide were placed in a three-neck flask having a capacity of 1 liter and stirred. After the R3CHO solid dissolved, 170 grams of Oxone (Oxone) was added and reacted at room temperature for 3 hours. After completion of the reaction, the solvent was dried by suction to obtain a solid, and the solid was washed with pure water and methanol. After washing, the solid was collected by filtration and dried under vacuum to obtain about 75 g of R3COOH as a pale yellow solid.
Then, 68.5 g of R3COOH as a pale yellow solid, 28.1 g of 2,4-dinitrophenol, 3.73 g of 4-dimethylaminopyridine and 1250 ml of 0.125M methylene chloride were put into a four-necked flask having a capacity of 1 liter and stirred. 34.5 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) were added during the stirring. Thereafter, the reaction was refluxed at 40 ℃ for 6 hours. After the reaction, water was added for extraction, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and dried. The solid obtained after draining was washed with isopropanol and heated. After washing, the solid was collected by filtration and dried under vacuum to obtain about 50 g of R3DiNO as a solid.
Then, 28.3 g of R3DiNO solid and 270 ml of anisole are put into a four-neck flask with the capacity of 2 liters and stirred; in addition, 115 ml of pure water and 6 g of Pt/C were placed in a 2-liter beaker and stirred, and then 0.08 g of ammonium metavanadate and 0.42 g of an aqueous hypophosphorous acid solution (50 wt%) were added to prepare a mixed solution. The mixture was poured into a four-necked flask and heated to 65 ℃. Subsequently, 18.4 g of hydrazine was added dropwise, and after the total amount was added dropwise, the temperature was raised to 80 ℃ and the reaction was carried out for 4 hours. Subsequently, the solution was filtered, and the filtrate was extracted with ethyl acetate and water and then drained to obtain a solid. Next, the solid was washed with heating with ethyl acetate, followed by refiltering and collecting the solid, to obtain about 10 g of RPADA3M solid (i.e., diamine compound b1-1-5 represented by formula (I-7)).
Preparation example 6
A compound represented by the formula (I-9) (hereinafter referred to as "diamine compound (b 1-1-6)") was synthesized according to the following scheme 6.
[ Synthesis route 6]
45 g of 4-formylcinnamic acid, 100 g of 5 α -Cholestan-3 β -ol (5 α -Cholestan-3 β -ol) and 3.2 g of 4-dimethylaminopyridine are placed in a four-neck flask having a capacity of 2 l. In a four-neck flask was added 520 ml of dichloromethane, and 60 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) was added while stirring. Thereafter, the reaction was carried out at 40 ℃ for 6 hours. After the reaction, water was added for extraction, and the organic layer was collected, dehydrated with anhydrous magnesium sulfate, filtered and drained. The solid obtained after draining was washed with isopropanol under heating. Thereafter, the solid was filtered and collected to obtain about 120 g of R6CHO solid.
Subsequently, 80 g of R6CHO solid and 500 ml of dimethylformamide were placed in a three-neck flask having a capacity of 1 liter and stirred. After the R6CHO solid dissolved, 135 g of Oxone (Oxone) was added and reacted at room temperature for 3 hours. After completion of the reaction, the solvent was dried by suction to obtain a solid, and the solid was washed with pure water and methanol. After washing, the solid was collected by filtration and dried under vacuum to obtain about 60 g of R6COOH solid.
Then, 120 g of the R6COOH solid and 200 ml of toluene were placed in a three-necked flask having a capacity of 1 liter and dissolved with stirring, and 0.2 g of dimethylformamide was added thereto and the temperature was raised to 75 ℃. Subsequently, 23 g of thionyl chloride was slowly dropped, and after completion of the dropping, the temperature was raised to 80 ℃ to react at 80 ℃ for 5 minutes. Subsequently, the temperature was reduced to 30 ℃. 40 g of 2, 4-dinitrophenylethanol and 1 g of 4-dimethylaminopyridine were dissolved in 40 g of pyridine and added dropwise to the three-necked flask, and stirring was continued for 12 hours. Thereafter, the temperature was raised to 60 ℃ and 150 ml of methanol was added, and the temperature was maintained at 45 ℃ for 1 hour. Finally, the solvent was drained and washed with methanol to obtain about 90 g of precipitated R6DiNO solid.
Then, 50 g of R6DiNO solid and 400 ml of anisole are put into a four-neck flask with the capacity of 1L and stirred; in addition, 160 ml of pure water and 10 g of Pt/C were placed in a 2-liter beaker and stirred, followed by addition of 0.12 g of ammonium metavanadate and 0.6 g of an aqueous hypophosphorous acid solution (50 wt%) to prepare a mixed solution. The mixture was poured into a four-necked flask and warmed to 65 ℃. Subsequently, 26 g of hydrazine was added dropwise, and after the addition of the total amount, the temperature was raised to 80 ℃ and the reaction was carried out for 4 hours. Subsequently, the solution was filtered, and the filtrate was extracted with ethyl acetate and water and then drained to obtain a solid. Next, the solid was washed with ethyl acetate under heating, followed by filtration and collection of the solid, to obtain about 20 g of RPADA6 solid (i.e., diamine compound b1-1-6 represented by formula (I-9)).
Preparation example of diamine Compound (b1-2)
For an example of the production of the diamine compound (b1-2), reference may be made to taiwan patent publication No. TW 201536862A. In detail, the process for producing the compound represented by the formula (II-10) (hereinafter referred to as "diamine compound (b 1-2-1)") can be referred to the contents on page 40, line 8 to page 41, line 21 of the aforementioned patent publication; as a method for producing the compound represented by the formula (II-18) (hereinafter referred to as "diamine compound (b 1-2-2)"), reference is made to the contents on page 41, line 22 to page 44, line 1 of the aforementioned patent publication; as a method for producing the compound represented by the formula (II-24) (hereinafter referred to as "diamine compound (b 1-2-3)"), the contents on page 44, line 2 to page 45, line 25 of the aforementioned patent publication; the process for producing the compound represented by the formula (II-22) (hereinafter referred to as "diamine compound (b 1-2-4)") can be referred to the contents of the aforementioned patent publication Nos. 45, 26 th to 47, 11 th lines; and a process for producing a compound represented by the formula (II-26) (hereinafter referred to as "diamine compound (b 1-2-5)") can be referred to the contents of the aforementioned patent publication from page 47, line 12 to page 49, line 4.
Preparation example of diamine Compound (b1-3)
For an example of the production of the diamine compound (b1-3), reference may be made to taiwan patent publication No. TW 201546120A. Specifically, the compound represented by the formula (III-1) (hereinafter referred to as "diamine compound (b 1-3-1)") can be produced by the method described in paragraphs [0144] to [0146] of the aforementioned patent publication; as a method for producing a compound represented by the formula (III-2) (hereinafter referred to as "diamine compound (b 1-3-2)"), the contents of paragraphs [0147] to [0149] of the aforementioned patent publication can be referred to; as a method for producing the compound represented by the formula (III-3) (hereinafter referred to as "diamine compound (b 1-3-3)"), the contents of the aforementioned patent publication paragraphs [0150] to [0152 ]; as a method for producing a compound represented by the formula (III-4) (hereinafter referred to as "diamine compound (b 1-3-4)"), the contents of the aforementioned patent publication paragraphs [0153] to [0155 ]; as a method for producing a compound represented by the formula (III-5) (hereinafter referred to as "diamine compound (b 1-3-5)"), the contents of the aforementioned patent publication paragraphs [0156] to [0158 ]; as a method for producing the compound represented by the formula (III-6) (hereinafter referred to as "diamine compound (b 1-3-6)"), the contents of paragraphs [0159] to [0161] of the aforementioned patent publication can be referred to.
Synthesis example of Polymer (A-1)
Synthesis examples A-1-1-1 to A-1-1-6, A-1-2-1 to A-1-2-6, A-1-3-1 to A-1-3-6 and A-1-4-1 to A-1-4-6 of the polymer (A-1) are described below.
Synthesis example A-1-1-1
A four-necked flask having a volume of 500 ml was equipped with a nitrogen inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced thereinto. Then, 0.025 mol (50 mol%) of the diamine compound b1-1-1 obtained in production example 1 and 0.025 mol (50 mol%) of the other diamine compound (b1-4-1) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) were added to a four-necked flask and stirred at room temperature until dissolved. Then, 0.05 mol (100 mol%) of 2,3,5-tricarboxycyclopentyl acetic dianhydride (abbreviated as a1-1) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and washing with methanol and filtering were repeated three times, and the polymer was placed in a vacuum oven and dried at a temperature of 60 ℃ to obtain polymer A-1-1-1.
Synthesis examples A-1-1-2 to A-1-1-6, A-1-2-1 to A-1-2-6, A-1-3-1 to A-1-3-6 and A-1-4-1 to A-1-4-6
Synthesis examples A-1-1-2 to A-1-1-6, A-1-2-1 to A-1-2-6, A-1-3-1 to A-1-3-6 and A-1-4-1 to A-1-4-6 were prepared in the same procedure as in Synthesis example A-1-1, except that: the kind of the raw materials of the polymer and the amount thereof used were changed (as shown in Table 1).
Synthesis example of Polymer (A-2)
Synthesis examples A-2-1 to A-2-6
Synthesis examples A-2-1 to A-2-6 were prepared in the same procedure as in Synthesis example A-1-1-1, except that: the kind of the raw materials of the polymer and the amount thereof used were changed (as shown in Table 2).
Comparative Synthesis example of Polymer (A-1)
Comparative Synthesis examples A '-1-1 to A' -1-5
Comparative Synthesis examples A '-1-1 to A' -1-5 were prepared in the same procedure as in Synthesis example A-1-1-1, except that: the kind of the raw materials of the polymer and the amount thereof used were changed (as shown in Table 3).
The compounds corresponding to the symbols in tables 1 to 3 are shown below.
TABLE 1
TABLE 1 (continuation)
TABLE 1 (continue)
TABLE 1 (continuation)
TABLE 2
TABLE 3
Liquid crystal aligning agent, liquid crystal alignment film, and examples and comparative examples of liquid crystal display device
Examples 1 to 36 and comparative examples 1 to 8 of the liquid crystal aligning agent, the liquid crystal alignment film, and the liquid crystal display device are described below.
Example 1
a. Liquid crystal aligning agent
The liquid crystal aligning agent of example 1 was prepared by adding 100 parts by weight of the polymer (A-1-1-1) to 1200 parts by weight of N-methyl-2-pyrrolidone (abbreviated as B-1) and 800 parts by weight of ethylene glycol N-butyl ether (abbreviated as B-2), and stirring and mixing at room temperature until dissolved.
b. Liquid crystal alignment film and liquid crystal display device
The liquid crystal alignment agent was applied to two glass substrates each having an electrically conductive film made of ITO (indium-tin-oxide) by a printer (model No. S15-036, manufactured by japan koku corporation) to form a precoat layer. Thereafter, the glass substrate was placed on a hot plate and pre-baked at a temperature of 100 ℃ for 5 minutes. Subsequently, post-baking was performed in a circulating oven at 220 ℃ for 30 minutes. Finally, after alignment treatment, the glass substrate on which the liquid crystal alignment film of example 1 was formed was obtained.
Two of the glass substrates obtained above, on which liquid crystal alignment films were formed, were coated with hot-press glue, and the other was sprayed with a spacer (spacer) of 4 μm. Then, two glass substrates were bonded, and then hot-pressed and bonded at a temperature of 150 ℃ by applying a pressure of 10kg to a hot press. Then, liquid crystal was injected by a liquid crystal injector (model ALIS-100X-CH, manufactured by Shimadzu corporation). Next, the liquid crystal injection port was sealed with an ultraviolet curing adhesive, the ultraviolet curing adhesive was cured by irradiation with an ultraviolet lamp, and liquid crystal tempering treatment (annealing treatment) was performed in an oven at 60 ℃ for 30 minutes, whereby the liquid crystal display element of example 1 was obtained.
The liquid crystal display element of example 1 was evaluated in the following evaluation methods, and the results are shown in table 4.
Example 2 to example 36
The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display device of examples 2 to 36 were respectively prepared in the same steps as example 1, except that: the kinds of the components and the amounts thereof used were changed as shown in Table 4. The liquid crystal display elements obtained in examples 2 to 36 were evaluated in the following evaluation manner, and the results are shown in Table 4.
Comparative examples 1 to 8
The liquid crystal aligning agents, the liquid crystal alignment films, and the liquid crystal display devices of comparative examples 1 to 8 were respectively prepared in the same steps as example 1, except that: the kinds of the components and the amounts thereof used were changed as shown in Table 5. The liquid crystal display devices obtained in comparative examples 1 to 8 were evaluated in the following evaluation manner, and the results are shown in Table 5.
The compounds identified by the reference numerals in tables 4 and 5 are shown below.
Evaluation method
< electric field memory Effect >
Liquid crystal display elements of examples 1 to 36 and comparative examples 1 to 8 were evaluated by a liquid crystal evaluation apparatus (manufactured by a central processor (LTD.) and having a model number of OMS-CM4RD) according to the method described in "t.j.scheffer, et al., j.appl.phys., vol.19,2013 (1980)". Specifically, the pretilt angle was measured by the crystal rotation method using He-Ne laser beam, and it was recorded as Pm. Then, an alternating current of 16 volts at 60Hz was applied, the sample was placed on a Light Emitting Diode (LED) backlight, and the pretilt angle was measured again after 36 hours, and recorded as Pn. And are provided withThe pretilt angle change is calculated by the following equation. The smaller the change in pretilt angle, the better the electric field memory effect of the liquid crystal display element. Conversely, a larger change in pretilt angle means that the electric field memory effect of the liquid crystal display element is worse, and there is a possibility that photoalignment cannot be performed.
Pretilt angle variation ═ Pm－Pn︱
The evaluation criteria for the change in pretilt angle are as follows:
very good: pretilt angle variation ≦ 0.3 °;
o: the variation of the pretilt angle is less than or equal to 0.6 degrees when the pretilt angle is less than 0.3 degrees;
and (delta): the variation of the pretilt angle is less than or equal to 1.0 degree between 0.6 degrees and less than or equal to 1.0 degrees;
gamma rays: 1.0 ° < pretilt angle variation, or photoalignment was not possible.
< environmental resistance >
The liquid crystal display elements of example 1 to example 36 and comparative example 1 to comparative example 8 were each placed in an environment at a temperature of 65 ℃ and a relative humidity of 85%. After 120 hours, the ion densities of the liquid crystal display elements of examples 1 to 36 and comparative examples 1 to 8 were measured by an electric measuring machine (Model 6254, manufactured by toyoyang corporation). Under the test conditions that a triangular wave of 0.01Hz and 1.7V was applied at a temperature of 60 ℃, the ion density (pC) was measured by calculating the peak area in the range of 0V to 1V in the current-voltage waveform. The lower the ion density, the better the environmental resistance. Conversely, a higher ion density indicates a lower environmental resistance.
The evaluation criteria for ion density are as follows:
very good: the ion density is less than 20;
o: 20 ≦ ion density < 40;
and (delta): 40 ≦ ion density < 50;
gamma rays: 50 ≦ ion density.
TABLE 4
Table 4 (continuation)
Table 4 (continuation)
TABLE 5
< evaluation results >
As is clear from tables 4 and 5, the liquid crystal alignment films and liquid crystal display devices formed by using the liquid crystal alignment agent (example 1 to example 36) containing the diamine compound (b1-1) had better electric field memory effect and environmental resistance than the liquid crystal alignment agent (comparative example 1 to comparative example 8) containing no diamine compound (b 1-1). Furthermore, the liquid crystal alignment film and the liquid crystal display device formed by the liquid crystal alignment agent (comparative examples 1 to 8) without using the diamine compound (b1-1) have the problems of the electric field memory effect and the poor environmental resistance.
When the amount of the polymer (A-1) in the liquid crystal aligning agent falls within the range of 30 to 95 parts by weight (examples 7 to 12), the liquid crystal alignment film and the liquid crystal display device formed by the liquid crystal aligning agent have better electric field memory effect.
When the diamine compound (b1) in the polymer (A-1) in the liquid crystal alignment agent comprises the diamine compound (b1-2) (examples 13 to 18, 31 and 32), the liquid crystal alignment film and the liquid crystal display device formed by the liquid crystal alignment agent have better electric field memory effect.
When the diamine compound (b1) in the polymer (A-1) in the liquid crystal aligning agent includes the diamine compound (b1-3) (examples 19 to 24, 33 and 34), the liquid crystal alignment film and the liquid crystal display device formed by the liquid crystal aligning agent can have better environmental resistance.
When the diamine compound (b1) in the polymer (A-1) in the liquid crystal alignment agent comprises the diamine compound (b1-2) and the diamine compound (b1-3) (examples 25 to 30, 35 and 36), the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have better electric field memory effect and better environment resistance.
As described above, the polymer in the liquid crystal aligning agent of the present invention is prepared by reacting a tetracarboxylic dianhydride compound and a diamine compound having a specific structure, so that when the liquid crystal aligning agent is used to form a liquid crystal alignment film, a liquid crystal display device using the liquid crystal alignment film has good electric field memory effect and environmental resistance, and thus is suitable for the liquid crystal alignment film and the liquid crystal display device.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.
Claims (18)
1. A diamine compound characterized by being a diamine compound b1-1 represented by the formula (I):
in the formula (I), the compound is shown in the specification,
X1and X2Each independently represents a single bond, -O-, or,
Wherein R is14Represents hydrogen or an alkyl group having 1 to 4 carbon atoms;
x represents 0 or 1;
y represents an integer of 0 to 4;
R1represents a methylene group or an alkylene group having 2 to 4 carbon atoms;
R3each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group;
R2represents an organic group represented by the formula (I-A) or a monovalent organic group having a steroid skeleton with a carbon number of 17 to 40;
in the formula (I-A),
R4represents fluorine or methyl;
R5、R6and R7Each independently represents a single bond, -O-, or,
Methylene or alkylene having 2 to 3 carbon atoms;
R8to represent
Wherein R is10And R11Each independently represents fluorine or methyl, and represents a bonding position;
R9represents hydrogen, fluorine, alkyl group having 1 to 12 carbon atoms, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, fluorine-substituted alkoxy group having 1 to 12 carbon atoms, -OCH2F、-OCHF2、-OCF3；
a represents an integer of 0 to 2;
b. c and d each independently represent an integer of 0 to 4;
e. f and g each independently represent an integer of 0 to 3;
i and j each independently represent an integer of 0 to 2;
indicates a bonding site;
when R is4、R5、R6、R7、R8、R10Or R11When plural, each independently represents the same or different groups.
2. Diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by formula (I),
when X is 0, X1is-O-),
Wherein R is14Represents hydrogen or an alkyl group having 1 to 4 carbon atoms;
when X is 1, X1Is a single bond.
3. Diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by formula (I),
when X is 0, X1is-O-),
4. Diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by the formula (I), R5、R6And R7Each independently represents a single bond, -O-, or,
Methylene or alkylene having 2 to 3 carbon atoms.
5. Diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by formula (I),
when e + f + g is less than 3, f and g are not 0 at the same time;
b ≧ 1 when f ≧ 1;
when g ≧ 1, c + d ≧ 1.
6. A polymer a-1, characterized in that it is produced by reacting a first mixture comprising a tetracarboxylic dianhydride compound a1 and a diamine compound b1, wherein the diamine compound b1 comprises the diamine compound b1-1 represented by the formula (I) as described in any one of claims 1 to 5.
7. The polymer a-1 of claim 6, wherein the diamine compound b1 further comprises a diamine compound b1-2 represented by formula (II):
in the formula (II), the compound is shown in the specification,
R15and R17Each independently represents-O-, -S-),
R16Represents an alkylene group having 2 to 10 carbon atoms;
R18represents a single bond, a methylene group or an ethylene group;
Y1represents a monovalent organic group having a steroid skeleton with a carbon number of 17 to 40.
8. The polymer a-1 of claim 6, wherein the diamine compound b1 further comprises a diamine compound b1-3 represented by formula (III):
in the formula (III), the compound represented by the formula (III),
Y2each independently represents-O-, -NH-,
-CH2O-、
Y3each independently represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group;
Y4each independently represents a single bond, -O-, -NH-,
wherein m represents an integer of 1 to 5;
Y5each independently represents a nitrogen-containing aromatic heterocyclic group;
k represents an integer of 1 to 4.
9. The polymer a-1 according to claim 6, wherein the diamine compound b1-1 represented by the formula (I) is used in an amount of 50 to 100 molar parts based on 100 molar parts of the diamine compound b 1.
10. The polymer a-1 according to claim 7, wherein the diamine compound b1-2 represented by the formula (II) is used in an amount of 5 to 30 molar parts based on 100 molar parts of the diamine compound b 1.
11. The polymer a-1 according to claim 8, wherein the diamine compound b1-3 represented by the formula (III) is used in an amount of 1 to 20 parts by mole, based on 100 parts by mole of the diamine compound b 1.
12. A liquid crystal aligning agent comprising the polymer a-1 according to any one of claims 6 to 11 and a solvent B.
13. The liquid crystal aligning agent of claim 12, further comprising a polymer a-2, wherein the polymer a-2 is prepared by reacting a second mixture, and the second mixture comprises a tetracarboxylic dianhydride compound a2 and a diamine compound b 2.
14. The liquid crystal aligning agent according to claim 12, wherein the solvent B is used in an amount of 1000 parts by weight to 3500 parts by weight, based on 100 parts by weight of the polymer a-1.
15. The liquid crystal aligning agent according to claim 13, wherein the polymer a-1 is used in an amount of 30 to 95 parts by weight, based on 100 parts by weight of the total amount of the polymer a-1 and the polymer a-2 used.
16. The liquid crystal aligning agent according to claim 13, wherein the solvent B is used in an amount of 1000 to 3500 parts by weight, based on 100 parts by weight of the total amount of the polymer a-1 and the polymer a-2 used.
17. A liquid crystal alignment film formed from the liquid crystal alignment agent according to any one of claims 12 to 16.
18. A liquid crystal display element comprising the liquid crystal alignment film according to claim 17.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100047482A1 (en) * | 2008-08-21 | 2010-02-25 | Samsung Electronics Co., Ltd. | Photo-reactive compounds and liquid crystal display device using the same |
| WO2011046397A2 (en) * | 2009-10-15 | 2011-04-21 | 주식회사 엘지화학 | Light-sensitive resin composition and a dry film comprising the same |
| CN103184054A (en) * | 2011-12-27 | 2013-07-03 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer and compound |
| CN104178181A (en) * | 2013-05-22 | 2014-12-03 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN105273724A (en) * | 2014-06-06 | 2016-01-27 | 奇美实业股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN105969404A (en) * | 2015-03-10 | 2016-09-28 | 奇美实业股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film formed by liquid crystal aligning agent and liquid crystal display element |
| TW201730274A (en) * | 2016-02-25 | 2017-09-01 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP2018045180A (en) * | 2016-09-16 | 2018-03-22 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display |
-
2020
- 2020-11-16 CN CN202011282222.9A patent/CN114507149A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100047482A1 (en) * | 2008-08-21 | 2010-02-25 | Samsung Electronics Co., Ltd. | Photo-reactive compounds and liquid crystal display device using the same |
| WO2011046397A2 (en) * | 2009-10-15 | 2011-04-21 | 주식회사 엘지화학 | Light-sensitive resin composition and a dry film comprising the same |
| CN103184054A (en) * | 2011-12-27 | 2013-07-03 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer and compound |
| CN104178181A (en) * | 2013-05-22 | 2014-12-03 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN105273724A (en) * | 2014-06-06 | 2016-01-27 | 奇美实业股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN105969404A (en) * | 2015-03-10 | 2016-09-28 | 奇美实业股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film formed by liquid crystal aligning agent and liquid crystal display element |
| TW201730274A (en) * | 2016-02-25 | 2017-09-01 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP2018045180A (en) * | 2016-09-16 | 2018-03-22 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display |
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