CN115449376A - Liquid crystal aligning agent and application thereof, polyamic acid ester, polyimide, diamine and tetracarboxylic dianhydride manufacturing method - Google Patents

Liquid crystal aligning agent and application thereof, polyamic acid ester, polyimide, diamine and tetracarboxylic dianhydride manufacturing method Download PDF

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CN115449376A
CN115449376A CN202210533247.4A CN202210533247A CN115449376A CN 115449376 A CN115449376 A CN 115449376A CN 202210533247 A CN202210533247 A CN 202210533247A CN 115449376 A CN115449376 A CN 115449376A
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liquid crystal
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formula
ring
carbon atoms
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石部彻
樫下幸志
冈田敬
菅野尚基
岸田高典
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JSR Corp
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Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal element, polyamic acid ester, polyimide and diamine, a method for preparing tetracarboxylic dianhydride and a method for preparing a polymer. Wherein the liquid crystal aligning agent can obtain a liquid crystal element which has good liquid crystal aligning performance and excellent voltage holding characteristic and can restrain the reduction of display quality caused by external force. The liquid crystal aligning agent contains a polymer [ A ] having a partial structure (a) represented by formula (1) in the main chain]. In the formula (1), R 1 And R 2 Is by using-C (R) 5 )(R 6 )‑、‑O‑、‑S‑、‑CO‑、‑COO‑、‑NR 7 ‑、‑NR 7 ‑NR 8 ‑、‑NR 7 ‑CO‑O‑、‑NR 7 ‑CO‑NR 8 A divalent group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to the carbonyl group in the formula (1). R 3 And R 4 Is a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 And ring structures formed by bonding the two to each other.

Description

Liquid crystal aligning agent and application thereof, polyamic acid ester, polyimide, diamine and tetracarboxylic dianhydride manufacturing method
Technical Field
The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal element, a polymer and a method for producing the same, and a method for producing a compound.
Background
Conventionally, various driving methods such as a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, a Vertical Alignment (VA) type, a Multi-domain Vertical Alignment (MVA) type, an In-Plane Switching (IPS) type, a Fringe Field Switching (FFS) type, and an Optically Compensated Bend (OCB) type have been developed as liquid crystal elements, which have different electrode structures and different properties of liquid crystal molecules used. These liquid crystal elements have a liquid crystal alignment film for aligning liquid crystal molecules. In general, a liquid crystal alignment film is formed on a substrate by applying, preferably heating, a liquid crystal alignment agent obtained by dissolving or dispersing a polymer component in an organic solvent to the surface of the substrate.
In recent years, liquid crystal televisions with large screens and high definition have become the main units, and small display terminals such as smart phones and tablet Personal Computers (PCs) have been widely used, and there has been a growing demand for higher quality liquid crystal devices. In order to meet such a demand for high quality, various liquid crystal aligning agents have been proposed (for example, see patent document 1). Patent document 1 discloses that a liquid crystal alignment agent contains a polyimide or a polyimide precursor together with a crosslinkable compound that is a low-molecular-weight compound for improving the hardness of a liquid crystal alignment film.
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2020/171128
Disclosure of Invention
[ problems to be solved by the invention ]
With the high definition of liquid crystal elements, the requirements for quality have become more stringent. For example, in the case of a liquid crystal device, it is required not only to further improve the liquid crystal alignment property and the voltage holding ratio but also to prevent the display quality from being impaired by physical stress such as vibration and tapping (tapping) during transportation. In particular, in a glass panel serving as a substrate of a liquid crystal element, the film thickness is becoming thinner, and the physical pressure applied to internal members is further increased. On the other hand, as in the prior art, it is difficult to maintain display quality only by adding a crosslinkable compound.
The present invention has been made in view of the above problems, and a main object of the present invention is to provide a liquid crystal aligning agent which can provide a liquid crystal element having good liquid crystal alignment properties and excellent voltage holding characteristics, and in which deterioration of display quality due to external force is suppressed.
[ means for solving problems ]
The present inventors have made extensive studies to solve the above problems and found that the above problems can be solved by using a polymer having a specific carbon-carbon unsaturated structure, thereby completing the present invention. Specifically, the following means is provided according to the present invention.
< 1 > a liquid crystal aligning agent comprising a polymer [ A ] having a partial structure (a) represented by the following formula (1) in the main chain,
[ solution 1]
Figure BDA0003646807250000021
(in the formula (1), R 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to a carbonyl group in the formula (1); r 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 A ring structure formed by the bonded carbons; r 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; r 7 And R 8 Each independently a hydrogen atom or a monovalent organic group; "" indicates a bond).
< 2 > a liquid crystal alignment film formed using the liquid crystal aligning agent according to the above < 1 >.
< 3 > a liquid crystal element comprising the liquid crystal alignment film according to said < 2 >.
< 4 > a polyamic acid, polyamic acid ester, and polyimide, which have a partial structure represented by the formula (1) in a main chain.
< 5 > a process for producing a diamine, which comprises using a compound represented by the following formula (5) as a raw material to produce a diamine represented by the following formula (2),
[ solution 2]
Figure BDA0003646807250000022
(in the formula (5), R 9 Is a single bond or a divalent organic radical)
[ solution 3]
Figure BDA0003646807250000023
(in the formula (2), A 1 And A 2 Each independently a single bond, a divalent alicyclic group or a divalent aromatic ring group; r is 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent organic group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to the carbonyl group in the formula (2); r 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 A ring structure formed by the bonded carbons; r 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; r 7 And R 8 Each independently is a hydrogen atom or a monovalent organic group; m1 is an integer of 1 to 3; in the case where m1 is 2 or 3, plural R' s 1 ～R 4 The same or different from each other).
< 6 > A method for producing a tetracarboxylic dianhydride, wherein a tetracarboxylic dianhydride represented by the following formula (3) or (4) is produced using the compound represented by the above formula (5) as a raw material,
[ solution 4]
Figure BDA0003646807250000031
(in formulae (3) and (4), A 3 And A 4 Each independently is a trivalent aromatic ring group or an aliphatic ring group; r is 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent organic group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to the carbonyl group in the formulae (3) and (4); r 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 Formed together with the bound carbonA ring structure; r 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; r 7 And R 8 Each independently is a hydrogen atom or a monovalent organic group; m2 is an integer of 1 to 3; n1 and n2 are each independently an integer of 1 to 3; in the case where m2 is 2 or 3, plural R' s 1 ～R 4 The same or different from each other).
< 7 > a method for producing a polymer, wherein the polyamic acid, polyamic acid ester, and polyimide according to the < 4 > are produced by polymerization using a monomer including at least one compound selected from the group consisting of a diamine obtained by the production method according to the < 5 > and a tetracarboxylic dianhydride obtained by the production method according to the < 6 >.
[ Effect of the invention ]
According to the liquid crystal aligning agent of the present invention, a liquid crystal element which has good liquid crystal alignment properties and excellent voltage holding characteristics and in which deterioration of display quality is suppressed even when an external force (for example, an external force due to vibration, or the like) is applied thereto can be obtained.
Detailed Description
Liquid crystal aligning agent
Hereinafter, each component contained in the liquid crystal aligning agent of the present disclosure and other components optionally blended as necessary will be described.
In the present specification, the term "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group having no cyclic structure in the main chain and consisting of only a chain structure. The polymer may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, the alicyclic hydrocarbon does not necessarily have to be constituted by only the alicyclic hydrocarbon structure, and includes a group having a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessary to be composed of only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.
By "backbone" is meant the portion of the longest "backbone" in the atomic chain of the polymer. Further, it is permissible for the "backbone" portion to comprise a loop structure. By "side chain" is meant a moiety that branches from the "backbone" of the polymer. The term "aromatic ring" means an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The "organic group" refers to an atomic group obtained by removing an arbitrary hydrogen atom from a compound containing carbon (i.e., an organic compound). "tetracarboxylic acid derivative" is intended to include tetracarboxylic dianhydrides, tetracarboxylic acid diesters, and tetracarboxylic acid diester dihalides.
The liquid crystal aligning agent disclosed by the invention contains a polymer [ A ] which has a partial structure (a) represented by the following formula (1) in a main chain.
[ solution 5]
Figure BDA0003646807250000041
(in the formula (1), R 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to a carbonyl group in the formula (1). R 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 The bonded carbons together form a ring structure. R 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. R 7 And R 8 Each independently a hydrogen atom or a monovalent organic group. "" indicates a bond)
< Polymer [ A ] >, and
concerning part of the structure (a)
R in the formula (1) 1 And R 2 To utilize-C (R) 5 )(R 6 ) -in the case of a divalent radical bonded to the carbonyl group in the formula (1), R 5 And R 6 The alkyl group having 1 to 8 carbon atoms, the alkenyl group having 1 to 8 carbon atoms and the alkoxy group having 1 to 8 carbon atoms may be either straight or branched. Wherein R is 5 And R 6 Also preferred is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferred is a hydrogen atom (i.e., -C (R) 5 )(R 6 ) -in the case of methylene).
R in the formula (1) 1 And R 2 To utilize-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-and-NR 7 -CO-NR 8 -in the case of a divalent radical bonded to the carbonyl group in the formula (1), R 7 And R 8 The monovalent organic group represented by the formula (i) is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent releasable group which is released by heat or light (hereinafter, also simply referred to as "releasable group").
At R 7 And R 8 When the monovalent organic group represented is a monovalent hydrocarbon group, specific examples of the hydrocarbon group include: an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms, and the like. Among these, an alkyl group having 1 to 3 carbon atoms and a phenyl group are preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
At R 7 And R 8 When the monovalent organic group is a monovalent releasable group, the releasable group is preferably a thermally releasable group which is released by heat (preferably, heating at the time of film formation). Specific examples of the thermally releasable group include: t-butoxycarbonyl (Boc group), benzyloxycarbonyl, 1-dimethyl-2-haloethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxycarbonyl, and the like. Among these, the Boc group is particularly preferable in terms of excellent releasability from heat and a reduction in the remaining amount of the released structure in the film.
Wherein R is 7 And R 8 Preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a monovalent heat-releasable group, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a tert-butoxycarbonyl group.
At R 1 And R 2 In the case where an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to the carbonyl group in the formula (1), examples of the aromatic hydrocarbon ring include: benzene ring, naphthalene ring, anthracene ring, and the like. As the aromatic heterocyclic ring, there may be mentioned: nitrogen-containing aromatic heterocycles, oxygen-containing aromatic heterocycles, sulfur-containing aromatic heterocycles, and the like. Specific examples of the nitrogen-containing aromatic heterocyclic ring include a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring; examples of the oxygen-containing aromatic heterocyclic ring include furan ring; examples of the sulfur-containing aromatic heterocyclic ring include a thiophene ring. Examples of the nitrogen-containing non-aromatic heterocyclic ring include a piperidine ring and a piperazine ring. These rings may have a substituent. As the substituent, there may be mentioned: an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom, a hydrogen atom, a cyano group, etc.
R 1 And R 2 Provided that it is a compound passing-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 The group to which the aromatic hydrocarbon ring, aromatic heterocycle or nitrogen-containing non-aromatic heterocycle is bonded to the carbonyl group in formula (1) may be any group, and the structure of the other moiety is not particularly limited. Further, in R 1 And R 2 R is bonded to the carbonyl group in the formula (1) via-COO- 1 And R 2 The bond with the carbonyl group in the formula (1) may be made by an oxygen atom, and may be made by a carbon atom. In addition, in R 1 And R 2 By using-NR 7 -CO-O-in case of being bonded to the carbonyl group in said formula (1), R 1 And R 2 The nitrogen atom may be bonded to the carbonyl group in the formula (1) or may be bonded to the carbonyl group by a carbon atom.
As R 1 And R 2 Specific examples of (3) include: -C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent chain hydrocarbon group, a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, and a divalent nitrogen-containing non-aromatic heterocyclic group. In addition, R 1 And R 2 May be a divalent hydrocarbon groupUnder the condition that methylene groups are not adjacent to each other, through-O-, -S-, -CO-, -COO-, -NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 Or a divalent organic group substituted with a heterocyclic group.
In terms of improving the Voltage Holding Ratio (VHR) of the liquid crystal device, obtaining a highly reliable liquid crystal device with little drop in the Voltage Holding Ratio even in the case of long-term driving, obtaining a liquid crystal device exhibiting good liquid crystal alignment properties, and having a high effect of suppressing the drop in display quality due to vibration or impact, R is 1 And R 2 One or both of them are preferably a group having a chain hydrocarbon structure with 1 or more carbon atoms or a divalent nitrogen-containing non-aromatic heterocyclic group. In particular, R 1 And R 2 One or both of them are preferably a divalent chain hydrocarbon group having 1 or more carbon atoms or a C2 or higher chain hydrocarbon group having at least two carbon atoms and optionally containing methylene groups not adjacent to each other 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-or-NR 7 -CO-NR 8 A divalent group formed by substitution (wherein-C (R) is used 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-or-NR 7 -CO-NR 8 -bonded to the carbonyl group in the formula (1), or a divalent nitrogen-containing non-aromatic heterocyclic group. In these, R 1 And R 2 One or both of them are particularly preferably a divalent chain hydrocarbon group having 1 or more carbon atoms or a C2 or higher chain hydrocarbon group having at least two carbon atoms and optionally containing methylene groups not adjacent to each other 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-or-NR 7 -CO-NR 8 A divalent radical derived from substitution. Further, with respect to R 5 、R 6 、R 7 And R 8 The specific examples and preferred examples of (3) can be applied to the above description.
At R 1 、R 2 In the case of a divalent chain hydrocarbon group, the chain hydrocarbon group may be saturated or unsaturated, or may be saturated or unsaturatedThe polymer may be linear or branched. In terms of improving the voltage holding ratio of the liquid crystal element, obtaining a highly reliable liquid crystal element with little decrease in the voltage holding ratio even in the case of long-term driving, obtaining a liquid crystal element exhibiting good liquid crystal alignment properties, and suppressing the decrease in display quality due to vibration or knocking, R is 1 、R 2 The chain hydrocarbon group is preferably an alkanediyl group, and more preferably a straight-chain alkanediyl group. At R 1 、R 2 In the case of a divalent chain hydrocarbon group, the number of carbons of the chain hydrocarbon group is preferably 2 or more, and more preferably 3 or more, from the viewpoint of obtaining a liquid crystal device exhibiting a high voltage holding ratio and from the viewpoint of obtaining a liquid crystal device exhibiting good liquid crystal alignment properties. In addition, from the viewpoint of achieving both improvement of film strength (and further improvement of rubbing resistance) and improvement of voltage holding ratio of the liquid crystal element, R is 1 、R 2 R in the case of a chain hydrocarbon group 1 、R 2 The number of carbon atoms of (a) is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
When R is 1 、R 2 Is formed by reacting-O-, -S-, -CO-, -COO-, -NR under the condition that arbitrary methylene groups of chain hydrocarbon groups with more than 2 carbon atoms are not adjacent 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-or-NR 7 -CO-NR 8 In the case of a divalent group (hereinafter, also referred to as "divalent group A") resulting from substitution, R 1 And R 2 One or both of them are preferably a group represented by the following formula (6).
-R 10 -X 1 -* 1 ···(6)
(in the formula (6), R 10 Is alkanediyl. X 1 is-O-, -S-, -CO-, -COO-, -NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-or-NR 7 -CO-NR 8 -。“* 1 "represents a bond bonded to the carbonyl group in the formula (1). R is 7 And R 8 The same as formula (1)
In the formula (6), R 10 The alkanediyl group represented is preferably straight. Said alkaneThe number of carbon atoms of the diradical is preferably 1 to 10, more preferably 2 to 10, and still more preferably 2 to 5.
At R 1 And R 2 In the case of a divalent nitrogen-containing non-aromatic heterocyclic group, the divalent nitrogen-containing non-aromatic heterocyclic group is preferably a substituted or unsubstituted 1, 4-piperidinediyl group or a substituted or unsubstituted 1, 4-piperazinediyl group.
In the formula (1), R 3 And R 4 Preferably a hydrogen atom, a fluorine atom or a methyl group, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 The bonded carbons together form a ring structure. As R 3 And R 4 Examples of the ring structure formed by bonding to each other include a cycloolefin ring having a ring number of 5 to 10. Among them, the ring structure is preferably a cycloalkene ring having a ring number of 5 to 8. Among these, R is for further improving the effect of improving the film strength 3 And R 4 Hydrogen atom, fluorine atom or methyl group is preferable, and hydrogen atom is particularly preferable.
-R in the formula (1) 4 C＝CR 3 The group represented by-may be either cis or trans. In terms of the effect of improving the film strength, R in the formula (1) 4 C＝CR 3 The radical represented by-is preferably of the cis-type.
Among them, the partial structure (a) is preferably a structure represented by the following formula (1-1) or the following formula (1-2).
[ solution 6]
Figure BDA0003646807250000061
(in the formula (1-1), R 11 And R 13 Is R 11 Is a hydrogen atom or a monovalent organic group and R 13 Is a single bond or alkanediyl, or represents R 11 And R 13 Are combined with each other and R 11 The bonded nitrogen atoms form a nitrogen-containing non-aromatic heterocyclic structure together. R 12 And R 14 Is R 12 Is a hydrogen atom or a monovalent organic group and R 14 Is a single bond or alkanediyl, or represents R 12 And R 14 Are combined with each other and R 12 The bonded nitrogen atoms form a nitrogen-containing non-aromatic heterocyclic structure together. R 3 And R 4 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. "" indicates a bond.
In the formula (1-2), R 15 And R 16 Each independently a single bond or an alkanediyl group. R 3 And R 4 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. "+" indicates a bond)
In the above formulae (1-1) and (1-2), with respect to R 11 、R 12 The monovalent organic group represented by the formula (1) includes R 7 And R 8 The same groups as those exemplified in the description of (1). With respect to R 3 And R 4 R in the above formula (1) is exemplified 3 And R 4 The same groups as exemplified in the description of (1) are exemplified.
At R 13 、R 14 In the case of an alkanediyl group, the alkanediyl group is preferably straight-chain alkanediyl group, and more preferably straight-chain alkanediyl group having 1 to 5 carbon atoms. R 11 And R 13 Ring structures bonded to each other, and R 12 And R 14 The ring structures bonded to each other are preferably a substituted or unsubstituted 1, 4-piperidinediyl group or a substituted or unsubstituted 1, 4-piperazinediyl group.
In the polymer [ a ], from the viewpoint of obtaining a liquid crystal element exhibiting good liquid crystal alignment properties and exhibiting high VHR and high reliability, the content ratio of the structural unit derived from a monomer having the partial structure (a) is preferably 2 mol% or more with respect to the total amount of the monomer units of the polymer [ a ]. From the above viewpoint, the content ratio of the constitutional unit derived from the monomer having the partial structure (a) is more preferably 5 mol% or more, and still more preferably 7 mol% or more, relative to the total amount of the monomer units of the polymer [ a ].
The content ratio of the structural unit derived from a monomer having the partial structure (a) may be appropriately set according to the main chain of the polymer [ a ], and is, for example, 60 mol% or less, preferably 50 mol% or less, relative to the total amount of the monomer units contained in the polymer [ a ]. In the polymer [ a ], the number of the constitutional units derived from a monomer having the partial structure (a) may be only one, or may be two or more.
The main skeleton of the polymer [ A ] is not particularly limited. In order to form a liquid crystal alignment film having high affinity for liquid crystal, high mechanical strength, and high reliability, the polymer [ a ] is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.
The method for producing the polymer [ A ] is not particularly limited as long as the partial structure (a) can be introduced into the main chain of the polymer. The polymer [ a ] is preferably produced by a method of polymerizing a monomer having the partial structure (a) in the main chain, from the viewpoint of ease of introduction of the partial structure (a) into the main chain of the polymer. In order to form a liquid crystal alignment film having high affinity for liquid crystal and high mechanical strength, the monomer having the partial structure (a) is preferably at least one selected from the group consisting of a diamine compound having the partial structure (a) (hereinafter, also referred to as "specific diamine") and a tetracarboxylic dianhydride having the partial structure (a) (hereinafter, also referred to as "specific acid anhydride").
(specific diamine)
The specific diamine is not particularly limited as long as it is a monomer having the partial structure (a) and two primary amino groups. Specifically, the specific diamine is preferably a compound represented by the following formula (2).
[ solution 7]
Figure BDA0003646807250000071
(in the formula (2), A 1 And A 2 Each independently is a single bond, a divalent alicyclic group or a divalent aromatic ring group. m1 is an integer of 1 to 3. R is 1 、R 2 、R 3 And R 4 The same as the formula (1). In the case where m1 is 2 or 3, plural R' s 1 ～R 4 Same or different from each other)
In the formula (2), the reaction mixture is,A 1 and A 2 The divalent alicyclic group represented by (a) is preferably a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted alicyclic hydrocarbon ring. Examples of the alicyclic hydrocarbon ring include: cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and the like. Examples of the substituent introduced into the ring portion of the alicyclic hydrocarbon ring include: an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, etc.
A 1 And A 2 The divalent aromatic ring group is a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aromatic ring. The aromatic ring is an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring or a nitrogen-containing aromatic heterocyclic ring. As the substituent introduced into the ring portion of the aromatic ring, there may be mentioned: an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, etc.
As A 1 And A 2 Specific examples of the divalent aromatic hydrocarbon ring group include a group obtained by removing an arbitrary hydrogen atom from the ring part of a benzene ring, biphenyl ring, naphthalene ring or anthracene ring; examples of the divalent nitrogen-containing aromatic heterocyclic group include groups obtained by removing two optional hydrogen atoms from the ring portion of a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring. From the viewpoint of achieving high density of the liquid crystal alignment film, A 1 、A 2 The divalent aromatic ring group represented is preferably a substituted or unsubstituted phenylene group, biphenylene group or pyridyldiyl group, and more preferably a substituted or unsubstituted phenylene group.
A liquid crystal element A having a low Voltage Holding Ratio (VHR) drop even in long-term driving and having high reliability and a liquid crystal element exhibiting good liquid crystal alignment properties 1 And A 2 Preferably a divalent alicyclic group or a divalent aromatic ring group, more preferably a divalent aromatic ring group.
From the viewpoint of liquid crystal alignment properties and ease of synthesis, m1 is preferably 1 or 2. In addition, m1 is preferably 2 or more from the viewpoint of enhancing the improvement effect by the introduction portion structure (a). M is particularly preferably 2 from the viewpoint of ease of liquid crystal alignment and synthesis, and improvement effect of improving the voltage holding ratio by the introduced partial structure (a).
Preferable specific examples of the specific diamine include a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2).
[ solution 8]
Figure BDA0003646807250000081
(formula (2-1) and (2-2) wherein Ar 1 And Ar 2 Each independently is a divalent aromatic ring group. m1 is an integer of 1 to 3. R is 3 、R 4 、R 11 、R 12 、R 13 、R 14 、R 15 And R 16 The same as the above formula (1-1) and formula (1-2)
Specific examples of the specific diamine include compounds represented by the following formulae (3-1) to (3-30). In the compounds represented by the following formulae (3-1) to (3-30), the carbon-carbon unsaturated bond between two carbonyl groups is not necessarily structurally different, and may be either a cis-form or a trans-form.
[ solution 9]
Figure BDA0003646807250000091
[ solution 10]
Figure BDA0003646807250000101
[ solution 11]
Figure BDA0003646807250000102
[ solution 12]
Figure BDA0003646807250000111
[ solution 13]
Figure BDA0003646807250000112
[ chemical 14]
Figure BDA0003646807250000121
(Synthesis of specific diamine)
The method for synthesizing the specific diamine is not particularly limited. The specific diamine can be produced, for example, by the following method: reacting maleic anhydride with a compound having the formula — "R" in the formula (2) 1 -A 1 -NH 2 "method of reacting amine compound having corresponding partial structure (method 1A); reacting fumaric chloride and a compound having an-R group represented by the formula (2) 1 -A 1 -NH 2 "method of reacting amine compound having corresponding partial structure" (method 2A). The specific diamine can also be produced by using a compound represented by the following formula (5) as a raw material (method 3A). From an industrial viewpoint, it is desirable that a useful diamine can be obtained through a small number of steps. In this respect, according to method 3A, it is preferable to introduce two or more partial structures (a) into a specific diamine in a small number of steps.
[ chemical 15]
Figure BDA0003646807250000122
(in the formula (5), R 9 Is a single bond or a divalent organic radical)
In the method 3A, the compound represented by the formula (5) and the compound having the formula (2) — R 1 -A 1 -NH 2 "the corresponding amine compound of partial structure is optionally reacted in a solvent. The solvent is preferably an organic solvent capable of dissolving the raw material. In the method 3A, the reaction temperature is, for example, 0 to 80 ℃ and the reaction time is, for example, 30 minute to 12 hours.
In the formula (5), as R 9 Examples of the divalent organic group include a divalent hydrocarbon group having 1 to 20 carbon atoms, and a divalent group containing-O-, -S-, etc., between carbon-carbon bonds of the hydrocarbon group. For example, by reacting the compound represented by the above formula (5) with the compound represented by the following formula (7), the compound represented by the following formula (8) can be obtained as the specific diamine.
[ solution 16]
Figure BDA0003646807250000123
(in the scheme, R 9 Is a single bond or a divalent organic group. A. The 1 Has the same meaning as the formula (2), R 1 The same as the above formula (1)
(specific acid anhydride)
The specific acid anhydride is not particularly limited as long as it is a monomer having the partial structure (a) and two acid anhydride groups. Specifically, the specific acid anhydride is preferably at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4).
[ chemical formula 17]
Figure BDA0003646807250000131
(in formula (3) and formula (4), A 3 And A 4 Each independently is a trivalent aromatic ring group or an aliphatic ring group. m2 is an integer of 1 to 3. n1 and n2 are each independently an integer of 1 to 3. R 1 、R 2 、R 3 And R 4 The same as the formula (1). In the case where m2 is 2 or 3, plural R' s 1 ～R 4 Identical or different from each other)
In the above formulae (3) and (4), A is 3 And A 4 Examples of the trivalent aliphatic cyclic group include a ring part obtained by removing three hydrogen atoms from an alicyclic hydrocarbon ring such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring or a cycloheptane ringA group formed by son. The alicyclic hydrocarbon ring may have a substituent. As the substituents, there may be mentioned: an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, etc.
A 3 And A 4 The trivalent aromatic ring group is a group obtained by removing three hydrogen atoms from the ring portion of a substituted or unsubstituted aromatic ring. The aromatic ring is an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring or a nitrogen-containing aromatic heterocyclic ring. As the substituent introduced into the ring portion of the aromatic ring, there may be mentioned: an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, etc. From the viewpoint of achieving high density of the liquid crystal alignment film, A 3 、A 4 The trivalent aromatic ring group represented is preferably a group having a benzene ring, a biphenyl ring or a pyridine ring, and more preferably a group having a benzene ring.
A liquid crystal element A having a low Voltage Holding Ratio (VHR) drop even in long-term driving and having high reliability and a liquid crystal element exhibiting good liquid crystal alignment properties 3 And A 4 A trivalent aromatic ring group is preferable, and a trivalent group having a benzene ring is more preferable.
From the viewpoint of liquid crystal alignment properties and ease of synthesis, m2 is preferably 1 or 2. In addition, m2 is preferably 2 or more from the viewpoint of enhancing the improvement effect by the introduction portion structure (a).
Preferred specific examples of the specific acid anhydride include: a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), a compound represented by the following formula (4-1), and a compound represented by the following formula (4-2).
[ solution 18]
Figure BDA0003646807250000141
(in formulae (3-1) and (3-2), ar 3 And Ar 4 Each independently is a trivalent aromatic ring group. m2 is an integer of 1 to 3. R 3 、R 4 、R 11 、R 12 、R 13 、R 14 、R 15 And R 16 The same as the above formula (1-1) and formula (1-2)
[ formula 19]
Figure BDA0003646807250000142
(in the formulas (4-1) and (4-2), m2 is an integer of 1-3, n1 and n2 are each independently an integer of 1-3, R 3 、R 4 、R 11 、R 12 、R 13 、R 14 、R 15 And R 16 The same as the above formula (1-1) and formula (1-2)
In the above formula (3-1), formula (3-2), formula (4-1) and formula (4-2), R is R from the viewpoint of ease of synthesis of the compound 13 、R 14 、R 15 And R 16 Preferably a single bond.
Specific examples of the specific acid anhydride include compounds represented by the following formulae (4-1) to (4-3). In the compounds represented by the following formulae (4-1) to (4-3), the carbon-carbon unsaturated bond between the two carbonyl groups is not necessarily structurally different, and may be either a cis-isomer or a trans-isomer.
[ solution 20]
Figure BDA0003646807250000143
(Synthesis of specific acid anhydride)
The method for synthesizing the specific acid anhydride is not particularly limited. The specific acid anhydride can be produced, for example, by the following method: reacting fumaric chloride and a compound having an "-R" group in the formula (3) or the formula (4) 1 Method of reacting amine compound having partial structure corresponding to acid anhydride group "(method 1B). The specific acid anhydride can also be produced by using a compound represented by the following formula (5) as a raw material (method 2B). From an industrial viewpoint, it is desirable that a useful tetracarboxylic dianhydride can be obtained by a small number of steps. In this respect, according to method 2B, two or more portions can be introduced into a specific acid anhydride by a small number of stepsThe structure (a) is preferable.
[ solution 21]
Figure BDA0003646807250000151
(in the formula (5), R 9 Is a single bond or a divalent organic radical)
In the method 2B, the compound represented by the formula (5) and the compound having the formula- (Y-O) -R in the formula (3) or the formula (4) 1 The amine compound of the partial structure corresponding to the-acid anhydride group "is optionally reacted in a solvent. The solvent is preferably an organic solvent capable of dissolving the raw material. In the method 2B, the reaction temperature is, for example, 0 to 80 ℃ and the reaction time is, for example, 30 minutes to 12 hours.
In the formula (5), as R 9 Examples of the divalent organic group include a divalent hydrocarbon group having 1 to 20 carbon atoms, and a divalent group containing-O-, -S-, and the like, among carbon-carbon bonds of the hydrocarbon group. For example, by reacting the compound represented by the above formula (5) with the compound represented by the following formula (9), the compound represented by the following formula (10) can be obtained as the specific acid anhydride.
[ solution 22]
Figure BDA0003646807250000152
(in the scheme, R 9 Is a single bond or a divalent organic group. A. The 5 Is a single bond or an alkanediyl group. R 1 The same as the formula (1). n1 is an integer of 1 to 3)
< Polyamic acid >
When the polymer [ A ] is a polyamic acid, examples of the polyamic acid (hereinafter, also referred to as "polyamic acid [ A ]") include: a method of reacting a tetracarboxylic dianhydride comprising a specific acid dianhydride with a diamine compound; a method of reacting a tetracarboxylic dianhydride with a diamine compound containing a specific diamine, and the like. Further, the method of [ 1] above may be combined with the method of [2 ].
(tetracarboxylic dianhydride)
In the synthesis of the polyamic acid [ A ], one kind of tetracarboxylic dianhydride may be used alone, or two or more kinds may be used in combination. The tetracarboxylic dianhydride used for synthesizing the polyamic acid [ a ] may be only a specific acid dianhydride, or may include a tetracarboxylic dianhydride not having the partial structure (a) (hereinafter, also referred to as "other acid dianhydride"). Examples of the other acid dianhydrides include: chain aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, and the like.
Specific examples of the other acid dianhydrides include chain aliphatic tetracarboxylic dianhydrides: 1,2,3, 4-butanetetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, etc.; examples of the alicyclic tetracarboxylic dianhydride include: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2, 5-dioxotetrahydrofuran-3-yl) -3a,4,5,9b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 2,4,6, 8-tetracarboxybicyclo [3.3.0] octane-2-4,6-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 3,5, 6-tricarboxy-2-carboxymethylnorbornane-2-3, 5-6-dianhydride, and the like; examples of the aromatic tetracarboxylic dianhydride include: other than pyromellitic dianhydride, 4,4'- (hexafluoroisopropylidene) diphthalic anhydride, ethylene glycol bistrimellitic anhydride ester, 4,4' -carbonyldiphthalic anhydride, and 3,3',4,4' -biphenyltetracarboxylic dianhydride, tetracarboxylic dianhydride described in japanese unexamined patent publication No. 2010-97188 can be used.
In order to obtain a liquid crystal alignment film having high solubility and exhibiting good liquid crystal alignment properties and electrical characteristics, the other acid dianhydride used in the synthesis of polyamic acid [ a ] preferably contains at least one selected from the group consisting of a chain aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride, and more preferably contains an alicyclic tetracarboxylic dianhydride. The proportion of the alicyclic tetracarboxylic dianhydride used is preferably 20 mol% or more, more preferably 40 mol% or more, and still more preferably 50 mol% or more, based on the total amount of the tetracarboxylic dianhydride used for synthesizing the polyamic acid [ a ].
In the case of producing the polyamic acid [ a ] by the method [ 1], the use ratio of the specific acid dianhydride is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% or more with respect to the total amount of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid [ a ].
(diamine Compound)
In the synthesis of the polyamic acid [ A ], one kind of diamine compound may be used alone, or two or more kinds may be used in combination. The diamine compound used for the synthesis of the polyamic acid [ a ] may be only a specific diamine, or may include a diamine compound having no partial structure (a) (hereinafter, also referred to as "other diamine"). Examples of the other diamines include: chain aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like.
Specific examples of the other diamines include chain aliphatic diamines: m-xylylenediamine (meta-xylylenediamine), hexamethylenediamine, etc.; examples of the alicyclic diamine include: 1, 4-diaminocyclohexane, 4' -methylenebis (cyclohexylamine), and the like; examples of the aromatic diamine include: <xnotran> ,4,4' - ,4,4' - ,4- -4- ,4,4' - ,3,5- ,1,5- (4- ) ,1,2- (4- ) ,1,3- (4- ) ,1,6- (4- ) ,6,6 ' - ( ) (3- ), N, N ' - (5- -2- ) -N, N ' - ( ) , [2- (4- ) ] ,4,4' - ,4,4' - ,4,4' - ,2,2- [4- (4- ) ] ,2,2- (4- ) ,1,4- (4- ) ,4,4' - (4- ) ,2,2 ' - -4,4' - ,4,4' - ( ) ,2,6- ,2,4- ,3,6- , N- -3,6- , </xnotran> 3, 6-diaminoacridine, monomer containing diphenylamine structure, the following formula (F-1)
[ solution 23]
Figure BDA0003646807250000161
(in the formula (F-1), R 21 And R 22 Each independently is an alkanediyl group. R 23 Is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a protecting group. r1 is an integer of 1 to 3. In the case where R1 is 2 or 3, plural R' s 22 A plurality of R, which may be the same or different from each other 23 Identical or different from each other)
Main chain type diamines such as the compounds represented by the above;
hexadecyloxy-2, 4-diaminobenzene, octadecyloxy-2, 5-diaminobenzene, cholestanyloxy-3, 5-diaminobenzene, cholestanyloxy-2, 4-diaminobenzene, cholestanyl ester of 3, 5-diaminobenzoate, lanostanyl ester of 3, 5-diaminobenzoate, 3, 6-bis (4-aminobenzoyloxy) cholestane, 3, 6-bis (4-aminophenoxy) cholestane, 4- (4' -trifluoromethoxybenzoyloxy) cyclohexyl-3, 5-diaminobenzoate, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 3, 5-diaminobenzoic acid =5 ξ -cholestane-3-yl, the following formula (E-1)
[ formula 24]
Figure BDA0003646807250000171
(in the formula (E-1), X I And X II Each independently a single bond, -O-, -COO-or-OCO- (wherein "" represents a bond to the diaminophenyl side). R I An alkanediyl group having 1 to 3 carbon atoms. R is II Is a single bond or an alkanediyl group having 1 to 3 carbon atoms. R is III Is alkyl, alkoxy, fluoroalkyl or fluoroalkoxy with 1-20 carbon atoms. a is 0 or 1.b is an integer of 0 to 3. c is an integer of 0 to 2. d is 0 or 1. Wherein 1 ≦ a + b + c ≦ 3)
Side chain diamines such as the compounds represented by the above;
examples of the diaminoorganosiloxane include 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane.
Examples of the compound represented by the formula (F-1) include compounds represented by the following formulae (F-1-1) to (F-1-3). Examples of the compound represented by the formula (E-1) include compounds represented by the following formulae (E-1-1) to (E-1-4). As the other diamine, one kind may be used alone or two or more kinds may be used in combination. In the formula, "Boc" represents a t-butyloxycarbonyl group (the same applies hereinafter).
[ solution 25]
Figure BDA0003646807250000172
In the case of producing the polyamic acid [ a ] by the method [ 2], the ratio of the specific diamine to be used is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% or more with respect to the total amount of the diamine compound used for the synthesis of the polyamic acid [ a ].
(Synthesis of Polyamic acid)
The polyamic acid [ A ] can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound together with a molecular weight modifier as required. As a preferred mode of the production method of polyamic acid [ A ], the following methods can be mentioned: a tetracarboxylic dianhydride is reacted with a diamine compound using a monomer including at least one selected from the group consisting of the specific diamine obtained by the method 3A and the specific acid dianhydride obtained by the method 2B.
In the synthesis reaction of polyamic acid [ a ], the tetracarboxylic dianhydride and the diamine compound are preferably used in a ratio of 0.2 to 2 equivalents of acid anhydride groups of the tetracarboxylic dianhydride to 1 equivalent of amino groups of the diamine compound. Examples of the molecular weight modifier include: and acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less with respect to 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine compound used.
The synthesis reaction of the polyamic acid [ A ] is preferably carried out in an organic solvent. The reaction temperature in this case is preferably-20 ℃ to 150 ℃ and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used for the reaction include: aprotic polar solvent, phenol solvent, alcohol solvent, ketone solvent, ester solvent, ether solvent, halogenated hydrocarbon, etc. Among these solvents, it is preferable to use one or more solvents selected from the group consisting of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol, and halogenated phenol as the reaction solvent, or to use a mixture of one or more of these solvents and another organic solvent (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of the organic solvent used is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 50% by mass based on the total amount of the reaction solution.
Thus, a polymer solution in which the polyamic acid [ A ] is dissolved can be obtained. The polymer solution can be directly used for preparing the liquid crystal aligning agent, and also can be used for preparing the liquid crystal aligning agent after the polyamic acid [ A ] contained in the polymer solution is separated.
Polyamic acid ester
In the case where the polymer [ a ] is a polyamic acid ester, the polyamic acid ester (hereinafter, also referred to as "polyamic acid ester [ a ]") can be obtained, for example, by the following method or the like: [I] a method of reacting the polyamic acid [ A ] with an esterifying agent; [ II ] a method of reacting a tetracarboxylic acid diester with a diamine compound containing a specific diamine; [ III ] A method for reacting a tetracarboxylic acid diester dihalide with a diamine compound containing a specific diamine. The polyamic acid ester [ A ] may have only an amic acid ester structure or may be a partially esterified product in which an amic acid structure and an amic acid ester structure are present at the same time. The reaction solution obtained by dissolving the polyamic acid ester [ A ] may be used as it is for the production of the liquid crystal aligning agent, or may be used for the production of the liquid crystal aligning agent after the polyamic acid ester [ A ] contained in the reaction solution is separated.
Polyimide (II)
In the case where the polymer [ a ] is a polyimide, the polyimide (hereinafter, also referred to as "polyimide [ a") can be obtained, for example, by subjecting the polyamic acid [ a ] synthesized in the above manner to dehydrative ring closure and imidization. The polyimide [ a ] may be a fully imidized product obtained by dehydrating and ring-closing all of the amic acid structure of the polyamic acid [ a ] which is a precursor thereof, or may be a partially imidized product obtained by dehydrating and ring-closing only a part of the amic acid structure to allow the amic acid structure and the imide ring structure to coexist. The polyimide [ A ] preferably has an imidization ratio of 20 to 99%, more preferably 30 to 90%. The imidization ratio is a percentage of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of the polyimide. Here, a part of the imide ring may be an imide ring.
The dehydration ring-closure of polyamic acid [ A ] is preferably carried out by: polyamic acid [ A ] is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added to the solution, followed by heating as necessary. In the above method, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride or the like can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles based on 1 mole of the amic acid structure of the polyamic acid [ A ]. As the dehydration ring-closing catalyst, for example, there can be used: tertiary amines such as pyridine, collidine, lutidine and triethylamine. The dehydration ring-closing catalyst is preferably used in an amount of 0.01 to 10 mol based on 1mol of the dehydrating agent used. The organic solvent used in the dehydration ring-closure reaction may be an organic solvent exemplified as an organic solvent used for the synthesis of polyamic acid [ A ]. The reaction temperature of the dehydration ring-closure reaction is preferably 0 ℃ to 180 ℃. The reaction time is preferably 1.0 to 120 hours. Further, the reaction solution containing the polyimide [ A ] may be directly used for the preparation of the liquid crystal aligning agent, or the polyimide [ A ] may be separated and then used for the preparation of the liquid crystal aligning agent.
When the polymer [ A ] is at least one selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, the solution viscosity of the polymer [ A ] is preferably 10 mPas to 800 mPas, more preferably 15 mPas to 500 mPas when the solution is prepared to have a concentration of 10 mass%. The solution viscosity (mPas) is a value measured at 25 ℃ with an E-type rotational viscometer for a 10 mass% polymer solution prepared using a good solvent for the polymer [ A ] (e.g., γ -butyrolactone, N-methyl-2-pyrrolidone, etc.).
The weight average molecular weight (Mw) of the polymer [ A ] as measured by Gel Permeation Chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 7 or less, more preferably 5 or less. In the preparation of the liquid crystal aligning agent, one polymer [ a ] may be used alone, or two or more polymers may be used in combination.
< other ingredients >
The liquid crystal aligning agent may contain, in addition to the polymer [ A ], a component different from the polymer [ A ] (hereinafter, also referred to as "other component") as necessary.
Polymers [ Q ]
The liquid crystal aligning agent of the present disclosure may further contain a polymer not having the partial structure (a) (hereinafter, also referred to as "polymer [ Q ]") as a polymer component.
The main skeleton of the polymer [ Q ] is not particularly limited. Examples of the polymer [ Q ] include: polyamic acids, polyamic acid esters, polyimides, polyorganosiloxanes, polyesters, polyalkylenamines (polyanilines), polyureas, polyamides, polyamideimides, polybenzoxazole precursors, polybenzoxazoles, cellulose derivatives, polyacetals, (meth) acrylic polymers, styrene polymers, maleimide polymers, styrene-maleimide copolymers, and the like. From the viewpoint of obtaining a highly reliable liquid crystal device, the polymer [ Q ] is preferably at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polyorganosiloxanes, and addition polymers. Examples of the addition polymer include: a (meth) acrylic polymer, a styrene polymer, a maleimide polymer, a styrene-maleimide copolymer, and the like.
When the liquid crystal aligning agent of the present disclosure contains both the polymer [ a ] and the polymer [ Q ], the content ratio of the polymer [ Q ] is preferably 1 mass% or more, more preferably 2 mass% or more, based on the total amount of the polymer [ a ] and the polymer [ Q ]. The content of the polymer [ Q ] is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total amount of the polymer [ A ] and the polymer [ Q ]. The polymer [ Q ] may be used singly or in combination of two or more.
Solvent(s)
The liquid crystal aligning agent of the present disclosure is preferably prepared as a liquid composition in which the polymer component and other components used as necessary are dispersed or dissolved in an appropriate solvent.
As the solvent, an organic solvent can be preferably used. Specific examples thereof include: n-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 2-dimethyl-2-imidazolidinone, 1, 3-dimethyl-2-imidazolidinone, phenol, gamma-butyrolactone, gamma-butyrolactam, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, 1-hexanol, 2-hexanol, propane-1, 2-diol, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, methyl lactate, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl propionate, 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 (butyl cellosolve), 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 acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene glycol monomethyl ether (propylene glycol monomethyl ether, monomethylether, PGME), PGME, diethylene glycol acetate, propylene glycol monomethyl ether acetate, cyclohexanone, propylene glycol diacetate, and the like. The solvent may be used singly or in combination of two or more.
Other components contained in the liquid crystal aligning agent include, for example: crosslinking agents, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, and the like. The blending ratio of the other components may be appropriately selected depending on each compound within a range not impairing the effect of the present disclosure.
The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 10 mass%. When the solid content concentration is 1 mass% or more, a liquid crystal alignment film exhibiting a more excellent liquid crystal alignment property can be obtained by sufficiently securing the film thickness of the coating film, which is preferable. On the other hand, when the solid content concentration is 10% by mass or less, the following tendency is exhibited: the coating film can be formed to have an appropriate thickness, and a liquid crystal alignment film exhibiting good liquid crystal alignment properties can be easily obtained.
According to the present disclosure described above, the liquid crystal aligning agent shown below is provided.
< 1 > a liquid crystal aligning agent comprising a polymer [ A ] having a partial structure (a) represented by the formula (1) in the main chain.
< 2 > the liquid crystal aligning agent according to the < 1 >, wherein the polymer [ A ] comprises a structural unit derived from a diamine having the partial structure (a).
< 3 > the liquid crystal aligning agent according to < 2 > wherein the diamine is a compound represented by the formula (2).
< 4 > the liquid crystal aligning agent according to any one of the < 1 > to < 3 >, wherein the polymer [ A ] contains a structural unit derived from a tetracarboxylic acid derivative having the partial structure (a).
< 5 > the liquid crystal aligning agent according to the < 4 >, wherein the tetracarboxylic acid derivative is at least one selected from the group consisting of the compound represented by the formula (3) and the compound represented by the formula (4).
< 6 > the liquid crystal aligning agent according to any one of < 1 > -5 >, wherein the polymer [ A ] is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.
< 7 > the liquid crystal aligning agent according to any one of < 1 > - < 6 >, wherein the polymer [ A ] contains a structural unit derived from an alicyclic tetracarboxylic dianhydride.
< 8 > the liquid crystal aligning agent according to any one of the < 1 > - < 7 >, further comprising a polymer [ Q ] having no said partial structure (a).
Liquid crystal alignment film and liquid crystal element
The liquid crystal alignment film of the present disclosure may be manufactured by the liquid crystal aligning agent prepared in the manner described. In addition, the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal aligning agent described above. The driving method of the liquid crystal in the liquid crystal device is not particularly limited, and the liquid crystal can be applied to various modes such as TN mode, STN mode, VA mode (including VA-MVA mode, VA-Pattern Vertical Alignment (PVA) mode, and the like), IPS mode, FFS mode, optically Compensated Bend (OCB) mode, polymer Stabilized Alignment (PSA) mode, and the like. The liquid crystal element can be manufactured by a method including the following steps 1 to 3, for example. The substrate used in step 1 differs depending on the desired operation mode. Step 2 and step 3 are common to the respective operation modes.
< step 1: formation of coating film >
First, a liquid crystal aligning agent is applied to a substrate, preferably to a substrateThe coated surface is heated to form a coating film on the substrate. As the substrate, for example: float glass, soda glass, and the like; transparent substrates comprising plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly (alicyclic olefin). As the transparent conductive film provided on one surface of the substrate, a transparent conductive film containing tin oxide (SnO) can be used 2 ) A Nessel (NESA) film (registered trademark of PPG corporation, USA) containing indium oxide-tin oxide (In) 2 O 3 -SnO 2 ) Indium Tin Oxide (ITO) film, and the like. In the case of manufacturing a TN-type, STN-type, or VA-type liquid crystal cell, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS-type or FFS-type liquid crystal device, a substrate provided with electrodes patterned into a comb-tooth shape and an opposing substrate provided with no electrodes are used.
The method of applying the liquid crystal aligning agent to the substrate is not particularly limited. The liquid crystal alignment agent can be applied to the substrate by, for example, a spin coating method, a printing method (e.g., an offset printing method, a flexographic printing method, etc.), an ink jet method, a slit coating method, a bar coater method, an extrusion die (extrusion die) method, a direct gravure coater method, a chamber knife coater method, an offset gravure coater method, an immersion coater method, an MB coater method, or the like.
After the liquid crystal aligning agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing sagging of the applied liquid crystal aligning agent and the like. The pre-baking temperature is preferably 30-200 ℃, and the pre-baking time is preferably 0.25-10 minutes. Then, the solvent is completely removed, and a calcination (post-baking) step is performed for the purpose of thermal imidization of the amic acid structure present in the polymer, if necessary. The calcination temperature (post-baking temperature) in this case is preferably 80 to 280 ℃, more preferably 80 to 250 ℃. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the formed film is preferably 0.001 to 1 μm.
< step 2: orientation processing
In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal cell, a treatment (alignment treatment) of imparting liquid crystal alignment ability to the coating film formed in the above-described step 1 is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the alignment treatment, rubbing treatment in which the surface of a coating film formed on a substrate is wiped with cotton, nylon, or the like, or photo-alignment treatment in which the coating film is irradiated with light to impart liquid crystal alignment ability to the coating film is preferably used. In the case of producing a vertical alignment type liquid crystal device, the coating film formed in the step 1 may be used as it is as a liquid crystal alignment film, and the coating film may be subjected to an alignment treatment in order to further improve the liquid crystal alignment ability.
Light irradiation for photo-alignment can be performed by the following method or the like: a method of irradiating the coating film after the post-baking step; a method of irradiating the coating film after the pre-baking step and before the post-baking step; a method of irradiating the coating film during the heating of the coating film in at least one of the pre-baking step and the post-baking step. As the radiation irradiated to the coating film, for example, there can be used: ultraviolet rays and visible rays including light having a wavelength of 150nm to 800 nm. Preferably ultraviolet light containing light having a wavelength of 200nm to 400 nm. When the radiation is polarized light, the radiation may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these directions. The irradiation direction of unpolarized radiation is an oblique direction.
Examples of the light source used include: low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. The irradiation dose of the radiation is preferably 200J/m 2 ～30,000J/m 2 More preferably 500J/m 2 ～10,000J/m 2 . After the light irradiation for imparting alignment ability, the surface of the substrate may be irradiated with, for example, water, an organic solvent (e.g., methanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.), or a mixture thereofCleaning, or heating the substrate.
< step 3: construction of liquid Crystal cell (cell)
Two substrates on which liquid crystal alignment films are formed in this manner are prepared, and liquid crystal is disposed between the two substrates disposed in opposition to each other to produce a liquid crystal cell. In the production of a liquid crystal cell, for example, the following methods can be mentioned: a method of arranging two substrates so that liquid crystal alignment films face each other with a gap therebetween, bonding peripheral portions of the two substrates with a sealant, filling a cell gap surrounded by the substrate surfaces and the sealant with a filling liquid crystal, and sealing the filling hole, and a method of an One Drop Fill (ODF) method. As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. Examples of the liquid crystal include nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (nematic liquid crystal), and among them, nematic liquid crystal is preferable.
In the PSA mode, the following processes are performed: a polymerizable compound (for example, a polyfunctional (meth) acrylate compound or the like) is filled in a cell gap together with a liquid crystal, and after a liquid crystal cell is constructed, the liquid crystal cell is irradiated with light in a state where a voltage is applied between conductive films provided on a pair of substrates. In the production of a PSA mode liquid crystal device, the polymerizable compound is used in an amount of 0.01 to 3 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total liquid crystal.
In the case of manufacturing a liquid crystal display device, a polarizing plate is then bonded to the outer surface of the liquid crystal cell. Examples of the polarizing plate include: a polarizing plate in which a polarizing film called an "H film" obtained by stretching and orienting polyvinyl alcohol and absorbing iodine is sandwiched between cellulose acetate protective films, or a polarizing plate including an H film itself.
The liquid crystal element of the present disclosure can be effectively applied to various uses. Specifically, the present invention can be used as various display devices, light control devices, phase difference films, and the like, for example, for watches, portable game machines (portable game machines), word processors (word processors), notebook Personal computers (notebook Personal computers), car navigation systems (car navigation systems), video cameras (camcorders), personal Digital Assistants (PDAs), digital cameras (Digital cameras), cellular phones, smart phones, various monitors, liquid crystal televisions, information displays, and the like.
[ examples ]
The embodiments are described in more detail below with reference to examples, but the present invention is not to be construed as being limited to the following examples.
In the following examples, the imidization ratio of polyimide in the polymer solution was measured by the following method. The required amounts of the raw material compounds and the polymer used in the following examples were secured by repeating the synthesis on the synthesis scale shown in the following synthesis examples as necessary.
[ imidization ratio of polyimide ]
Adding polyimide solution into pure water, drying the obtained precipitate at room temperature under reduced pressure, dissolving in deuterated dimethyl sulfoxide, and performing reaction at room temperature with tetramethylsilane as reference substance 1 H-Nuclear Magnetic Resonance (NMR) measurement. According to the obtained 1 H-NMR Spectroscopy the percentage of imidization [% was determined by the following numerical formula (1)]。
Imidization rate [% ]]＝(1-(A 1 /(A 2 ×α)))×100···(1)
(in the numerical formula (1), A 1 Is the peak area of a proton derived from an NH group, A, occurring in the vicinity of a chemical shift of 10ppm 2 The peak area derived from other protons, and α is the ratio of the number of other protons to one proton of NH group in the precursor (polyamic acid) of the polymer)
The compounds are abbreviated as follows. In the following, the compound represented by the formula (X) may be simply referred to as "compound (X)".
(tetracarboxylic dianhydride)
[ solution 26]
Figure BDA0003646807250000231
[ solution 27]
Figure BDA0003646807250000232
(diamine Compound)
[ solution 28]
Figure BDA0003646807250000241
[ solution 29]
Figure BDA0003646807250000242
[ solution 30]
Figure BDA0003646807250000251
[ solution 31]
Figure BDA0003646807250000252
[ chemical No. 32]
Figure BDA0003646807250000261
(other Compounds)
[ chemical formula 33]
Figure BDA0003646807250000262
[ chemical 34]
Figure BDA0003646807250000271
< Synthesis of monomer >
1. Synthesis of Compound (DA-1), compound (DA-8) and Compound (DA-9)
The compound (DA-1), the compound (DA-8) and the compound (DA-9) were synthesized by a method similar to that described in Japanese patent No. 6013823. The following shows the production recipe of the compound (DA-1).
Synthesis of Compound (DA-1)
To a reaction vessel were added 30g (0.2 mol) of 4- (2-methylamino-ethyl) -phenylamine and 200ml of tetrahydrofuran. A solution of maleic anhydride (20 g, 0.2 mol) dissolved in tetrahydrofuran (30 ml) was added dropwise thereto under cooling in an ice bath, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid was collected by filtration, washed 3 times with 20ml of tetrahydrofuran, and dried at 60 ℃ for 3 hours to obtain a brown solid. Next, 30g (0.2 mol) of 4- (2-methylamino-ethyl) -phenylamine, 0.5g of dimethylaminopyridine and 100ml of dimethylformamide were put into a reaction vessel in which the obtained solid was placed. 38g (0.2 mol) of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride was added thereto under cooling in an ice bath, and stirred at room temperature overnight. After the reaction, 300ml of water was added, and the mixture was extracted 3 times with 300ml of ethyl acetate. After drying over sodium sulfate, the solvent was distilled off to obtain 28g of a brown viscous solid. To the resulting solid was added 80ml of methanol, and insoluble solids were collected by filtration, whereby 20g of compound (DA-1) was obtained as a brown solid. Of Compound (DA-1) 1 The results of H-NMR measurement are shown below.
1 H-NMR(300MHz,DMSO-d 6 )δppm:7.02(4H,d),6.53(4H,d),6.44(2H,s),3.22-3.57(10H,m),2.62(4H,t).
2. Synthesis of Compounds (DA-2) to (DA-7)
The compounds (DA-2) to (DA-7) were first prepared by a method described in the reference (journal OF Polymer SCIENCE (JOUNAL OF PLYMER SCIENCE): POLYMER CHEMISTRY EDITION 1975, VOL.13, 1691-1698) and a synthetic method using the obtained compounds (D-1) to (D-4) as intermediates. The following shows a production recipe of the compound (DA-2). Further, the compounds (DA-2) to (DA-7) are cis-isomers.
Synthesis of Compound (DA-2)
19.6g (0.2 mol) of maleic anhydride and 100ml of acetic acid were charged into the reaction vessel. A solution of hydrazine monohydrate 5.0g (0.1 mol) dissolved in acetic acid 25ml was added dropwise thereto. During the dropwise addition, the reaction temperature was controlled using an ice bath so that the reaction solution did not reach more than 25 ℃. After the completion of the dropwise addition, the mixture was allowed to stand for 3 hours, and the precipitate was collected by filtration and washed with 30ml of ethanol 3 times. Then, it was dried at 60 ℃ for 5 hours to obtain 21g of a pale yellow solid. The resulting solid was transferred to a reaction vessel, 110ml of thionyl chloride was added, and stirred at 75 ℃ for 6 hours. After the reaction, it was cooled to room temperature, and the precipitate was collected by filtration. The precipitate was washed with hexane and dried at 60 ℃ for 5 hours, whereby 10g (0.05 mol) of compound (D-1) was obtained. The resulting compound (D-1) was dissolved in 50ml of N-methyl-2-pyrrolidone, and 14g (0.1 mol) of 2- (4-aminophenyl) ethylamine was added dropwise over 30 minutes. After the dropwise addition, the reaction solution was stirred at room temperature for 1 hour, and the reaction solution was added to 500ml of water, whereby a precipitate was obtained. The obtained precipitate was collected by filtration, washed with water, and dried at 60 ℃ for 5 hours, whereby 20g of the compound (DA-2) was obtained. Process for producing Compound (DA-2) 1 The results of H-NMR measurement are shown below.
1 H-NMR(300MHz,DMSO-d 6 )δppm:8.96(2H,s),6.89(4H,m),6.51(4H,m),6.19-6.31(4H,m),3.29(4H,m),2.60(4H,m).
3. Synthesis of Compound (DA-10)
13.9g (0.1 mol) of 2-amino-5-nitropyridine, 7.9g (0.1 mol) of pyridine and 50ml of tetrahydrofuran were charged in a reaction vessel. To this was added dropwise a solution obtained by dissolving 7.6g (0.05 mol) of fumaric chloride in 25ml of tetrahydrofuran. After the end of the dropwise addition, the mixture was stirred at room temperature for 8 hours. The obtained reaction solution was poured into water, and the precipitate was collected by filtration. The obtained solid was washed with water and ethanol, and dried at 60 ℃ for 5 hours to obtain 14.5g of an intermediate as a brown solid. Subjecting the obtainedThe intermediate was transferred to a reaction vessel, to which 10wt% palladium on carbon (2 g) and N, N-dimethylformamide (30 ml) were added, and heated at 50 ℃ for 8 hours under a hydrogen atmosphere. After the reaction solution was filtered to remove the catalyst, the filtrate was poured into ice water, and the resulting precipitate was filtered and recovered. The resulting solid was washed with ethanol and dried at 60 ℃ for 5 hours, whereby 12.2g of the compound (DA-10) was obtained. Of Compound (DA-10) 1 The results of H-NMR measurement are shown below.
1 H-NMR(300MHz,DMSO-d 6 )δppm:11.2(2H,s),7.13-7.44(6H,m),6.18(2H,s).
4. Synthesis of Compound (DA-12)
Compound (DA-12) was synthesized in the same manner as in the synthesis of compound (DA-10) except that 4-nitroaniline was used instead of 2-amino-5-nitropyridine as the starting material.
5. Synthesis of Compound (DA-11)
13.9g (0.1 mol) of 2-amino-5-nitropyridine, 7.9g (0.1 mol) of pyridine and 50ml of tetrahydrofuran were charged in a reaction vessel. To this was added dropwise a solution obtained by dissolving 7.6g (0.05 mol) of fumaric chloride in 25ml of tetrahydrofuran. After the end of the dropwise addition, the mixture was stirred at room temperature for 8 hours. The obtained reaction solution was poured into water, and the precipitate was collected by filtration. The obtained solid was washed with water and ethanol, and dried at 60 ℃ for 5 hours to obtain 14.5g of an intermediate as a brown solid. The resulting intermediate was transferred to a reaction vessel, and 25ml of dimethylformamide was added. 18g (0.08 mmol) of di-tert-butyl dicarbonate was added thereto, and the mixture was stirred at room temperature for 16 hours. The reaction solution was dropped into water, and the precipitate was collected by filtration, washed with water, and dried at 60 ℃ for 3 hours to obtain 13.2g of a pale brown solid. The resulting solid was transferred to a reaction vessel, to which 10wt% palladium on carbon (1.8 g) and N, N-dimethylformamide (30 ml) were added, and heated at 50 ℃ for 8 hours under a hydrogen atmosphere. After the reaction solution was filtered to remove the catalyst, the filtrate was poured into ice water, and the resulting precipitate was filtered and recovered. The obtained solid was washed with ethanol and dried at 60 ℃ for 5 hours, whereby 9.8g of the compound was obtained(DA-11). Of Compound (DA-11) 1 The results of H-NMR measurement are shown below.
1 H-NMR(300MHz,DMSO-d 6 )δppm:8.09(2H,m),7.28-7.44(4H,m),6.93(2H,s),1.39(18H,s).
6. Synthesis of Compound (DA-13)
Compound (DA-13) was synthesized in the same manner as in the synthesis of (DA-11) except that 4-nitroaniline was used instead of 2-amino-5-nitropyridine as the starting material.
7. Synthesis of Compound (TA-1)
To the reaction vessel were added 11.5g (0.1 mol) of 3-aminodihydrofuran-2, 5-dione, 7.9g (0.1 mol) of pyridine and 300ml of tetrahydrofuran. The reaction mixture was cooled to 0 ℃ in an ice bath, and a solution prepared by dissolving 7.6g (0.05 mol) of fumaric chloride in 50ml of tetrahydrofuran was added dropwise thereto. After the completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours. After the reaction, the solvent was removed under reduced pressure. Then, 50g of acetic acid and 50g of acetic anhydride were added thereto, and the mixture was stirred at 100 ℃ for 3 hours. The obtained precipitate was collected by filtration, washed with acetic acid and n-hexane, and dried at 60 ℃ under reduced pressure for 5 hours to obtain compound (TA-1).
8. Synthesis of Compound (TA-2)
Compound (TA-2) was synthesized in the same manner as in the synthesis of compound (TA-1) except that 5-hydroxyisobenzofuran-1, 3-dione was used as a starting material instead of 3-aminodihydrofuran-2, 5-dione.
9. Synthesis of Compound (TA-3)
19.6g (0.2 mol) of maleic anhydride and 100ml of acetic acid were charged into a reaction vessel. A solution of hydrazine monohydrate 5.0g (0.1 mol) dissolved in acetic acid 25ml was added dropwise thereto. During the dropwise addition, the reaction temperature was controlled using an ice bath so that the reaction solution did not reach more than 25 ℃. After the completion of the dropwise addition, the mixture was allowed to stand for 3 hours, and the precipitate was collected by filtration and washed with 30ml of ethanol 3 times. Then, it was dried at 60 ℃ for 5 hours to obtain 21g of a pale yellow solid. The resulting solid was transferred to a reaction vessel, 110ml of thionyl chloride was added, and stirred at 75 ℃ for 6 hours. After the reaction, it was cooled to room temperature, and the precipitate was filtered. The precipitate was washed with hexane and dried at 60 ℃ for 5 hours, whereby 10g (0.05 mol) of compound (D-1) was obtained. The resulting compound (D-1) was dissolved in 50ml of N-methyl-2-pyrrolidone, and 11.5g (0.1 mol) of 3-aminodihydrofuran-2, 5-dione was added dropwise over 30 minutes. After the completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours. After the reaction, the solvent was removed under reduced pressure. Then, 50g of acetic acid and 50g of acetic anhydride were added thereto, and the mixture was stirred at 100 ℃ for 3 hours. The obtained precipitate was collected by filtration, washed with acetic acid and n-hexane, and dried at 60 ℃ under reduced pressure for 5 hours to obtain compound (TA-3). Further, the compound (TA-3) is a cis-isomer.
< Synthesis of Polymer >
1. Synthesis of Polyamic acid
[ Synthesis example 1]
100 parts by mole of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (compound (TB-1)) as a tetracarboxylic dianhydride and 100 parts by mole of compound (DA-2) as a diamine compound were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours to obtain a solution containing 15 mass% of polyamic acid (which was referred to as polymer (PAA-1)).
Further, the polymer (PAA-1) can also be obtained by using the compound (D-1) as an intermediate and conducting polymerization without using the isolated compound (DA-2). The different syntheses of the polymer (PAA-1) are shown below.
[ alternative Synthesis of PAA-1 ]
100 parts by mole of compound (D-1) was dissolved in N-methyl-2-pyrrolidone, and 200 parts by mole of 2- (4-aminophenyl) ethylamine was added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mole of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added as tetracarboxylic dianhydride, and the reaction was carried out at room temperature for 6 hours to obtain a solution containing 15 mass% of polymer (PAA-1).
Synthesis examples 2 to 24
Polyamic acids (polymers (PAA-2) to (PAA-20) and polymers (PAA-1) to (PAA-4)) were obtained in the same manner as in Synthesis example 1, except that the kinds and amounts of the tetracarboxylic dianhydride and diamine compound used were changed as described in Table 1. In table 1, the numerical values of the tetracarboxylic dianhydrides (acid dianhydride 1, acid dianhydride 2) represent the proportions (molar ratios) of the respective compounds relative to 100 parts by mole of the total amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid. The numerical values of the diamine compounds (diamine 1 to diamine 3) represent the ratio (molar ratio) of each compound to 100 parts by mole of the total amount of the diamine compounds used for synthesis of the polyamic acid.
[ Table 1]
Figure BDA0003646807250000301
2. Synthesis of polyimide
[ Synthesis example 25]
60 parts by mole of a compound (TB-1) and 40 parts by mole of a compound (TB-3) as tetracarboxylic dianhydride, 20 parts by mole of a compound (DA-2) as a diamine compound, 60 parts by mole of a compound (DB-2) and 20 parts by mole of a compound (DB-3) were dissolved in NMP and reacted at room temperature for 6 hours to obtain a solution containing 15 mass% of polyamic acid. Then, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 10% by mass, pyridine and acetic anhydride were added thereto, and a dehydration ring-closure reaction was performed at 60 ℃ for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was subjected to solvent substitution with fresh NMP to obtain a solution containing polyimide (polymer (PI-1)) having an imidization rate of about 80% by mass at 15%.
[ Synthesis examples 26 to 30]
Polyimides (polymers (PI-2) to (PI-3) and polymers (PI-1) to (PI-3)) were obtained in the same manner as in Synthesis example 25, except that the kinds and amounts of the tetracarboxylic dianhydride and diamine compound used were changed as described in Table 2. In table 2, the numerical values of the tetracarboxylic dianhydrides (acid dianhydride 1 to acid dianhydride 3) represent the proportions (molar ratios) of the respective compounds relative to 100 parts by mole of the total amount of the tetracarboxylic dianhydrides used in the synthesis of the polyimide. The numerical values of the diamine compounds (diamine 1 to diamine 4) represent the proportions (molar ratios) of the respective compounds relative to 100 parts by mole of the total amount of diamine compounds used in the synthesis of polyimide.
[ Table 2]
Figure BDA0003646807250000311
3. Synthesis of polyorganosiloxanes
Synthesis example 31
100.0g of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (compound (s-1)) was charged in a 1000ml three-necked flask, 500g of methyl isobutyl ketone and 10.0g of triethylamine were added thereto, and the mixture was mixed at room temperature. Then, after 100g of deionized water was added dropwise over 30 minutes from the addition funnel, mixed under reflux and reacted at 80 ℃ for 6 hours. After the reaction was completed, the organic layer was taken out, washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. A suitable amount of methyl isobutyl ketone was added to obtain a 50 mass% solution of a polymer of polyorganosiloxane with an epoxy group (ESSQ-1).
A500 ml three-necked flask was charged with 3.10g of compound (c-1) (20 mol% based on the amount of epoxy group in polymer (ESSQ-1)), 3.24g of compound (c-2) (10 mol% based on the amount of epoxy group in polymer (ESSQ-1)), 1.00g of tetrabutylammonium bromide, 20.0g of a solution containing polymer (ESSQ-1), and 290.0g of methyl isobutyl ketone, and the mixture was stirred at 90 ℃ for 18 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. Then, the organic layer was collected, and after concentration and dilution with NMP were repeated 2 times by a rotary evaporator, NMP was used to adjust the solid content concentration to 10 mass%, thereby obtaining an NMP solution of polyorganosiloxane (referred to as polymer (PSQ-1)).
4. Synthesis of styrene-maleimide copolymer
[ Synthesis example 32]
5.00g of compound (M-1), 1.05g of compound (M-2), 4.80g of compound (M-3), 2.26g of compound (M-4), 0.39g of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a radical polymerization initiator, 0.39g of 2, 4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 52.5mL of N-methyl-2-pyrrolidone (NMP) as a solvent were charged into a 100mL two-necked flask under nitrogen and polymerized at 70 ℃ for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum-dried at room temperature for 8 hours, thereby obtaining the objective polymer (which was designated as polymer (MI-1)).
5. Synthesis of polyamides
[ Synthesis example 33]
Reference is made to the synthesis described in the literature reference (journal OF Polymer SCIENCE (JOUNAL OF PLYMER SCIENCE): polymer CHEMISTRY EDITION (POLYMER CHEMISTRY EDITION) 1975, VOL.13, 1691-1698). 100 parts by mole of the compound (D-1) as a bisisomaleimide and 100 parts by mole of the compound (DB-18) as a diamine compound were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours to obtain a solution containing 15% by mass of a polyamide (referred to as a polymer (pa-1)).
< evaluation as Polymer >
Example 1: evaluation of residual amine and storage stability
1. Evaluation of residual amine
The solution of the polymer (PAA-1) obtained in Synthesis example 1 was added dropwise to acetone to precipitate the polymer. A portion of the supernatant was removed and evaluated by Liquid Chromatography (LC). The peak value of the diamine used as the raw material is observed and the peak value is "present" and the peak value is not observed and the peak value is "absent". As a result, the peak value of the residual amine in example 1 was "none".
2. Evaluation of storage stability
The storage stability of the polymer (PAA-1) solution obtained in Synthesis example 1 was evaluated by the rate of change ([ (D2-D1)/D1) ] × 100 (%)) between the solution viscosity D1 of the polymer solution immediately after preparation and the solution viscosity D2 after 7 days of storage at room temperature. The evaluation was "poor (x)", when the rate of change in viscosity was 5% or more, and was "good (o)", when the rate of change in viscosity was less than 5%. As a result, the storage stability in example 1 was "good (°)".
[ reference example 1]
The residual amine and the storage stability were evaluated in the same manner as in example 1, except that the polymer was changed as shown in table 3. The results are shown in table 3.
[ Table 3]
Class of polymers Residual amine Storage stability
Example 1 PAA-1 Is free of ○
Reference example 1 pa-1 Is provided with ×
As shown in Table 3, the polymer (PAA-1) had a smaller amount of residual amine than the polymer (pa-1) which is a polyamide, and also had good storage stability as a solution.
< preparation and evaluation of liquid Crystal alignment agent >
Example 2: friction FFS type liquid crystal display element
1. Preparation of liquid crystal aligning agent
The polymer (PAA-2) solution obtained in synthesis example 2 was diluted with NMP and Butyl Cellosolve (BC) to prepare a solution having a solvent composition of NMP/BC =80/20 (mass ratio) and a solid content concentration of 3.5 mass%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-1).
2. Manufacture of FFS type liquid crystal display element using rubbing method
A glass substrate (referred to as a first substrate) on one surface of which a plate electrode (bottom electrode), an insulating layer, and a comb-shaped electrode (top electrode) are sequentially laminated, and a glass substrate (referred to as a second substrate) on which no electrode is provided were prepared. Then, a liquid crystal aligning agent (AL-1) was applied to the electrode formation surface of the first substrate and the single surface of the second substrate using a spinner, and the resultant was heated (prebaked) for 3 minutes using a 110 ℃. Then, the film was dried (post-baked) in an oven at 230 ℃ in which nitrogen substitution was performed in the storage room for 30 minutes, to form a coating film having an average film thickness of 0.08. Mu.m. Then, the surface of the coating film was rubbed with a rubbing machine having a roller around which a rayon cloth was wound at a roller rotation speed of 1000rpm, a stage moving speed of 3 cm/sec and a capillary penetration length of 0.3 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a pair of substrates having liquid crystal alignment films.
Then, a liquid crystal injection port was left in the edge of the surface on which the liquid crystal alignment film was formed for the pair of substrates having the liquid crystal alignment film, and an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied by screen printing. Then, the substrates were stacked and pressed, and the adhesive was thermally cured at 150 ℃ for 1 hour. Then, a gap between the pair of substrates is filled with negative type liquid crystal (MLC-6608, manufactured by Merck) from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal cell was manufactured by heating the liquid crystal at 120 ℃ and then gradually cooling the liquid crystal to room temperature. When a pair of substrates is stacked, the rubbing method of the substrates becomes antiparallel.
3. Evaluation of liquid Crystal alignment Properties
The liquid crystal cell manufactured in the 2. Is 27,000cd/m 2 When the liquid crystal was left standing for 500 hours on the high-luminance backlight, the liquid crystal alignment was evaluated from the rate of change in retardation before and after irradiation of the backlight. First, retardation was measured using ecksu (Axoscan) manufactured by optoelectronics Science (Opto Science) in the liquid crystal display device manufactured in the above 2, and the change rate α of retardation before and after backlight irradiation was calculated using the following equation (z-1). It can be said that the smaller the change rate α, the better the liquid crystal alignment property. The case where the change rate α is 1% or less is "good (o)", the case where the change rate α is more than 1% and 2% or less is "acceptable (Δ)", and the case where the change rate α is more than 2% is "poor (x)".
α＝Δθ/θ1···(z-1)
(in the formula (z-1), Δ θ represents the retardation difference before and after irradiation, and θ 1 represents the retardation value before irradiation.)
As a result, the liquid crystal alignment properties of the examples were evaluated as "good (o)".
4. Evaluation of initial VHR
After the liquid crystal cell manufactured in 2. Above was left to stand in an oven at 60 ℃, a Voltage Holding Ratio (VHR) was measured under conditions of 1V and 1670msec using a VHR measuring device "VHR-1" manufactured by Toyo Technica corporation. As evaluation criteria, "good (°)" is set when VHR is higher than 70%, "acceptable (°)" is set when VHR is 70% or lower and 60% or higher, and "poor (×)" is set when VHR is lower than 60%. As a result, the initial VHR of the example was evaluated as "good (∘)".
Evaluation of VHR reliability
For the liquid crystal cell manufactured in the 2, reliability (VHR reliability) was evaluated by a voltage holding ratio. The evaluation was performed in the following manner. First, after a voltage of 1V was applied to the liquid crystal cell for 60 microseconds, a voltage holding ratio (VHR 1) was measured 1670 milliseconds after the release of the application. Then, the liquid crystal cell was irradiated with a Cold Cathode Fluorescent Lamp (CCFL) (backlight) for one week at 60 ℃, and then allowed to stand at room temperature to be naturally cooled to room temperature. After cooling, a voltage of 1V was applied to the liquid crystal cell for 60 microseconds, and then the voltage holding ratio (VHR 2) was measured 1670 milliseconds after the start of release of application. The measurement apparatus used was a VHR measurement apparatus "VHR-1" manufactured by Toyo Technica, inc. The rate of change of VHR (Δ VHR) at that time is calculated from the difference between VHR1 and VHR2 (Δ VHR = VHR1-VHR 2), and VHR reliability is evaluated from Δ VHR. When Δ VHR is less than 15%, it is determined as "good (°), when Δ VHR is 15% or more and 20% or less, it is determined as" acceptable (°), and when Δ VHR is more than 20%, it is determined as "poor (×)". As a result, the VHR reliability in the embodiment is "good (∘)".
6. Evaluation of film Strength (rub resistance)
The liquid crystal aligning agent (AL-1) prepared in the above 1. Was coated on a glass substrate using a spinner, and heated (pre-baked) for 3 minutes using a hot plate at 110 ℃. Then, the film was dried (post-baked) in an oven at 230 ℃ in which nitrogen substitution was performed in the storage room for 30 minutes, to form a coating film having an average film thickness of 0.08. Mu.m. For the coating film, the haze value of the coating film was measured using a haze meter. Then, the coating film was rubbed 5 times with a rubbing machine having a roller around which cotton cloth was wound at a roller rotation speed of 1000rpm, a stage moving speed of 3 cm/sec, and a capillary penetration length of 0.3 mm. Then, the haze value of the liquid crystal alignment film was measured using a haze meter, and the difference from the haze value before the rubbing treatment (haze change value) was calculated. When the haze value of the film before the rubbing treatment was Hz1 (%) and the haze value of the film after the rubbing treatment was Hz2 (%), the haze change value was represented by the following formula (z-2).
Haze Change value (%) = Hz2-Hz 1. Cndot. (z-2)
The liquid crystal alignment film was evaluated as "optimal (. Circleincircle.)" when the haze variation value was less than 0.5, as "good (. Smallcircle.)" when the haze variation value was 0.5 or more and less than 1.0, as "acceptable (. DELTA.)" when the haze variation value was 1.0 or more and 1.5 or less, and as "poor (. Times.)" when the haze variation value was more than 1.5. When the haze change value is 1.5 or less (more preferably less than 1.0, and even more preferably less than 0.5), the film strength is sufficiently high, the rubbing resistance is high, and the mechanical properties of the film are good. As a result, the film strength was evaluated as "good (o)" in the examples.
7. Evaluation of film Strength (resistance to Key test)
The liquid crystal cell produced in the 2. Was evaluated for resistance to a key press test. The evaluation was performed in the following manner. First, the liquid crystal cell was observed under crossed nicols using a polarizing microscope, and the number of bright spots was counted. Next, the liquid crystal cell is fixed on the fixed disk, and a load is repeatedly applied to the liquid crystal cell by moving the key bar up and down. The load at this time was 250gf, the number of repetitions was 10 ten thousand, and the speed was 10Hz/sec. After the key is pressed, the liquid crystal unit is observed again, and the number of the bright spots is counted. The evaluation is "optimal (excellent)" when the difference in the number of bright spots before and after the key press is less than 5, is "good (o)" when 5 or more and less than 10, is "acceptable (Δ)" when 10 or more and less than 50, and is "not acceptable (x)" when 50 or more. If the difference in the number of bright spots is less than 10 (more preferably less than 5), the film can be said to have good mechanical strength for the keys. As a result, the film strength was evaluated as "good (o)" in the examples.
Examples 2 to 15, comparative examples 2 and 3
Liquid crystal aligning agents were prepared in the same manner as in example 2, except that the composition of the liquid crystal aligning agent was changed as shown in table 4. Further, using the obtained liquid crystal aligning agent, an FFS type liquid crystal cell was produced by a rubbing method in the same manner as in example 2, and various evaluations were performed. These results are shown in table 4. In examples 3,4, 7, and 12 to 15, two kinds of polymers were used as polymer components. In table 4, the numerical values in the column of polymers represent blending ratios (parts by mass) of the respective polymers in terms of solid content with respect to 100 parts by mass of the total amount of the polymer components used in the preparation of the liquid crystal aligning agent.
[ Table 4]
Figure BDA0003646807250000351
As shown in table 4, examples 2 to 15 using the liquid crystal aligning agent containing the polymer [ a ] showed better or more excellent results in terms of film strength, particularly, resistance to a push-button test, than comparative examples 2 and 3 using the liquid crystal aligning agent not containing the polymer [ a ]. In examples 2 to 15, the liquid crystal alignment property and the initial VHR and VHR reliability were also good.
Example 16: optical FFS type liquid crystal display element
1. Preparation of liquid crystal aligning agent
A solution containing 30 parts by mass of the polymer (PAA-15) obtained in synthesis example 15 and a solution containing 70 parts by mass of the polymer (PAA-2) obtained in synthesis example 18 were mixed and diluted with NMP and BC to prepare a solution having a solvent composition of NMP/BC =80/20 (mass ratio) and a solid content concentration of 3.5 mass%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-17).
2. Manufacture of FFS type liquid crystal display element using optical alignment method
The same first substrate and second substrate as in example 1 were prepared. Then, a liquid crystal aligning agent (AL-17) was applied to the electrode formation surface of the first substrate and the surface of one of the second substrates using a spinner, and the resultant was heated (prebaked) for 1 minute using a hot plate at 80 ℃. Then, the resultant was dried in an oven at 230 ℃ in which nitrogen was substituted in the chamber (post-baking) for 30 minutes to form a coating film having an average film thickness of 0.1. Mu.m. The obtained coating film was irradiated with ultraviolet rays of 1,000J/m containing a linearly polarized 254nm bright line from the substrate normal direction using an Hg-Xe lamp 2 And photo-alignment treatment is performed. The irradiation dose is a value measured by using a light quantity meter measured with a wavelength of 254nm as a reference. Then, the photo-alignment treated coating film was heated in a clean oven at 230 ℃ for 30 minutes to be heat-treated, thereby forming a liquid crystal alignment film.
Next, an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied to one of the pair of substrates on which the liquid crystal alignment film was formed by screen printingThe outer edge of the face having the liquid crystal alignment film. Then, the substrates were laminated and pressure-bonded so that the projection direction of the polarizing axis on the substrate surface was antiparallel to each other at the time of light irradiation, and the adhesive was thermally cured at 150 ℃ for 1 hour. Then, a negative type liquid crystal (MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive to obtain a liquid crystal cell. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal was heated at 120 ℃ and then gradually cooled to room temperature. The ultraviolet irradiation amount after post-baking was 100J/m 2 ～10,000J/m 2 The above-described series of operations was performed while changing the range of (a) to (b), three or more liquid crystal cells having different ultraviolet irradiation amounts were manufactured, and the liquid crystal cell having the exposure amount (optimum exposure amount) showing the best alignment property was used for the following evaluation of the liquid crystal alignment property, initial VHR, VHR reliability, and film strength.
3. Evaluation of
For the liquid crystal cell manufactured in the 2, the liquid crystal alignment property, the initial VHR, and the VHR reliability were evaluated by the same method as in example 2. Further, the film strength was evaluated in the same manner as in example 2 using the liquid crystal aligning agent (AL-17). The evaluation results are shown in table 5.
Examples 17 to 23, comparative examples 4 and 5
A liquid crystal aligning agent was prepared in the same manner as in example 16, except that the composition of the liquid crystal aligning agent was changed as shown in table 5. Further, using the obtained liquid crystal aligning agent, an FFS type liquid crystal cell was produced by a photo-alignment method in the same manner as in example 16, and various evaluations were performed. The results are shown in table 5. In example 23 and comparative example 5, N '-tetraglycidyl-4, 4' -diaminodiphenylmethane (compound (N-1)) was blended as an additive component together with the polymer component. In table 5, the numerical values in the column of the polymer indicate the blending ratio (parts by mass) of each polymer in terms of solid content with respect to 100 parts by mass of the total amount of solid components (polymer components and additive components) used in the preparation of the liquid crystal aligning agent.
[ Table 5]
Figure BDA0003646807250000361
As shown in table 5, the results of examples 16 to 23 using the liquid crystal aligning agent containing the polymer [ a ] were better or more optimal in terms of film strength, particularly, resistance to a push-button test, than those of comparative examples 4 and 5 using the liquid crystal aligning agent not containing the polymer [ a ], and the liquid crystal aligning property and the initial VHR and VHR reliability were balanced.
Example 24: PSA type liquid crystal display element
1. Preparation of liquid crystal aligning agent
A solution containing 5 parts by mass of the polymer (PSQ-1) obtained in synthesis example 31 and a solution containing 95 parts by mass of the polymer (PI-3) obtained in synthesis example 27 were mixed and diluted with NMP and BC to prepare a solution having a solvent composition of NMP/BC =50/50 (mass ratio) and a solid content concentration of 3.5 mass%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-27).
2. Preparation of liquid Crystal composition
A liquid crystal composition LC1 was obtained by adding and mixing 5 mass% of a liquid crystal compound represented by the following formula (L1-1) and 0.3 mass% of a photopolymerizable compound represented by the following formula (L2-1) to 10g of nematic liquid crystal (MLC-6608, merck).
[ solution 35]
Figure BDA0003646807250000371
Production of PSA type liquid Crystal display element
The prepared liquid crystal aligning agent (AL-27) was applied to the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, prebaked on a hot plate at 80 ℃ for 1 minute, and then heated in an oven substituted with nitrogen at 200 ℃ for 1 hour to remove the solvent, thereby forming a coating film (liquid crystal alignment film) having a film thickness of 0.08 μm. The coating film was rubbed with a rubbing machine having a roller around which rayon cloth was wound at a roller rotation speed of 400rpm, a stage moving speed of 3 cm/sec and a capillary penetration length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. The operation was repeated to obtain a pair (two) of substrates having liquid crystal alignment films. The rubbing treatment is a weak rubbing treatment for the purpose of controlling collapse of the liquid crystal and performing alignment division by a simple method.
An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied by screen printing to the outer periphery of the surface having the liquid crystal alignment film of one of the substrates, and then the liquid crystal alignment films of the pair of substrates were faced to each other, stacked and pressure bonded, and the adhesive was heat-cured by heating at 150 ℃ for 1 hour. Then, after filling the gap between the substrate and the liquid crystal composition LC1 from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive, and further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal was heated at 150 ℃ for 10 minutes and then gradually cooled to room temperature.
Then, an AC 10V was applied between the electrodes at a frequency of 60Hz to the obtained liquid crystal cell, and the UV irradiation apparatus using a metal halide lamp as a light source was set to 50,000J/m in a state of liquid crystal driving 2 The irradiation amount of (3) is irradiated with ultraviolet rays. The irradiation dose is a value measured by using a light meter which measures with a wavelength of 365nm as a reference. Thus, a PSA type liquid crystal cell was manufactured.
4. Evaluation of
For the liquid crystal cell manufactured in the above 3, the liquid crystal alignment property, the initial VHR, the VHR reliability, and the film strength were evaluated by the same method as in example 2. The evaluation results are shown in table 6.
Comparative example 6
A liquid crystal aligning agent was prepared in the same manner as in example 24, except that the composition of the liquid crystal aligning agent was changed as shown in table 6. Further, a PSA-type liquid crystal cell was produced using the obtained liquid crystal aligning agent in the same manner as in example 24, and various evaluations were performed. The evaluation results are shown in table 7. In table 7, the numerical values in the column of the polymer indicate the blending ratio (parts by mass) of each polymer in terms of solid content with respect to 100 parts by mass of the total amount of the polymer components used in the preparation of the liquid crystal aligning agent.
[ Table 6]
Figure BDA0003646807250000372
As shown in table 6, in example 24 using the liquid crystal aligning agent containing the polymer [ a ], the liquid crystal alignment property, the initial VHR and the VHR reliability were all evaluated well, and the film strength was evaluated optimally. On the other hand, in comparative example 6 using the liquid crystal aligning agent not containing the polymer [ A ], the film strength (rubbing resistance) was evaluated as "ok", and the film strength (resistance to key test) was evaluated as "bad".
Example 25: optical VA type liquid crystal display element
1. Preparation of liquid crystal aligning agent
A solution containing 30 parts by mass of the polymer (MI-1) obtained in synthesis example 32 and a solution containing 70 parts by mass of the polymer (PAA-14) obtained in synthesis example 14 were mixed and diluted with NMP and BC to prepare a solution having a solvent composition of NMP/BC =80/20 (mass ratio) and a solid content concentration of 3.5 mass%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-29).
2. Production of optical VA type liquid crystal display element
The prepared liquid crystal aligning agent (AL-29) was coated on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, and pre-baked on a hot plate at 80 ℃ for 1 minute. Then, the resultant was heated at 230 ℃ for 1 hour in an oven in which the inside of the container was replaced with nitrogen to form a coating film having a thickness of 0.1 μm. Then, the surface of the coating film was irradiated with polarized ultraviolet light 1,000J/m containing 313nm bright lines from a direction inclined at 40 ℃ from the substrate normal line using an Hg-Xe lamp and a Glan-Taylor prism (glan-taylor prism) 2 Thereby imparting the liquid crystal alignment ability. Repeat (R) toThe same operation was performed to produce a pair (two) of substrates having liquid crystal alignment films.
After an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of one of the substrates by screen printing, the liquid crystal alignment film surfaces of the pair of substrates were opposed to each other, and pressure-bonded so that the optical axes of ultraviolet rays of the respective substrates were antiparallel to each other in the projection direction of the substrate surfaces, and the adhesive was heat-cured at 150 ℃ for 1 hour. Then, a gap between the substrates was filled with negative type liquid crystal (MLC-6608, manufactured by Merck) from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal was heated at 130 ℃ and then gradually cooled to room temperature.
3. Evaluation of
For the liquid crystal cell manufactured in the 2 above, the liquid crystal alignment property, the initial VHR, the VHR reliability, and the film strength were evaluated by the same method as example 2. The evaluation results are shown in table 7.
Comparative example 7
A liquid crystal aligning agent was prepared in the same manner as in example 25, except that the composition of the liquid crystal aligning agent was changed as shown in table 7. Using the obtained liquid crystal aligning agent, a light VA liquid crystal cell was produced in the same manner as in example 25, and various evaluations were performed. These results are shown in table 7. In table 7, the numerical values in the column of polymers represent blending ratios (parts by mass) of the respective polymers in terms of solid content with respect to 100 parts by mass of the total amount of the polymer components used in the preparation of the liquid crystal aligning agent.
[ Table 7]
Figure BDA0003646807250000381
As shown in table 7, in example 25 in which the liquid crystal aligning agent containing the polymer [ a ] was used, the liquid crystal alignment property, the initial VHR and the VHR reliability were all evaluated well, and the film strength was evaluated optimally. On the other hand, in comparative example 7 in which the liquid crystal aligning agent containing no polymer [ A ] was used, the film strength (rubbing resistance) was evaluated as "ok", and the film strength (resistance to key test) was evaluated as "bad".
From the above results, it is clear that: according to the liquid crystal aligning agent containing the polymer having the partial structure (a) in the main chain, a liquid crystal element having good liquid crystal aligning property, high voltage holding ratio and excellent reliability can be obtained, and high hardening film strength can be obtained.

Claims (14)

1. A liquid crystal aligning agent comprising a polymer [ A ] having a partial structure (a) represented by the following formula (1) in the main chain,
Figure FDA0003646807240000011
in the formula (1), R 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to a carbonyl group in the formula (1); r is 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 A ring structure formed by the bonded carbons; r 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; r is 7 And R 8 Each independently a hydrogen atom or a monovalent organic group; "" indicates a bond.
2. The liquid crystal aligning agent according to claim 1, wherein the polymer [ A ] contains a structural unit derived from a diamine having the partial structure (a).
3. The liquid crystal aligning agent according to claim 2, wherein the diamine is a compound represented by the following formula (2),
Figure FDA0003646807240000012
in the formula (2), A 1 And A 2 Each independently is a single bond, a divalent alicyclic group or a divalent aromatic ring group; m1 is an integer of 1 to 3; r is 1 、R 2 、R 3 And R 4 The same as the formula (1); in the case where m1 is 2 or 3, plural R' s 1 ～R 4 The same or different from each other.
4. The liquid crystal aligning agent according to claim 1, wherein the polymer [ A ] comprises a structural unit derived from a tetracarboxylic acid derivative having the partial structure (a).
5. The liquid crystal aligning agent according to claim 4, wherein the tetracarboxylic acid derivative is at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4),
Figure FDA0003646807240000021
in the formulas (3) and (4), A 3 And A 4 Each independently is a trivalent aromatic ring group or an aliphatic ring group; m2 is an integer of 1 to 3; n1 and n2 are each independently an integer of 1 to 3; r is 1 、R 2 、R 3 And R 4 The same as the formula (1); in the case where m2 is 2 or 3, plural R' s 1 ～R 4 The same or different from each other.
6. The liquid crystal aligning agent according to claim 1, wherein the polymer [ A ] is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.
7. The liquid crystal aligning agent according to claim 6, wherein the polymer [ A ] comprises a structural unit derived from an alicyclic tetracarboxylic dianhydride.
8. The liquid crystal aligning agent according to claim 1, further comprising a polymer [ Q ] having no said partial structure (a).
9. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 8.
10. A liquid crystal cell comprising the liquid crystal alignment film according to claim 9.
11. A polyamic acid, a polyamic acid ester, and a polyimide, having a partial structure represented by the following formula (1) in a main chain,
Figure FDA0003646807240000022
in the formula (1), R 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to a carbonyl group in the formula (1); r 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 A ring structure formed by the bonded carbons; r 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; r 7 And R 8 Each independently a hydrogen atom or a monovalent organic group; "" indicates a bond.
12. A process for producing a diamine, which comprises using a compound represented by the following formula (5) as a raw material to produce a diamine represented by the following formula (2),
Figure FDA0003646807240000023
in the formula (5), R 9 Is a single bond or a divalent organic radical
Figure FDA0003646807240000031
In the formula (2), A 1 And A 2 Each independently is a single bond, a divalent alicyclic group or a divalent aromatic ring group; r 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to the carbonyl group in the formula (2); r 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 A ring structure formed by the bonded carbons; r 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; r is 7 And R 8 Each independently is a hydrogen atom or a monovalent organic group; m1 is an integer of 1 to 3; in the case where m1 is 2 or 3, plural R' s 1 ～R 4 The same or different from each other.
13. A method for producing a tetracarboxylic dianhydride, wherein a tetracarboxylic dianhydride represented by the following formula (3) or (4) is produced by using a compound represented by the following formula (5) as a raw material,
Figure FDA0003646807240000032
in the formula (5), R 9 Is a single bond or a divalent organic radical
Figure FDA0003646807240000033
In the formulae (3) and (4), A 3 And A 4 Each independently is a trivalent aromatic ring group or an aliphatic ring group; r 1 And R 2 Each independently is a utilization of-C (R) 5 )(R 6 )-、-O-、-S-、-CO-、-COO-、-NR 7 -、-NR 7 -NR 8 -、-NR 7 -CO-O-、-NR 7 -CO-NR 8 A divalent group in which an aromatic hydrocarbon ring, an aromatic heterocyclic ring or a nitrogen-containing non-aromatic heterocyclic ring is bonded to the carbonyl group in the formulae (3) and (4); r is 3 And R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, or R 3 And R 4 Are combined with each other and R 3 Bound carbon and R 4 A ring structure formed by the bonded carbons; r is 5 And R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; r 7 And R 8 Each independently is a hydrogen atom or a monovalent organic group; m2 is an integer of 1 to 3; n1 and n2 are each independently an integer of 1 to 3; in the case where m2 is 2 or 3, plural R' s 1 ～R 4 The same or different from each other.
14. A method for producing a polymer, wherein the polyamic acid, polyamic acid ester, and polyimide according to claim 11 are produced by polymerization of a monomer using at least one compound selected from the group consisting of a diamine obtained by the production method according to claim 12 and a tetracarboxylic dianhydride obtained by the production method according to claim 13.
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