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CN114702393A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

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

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Publication number
CN114702393A
CN114702393A CN202210349222.9A CN202210349222A CN114702393A CN 114702393 A CN114702393 A CN 114702393A CN 202210349222 A CN202210349222 A CN 202210349222A CN 114702393 A CN114702393 A CN 114702393A
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liquid crystal
substrate
formula
display element
film
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永井健太郎
铁谷尚士
石井秀则
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
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    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
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    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

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Abstract

The invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element. According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element, which is provided with an alignment control ability with high efficiency and has excellent afterimage characteristics, an in-plane-switching-type liquid crystal display element having the substrate, and a compound for providing the same, and more specifically, a novel diamine which can improve reliability without affecting alignment properties by adding a small amount.

Description

Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
The present application is a divisional application of chinese patent application having an application date of 2017, 12 and 20, and an application number of 201780086602.5, entitled "liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element".
Technical Field
The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element for manufacturing a liquid crystal display element having excellent after-image characteristics.
Background
Liquid crystal display elements are known as display devices that are lightweight, thin, and consume low power, and have been used for large-sized televisions and the like in recent years, and remarkable progress has been made. The liquid crystal display element is configured by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes, for example. Also, in the liquid crystal display element, an organic film formed of an organic material is used as a liquid crystal alignment film to cause the liquid crystal to assume a desired alignment state between the substrates.
That is, the liquid crystal alignment film is a component of the liquid crystal display element, is formed on a surface of the substrate that is in contact with the liquid crystal and holds a role of aligning the liquid crystal in a specific direction between the substrates. In addition, the liquid crystal alignment film is sometimes required to have a function of aligning the liquid crystal in a specific direction, for example, a direction parallel to the substrate, and a function of controlling the pretilt angle of the liquid crystal. The ability of such a liquid crystal alignment film to control the alignment of liquid crystals (hereinafter referred to as alignment control ability) is imparted by performing alignment treatment on an organic film constituting the liquid crystal alignment film.
As an alignment treatment method of a liquid crystal alignment film for imparting alignment controllability, a brushing method has been known. The brushing method refers to the following method: the surface of an organic film of polyvinyl alcohol, polyamide, polyimide, or the like on a substrate is rubbed (brushed) with a cloth of cotton, nylon, polyester, or the like in a certain direction, thereby aligning the liquid crystal in the rubbing direction (brushing direction). This brushing method is used in the manufacturing process of a conventional liquid crystal display element because it can easily realize a relatively stable liquid crystal alignment state. As the organic film used for the liquid crystal alignment film, a polyimide-based organic film having excellent reliability such as heat resistance and electrical characteristics is mainly selected.
However, the brush rubbing method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like has a problem of generation of dust and static electricity. Further, in recent years, the resolution of liquid crystal display elements has been increased, and unevenness due to electrodes on substrates or switching active elements for driving liquid crystals has resulted in the case where the surface of a liquid crystal alignment film is not uniformly rubbed with a cloth, and uniform liquid crystal alignment cannot be achieved.
Therefore, as another alignment treatment method of a liquid crystal alignment film without brushing, a photo-alignment method has been actively studied.
In the photo-alignment method, there are various methods of forming anisotropy in an organic film constituting a liquid crystal alignment film using linearly polarized light or collimated light, and aligning liquid crystal according to the anisotropy.
As a main photo-alignment method, a decomposition type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet light, and the molecular structure is decomposed anisotropically by utilizing the polarization dependence of ultraviolet absorption. Then, the liquid crystal is aligned by the polyimide remaining without decomposition (see, for example, patent document 1).
Further, photo-alignment methods of photo-crosslinking type and photo-isomerization type are also known. For example, polyvinyl cinnamate is irradiated with polarized ultraviolet rays to cause dimerization reaction (crosslinking reaction) of double bond moieties of 2 side chains parallel to polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, non-patent document 1). In addition, when a side chain type polymer having azobenzene in a side chain is used, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene portion of the side chain parallel to the polarized light, thereby aligning the liquid crystal in a direction perpendicular to the polarization direction (see, for example, non-patent document 2).
As in the above example, in the method of aligning the liquid crystal alignment film by the photo-alignment method, it is not necessary to perform brushing, and there is no fear of generation of dust or static electricity. Further, the alignment treatment can be performed even on the substrate of the liquid crystal display element having the surface with irregularities, and thus the method for aligning the liquid crystal alignment film is suitable for an industrial production process.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3893659
Non-patent document
Non-patent document 1: m.shadt et al, jpn.j.appl.phys.31,2155(1992).
Non-patent document 2: k.ichimura et al, chem.rev.100,1847(2000).
Disclosure of Invention
Problems to be solved by the invention
As described above, the photo-alignment method has a significant advantage in that it does not require a brushing process, as compared with a brushing method which has been used industrially as an alignment treatment method for a liquid crystal display element. In addition, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light, compared to the brushing method in which the alignment control ability is substantially fixed by brushing. However, in the case of the photo-alignment method, when it is intended to achieve the same degree of alignment controllability as that in the case of the rubbing method, a large amount of polarized light irradiation is required, or stable liquid crystal alignment cannot be achieved in some cases.
For example, in the decomposition type photo-alignment method described in patent document 1, it is necessary to irradiate the polyimide film with ultraviolet light or the like emitted from a high-pressure mercury lamp with a power of 500W for 60 minutes, and it is necessary to irradiate a large amount of ultraviolet light for a long time. In addition, in the case of the dimerization type or photoisomerization type photoalignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required. Further, in the photo-alignment method of photo-crosslinking type or photo-isomerization type, since thermal stability and photo stability of liquid crystal alignment are poor, there is a problem that alignment failure occurs and afterimage is displayed when a liquid crystal display element is manufactured. In particular, in the case of a transverse electric field driven liquid crystal display element, since liquid crystal molecules are switched in a plane, liquid crystal alignment shift after liquid crystal driving is likely to occur, and display afterimage due to AC driving becomes a significant problem.
Therefore, in the photo-alignment method, it is required to achieve high efficiency of alignment treatment and stable liquid crystal alignment, and a liquid crystal alignment film, a liquid crystal alignment agent, and a compound providing the same, which can efficiently impart high alignment controllability to the liquid crystal alignment film, are required.
An object of the present invention is to provide a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which is provided with an alignment controllability with high efficiency and has excellent afterimage characteristics, a transverse electric field driven liquid crystal display element having the substrate, and a compound for providing the same, and more specifically, a novel diamine which can be added in a small amount to improve reliability without affecting alignment properties.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, have found the following means.
1. A liquid crystal aligning agent contains a polymer obtained from a diamine component containing a diamine having a structure represented by the following formula (1), and an organic solvent.
Figure BDA0003578692730000041
(in the formula (1), X is a single bond or a 2-valent organic group, Y and Z are each independently a 2-valent organic group containing an alkylene group, R1And R2Each independently of the other is a valence of 1Organic radical, R3Is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4. )
2. The liquid crystal aligning agent according to claim 1, which comprises at least 1 polymer selected from the group consisting of a polyimide precursor and a polyimide that is an imide thereof, and an organic solvent, wherein the polyimide precursor is a polymer comprising a diamine component of the diamine and a tetracarboxylic dianhydride.
3. The liquid crystal aligning agent according to the above 1 or 2, wherein the diamine is represented by the following formula (2).
Figure BDA0003578692730000042
(in the formula (2), X, Y, Z, R1～R3M and n are as defined above for formula (1). )
4. The liquid crystal aligning agent according to any one of the above 1 to 3, wherein the polyimide precursor is represented by the following formula (3).
Figure BDA0003578692730000051
(in the formula (3), X1Is a 4-valent organic radical derived from a tetracarboxylic acid derivative, Y1Is a 2-valent organic radical derived from a diamine comprising the structure of formula (1), R11Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R3Is an alkyl group having 1 to 4 carbon atoms. )
5. The liquid crystal aligning agent according to the above 4, wherein in the formula (3), X1The structural formula (A) is at least 1 selected from the group consisting of the following structural formulae (A-1) to (A-21).
Figure BDA0003578692730000052
6. The liquid crystal aligning agent according to the above 4 or 5, wherein the polymer having the structural unit represented by the above formula (3) is contained in an amount of 10 mol% or more based on the total polymer contained in the liquid crystal aligning agent.
7. The liquid crystal aligning agent according to any one of claims 4 to 6, wherein the organic solvent contains at least 1 selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether.
8. A method for manufacturing a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, the method comprising the steps of:
a step [ I ] of applying the composition according to any one of 1 to 7 on a substrate having a conductive film for driving a transverse electric field to form a coating film;
a step [ II ] of irradiating the coating film obtained in [ I ] with polarized ultraviolet light; and
and (III) heating the coating film obtained in (II).
9. A substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which is produced by the method described in the above 8.
10. A transverse electric field driven liquid crystal display element comprising the substrate according to claim 9.
11. A method for manufacturing a transverse electric field driven liquid crystal display element, comprising the steps of:
a step of preparing a 1 st substrate which is the substrate described in the above 9;
a step of obtaining a 2 nd substrate having a liquid crystal alignment film, the liquid crystal alignment film being provided with an alignment control capability by including the following steps [ I ' ], [ II ' ], and [ III ' ]; and
a step [ IV ] of disposing the 1 st substrate and the 2 nd substrate in opposition to each other with the liquid crystal alignment films of the 1 st substrate and the 2 nd substrate facing each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element,
the steps [ I ' ], [ II ' ], and [ III ' ] are:
a step [ I' ] of applying the composition according to claims 1 to 7 on a 2 nd substrate to form a coating film;
a step [ II '] of irradiating the coating film obtained in [ I' ] with polarized ultraviolet rays;
step [ III '], the coating film obtained in [ II' ] is heated.
12. A transverse electric field drive type liquid crystal display element produced by the method as recited in the above 11.
13. A polymer which is at least 1 polymer selected from the group consisting of polyimide which is a polyimide precursor and imide thereof, wherein the polyimide precursor is a polymer of a diamine component of a diamine having a structure represented by the following formula (1) and a tetracarboxylic dianhydride,
Figure BDA0003578692730000071
(in the formula (1), X is a single bond or a 2-valent organic group, Y and Z are each independently a 2-valent organic group containing an alkylene group, R1And R2Each independently is a 1-valent organic radical, R3Is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4. )
14. The polymer according to 13, wherein the diamine is represented by the following formula (2).
Figure BDA0003578692730000072
(in the formula (2), X, Y, Z, R1～R3M and n are as defined above for formula (1). )
15. The polymer according to 13 or 14 above, wherein the polyimide precursor is represented by the following formula (3).
Figure BDA0003578692730000073
(in the formula (3), X1Is a 4-valent organic radical derived from a tetracarboxylic acid derivative, Y1Is a 2-valent organic radical derived from a diamine comprising the structure of formula (1), R11Is a hydrogen atom or a carbon number1 to 5 alkyl, R3Is an alkyl group having 1 to 4 carbon atoms. )
16. The polymer according to 15, wherein in the formula (3), X represents1The structural formula (A) is at least 1 selected from the group consisting of the following structural formulae (A-1) to (A-21).
Figure BDA0003578692730000081
17. A diamine represented by the above formula (2).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a transverse electric field driven type liquid crystal display element, which is provided with an alignment control capability with high efficiency and has excellent afterimage characteristics, and a transverse electric field driven type liquid crystal display element having the substrate.
The liquid crystal display element of the transverse electric field type manufactured by the method of the present invention is imparted with an alignment control capability with high efficiency, and therefore, even if it is continuously driven for a long time, the display characteristics are not impaired.
The polymer composition used in the production method of the present invention has a photosensitive main chain type polymer capable of exhibiting self-assembly ability (hereinafter also simply referred to as main chain type polymer), and a coating film obtained using the polymer composition is a film having a photosensitive main chain type polymer capable of exhibiting self-assembly ability. The coating film was not subjected to brushing treatment, but was subjected to alignment treatment by polarized light irradiation. After the polarized light irradiation, the main chain polymer film is subjected to a heating step, thereby forming a coating film (hereinafter also referred to as a liquid crystal alignment film) to which an alignment controlling ability is imparted. At this time, the fine anisotropy exhibited by the polarized light irradiation becomes a driving force, and the main chain type polymer itself is effectively reoriented by self-assembly. As a result, a liquid crystal alignment film to which high alignment controllability is imparted by realizing efficient alignment treatment can be obtained as a liquid crystal alignment film.
Detailed Description
Embodiments of the present invention will be described in detail below.
The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer (hereinafter, also referred to as a specific polymer or a main chain polymer) obtained from a diamine component containing a diamine having a structure represented by the following formula (1). Next, each condition will be described in detail.
< diamine having a specific Structure >
The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer obtained from a diamine having a structure represented by the following formula (1) (also referred to as a specific diamine in the present invention) and an organic solvent.
Figure BDA0003578692730000091
(in the formula (1), X is a single bond or a 2-valent organic group, Y and Z are each independently a 2-valent organic group containing an alkylene group, R1And R2Each independently is a 1-valent organic radical, R3Is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4. )
Examples of the 1-valent organic group include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, and a fluoroalkoxy group having 1 to 10, preferably 1 to 3 carbon atoms. Among them, as the 1-valent organic group, a methyl group is preferable.
Examples of the 2-valent organic group include benzene, naphthalene, cyclohexyl, and groups in which a hydrogen atom of these groups is substituted with a 1-valent organic group. Among them, benzene is preferable as the 2-valent organic group.
Examples of the alkylene group-containing 2-valent organic group include an alkylene group, a group composed of an alkylene group and an ether bond, a group composed of an alkylene group and an ester bond, a group composed of an alkylene group in which part or all of hydrogen atoms are substituted with halogen and an ether bond, and a group composed of an alkylene group in which part or all of hydrogen atoms are substituted with halogen and an ester bond. Among these, the alkylene group-containing 2-valent organic group is preferably an alkylene group or a group composed of an alkylene group and an ether bond. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10.
Among the total number of atoms of Y and Z, a polymer obtained when the total number of carbon atoms and oxygen atoms, which is an even number in terms of the length of the main chain, is an even number is preferably used because the linearity of the resulting polymer is increased, and as a result, the liquid crystal alignment film to which a high alignment controllability is imparted can be obtained by performing re-alignment more orderly in the heating step after irradiation with polarized light.
As R3From the viewpoint of ease of reaction in polymerization, methyl and ethyl groups are preferred, and methyl groups are more preferred.
M and n are preferably 0 from the viewpoint of small steric hindrance and easy superposition of phenyl groups to each other, thereby allowing more orderly reorientation.
The diamine is preferably a diamine represented by the following formula (2).
Figure BDA0003578692730000101
(in the formula (2), X, Y, Z, R1～R3M and n are as defined above for formula (1). )
Specific examples of the diamine having the structure of the formula (2) include, but are not limited to, the following.
Figure BDA0003578692730000111
Figure BDA0003578692730000121
Figure BDA0003578692730000131
< Synthesis method of specific diamine >
The method for synthesizing the above-mentioned specific diamine is not particularly limited. For example, a method of using a nitro compound represented by the following formula (5) and converting the nitro group contained therein into an amino group by a reduction reaction is exemplified.
Figure BDA0003578692730000141
The catalyst used in the reduction reaction is preferably an activated carbon-supported metal which is commercially available, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. Further, palladium hydroxide, platinum oxide, raney nickel, iron, zinc, tin, etc. may be used, and it is not necessarily an activated carbon-supported metal catalyst. Iron, zinc and tin, which are generally widely used, are preferable because good results can be obtained.
In order to more efficiently perform the reduction reaction, the reaction may be performed in the presence of activated carbon. In this case, the amount of the activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass, based on the dinitro compound X1. For the same reason, the reaction may be carried out under pressure. In this case, the reduction of the benzene nucleus is carried out in a pressurized range of at most 20 atmospheres. The reaction is preferably carried out in a range of up to 10 atmospheres. If necessary, an acid catalyst may be added to shorten the time.
The solvent may be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et)2O、i-Pr2O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); polar organic solvent (methanol, ethanol, H) of protic solvent2O, etc.) and the like. These solvents may be appropriately selected in consideration of the ease of reaction, and may be used alone in 1 kind or in a mixture of 2 or more kinds. Or can be used according to the needsThe solvent is dried with a suitable dehydrating agent or drying agent and used as a nonaqueous solvent.
The amount of the solvent (reaction concentration) is not particularly limited, and is 0.1 to 100 times by mass relative to the nitro compound. Preferably 0.5 to 30 times by mass, and more preferably 1 to 10 times by mass.
The reaction temperature is not particularly limited, and is in the range from-100 ℃ to the boiling point of the solvent used, preferably-50 to 150 ℃. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
[ production method of formula (5) ]
The method for synthesizing the compound of formula (5) is not particularly limited, and for example, a method of synthesizing a nitrobenzene derivative having a leaving group X represented by the following formula (7) by reacting it with a commercially available methylamine solution is exemplified. Preferred examples of the leaving group X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonate group (-OTs), a methanesulfonate group (-OMs), and the like.
Figure BDA0003578692730000151
As the amount of the reaction substrate, 1 to 20 equivalents of methylamine may be used with respect to 1 equivalent of the compound represented by the general formula (7).
When a solvent is used, the solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 1-trichloroethane, trichloroethylene, and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1, 2-dimethoxyethane, tetrahydrofuran, and 1, 4-dioxane; esters such as ethyl acetate and ethyl propionate; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N, N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile, and dimethyl sulfoxide, and the like. These solvents may be used alone, or 2 or more of these may be used in combination.
When a base is used, for example, an organic base such as triethylamine, tributylamine, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, or 1, 8-diazabicyclo [5,4,0] -7-undecene can be used in an amount of 1 to 4 equivalents relative to the compound represented by the general formula (7).
The reaction temperature may be set to any temperature from-60 ℃ to the reflux temperature of the reaction mixture, and the reaction time may vary depending on the concentration of the reaction substrate and the reaction temperature, and may be set to any temperature within the range of usually 5 minutes to 100 hours.
In general, it is preferable to carry out the reaction for 10 minutes to 24 hours at a temperature in the range of 0 ℃ to the reflux temperature of a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, and 1, 4-dioxane without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, and 1, 4-dioxane in the presence of 1 to 20 equivalents of methylamine and, if necessary, 1 to 4 equivalents of a base such as potassium carbonate, triethylamine, pyridine, and 4- (dimethylamino) pyridine to 1 equivalent of the compound represented by the general formula (7).
[ production method of formula (7) ]
The method for synthesizing the compound of formula (7) is not particularly limited, and for example, a method of synthesizing a nitrobenzene derivative having a hydroxyl group represented by the following formula (8) by reacting it with commercially available methanesulfonyl chloride is exemplified. From the viewpoint of ease of synthesis, the leaving group X is preferably a mesylate group (-OMs), and other preferred leaving groups X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonate group (-OTs), and the like.
Figure BDA0003578692730000161
As the amount of the reaction substrate, 1 to 4 equivalents of methanesulfonyl chloride may be used with respect to 1 equivalent of the compound represented by formula (8).
When a solvent is used, the solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 1-trichloroethane, trichloroethylene, and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1, 2-dimethoxyethane, tetrahydrofuran, and 1, 4-dioxane; esters such as ethyl acetate and ethyl propionate; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N, N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile, and dimethyl sulfoxide, and the like. These solvents may be used alone, or 2 or more of these may be used in combination.
When a base is used, for example, an organic base such as triethylamine, tributylamine, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, or 1, 8-diazabicyclo [5,4,0] -7-undecene can be used in an amount of 1 to 4 equivalents relative to the compound represented by the general formula (8).
The reaction temperature may be set to any temperature within the range of-60 ℃ to 25 ℃ and the reaction time may vary depending on the concentration of the substrate and the reaction temperature, and may be set to any temperature within the range of usually 5 minutes to 100 hours.
In general, it is preferable to carry out the reaction for 10 minutes to 24 hours at 0 to 10 ℃ in the presence of 1 to 4 equivalents of methanesulfonyl chloride, and if necessary, 1 to 4 equivalents of a base such as potassium carbonate, triethylamine, pyridine, or 4- (dimethylamino) pyridine, based on 1 equivalent of the compound represented by the formula (8), without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, or 1, 4-dioxane.
[ production method of formula (8) ]
The method for synthesizing the compound of formula (8) is not particularly limited, and for example, a method of synthesizing a commercially available phenol derivative (9) by reacting it with a nitrobenzene derivative having a leaving group represented by formula (10) below is exemplified. Preferred examples of the leaving group X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonate group (-OTs), a methanesulfonate group (-OMs), and the like.
Figure BDA0003578692730000171
The amount of the reaction substrate may be 1 to 4 equivalents of the compound represented by the formula (10) to 1 equivalent of the compound represented by the formula (9).
When a solvent is used, the solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 1-trichloroethane, trichloroethylene, and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1, 2-dimethoxyethane, tetrahydrofuran, and 1, 4-dioxane; esters such as ethyl acetate and ethyl propionate; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N, N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile, and dimethyl sulfoxide, and the like. These solvents may be used alone, or 2 or more of these may be used in combination.
When a base is used, for example, an organic base such as triethylamine, tributylamine, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, or 1, 8-diazabicyclo [5,4,0] -7-undecene can be used in an amount of 1 to 4 equivalents relative to the compound represented by the general formula (10).
The reaction temperature may be set to any temperature from-60 ℃ to the reflux temperature of the reaction mixture, and the reaction time may vary depending on the concentration of the reaction substrate and the reaction temperature, and may be set to any temperature within the range of usually 5 minutes to 100 hours.
In general, it is preferable to carry out the reaction for 10 minutes to 24 hours at a temperature in the range of 0 ℃ to the reflux temperature of the solvent without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1, 4-dioxane or the like in the presence of 1 to 4 equivalents of the compound represented by the formula (9) and, if necessary, 1 to 4 equivalents of a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine or the like with respect to 1 equivalent of the compound represented by the formula (10).
< Polymer >
The polymer of the present invention is a polymer obtained using the diamine described above. Specific examples thereof include polyamic acids, polyamic acid esters, polyimides, polyureas, polyamides, and the like, and from the viewpoint of use as a liquid crystal aligning agent, at least 1 selected from polyimide precursors containing a structural unit represented by the following formula (3) and polyimides which are imide compounds thereof is more preferable.
Figure BDA0003578692730000191
In the above formula (3), X1Is a 4-valent organic radical derived from a tetracarboxylic acid derivative, Y1Is a 2-valent organic radical derived from a diamine comprising the structure of formula (1), R11Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R3Is an alkyl group having 1 to 4 carbon atoms. R is R from the viewpoint of ease of imidation by heating11Preferably a hydrogen atom, a methyl group or an ethyl group. As R3From the viewpoint of ease of reaction in polymerization, a methyl group is preferred.
< tetracarboxylic dianhydride >
X1The group is a 4-valent organic group derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. In addition, X in the polyimide precursor1The solubility of the polymer in a solvent, the coating properties of a liquid crystal aligning agent, and the properties of the liquid crystal alignment filmThe degree of the desired properties such as the alignment property, voltage holding ratio, and accumulated charge of the liquid crystal is appropriately selected, and 1 kind or 2 or more kinds may be mixed in the same polymer.
If X is not to be shown1Specific examples of (4) include the structures of formulae (X-1) to (X-46) described in International patent publication No. 2015/119168, pages 13 to 14.
Preferred X is shown below1But the present invention is not limited to these structures.
Figure BDA0003578692730000201
Among the above structures, (A-1), (A-2) and (A-4) are preferable, and (A-1) is particularly preferable, from the viewpoint of photo-alignment properties.
< diamine >
In the formula (3), as Y1Specific examples of (3) include a structure obtained by removing an amino group and an alkylamino group from a diamine having the structure of the formula (1). Wherein Y is1Particularly preferred is a structure obtained by removing an amino group and an alkylamino group from the structure of the formula (2).
< Polymer (other structural Unit) >)
The polyimide precursor containing the structural unit represented by the formula (3) may contain at least 1 selected from the structural units represented by the following formula (4) and polyimides which are imide compounds thereof, within a range not impairing the effects of the present invention.
Figure BDA0003578692730000211
In the formula (4), X2Is a 4-valent organic radical derived from a tetracarboxylic acid derivative, Y2Is a 2-valent organic group derived from a diamine not containing the structure of formula (1) in the main chain direction, R12And R in the formula (3)11The same definition is applied.
As X2Specific examples of (3) include X of the formula (6) and preferable examples1As recited inThe same structure is exemplified. In addition, Y in the polyimide precursor2Is a 2-valent organic group derived from a diamine not containing the structure of formula (1) in the main chain direction. The structure thereof is not particularly limited. In addition, Y2The amount of the polymer to be used may be appropriately selected depending on the degree of the desired properties such as solubility in a solvent, coatability of a liquid crystal aligning agent, alignment properties of liquid crystal when a liquid crystal alignment film is formed, voltage holding ratio, and accumulated charge, and may be 1 kind or 2 or more kinds mixed in the same polymer.
If not to show Y2Specific examples of the above-mentioned compounds include the structure of the formula (2) on page 4 of International publication No. 2015/119168, and the structures of the formulae (Y-1) to (Y-97) and (Y-101) to (Y-118) on pages 8 to 12; a 2-valent organic group obtained by removing 2 amino groups from formula (2) described in page 6 of International publication No. 2013/008906; a 2-valent organic group obtained by removing 2 amino groups from the formula (1) described in page 8 of International publication No. 2015/122413; a structure of formula (3) described in page 8 of International publication No. 2015/060360; a 2-valent organic group obtained by removing 2 amino groups from the formula (1) described in Japanese laid-open patent publication No. 2012-173514 page 8; a 2-valent organic group obtained by removing 2 amino groups from the formulae (A) to (F) described in International publication No. 2010-050523 on page 9, and the like.
As preferred Y2The structure of (3) includes the structure of the following formula (11).
Figure BDA0003578692730000212
In the formula (11), R32Is a single bond or a 2-valent organic group, preferably a single bond.
R33Is- (CH)2)r-the structure shown. r is an integer of 2 to 10, preferably 3 to 7. In addition, any of-CH2Optionally replaced by ether, ester, amide, urea, urethane bonds, provided that they are not adjacent to each other.
R34Is a single bond or a 2-valent organic group.
Any hydrogen atom on the phenyl ring is optionally substituted with a 1-valent organic group, preferably a fluorine atom or a methyl group.
Specific examples of the structure represented by formula (11) include, but are not limited to, the following structures.
Figure BDA0003578692730000221
Figure BDA0003578692730000231
Among them, it is preferable that the polyimide resin composition contains the same partial structure as the benzene ring-Y-benzene ring portion of the specific diamine (2) from the viewpoint of not inhibiting the reorientation of at least 1 selected from the polyimide precursor containing the structural unit represented by the formula (3) and the polyimide which is an imide compound thereof.
When the polyimide precursor containing the structural unit represented by formula (3) contains the structural unit represented by formula (4) at the same time, the liquid crystal alignment properties may be further improved when the structural unit represented by formula (3) is small. The reason is that R of the formula (3)21The alkyl group does not cause imidization when heated, and the alignment ability of liquid crystal molecules is lowered. Therefore, the structural unit represented by the formula (3) is preferably 1 to 70 mol%, more preferably 5 to 50 mol%, and particularly preferably 10 to 30 mol% with respect to the total of the formulae (3) and (4).
The molecular weight of the polyimide precursor used in the present invention is preferably 2000 to 500000, more preferably 5000 to 300000, and further preferably 10000 to 100000 in terms of weight average molecular weight.
Examples of the polyimide having a main chain having a 2-valent group represented by the formula (1) include polyimides obtained by ring-closing the above polyimide precursor. In the polyimide, the ring-closure ratio of the amic acid group (also referred to as imidization ratio) does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.
Examples of the method for imidizing the polyimide precursor include: thermal imidization in which a solution of a polyimide precursor is heated directly, or catalytic imidization in which a catalyst is added to a solution of a polyimide precursor.
< liquid Crystal Aligning agent >
The liquid crystal aligning agent of the present invention contains a polymer (specific polymer) obtained from a diamine component containing a diamine having a structure represented by formula (1), but may contain 2 or more specific polymers having different structures within limits that achieve the effects described in the present invention. In addition to the specific polymer, the polymer may contain another polymer, that is, the polymer may contain a group having no valence 2 represented by the formula (1). Examples of the other polymer include polyamic acids, polyimides, polyamic acid esters, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrenes or derivatives thereof, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates. When the liquid crystal aligning agent of the present invention contains another polymer, the proportion of the specific polymer to the entire polymer component is preferably 5% by mass or more, and an example thereof is 5 to 95% by mass.
The liquid crystal aligning agent is used for producing a liquid crystal alignment film, and is generally in the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating solution containing the above-mentioned polymer component and an organic solvent capable of dissolving the polymer component. In this case, the concentration of the polymer in the liquid crystal aligning agent may be appropriately changed according to the setting of the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. The concentration of the polymer is particularly preferably 2 to 8 mass%.
The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as it is an organic solvent in which the polymer component can be uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, and cyclopentanone. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone is preferably used.
In addition, as the organic solvent contained in the liquid crystal aligning agent, a mixed solvent in which a solvent capable of improving coatability when the liquid crystal aligning agent is coated and surface smoothness of a coating film are used in combination with the above-mentioned solvent is generally used, and such a mixed solvent is preferably used in the liquid crystal aligning agent of the present invention. Specific examples of the organic solvent used in combination are listed below, but not limited to these examples.
Examples thereof include ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentanol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1, 2-ethanediol, 1, 2-propanediol, isobutanol, 2-butanol, 2-pentanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-pentanol, 2-hexanol, 3-methyl-cyclohexanol, 1, 2-ethanediol, 1, 2-propanediol, 2-butanol, and mixtures thereof, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monohexyl ether, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, and propylene glycol, and propylene glycol, and propylene glycol, and propylene glycol mono-ethylene glycol mono-ethyl ether acetate, Diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and solvents represented by the following formulae [ D-1] to [ D-3], and the like.
Figure BDA0003578692730000261
Formula [ D-1]In (D)1Represents an alkyl group having 1 to 3 carbon atoms of the formula [ D-2 ]]In (D)2Represents an alkyl group having 1 to 3 carbon atoms, formula [ D-3]]In (D)3Represents an alkyl group having 1 to 4 carbon atoms.
Among them, 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, or dipropylene glycol dimethyl ether is preferably used. The kind and content of such a solvent can be appropriately selected depending on the coating apparatus, coating conditions, coating environment, and the like of the liquid crystal aligning agent.
The liquid crystal aligning agent of the present invention may further contain components other than the polymer component and the organic solvent within a range not impairing the effects of the present invention. Examples of such additional components include: an adhesion promoter for improving adhesion between the liquid crystal alignment film and the substrate and adhesion between the liquid crystal alignment film and the sealing material; a crosslinking agent for improving the strength of the liquid crystal alignment film; a dielectric or conductive substance for adjusting the dielectric constant and resistance of the liquid crystal alignment film. Specific examples of these additional components include various components disclosed in publicly known documents relating to liquid crystal aligning agents, and examples thereof include components disclosed on pages 53 [0105] to 55 [0116] of the pamphlet of laid-open publication No. 2015/060357.
Method for manufacturing substrate having liquid crystal alignment film and method for manufacturing liquid crystal display element
The method for manufacturing a substrate having a liquid crystal alignment film of the present invention includes the steps of:
a step (I) of applying a polymer composition containing (A) a polymer obtained from a diamine component containing a diamine having a structure represented by formula (1) and (B) an organic solvent onto a substrate having a conductive film for driving a transverse electric field to form a coating film;
a step [ II ] of irradiating the coating film obtained in [ I ] with polarized ultraviolet light; and
and (III) heating the coating film obtained in (II).
Through the above steps, a liquid crystal alignment film for a transverse electric field driven liquid crystal display element to which an alignment control capability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
In addition to the substrate (1 st substrate) obtained above, a 2 nd substrate was prepared, and a transverse electric field driven liquid crystal display element was obtained.
The 2 nd substrate can be obtained as a 2 nd substrate having a liquid crystal alignment film to which an alignment control capability is imparted by using the above-mentioned steps [ I ] to [ III ] (for convenience, the steps [ I '] to [ III' ] may be abbreviated in the present application since a substrate not having a transverse electric field driving conductive film is used instead of the substrate having a transverse electric field driving conductive film).
A method for manufacturing a transverse electric field drive type liquid crystal display element includes:
and a step [ IV ] of disposing the 1 st substrate and the 2 nd substrate obtained as described above in such a manner that the liquid crystal alignment films of the 1 st substrate and the 2 nd substrate face each other with the liquid crystal interposed therebetween, thereby obtaining a liquid crystal display element. This makes it possible to obtain a transverse electric field drive type liquid crystal display element.
The respective steps of [ I ] to [ III ] and [ IV ] included in the production method of the present invention will be described below.
< Process [ I ] >, and
in the step [ I ], a polymer composition containing a photosensitive main chain polymer and an organic solvent is applied to a substrate having a conductive film for driving a transverse electric field to form a coating film.
< substrate >
The substrate is not particularly limited, and when the liquid crystal display element to be manufactured is transmissive, a substrate having high transparency is preferably used. In this case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
In addition, an opaque substrate such as a silicon wafer may be used in consideration of application to a reflective liquid crystal display element.
< conductive film for driving transverse electric field >
The substrate has a conductive film for driving a transverse electric field.
When the conductive film is a liquid crystal display element of a transmissive type, examples thereof include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide).
In the case of a reflective liquid crystal display element, examples of the conductive film include, but are not limited to, materials that reflect light, such as aluminum.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.
The method for applying the polymer composition to a substrate having a conductive film for driving a lateral electric field is not particularly limited.
As the coating method, a method using screen printing, offset printing, flexographic printing, inkjet method, or the like is generally industrially used. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method), a spray coating method, and the like, and these methods can be used according to the purpose.
After coating the polymer composition on the substrate having the conductive film for driving a transverse electric field, the solvent can be evaporated at 50 to 300 ℃, preferably 50 to 180 ℃ by a heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven to obtain a coating film. From the viewpoint of stability of liquid crystal alignment, the drying temperature in this case is preferably lower than in the step [ III ].
When the thickness of the coating film is too large, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too small, the reliability of the liquid crystal display element may be lowered, and therefore, it is preferably 5nm to 300nm, more preferably 10nm to 150 nm.
After the step [ I ] and before the next step [ II ], a step of cooling the substrate having the coating film formed thereon to room temperature may be provided.
< Process [ II ] >
In the step [ II ], the coating film obtained in the step [ I ] is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet light, the substrate is irradiated with polarized ultraviolet light from a specific direction through a polarizing plate. As the ultraviolet ray to be used, ultraviolet rays having a wavelength in the range of 100nm to 400nm can be used. Preferably, the optimum wavelength is selected by means of a filter or the like according to the type of the coating film used. Further, for example, ultraviolet rays having a wavelength in the range of 240nm to 400nm may be selectively used so as to selectively induce the photolytic reaction. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp or a metal halide lamp can be used.
The irradiation amount of the polarized ultraviolet ray depends on the coating film used. The irradiation amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%, of the amount of polarized ultraviolet light that achieves the maximum value of Δ a (hereinafter also referred to as Δ Amax), which is the difference between the ultraviolet light absorbance of the coating film in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet light absorbance of the coating film in the direction perpendicular to the polarization direction of the polarized ultraviolet light.
< Process [ III ] >
In the step [ III ], the coating film irradiated with the polarized ultraviolet ray in the step [ II ] is heated. By heating, the coating film can be imparted with an orientation controlling ability.
Heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared ray) type oven can be used for heating. The heating temperature may be determined in consideration of a temperature at which the coating film used exhibits good liquid crystal alignment stability and electrical characteristics.
The heating temperature is preferably within a temperature range in which the main chain type polymer exhibits good liquid crystal alignment stability. When the heating temperature is too low, the effect of increasing anisotropy from the heat band and thermal imidization tend to be insufficient, and when the heating temperature is too high, the anisotropy imparted by polarized light exposure tends to disappear, and in this case, it may be difficult to reorient the film in one direction by self-assembly.
The thickness of the coating film formed after heating is preferably 5nm to 300nm, more preferably 50nm to 150nm, for the same reason as described in the step [ I ].
By having the above steps, the production method of the present invention can efficiently introduce anisotropy into a coating film. Further, a substrate with a liquid crystal alignment film can be efficiently produced.
< Process [ IV ] >, and
the step [ IV ] is a step of: the substrate (1 st substrate) having the liquid crystal alignment film on the electric conductive film for driving in the transverse electric field obtained in [ III ] and the substrate (2 nd substrate) having the liquid crystal alignment film without the electric conductive film obtained in the same manner as in [ I ']to [ III' ] are disposed facing each other so that the liquid crystal alignment films of both are opposed to each other with the liquid crystal interposed therebetween, and a liquid crystal cell is produced by a known method to produce a liquid crystal display element of the transverse electric field driving type. The steps [ I '] to [ III' ] can be performed in the same manner as the steps [ I ] to [ III ], except that a substrate having no conductive film for driving a transverse electric field is used in the step [ I ] instead of the substrate having the conductive film for driving a transverse electric field. The steps [ I ] to [ III ] are different from the steps [ I '] to [ III' ] only in the presence or absence of the conductive film, and therefore, the description of the steps [ I '] to [ III' ] is omitted.
If one example of the production of a liquid crystal cell or a liquid crystal display element is mentioned, the following method can be exemplified: a method of preparing the 1 st substrate and the 2 nd substrate, spreading spacers on the liquid crystal alignment film of one substrate, bonding the other substrate with the liquid crystal alignment film surface facing the inside, injecting liquid crystal under reduced pressure, and sealing; or a method of dropping a liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and then bonding and sealing the substrates. In this case, it is preferable to use a substrate having an electrode with a structure such as a comb for driving a transverse electric field as the substrate on one side. The diameter of the spacer in this case is preferably 1 to 30 μm, more preferably 2 to 10 μm. The spacer diameter will determine the distance between a pair of substrates for sandwiching the liquid crystal layer, i.e. the thickness of the liquid crystal layer.
In the method for producing a substrate with a coating film of the present invention, after a coating film is formed by applying the polymer composition onto a substrate, polarized ultraviolet rays are irradiated. Then, by heating, anisotropy is efficiently introduced into the main chain polymer film, and a substrate with a liquid crystal alignment film having liquid crystal alignment controllability is manufactured.
The coating film used in the present invention utilizes the principle that the self-assembly of the main chain by photoreaction induces molecular reorientation, and thus realizes efficient introduction of anisotropy into the coating film. In the production method of the present invention, when the main chain polymer has a structure in which a photolytic group is a photoreactive group, a liquid crystal display element is produced by forming a coating film on a substrate using the main chain polymer, irradiating the coating film with polarized ultraviolet rays, and then heating the coating film.
Therefore, the coating film used in the method of the present invention is irradiated with polarized ultraviolet rays and heat-treated in this order, so that anisotropy is efficiently introduced into the coating film, and a liquid crystal alignment film having excellent alignment controllability can be obtained.
The coating film used in the method of the present invention is optimized in the irradiation amount of polarized ultraviolet rays to be irradiated to the coating film and the heating temperature in the heating treatment. This enables efficient introduction of anisotropy into the coating film.
The irradiation amount of polarized ultraviolet ray which is optimal for efficiently introducing anisotropy into the coating film used in the present invention corresponds to the irradiation amount of polarized ultraviolet ray which is optimal for the photolytic reaction of the photosensitive group in the coating film. When the coating film used in the present invention is irradiated with polarized ultraviolet rays, a sufficient photoreactive amount cannot be obtained if the photosensitive group that undergoes photolysis reaction is small. In this case, sufficient self-assembly does not proceed even when heating is performed subsequently.
Therefore, in the coating film used in the present invention, the optimum amount of the photosensitive group for the photolytic reaction by irradiation of polarized ultraviolet rays is preferably 0.1 to 90 mol%, more preferably 0.1 to 80 mol% of the polymer film. When the amount of the photoreactive photosensitive group is in this range, self-assembly in the subsequent heat treatment advances efficiently, and anisotropy can be formed efficiently in the film.
The amount of photolysis reaction of the photosensitive group in the main chain of the polymer film is optimized by optimizing the irradiation amount of polarized ultraviolet rays for the coating film used in the method of the present invention. Further, the anisotropic property can be efficiently introduced into the coating film used in the present invention together with the subsequent heat treatment. In this case, the appropriate amount of polarized ultraviolet light can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.
That is, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the direction perpendicular to the polarization direction of the polarized ultraviolet ray after irradiation with the polarized ultraviolet ray were measured for the coating film used in the present invention. Evaluation of Δ a, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet ray in the coating film, was made based on the measurement result of the ultraviolet absorption. Then, the maximum value (Δ Amax) of Δ a that can be realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes the maximum value are obtained. In the production method of the present invention, the amount of polarized ultraviolet light irradiated in a preferred amount in the production of the liquid crystal alignment film can be determined based on the amount of polarized ultraviolet light irradiated to realize Δ Amax.
As described above, in the production method of the present invention, in order to efficiently introduce anisotropy into a coating film, the above-mentioned suitable heating temperature can be determined based on the temperature range in which the main chain polymer imparts liquid crystal alignment stability. Therefore, for example, the temperature range in which the main chain type polymer used in the present invention imparts liquid crystal alignment stability can be determined in consideration of the temperature at which the coating film used exhibits good liquid crystal alignment stability and electrical characteristics, and can be set in accordance with the temperature range of a conventional liquid crystal alignment film made of polyimide or the like. That is, it is more preferable to set the heating temperature after the irradiation of the polarized ultraviolet rays to 100 to 300 ℃ and to 150 to 250 ℃. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external stress such as light, heat, and the like.
In the above-described manner, the substrate for a transverse electric field driven liquid crystal display element produced using the polymer of the present invention or the transverse electric field driven liquid crystal display element having the substrate is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like. In addition, the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, and thus can also be used for a variable phase shifter using liquid crystal, which can be suitably used for, for example, an antenna or the like whose resonance frequency is variable.
Examples
Abbreviations used in the examples are as follows.
DMF: n, N-dimethylformamide
MeOH: methanol
NMP: n-methyl-2-pyrrolidone
BCS: butyl cellosolve
DA-1: a compound represented by the following structural formula (DA-1)
DA-2: a compound represented by the following structural formula (DA-2)
DA-3: a compound represented by the following structural formula (DA-3)
CA-1: a compound represented by the following structural formula (CA-1)
Figure BDA0003578692730000331
＜1Measurement of HNMR
The device comprises the following steps: fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) 'INOVA-400' (manufactured by Varian) 400 MHz.
Solvent: deuterated N, N-dimethyl sulfoxide (DMSO-d)6)。
Reference substance: tetramethylsilane (TMS).
< measurement of viscosity >
In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toyobo Co., Ltd.) under conditions of a sample volume of 1.1mL, a conical rotor TE-1(1 ℃ 34', R24) and a temperature of 25 ℃.
< diamine Compound >
DA-1 is a novel compound which is not disclosed in the literature and the like, and the synthesis method thereof is described in detail in the following synthetic example 1.
< Synthesis example 1 >
[ DA-1 ]: synthesis of 4- (2- (4- (2- (methylamino) ethyl) phenoxy) ethoxy) aniline
An aromatic diamine compound (DA-1) was synthesized according to the following 4-step route. The aromatic diamine compound (DA-1) is classified into the above-mentioned specific diamine compound.
Step 1: synthesis of 2- (4- (2- (4-nitrophenoxy) ethoxy) phenyl) ethanol (DA-1-1)
Figure BDA0003578692730000341
4- (2-hydroxyethyl) phenol (15.0g, 108.6mmol) was dissolved in DMF (22.5g), potassium carbonate (22.5g, 162.9mmol) was added, and a solution of β -bromo-4-nitrophenyl ether (29.4g, 119.4mmol) in DMF (22.5g) was added dropwise at 80 ℃. The mixture was stirred at 80 ℃ for 5 hours, and the disappearance of the starting material was confirmed by high performance liquid chromatography (hereinafter, abbreviated as HPLC). Then, the reaction mixture was cooled to room temperature, water (540.0g) was added thereto, and dichloroethane (270.0g) was added thereto to conduct a liquid separation operation, thereby extracting an organic layer. The extract was again extracted with purified water (540.0g), dried over magnesium sulfate (5.0g), and concentrated. Tetrahydrofuran (50.0g) and heptane (40.0g) were added to the concentrated crude product, and after dissolving all of them at 60 ℃, it was cooled to 0 ℃ and the precipitate was filtered. The filtered precipitate was washed with MeOH (50.0g), and dried under reduced pressure at 40 ℃ to obtain 2- (4- (2- (4-nitrophenoxy) ethoxy) phenyl) ethanol (white powder, yield: 14.0g, yield: 42%).
1H NMR(DMSO-d6)：δ8.22(d，J＝9.2Hz，2H，C6H4)，7.22(d，J＝9.2Hz，2H，C6H4)，7.14(d，J＝8.4Hz，2H，C6H4)，6.89(d，J＝8.4Hz，2H，C6H4)，4.47-4.32(m，4H，CH2)，3.55(t，J＝7.2Hz，2H，CH2)，2.66(t，J＝7.2Hz，2H，CH2)。
Step 2: synthesis of 4- (2- (4-nitrophenoxy) ethoxy) phenethyl methanesulfonate (DA-1-2)
Figure BDA0003578692730000342
2- (4- (2- (4-nitrophenoxy) ethoxy) phenyl) ethanol (5.0g, 16.5mmol) was dissolved in dichloroethane (30.0g), triethylamine (2.50g, 24.7mmol) was added, the mixture was cooled to 5 ℃ and a solution obtained by dissolving methanesulfonyl chloride (2.3g, 19.8mmol) in dichloroethane (15.0g) was added dropwise while paying attention to heat generation. The mixture was stirred at 5 ℃ for 1 hour directly, and the disappearance of the starting material was confirmed by HPLC. Then, water (60.0g) was added to the reaction mixture, followed by addition of dichloroethane (40.0g) and liquid separation, to extract an organic layer. The organic layer was extracted again with water (50.0g), dried over sodium sulfate (5.0g) together with the previous organic layer, and concentrated. The concentrate was used as a crude product to obtain 4- (2- (4-nitrophenoxy) ethoxy) phenethylmethanesulfonate (white powder, yield: 6.3g, yield: 99%).
1H NMR(DMSO-d6)：δ8.22(d，J＝9.2Hz，2H，C6H4)，7.23-7.20(m，4H，C6H4)，7.14(d，J＝8.4Hz，2H，C6H4)，6.89(d，J＝8.4Hz，2H，CH2)，4.49-4.47(m，2H，CH2)，4.37-4.33(m，4H，CH2)，3.10(s，3H，CH3)，2.93(t，J＝6.8Hz，2H，CH2)。
And 3, step 3: synthesis of N-methyl-2- (4- (2- (4-nitrophenoxy) ethoxy) phenyl) ethylamine (DA-1-3)
Figure BDA0003578692730000351
4- (2- (4-Nitrophenoxy) ethoxy) phenethyl methanesulfonate (20.0g, 52.4mmol) was dissolved in tetrahydrofuran (200.0g), 40% methylamine in MeOH (81.4g, 1048.8mmol) was added and the temperature was raised to 40 ℃. The mixture was stirred at 40 ℃ for 24 hours, and the disappearance of the starting material was confirmed by HPLC. Then, the reaction solution was concentrated, ethyl acetate (400.0g) was added thereto, and a 2 wt% aqueous sodium hydroxide solution (400.0g) was added thereto to conduct a liquid separation operation, thereby extracting an organic layer. The organic layer was extracted again with water (400.0g), dried over sodium sulfate (10.0g) together with the previous organic layer, and concentrated. Heptane (80.0g) was added to the concentrated crude product, and the precipitate was filtered off. The filtered precipitate was dried under reduced pressure at 40 ℃ to obtain N-methyl-2- (4- (2- (4-nitrophenoxy) ethoxy) phenyl) ethanamine (yellow powder, yield: 15.6g, yield: 94%).
1H NMR(DMSO-d6)：δ8.22(d，J＝9.2Hz，2H，C6H4)，7.21(d，J＝9.2Hz，2H，C6H4)，7.13(d，J＝8.4Hz，2H，C6H4)，6.89(d，J＝8.4Hz，2H，CH2)，4.48-4.30(m，4H，CH2)，2.62(s，4H，CH2)，2.27(s，3H，CH3)，1.49(br，1H，NH).
And 4, step 4: synthesis of 4- (2- (4- (2-methylamino) ethyl) phenoxy) ethoxy) aniline (DA-1)
Figure BDA0003578692730000361
N-methyl-2- (4- (2- (4-nitrophenoxy) ethoxy) phenyl) ethanamine (10.0g, 31.6mmol) was dissolved in tetrahydrofuran (100.0g), and 5% palladium on carbon (0.5g) was added to the solution, followed by stirring at 50 ℃ for 5 hours under a hydrogen atmosphere. Disappearance of the starting material was confirmed by HPLC, and the starting material was dissolved in tetrahydrofuran (50.0g), and after removing the catalyst by filtration, the filtrate was concentrated. This was washed with heptane (50.0g), and the precipitated solid was filtered and dried under reduced pressure at 50 ℃ to obtain DA-1 (white powder, yield: 9.0g, yield: 98%).
1H NMR(DMSO-d6)：δ7.11(d，J＝9.2Hz，2H，C6H4)，6.87(d，J＝9.2Hz，2H，C6H4)，6.68(d，J＝6.6Hz，2H，C6H4)，6.51(d，J＝6.6Hz，2H，CH2)，4.63(br，2H，NH2)，4.20-4.12(m，4H，CH2)，2.62(s，4H，CH2)，2.26(s，3H，CH3)，1.48(br，1H，NH)。
Polymerization example and preparation example of alignment agent
< Synthesis example 2 >
1.00g (3.50mmol) of DA-1 and 2.86g (10.5mmol) of DA-2 were weighed into a 100mL four-necked flask equipped with a stirrer and a nitrogen inlet, 37.6g of NMP was added thereto, and the mixture was dissolved with stirring while feeding nitrogen. While this diamine solution was stirred under water cooling, 2.59g (13.2mmol) of CA-1 and 9.41g of NMP were added thereto, and the mixture was stirred at 23 ℃ for 15 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The solution of the polyamic acid had a viscosity of 270 mPas at a temperature of 25 ℃.
14.5g of the polyamic acid solution was taken out and put into a 100mL Erlenmeyer flask equipped with a stirrer, and 12.6g of NMP and 11.6g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-1).
Comparative Synthesis example 1
4.09g (15.0mmol) of DA-2 was weighed into a 100mL four-necked flask equipped with a stirrer and a nitrogen inlet, 39.3g of NMP was added thereto, and the mixture was dissolved with stirring while feeding nitrogen. While this diamine solution was stirred under water cooling, 2.77g (14.1mmol) of CA-1 and 9.83g of NMP were added, and the mixture was stirred at 23 ℃ for 3 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The solution of the polyamic acid had a viscosity of 263 mPas at a temperature of 25 ℃.
14.9g of the polyamic acid solution was taken out and put into a 100mL Erlenmeyer flask equipped with a stirrer, and 12.9g of NMP and 11.9g of BCS were added and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-1).
Comparative Synthesis example 2
2.86g (10.5mmol) of DA-2 and 0.526g (3.50mmol) of DA-3 were weighed into a 100mL four-necked flask with a stirrer and a nitrogen inlet, 34.8g of NMP was added, and the mixture was dissolved with stirring while sending nitrogen. While this diamine solution was stirred under water cooling, 2.62g (13.4mmol) of CA-1 and 8.71g of NMP were added thereto, and the mixture was stirred at 23 ℃ for 15 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The solution of the polyamic acid had a viscosity of 299 mPas at a temperature of 25 ℃.
14.6g of the polyamic acid solution was taken out and put into a 100mL Erlenmeyer flask equipped with a stirrer, and 12.6g of NMP and 11.7g of BCS were added thereto, followed by stirring with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-2).
< production of liquid Crystal cell for evaluating liquid Crystal alignment >
A method for manufacturing a liquid crystal cell for evaluating liquid crystal alignment properties is described below.
A liquid crystal cell having a liquid crystal display element structure of FFS mode was produced. First, a substrate with an electrode is prepared. The substrate is a glass substrate with the size of 30mm multiplied by 35mm and the thickness of 0.7 mm. An IZO electrode constituting a counter electrode was formed on the entire surface of the substrate as a 1 st layer. On the counter electrode of the 1 st layer, a SiN (silicon nitride) film formed by a CVD method was formed as the 2 nd layer. The SiN film of the 2 nd layer has a film thickness of 500nm and functions as an interlayer insulating film. On the SiN film of the 2 nd layer, a comb-shaped pixel electrode formed by patterning an IZO film is disposed as a 3 rd layer, thereby forming two pixels, i.e., a 1 st pixel and a 2 nd pixel. The size of each pixel was 10mm in length and 5mm in width. At this time, the counter electrode of the 1 st layer and the pixel electrode of the 3 rd layer are electrically insulated by the SiN film of the 2 nd layer.
The pixel electrode of the 3 rd layer has a comb-teeth shape formed by arranging a plurality of "<" shaped electrode elements whose central portions are bent, as in the case of the figure described in japanese patent application laid-open No. 2014-77845 (japanese laid-open patent publication). The width of each electrode element in the width direction was 3 μm, and the interval between the electrode elements was 6 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of "<" -shaped electrode elements whose central portions are bent, the shape of each pixel is not rectangular, but has a shape similar to a bold "<" -shaped electrode which is bent at the central portion like the electrode elements. Each pixel is divided vertically with a curved portion at the center as a boundary, and has a 1 st region on the upper side and a 2 nd region on the lower side of the curved portion.
When comparing the 1 st region and the 2 nd region of each pixel, the forming directions of the electrode elements constituting the pixel electrodes are different. That is, with reference to the line direction when the polarization plane of the polarized ultraviolet light is projected onto the substrate, the electrode elements of the pixel electrode are formed so as to form an angle of +10 ° (clockwise) in the 1 st region of the pixel, and the electrode elements of the pixel electrode are formed so as to form an angle of-10 ° (clockwise) in the 2 nd region of the pixel. That is, the 1 st region and the 2 nd region of each pixel are configured as follows: the directions of the rotational movement (planar inversion) of the liquid crystal in the substrate plane induced by applying a voltage between the pixel electrode and the counter electrode are opposite to each other.
Next, the liquid crystal aligning agents obtained in the synthesis examples and comparative synthesis examples were filtered through a 1.0 μm filter, and then applied onto the prepared electrode-carrying substrate by spin coating. Next, the plate was dried on a hot plate set at 70 ℃ for 90 seconds. Next, using an exposure apparatus manufactured by Ushio motor (ltd): APL-L050121S1S-APW01 irradiates a linear polarized light of ultraviolet rays from a direction perpendicular to the substrate through a wavelength selective filter and a polarizing plate. At this time, the polarization plane direction was set so that the line direction when the polarization plane of the polarized ultraviolet rays was projected onto the substrate was inclined by 10 ° with respect to the 3 rd layer IZO comb electrode. Then, the substrate was baked in an IR (infrared ray) type oven set at 230 ℃ for 30 minutes to obtain an alignment-treated substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm. Further, as the counter substrate, a glass substrate having an ITO electrode formed on the back surface thereof and a column spacer having a height of 4 μm was subjected to an alignment treatment in the same manner as described above, to obtain a substrate with a polyimide liquid crystal alignment film. These 2 substrates with liquid crystal alignment films were set as 1 set, and a sealant was printed on one substrate with a liquid crystal injection port left, and the other substrate was bonded and pressure-bonded so that the liquid crystal alignment films were opposed to each other and the line segment directions when the polarization plane of the polarized ultraviolet light was projected onto the substrates were parallel. Then, the sealant was cured to produce an empty cell having a cell gap of 4 μm. Liquid crystal ML-7026-100 (negative liquid crystal manufactured by Merck) was injected into the empty cell by injection under reduced pressure, and the injection port was sealed to obtain an FFS mode liquid crystal cell. Then, the liquid crystal cell obtained was heated at 120 ℃ for 30 minutes, left at 23 ℃ overnight, and then used for evaluation of liquid crystal alignment properties.
< evaluation of liquid Crystal alignment >
Using this liquid crystal cell, 16VPP AC voltage was applied at a frequency of 30Hz for 120 hours in a constant temperature environment of 70 ℃. Then, the pixel electrode and the counter electrode of the liquid crystal cell were brought into a short-circuited state, and the liquid crystal cell was left at 23 ℃ for one night.
After the placement, the liquid crystal cell was placed between 2 polarizing plates arranged so that the polarization axes were orthogonal, the backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted so as to minimize the brightness of transmitted light. Then, the rotation angle when the liquid crystal cell is rotated from the angle at which the 2 nd area of the 1 st pixel becomes darkest to the angle at which the 1 st area becomes darkest is calculated as an angle Δ. Similarly, the 2 nd area and the 1 st area are compared for the 2 nd pixel, and the same angle Δ is calculated. Then, the average value of the angle Δ values of the 1 st pixel and the 2 nd pixel is calculated as the angle Δ of the liquid crystal cell. The liquid crystal cell was defined and evaluated as "good" when the angle Δ value was less than 0.3 °, and was defined and evaluated as "poor" when the angle Δ value was 0.3 ° or more.
< production of liquid Crystal cell for evaluation of Voltage holding ratio >
A liquid crystal cell for voltage holding ratio measurement was produced in the same procedure as the production of the liquid crystal cell for liquid crystal alignment evaluation described above, except that a glass substrate with an ITO electrode was used, and spacer microspheres of 4 μm were spread on the liquid crystal alignment film surface on one substrate before the sealant was printed.
< evaluation of Voltage holding ratio >
The liquid crystal cell was used to evaluate the voltage holding ratio. Specifically, the 2VPP ac voltage was applied to the liquid crystal cell obtained in the above manner at a temperature of 70 ℃ for 60 μ s, the voltage after 1 second was measured, and how much the voltage could be held was calculated as a voltage holding ratio (also referred to as VHR). The Voltage holding ratio was measured by a Voltage holding ratio measuring apparatus (VHR-1, manufactured by Toyo Technica Co., Ltd.) using a Voltage (Voltage): ± 1V, Pulse Width (Pulse Width): 60 microseconds, frame Period (Flame Period): the measurement is performed at a setting of 1000 milliseconds. The liquid crystal cell was defined and evaluated as "good" when the voltage holding ratio was 80% or more, and was defined and evaluated as "poor" when the voltage holding ratio was less than 80%.
(example 1)
Using the liquid crystal aligning agent (a-1) obtained in synthesis example 2, 2 liquid crystal cells were produced as described above. Using a high-pressure mercury lamp with a wavelength selective filter: the 240LCF and 254nm type polarizing plates were irradiated with polarized ultraviolet rays. The amount of the polarized ultraviolet light is measured by using a luminometer UVD-S254SB manufactured by Ushio motor, Inc., and the wavelength is 254nm, and the intensity is 600-1800 mJ/cm2The above steps are performed while changing the range of (1) to (3) or more liquid crystal cells with different polarized ultraviolet ray irradiation amounts.
As a result of evaluation of the liquid crystal alignment properties of these liquid crystal cells, the polarized ultraviolet ray irradiation amount at the optimum angle Δ was 1800mJ/cm2The angle Δ is 0.15 °, which is good.
Further, as a result of evaluating the voltage holding ratio of the liquid crystal cell manufactured by the same polarized ultraviolet irradiation dose, the voltage holding ratio was 92.4%, which was good.
Comparative examples 1 to 2
Liquid crystal alignment properties and voltage holding ratios were evaluated in the same manner as in example 1, except that the liquid crystal aligning agents obtained in comparative synthesis examples 1 to 2 were used.
Table 1 shows the results of evaluation of the polarized ultraviolet ray irradiation amount at the optimum angle Δ, the liquid crystal alignment properties, and the voltage holding ratio when the liquid crystal aligning agents obtained in the synthesis examples and the comparative synthesis examples were used.
[ Table 1]
Figure BDA0003578692730000401
As shown in table 1, in example 1, the difference in orientation azimuth angle between before and after ac driving, that is, the angle Δ is preferably smaller than 0.3 °, and the voltage holding ratio is 80% or more, and the characteristics are also excellent, and both of them are good afterimage characteristics, and therefore, the display quality of the liquid crystal display element is excellent. On the other hand, in comparative examples 1 to 2, the characteristics of both the angle Δ and the voltage holding ratio were not observed.
From this, it was confirmed that the liquid crystal display element produced by the method of the present invention exhibited very excellent afterimage characteristics.
Industrial applicability
The substrate for a transverse electric field driven liquid crystal display element produced using the composition of the present invention or the transverse electric field driven liquid crystal display element having the substrate is excellent in reliability and can be suitably used for a large-screen and high-definition liquid crystal television or the like. In addition, the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, and thus can also be used for a variable phase shifter using liquid crystal, which can be suitably used for, for example, an antenna or the like whose resonance frequency is variable.

Claims (1)

1. A diamine represented by the following formula (2),
Figure FDA0003578692720000011
in the formula (2), X is a single bond or a 2-valent organic group, Y and Z are each independently a 2-valent organic group containing an alkylene group, R1And R2Each independently is a 1-valent organic radical, R3Is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4.
CN202210349222.9A 2016-12-21 2017-12-20 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Pending CN114702393A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-248111 2016-12-21
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