CN112219159B - Liquid crystal display element and method for manufacturing liquid crystal display element - Google Patents
Liquid crystal display element and method for manufacturing liquid crystal display element Download PDFInfo
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- CN112219159B CN112219159B CN201980037328.1A CN201980037328A CN112219159B CN 112219159 B CN112219159 B CN 112219159B CN 201980037328 A CN201980037328 A CN 201980037328A CN 112219159 B CN112219159 B CN 112219159B
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- RPOCQUTXCSLYFJ-UHFFFAOYSA-N n-(4-ethylphenyl)-2-(2-methyl-3,5-dioxothiomorpholin-4-yl)acetamide Chemical compound C1=CC(CC)=CC=C1NC(=O)CN1C(=O)C(C)SCC1=O RPOCQUTXCSLYFJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Provided are a liquid crystal display element capable of displaying an image having a high contrast, and a method for manufacturing the liquid crystal display element. The liquid crystal display element (1) is formed by sandwiching a liquid crystal layer (4) containing liquid crystal molecules between two substrates (AM, CF). One of the substrates AM, CF is provided with a polymer of a polymerizable monomer having a polymerizable group that is present in contact with the liquid crystal layer (4) and is polymerizable by irradiation with an active energy ray, and the surface roughness (Ra) of the surface in contact with the liquid crystal layer (4) is 1 to 30nm by the presence of the polymer. The polymerizable monomer preferably contains an alignment aid having a function of spontaneously aligning liquid crystal molecules, and having a polymerizable group, and the alignment aid preferably further has a polar group.
Description
Technical Field
The present invention relates to a liquid crystal display element and a method for manufacturing the liquid crystal display element.
Background
Conventionally, in a VA-mode liquid crystal display (liquid crystal display element), in order to induce vertical alignment of liquid crystal molecules when no voltage is applied, a Polyimide (PI) alignment film functioning as an alignment film is provided on an electrode in order to achieve horizontal alignment of liquid crystal molecules when a voltage is applied. However, since the PI alignment film requires a huge cost for forming the film, in recent years, a method for achieving alignment of liquid crystal molecules in spite of omitting the PI alignment film has been studied.
However, in the alignment of liquid crystal molecules, the surface properties of the substrate surface are also important. There is a document in which the surface roughness of a PI alignment film is specified in a liquid crystal display element provided with the PI alignment film (for example, see patent document 1). However, no example of investigation of the surface properties of a substrate in a liquid crystal display element in which a PI alignment film is omitted has been found, and there is room for further improvement in the properties.
Prior art literature
Patent literature
Patent document 1: WO2008/075419
Disclosure of Invention
Problems to be solved by the invention
The invention provides a liquid crystal display element capable of displaying images with high contrast and a method for manufacturing the liquid crystal display element.
Means for solving the problems
This object is achieved by the present invention of the following (1) to (13).
(1) A liquid crystal display element comprising a liquid crystal layer containing liquid crystal molecules sandwiched between two substrates, characterized in that:
One of the substrates includes a polymer of a polymerizable monomer that is present in contact with the liquid crystal layer and is polymerizable by irradiation with an active energy ray, and the surface roughness (Ra) of the surface in contact with the liquid crystal layer is 1 to 30nm by the presence of the polymer.
(2) The liquid crystal display element according to the above (1), wherein the polymerizable monomer contains an alignment aid having a function of spontaneously aligning the liquid crystal molecules, and the alignment aid has a polar group.
(3) The liquid crystal display element according to the item (1) or (2), wherein the polymerizable monomer contains a pretilt angle forming additive having a function of forming a pretilt angle of the liquid crystal molecules.
(4) The liquid crystal display element according to any one of (1) to (3), wherein the one substrate is a substrate that is in direct contact with the liquid crystal layer without an alignment film.
(5) The liquid crystal display element according to any one of the above (1) to (4), wherein the one substrate is a substrate provided with a pixel electrode.
(6) The liquid crystal display element according to any one of the above (1) to (5), wherein the other substrate is also provided with the polymer existing in contact with the liquid crystal layer, and a surface roughness (Ra) of a surface in contact with the liquid crystal layer is 1 to 30nm by the presence of the polymer.
(7) The liquid crystal display element according to the above (6), wherein the other substrate is a substrate directly contacting the liquid crystal layer without an alignment film.
(8) The liquid crystal display element according to the above (6) or (7), wherein the other substrate is a substrate provided with a color filter.
(9) The liquid crystal display element according to any one of the above (1) to (8), wherein the dielectric anisotropy of the liquid crystal molecules is negative.
(10) The liquid crystal display element according to any one of the above (1) to (9), wherein the liquid crystal display element is of a PSA type, a PSVA type, a VA type, an IPS type, an FFS type or an ECB type.
(11) A method for producing a liquid crystal display element according to any one of the above (1) to (10), comprising the steps of:
the two substrates are disposed so as to face each other in contact with a liquid crystal composition containing the liquid crystal molecules and the polymerizable monomer; and
The polymer is obtained by applying an electric field to the liquid crystal composition and simultaneously irradiating the active energy rays to polymerize the polymerizable monomer.
(12) The method for producing a liquid crystal display element according to the above (11), wherein the polymerizable monomer contains an alignment aid having a function of spontaneously aligning the liquid crystal molecules,
The amount of the alignment aid contained in the liquid crystal composition is 0.1 to 3% by weight.
(13) The method for manufacturing a liquid crystal display element according to (11) or (12), wherein the irradiation time of the active energy ray is 10 to 7200 seconds.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a liquid crystal display element capable of displaying an image having high contrast can be obtained.
Drawings
Fig. 1 is an exploded perspective view schematically showing one embodiment of a liquid crystal display element.
Fig. 2 is an enlarged plan view of the region surrounded by the line I in fig. 1.
Detailed Description
Hereinafter, a method for manufacturing a liquid crystal display element according to the present invention will be described in detail based on preferred embodiments.
First, the liquid crystal composition used in the present invention will be described.
(Liquid Crystal composition)
The liquid crystal composition contains liquid crystal molecules and an alignment aid having a function of spontaneously aligning the liquid crystal molecules and having a polar group.
((Orientation aid))
The orientation aid (spontaneous orientation compound) has the following functions: the vertical alignment or the horizontal alignment of the liquid crystal molecules contained in the liquid crystal layer is caused by interaction with a member (for example, ITO), a substrate (for example, a glass substrate, an acrylic substrate, a transparent substrate, a flexible substrate, or the like), a resin layer (for example, a color filter, an alignment film, an overcoat layer, or the like), or an insulating film (for example, an inorganic material film, siNx, or the like)) directly contacting the liquid crystal layer containing the liquid crystal composition.
The alignment aid preferably has a polymerizable group for polymerization, a mesogen group (mesogen group) similar to a liquid crystal molecule, an adsorption group (polar group) capable of interacting with a member directly abutting on the liquid crystal layer, and an alignment inducing group that causes alignment of the liquid crystal molecule.
Preferably, the adsorption group and the orientation inducing group are bonded to the mesogenic group, and the polymerizable group is substituted with Cheng Jiejing groups, adsorption groups and orientation inducing groups directly or optionally via a spacer. The polymerizable group may be substituted with a mesogenic group in a state of being incorporated into the adsorbing group.
The left and right side groups in the chemical formula are denoted as bond.
"Orientation inducing group"
The alignment inducing group has a function of inducing alignment of liquid crystal molecules, and is preferably a group represented by the following general formula (AK).
[ Chemical 1]
RAK1-* (AK)
Wherein R AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms. Wherein, -CH 2 -in the alkyl group may be independently substituted with-CH=CH-, -C≡C-, -O-, -CO-, -COO-or-OCO-respectively without direct bonding of oxygen atoms, and one or more hydrogen atoms in the alkyl group may be independently substituted with halogen groups respectively.
R AK1 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and still more preferably a linear alkyl group having 1 to 8 carbon atoms.
In addition, one or two or more of non-adjacent-CH 2 -groups in the alkyl group may be independently substituted with-CH=CH-, -C≡C-, -O-, -CO-, -COO-, or-OCO-.
Further, the hydrogen atom in the alkyl group may be substituted with a fluorine atom or a chlorine atom, or may be substituted with a fluorine atom.
The alignment inducing group is preferably directly bonded to the mesogenic group or bonded to the mesogenic group via a spacer as needed, from the viewpoint of imparting so-called amphiphilicity to the alignment aid with respect to the liquid crystal layer.
"Polymerizable group"
The polymerizable group is preferably represented by P AP1－SpAP1 -.
P AP1 is preferably a group selected from the group represented by the following general formulae (AP-1) to (AP-9).
[ Chemical 2]
Wherein R AP1 and R AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms. Wherein one or more of the-CH 2 -groups in the alkyl group may be substituted with-O-or-CO-, one or two or more hydrogen atoms in the alkyl group may be each independently substituted with a halogen atom or a hydroxyl group.
W AP1 represents a single bond, -O-, -COO-, or-CH 2 -.
T AP1 represents 0, 1 or 2.
P AP1 is preferably a group represented by the following general formulae (AP-1) to (AP-7), more preferably a group represented by the following general formula (AP-1) or (AP-2), and still more preferably a group represented by the following general formula (AP-1).
Sp AP1 preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably represents a single bond or a linear alkylene group having 1 to 20 carbon atoms, and still more preferably represents a single bond or a linear alkylene group having 2 to 10 carbon atoms.
In Sp AP1, one or two or more of the non-adjacent-CH 2 -groups in the alkylene groups may be independently substituted with-CH=CH-, -C≡C-, -O-, -CO-, -COO-groups or-OCO-groups.
In the orientation aid, the number of polymerizable groups (P AP1－SpAP1 -) is preferably 1 to 5, more preferably 1 to 4, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The hydrogen atoms in p AP1－SpAP1 -may be substituted with polymerizable groups, adsorbing groups, and/or orientation inducing groups.
The polymerizable group (P AP1－SpAP1 -) may also be bound to a polymerizable group, a mesogenic group, an adsorbing group and/or an orientation inducing group.
The polymerizable group (P AP1－SpAP1 -) is preferably bonded to a mesogenic group, an adsorptive group or an orientation inducing group, more preferably bonded to a mesogenic group or an adsorptive group.
In the case where a plurality of P AP1 and/or Sp AP1 -exist in the molecule, they may be the same or different from each other.
"Mesogenic group"
The mesogenic group is a group having a rigid portion, for example, a group having 1 or more cyclic groups, preferably a group having 2 to 4 cyclic groups, and more preferably a group having 3 to 4 cyclic groups. Furthermore, the cyclic groups may be optionally linked via a linking group. The mesogenic group preferably has a skeleton similar to the liquid crystal molecules (liquid crystal compounds) used in the liquid crystal layer.
In the present specification, "cyclic group" means an atomic group in which constituent atoms are bonded to form a ring, and includes carbocycles, heterocycles, saturated or unsaturated cyclic structures, monocyclic, bicyclic structures, polycyclic structures, aromatic groups, non-aromatic groups, and the like.
The cyclic group may contain at least 1 heteroatom, and may be substituted with at least 1 substituent (halogen group, polymerizable group, organic group (alkyl group, alkoxy group, aryl group, etc.)). In the case where the cyclic group is a single ring, the mesogenic group preferably contains two or more single rings.
The aforementioned mesogenic group is preferably represented by, for example, general formula (AL).
[ Chemical 3]
Wherein Z AL1 represents a single bond 、－CH＝CH－、－CF＝CF－、－C≡C－、－COO－、－OCO－、－OCOO－、－CF2O－、－OCF2－、－CH＝CHCOO－、－OCOCH＝CH－、－CH2－CH2COO－、－OCOCH2－CH2－、－CH＝C(CH3)COO－、－OCOC(CH3)＝CH－、－CH2－CH(CH3)COO－、－OCOCH(CH3)－CH2－、－OCH2CH2O－ or an alkylene group having 1 to 20 carbon atoms. Wherein, one or two or more of non-adjacent-CH 2 -groups in the alkylene group may be substituted with-O-, -COO-or-OCO-.
A AL1 and A AL2 each independently represent a divalent cyclic group.
One or more hydrogen atoms in Z AL1、AAL1 and A AL2 may be independently substituted with a halogen group, an adsorbing group, P AP1－SpAP1 -or a monovalent organic group, and in the case where a plurality of Z AL1 and A AL1 are present in the molecule, they may be the same or different.
M AL1 represents an integer of 1 to 5.
In the general formula (AL), Z AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, more preferably a single bond one or more non-adjacent-CH 2 -of- (CH 2)2 -or- (CH 2)4 -) alkylene groups may be substituted by-O-; -COO-or-OCO-.
Further, in order to improve the linearity of the rod-like molecule, Z AL1 is preferably a single bond in which a ring is directly connected to a ring or in which the number of atoms directly connecting a ring to a ring is an even number. For example, in the case of-CH 2－CH2 COO-the number of atoms directly connecting the rings to the rings is 4.
In the general formula (AL), a AL1 and a AL2 each independently represent a divalent cyclic group. The divalent cyclic group is preferably selected from the group consisting of 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, tetrahydrothiopyran-2, 5-diyl, thiophene-2, 5-diyl, 1, 4-bicyclo (2, 2) octylene, decalin-2, 6-diyl, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, pyrazine-2, 5-diyl, thiophene-2, 5-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, 2, 6-naphthylene, phenanthrene-2, 7-diyl, 9, 10-dihydrophenanthrene-2, 7-diyl, 1,2,3, 4a,9,10 a-octahydrophenanthrene-2, 7-diyl, 1, 4-naphthylene, and benzo [1,2-b ]: 4,5-b' ] dithiophene-2, 6-diyl, benzo [1,2-b:4,5-b' ] diselenophene-2, 6-diyl, [1] benzothiophene [3,2-b ] thiophene-2, 7-diyl, [1] benzoselenophene [3,2-b ] selenophene-2, 7-diyl and fluorene-2, 7-diyl, more preferably 1, 4-phenylene, 1, 4-cyclohexylene, 2, 6-naphthylene or phenanthrene-2, 7-diyl, still more preferably 1, 4-phenylene or 1, 4-cyclohexylene.
Furthermore, these groups may be unsubstituted or may be substituted with a substituent. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Further, the alkyl group may be substituted with a fluorine atom or a hydroxyl group.
In addition, one or more hydrogen atoms in the cyclic group may be substituted with a halogen group, an adsorption group, P AP1－SpAP1 -or a monovalent organic group.
In the general formula (AL), the monovalent organic group is a group having a chemical structure formed by converting an organic compound into a monovalent group, and is an atomic group in which 1 hydrogen atom is removed from the organic compound.
Examples of the monovalent organic group include: alkyl group having 1 to 15 carbon atoms, alkenyl group having 2 to 15 carbon atoms, alkoxy group having 1 to 14 carbon atoms, alkenyloxy group having 2 to 15 carbon atoms, etc.; the alkyl group having 1 to 15 carbon atoms or the alkoxy group having 1 to 14 carbon atoms is preferable, the alkyl group having 1 to 8 carbon atoms or the alkoxy group having 1 to 8 carbon atoms is more preferable, the alkyl group having 1 to 5 carbon atoms or the alkoxy group having 1 to 4 carbon atoms is more preferable, the alkyl group having 1 to 3 carbon atoms or the alkoxy group having 1 to 2 carbon atoms is particularly preferable, and the alkyl group having 1 or 2 carbon atoms or the alkoxy group having 1 carbon atom is most preferable.
In addition, one or two or more of the above alkyl groups, alkenyl groups, alkoxy groups, and alkenyloxy groups, which are not adjacent to each other, -CH 2 -, may be substituted with-O-, -COO-, or-OCO-. The monovalent organic group may also function as an orientation-inducing group described below.
In the general formula (AL), m AL1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and further preferably 2 or 3.
As a preferable embodiment of the above mesogenic group, the following formulas (me-1) to (me-45) are exemplified.
[ Chemical 4]
[ Chemical 5]
[ Chemical 6]
[ Chemical 7]
[ Chemical 8]
The general formula (AL) is a structure obtained by detaching two hydrogen atoms from these compounds.
In these formulae (me-1) to (me-45), one or two or more hydrogen atoms in the cyclohexane ring, the benzene ring or the naphthalene ring may be each independently substituted with a halogen group, a P AP1－SpAP1 -, a monovalent organic group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorption group or an orientation-inducing group.
Among the above mesogenic groups, preferred are the formulae (me-8) to (me-45), more preferred are the formulae (me-8) to (me-10), the formulae (me-12) to (me-18), the formulae (me-22) to (me-24), the formulae (me-26) to (me-27) and the formulae (me-29) to (me-45), and still more preferred are the formulae (me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36) to (me-37) and (me-42) to (me-45).
Of the above mesogenic groups, a particularly preferred embodiment is the following general formula (AL-1) or (AL-2), and a most preferred embodiment is the following general formula (AL-1).
[ Chemical 9]
Wherein X AL101～XAL118、XAL201～XAL214 each independently represents a hydrogen atom, a halogen group, a P AP1－SpAP1 -, an adsorbing group or an orientation inducing group.
Ring a AL11, ring a AL12 and ring a AL21 each independently represent a cyclohexane ring or a benzene ring.
Any 1 or more than 2 of X AL101～XAL118、XAL201～XAL214 are substituted by an adsorption group.
Any 1 or 2 or more of X AL101～XAL118、XAL201～XAL214 are substituted with an orientation inducing group.
The adsorption group and the orientation inducing group may be substituted with P AP1－SpAP1 -.
The general formula (AL-1) or the general formula (AL-2) has 1 or more than 2 kinds of P AP1－SpAP1 -in the molecule.
In the general formula (AL-1), X AL101 is preferably an orientation-inducing group.
In the general formula (AL-1), at least 1 of X AL109、XAL110 and X AL111 is preferably an adsorption group, more preferably X AL109 and X AL110 are both adsorption groups or X AL110 is an adsorption group, and still more preferably X AL110 is an adsorption group.
In the general formula (AL-1), at least 1 of X AL109、XAL110 and X AL111 is preferably P AP1－SpAP1 -or an adsorption group having a polymerizable site in the structure, and more preferably, both or one of X AL109 and X AL111 is P AP1－SpAP1 -.
In the general formula (AL-1), one or both of X AL104～XAL108、XAL112～XAL116 are preferably independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. Particularly preferably, X AL105、XAL106 or X AL107 is independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.
In the general formula (AL-2), X AL201 is preferably an orientation-inducing group.
In the general formula (AL-2), at least 1 of X AL207、XAL208 and X AL209 is preferably an adsorption group, more preferably X AL207 and X AL208 are both adsorption groups or X AL208 is an adsorption group, and still more preferably X AL208 is an adsorption group.
In the general formula (AL-2), at least 1 of X AL207、XAL208 and X AL209 is preferably P AP1－SpAP1 -or an adsorption group having a polymerizable site in the structure, and more preferably, both or one of X AL207 and X AL209 is P AP1－SpAP1 -.
In the general formula (AL-2), one or both of X AL202～XAL206、XAL210～XAL214 are preferably independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. Particularly preferably, X AL204、XAL205 or X AL206 is independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.
Adsorption group "
The adsorption group is a group having a function of adsorbing an adsorption medium such as a substrate, a film, or an electrode, which is a layer in contact with the liquid crystal composition.
Adsorption is generally classified into chemisorption in which chemical bonds (covalent bonds, ionic bonds, or metal bonds) are formed to adsorb between an adsorption medium and an adsorption substance, and physisorption other than chemisorption. In the present specification, the adsorption may be either chemisorption or physisorption, and preferably physisorption. Therefore, the adsorption group is preferably a group that can physically adsorb to the adsorption medium, and more preferably a group that can bind to the adsorption medium by intermolecular force.
Examples of the means for bonding the adsorption medium by intermolecular force include a means formed by interaction such as permanent dipole, permanent quadrupole, dispersion force, charge transfer force, and hydrogen bond.
Preferred modes of the adsorption group include a mode in which the adsorption group is bonded to the adsorption medium by hydrogen bond. In this case, the adsorbing group may function as either or both of a donor and an acceptor of protons present between hydrogen bonds.
The adsorption group is preferably a group containing a polar element having an atomic group in which a carbon atom and a heteroatom are connected (hereinafter, the "adsorption group" may be referred to as a "polar group"). In the present specification, the polar element refers to an atomic group in which a carbon atom and a hetero atom are directly connected.
The heteroatom is preferably at least 1 selected from the group consisting of N, O, S, P, B and Si, more preferably at least 1 selected from the group consisting of N, O and S, still more preferably at least 1 selected from the group consisting of N and O, and particularly preferably O.
In addition, in the orientation aid, the valence of the polar element is not particularly limited to monovalent, divalent, trivalent, etc., and the number of polar elements in the adsorption group is also not particularly limited.
The orientation aid preferably has 1 to 8 adsorption groups in one molecule, more preferably 1 to 4 adsorption groups, and still more preferably 1 to 3 adsorption groups.
Furthermore, the polymerizable group and the orientation inducing group are removed from the adsorbing group, but the adsorbing group includes a structure in which a hydrogen atom in the adsorbing group is substituted with P AP1－SpAP1 -and a structure in which a hydrogen atom in P AP1－SpAP1 -is substituted with-OH.
The adsorption group contains one or more polar elements and is roughly divided into a cyclic base type and a chain base type.
The cyclic base is a system in which a cyclic base having a cyclic structure including a polar element is included in the structure, and the chain base is a system in which a cyclic base having a cyclic structure including a polar element is not included in the structure.
The chain base type is a type having a polar element in a linear or branched chain base, and may have a cyclic structure in which the polar element is not included in a part thereof.
The cyclic group-type adsorbing group means a structure having at least 1 polar element in a cyclic atomic arrangement.
In the present specification, the cyclic group means the above. Therefore, the cyclic group-type adsorbing group may include a cyclic group containing a polar element, and the adsorbing group may be branched or linear as a whole.
On the other hand, the chain-based adsorption group means a structure having a structure in which a cyclic atomic arrangement including a polar element is not included in a molecule, and at least 1 polar element is included in a linear atomic arrangement (branching).
In the present specification, a chain group refers to an atomic group in which atoms constituting the chain group are bonded in a linear (branched) form without including a cyclic atomic arrangement in the structural formula, and refers to an acyclic group. In other words, the chain group means a linear or branched aliphatic group, and may include either a saturated bond or an unsaturated bond.
Thus, chain groups include, for example, alkyl, alkenyl, alkoxy, ester, ether, ketone, or the like. Further, the hydrogen atom in these groups may be substituted with at least 1 substituent (a reactive functional group (vinyl group, acrylic group, methacrylic group (METHACRYLIC GROUP) or the like), a chain-like organic group (alkyl group, cyano group or the like)). The chain group may be either a straight chain or a branched chain.
The adsorbing group of the ring-type group is preferably a heteroaryl group having 3 to 20 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 20 carbon atoms (including a condensed ring), more preferably a heteroaryl group having 3 to 12 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 12 carbon atoms (including a condensed ring), still more preferably a heteroaryl group having 5-membered ring, a heteroalicyclic group having 5-membered ring, a heteroaryl group having 6-membered ring or a heteroalicyclic group having 6-membered ring. The hydrogen atom in these ring structures may be substituted with a halogen group, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkoxy group.
As the chain-based adsorption group, a linear or branched alkyl group having 1 to 20 carbon atoms in which a hydrogen atom, -CH 2 -in the structure is substituted with a polar element is preferable. Furthermore, one or two or more of the non-adjacent-CH 2 -groups in the alkyl group may be substituted with-CH=CH-, -C≡C-, -O-, -CO-, -COO-or-OCO-. The chain-based adsorption group preferably contains 1 or more polar elements at its end.
The hydrogen atoms in the adsorbing groups may be substituted with polymerizable groups.
Specific examples of the polar element include: an oxygen atom-containing polar element (hereinafter, an oxygen-containing polar element), a nitrogen atom-containing polar element (hereinafter, a nitrogen-containing polar element), a phosphorus atom-containing polar element (hereinafter, a phosphorus-containing polar element), a boron atom-containing polar element (hereinafter, a boron-containing polar element), a silicon atom-containing polar element (hereinafter, a silicon-containing polar element), or a sulfur atom-containing polar element (hereinafter, a sulfur-containing polar element). From the viewpoint of adsorption capacity, the polar element is preferably a nitrogen-containing polar element, or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.
The oxygen-containing polar element is preferably at least 1 group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group (alkylol group), an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group, and an ester group, or a group to which the group is attached to a carbon atom.
The nitrogen-containing polar element is preferably at least 1 group selected from the group consisting of a cyano group, a primary amine group, a secondary amine group, a tertiary amine group, a pyridyl group, a carbamoyl group, and a ureido group, or a group having the group attached to a carbon atom.
The phosphorus-containing polar element is preferably at least 1 group selected from the group consisting of a phosphinyl group (phosphinyl group) and a phosphate group, or a group having the group attached to a carbon atom.
Therefore, the adsorption group is preferably one or more groups selected from 1 or 2 or more groups selected from the group consisting of a cyclic group having an oxygen-containing polar element (hereinafter, an oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter, a nitrogen-containing cyclic group), a cyclic group having a sulfur-containing polar element (hereinafter, a sulfur-containing cyclic group), a chain group having an oxygen-containing polar element (hereinafter, an oxygen-containing chain group), and a chain group having a nitrogen-containing polar element (hereinafter, a nitrogen-containing chain group), or the groups themselves or the groups are included, and more preferably 1 or 2 or more groups selected from the group consisting of an oxygen-containing cyclic group, a sulfur-containing cyclic group, an oxygen-containing chain group, and a nitrogen-containing chain group from the viewpoint of adsorption ability.
The oxygen-containing cyclic group preferably includes any of the following groups having an oxygen atom as an ether group in the ring structure.
[ Chemical 10]
The oxygen-containing cyclic group preferably includes any of the following groups having an oxygen atom in the ring structure as a carbonyl group, a carbonate group, and an ester group.
[ Chemical 11]
The nitrogen-containing cyclic group preferably contains any of the following groups.
[ Chemical 12]
As the oxygen-containing chain group, any one of the following groups is preferably contained.
[ Chemical 13]
/>
Wherein R at1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Z at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. Wherein, -CH 2 -in alkylene or alkenylene groups may be substituted by-O-, -COO-, -C (=o) -, -OCO-in such a way that the oxygen atoms are not directly adjacent.
X at1 represents an alkyl group having 1 to 15 carbon atoms. Wherein, -CH 2 -in the alkyl group may be substituted by-O-, -COO-, -C (=o) -, -OCO-in such a way that the oxygen atoms are not directly adjacent.
As the nitrogen-containing chain group, any one of the following groups is preferably contained.
[ Chemical 14]
Wherein R at、Rbt、Rct and R dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The adsorption group is preferably a group represented by the following general formula (AT).
[ 15]
Wherein Sp AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atom in the alkylene group may be substituted with-OH, -CN, -W AT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkylene group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, -ch=ch-in such a manner that the oxygen atom is not directly bonded.
W AT1 represents a single bond or a general formula (WAT 1) or (WAT 2) shown below.
Z AT1 represents a monovalent group containing a polar element. Wherein the hydrogen atom in Z AT1 may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -.
[ 16]
(Wherein Sp WAT1 and Sp WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and a hydrogen atom in the alkylene group may be substituted with-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in alkylene groups may be substituted by cyclic groups, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a way that the oxygen atoms are not directly bound
Sp AT1、SpWAT1 and Sp WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms, still more preferably a single bond or a linear alkylene group having 2 to 10 carbon atoms.
In Sp AT1、SpWAT1 and Sp WAT2, one or two or more non-adjacent-CH 2 -groups in the alkylene groups can be independently represented by-CH=CH-, -C.ident.C-, -O-, -CO-, -COO-, or-OCO-substitution.
In addition, the hydrogen atoms in Sp AT1 and Sp WAT1 may each be independently substituted by-Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -.
Z AT1 represents a monovalent group containing a polar element, and is preferably a group represented by the following general formula (ZAT 1-1) or (ZAT 1-2).
[ Chemical 17]
Wherein Sp ZAT11 and Sp ZAT12 each independently represent a linear or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atom in the alkylene group may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkylene group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a manner that the oxygen atoms are not directly adjacent.
Z ZAT11 represents a group containing a polar element.
The structure represented by the ring containing Z ZAT12 in the general formula (ZAT 1-2) represents a 5-to 7-membered ring.
The hydrogen atoms in Z ZAT11 and Z ZAT12 may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -.
R ZAT11 and R ZAT12 each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms. Wherein the hydrogen atom in the alkyl group may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkyl group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a manner that the oxygen atom is not directly bonded.
As the group represented by the general formula (ZAT 1-1), groups represented by the following general formulae (ZAT 1-1-1) to (ZAT 1-1-30) are preferable.
[ Chemical 18]
[ Chemical 19]
In the formula, the hydrogen atom bonded to the carbon atom may be substituted with-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -.
Sp ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atom in the alkylene group may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkylene group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a manner that the oxygen atoms are not directly adjacent.
R ZAT11 represents a linear or branched alkyl group having 1 to 8 carbon atoms. Wherein the hydrogen atom in the alkyl group may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkyl group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a manner that the oxygen atom is not directly bonded.
As the group represented by the general formula (ZAT 1-2), groups represented by the following general formulae (ZAT 1-2-1) to (ZAT 1-2-9) are preferable.
[ Chemical 20]
In the formula, the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, -OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -.
Sp ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atom in the alkylene group may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkylene group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a manner that the oxygen atoms are not directly adjacent.
As the group represented by the general formula (ZAT 1-1), the following groups can be mentioned.
[ Chemical 21]
[ Chemical 22]
[ Chemical 23]
[ Chemical 24]
[ Chemical 25]
[ Chemical 26]
Wherein R tc represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or P AP1－SpAP1 -. Wherein the hydrogen atom in the alkyl group may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkyl group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a manner that the oxygen atoms are not directly adjacent.
The hydrogen atoms within the molecule may be substituted with P AP1－SpAP1 -.
And represents a bond.
The orientation aid is preferably one in which the polar element contained in the adsorption group and the polar element contained in the polymerizable group are locally present. The adsorption group is a structure important for vertically aligning liquid crystal molecules, and by making the adsorption group adjacent to the polymerizable group, a better alignment property is obtained, and further, a good solubility to the liquid crystal composition is exhibited.
Specifically, the orientation aid is preferably one having a polymerizable group and an adsorbing group on the same ring of the mesogenic group. The form comprises: a mode in which 1 or more polymerizable groups and 1 or more adsorbing groups are bonded to the same ring; and at least one of 1 or more polymerizable groups or at least one of 1 or more adsorbing groups, wherein one of the groups is bonded to the other and has a polymerizable group and an adsorbing group on the same ring.
In addition, in this case, a hydrogen atom in a spacer group which the polymerizable group has may be substituted with an adsorbing group, and further, a hydrogen atom in the adsorbing group may be substituted with the polymerizable group via the spacer group.
As the orientation aid, a compound represented by the following general formula (SAL) is preferable.
[ Chemical 27]
In the formula, the hydrogen atom bonded to the carbon atom may be substituted with a linear or branched alkyl group having 1 to 25 carbon atoms, -OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -. Wherein the hydrogen atom in the alkyl group may be substituted by-OH, -CN, -Sp AT1－WAT1－ZAT1 or P AP1－SpAP1 -, -CH 2 -in the alkyl group may be substituted with a cyclic group, -O-, -COO-, -C (=o) -, -OCO-, or-ch=ch-in such a manner that the oxygen atom is not directly bonded.
R AK1 represents the same meaning as R AK1 in the general formula (AK).
Each of a AL1 and a AL2 independently represents the same meaning as a AL1 and a AL2 in the general formula (AL).
Z AL1 represents the same meaning as Z AL1 in the general formula (AL).
M AL1 represents the same meaning as m AL1 in the general formula (AL).
Sp AT1 represents the same meaning as Sp AT1 in the general formula (AT).
W AT1 represents the same meaning as W AT1 in the general formula (AT).
Z AT1 represents the same meaning as Z AT1 in the general formula (AT).
The compounds represented by the general formula (SAL) are preferably compounds represented by the following formulas (SAL-1.1) to (SAL-2.9).
[ Chemical 28]
[ Chemical 29]
[ Chemical 30]
[ 31]
[ Chemical 32]
[ 33]
[ Chemical 34]
[ 35]
[ 36]
[ 37]
[ 38]
[ 39]
The amount of the alignment aid contained in the liquid crystal composition is preferably about 0.01 to 50 mass%. The lower limit value is more preferably 0.05% by mass or 0.1% by mass in terms of more properly aligning the liquid crystal molecules. On the other hand, from the viewpoint of improving response characteristics, the upper limit value is more preferably 30 mass%, 10 mass%, 7 mass%, 5 mass%, 4 mass%, 3 mass%.
((Liquid Crystal molecule))
The liquid crystal molecule preferably contains at least 1 of the compounds represented by the general formulae (N-1) to (N-3).
[ 40]
Wherein R N11、RN12、RN21、RN22、RN31 and R N32 each independently represent an alkyl group having 1 to 8 carbon atoms. Wherein any one or not adjacent two or more of-CH 2 -groups present in the alkyl groups may be substituted with-CH=CH-, -C≡C-, -O-, -CO-, -COO-or-OCO-.
Each of a N11、AN12、AN21、AN22、AN31 and a N32 independently represents a group selected from the group consisting of (a) to (d):
(a) 1, 4-cyclohexylene (any one or not two or more of which groups may be-CH 2 -substituted by-O-),
(B) 1, 4-phenylene (any one or two or more non-adjacent-CH=groups in the group may be substituted with-N=groups),
(C) Naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (any one or two or more non-adjacent-ch=groups present in these groups may be substituted by-n=), and
(D) 1, 4-cyclohexenylene;
The aforementioned group (a), group (b), group (c) and group (d) may each be independently substituted with a cyano group, a fluorine atom or a chlorine atom.
Z N11、ZN12、ZN21、ZN22、ZN31 and Z N32 each independently represent a single bond 、－CH2CH2－、－(CH2)4－、－OCH2－、－CH2O－、－COO－、－OCO－、－OCF2－、－CF2O－、－CH＝N－N＝CH－、－CH＝CH－、－CF＝CF－ or-C.ident.C-.
X N21 represents a hydrogen atom or a fluorine atom.
T N31 represents-CH 2 -or an oxygen atom.
N N11、nN12、nN21、nN22、nN31 and n N32 each independently represent an integer of 0 to 3, and n N11+nN12、nN21+nN22 and n N31+nN32 each independently represent 1, 2 or 3.
When n N11、nN12、nN21、nN22、nN31 and n N32 are 2 or more, a N11～AN32、ZN11～ZN32 may be the same or different from each other.
The compound represented by any one of the above general formulae (N-1) to (N-3) preferably has a negative dielectric anisotropy (. DELTA.. Epsilon.) and an absolute value of more than 3.
R N11～RN32 is preferably independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, particularly preferably an alkyl group having 2 to 5 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms, and most preferably an alkenyl group having 3 carbon atoms (i.e., a propenyl group).
When the ring structure to which they are bonded is a benzene ring (aromatic ring), R N11～RN32 is preferably each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 4 to 5 carbon atoms.
When the ring structure to which they are bonded is a saturated ring structure such as a cyclohexane ring, a pyran ring, or a dioxane ring, R N11～RN32 is preferably each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms (when present) of R N11～RN32 is preferably 5 or less, and more preferably straight-chain.
The alkenyl group is preferably a group selected from the group represented by the following formulas (R1) to (R5).
[ Chemical 41]
In the formulas, black dots represent bond keys.
In the case of increasing the refractive index anisotropy (Δn) of the liquid crystal molecules, a N11～AN32 is preferably an aromatic group independently, and in the case of improving the response speed of the liquid crystal molecules, an aliphatic group is preferably used.
The aromatic or aliphatic group is preferably trans-1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2] octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, more preferably a structure represented by the following formula, and still more preferably trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene or 1, 4-phenylene.
[ Chemical 42]
Z N11～ZN32 is preferably each independently-CH 2O－、－CF2O－、－CH2CH2－、－CF2CF2 -or a single bond, more preferably-CH 2O－、－CH2CH2 -or a single bond, particularly preferably-CH 2 O-or a single bond.
X N21 is preferably a fluorine atom.
T N31 is preferably an oxygen atom.
Preferably, n N11+nN12、nN21+nN22 and n N31+nN32 are each independently 1 or 2, more preferably a combination of n N11 being 1 and n N12 being 0, a combination of n N11 being 2 and n N12 being 0, a combination of n N11 being 1 and n N12 being 1, a combination of n N11 being 2 and n N12 being 1, a combination of n N21 being 1 and n N22 being 0, a combination of n N21 being 2 and n N22 being 0, a combination of n N31 being 1 and n N32 being 0, and a combination of n N31 being 2 and n N32 being 0.
The amounts of the compounds represented by the general formulae (N-1) to (N-3) contained in the liquid crystal composition are preferably as follows. That is, the preferable lower limit value is 1 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 75 mass%, 80 mass%. On the other hand, the preferable upper limit is 95 mass%, 85 mass%, 75 mass%, 65 mass%, 55 mass%, 45 mass%, 35 mass%, 25 mass%, 20 mass%.
In the case where the viscosity (. Eta.) of the liquid crystal composition is kept low and the response speed is improved, the amount of the compound represented by the general formulae (N-1) to (N-3) is preferably low at the lower limit and low at the upper limit. Further, in the case of keeping the nematic phase-isotropic liquid phase transition temperature (Tni) of the liquid crystal composition high and improving the temperature stability, the amount thereof is preferably low in the lower limit and low in the upper limit. In addition, in the case of increasing the dielectric anisotropy (Δε) of the liquid crystal composition in order to keep the driving voltage of the liquid crystal display element low, the amount thereof is preferably high at the lower limit value and high at the upper limit value.
As the compound represented by the general formula (N-1), compounds represented by the following general formulae (N-1 a) to (N-1 g) are mentioned.
[ Chemical 43]
Wherein R N11 and R N12 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
N Na11、nNb11、nNc11 and n Nd11 each independently represent 0 to 2.
N Ne11、nNf11 and n Ng11 each independently represent 1 or 2.
A Ne11 represents trans-1, 4-cyclohexylene or 1, 4-phenylene.
A Ng11 represents trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene or 1, 4-phenylene, at least 1 representing 1, 4-cyclohexenylene.
Z Ne11 represents a single bond or ethylene, and at least 1 represents ethylene.
In the general formulae (N-1 a) to (N-1 g), N Na11 preferably represents 0 or 1.n Nb11 preferably represents 1 or 2.n Nc11 preferably represents 0 or 1.n Nd11 preferably represents 1 or 2.n Ne11 preferably represents 1 or 2.n Nf12 preferably represents 1 or 2.n Ng11 preferably represents 1 or 2. In the general formulae (N-1 e) and (N-1 g), the plurality of A Ne11、ZNe11 and/or A Ng11 present in the molecule may be the same or different.
More specifically, the compounds represented by the general formula (N-1) are preferably compounds represented by the following general formulae (N-1-1) to (N-1-5), general formulae (N-1-10) to (N-1-18) or general formulae (N-1-20) to (N-1-22).
The compound represented by the general formula (N-1-1) is the following compound.
[ 44]
Wherein R N111 and R N112 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably a propyl group, a pentyl group or a vinyl group.
R N112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group or a butoxy group.
The compound represented by the general formula (N-1-1) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-1) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 33 mass%, 35 mass%. On the other hand, the preferable upper limit value is 50 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-1) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be low. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-1) to the middle of the above range.
The compounds represented by the general formula (N-1-1) are preferably compounds represented by the following formulas (N-1-1.1) to (N-1-1.4), formulas (N-1-1.11) to (N-1-1.14) or (N-1-1.20) to (N-1-1.22), more preferably compounds represented by the formulas (N-1-1.1) to (N-1-1.4), and still more preferably compounds represented by the formulas (N-1-1.1) or (N-1-1.3).
[ 45]
The compound represented by the general formula (N-1-2) is the following compound.
[ Chemical 46]
Wherein R N121 and R N122 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, propyl group, butyl group or pentyl group.
R N122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group.
The compound represented by the general formula (N-1-2) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 5 mass%, 7 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 33 mass%, 35 mass%, 37 mass%, 40 mass%, 42 mass%. On the other hand, the preferable upper limit value is 50 mass%, 48 mass%, 45 mass%, 43 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%.
In the case where improvement of Δε is important, it is preferable that the amount of the compound represented by the general formula (N-1-2) is set to be high, and if solubility at low temperature is important, the effect is high if the amount is set to be small, and if Tni is important, the effect is high if the amount is set to be large. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-2) to the middle of the above range.
The compounds represented by the general formula (N-1-2) are preferably compounds represented by the following formulas (N-1-2.1) to (N-1-2.7), formulas (N-1-2.10) to (N-1-2.13) or formulas (N-1-2.20) to (N-1-2.22), more preferably compounds represented by the formulas (N-1-2.3) to (N-1-2.7), formulas (N-1-2.10), formulas (N-1-2.11), formulas (N-1-2.13) or formulas (N-1-2.20).
In the case where improvement of Δε is important, the compounds represented by the formulas (N-1-2.3) to (N-1-2.7) are preferable. In the case where improvement of Tni is important, the compound represented by the formula (N-1-2.10), the formula (N-1-2.11) or the formula (N-1-2.13) is preferable. In addition, in the case where improvement of the response speed is important, the compound represented by the formula (N-1-2.20) is preferable.
[ 47]
The compound represented by the general formula (N-1-3) is the following compound.
[ 48]
Wherein R N131 and R N132 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
R N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably a 1-propenyl group, an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-3) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
In the case where improvement of Δε is important, it is preferable that the amount of the compound represented by the general formula (N-1-3) is set to be high, and if solubility at low temperature is important, the effect is high if the amount is set to be large, and if Tni is important, the effect is high if the amount is set to be large. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-3) to the middle of the above range.
The compound represented by the general formula (N-1-3) is preferably a compound represented by the following formulae (N-1-3.1) to (N-1-3.7), formula (N-1-3.10), formula (N-1-3.11), formula (N-1-3.20) or formula (N-1-3.21), more preferably a compound represented by the following formulae (N-1-3.1) to (N-1-3.7) or formula (N-1-3.21), and still more preferably a compound represented by the following formulae (N-1-3.1) to (N-1-3.4) or formula (N-1-3.6).
[ 49]
The compounds represented by the formulae (N-1-3.1) to (N-1-3.4), the formulae (N-1-3.6) and (N-1-3.21) may be used singly or in combination of at least 2 kinds. Among them, a combination of the compound represented by the formula (N-1-3.1) and the compound represented by the formula (N-1-3.2), 2 or 3 combinations selected from the group consisting of the compound represented by the formula (N-1-3.3), the compound represented by the formula (N-1-3.4) and the compound represented by the formula (N-1-3.6) is preferable.
The compound represented by the general formula (N-1-4) is the following compound.
[ 50]
Wherein R N141 and R N142 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N141 and R N142 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably a methyl group, a propyl group, an ethoxy group or a butoxy group.
The compound represented by the general formula (N-1-4) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-4) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 3 mass%, 5 mass%, 7 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 11 mass%, 10 mass%, 8 mass%.
Further, when attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-4) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be low. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-4) to the middle of the above range.
The compound represented by the general formula (N-1-4) is preferably a compound represented by the following formulas (N-1-4.1) to (N-1-4.4) or (N-1-4.11) to (N-1-4.14), more preferably a compound represented by the following formulas (N-1-4.1) to (N-1-4.4), still more preferably a compound represented by the following formulas (N-1-4.1), formula (N-1-4.2) or formula (N-1-4.4).
[ 51]
The compound represented by the general formula (N-1-5) is the following compound.
[ 52]
/>
Wherein R N151 and R N152 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N151 and R N152 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
The compound represented by the general formula (N-1-5) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-5) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 8 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 33 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
Further, when attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by the general formula (N-1-5) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be small, and when attention is paid to Tni, the effect is high if the amount is set to be large. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-5) to the middle of the above range.
The compound represented by the general formula (N-1-5) is preferably a compound represented by the following formulas (N-1-5.1) to (N-1-5.6), more preferably a compound represented by the formula (N-1-5.1), formula (N-1-5.2) or formula (N-1-5.4).
[ 53]
The compound represented by the general formula (N-1-10) is the following compound.
[ 54]
/>
Wherein R N1101 and R N1102 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, propyl group, butyl group, vinyl group or 1-propenyl group.
R N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-10) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-10) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
Further, when attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by the general formula (N-1-10) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-10) to the middle of the above range.
The compounds represented by the general formula (N-1-10) are preferably compounds represented by the following formulas (N-1-10.1) to (N-1-10.5) or formulas (N-1-10.11) to (N-1-10.14), more preferably compounds represented by the formulas (N-1-10.1) to (N-1-10.5), still more preferably compounds represented by the formulas (N-1-10.1) or (N-1-10.2).
[ 55]
The compound represented by the general formula (N-1-11) is the following compound.
[ 56]
Wherein R N1111 and R N1112 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, propyl group, butyl group, vinyl group or 1-propenyl group.
R N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-11) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-11) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
Further, when attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by the general formula (N-1-11) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be low, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-11) to the middle of the above range.
The compounds represented by the general formula (N-1-11) are preferably compounds represented by the following formulas (N-1-11.1) to (N-1-11.5) or formulas (N-1-11.11) to (N-1-11.14), more preferably compounds represented by the formulas (N-1-11.1) to (N-1-11.5), still more preferably compounds represented by the formulas (N-1-11.2) or (N-1-11.4).
[ 57]
The compound represented by the general formula (N-1-12) is the following compound.
[ 58]
Wherein R N1121 and R N1122 each represent R N11 and R N12 in the general formula (N-1).
R N1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
R N1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-12) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-12) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-12) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-12) to the middle of the above range.
The compound represented by the general formula (N-1-13) is the following compound.
[ 59]
Wherein R N1131 and R N1132 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
R N1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-13) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-13) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
In the case where improvement of Δε is important, it is preferable that the amount of the compound represented by the general formula (N-1-13) is set to be high, and if solubility at low temperature is important, the effect is high if the amount is set to be large, and if Tni is important, the effect is high if the amount is set to be large. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-13) to the middle of the above range.
The compound represented by the general formula (N-1-14) is the following compound.
[ Chemical 60]
Wherein R N1141 and R N1142 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
R N1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-14) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-1-14) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-14) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-14) to the middle of the above range.
The compound represented by the general formula (N-1-15) is the following compound.
[ Chemical 61]
Wherein R N1151 and R N1152 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
R N1152 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-15) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-15) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
In the case where improvement of Δε is important, it is preferable that the amount of the compound represented by the general formula (N-1-15) is set to be high, and if solubility at low temperature is important, the effect is high if the amount is set to be large, and if Tni is important, the effect is high if the amount is set to be large. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-15) to the middle of the above range.
The compound represented by the general formula (N-1-16) is the following compound.
[ 62]
Wherein R N1161 and R N1162 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
R N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-16) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-16) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-16) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-16) to the middle of the above range.
The compound represented by the general formula (N-1-17) is the following compound.
[ 63]
Wherein R N1171 and R N1172 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
R N1172 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compound represented by the general formula (N-1-17) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-17) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
Further, when attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-17) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-17) to the middle of the above range.
The compound represented by the general formula (N-1-18) is the following compound.
[ 64]
/>
Wherein R N1181 and R N1182 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group or a butyl group.
R N1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group, a propoxy group or a butoxy group.
The compounds represented by the general formula (N-1-18) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-18) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-18) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-18) to the middle of the above range.
The compounds represented by the general formula (N-1-18) are preferably compounds represented by the following formulas (N-1-18.1) to (N-1-18.5), more preferably compounds represented by the formulas (N-1-18.1) to (N-1-18.3), and still more preferably compounds represented by the formulas (N-1-18.2) or (N-1-18.3).
[ 65]
The compound represented by the general formula (N-1-20) is the following compound.
[ Chemical 66]
/>
Wherein R N1201 and R N1202 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1201 and R N1202 are each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
The compound represented by the general formula (N-1-20) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-20) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-20) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-20) to the middle of the above range.
The compound represented by the general formula (N-1-21) is the following compound.
[ 67]
R N1211 and R N1212 are each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
The compound represented by the general formula (N-1-21) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-21) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by the general formula (N-1-21) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-21) to the middle of the above range.
The compound represented by the general formula (N-1-22) is the following compound.
[ Chemical 68]
Wherein R N1221 and R N1222 each represent the same meaning as R N11 and R N12 in the general formula (N-1).
R N1221 and R N1222 are each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.
The compound represented by the general formula (N-1-22) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2, 3,4, 5 or more.
The amount of the compound represented by the general formula (N-1-22) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 1 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit value is 35 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 10 mass%, 5 mass%.
When attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-1-22) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be high. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-1-22) to the middle of the above range.
The compounds represented by the general formula (N-1-22) are preferably compounds represented by the following formulas (N-1-22.1) to (N-1-22.6), formulas (N-1-22.11) or (N-1-22.12), more preferably compounds represented by the formulas (N-1-22.1) to (N-1-22.5), and still more preferably compounds represented by the formulas (N-1-22.1) to (N-1-22.4).
[ 69]
The compound represented by the general formula (N-3) is preferably a compound represented by the following general formula (N-3-2).
[ 70]
Wherein R N321 and R N322 each represent the same meaning as R N31 and R N32 in the general formula (N-3).
R N321 and R N322 are preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably a propyl group or a pentyl group.
The compound represented by the general formula (N-3-2) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2,3, 4, 5 or more.
The amount of the compound represented by the general formula (N-3-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 3 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 33 mass%, 35 mass%. On the other hand, the preferable upper limit value is 50 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%.
Further, when attention is paid to improvement of Δε, it is preferable that the amount of the compound represented by general formula (N-3-2) is set to be high, and when attention is paid to solubility at low temperature, the effect is high if the amount is set to be high, and when attention is paid to Tni, the effect is high if the amount is set to be low. Further, in the case of improving the drop mark and burn-in characteristics, it is preferable to set the amount of the compound represented by the general formula (N-3-2) to the middle of the above range.
The compounds represented by the general formula (N-3-2) are preferably compounds represented by the following formulas (N-3-2.1) to (N-3-2.3).
[ Chemical 71]
The liquid crystal molecule may further comprise a compound represented by the following general formula (L).
[ Chemical 72]
Wherein R L1 and R L2 each independently represent an alkyl group having 1 to 8 carbon atoms. Wherein any one or not adjacent two or more of-CH 2 -present in the alkyl group may be independently substituted with-CH=CH-, -C≡C-, -O-, -CO-, -COO-, or-OCO-, respectively.
N L1 represents 0, 1,2 or 3.
Each of a L1、AL2 and a L3 independently represents a group selected from the group consisting of (a) to (c):
(a) 1, 4-cyclohexylene (any one or not two or more of which groups may be-CH 2 -substituted by-O-),
(B) 1, 4-phenylene (any one or not two or more of which-CH=may be substituted with-N=be present in the group)
(C) Naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (any one or not adjacent two or more of these groups may be substituted with-N =ch =)
The aforementioned group (a), group (b) and group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom.
Z L1 and Z L2 each independently represent a single bond 、－CH2CH2－、－(CH2)4－、－OCH2－、－CH2O－、－COO－、－OCO－、－OCF2－、－CF2O－、－CH＝N－N＝CH－、－CH＝CH－、－CF＝CF－ or-C.ident.C-.
When N L1 is 2 or more, A L2 and Z L2 may be the same or different from each other, except for the compounds represented by the general formulae (N-1) to (N-3).
The compound represented by the general formula (L) corresponds to a compound that is substantially neutral in dielectric property (the value of Δε is-2 to 2). The compound may be used alone or in combination of 1. The type of the compound to be combined is not particularly limited, and is appropriately selected according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 3, 4, 5, 6, 7, 8, 9,10 or more.
The amount of the compound represented by the general formula (L) contained in the liquid crystal composition is appropriately adjusted in accordance with the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dropping marks, burn-in, dielectric anisotropy, and the like.
The lower limit value is preferably 1 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 75 mass%, or 80 mass%. On the other hand, the preferable upper limit is 95 mass%, 85 mass%, 75 mass%, 65 mass%, 55 mass%, 45 mass%, 35 mass%, 25 mass%.
In the case where the viscosity (η) of the liquid crystal composition is kept low to improve the response speed, the amount of the compound represented by the general formula (L) is preferably high at the lower limit value and high at the upper limit value. Further, in the case where Tni of the liquid crystal composition is kept high and temperature stability is improved, the amount thereof is preferably high at the lower limit value and high at the upper limit value. In the case of increasing Δεof the liquid crystal composition in order to keep the driving voltage of the liquid crystal display element low, the amount is preferably low in the lower limit and low in the upper limit.
In the case where reliability is important, R L1 and R L2 are preferably each independently an alkyl group, in the case where volatility of the compound is important to be reduced, R L1 and R L2 are preferably each independently an alkoxy group, and in the case where tackiness is important to be reduced, at least one of R L1 and R L2 is preferably an alkenyl group.
The number of halogen atoms present in the compound represented by the general formula (L) is preferably 0,1,2 or 3, more preferably 0 or 1. In addition, in the case where compatibility with other liquid crystal molecules is important, the number of halogen atoms is preferably 1.
When the ring structure to which they are bonded is a benzene ring (aromatic ring), R L1 and R L2 are each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 4 to 5 carbon atoms.
When the ring structure to which they are bonded is a saturated ring structure such as a cyclohexane ring, a pyran ring, or a dioxane ring, R L1 and R L2 are each independently preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms (when present) of R L1 and R L2 is preferably 5 or less, and more preferably straight-chain.
The alkenyl group is preferably a group selected from the group represented by the following formulas (R1) to (R5).
[ 73]
The black dots in the formulas represent bond bonds.
When importance is attached to the response speed of the liquid crystal molecules, n L1 is preferably 0, when the upper limit temperature of the nematic phase of the liquid crystal molecules is improved, 2 or 3 is preferable, and when the balance is obtained, 1 is preferable. In order to satisfy the characteristics required for the liquid crystal composition, it is preferable to combine compounds having different values of n L1.
In the case of increasing Δn of the liquid crystal molecule, a L1、AL2 and a L3 are each preferably an aromatic group, and in the case of improving the response speed of the liquid crystal molecule, an aliphatic group is preferably used.
The aromatic or aliphatic group is preferably a trans-1, 4-cyclohexylene group, 1, 4-phenylene group, 2-fluoro-1, 4-phenylene group, 3, 5-difluoro-1, 4-phenylene group, 1, 4-cyclohexenylene group, 1, 4-bicyclo [2.2.2] octylene group, piperidine-1, 4-diyl group, naphthalene-2, 6-diyl group, decalin-2, 6-diyl group, or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl group, more preferably a structure represented by the following formula 74, and still more preferably trans-1, 4-cyclohexylene group or 1, 4-phenylene group.
[ Chemical 74]
In order to pay attention to the response speed of the liquid crystal molecules, Z L1 and Z L2 are preferably each independently a single bond.
The compounds represented by the general formula (L) are preferably compounds represented by the following general formulae (L-1) to (L-7).
The compound represented by the general formula (L-1) is the following compound.
[ 75]
Wherein R L11 and R L12 each represent the same meaning as R L1 and R L2 in the general formula (L).
R L11 and R L12 are preferably each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
The compound represented by the general formula (L-1) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2,3, 4, 5 or more.
The amount of the compound represented by the general formula (L-1) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 15 mass%, 20 mass%, 25 mass%, 30 mass%, 35 mass%, 40 mass%, 45 mass%, 50 mass%, 55 mass%. On the other hand, the preferable upper limit value is 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%.
In the case where the viscosity (. Eta.) of the liquid crystal composition is kept low to improve the response speed, the amount of the compound represented by the general formula (L-1) is preferably high at the lower limit and high at the upper limit. Further, in the case where Tni of the liquid crystal composition is kept high and temperature stability is improved, the amount thereof is preferably moderate in the lower limit and moderate in the upper limit. In the case of increasing Δεof the liquid crystal composition in order to keep the driving voltage of the liquid crystal display element low, the amount is preferably low in the lower limit and low in the upper limit.
The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-1).
[ Chemical 76]
/>
Wherein R L12 represents the same meaning as in the general formula (L-1).
The compound represented by the general formula (L-1-1) is preferably a compound represented by the following formulae (L-1-1.1) to (L-1-1.3), more preferably a compound represented by the following formulae (L-1-1.2) or (L-1-1.3), and still more preferably a compound represented by the following formulae (L-1-1.3).
[ Chemical 77]
The amount of the compound represented by the formula (L-1-1.3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%. On the other hand, the preferable upper limit is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass%.
The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-2).
[ 78]
Wherein R L12 represents the same meaning as in the general formula (L-1).
The amount of the compound represented by the general formula (L-1-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 5 mass%, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass%. On the other hand, the preferable upper limit value is 60 mass%, 55 mass%, 50 mass%, 45 mass%, 42 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass%.
The compounds represented by the general formula (L-1-2) are preferably compounds represented by the following formulas (L-1-2.1) to (L-1-2.4), more preferably compounds represented by the formulas (L-1-2.2) to (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because of its high effect of improving the response speed of the liquid crystal composition.
In the case where an improvement in Tni is required as compared with the response speed of the liquid crystal composition, the compound represented by the formula (L-1-2.3) or the formula (L-1-2.4) is preferably used. In order to improve the solubility at low temperature, the amount of the compound represented by the formula (L-1-2.3) or the formula (L-1-2.4) contained in the liquid crystal composition is preferably set to less than 30 mass%.
[ Chemical 79]
The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-3).
[ 80]
Wherein R L13 and R L14 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
R L13 and R L14 are preferably each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
The amount of the compound represented by the general formula (L-1-3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 30 mass%. On the other hand, the preferable upper limit value is 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 37 mass%, 35 mass%, 33 mass%, 30 mass%, 27 mass%, 25 mass%, 23 mass%, 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass%.
The compound represented by the general formula (L-1-3) is preferably a compound represented by the following formulae (L-1-3.1) to (L-1-3.4) or (L-1-3.11) to (L-1-3.13), more preferably a compound represented by the following formulae (L-1-3.1), formula (L-1-3.3) or formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferable because of its high effect of improving the response speed of the liquid crystal composition.
In the case where an improvement in Tni is required to be higher than the response speed of the liquid crystal composition, the compound represented by the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1-3.11) or the formula (L-1-3.12) is preferably used. In order to improve the solubility at low temperatures, the total amount of the compounds represented by the formulas (L-1-3.3), (L-1-3.4), (L-1-3.11) and (L-1-3.12) in the liquid crystal composition is preferably less than 20%.
[ 81]
The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-4) or (L-1-5).
[ Chemical 82]
Wherein R L15 and R L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
R L15 and R L16 are preferably each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
The amount of the compound represented by the general formula (L-1-4) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 1 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit is 25 mass%, 23 mass%, 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass%.
The amount of the compound represented by the general formula (L-1-5) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit is 1 mass%, 5 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, 20 mass%. On the other hand, the preferable upper limit is 25 mass%, 23 mass%, 20 mass%, 17 mass%, 15 mass%, 13 mass%, 10 mass%.
The compounds represented by the general formulae (L-1-4) or (L-1-5) are preferably compounds represented by the following formulae (L-1-4.1) to (L-1-4.3) or (L-1-5.1) to (L-1-5.3), more preferably compounds represented by the following formulae (L-1-4.2) or (L-1-5.2).
[ 83]
The compound represented by the general formula (L-1) is preferably a compound represented by 2 or more selected from the group consisting of the compounds represented by the formulas (L-1-1.3), L-1-2.2, L-1-3.1), L-1-3.3, L-1-3.4, L-1-3.11) and L-1-3.12, more preferably a compound represented by 2 or more selected from the group consisting of the compounds represented by the formulas (L-1-1.3), L-1-2.2, L-1-3.1), L-1-3.3, L-1-3.4 and L-1-4.2.
In the case where the reliability of the liquid crystal composition is important, 2 or more compounds selected from the group consisting of the compounds represented by the formulas (L-1-3.1), (L-1-3.3) and (L-1-3.4) are preferably combined, and in the case where the response speed of the liquid crystal composition is important, 2 or more compounds selected from the group consisting of the compounds represented by the formulas (L-1-1.3) and (L-1-2.2) are preferably combined.
The compound represented by the general formula (L-1) is also preferably a compound represented by the following general formula (L-1-6).
[ Chemical 84]
Wherein R L17 and R L18 each independently represent a methyl group or a hydrogen atom.
The amount of the compound represented by the general formula (L-1-6) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 5 mass%, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass%. On the other hand, the preferable upper limit value is 60 mass%, 55 mass%, 50 mass%, 45 mass%, 42 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass%.
The compounds represented by the general formula (L-1-6) are preferably compounds represented by the following formulas (L-1-6.1) to (L-1-6.3).
[ Chemical 85]
The compound represented by the general formula (L-2) is the following compound.
[ 86]
Wherein R L21 and R L22 each represent the same meaning as R L1 and R L2 in the general formula (L).
R L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.
R L22 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
The compound represented by the general formula (L-2) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2,3, 4, 5 or more.
The amount of the compound represented by the general formula (L-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%. On the other hand, the preferable upper limit is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass%.
When importance is attached to the solubility of the liquid crystal molecules at low temperatures, the effect is high if the amount of the compound represented by the general formula (L-2) is set to be large, and when importance is attached to the response speed of the liquid crystal composition, the effect is high if the amount is set to be small. Further, in the case of improving the drop mark and burn-in characteristics, the amount of the compound represented by the general formula (L-2) is preferably set to the middle of the above range.
The compound represented by the general formula (L-2) is preferably a compound represented by the following formulae (L-2.1) to (L-2.6), more preferably a compound represented by the following formulae (L-2.1), (L-2.3), (L-2.4) or (L-2.6).
[ 87]
The compound represented by the general formula (L-3) is the following compound.
[ 88]
Wherein R L31 and R L32 each represent the same meaning as R L1 and R L2 in the general formula (L).
R L31 and R L32 are preferably each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
The compound represented by the general formula (L-3) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2,3, 4, 5 or more.
The amount of the compound represented by the general formula (L-3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%. On the other hand, the preferable upper limit is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass%.
Further, in the case where a high birefringence is obtained, the effect is high if the amount of the compound represented by the general formula (L-3) is set to be large, and in the case where high Tni is emphasized, the effect is high if the amount is set to be small. Further, in the case of improving the drop mark and burn-in characteristics, the amount of the compound represented by the general formula (L-3) is preferably set to the middle of the above range.
The compound represented by the general formula (L-3) is preferably a compound represented by the following formulae (L-3.1) to (L-3.4), formula (L-3.6) or formula (L-3.7), more preferably a compound represented by the following formulae (L-3.2) to (L-3.4), formula (L-3.6) or formula (L-3.7).
[ Chemical 89]
The compound represented by the general formula (L-4) is the following compound.
[ Chemical 90]
Wherein R L41 and R L42 each represent the same meaning as R L1 and R L2 in the general formula (L).
R L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.
R L42 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
The compound represented by the general formula (L-4) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2,3, 4, 5 or more.
The amount of the compound represented by the general formula (L-4) contained in the liquid crystal composition is appropriately adjusted in accordance with the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dropping marks, burn-in, dielectric anisotropy, etc.
The lower limit value is preferably 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, 20 mass%, 23 mass%, 26 mass%, 30 mass%, 35 mass%, 40 mass%. On the other hand, the preferable upper limit is 50 mass%, 40 mass%, 35 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%.
The compounds represented by the general formula (L-4) are preferably compounds represented by the following formulas (L-4.1) to (L-4.3).
[ 91]
The liquid crystal composition may contain only the compound represented by the formula (L-4.1), or only the compound represented by the formula (L-4.2), or both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2), or all the compounds represented by the formulas (L-4.1) to (L-4.3), depending on the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence.
The compound represented by the general formula (L-4) is preferably a compound represented by the following formulae (L-4.4) to (L-4.6), more preferably a compound represented by the following formula (L-4.4).
[ Chemical 92]
The liquid crystal composition may contain only the compound represented by the formula (L-4.4), only the compound represented by the formula (L-4.5), or both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) depending on the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence.
The compound represented by the general formula (L-4) is preferably a compound represented by the following formulae (L-4.7) to (L-4.10), more preferably a compound represented by the following formula (L-4.9).
[ 93]
The compound represented by the general formula (L-5) is the following compound.
[ 94]
Wherein R L51 and R L52 each represent the same meaning as R L1 and R L2 in the general formula (L).
R L51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.
R L52 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
The compound represented by the general formula (L-5) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2,3, 4, 5 or more.
The amount of the compound represented by the general formula (L-5) contained in the liquid crystal composition is appropriately adjusted in accordance with the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dropping marks, burn-in, dielectric anisotropy, etc.
The lower limit value is preferably 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, 20 mass%, 23 mass%, 26 mass%, 30 mass%, 35 mass%, 40 mass%. On the other hand, the preferable upper limit is 50 mass%, 40 mass%, 35 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%.
The compound represented by the general formula (L-5) is preferably a compound represented by the following formula (L-5.1) or formula (L-5.2), more preferably a compound represented by the following formula (L-5.1).
[ 95]
The compound represented by the general formula (L-5) is also preferably a compound represented by the following formula (L-5.3) or formula (L-5.4).
[ Chemical 96]
The compound represented by the general formula (L-5) is preferably a compound represented by the following formulae (L-5.5) to (L-5.7), more preferably a compound represented by the following formula (L-5.7).
[ 97]
The compound represented by the general formula (L-6) is the following compound.
[ 98]
/>
Wherein R L61 and R L62 each represent the same meaning as R L1 and R L2 in the general formula (L).
X L61 and X L62 each independently represent a hydrogen atom or a fluorine atom.
R L61 and R L62 are preferably each independently an alkyl group having 1to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.
Preferably, one of X L61 and X L62 is a fluorine atom, and the other is a hydrogen atom.
The compound represented by the general formula (L-6) may be used alone or in combination of 1 or more than 2. The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1, 2,3, 4, 5 or more.
The amount of the compound represented by the general formula (L-6) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, 20 mass%, 23 mass%, 26 mass%, 30 mass%, 35 mass%, 40 mass%. On the other hand, the preferable upper limit is 50 mass%, 40 mass%, 35 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%.
In the case of increasing Δn, the amount of the compound represented by the general formula (L-6) is preferably large, and in the case of precipitating at a low temperature, the amount is preferably small.
The compounds represented by the general formula (L-6) are preferably compounds represented by the following formulas (L-6.1) to (L-6.9).
[ Chemical 99]
The types of the compounds to be combined are not particularly limited, but 1 to 3, more preferably 1 to 4, are preferably used. The selected compound has a broad molecular weight distribution and is effective in terms of solubility, and for example, 1 compound selected from the compounds represented by the formulas (L-6.1) and (L-6.2), 1 compound selected from the compounds represented by the formulas (L-6.4) and (L-6.5), 1 compound selected from the compounds represented by the formulas (L-6.6) and (L-6.7), and 1 compound selected from the compounds represented by the formulas (L-6.8) and (L-6.9) are preferable, and these compounds are appropriately combined. Among them, the combination of the compounds represented by the formula (L-6.1), the formula (L-6.3), the formula (L-6.4), the formula (L-6.6) and the formula (L-6.9) is more preferable.
The compound represented by the general formula (L-6) is preferably a compound represented by the following formulae (L-6.10) to (L-6.17), more preferably a compound represented by the following formula (L-6.11).
[ 100]
The compound represented by the general formula (L-7) is the following compound.
[ 101]
Wherein R L71 and R L72 each represent the same meaning as R L1 and R L2 in the general formula (L).
A L71 and A L72 each have the same meaning as A L2 and A L3 in the general formula (L). Wherein any hydrogen atom present in a L71 and a L72 may be substituted with a fluorine atom.
Z L71 represents the same meaning as Z L2 in the general formula (L).
X L71 and X L72 each independently represent a fluorine atom or a hydrogen atom.
In the formula, R L71 and R L72 are preferably each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
Preferably, A L71 and A L72 are each independently 1, 4-cyclohexylene or 1, 4-phenylene. Wherein any hydrogen atom present in a L71 and a L72 may be substituted with a fluorine atom.
Z L71 is preferably a single bond or COO-, more preferably a single bond.
Preferably, X L71 and X L72 are each a hydrogen atom.
The type of the compound to be combined is not particularly limited, and is appropriately selected according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of the compounds used are, for example, 1,2, 3, 4.
The amount of the compound represented by the general formula (L-7) contained in the liquid crystal composition is appropriately adjusted in accordance with the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dropping marks, burn-in, dielectric anisotropy, etc.
The lower limit value is preferably 1 mass%, 2 mass%, 3 mass%, 5 mass%, 7 mass%, 10 mass%, 14 mass%, 16 mass%, or 20 mass%. On the other hand, the preferable upper limit is 30 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 10 mass%, 5 mass%.
In the case where a high Tni of the liquid crystal composition is required, the amount of the compound represented by the general formula (L-7) is preferably large, and in the case where a low viscosity is desired, the amount is preferably small.
The compound represented by the general formula (L-7) is preferably a compound represented by the following formulas (L-7.1) to (L-7.4), more preferably a compound represented by the formula (L-7.2).
[ Chemical 102]
The compound represented by the general formula (L-7) is preferably a compound represented by the following formulae (L-7.11) to (L-7.13), more preferably a compound represented by the following formula (L-7.11).
[ 103]
The compound represented by the general formula (L-7) is preferably a compound represented by the following formulae (L-7.21) to (L-7.23), more preferably a compound represented by the following formula (L-7.21).
[ Chemical 104]
The compound represented by the general formula (L-7) is preferably a compound represented by the following formulae (L-7.31) to (L-7.34), more preferably a compound represented by the following formulae (L-7.31) or (L-7.32).
[ 105]
The compound represented by the general formula (L-7) is preferably a compound represented by the following formulae (L-7.41) to (L-7.44), more preferably a compound represented by the following formulae (L-7.41) or (L-7.42).
[ 106]
Further, the compounds represented by the general formula (L-7) are preferably compounds represented by the following formulas (L-7.51) to (L-7.53).
[ Chemical 107]
((Polymerizable Compound))
The liquid crystal composition may further contain a polymerizable compound that can be polymerized by irradiation with an active energy ray. The polymerizable compound is preferably a compound represented by the following general formula (P). The liquid crystal composition preferably contains 1 or 2 or more kinds of the polymerizable compounds.
[ Chemical 108]
In the formula (P), R p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or-Sp p2－Pp2. Wherein one or non-adjacent two or more-CH 2 -of the alkyl groups may each be independently substituted by-CH=CH-, -C≡C-, -O-, -CO-, -COO-, or-OCO-. In addition, one or two or more hydrogen atoms in the alkyl group may be substituted with a cyano group, a fluorine atom or a chlorine atom, respectively and independently.
P p1 and P p2 each independently represent any one of the following general formulae (P p1 -1) to (P p1 -9).
[ 109]
(Wherein R p11 and R p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms, W p11 represents a single bond, -O-, -COO-or methylene, t p11 represents 0, 1 or 2, and when a plurality of R p11、Rp12、Wp11 and/or t p11 are present in a molecule, they may be the same or different)
Sp p1 and Sp p2 each independently represent a single bond or a spacer.
Z p1 and Z p2 each independently represent a single bond 、－O－、－S－、－CH2－、－OCH2－、－CH2O－、－CO－、－C2H4－、－COO－、－OCO－、－OCOOCH2－、－CH2OCOO－、－OCH2CH2O－、－CO－NRZP1－、－NRZP1－CO－、－SCH2－、－CH2S－、－CH＝CRZP1－COO－、－CH＝CRZP1－OCO－、－COO－CRZP1＝CH－、－OCO－CRZP1＝CH－、－COO－CRZP1＝CH－COO－、－COO－CRZP1＝CH－OCO－、－OCO－CRZP1＝CH－COO－、－OCO－CRZP1＝CH－OCO－、－(CH2)2－COO－、－(CH2)2－OCO－、－OCO－(CH2)2－、－(C＝O)－O－(CH2)2－、－CH＝CH－、－CF＝CF－、－CF＝CH－、－CH＝CF－、－CF2－、－CF2O－、－OCF2－、－CF2CH2－、－CH2CF2－、－CF2CF2－ or-C≡C- (wherein R ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ZP1 are present in the molecule, they may be the same or different).
A p1、Ap2 and a p3 each independently represent a group selected from the group consisting of (a p)～(cp):
(a p) 1, 4-cyclohexylene (one or more than two of the non-adjacent-CH 2 -groups present in the radical may be substituted by-O-)
(B p) 1, 4-phenylene (one or more than two non-adjacent-CH=groups present in the group may be substituted by-N=)
(C p) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, phenanthrene-2, 7-diyl or anthracene-2, 6-diyl (one or two or more non-adjacent ones of these groups may be substituted with-N=and the hydrogen atom present in the group may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms)
The group (a p), the group (b p) and the group (c p) may be independently substituted with an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, a cyano group, a fluorine atom, a chlorine atom or-Sp p2－Pp2.
M p1 represents 0, 1,2 or 3.
In the case where a plurality of Z p1、Ap2、Spp2 and/or P p2 exist in the molecule, they may be the same or different. Wherein, in the case where m p1 is 0 and a p1 is phenanthrene-2, 7-diyl or anthracene-2, 6-diyl, a p3 represents a single bond.
Wherein the orientation aid is excluded from the polymerizable compounds.
R p1 is preferably-Sp p2－Pp2.
Preferably, each of P p1 and P p2 is independently any one of the formulae (P p1 -1) to (P p1 -3), and more preferably (P p1 -1).
Preferably, R p11 and R p12 are each independently a hydrogen atom or a methyl group.
T p11 is preferably 0 or 1.
W p11 is preferably a single bond, methylene or ethylene.
M p1 is preferably 0, 1 or 2, preferably 0 or 1.
Preferably, Z p1 and Z p2 are each independently a single bond 、－OCH2－、－CH2O－、－CO－、－C2H4－、－COO－、－OCO－、－COOC2H4－、－OCOC2H4－、－C2H4OCO－、－C2H4COO－、－CH＝CH－、－CF2－、－CF2O－、－(CH2)2－COO－、－(CH2)2－OCO－、－OCO－(CH2)2－、－CH＝CH－COO－、－COO－CH＝CH－、－OCOCH＝CH－、－COO－(CH2)2－、－OCF2－ or-C.ident.C-, more preferably a single bond 、－OCH2－、－CH2O－、－C2H4－、－COO－、－OCO－、－COOC2H4－、－OCOC2H4－、－C2H4OCO－、－C2H4COO－、－CH＝CH－、－(CH2)2－COO－、－(CH2)2－OCO－、－OCO－(CH2)2－、－CH＝CH－COO－、－COO－CH＝CH－、－OCOCH＝CH－、－COO－(CH2)2－ or-C.ident.C-.
Furthermore, it is preferable that only one of Z p1 and Z p2 present in the molecule is －OCH2－、－CH2O－、－C2H4－、－COO－、－OCO－、－COOC2H4－、－OCOC2H4－、－C2H4OCO－、－C2H4COO－、－CH＝CH－、－(CH2)2－COO－、－(CH2)2－OCO－、－OCO－(CH2)2－、－CH＝CH－COO－、－COO－CH＝CH－、－OCOCH＝CH－、－COO－(CH2)2－ or-C.ident.C-, and the other is a single bond, more preferably, only one of Z p1 and Z p2 present in the molecule is-OCH 2－、－CH2O－、－C2H4 -, -COO-or-OCO-, the others are single bonds, and it is further preferable that all of Z p1 and Z p2 present in the molecule are single bonds.
It is preferable that only one of Z p1 and Z p2 present in the molecule is a linking group selected from the group consisting of －CH＝CH－COO－、－COO－CH＝CH－、－(CH2)2－COO－、－(CH2)2－OCO－、－O－CO－(CH2)2－、－COO－(CH2)2－, and the other is a single bond.
Sp p1 and Sp p2 each independently represent a single bond or a spacer, and the spacer is preferably an alkylene group having 1 to 30 carbon atoms. Wherein, as long as the oxygen atoms are not directly connected to each other, then-CH 2 -in the alkylene group may be replaced by-O-, -CO-, -COO-, -OCO-, -CH=CH-, or-C≡C-substitution, the hydrogen atom in the alkylene group may be substituted with a halogen atom.
Among them, each of Sp p1 and Sp p2 is preferably independently a straight-chain alkylene group having 1 to 10 carbon atoms or a single bond.
A p1、Ap2 and A p3 are each preferably independently 1, 4-phenylene or 1, 4-cyclohexylene, more preferably 1, 4-phenylene.
In order to improve the compatibility with liquid crystal molecules (liquid crystal compounds), the 1, 4-phenylene group is preferably substituted with 1 fluorine atom, 1 methyl group or 1 methoxy group.
The total content of the compounds represented by the general formula (P) is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, still more preferably 0.1 to 5% by mass, still more preferably 0.1 to 3% by mass, still more preferably 0.2 to 2% by mass, still more preferably 0.2 to 1.3% by mass, particularly preferably 0.2 to 1% by mass, and most preferably 0.2 to 0.56% by mass, relative to the liquid crystal composition.
The preferable lower limit value of the total content of the compounds represented by the general formula (P) is 0.01 mass%, 0.03 mass%, 0.05 mass%, 0.08 mass%, 0.1 mass%, 0.15 mass%, 0.2 mass%, 0.25 mass%, 0.3 mass% with respect to the liquid crystal composition.
The preferable upper limit value of the total content of the compounds represented by the general formula (P) is 10 mass%, 8 mass%, 5 mass%, 3 mass%, 1.5 mass%, 1.2 mass%, 1 mass%, 0.8 mass%, 0.5 mass% with respect to the liquid crystal composition.
If the content of the compound represented by the general formula (P) is small, there are cases where: it is difficult to exhibit the effect of adding the compound to the liquid crystal composition, and for example, there is a problem that alignment regulating force of liquid crystal molecules is weak or becomes weak with time depending on the kind of liquid crystal molecules, alignment aids, and the like. On the other hand, if the content of the compound represented by the general formula (P) is too large, there are cases where: for example, problems such as an increase in the amount of the compound remaining after curing, a time required for curing, and a decrease in the reliability of the liquid crystal composition, or problems such as precipitation as storage stability of the solution, occur depending on the illuminance of the active energy ray. Therefore, the content thereof is preferably set in consideration of their balance.
The total content of the compound represented by the general formula (SAL) (i.e., as an alignment aid for the compound containing the adsorbing group Z AT1) and the compound represented by the general formula (P) is preferably 0.05 to 10% by mass, preferably 0.1 to 8% by mass, preferably 0.1 to 5% by mass, preferably 0.1 to 3% by mass, preferably 0.2 to 2% by mass, preferably 0.2 to 1.3% by mass, preferably 0.2 to 1% by mass, and preferably 0.2 to 0.56% by mass, relative to the liquid crystal composition.
The preferable lower limit value of the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is 0.01 mass%, 0.03 mass%, 0.05 mass%, 0.08 mass%, 0.1 mass%, 0.15 mass%, 0.2 mass%, 0.25 mass%, 0.3 mass% with respect to the liquid crystal composition.
The preferable upper limit value of the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is 10 mass%, 8 mass%, 5 mass%, 3 mass%, 1.5 mass%, 1.2 mass%, 1 mass%, 0.8 mass%, 0.5 mass% with respect to the liquid crystal composition.
If the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is small, there are cases where: it is difficult to exhibit the effect of adding these compounds to a liquid crystal composition, and for example, there are problems that alignment regulating force of liquid crystal molecules is weak or becomes weak with time, depending on the kind of liquid crystal molecules and the like. On the other hand, if the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is too large, there are cases where: for example, the amount of the compound remaining after curing increases depending on the illuminance of the active energy ray, etc., and the curing takes time, and the reliability of the liquid crystal composition decreases. Therefore, it is preferable to set their contents in consideration of their balance.
As preferable examples of the compound represented by the general formula (P), polymerizable compounds represented by the following formulas (P-1-1) to (P-1-46) are given.
[ 110]
[ Chemical 111]
[ 113]
[ 114]
[ 115]
Wherein P p11、Pp12、Spp11 and Sp p12 have the same meanings as those of P p1、Pp2、Spp1 and Sp p2 in the general formula (P).
As preferable examples of the compound represented by the general formula (P), polymerizable compounds represented by the following formulas (P-2-1) to (P-2-12) can be given.
[ 116]
Wherein P p21、Pp22、Spp21 and Sp p22 have the same meanings as those of P P1、Pp2、Spp1 and Sp p2 in the general formula (P).
Further, preferable examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).
[ Chemical 117]
[ Chemical 118]
Wherein P p31、Pp32、Spp31 and Sp p32 have the same meanings as those of P p1、Pp2、Spp1 and Sp p2 in the general formula (P).
As preferable examples of the compound represented by the general formula (P), polymerizable compounds represented by the following formulas (P-4-1) to (P-4-15) can be given.
[ 119]
[ 120]
[ Chemical 121]
[ Chemical 122]
Wherein P p41、Pp42、Spp41 and Sp p42 have the same meanings as those of P p1、Pp2、Spp1 and Sp p2 in the general formula (P).
In the case where the liquid crystal composition further contains a polymerizable compound in addition to the alignment aid, a pretilt angle of the liquid crystal molecules may be preferably formed. The polymerizable compound is a pretilt angle formation aid having a function of forming a pretilt angle of liquid crystal molecules.
The liquid crystal composition preferably contains no compound having a structure in which oxygen atoms such as a peracid (-CO-OO-) structure are bonded to each other.
In the case where importance is attached to the reliability and long-term stability of the liquid crystal composition, the amount of the compound having a carbonyl group contained in the liquid crystal composition is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably substantially 0% by mass.
In the case where importance is attached to the stability of the liquid crystal composition by UV irradiation, the amount of the compound substituted with a chlorine atom contained in the liquid crystal composition is preferably 15% by mass or less, more preferably 10% by mass or less, more preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably substantially 0% by mass.
The amount of the compound having all 6-membered rings in the molecular structure contained in the liquid crystal composition is preferably large, specifically, 80 mass% or more, more preferably 90 mass% or more, still more preferably 95 mass% or more, and particularly preferably substantially 100 mass%.
In order to suppress deterioration due to oxidation of the liquid crystal composition, the amount of the compound having a cyclohexene group as a ring structure contained in the liquid crystal composition is preferably made small, specifically, 10 mass% or less, preferably 8 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass% or less, and particularly preferably substantially 0 mass%.
In order to pay attention to the improvement of the viscosity of the liquid crystal composition and the improvement of Tni, the amount of the compound having a 2-methylbenzene-1, 4-diyl group in which a hydrogen atom can be substituted with a halogen in a molecule is preferably small, specifically, 10 mass% or less, more preferably 8 mass% or less, still more preferably 5 mass% or less, particularly preferably 3 mass% or less, and most preferably substantially 0 mass% in the liquid crystal composition.
In the present specification, the term "the amount of the compound X contained in the liquid crystal composition is substantially 0% by mass" means an amount of the compound X which is allowed to be unintentionally (inevitably) mixed into the liquid crystal composition.
The preferred lower limit value of the average elastic constant (K AVG) of the liquid crystal composition is 10、10.5、11、11.5、12、12.3、12.5、12.8、13、13.3、13.5、13.8、14、14.3、14.5、14.8、15、15.3、15.5、15.8、16、16.3、16.5、16.8、17、17.3、17.5、17.8、18., and the preferred upper limit value thereof is 25、24.5、24、23.5、23、22.8、22.5、22.3、22、21.8、21.5、21.3、21、20.8、20.5、20.3、20、19.8、19.5、19.3、19、18.8、18.5、18.3、18、17.8、17.5、17.3、17.
When importance is attached to reducing power consumption of the liquid crystal display device, it is effective to suppress the amount of light of a backlight (back light), and it is preferable to increase the light transmittance of the liquid crystal display device, so that the value of K AVG is preferably set to be low. In the case where improvement of the response speed of the liquid crystal display element (liquid crystal composition) is important, the value of K AVG is preferably set to be high.
In the present embodiment, the polymerizable monomer contains both the orientation aid and the pretilt angle-forming aid (polymerizable compound), but in the present invention, the polymerizable monomer may contain only either one of the orientation aid and the pretilt angle-forming aid.
(Liquid Crystal display element)
Next, a liquid crystal display element including a liquid crystal layer formed of the above liquid crystal composition will be described.
Fig. 1 is an exploded perspective view schematically showing one embodiment of a liquid crystal display element, and fig. 2 is a plan view of an area surrounded by an I line in fig. 1, which is enlarged.
In fig. 1 and 2, the dimensions of each part and the ratio thereof are exaggerated for convenience of explanation, and may be different from the actual case. The materials, dimensions, and the like shown below are examples, and the present invention is not limited to these, and can be appropriately modified within a range not departing from the gist thereof.
The liquid crystal display element 1 shown in fig. 1 includes an active matrix substrate AM and a color filter substrate CF arranged to face each other, and a liquid crystal layer 4 interposed between the active matrix substrate AM and the color filter substrate CF.
The active matrix substrate AM includes a1 st substrate 2, a pixel electrode layer 5 provided on a surface of the 1 st substrate 2 on the liquid crystal layer 4 side, and a1 st polarizing plate 7 provided on a surface of the 1 st substrate 2 on the opposite side of the liquid crystal layer 4.
On the other hand, the color filter substrate CF includes a 2 nd substrate 3, a common electrode layer 6 provided on the liquid crystal layer 4 side of the 2 nd substrate 3, a 2 nd polarizing plate 8 provided on the surface of the 2 nd substrate 3 opposite to the liquid crystal layer 4, and a color filter 9 provided between the 2 nd substrate 3 and the common electrode layer 6.
That is, the liquid crystal display element 1 of the present embodiment has a structure in which the 1 st polarizing plate 7, the 1 st substrate 2, the pixel electrode layer 5, the liquid crystal layer 4, the common electrode layer 6, the color filter 9, the 2 nd substrate 3, and the 2 nd polarizing plate 8 are laminated in this order.
The 1 st substrate 2 and the 2 nd substrate 3 are each formed of a material having flexibility (pliability), such as a glass material or a plastic material.
The 1 st substrate 2 and the 2 nd substrate 3 may both have light transmittance, or only one of them may have light transmittance. In the latter case, the other substrate may be composed of an opaque material such as a metallic material, a silicon material, or the like.
As shown in fig. 2, the pixel electrode layer 5 has a plurality of gate bus lines 11 for supplying scan signals, a plurality of data bus lines 12 for supplying display signals, and a plurality of pixel electrodes 13. Further, in fig. 2, a pair of gate bus lines 11, 11 and a pair of data bus lines 12, 12 are shown.
The plurality of gate bus lines 11 and the plurality of data bus lines 12 are arranged in a matrix so as to intersect each other, and the unit pixel of the liquid crystal display element 1 is formed by the region surrounded by these gate bus lines and the data bus lines. 1 pixel electrode 13 is formed in each unit pixel.
The pixel electrode 13 has a structure including two trunk portions formed in a cross shape orthogonal to each other and a plurality of branch portions branched from each trunk portion and extending outward (so-called a fishbone structure).
Between the pair of gate bus lines 11, a Cs electrode 14 is provided substantially parallel to the gate bus line 11. In addition, a thin film transistor including a source electrode 15 and a drain electrode 16 is provided near an intersection where the gate bus line 11 and the data bus line 12 intersect with each other. The drain electrode 16 is provided with a contact hole 17.
The gate bus line 11 and the data bus line 12 are preferably each formed of Al, cu, au, ag, cr, ta, ti, mo, W, ni or an alloy containing them, and more preferably Mo, al, or an alloy containing them.
In order to increase the transmittance of light, the pixel electrode 13 is constituted of, for example, a transparent electrode. The transparent electrode is formed by sputtering a compound such as ZnO, inGaZnO, siGe, gaAs, IZO (Indium Zinc Oxide ), ITO (Indium Tin Oxide), snO, tiO, AZTO (AlZnSnO), or the like.
The transparent electrode preferably has an average thickness of about 10 to 200 nm. In order to reduce the resistance, the transparent electrode may be formed by firing an amorphous ITO film to form a polycrystalline ITO film.
On the other hand, the common electrode layer 6 has, for example, a plurality of stripe-shaped common electrodes (transparent electrodes) juxtaposed. The common electrode may be formed in the same manner as the pixel electrode 13.
The color filter 9 can be manufactured by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like.
In the pigment dispersion method, the curable coloring composition for color filters is supplied onto the 2 nd substrate 3 in a predetermined pattern, and then cured by heating or light irradiation. This operation is performed for red, green, and blue 3 colors, whereby the color filter 9 can be obtained.
The color filter 9 may be disposed on the 1 st substrate 2 side.
In addition, from the viewpoint of preventing light leakage, the liquid crystal display element 1 may be provided with a black matrix (not shown). The black matrix is preferably formed at a portion corresponding to the thin film transistor.
The black matrix may be disposed on the 2 nd substrate 3 side together with the color filter 9, may be disposed on the 1 st substrate 2 side together with the color filter 9, or may be disposed on the 1 st substrate 2 side and the color filter 9 may be disposed on the 2 nd substrate 3 side separately. The black matrix may be formed by a portion overlapping each color of the color filter 9 to reduce the transmittance.
The active matrix substrate AM and the color filter substrate CF are bonded to each other at their peripheral regions by a sealing material (sealing material) composed of an epoxy thermosetting composition or the like.
Further, a spacer for maintaining a distance between the active matrix substrate AM and the color filter substrate CF may be disposed between them. Examples of the spacers include granular spacers such as glass particles, plastic particles, and alumina particles, and resin spacers formed by photolithography.
The average distance between the active matrix substrate AM and the color filter substrate CF (i.e., the average thickness of the liquid crystal layer 4) is preferably about 1 to 100 μm.
The 1 st polarizing plate 7 and the 2 nd polarizing plate 8 can be designed so that the viewing angle and contrast can be improved by adjusting the positional relationship of their transmission axes. Specifically, the 1 st polarizing plate 7 and the 2 nd polarizing plate 8 are preferably arranged such that their transmission axes are orthogonal to each other while operating in a normally black mode (normally black mode). In particular, it is preferable that either one of the 1 st polarizing plate 7 and the 2 nd polarizing plate 8 is arranged such that the transmission axis thereof is parallel to the alignment direction of the liquid crystal molecules when no voltage is applied.
In the case of using the 1 st polarizing plate 7 and the 2 nd polarizing plate 8, the product of the refractive index anisotropy (Δn) of the liquid crystal layer 4 and the average thickness of the liquid crystal layer 4 is preferably adjusted so that the contrast ratio becomes maximum. Further, the liquid crystal display element 1 may include a retardation film for expanding the viewing angle.
The active matrix substrate AM may further include an organic insulating film covering a part of the pixel electrode layer 5 (the gate bus line 11, the data bus line 12, the pixel electrode 13, the Cs electrode 14, and the thin film transistor) or the entire pixel electrode layer 5.
The color filter substrate CF may further include an organic insulating film that covers a part of the common electrode layer 6 (common electrode) or the entire common electrode layer 6.
Examples of the constituent material of the organic insulating film include an acrylic resin, an epoxy resin, a styrene resin, and a copolymer thereof. These resins may be used singly or in combination of 2 or more.
In the present embodiment, the active matrix substrate AM and the color filter substrate CF each include a polymer of a polymerizable monomer, and the surface roughness (Ra) of the surface of the polymer in contact with the liquid crystal layer 4 (hereinafter, also referred to as "contact surface of the substrates AM and CF") is a predetermined value.
The polymer of the polymerizable monomer may be formed as a film on the inner surface of the pixel electrode layer 5 or the common electrode layer 6, or may be formed as a plurality of island-shaped dots (spots).
In the former case, the contact surfaces of the substrates AM, CF are surfaces of films formed of polymers (surfaces on the opposite sides of the pixel electrode layer 5 or the common electrode layer 6). In the latter case, on the other hand, the contact surfaces of the substrates AM and CF are surfaces formed by the inner surfaces of the pixel electrode layer 5 or the common electrode layer 6 exposed from the dots and the surfaces of the dots.
Here, the surface roughness (Ra) affects the vertical alignment of the liquid crystal molecules. If the surface roughness (Ra) is too small, sufficient vertical alignment of the liquid crystal molecules cannot be obtained, and therefore there is a lower limit value of the surface roughness (Ra). On the other hand, in order to improve the vertical alignment of the liquid crystal molecules, the surface roughness (Ra) is preferably large to some extent.
However, according to the study of the present inventors, etc., it is clear that: if the surface roughness (Ra) is too large, the alignment of the liquid crystal molecules is disturbed by the irregularities present on the contact surfaces of the substrates AM and CF, and the contrast of the image displayed on the liquid crystal display element 1 is lowered due to the disorder. Therefore, there is also an upper limit value for the surface roughness (Ra).
The present inventors have further studied and found that: the present invention has been completed by setting the surface roughness (Ra) to 1 to 30nm, whereby a liquid crystal display element 1 capable of sufficiently vertically aligning liquid crystal molecules and displaying an image having a high contrast can be obtained.
The surface roughness (Ra) is 1 to 30nm, preferably 1 to 20nm, more preferably 1 to 10nm. By setting the surface roughness (Ra) in this range, the aforementioned effects can be further improved.
Further, the surface roughness (Ra) is JIS B0601: 2003, and an arithmetic average roughness specified in 2003.
(Method for manufacturing liquid Crystal display element)
Next, a method of manufacturing such a liquid crystal display element 1 will be described.
The method for manufacturing a liquid crystal display element according to the present embodiment includes: a preparation step [1] of preparing a substrate and a liquid crystal composition; a hydrophilization treatment step (2) of hydrophilizing a substrate; an assembling step (3) for assembling the liquid crystal display element (1); a polymerization step [4] of polymerizing an orientation aid and/or a polymerizable compound; and a curing step [5] for curing the sealing material.
[1] Preparation step
First, an active matrix substrate AM, a color filter substrate CF, and a liquid crystal composition as described above are prepared.
[2] Hydrophilization treatment Process (Process 1)
Then, hydrophilization treatment is performed on the surfaces of the active matrix substrate AM and the color filter substrate CF which are in contact with the liquid crystal layer 4 (i.e., the contact surfaces of the substrates AM and CF), respectively. The present step may be performed as needed, or may be omitted.
By performing the hydrophilization treatment, the hydrophilicity of the contact surface (hereinafter, also simply referred to as "contact surface") of the substrates AM and CF can be improved. Therefore, the polar group of the alignment aid contained in the liquid crystal composition can be firmly fixed to the inner side surface. In addition, the orientation aid may be oriented such that the mesogenic groups leave the contact surface. As a result, it becomes easy to set the surface roughness (Ra) of the contact surface in the above-described range, and the liquid crystal layer 4 can be held more reliably in a state where the liquid crystal molecules are vertically aligned.
Examples of the hydrophilization treatment (polarity improvement treatment) include physical treatments such as ozone treatment, corona treatment, and oxygen plasma treatment; and chemical treatments such as the addition of surfactants, polyethylene glycol, polyvinyl alcohol, and the like, and the introduction of hydrophilic functional groups. These treatments may be used alone or in combination of 1 or more than 2.
Among them, the hydrophilization treatment is preferably a physical treatment, and more preferably an ozone treatment. The hydrophilic property (polarity) can be improved by introducing hydroxyl groups to the contact surface by ozone treatment. Further, since ozone treatment (physical treatment) also has a high washing effect, impurities (for example, resist residues) adhering to the inner surface can be removed. Thus, the polar groups of the orientation aid are more readily adsorbed to the contact surface.
< Ozone treatment >)
Ozone treatment is a method of converting oxygen in the air into ozone by Ultraviolet (UV) irradiation and performing surface modification by an ozone-containing environment.
As the UV light source, a low-pressure mercury lamp is preferable. It is known that a low-pressure mercury lamp has an emission spectrum at wavelengths near 185nm and near 254nm, generates ozone by using light having a wavelength near 185nm, and generates active oxygen by decomposing ozone by using light having a wavelength near 254 nm. Therefore, hydrophilization treatment can be efficiently performed on the contact surface by using the low-pressure mercury lamp.
The gas to be the source of ozone may be a gas containing oxygen, and oxygen, dry air, or the like may be used.
In addition, the environmental pressure of the ozone treatment may be any of reduced pressure and atmospheric pressure.
The time of ozone treatment (UV irradiation time) is not particularly limited, but is preferably about 10 to 100 seconds, and more preferably about 20 to 60 seconds.
< Corona treatment >
Corona treatment is a method of surface modification by corona discharge excited by applying high-voltage alternating current to a pair of electrodes at atmospheric pressure.
< Oxygen plasma treatment >)
The oxygen plasma treatment is a method of ionizing a treatment gas containing oxygen by arc discharge and performing surface modification by using oxygen plasma generated at this time.
The process gas may be a mixture of oxygen and inert gases such as nitrogen, argon, helium, or the like.
The oxygen supply amount is preferably about 0.5 to 50sccm, and the ambient pressure is preferably about 0.1 to 50 Pa.
The applied power from the power supply during arc discharge is preferably about 10 to 500W, and the frequency of the power supply is preferably about 1 to 50 kHz.
The static contact angle of water at 25 ℃ is preferably 70 ° or less, more preferably 60 ° or less, over the entire area of the contact surface after hydrophilization treatment.
When the pixel electrode layer 5 and the common electrode layer 9 include an organic insulating film, the static contact angle of water at 25 ° on the surface of the organic insulating film is preferably 70 ° or less, and more preferably about 40 to 55 °. The static contact angle of water at 25℃on the surface of the ITO film (metal oxide film) is preferably 30℃or less, more preferably about 10 to 20 ℃.
The free energy of the surface is preferably 50mN/m or more, more preferably 60mN/m or more, in the entire contact surface after hydrophilization treatment.
When the pixel electrode layer 5 and the common electrode layer 9 include an organic insulating film, the surface free energy of the surface of the organic insulating film is preferably 50mN/m or more, and more preferably about 55 to 65 mN/m. The surface free energy of the surface of the ITO film (metal oxide film) is preferably 70mN/m or more, more preferably about 75 to 85 mN/m.
By setting the static contact angle and the surface free energy to the aforementioned ranges, the orientation aid can be uniformly supplied to almost the entire surface of the contact surface, and the orientation aid can be more firmly adsorbed (fixed) to the contact surface.
[3] Assembling process (process 2)
Then, along the edge of at least one of the active matrix substrate AM and the color filter substrate CF, the sealing material is drawn into a dead-cycle bank shape using a dispenser.
Thereafter, a predetermined amount of the liquid crystal composition is dropped to the inside of the sealing material under reduced pressure, and then the active matrix substrate AM is disposed so as to face the color filter substrate CF in contact with the liquid crystal composition.
In such a dropping filling (ODF: one Drop Fill) method, the most preferable amount of filling needs to be dropped according to the size of the liquid crystal display element 1. For example, the liquid crystal composition can be stably and continuously dropped for a long period of time with little impact due to rapid pressure change in the dropping device generated during the dropping. Therefore, the yield of the liquid crystal display element 1 can be maintained high.
In particular, since the most preferable injection amount of the liquid crystal composition is small in a small liquid crystal display element frequently used in a smart phone, it is difficult to control the deviation amount thereof within a certain range. However, by using the liquid crystal composition as described above, a stable and most preferable injection amount can be accurately dropped even in a small-sized liquid crystal display element.
In addition, by the ODF method, the occurrence of drop marks when the liquid crystal composition is dropped onto the substrate can be suppressed. The drop mark is a phenomenon in which a mark of the liquid crystal composition is white when the drop mark is black.
[4] Polymerization Process (Process 3)
When the alignment aid contains a polymerizable group and/or when the liquid crystal composition contains a polymerizable compound, the alignment aid and/or the polymerizable compound is polymerized by irradiation of the liquid crystal composition with an active energy ray such as ultraviolet rays or electron beams.
Thereby, the liquid crystal layer 4 is formed, and the liquid crystal display element 1 is obtained. At this time, since the alignment aid is fixed to the two substrates AM and CF, the alignment aid and/or the polymer of the polymerizable compound is present on the substrates AM and CF side in the liquid crystal layer 4.
In order to obtain good alignment of liquid crystal molecules, a proper polymerization rate is expected. Therefore, in the polymerization, it is preferable to irradiate the active energy ray singly, concurrently or sequentially. In the case of using ultraviolet rays, a polarized light source may be used, or a non-polarized light source may be used.
In the case of polymerizing the two substrates in a state of being in contact with the liquid crystal composition so as to face each other as in the present embodiment, at least the substrate located on the irradiation surface side must have an appropriate permeability to the active energy rays.
The polymerization may be performed in several stages as described below. Specifically, first, only the alignment aid and/or the polymerizable compound present in a specific region of the liquid crystal composition is polymerized using a mask. Thereafter, conditions such as an electric field, a magnetic field, and a temperature are adjusted to change the alignment state of the liquid crystal molecules in the unpolymerized region. In this state, an active energy ray is further irradiated to polymerize the orientation aid and/or the polymerizable compound present in the unpolymerized region.
Particularly, in the case of using ultraviolet rays, it is preferable to apply an alternating electric field to the liquid crystal composition and simultaneously irradiate ultraviolet rays.
The frequency of the applied alternating current is preferably about 10Hz to 10kHz, more preferably about 60Hz to 10 kHz.
The voltage of the applied alternating current is selected depending on the desired pretilt angle of the liquid crystal display element 1. That is, by adjusting the voltage of the applied alternating current, the pretilt angle of the liquid crystal display element 1 can be controlled.
In the liquid crystal display element of the transverse electric field MVA mode, the pretilt angle is preferably controlled to 80 to 89.9 ° from the viewpoints of alignment stability and contrast.
The applied voltage (electric field) may be a direct current, depending on the type of the liquid crystal display element 1 to be manufactured, the degree of the pretilt angle to be formed, or the like.
The temperature at which ultraviolet light is irradiated is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. The specific temperature is preferably a temperature close to room temperature, that is, typically about 15 to 35 ℃.
As the lamp for generating ultraviolet rays, a metal halogen lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like can be used.
The ultraviolet light to be irradiated is preferably ultraviolet light having a wavelength other than the absorption wavelength range of the liquid crystal composition, and more preferably is used after cutting off a predetermined wavelength if necessary.
In this case, the surface roughness (Ra) caused by the polymer of the polymerizable monomer can be set to the above range by adjusting the irradiation time of the active energy rays to be irradiated, the amount of the alignment aid contained in the liquid crystal composition, and the like.
The intensity of the active energy ray (particularly ultraviolet ray) to be irradiated is preferably about 0.1mW/cm 2～100W/cm2, more preferably about 2mW/cm 2～50W/cm2. Further, the intensity may be changed and the active energy ray may be irradiated at the same time.
The energy of the active energy ray (particularly, ultraviolet ray) to be irradiated can be appropriately adjusted, and is preferably about 10mJ/cm 2～500J/cm2, more preferably about 100mJ/cm 2～200J/cm2.
The time for irradiation of the active energy ray (particularly, ultraviolet ray) is appropriately selected according to the intensity, and is preferably about 10 to 7200 seconds, more preferably about 10 to 3600 seconds, and even more preferably about 10 to 600 seconds.
On the other hand, the amount of the alignment aid contained in the liquid crystal composition is preferably about 0.1 to 3% by mass, more preferably about 0.2 to 1.5% by mass, and still more preferably about 0.3 to 1% by mass.
In the liquid crystal composition described above, since the alignment aid does not inhibit the polymerization reaction of the polymerizable compounds, the polymerizable compounds can be appropriately polymerized with each other, and the unreacted polymerizable compounds can be prevented from remaining in the liquid crystal composition.
In the assembly step [3], a vacuum injection method may be used instead of the drop fill (ODF) method. For example, in the vacuum injection method, first, the sealing material is screen-printed along the edge of at least one of the active matrix substrate AM and the color filter substrate CF so as to leave the injection port. Thereafter, the sealing material is thermally cured by bonding and heating the two substrates AM and CF. Then, after sealing the inlet, the process proceeds to the polymerization step [4 ].
The liquid crystal display element 1 obtained in the above manner is preferably a PSA-type, PSVA-type, VA-type, IPS-type, FFS-type or ECB-type liquid crystal display element, and more preferably a PSA-type liquid crystal display element.
The liquid crystal display element and the method of manufacturing the liquid crystal display element according to the present invention have been described above, but the present invention is not limited to the foregoing embodiments.
For example, the liquid crystal display element of the present invention may have a part of its structure replaced with another structure that performs the same function, or may have any structure added thereto. The method for manufacturing a liquid crystal display element according to the present invention may have a step added for any purpose, or may be replaced with any step that can obtain the same operation and effect.
In the liquid crystal display element of the above embodiment, both the active matrix substrate AM and the color filter substrate CF are in direct contact with the liquid crystal layer 4 without interposing a Polyimide (PI) alignment film, but the PI alignment film may be provided in either one of them. In this case, the surface of the PI alignment film may be subjected to hydrophilization treatment or not. In this case, the surface roughness (Ra) of the surface of the PI alignment film may not be in the above range.
In addition, if the influence of heat at the time of forming the PI alignment film is taken into consideration, it is preferable to provide the PI alignment film on the color filter substrate CF if it is to be provided. In other words, in the case where hydrophilization treatment is performed on only one of the substrates, hydrophilization treatment is preferably performed on the active matrix substrate AM (the substrate having the pixel electrode 13).
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
10 Kinds of the aforementioned liquid crystal molecules were mixed to prepare a liquid crystal mixture. The properties of the resulting liquid crystal mixture were as follows.
Nematic-isotropic liquid phase transition temperature (Tni): 75 DEG C
Refractive index anisotropy (Δn) at 293K: 0.112
Dielectric constant anisotropy at 293K (. DELTA.. Epsilon.): -3.0
Rotational viscosity at 293K (. Gamma.1): 122 mPas
Diffusion elastic constant at 293K (K11): 14.1pN
Elastic constant of bending at 293K (K33): 13.9pN
1. Sample preparation
(Sample No. 1)
First, a1 st substrate having an ITO film and a 2 nd substrate having an ITO film and an organic insulating film made of acrylic resin (manufactured by JSR corporation, "Optomer SS") formed on the ITO film are prepared.
Then, along the edge of the 1 st substrate, the sealing material was drawn into a dead-circulation bank shape using a dispenser.
Then, a predetermined amount of the liquid crystal composition was dropped into a frame drawn with a sealing material under normal pressure, and then the 1 st substrate and the 2 nd substrate were opposed to each other in contact with the liquid crystal composition under reduced pressure, and then the 1 st substrate and the 2 nd substrate were bonded. Here, in order to temporarily cure the sealing material, a portion corresponding to the liquid crystal composition was masked, and only a portion of the sealing material was irradiated with ultraviolet light having a wavelength of 365nm and an illuminance of 4.0mW/cm 2 using a high-pressure mercury lamp.
In sample No.1, a liquid crystal composition containing a liquid crystal mixture and a pretilt angle forming additive (polymerizable compound) as a polymerizable monomer was used. The amount of the pretilt angle forming additive contained in the liquid crystal composition was 0.3 mass%.
Then, a rectangular alternating current wave of 10V and 100Hz was applied, and ultraviolet rays having a wavelength of 365nm and an illuminance of 100m/cm 2 were irradiated for 50 seconds using a high-pressure mercury lamp. Further, in order to cure the sealing material formally, the liquid crystal cell for evaluation was obtained by annealing at 120℃for 1 hour and leaving it to stand at room temperature.
Then, a liquid crystal cell was sandwiched between a pair of polarizing plates having transmission axes arranged in an orthogonal manner, and a sample was produced.
(Sample No. 2)
A sample was produced in the same manner as in the aforementioned sample No.1, except that the kind of the liquid crystal composition was changed.
In sample No.2, a liquid crystal composition containing a liquid crystal mixture, an alignment aid 1 as a polymerizable monomer, and a pretilt angle forming aid was used. The amount of the alignment aid 1 contained in the liquid crystal composition was 0.3 mass% and the amount of the polymerizable compound was 0.3 mass%.
(Sample No. 3)
A sample was produced in the same manner as in the aforementioned sample No.2, except that the amount of the alignment aid 1 contained in the liquid crystal composition was changed to 0.5 mass%.
(Sample No. 4)
A sample was produced in the same manner as in the aforementioned sample No.2, except that the amount of the alignment aid 1 contained in the liquid crystal composition was changed to 1.0 mass%.
(Sample No. 5)
A sample was produced in the same manner as in the aforementioned sample No.1, except that the kind of the liquid crystal composition was changed.
In sample No.5, a liquid crystal composition containing a liquid crystal mixture, an alignment aid 1 as a polymerizable monomer, an alignment aid 2, and a pretilt angle forming aid was used. The amount of the alignment aid 1 contained in the liquid crystal composition was 1.0 mass%, the amount of the alignment aid 2 was 0.6 mass%, and the amount of the pretilt angle forming aid was 0.3 mass%.
(Sample No. 6-10)
Samples were prepared in the same manner as in the aforementioned samples nos. 1 to 5, except that the irradiation time of ultraviolet rays was changed to 100 seconds.
(Sample No. 11-15)
Samples were prepared in the same manner as in the aforementioned samples nos. 1 to 5, except that the irradiation time of ultraviolet rays was changed to 200 seconds.
Further, two samples were prepared.
2. Measurement and evaluation
2-1. Measurement of surface roughness (Ra)
Each sample was decomposed, and the surface roughness (Ra) of the surface of the ITO film and the surface of the organic insulating film were measured.
The surface roughness (Ra) was measured using an atomic force microscope (manufactured by Pacific Nanotechnology, inc., "Nano-DST") using a close contact mode (measurement mode) and a cantilever (cantilever) (manufactured by Nanoworld, inc., "NCH-W").
2-2. Evaluation of vertical orientation
The degree of light transmittance (brightness unevenness) of each sample was evaluated based on the following 3-stage standard.
< Evaluation criterion >
O: the sample showed black color almost throughout the entire surface.
Delta: only the vicinity of the liquid crystal composition to which the sample was added dropwise showed black.
X: the sample showed no black color almost throughout the entire surface.
2-3. Determination of pretilt angle
For each sample, a pretilt angle was measured using a pretilt angle measurement system (manufactured by TOYO Corporation, "PSA-301 type").
2-4. Evaluation of response characteristics
For each sample, the response speed at 20℃was measured by an electro-optical measurement device (manufactured by AUTORONIC-MELCHERS Corporation, "DMS 703"), and the response characteristics were evaluated based on the following criteria.
< Evaluation criterion >
And (3) the following materials: less than 9.0ms
And (2) the following steps: 9.0ms or more and less than 10.0ms
Delta: 10.0ms or more and less than 11.0ms
X: 11.0ms or more
2-5. Evaluation of contrast
For each sample, the electro-optical characteristics were measured by an electro-optical measuring device (AUTORONIC-MELCHERS Corporation, "DMS 703"), and "maximum luminance/minimum luminance" was calculated. Based on the calculated values, the contrast is evaluated according to the following criteria.
< Evaluation criterion >
And (3) the following materials: 1600 or more
And (2) the following steps: 1400 or more and less than 1600
Delta: 1200 or more and less than 1400
X: less than 1200
The measurement and evaluation results are shown in table 1.
TABLE 1
The measurement and evaluation were performed using various compounds as the orientation aids 1 and 2, and as a result, it was confirmed that: the surface roughness of the ITO film and the organic insulating film varies depending on the amount of the alignment aid 1 and the alignment aid 2 contained in the liquid crystal composition and/or the irradiation time of ultraviolet rays, not depending on the kind of the alignment aid 1 and the kind of the alignment aid 2. The difference in the surface roughness values due to the difference in the types of the orientation aids 1 and 2 is not so large.
(Sample No. H-1 to H-4)
Samples No. H-1 to H-4 were prepared as comparative examples in the same manner as in sample No.1 except that the presence or absence of each component and the amount of each component used were changed as shown in Table 2.
The same measurement and evaluation as described above were performed for each sample obtained. The measurement and evaluation results are shown in table 2.
TABLE 2
From the comparison of tables 1 and 2, it was confirmed that samples No.1 to 15 (examples) exhibited superior properties to samples No. H-1 to H-4 (comparative examples).
[ Symbolic description ]
1: Liquid crystal display element
AM: active matrix substrate
CF: color filter substrate
2: 1 St substrate
3: 2 Nd substrate
4: Liquid crystal layer
5: Pixel electrode layer
6: Common electrode layer
7: 1 St polarizing plate
8: 2 Nd polarizing plate
9: Color filter
11: Gate bus line
12: Data bus line
13: Pixel electrode
14: Cs electrode
15: Source electrode
16: Drain electrode
17: Contact hole
Claims (10)
1. A liquid crystal display element comprising a liquid crystal layer containing liquid crystal molecules sandwiched between two substrates, characterized in that:
One substrate is provided with a polymer of a polymerizable monomer which is present in contact with the liquid crystal layer and is polymerizable by irradiation with an active energy ray, and the surface roughness Ra of the surface in contact with the liquid crystal layer is 1 to 30nm by the presence of the polymer,
The polymerizable monomer contains an alignment aid having a function of spontaneously aligning the liquid crystal molecules and having a polar group,
The polymerizable monomer contains a pretilt angle forming auxiliary agent having a function of forming a pretilt angle of the liquid crystal molecules,
The one substrate is a substrate which is directly in contact with the liquid crystal layer without an alignment film interposed therebetween,
The alignment aid has a polymerizable group for polymerization, a mesogenic group similar to a liquid crystal molecule, the polar group capable of interacting with a member directly abutting against the liquid crystal layer, and an alignment inducing group causing alignment of the liquid crystal molecule,
The polar group is 1 or more than 2 kinds of groups selected from the group consisting of an oxygen-containing cyclic group, a nitrogen-containing cyclic group, an oxygen-containing chain group and a nitrogen-containing chain group, or comprises the groups,
The oxygen-containing cyclic group is any one of the following groups,
Wherein, the formula (I) represents a bond,
The nitrogen-containing cyclic group is any one of the following groups,
Wherein, the formula (I) represents a bond,
The oxygen-containing chain group is any one of the following groups,
Wherein, the formula (I) represents a bond,
R at1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
Z at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms or a linear or branched alkenylene group having 2 to 18 carbon atoms, wherein, -CH 2 -in alkylene or alkenylene groups may be substituted by-O-, -COO-, -C (=O) -, -OCO-in such a way that the oxygen atoms are not directly adjacent,
X at1 represents an alkyl group having 1 to 15 carbon atoms, -CH 2 -in the alkyl group may be substituted by-O-, -COO-, -C (=O) -, -OCO-in such a manner that the oxygen atoms are not directly adjacent,
The nitrogen-containing chain group is any one of the following groups,
Wherein, the formula (I) represents a bond,
R at、Rbt、Rct and R dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
2. The liquid crystal display element according to claim 1, wherein the one substrate is a substrate provided with a pixel electrode.
3. The liquid crystal display element according to claim 1 or 2, wherein the other substrate is also provided with the polymer existing in contact with the liquid crystal layer, and a surface roughness Ra of a surface in contact with the liquid crystal layer is1 to 30nm by the presence of the polymer.
4. The liquid crystal display element according to claim 3, wherein the other substrate is a substrate directly in contact with the liquid crystal layer without an alignment film interposed therebetween.
5. A liquid crystal display element according to claim 3, wherein the other substrate is a substrate provided with a color filter.
6. The liquid crystal display element according to claim 1 or 2, wherein dielectric constant anisotropy of the liquid crystal molecules is negative.
7. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal display element is of PSA type, PSVA type, VA type, IPS type, FFS type, or ECB type.
8. A method for manufacturing the liquid crystal display element according to any one of claims 1 to 7, comprising the steps of:
The two substrates are disposed so as to face each other in contact with a liquid crystal composition containing the liquid crystal molecules and the polymerizable monomer; and
Applying a voltage to the liquid crystal composition and simultaneously irradiating the active energy rays, thereby polymerizing the polymerizable monomer, thereby obtaining the polymer.
9. The method for manufacturing a liquid crystal display element according to claim 8, wherein the polymerizable monomer contains an alignment aid having a function of spontaneously aligning the liquid crystal molecules,
The total amount of the alignment aids contained in the liquid crystal composition is 0.1 to 3 mass%.
10. The method for manufacturing a liquid crystal display element according to claim 8 or 9, wherein the irradiation time of the active energy ray is 10 to 7200 seconds.
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