CN111868615A - Liquid crystal display element - Google Patents

Liquid crystal display element Download PDF

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Publication number
CN111868615A
CN111868615A CN201980019741.5A CN201980019741A CN111868615A CN 111868615 A CN111868615 A CN 111868615A CN 201980019741 A CN201980019741 A CN 201980019741A CN 111868615 A CN111868615 A CN 111868615A
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liquid crystal
formula
benzene ring
coo
single bond
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保坂和义
片山雅章
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • 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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • 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

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Abstract

Provided is a liquid crystal display element which has improved adhesion between a liquid crystal layer and an electrode, and can suppress peeling of the element, generation of bubbles, and deterioration of optical characteristics even when exposed to a severe environment of high temperature and high humidity or irradiation of light for a long period of time. A liquid crystal display element having a liquid crystal layer which is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied, the liquid crystal layer being disposed between a pair of substrates having electrodesThe liquid crystal composition containing a liquid crystal and a polymerizable compound, wherein the liquid crystal composition contains the following formula [1 ]]The compounds shown. (wherein each symbol is as defined in the description.)

Description

Liquid crystal display element
Technical Field
The present invention relates to a transmission/scattering type liquid crystal display device.
Background
As a liquid crystal display element, a Twisted Nematic (TN, Twisted Nematic) mode has been put to practical use. In this mode, since light is switched by utilizing the optical rotation characteristics of liquid crystal, a polarizing plate needs to be used. When the polarizing plate is used, the light use efficiency is lowered.
As a liquid crystal display element not using a polarizing plate, there is an element that switches between a transmission state (also referred to as a transparent state) and a scattering state of liquid crystal. It is generally known to use polymer dispersed Liquid crystal (also referred to as pdlc (polymer dispersed Liquid crystal)) and polymer Network Liquid crystal (also referred to as pnlc (polymer Network Liquid crystal)).
In these liquid crystal display devices, a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet light is disposed between a pair of substrates having electrodes, and the liquid crystal composition is cured by irradiation of ultraviolet light to form a composite of the liquid crystal and a cured product (e.g., a polymer network) of the polymerizable compound. In the liquid crystal display element, the scattering state and the transmission state of the liquid crystal are controlled by applying a voltage.
Among liquid crystal display elements using PDLC and PNLC, there is a liquid crystal display element (also referred to as a standard type element) in which liquid crystal is in a white turbid (scattering) state because the liquid crystal is oriented in a random direction when no voltage is applied, and the liquid crystal is aligned in an electric field direction when a voltage is applied, and light is transmitted therethrough. In this case, since the liquid crystal is random when no voltage is applied, a liquid crystal alignment film or an alignment treatment for aligning the liquid crystal in one direction is not necessary. Therefore, in this liquid crystal display device, the electrode and the liquid crystal layer (the composite of the liquid crystal and the cured product of the polymerizable compound) are directly connected (see patent documents 1 and 2).
On the other hand, liquid crystal display elements (also referred to as inversion elements) using PDLC that are in a transmissive state when no voltage is applied and in a scattering state when a voltage is applied have been proposed (see patent documents 3 and 4).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3552328
Patent document 2: japanese patent No. 4630954
Patent document 3: japanese patent No. 2885116
Patent document 4: japanese patent No. 4132424
Disclosure of Invention
Problems to be solved by the invention
The polymerizable compound in the liquid crystal composition has an action of forming a polymer network to obtain desired optical characteristics and an action of improving adhesion between the liquid crystal layer and the electrode. However, since an inorganic electrode such as Indium Tin Oxide (ITO) is generally used for a liquid crystal display element, compatibility with a polymerizable compound of an organic material, that is, adhesiveness tends to decrease. When the adhesiveness is lowered, peeling of the element, generation of bubbles, and further deterioration of optical properties in a scattering state and a transparent state are likely to occur due to long-term use, particularly, severe environments such as environments exposed to high temperature and high humidity and irradiation of light.
Under the above circumstances, an object of the present invention is to provide a liquid crystal display element in which adhesion between a liquid crystal layer and an electrode is improved, and peeling of the element, generation of bubbles, and reduction in optical characteristics can be suppressed even when the element is exposed to a severe environment of high temperature and high humidity or irradiation of light for a long time.
Means for solving the problems
The present inventors have conducted extensive studies to achieve the above object, and as a result, have completed the present invention having the following gist.
That is, the liquid crystal display element of the present invention is characterized by comprising a liquid crystal layer which is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied, wherein the liquid crystal layer is obtained by irradiating a liquid crystal composition containing a liquid crystal and a polymerizable compound, which is disposed between a pair of substrates provided with electrodes, with ultraviolet light and curing the liquid crystal composition, and the liquid crystal composition contains a compound represented by the following formula [1 ].
Figure BDA0002684866400000031
(X1Represents the following formula [1-a]Or formula [1-b]。X2Represents an alkylene group having 2 to 24 carbon atoms, the alkylene group being different from X1any-CH adjacent to O2-optionally substituted by-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-or-CON (CH)3) -replacing. Xm represents an integer of 1 or 2. Xn represents an integer of 1 or 2. Wherein Xm + Xn is 3. )
Figure BDA0002684866400000032
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a liquid crystal display element is obtained which has improved adhesion between a liquid crystal layer and an electrode, and which can be in a scattering state when no voltage is applied and in a transparent state when a voltage is applied, and which can suppress peeling of the element, generation of bubbles, and degradation of optical characteristics even when exposed to a severe environment of high temperature and high humidity or irradiation of light for a long period of time. Therefore, the element of the present invention can be used for a liquid crystal display, a light control window for controlling the blocking and transmission of light, a shutter element, and the like.
The mechanism why the liquid crystal display element having the above-described excellent characteristics is obtained by the present invention is not necessarily clear, but is estimated as follows.
The liquid crystal composition used in the present invention contains a liquid crystal, a polymerizable compound and the compound of the formula [1 ]]The compounds shown (also referred to as specific compounds). Specific compounds have the formula [1]X in (1)1Shown passing ultraviolet lightThe site where the polymerization reaction proceeds and the phosphate group. Therefore, it is considered that when a specific compound is contained in the liquid crystal composition, the interaction between the phosphate group and an inorganic electrode such as an ITO electrode occurs, and further, the formula [1 ]]X in (1)1The site (b) reacts with the polymerizable compound, whereby the adhesion between the polymer network in the liquid crystal layer and the electrode is improved.
From the above, it is understood that the liquid crystal display element using the liquid crystal composition of the present invention has improved adhesion between the liquid crystal layer and the electrode, and can suppress peeling of the element, generation of bubbles, and deterioration of optical characteristics even when exposed to a severe environment of high temperature and high humidity or irradiation of light for a long time. In particular, the present invention can be suitably used for a standard type element which is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied.
Detailed Description
< liquid crystal composition >
The liquid crystal composition of the present invention comprises a liquid crystal, a polymerizable compound and a specific compound represented by the formula [1 ].
As the liquid crystal, nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal can be used. Among them, the normal type element is preferably a liquid crystal having positive dielectric anisotropy, and the reverse type element is preferably a liquid crystal having negative dielectric anisotropy. In this case, from the viewpoint of low-voltage driving and scattering characteristics, the dielectric anisotropy is preferably large, and the refractive index anisotropy is preferably large. In addition, 2 or more kinds of liquid crystals can be mixed and used according to the above-described respective physical property values of the phase transition temperature, the dielectric anisotropy, and the refractive index anisotropy.
In order to drive a liquid crystal display element as an active element such as a Thin Film Transistor (TFT) or the like, the liquid crystal is required to have high resistance and high voltage holding ratio (also referred to as VHR). Therefore, fluorine-based or chlorine-based liquid crystals having high resistance and free from VHR degradation by active energy rays such as ultraviolet rays are preferably used as the liquid crystals.
Further, the liquid crystal display element may be a host-guest type element formed by dissolving the dichroic dye in the liquid crystal composition. In this case, in the case of the standard type element, an element which is absorbing (scattering) when no voltage is applied and becomes transparent when a voltage is applied is obtained. In this element, the direction of the director (direction of alignment) of the liquid crystal changes by 90 degrees depending on the presence or absence of voltage application. Therefore, this element utilizes the difference in light absorption characteristics of the dichroic dye, and thus obtains a higher contrast ratio than a conventional host-guest type element in which random alignment and vertical alignment are switched. In a host-guest type element in which a dichroic dye is dissolved, the element becomes colored when the liquid crystal is aligned in the horizontal direction, and becomes opaque only in a scattering state. Therefore, an element which changes from colored opaque when no voltage is applied to colored transparent to colorless transparent state with voltage application can be obtained.
The polymerizable compound in the liquid crystal composition is used for forming a polymer network (also referred to as a curable resin) by polymerization reaction by ultraviolet irradiation at the time of manufacturing the liquid crystal display element. Therefore, a polymer obtained by previously polymerizing a polymerizable compound may be introduced into the liquid crystal composition. However, even when a polymer is formed, it is necessary to have a site where a polymerization reaction proceeds by irradiation of ultraviolet rays. The polymerizable compound is preferably used from the viewpoint of handling of the liquid crystal composition, that is, suppression of an increase in viscosity of the liquid crystal composition, and solubility in a liquid crystal.
The polymerizable compound is not particularly limited as long as it is dissolved in the liquid crystal, and when the polymerizable compound is dissolved in the liquid crystal, a temperature at which a liquid crystal phase is expressed needs to be present in part or all of the liquid crystal composition. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, the transparency and scattering properties of the entire device can be substantially the same as each other if the liquid crystal display device is visually confirmed.
The polymerizable compound may be a compound that is polymerized by ultraviolet rays, and in this case, the polymerizable compound may be polymerized in any reaction form to form a curable resin. Specific reaction forms include radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization.
Among them, the reaction form of the polymerizable compound is preferably radical polymerization from the viewpoint of optical characteristics of the liquid crystal display element. In this case, the following radical type polymerizable compound or oligomer thereof can be used as the polymerizable compound. As described above, a polymer obtained by polymerizing these polymerizable compounds may be used.
Specific examples of the radical type polymerizable compound or oligomer thereof include radical type polymerizable compounds described on pages 69 to 71 of International publication No. WO 2015/146987.
The ratio of the radical polymerizable compound or oligomer thereof to be used is preferably 70 to 150 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition, from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the electrode. More preferably 80 to 110 parts by mass. The radical polymerizable compound may be used in a mixture of 1 or 2 or more depending on the characteristics.
In order to promote the formation of the curable resin, it is preferable to introduce a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays into the liquid crystal composition in order to promote radical polymerization of the polymerizable compound. Specifically, the radical initiator is described in International publication No. 2015/146987, pages 71 to 72.
The ratio of the radical initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition, from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the electrode. More preferably 0.05 to 10 parts by mass. The radical initiator may be used in a mixture of 1 or 2 or more species depending on the characteristics.
< specific Compound >
The specific compound is a compound represented by the formula [1 ].
Formula [1]In, X1、X2Xm, Xn are as defined above, but the following examples are preferred among them.
X1Preferably the above formula1-a]Or formula [1-b]。X2Preferably C2-C12 alkylene, not related to X1any-CH adjacent to O2-is optionally replaced by-O-, -COO-or-OCO-. Xm is preferably an integer of 1 or 2. Xn is preferably an integer of 1 or 2. Wherein Xm + Xn is 3.
Specific examples of the specific compound include compounds selected from the group consisting of the following formulas [1a-1] to [1a-3], and these compounds are preferably used.
Figure BDA0002684866400000071
XaRepresents the aforementioned formula [1-a]Or formula [1-b]。XbRepresents an alkylene group having 2 to 18 carbon atoms. Xcrepresents-COO-or-OCO-. XdRepresents an alkylene group having 2 to 12 carbon atoms. p1 represents an integer of 1 or 2. p2 represents an integer of 1 or 2. Wherein p1+ p2 is 3. p3 represents an integer of 2 to 8.
More specifically, there are exemplified Phosmer M, Phosmer PE, Phosmer PP (manufactured by DAP Co., Ltd.), Lightacrylate P-1A (N), Lightester P-1M (manufactured by Kyodo chemical Co., Ltd.), KAYAMER PM-2 and KAYAMER PM-21 (manufactured by Nippon Kagaku K.K.).
The content ratio of the specific compound is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and most preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the liquid crystal in the liquid crystal composition, from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the electrode. The specific compound may be used in a mixture of 1 or 2 or more depending on the characteristics.
< Compound No. 2 >
The liquid crystal composition of the present invention preferably contains a compound represented by the following formula [2] (also referred to as a specific compound 2).
Figure BDA0002684866400000072
Y1Represents the following formula [2-a]-formula [2-j]. Among them, preferred is the formula [2-a ]]Is of the formula [2-b]Is of the formula [2-c]Is of the formula [2-d]Formula [2-e]Or formula[2-f]. More preferably [2-a ]]Is of the formula [2-b]Is of the formula [2-c]Or formula [2-e]. Most preferred is the formula [2-a]Or formula [2-b]。
Figure BDA0002684866400000081
YARepresents a hydrogen atom or a benzene ring.
Y2Represents a single bond, -O-, -NH-, -N (CH)3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-. Among them, a single bond, -O-, -CH is preferable2O-, -CONH-, -COO-or-OCO-, more preferably a single bond, -O-, -COO-or-OCO-.
Y3Represents a single bond or- (CH)2)a- (a is an integer of 1 to 15). Among them, preferred is a single bond or- (CH)2)a- (a is an integer of 1 to 10), particularly preferably- (CH)2)a- (a is an integer of 1 to 10).
Y4Represents a single bond, -O-, -OCH2-, -COO-or-OCO-. Among these, a single bond, -O-or-COO-, particularly-O-is preferable.
Y5Represents a 2-valent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, or a 2-valent organic group having 17 to 51 carbon atoms and having a steroid skeleton, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom. Among them, preferred is a benzene ring, a cyclohexane ring, or a C17-51 organic group having a steroid skeleton. More preferably a benzene ring or a C17-51 organic group having a steroid skeleton.
Y6Represents a single bond, -O-, -CH2-、-OCH2-、-CH2O-, -COO-or-OCO-. Among them, a single bond, -O-, -COO-or-OCO-is preferable, and a single bond, -COO-or-OCO-is more preferable.
Y7Represents a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms,A C1-3 fluoroalkyl group, a C1-3 fluoroalkoxy group, or a fluorine atom. Among them, preferred is a benzene ring or a cyclohexane ring.
Y8Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 18 carbon atoms. Among them, preferred is an alkyl group or an alkoxy group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. More preferably an alkyl group or alkoxy group having 1 to 12 carbon atoms.
Ym represents an integer of 0 to 4. Among them, an integer of 0 to 2 is preferable.
Formula [2 ]]Preferred Y in (1)1～Y8The combinations with Ym are shown in tables 1 to 9 below. In tables 1 to 9, Y is shown3Of (CH)2) A in the formula (II) represents an integer of 1 to 10.
[ Table 1]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-1a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkyl group 0
2-2a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkoxy group 0
2-3a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-4a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-5a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-6a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-7a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-8a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-9a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkyl group 0
2-10a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkoxy group 0
2-11a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-12a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-13a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-14a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-15a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-16a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-17a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-18a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-19a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-20a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 2]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-21a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-22a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-23a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-24a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-25a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-26a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
2-27a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-28a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-29a Formula [2-a ] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-30a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-31a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-32a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-33a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkaneBase of 1
2-34a Formula [2-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
2-35a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-36a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-37a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-38a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-39a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
2-40a Formula [2-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 3]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-41a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkyl group 0
2-42a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkoxy group 0
2-43a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-44a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-45a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-46a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-47a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-48a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-49a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkyl group 0
2-50a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkoxy group 0
2-51a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-52a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-53a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-54a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-55a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-56a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-57a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-58a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-59a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-60a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 4]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-61a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-62a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-63a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-64a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-65a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-66a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
2-67a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-68a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-69a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-70a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-71a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-72a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-73a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
2-74a Formula [2-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
2-75a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-76a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-77a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-78a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-79a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
2-80a Formula [2-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 5]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-81a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkyl group 0
2-82a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkoxy group 0
2-83a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-84a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-85a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-86a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-87a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-88a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-89a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkyl group 0
2-90a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkoxy group 0
2-91a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-92a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-93a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-94a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-95a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-96a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-97a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-98a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-99a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-100a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 6]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-101a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-102a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-103a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-104a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-105a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-106a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
2-107a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-108a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-109a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-110a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-111a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-112a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-113a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
2-114a Formula [2-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
2-115a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-116a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-117a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-118a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-119a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
2-120a Formula [2-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 7]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-121a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkyl group 0
2-122a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond - C1-C12 alkoxy group 0
2-123a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-124a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-125a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-126a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-127a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkyl group 0
2-128a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond - C1-C12 alkoxy group 0
2-129a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
2-130a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
2-131a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
2-132a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
2-133a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-134a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-135a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-136a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
2-137a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
2-138a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
2-139a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
2-140a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 8]
Y1 Y2 Y3 Y4 Y5 Y6 Y7 Y8 Ym
2-141a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-142a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-143a Formula [2-e ] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-144a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-145a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
2-146a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
2-147a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
2-148a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
2-149a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-150a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-151a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
2-152a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
2-153a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-154a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-155a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
2-156a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
2-157a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
2-158a Formula [2-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
2-159a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
2-160a Formula [2-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 9]
Figure BDA0002684866400000171
Of these, (2-3a) to (2-8a), (2-11a) to (2-24a), (2-27a) to (2-36a), (2-39a), (2-40a), (2-43a) to (2-48a), (2-51a) to (2-64a), (2-67a) to (2-76a), (2-79a), (2-80a), (2-83a) to (2-88a), (2-91a) to (2-104a), (2-107a) to (2-116a), (2-119a), (2-120a), (2-123a), (2-124a), (2-129a), and (2-130a) are preferable, (2-133a), (2-134a), (2-137a), (2-138a), (2-141a), (2-142a), (2-145a), (2-146a), or (2-149a) to (2-172 a).
More preferably (2-3a) - (2-8a), (2-11a), (2-12a), (2-15a) - (2-18a), (2-21a), (2-22a), (2-27a) - (2-30a), (2-33a), (2-34a), (2-39a), (2-40a), (2-43a) - (2-48a), (2-51a), (2-52a), (2-55a) - (2-58a), (2-61a), (2-62a), (2-67a) - (2-70a), (2-73a), (2-74a), (2-79a), (2-80a), (2-83a) - (2-88a), (2-91a), (2-92a), (2-95a) to (2-98a), (2-101a), (2-102a), (2-107a) to (2-110a), (2-113a), (2-114a), (2-119a), (2-120a), (2-123a), (2-124a), (2-129a), (2-130a), (2-133a), (2-134a), (2-137a), (2-138a), (2-141a), (2-142a), (2-145a), (2-146a), or (2-149a) to (2-172 a).
Most preferably (2-3a) - (2-8a), (2-15a) - (2-18a), (2-29a), (2-30a), (2-43a) - (2-48a), (2-55a) - (2-58a), (2-69a), (2-70a), (2-83a) - (2-88a) and (2-95a) - (2-98a), (2-109a), (2-110a), (2-123a), (2-124a), (2-133a), (2-134a), (2-141a), (2-142a), (2-149a) to (2-152a), or (2-161a) to (2-172 a).
More specific compound 2 includes compounds selected from the group consisting of the following formulas [2a-1] to [2a-11], and these compounds are preferably used.
Figure BDA0002684866400000181
The above formulaIn, Yarepresents-O-or-COO-. Y isbRepresents an alkyl group having 1 to 12 carbon atoms. q1 represents an integer of 1 to 10. q2 represents an integer of 1 or 2.
Figure BDA0002684866400000191
Formula [2a-5]-formula [2a-8]In, YcRepresents a single bond, -COO-or-OCO-. Y isdRepresents an alkyl group or an alkoxy group having 1 to 12 carbon atoms. q3 represents an integer of 1 to 10. q4 represents an integer of 1 or 2.
Figure BDA0002684866400000192
Formula [2a-9]-formula [2a-11]In, Yerepresents-O-or-COO-. Y isfRepresents a C17-51 organic group having a steroid skeleton and a valence of 2. Y isgRepresents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. q5 represents an integer of 1 to 10.
The content ratio of the 2 nd specific compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, most preferably 1 to 10 parts by mass, relative to 100 parts by mass of the liquid crystal in the liquid crystal composition, from the viewpoint of adhesion between the liquid crystal layer and the electrode of the liquid crystal display element. The 2 nd specific compound may be used in combination of 1 or 2 or more depending on the characteristics.
Examples of the method for producing the liquid crystal composition include a method in which a liquid crystal, a polymerizable compound, and a specific compound are mixed together; a method of mixing a polymerizable compound and a specific compound in advance to obtain a mixture, and mixing the mixture with a liquid crystal. Among these, a method of mixing a polymerizable compound and a specific compound in advance to obtain a mixture and mixing the mixture with a liquid crystal is preferable.
Further, there may be mentioned a method of adding the 2 nd specific compound to a liquid crystal in which a polymerizable compound and the specific compound are mixed; a method of preparing a mixture obtained by adding the 2 nd specific compound to a liquid crystal in advance, and a mixture obtained by adding a polymerizable compound and a specific compound to the mixture.
In the case of producing the liquid crystal composition as described above, heating may be performed depending on the solubility of the polymerizable compound, the specific compound, and the 2 nd specific compound. The temperature at this time is preferably less than 100 ℃.
< method for manufacturing liquid crystal display element >
The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, or the like, and a film thereof may be used in addition to the glass substrate. In particular, when used for a light control window or the like, a plastic substrate or a film is preferable. In view of process simplification, a substrate on which an ITO electrode for driving a liquid crystal, an Indium Zinc Oxide (IZO) electrode, an Indium Gallium Zinc Oxide (IGZO) electrode, an organic conductive film, and the like are formed is preferable. In the case of forming a reflective liquid crystal display element, a substrate formed with a silicon wafer, a metal such as aluminum, or a dielectric multilayer film may be used as long as the substrate is a single-sided substrate.
In the case of a reverse liquid crystal display element, a liquid crystal alignment film for vertically aligning liquid crystal molecules is preferably attached to at least one of the substrates. The liquid crystal alignment film is produced by applying a liquid crystal alignment treatment agent to a substrate and baking the applied liquid crystal alignment treatment agent. In this case, alignment treatment such as rubbing treatment and light irradiation may be performed after the baking.
The liquid crystal composition used for the liquid crystal display element is as described above, and a spacer for controlling an electrode gap (also referred to as a void) of the liquid crystal display element may be introduced therein.
The method of injecting the liquid crystal composition is not particularly limited, and the following methods may be mentioned. That is, when a glass substrate is used as the substrate, a pair of substrates is prepared, a sealant is applied to 4 substrates on one side except a part thereof, and then the other substrate is bonded with the electrode surface facing the inside to form an empty cell. And then injecting the liquid crystal composition under reduced pressure from a portion where the sealant is not applied to obtain a cell into which the liquid crystal composition is injected. Further, when a plastic substrate or a film is used as the substrate, a method may be mentioned in which a pair of substrates are prepared, a liquid crystal composition is dropped on one substrate by an odf (one Drop filling) method, an ink jet method, or the like, and then the other substrate is bonded to obtain a unit into which the liquid crystal composition is injected. In the liquid crystal display element of the present invention, since the liquid crystal layer has high adhesion to the electrodes, the 4 substrates need not be coated with the sealant.
The gap of the liquid crystal display element can be controlled by the aforementioned spacer or the like. As described above, this method includes a method of introducing a spacer having a target size into a liquid crystal composition, a method of using a substrate having a post spacer having a target size, and the like. In addition, when the substrates are laminated using a plastic or film substrate, the gap can be controlled without introducing a spacer.
The size of the gap of the liquid crystal display element is preferably 1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 2 to 30 μm. If the gap is too small, the contrast of the liquid crystal display element decreases, and if it is too large, the driving voltage of the element increases.
The liquid crystal display element is obtained by curing a liquid crystal composition to form a liquid crystal layer. The liquid crystal composition is cured by irradiating a cell into which the liquid crystal composition is injected with ultraviolet rays. Examples of the light source include a metal halide lamp and a high-pressure mercury lamp. The wavelength of the ultraviolet ray is preferably 250 to 400nm, more preferably 310 to 370 nm. After the irradiation with ultraviolet rays, heat treatment may be performed. The temperature at this time is preferably 20 to 120 ℃, more preferably 30 to 100 ℃.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The abbreviations used in the following are as follows.
< specific Compound >
X1: phosmer PE (manufactured by DAP Co., Ltd.)
X2: KAYAMER PM-21 (manufactured by Nippon Kabushiki Kaisha)
< Compound No. 2 >
Figure BDA0002684866400000221
< polymerizable Compound >
R1: IBXA (Osaka organic chemical industry Co., Ltd.)
R2: 2-Hydroxyethyl methacrylate
R3: KAYARAD FM-400 (manufactured by Nippon Kabushiki Kaisha)
R4: EBECRYL 230 (manufactured by DAICEL-ALLNEX LTD. system)
R5: EBECRYL 4858 (manufactured by DAICEL-ALLNEX LTD. system.)
R6: karenz MT PE1 (Showa Denko K.K.)
< photo radical initiator >
P1: IRGACURE 184 (manufactured by BASF corporation)
< liquid Crystal >
L1: MLC-3018 (made by Merck Ltd.)
< preparation of liquid Crystal composition (1) >
R1(1.35g), R2(0.20g), R3(1.00g), R4(0.80g), R5(0.20g) and R6(0.30g) were mixed and stirred at 60 ℃ for 2 hours. Then, X1(0.05g) was added to the reaction solution to prepare a polymerizable compound solution. A solution of a polymerizable compound, L1(6.00g) and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (1).
< preparation of liquid Crystal composition (2) >
R1(1.30g), R2(0.20g), R3(1.00g), R4(0.80g), R5(0.20g) and R6(0.30g) were mixed and stirred at 60 ℃ for 2 hours. Then, X2(0.10g) was added to the reaction solution to prepare a polymerizable compound solution. A solution of a polymerizable compound, L1(6.00g) and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (2).
< preparation of liquid Crystal composition (3) >
R1(1.40g), R2(0.20g), R3(1.00g), R4(0.80g), R5(0.20g) and R6(0.30g) were mixed and stirred at 60 ℃ for 2 hours. Then, X2(0.10g) was added to the reaction solution to prepare a polymerizable compound solution. On the other hand, S1(0.20g) and L1(5.80g) were mixed and stirred at 25 ℃ for 2 hours to prepare a liquid crystal containing the 2 nd specific compound. A liquid crystal composition (3) was obtained by mixing a solution of a polymerizable compound, a liquid crystal containing the 2 nd specific compound, and P1(0.10g), and stirring at 25 ℃ for 6 hours.
< preparation of liquid Crystal composition (4) >
R1(1.20g), R2(0.20g), R3(1.00g), R4(0.80g), R5(0.20g) and R6(0.30g) were mixed and stirred at 60 ℃ for 2 hours. Then, X2(0.20g) was added to the reaction solution to prepare a polymerizable compound solution. On the other hand, S1(0.20g), S2(0.20g) and L1(5.60g) were mixed and stirred at 25 ℃ for 2 hours to prepare a liquid crystal containing the 2 nd specific compound. A liquid crystal composition (4) was obtained by mixing a solution of a polymerizable compound, a liquid crystal containing the 2 nd specific compound, and P1(0.10g), and stirring at 25 ℃ for 6 hours.
< preparation of liquid Crystal composition (5) >
R1(1.40g), R2(0.20g), R3(1.00g), R4(0.80g), R5(0.20g) and R6(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. A solution of the polymerizable compound, L1(6.00g) and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (5).
Production of liquid Crystal display element (glass substrate) "
2 pieces of ITO electrode-equipped glass substrates (100 mm in length: 100mm in width: 100mm in thickness: 0.7mm) washed with pure water and IPA (isopropyl alcohol) were prepared, and spacers (trade name: Micropearl, manufactured by waterlogging chemical Co., Ltd.) having a particle size of 15 μm were coated on the ITO surface of the 1 piece of substrate. Then, the spacers were applied to the surfaces of the substrates, and the liquid crystal compositions (1) to (5) were dropped by an odf (one Drop filling) method, followed by bonding the substrates so that the ITO surfaces of the other substrates were opposed to each other, to obtain a liquid crystal display element before treatment.
The liquid crystal display element before the treatment was used at an illuminance of 20mW/cm2The metal halide lamp of (1), wherein the ultraviolet ray irradiation is performed for 60 seconds with the wavelength of 350nm or less removed. Thus, a liquid crystal display element (glass substrate) was obtained.
Production of liquid Crystal display element (Plastic substrate) "
2 pieces of PET substrate (150 mm in vertical direction, 150mm in horizontal direction, and 0.1mm in thickness) with ITO electrodes washed with pure water were prepared, and the spacers of 15 μm were coated on the ITO surface of the 1 piece of substrate. Then, the liquid crystal compositions (1) to (5) were dropped on the ITO surface of the substrate coated with the spacer by the ODF method, and then bonded so that the ITO surface of the other substrate faces each other, to obtain a liquid crystal display element before treatment. When the liquid crystal composition was dropped and bonded by the ODF method, a glass substrate was used as a support substrate for the PET substrate with ITO electrode. The support substrate is then removed before the ultraviolet radiation is applied.
The liquid crystal display element before the treatment was irradiated with ultraviolet light in the same manner as in the above-described "production of liquid crystal display element (glass substrate)", to obtain a liquid crystal display element (plastic substrate).
"evaluation of optical characteristics (scattering characteristics and transparency)"
The evaluation was carried out by measuring Haze (Haze) of a liquid crystal display element (glass substrate and plastic substrate) in a state of no voltage application (0V) and in a state of voltage application (AC drive: 10V to 50V). In this case, Haze was measured by a Haze meter (HZ-V3, Suga Test Instruments Co., Ltd.) according to JIS K7136. In this evaluation, the higher the Haze in the state where no voltage was applied, the more excellent the scattering properties, and the lower the Haze in the state where a voltage was applied, the more excellent the transparency.
In addition, as a stability test in a high-temperature and high-humidity environment of the liquid crystal display element, a measurement was also performed after storing the liquid crystal display element in a constant-temperature and constant-humidity tank at a temperature of 80 ℃ and a humidity of 90% RH for 24 hours. Specifically, the evaluation is more excellent as the change in Haze after storage in the constant temperature and humidity chamber is smaller than the initial Haze.
Further, as a test for stability of the liquid crystal display element against light irradiation, irradiation with 5J/cm in terms of 365nm using a desktop UV curing apparatus (HCT3B28HEX-1, manufactured by センライト Co., Ltd.) was also carried out 2Ultraviolet light (c) was observed. Specifically, the evaluation is more excellent as the change in Haze after ultraviolet irradiation is smaller than that of the initial Haze.
Initially, the results of Haze measurement after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet ray) are summarized in table 10.
Evaluation of adhesion between liquid Crystal layer and electrode "
This evaluation was carried out by storing the liquid crystal display element (glass substrate and plastic substrate) in a constant temperature and humidity chamber at a temperature of 80 ℃ and a humidity of 90% RH for 24 hours, and confirming the peeling of the liquid crystal display element and the presence or absence of air bubbles (stability test in a high temperature and high humidity environment as a liquid crystal display element). Specifically, the case where the element was not peeled off (the state where the liquid crystal layer and the resin film or the resin film and the electrode were peeled off) and the case where no bubble was generated in the element were excellent in the present evaluation (the table shows good results).
Further, for the liquid crystal display element, irradiation was performed by 5J/cm in terms of 365nm using a desktop UV curing apparatus (HCT3B28HEX-1, manufactured by センライト K.K.) as well2Ultraviolet light (stability test of the liquid crystal display element against light irradiation). Specifically, the case where the element was not peeled off and the case where no air bubbles were generated in the element were excellent in the present evaluation (the table shows good results).
Initially, the results of the adhesion between the liquid crystal layer and the electrode (adhesion) after storage in the constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet light (ultraviolet light) are summarized in table 11.
< examples 1 to 8 and comparative examples 1 and 2 >
As shown in tables 10 and 11 below, the liquid crystal display elements were produced, optical characteristics (scattering characteristics and transparency) were evaluated, and adhesion between the liquid crystal layer and the electrodes was evaluated by the methods described above using the liquid crystal compositions (1) to (5).
In this case, examples 1, 3, 5, and 7 and comparative example 1 were each performed by using a glass substrate for the production of a liquid crystal display element and each evaluation, and examples 2, 4, 6, and 8 and comparative example 2 were each performed by using a plastic substrate.
[ Table 10]
Figure BDA0002684866400000261
[ Table 11]
Figure BDA0002684866400000271
*1: a small amount of air bubbles was found in the cell.
*2: bubbles (more than 1) were found inside the element.
As is clear from tables 10 and 11, the liquid crystal display elements of the examples obtained better optical properties than the comparative examples, i.e., the Haze changes less after storage in the constant temperature and humidity chamber and after ultraviolet irradiation than at the beginning. Further, a liquid crystal display element having high adhesion between the liquid crystal layer and the electrode was formed, and even after exposure to these severe environments, the liquid crystal display element was free from peeling and bubbles. In particular, these characteristics are excellent even when a plastic substrate is used as a substrate of the liquid crystal display element. Specifically, the comparison under the same conditions is a comparison between examples 1 and 3 and comparative example 1 and a comparison between examples 2 and 4 and comparative example 2.
When the specific compound 2 is incorporated into the liquid crystal composition, Haze decreases at a lower voltage. Specifically, the comparison under the same conditions is the comparison between example 3 and example 5 and the comparison between example 4 and example 6.
Industrial applicability
The liquid crystal display element of the present invention can be suitably used for a standard type element which is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied. The present element can be used for a liquid crystal display for display purposes, a light control window for controlling the blocking and transmission of light, a shutter element, and the like, and a plastic substrate can be used as a substrate of the standard type element.
It should be noted that the entire contents of the specification, claims, drawings and abstract of japanese patent application No. 2018-052661, which was filed 3/20/2018, are incorporated herein by reference as if the specification of the present invention were published.

Claims (8)

1. A liquid crystal display element having a liquid crystal layer which is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied, wherein the liquid crystal layer is obtained by irradiating a liquid crystal composition containing a liquid crystal and a polymerizable compound, which is disposed between a pair of substrates having electrodes, with ultraviolet rays and is cured, the liquid crystal composition containing a compound represented by the following formula [1],
Figure FDA0002684866390000011
Formula [1]In, X1Represents the following formula [1-a]Or formula [1-b]，X2Represents an alkylene group having 2 to 24 carbon atoms, the alkylene group being different from X1any-CH adjacent to O2-optionally substituted by-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-or-CON (CH)3) -alternatively, Xm represents an integer of 1 or 2 and Xn represents an integer of 1 or 2, where Xm + Xn is 3,
Figure FDA0002684866390000012
2. the liquid crystal display element according to claim 1, wherein the amount of the compound represented by the formula [1] introduced is 0.05 to 10 parts by mass per 100 parts by mass of the liquid crystal.
3. The liquid crystal display element according to claim 1 or 2, wherein the compound represented by the formula [1] is at least one selected from the group consisting of the following formulae [1a-1] to [1a-3],
Figure FDA0002684866390000021
wherein, XaRepresents said formula [1-a]Or formula [1-b]，XbX represents a C2-18 alkylene groupcrepresents-COO-or-OCO-, XdRepresents an alkylene group having 2 to 12 carbon atoms, p1 represents an integer of 1 or 2, p2 represents an integer of 1 or 2, wherein p1+ p2 is 3, and p3 represents an integer of 2 to 8.
4. The liquid crystal display element according to any one of claims 1 to 3, wherein the liquid crystal composition comprises a compound represented by the following formula [2],
Figure FDA0002684866390000022
formula [2]]In, Y1Represents the following formula [2-a]-formula [2-j]，Y2Represents a single bond, -O-, -NH-, -N (CH) 3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-, Y3Represents a single bond or- (CH)2)a-, wherein a is an integer of 1 to 15, Y4Represents a single bond, -O-, -OCH2-, -COO-or-OCO-, Y5Represents a 2-valent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle, or a 2-valent organic group having a steroid skeleton and having 17 to 51 carbon atoms, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y is6Represents a single bond, -O-, -CH2-、-OCH2-、-CH2O-, -COO-or-OCO-, Y7Represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom in these cyclic groups is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y is8Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms, Ym represents an integer of 0 to 4,
Figure FDA0002684866390000031
wherein, YARepresents a hydrogen atom or a benzene ring.
5. The liquid crystal display element according to claim 4, wherein the amount of the compound represented by the formula [2] introduced is 0.5 to 20 parts by mass per 100 parts by mass of the liquid crystal.
6. The liquid crystal display element according to claim 4 or 5, wherein the compound represented by the formula [2] is at least one selected from the group consisting of the following formulae [2a-1] to [2a-11],
Figure FDA0002684866390000032
formula [2a-1]-formula [2a-4]In, Yarepresents-O-or-COO-, YbRepresents an alkyl group having 1 to 12 carbon atoms, q1 represents an integer of 1 to 10, q2 represents an integer of 1 or 2,
Figure FDA0002684866390000041
formula [2a-5]-formula [2a-8]In, YcRepresents a single bond, -COO-or-OCO-, YdRepresents an alkyl group or an alkoxy group having 1 to 12 carbon atoms, q3 represents an integer of 1 to 10, q4 represents an integer of 1 or 2,
Figure FDA0002684866390000042
formula [2a-9]-formula [2a-11]In, Yerepresents-O-or-COO-, YfY represents a C17-51 organic group having a steroid skeleton and a valence of 2gRepresents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, and q5 represents an integer of 1 to 10.
7. The liquid crystal display element according to any one of claims 1 to 6, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.
8. A liquid crystal display element according to any one of claims 1 to 7, wherein the liquid crystal display element is a light modulating window or shutter element.
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