CN111868616A - Liquid crystal display element - Google Patents

Liquid crystal display element Download PDF

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CN111868616A
CN111868616A CN201980019749.1A CN201980019749A CN111868616A CN 111868616 A CN111868616 A CN 111868616A CN 201980019749 A CN201980019749 A CN 201980019749A CN 111868616 A CN111868616 A CN 111868616A
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formula
liquid crystal
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benzene ring
carbon atoms
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CN111868616B (en
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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
    • C09K19/06—Non-steroidal liquid crystal compounds
    • 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 can suppress element peeling, bubble generation, and optical property degradation even when exposed to a severe environment of high temperature, high humidity, or light irradiation for a long period of time. A liquid crystal display element having a liquid crystal layer and a resin film on at least one of substrates, wherein the liquid crystal display element is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied, and the liquid crystal layer is provided on one of the substrates having an electrodeA liquid crystal composition containing a liquid crystal and a polymerizable compound between substrates, wherein the liquid crystal has positive dielectric anisotropy, and the liquid crystal composition contains the following formula [1]The resin film is composed of a resin composition containing a compound represented by the following formula [2-a ]]-formula [2-i]A resin composition of a polymer having at least one structure of the group consisting of. (wherein the symbols are as defined in the description.)

Description

Liquid crystal display element
Technical Field
The present invention relates to a transmission/scattering type liquid crystal display element which is brought into a transmission state when a voltage is applied.
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.
Liquid crystal display elements using PDLC and PNLC are in a state of white turbidity (scattering) because liquid crystals are oriented in random directions when no voltage is applied, and are in a state of transmitting light when the liquid crystals are aligned in the direction of an electric field when a voltage is applied (also referred to as a normal type element). 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).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3552328
Patent document 2: japanese patent No. 4630954
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, in order to realize them, a tight polymer network needs to be formed, and thus driving of liquid crystal molecules for voltage application is hindered. Therefore, the driving voltage of the present cell is higher than that of a liquid crystal display cell such as a TN mode.
In addition, since the element uses an inorganic electrode such as Indium Tin Oxide (ITO) or the like, compatibility with a polymerizable compound of an organic material, that is, adhesiveness tends to be lowered. 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.
In view of the above, an object of the present invention is to provide a liquid crystal display element that exhibits good optical characteristics, has high adhesion between a liquid crystal layer and an electrode, and has a reduced driving voltage. In particular, an object of the present invention is to provide a liquid crystal display element which can suppress the peeling of the element, the generation of bubbles, and the 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.
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 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 rays and curing the composition, and by comprising a resin film on at least one of the substrates, the liquid crystal display element being in a scattering state when no voltage is applied and being in a transparent state when a voltage is applied,
the liquid crystal has positive dielectric anisotropy, the liquid crystal composition contains a compound represented by the following formula [1], and the resin film is obtained from a resin composition containing a polymer having at least one structure selected from the group consisting of the following formulae [2-a ] to [2-i ].
Figure BDA0002684988800000031
(X1Represents the following formula [1-a]-formula [1-j]。X2Represents a single bond, -O-, -NH-, -N (CH)3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-. X3Represents a single bond or- (CH)2)a- (a is an integer of 1 to 15). X4Represents a single bond, -O-, -OCH2-, -COO-or-OCO-. X5Represents 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 fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. X 6Represents a single bond, -O-, -CH2-、-OCH2-、-CH2O-, -COO-or-OCO-. X7Represents a cyclic group selected from the group consisting of 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, or a carbon atomA fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. X8Represents 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. Xm represents an integer of 0 to 4. )
Figure BDA0002684988800000032
(XARepresents a hydrogen atom or a benzene ring. )
Figure BDA0002684988800000041
(YARepresents a hydrogen atom or a benzene ring. )
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a liquid crystal display element exhibiting good optical characteristics, having high adhesion between a liquid crystal layer and an electrode, and further having a reduced driving voltage of the liquid crystal display element is obtained. In particular, even when exposed to a severe environment such as high temperature and high humidity or irradiation of light for a long period of time, the liquid crystal display element can be suppressed in peeling of the element, generation of bubbles, and deterioration of optical characteristics. 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 having positive dielectric anisotropy, a polymerizable compound, and the compound represented by the formula [1 ]]The compounds shown (also referred to as specific compounds). The specific compound has a site having a rigid structure such as a benzene ring or a cyclohexane ring, and the formula [1 ]]X in (1)1The sites shown are those where polymerization reaction proceeds by ultraviolet light. Therefore, when the specific compound is contained in the liquid crystal composition, the portion of the rigid structure of the specific compound improves the vertical alignment property of the liquid crystal, promotes the driving of the liquid crystal by the voltage application, and makes it possible to obtain a liquid crystal composition having a high liquid crystal display qualityThe driving voltage of the liquid crystal display element is lowered. In addition, the general formula [1 ]]X in (1)1The site (b) reacts with the polymerizable compound to maintain the polymer network in a compact state.
The resin film used for the liquid crystal display element is obtained from a resin composition containing a polymer (also referred to as a specific polymer) having at least one structure (also referred to as a specific structure) selected from the group consisting of the above-described formulas [2-a ] to [2-i ].
These specific structures undergo photoreaction with reactive groups of the polymerizable compound in the liquid crystal composition in a step of irradiating ultraviolet rays, which is a step in producing a liquid crystal display element, and the adhesion between the liquid crystal layer and the resin film becomes strong. Further, since the resin film is obtained from a resin composition containing a specific polymer having a specific structure, it is considered that the adhesion to the electrode is improved as compared with a liquid crystal layer formed from a polymerizable compound having a low molecular weight.
As is clear from the above, the liquid crystal display element using the liquid crystal composition and the resin film of the present invention has good optical properties, high adhesion between the liquid crystal layer and the electrode, and a reduced driving voltage of the liquid crystal display element. In particular, a standard type element is formed which can suppress the peeling of the element, the generation of bubbles, and the reduction of optical characteristics even when exposed to a severe environment of high temperature and high humidity or irradiation of light for a long time.
Detailed Description
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 present invention has positive dielectric anisotropy. In addition, from the viewpoint of low voltage driving and scattering characteristics, it is preferable that the anisotropy of dielectric constant is large and the anisotropy of refractive index is 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, an element which absorbs (scatters) when no voltage is applied and becomes transparent when a voltage is applied is obtained. In this liquid crystal display 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, the liquid crystal display element utilizes the difference in light absorption characteristics of the dichroic dye, and thus achieves 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 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 polymerizable compound or oligomer thereof include radical polymerizable compounds described in international publication No. 2015/146987, pages 69 to 71.
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.
The specific compound is a compound represented by the formula [1 ].
Formula [1]In, X1～X8And Xm are as defined above, but the following examples are preferred among them, respectively.
X1Preferably the aforementioned formula [1-a]Formula [1-b ]]Formula [1-c ]]Formula [1-d]Formula [1-e]Or formula [1-f]. More preferably [1-a ]]Formula [1-b ]]Formula [1-c ]]Or formula [1-e]. Most preferred is the formula [1-a]Or formula [1-b]。
X2Preferably a single bond, -O-, -CH2O-, -CONH-, -COO-or-OCO-. More preferably a single bond, -O-, -COO-or-OCO-.
X3Preferably a single bond or- (CH)2)a- (a is an integer of 1 to 10). More preferably- (CH)2)a- (a is an integer of 1 to 10).
X4Preferably a single bond, -O-or-COO-. More preferably-O-.
X5Preferably 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.
X6Preferably a single bond, -O-, -COO-or-OCO-. More preferably a single bond, -COO-or-OCO-.
X7Preferably a benzene ring or a cyclohexane ring.
X8Preferably 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.
Xm is preferably an integer of 0 to 2.
Formula [1]Preferred X in (1)1～X8The combinations of Xm and Xm are shown in tables 1 to 9 below. In tables 1 to 9, a represents an integer of 1 to 10.
[ Table 1]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-1a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkyl group 0
1-2a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkoxy group 0
1-3a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-4a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-5a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-6a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-7a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
1-8a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-9a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkyl group 0
1-10a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkoxy group 0
1-11a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-12a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-13a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-14a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-15a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
1-16a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-17a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-18a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-19a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-20a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 2]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-21a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-22a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-23a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-24a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-25a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-26a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
1-27a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-28a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-29a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-30a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-31a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-32a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-33a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-34a Formula [1-a] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
1-35a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-36a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-37a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-38a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-39a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-40a Formula [1-a] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 3]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-41a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkyl group 0
1-42a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkoxy group 0
1-43a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-44a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-45a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-46a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-47a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
1-48a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-49a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkyl group 0
1-50a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkoxy group 0
1-51a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-52a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-53a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-54a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-55a Formula [1-b ] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
1-56a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-57a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-58a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-59a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-60a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 4]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-61a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-62a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-63a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-64a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-65a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-66a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
1-67a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-68a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-69a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-70a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-71a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-72a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-73a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-74a Formula [1-b] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
1-75a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-76a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-77a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-78a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-79a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-80a Formula [1-b] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 5]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-81a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkyl group 0
1-82a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkoxy group 0
1-83a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-84a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-85a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-86a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-87a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
1-88a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-89a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkyl group 0
1-90a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkoxy group 0
1-91a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-92a Formula [1-c ] ] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-93a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-94a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-95a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring Carbon number1 to 12 alkyl groups 1
1-96a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-97a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-98a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-99a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-100a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 6]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-101a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-102a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-103a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-104a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-105a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-106a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
1-107a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-108a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-109a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-110a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-111a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-112a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-113a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-114a Formula [1-c ]] Single bond -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
1-115a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-116a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-117a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-118a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-119a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-120a Formula [1-c ]] Single bond -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 7]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-121a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkyl group 0
1-122a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond － C1-C12 alkoxy group 0
1-123a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-124a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-125a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-126a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-127a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkyl group 0
1-128a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond － C1-C12 alkoxy group 0
1-129a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 1
1-130a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 1
1-131a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkyl group 2
1-132a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Benzene ring C1-C12 alkoxy group 2
1-133a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-134a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-135a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-136a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
1-137a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 1
1-138a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 1
1-139a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkyl group 2
1-140a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring C1-C12 alkoxy group 2
[ Table 8]
X1 X2 X3 X4 X5 X6 X7 X8 Xm
1-141a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-142a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-143a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-144a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-145a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 1
1-146a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 1
1-147a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkyl group 2
1-148a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring C1-C12 alkoxy group 2
1-149a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
1-150a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-151a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 1
1-152a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring Single bond Cyclohexane ring C1-C12 alkyl group 2
1-153a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-154a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-155a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 1
1-156a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring C1-C12 alkyl group 2
1-157a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-158a Formula [1-e] -COO- -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
1-159a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 1
1-160a Formula [1-e] -COO- -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring C1-C12 alkyl group 2
[ Table 9]
Figure BDA0002684988800000131
Of these, (1-3a) - (1-8a), (1-11a) - (1-24a), (1-27a) - (1-36a), (1-39a), (1-40a), (1-43a) - (1-48a), (1-51a) - (1-64a), (1-67a) - (1-76a), (1-79a), (1-80a), (1-83a) - (1-88a), (1-91a) - (1-104a), (1-107a) - (1-116a), (1-119a), (1-120a), (1-123a), (1-124a), (1-129a), (1-130a), (1-133a), (1-134a), (1-137a), (1-138a), (1-141a), (1-142a), (1-145a), (1-146a), or (1-149a) to (1-172 a).
More preferably (1-3a) - (1-8a), (1-11a), (1-12a), (1-15a) - (1-18a), (1-21a), (1-22a), (1-27a) - (1-30a), (1-33a), (1-34a), (1-39a), (1-40a), (1-43a) - (1-48a), (1-51a), (1-52a), (1-55a) - (1-58a), (1-61a), (1-62a), (1-67a) - (1-70a), (1-73a), (1-74a), (1-79a), (1-80a), (1-83a) - (1-88a), (1-91a), (1-92a), (1-95a) - (1-98a), (1-101a), (1-102a), (1-107a) - (1-110a), (1-113a), (1-114a), (1-119a), (1-120a), (1-123a), (1-124a), (1-129a), (1-130a), (1-133a), (1-134a), (1-137a), (1-138a), (1-141a), (1-142a), (1-145a), (1-146a) or (1-149a) - (1-172 a).
Most preferably (1-3a) - (1-8a), (1-15a) - (1-18a), (1-29a), (1-30a), (1-43a) - (1-48a), (1-55a) - (1-58a), (1-69a), (1-70a), (1-83a) - (1-88a), (1-95a) - (1-98a), (1-109a), (1-110a), (1-123a), (1-124a), (1-133a), (1-134a), (1-141a), (1-142a), (1-149a) to (1-152a), or (1-161a) to (1-172 a).
More specific compounds include compounds represented by the following formulae [1a-1] to [1a-11], and these compounds are preferably used.
Figure BDA0002684988800000141
Xarepresents-O-or-COO-. XbRepresents an alkyl group having 1 to 12 carbon atoms. p1 represents an integer of 1 to 10. p2 represents an integer of 1 or 2.
Figure BDA0002684988800000151
XcRepresents a single bond, -COO-or-OCO-. XdRepresents an alkyl group or an alkoxy group having 1 to 12 carbon atoms. p3 represents an integer of 1 to 10. p4 represents an integer of 1 or 2.
Figure BDA0002684988800000152
Xerepresents-O-or-COO-. XfRepresents a C17-51 organic group having a steroid skeleton and a valence of 2. XgRepresents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. p5 represents an integer of 1 to 10.
The ratio of the specific compound is preferably 0.1 to 30 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 0.5 to 20 parts by mass. Most preferably 1 to 10 parts by mass. The specific compound may be used in a mixture 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 is added with a single or a mixture of a plurality of polymerizable compounds and a specific compound; a method of adding a specific compound to a liquid crystal in advance to prepare a mixture, and adding one or more polymerizable compounds to the mixture.
When a plurality of polymerizable compounds are used, heating may be performed depending on the solubility of the polymerizable compounds when they are mixed. The temperature at this time is preferably less than 100 ℃. The same applies to the case where the polymerizable compound and the specific compound are mixed, and the case where the liquid crystal and the specific compound are mixed.
< resin composition >
The resin film is obtained from a resin composition containing a polymer having a specific structure represented by the formulae [2-a ] to [2-i ].
As the specific structure, the above-mentioned formulas [2-a ] to [2-c ], [2-e ], [2-h ] or [2-i ] are preferable. More preferably formula [2-a ], formula [2-b ], formula [2-h ] or formula [2-i ].
The specific polymer having a specific structure is not particularly limited, and is preferably at least one polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, a polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane. More preferably a polyimide precursor, polyimide or polysiloxane.
When a polyimide precursor or a polyimide (also collectively referred to as a polyimide-based polymer) is used as the specific polymer, it is preferably a polyimide precursor or a polyimide obtained by reacting a diamine component with a tetracarboxylic acid component.
The polyimide precursor has a structure represented by the following formula [ A ].
Figure BDA0002684988800000161
R1Represents a 4-valent organic group. R2Represents a 2-valent organic group. A. the1And A2Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A. the3And A4Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group. n represents a positive integer.
The diamine component is a diamine having 2 primary or secondary amino groups in the molecule, and examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound.
The polyimide polymer is preferably a polyamic acid having a structural formula including a repeating unit represented by the following formula [ D ] or a polyimide obtained by imidizing the polyamic acid, because the polyimide polymer can be obtained relatively easily from a tetracarboxylic dianhydride represented by the following formula [ B ] and a diamine represented by the following formula [ C ].
Figure BDA0002684988800000171
R1And R2Is defined by the formula [ A ]]The same as defined in (1).
Figure BDA0002684988800000172
R1And R 2Is defined by the formula [ A ]]The same as defined in (1).
Further, the compound represented by the formula [ D ] can be obtained by a general synthesis method]Is of the polymer introduction formula [ A ]]A in (A)1And A2An alkyl group having 1 to 8 carbon atoms and the formula [ A]A in (A)3And A4An alkyl group or acetyl group having 1 to 5 carbon atoms.
As a method for introducing a specific structure into a polyimide-based polymer, a diamine having a specific structure is preferably used as a part of the raw material. In particular, a diamine having a structure represented by the following formula [2] (also referred to as a specific diamine) is preferably used.
Figure BDA0002684988800000173
Y1Represents 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-, -CH2O-or-COO-.
Y2Represents a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms and having a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, 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, a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is preferable. More preferably a single bond or an alkylene group having 1 to 12 carbon atoms.
Y3Represents a single bond, -O-, -NH-, -N (CH)3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-. Among these, a single bond, -O-, -COO-or-OCO-is preferable. More preferably a single bond or-OCO-.
Y4Is selected from the group consisting of the foregoing formula [2-a]-formula [2-i]Structures in the group. Among them, preferred is the formula [2-a ]]-formula [2-e]Formula [2-h ]]Or formula [2-i]. More preferably [2-a ]]Is of the formula [2-b]Is of the formula [2-d]Formula [2-e]Or formula [2-i]. Most preferred is the formula [2-a]Is of the formula [2-b]Or formula [2-i]. Ym represents an integer of 1 to 4. Among them, 1 or 2 is preferable.
As the specific diamine, a diamine represented by the following formula [2a ] is preferably used.
Figure BDA0002684988800000181
Formula [2a ]]Wherein Y represents the above formula [ 2]]. In addition, formula [2]Y in (1)1～Y4And Ym is as described in the aforementioned formula [ 2]]The method is as follows.
Yn represents an integer of 1 to 4. Among them, 1 is preferable.
More specific diamines include the following formulas [2a-1] to [2a-12], and they are preferably used.
Figure BDA0002684988800000191
n1 represents an integer of 1 to 12.
Figure BDA0002684988800000192
n2 represents an integer of 0 to 12. n3 represents an integer of 2 to 12.
Among them, preferred is the formula [2a-1], the formula [2a-2], the formula [2a-5] to the formula [2a-7], the formula [2a-11] or the formula [2a-12 ]. More preferred are formulae [2a-5] to [2a-7], formula [2a-11] or formula [2a-12 ].
The amount of the specific diamine used is preferably 10 to 70 mol% based on the total diamine components. More preferably 20 to 60 mol%. The specific diamine may be used in a mixture of 1 or 2 or more depending on the characteristics.
As the diamine component for producing the polyimide-based polymer, a diamine represented by the following formula [3a ] (also referred to as a 2 nd diamine) is preferably used.
Figure BDA0002684988800000201
W represents the following formulae [3-a ] to [3-d ].
Wm represents an integer of 1 to 4. Among them, 1 is preferable.
Figure BDA0002684988800000202
a represents an integer of 0 to 4. Among them, 0 or 1 is preferable.
b represents an integer of 0 to 4. Among them, 0 or 1 is preferable.
WAAnd WBRepresents an alkyl group having 1 to 12 carbon atoms.
WCRepresents an alkyl group having 1 to 5 carbon atoms.
Specific examples of the 2 nd diamine include the following.
Examples thereof include 2, 4-dimethyl-m-phenylenediamine, 2, 6-diaminotoluene, 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 5-diaminobenzoic acid, and diamines of the following formulae [3a-1] and [3a-2 ].
Figure BDA0002684988800000203
Among them, preferred is 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 5-diaminobenzoic acid, formula [3a-1] or formula [3a-2 ]. More preferably 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 3, 5-diaminobenzoic acid or formula [3a-1 ].
As the diamine component used for producing the polyimide-based polymer, diamines other than the diamines of the formulae [2a ] and [3a ] (also referred to as other diamines) may be used.
Specifically, there may be mentioned other diamine compounds described on pages 27 to 30 of International publication WO2015/012368 and diamine compounds of the formulae [ DA1] to [ DA14] described on pages 30 to 32 of International publication WO 2015/012368. The other diamines may be used in a mixture of 1 or 2 or more depending on the characteristics.
As the tetracarboxylic acid component used for producing the polyimide-based polymer, a tetracarboxylic dianhydride represented by the following formula [4], a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound as a tetracarboxylic acid derivative thereof (all of them will be collectively referred to as a specific tetracarboxylic acid component) is preferably used.
Figure BDA0002684988800000211
Z represents the following formulas [4a ] to [4l ].
Figure BDA0002684988800000212
ZA～ZDRepresents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. ZEAnd ZFRepresents a hydrogen atom or a methyl group.
Z in the formula [4] is preferably a group represented by the formula [4a ], formula [4c ], formula [4d ], formula [4e ], formula [4f ], formula [4g ], formula [4k ] or formula [4l ]. More preferred is the formula [4a ], the formula [4e ], the formula [4f ], the formula [4g ], the formula [4k ] or the formula [4l ]. Particularly preferred is the formula [4a ], the formula [4e ], the formula [4f ], the formula [4g ] or the formula [4l ].
The ratio of the specific tetracarboxylic acid component to be used is preferably 1 mol% or more based on the total tetracarboxylic acid components. More preferably 5 mol% or more. Particularly preferably 10 mol% or more. Most preferably 10 to 90 mol%.
In the present invention, the polyimide-based polymer may contain a tetracarboxylic acid component other than the specific tetracarboxylic acid component. Examples of the other tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, or dialkyl ester dihalide compounds shown below.
Specifically, other tetracarboxylic acid components described in International publication WO2015/012368 on pages 34 to 35 can be mentioned.
The specific tetracarboxylic acid component and the other tetracarboxylic acid components may be used in a mixture of 1 or 2 or more depending on the characteristics.
The method for synthesizing the polyimide-based polymer is not particularly limited. Usually, the diamine component and the tetracarboxylic acid component are reacted. Specifically, the method described in International publication WO2015/012368, pages 35 to 36, can be mentioned.
The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent used in this case is not particularly limited as long as it is a solvent in which the polyimide precursor to be produced is dissolved.
Specific examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and 1, 3-dimethyl-imidazolidinone. When the polyimide precursor has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formulae [ D1] to [ D3] may be used.
Figure BDA0002684988800000231
D1And D2Represents an alkyl group having 1 to 3 carbon atoms. D3Represents an alkyl group having 1 to 4 carbon atoms.
In addition, they may be used alone or in admixture. Further, even in the case of a solvent which does not dissolve the polyimide precursor, the solvent may be mixed and used within a range where the produced polyimide precursor is not precipitated. In addition, the moisture in the organic solvent suppresses the polymerization reaction and further causes hydrolysis of the polyimide precursor to be produced, and therefore, it is preferable to use an organic solvent which has been dehydrated and dried.
The polyimide is obtained by ring-closing a polyimide precursor, and the ring-closing ratio of the amic acid group (also referred to as imidization ratio) in this polyimide is not necessarily 100%, and can be arbitrarily produced according to the application and purpose. Among them, from the viewpoint of solubility of the polyimide polymer in a solvent, 30 to 80% is preferable. More preferably 40 to 70%.
The molecular weight of the polyimide polymer is preferably 5000 to 1000000, more preferably 10000 to 150000, in terms of Mw (weight average molecular weight) measured by gpc (gel polymerization chromatography) method, in consideration of the strength of the resin film obtained therefrom, workability in forming the resin film, and coatability.
When a polysiloxane is used as the specific polymer, it is preferable to use a polysiloxane obtained by polycondensing an alkoxysilane of the following formula [ a1], or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ a1] and an alkoxysilane of the following formula [ a2 ].
An alkoxysilane of the formula [ A1 ]:
(A1)mSi(A2)n(OA3)p[A1]
A1represents a compound having a formula selected from the group consisting of [2-a ] of the foregoing formula]-formula [2-i]An organic group having 2 to 12 carbon atoms in the structure of the group. Among them, preferred is the formula [2-a ]]-formula [2-e]Formula [2-h ]]Or formula [2-i]. More preferably [2-a ]]Is of the formula [2-b]Is of the formula [2-d]Formula [2-e]Or formula [2-i]. Most preferred is the formula [2-a]Is of the formula [2-b]Or formula [2-i]。
A2Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A. the3Is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. m is an integer of 1 or 2, preferably 1. n is an integer of 0 to 2. p is an integer of 0 to 3, preferably an integer of 1 to 3, more preferably an integer of 2 or 3. m + n + p is 4.
Specific examples of the alkoxysilane of the formula [ A1] include the following.
Examples thereof include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate, and these are preferably used.
The alkoxysilane of the formula [ a1] may be used in a mixture of 1 or 2 or more depending on the characteristics.
An alkoxysilane of the formula [ A2 ]:
(B1)nSi(OB2)4-n[A2]
B1is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
B2Is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. n is an integer of 0 to 3.
Specific examples of the alkoxysilane of the formula [ A2] include alkoxysilanes of the formula [2c ] described in International publication WO2015/008846 on pages 24 to 25.
Further, examples of the alkoxysilane in which n is 0 in the formula [ a2] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. As the alkoxysilane of the formula [ A2], it is preferable to use these alkoxysilanes.
The alkoxysilane of the formula [ a2] may be used in a mixture of 1 or 2 or more depending on the characteristics.
The polysiloxane polymer is preferably a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1], or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1] and an alkoxysilane of the formula [ A2 ].
Among these, polysiloxanes obtained by polycondensing a plurality of kinds of alkoxysilanes are preferable from the viewpoints of reactivity in polycondensation and solubility of the polysiloxane polymer in a solvent. That is, it is preferable to use a polysiloxane obtained by polycondensation of 2 kinds of alkoxysilanes of the formulae [ A1] and [ A2 ]. In this case, the alkoxysilane of the formula [ A1] is used in an amount of preferably 1 to 70 mol%, more preferably 1 to 50 mol%, and particularly preferably 1 to 30 mol% based on the total alkoxysilane.
The ratio of the alkoxysilane of the formula [ a2] is preferably 30 to 99 mol%, more preferably 50 to 99 mol%, and particularly preferably 70 to 99 mol% based on the total amount of the alkoxysilane.
The method for polycondensing the polysiloxane polymer is not particularly limited. Specifically, the method described in International publication WO2015/008846, pages 26 to 29, can be mentioned.
When a plurality of alkoxysilanes of the formulae [ A1] and [ A2] are used in the polycondensation reaction for producing the polysiloxane polymer, the reaction may be carried out using a mixture of a plurality of alkoxysilanes mixed in advance, or may be carried out while adding a plurality of alkoxysilanes in sequence.
In the present invention, the solution of the polysiloxane polymer obtained by the above-mentioned method may be used as it is as the specific polymer, or the solution of the polysiloxane polymer obtained by the above-mentioned method may be concentrated or diluted with a solvent as necessary, and replaced with another solvent to be used as the specific polymer.
The solvent (also referred to as an additive solvent) used for dilution may be a solvent used for the polycondensation reaction or another solvent. The solvent to be added is not particularly limited as long as the polysiloxane polymer is uniformly dissolved, and 1 or 2 or more kinds thereof can be arbitrarily selected. Examples of such an additive solvent include, in addition to the solvents used in the polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate.
Further, when the polysiloxane polymer and the other polymers are used as the specific polymer, it is preferable that alcohol generated in the polycondensation reaction of the polysiloxane polymer is distilled off in advance under normal pressure or reduced pressure before the other polymers are mixed with the polysiloxane polymer.
The resin composition is a solution for forming a resin film, and is a solution containing a specific polymer having a specific structure and a solvent. In this case, 2 or more specific polymers may be used.
The polymer components in the resin composition may be all specific polymers, or may be mixed with other polymers. In this case, the content of the other polymer is preferably 0.5 to 15 parts by mass per 100 parts by mass of the specific polymer. More preferably 1 to 10 parts by mass. Examples of the other polymers include the above-mentioned polymers having no specific structure.
The content of the solvent in the resin composition can be appropriately selected from the viewpoint of the method of applying the resin composition and the film thickness to be obtained. Among them, the content of the solvent in the resin composition is preferably 50 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. Among them, it is preferably 60 to 99% by mass. More preferably 65 to 99 mass%.
The solvent used in the resin composition is not particularly limited as long as it dissolves the specific polymer. Among them, when the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of an acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in a solvent is low, the following solvent (also referred to as solvent a) is preferably used.
Examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone is preferable. In addition, they may be used alone or in admixture.
When the specific polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose, or polysiloxane, and further the specific polymer is a polyimide precursor, polyimide, polyamide, or polyester, and when the solubility of these specific polymers in a solvent is high, the following solvent (also referred to as solvent B) can be used.
Specific examples of the solvent B include the solvents B described in International publication WO2014/171493, pages 58 to 60. Among them, 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, or the foregoing formulas [ D1] to [ D3] are preferable.
When these solvents B are used, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone of the above solvents A in combination in order to improve the coatability of the resin composition. More preferably gamma-butyrolactone.
Since these solvents B can improve the film coatability and surface smoothness of the resin film when the resin composition is applied, it is preferable to use them in combination with the above-mentioned solvents a when a polyimide precursor, a polyimide, a polyamide or a polyester is used as the specific polymer. In this case, the solvent B is preferably 1 to 99% by mass of the total solvent contained in the resin composition. Among them, 10 to 99% by mass is preferable. More preferably 20 to 95 mass%.
In the resin composition, in order to improve the film strength of the resin film, it is preferable to introduce a compound having an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group (also collectively referred to as a specific crosslinkable compound). In this case, it is necessary to have 2 or more of these groups in the compound.
Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include crosslinkable compounds having an epoxy group or an isocyanate group described in international publication No. WO2014/171493, pages 63 to 64.
Specific examples of the crosslinkable compound having an oxetanyl group include crosslinkable compounds of the formulae [4a ] to [4k ] described in pages 58 to 59 of International publication No. WO 2011/132751.
Specific examples of the crosslinkable compound having a cyclocarbonate group include crosslinkable compounds of the formulae [5-1] to [5-42] described in pages 76 to 82 of International publication No. WO 2012/014898.
Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include melamine derivatives and benzoguanamine derivatives described on pages 65 to 66 of international publication No. 2014/171493, and crosslinkable compounds represented by formulae [6-1] to [6-48] described on pages 62 to 66 of international publication No. WO 2011/132751.
The content of the specific crosslinkable compound in the resin composition is preferably 0.1 to 100 parts by mass per 100 parts by mass of the total polymer components. In order to perform the crosslinking reaction and exhibit the intended effect, the amount is more preferably 0.1 to 50 parts by mass, most preferably 1 to 30 parts by mass, per 100 parts by mass of the total polymer components.
In the resin composition, at least one kind of generator (specific generator) selected from a photoradical generator, a photoacid generator and a photobase generator is preferably introduced.
Specific examples of the specific propellant include those described on pages 54 to 56 of the International publication No. 2014/171493. Among them, the specific generating agent is preferably a photo radical generating agent from the viewpoint of adhesion between a liquid crystal layer of the liquid crystal display element and an electrode.
In the resin composition, a compound which improves the uniformity of the film thickness and the surface smoothness of the resin film when the resin composition is applied can be used as long as the effect of the present invention is not impaired. Further, a compound or the like which improves the adhesion between the resin film and the substrate may be used.
Examples of the compound for improving the uniformity of the film thickness and the surface smoothness of the resin film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specifically, the surfactant described in international publication WO2014/171493, page 67, can be mentioned. The amount of the polymer is preferably 0.01 to 2 parts by mass per 100 parts by mass of the total polymer components contained in the resin composition. More preferably 0.01 to 1 part by mass.
Specific examples of the compound for improving the adhesion between the resin film and the substrate include compounds described in pages 67 to 69 of international publication No. WO 2014/171493. The amount of the polymer is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total polymer components contained in the resin composition. More preferably 1 to 20 parts by mass.
In addition to the compounds described above, a dielectric or conductive substance to be changed in electrical characteristics such as dielectric constant and conductivity of the resin film may be added to the resin composition.
< method for producing resin film and 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, it is preferable to use a substrate on which an ITO electrode, an Indium Zinc Oxide (IZO) electrode, an Indium Gallium Zinc Oxide (IGZO) electrode, an organic conductive film, and the like are formed for driving a liquid crystal. 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.
The liquid crystal display element has a resin film obtained from a resin composition having a specific polymer on at least one of substrates. In particular, the presence of the resin film on both substrates is preferable.
The method for applying the resin composition is not particularly limited, and there are industrially screen printing, offset printing, flexographic printing, inkjet printing, dipping, roll coating, slit coating, spin coating, spraying and the like, and it can be appropriately selected depending on the kind of substrate and the film thickness of the target resin film.
After coating the resin composition on a substrate, the temperature is preferably 30 to 300 ℃ depending on the kind of the substrate and the solvent used in the resin composition by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared ray) oven. More preferably 30 to 250 ℃ to evaporate the solvent, thereby forming a resin film. Particularly, when a plastic substrate is used as the substrate, the substrate is preferably treated at a temperature of 30 to 150 ℃.
If the thickness of the resin film after baking is too large, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too small, reliability of the element may be lowered, and therefore, it is preferably 5 to 500 nm. More preferably 10 to 300nm, particularly preferably 10 to 250 nm.
The liquid crystal composition used for the liquid crystal display element is the liquid crystal composition 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.
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 on which a resin film is formed 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 surface of the resin film 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 having a resin film formed thereon is 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 impregnated with the liquid crystal composition. 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 spacers. 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. 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 of the ultraviolet irradiation device used in this case include a metal halide lamp and a high-pressure mercury lamp. The wavelength of the ultraviolet ray is preferably 250 to 400 nm. Among them, it is 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 >
Figure BDA0002684988800000301
< 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: 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.)
< specific diamine >
Figure BDA0002684988800000311
< 2 nd diamine >
Figure BDA0002684988800000312
< other diamines >
Figure BDA0002684988800000313
< specific tetracarboxylic acid component >
Figure BDA0002684988800000321
< monomers for producing polysiloxane polymers >
E1: 3-methacryloxypropyltrimethoxysilane
E2: tetraethoxysilane
< specific crosslinkable Compound >
Figure BDA0002684988800000322
< specific Generator >
Figure BDA0002684988800000323
< solvent >
NMP: n-methyl-2-pyrrolidone
gamma-BL: gamma-butyrolactone
BCS: ethylene glycol monobutyl ether
PB: propylene glycol monobutyl ether
PGME: propylene glycol monomethyl ether
And (3) ECS: ethylene glycol monoethyl ether
EC: diethylene glycol monoethyl ether
[ measurement of molecular weight of polyimide-based Polymer ]
The measurement was carried out by using a Gel Permeation Chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.) and chromatography columns (KD-803, KD-805) (manufactured by Shodex Co., Ltd.) as follows.
Column temperature: 50 deg.C
Eluent: n, N' -dimethylformamide (as additive, lithium bromide monohydrate (LiBr. H)2O) 30 mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) 30 mmol/L, Tetrahydrofuran (THF) 10ml/L)
Flow rate: 1.0 ml/min
Standard curve preparation standard samples: TSK Standard polyethylene oxides (molecular weight, about 900000, 150000, 100000 and 30000) (manufactured by TOSOH CORPORATION) and polyethylene glycols (molecular weight, about 12000, 4000 and 1000) (manufactured by Polymer Laboratories Ltd.)
[ measurement of imidization ratio of polyimide-based Polymer ]
20mg of the polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (. phi.5, NMR sample tube Standard, manufactured by Softweed scientific Co., Ltd.), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53ml) was added thereto, followed by completely dissolving the polyimide powder by applying ultrasonic waves. For this solution, proton NMR at 500MHz was measured by an NMR spectrometer (JNW-ECA500) (manufactured by JEOL DATUMLtd). The imidization ratio was determined using a proton derived from a structure which did not change before and after imidization as a reference proton, and the peak cumulative value of the proton derived from the NH group of amic acid appearing in the vicinity of 9.5ppm to 10.0ppm were obtained by the following formula.
Imidization ratio (%) - (1-. alpha.x/y). times.100
(x is the peak cumulative value of the NH group-derived NH group of amic acid, y is the peak cumulative value of the standard proton, and α is the number ratio of the standard protons to 1 NH group proton of amic acid (imidization ratio of 0%))
Synthesis of polyimide-based Polymer "
< Synthesis example 1 >
D2(3.06g, 12.2 mmol), A1(4.10g, 15.5 mmol) and C1(1.68g, 15.5 mmol) were mixed with NMP (33.2g) and reacted at 80 ℃ for 4 hours, then D1(3.60g, 18.4 mmol) and NMP (16.6g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 20% by mass. The polyamic acid had a number-average molecular weight (also referred to as Mn) of 18500 and a weight-average molecular weight (also referred to as Mw) of 66500.
< Synthesis example 2 >
To the polyamic acid solution (1) (30.0g) obtained in Synthesis example 1 was added NMP and diluted to 6% by mass, and acetic anhydride (3.60g) and pyridine (2.30g) as imidization catalysts were added and reacted at 60 ℃ for 1.5 hours. The reaction solution was poured into methanol (450ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (2). The polyimide had an imidization ratio of 51%, Mn of 16100 and Mw of 43500.
< Synthesis example 3 >
D4(1.01g, 5.10 mmol) and A1(3.41g, 12.9 mmol) were mixed with γ -BL (15.8g) and reacted at 60 ℃ for 6 hours, then D1(1.50g, 7.65 mmol) and γ -BL (7.90g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 20 mass%. The polyamic acid had Mn of 10500 and Mw of 34700.
< Synthesis example 4 >
D2(1.70g, 6.80 mmol), A2(2.80g, 13.8 mmol) and B1(0.52g, 3.44 mmol) were mixed with γ -BL (18.7g) and reacted at 60 ℃ for 6 hours, then D1(2.00g, 10.2 mmol) and γ -BL (9.37g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (4) having a resin solid content of 20 mass%. The polyamic acid had Mn of 10900 and Mw of 35100.
< Synthesis example 5 >
D2(1.62g, 6.46 mmol), A3(2.32g, 6.54 mmol), B1(1.00g, 6.54 mmol) and C1(0.35g, 3.27 mmol) were mixed with gamma-BL (19.2g) and reacted at 60 ℃ for 6 hours, then D1(1.90g, 9.69 mmol) and gamma-BL (9.58g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (5) having a resin solid content of 20 mass%. The polyamic acid had Mn of 13200 and Mw of 45100.
< Synthesis example 6 >
D3(3.80g, 17.0 mmol), A1(2.72g, 10.3 mmol), A2(0.70g, 3.44 mmol) and C1(0.37g, 3.43 mmol) were mixed with NMP (30.4g) and reacted at 40 ℃ for 12 hours to obtain a polyamic acid solution (6) having a resin solid concentration of 20% by mass. The polyamic acid had Mn of 15800 and Mw of 52500.
< Synthesis example 7 >
To the polyamic acid solution (7) (30.0g) obtained in Synthesis example 7 was added NMP and diluted to 6% by mass, and acetic anhydride (3.60g) and pyridine (2.35g) as imidization catalysts were added and reacted at 60 ℃ for 2 hours. The reaction solution was poured into methanol (450ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (7). The polyimide had an imidization ratio of 48%, Mn of 14600 and Mw of 40900.
< Synthesis example 8 >
D2(2.13g, 8.50 mmol) and C1(2.33g, 21.5 mmol) were mixed with NMP (18.5g) and reacted at 80 ℃ for 4 hours, then D1(2.50g, 12.8 mmol) and NMP (9.27g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (8) having a resin solid concentration of 20 mass%. The polyamic acid had Mn of 22800 and Mw of 70200.
< synthetic example 9 >
D4(1.35g, 6.80 mmol), B1(1.31g, 8.61 mmol) and C1(0.93g, 8.61 mmol) were mixed with γ -BL (14.9g) and reacted at 60 ℃ for 6 hours, then D1(2.00g, 10.2 mmol) and γ -BL (7.45g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (9) having a resin solid content of 20 mass%. The polyamic acid had Mn of 14800 and Mw of 43200.
The polyimide-based polymers obtained in the synthesis examples are shown in table 10.
In table 10, a 1 denotes a polyamic acid.
[ Table 10]
Figure BDA0002684988800000361
Synthesis of polysiloxane Polymer "
< synthetic example 10 >
A solution of an alkoxysilane monomer was prepared by mixing EC (29.0g), E1(8.80g), and E2(36.2g) in a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube. To this solution, a solution prepared by mixing EC (14.5g), water (11.0g) and oxalic acid (0.50g) as a catalyst in advance was added dropwise at 25 ℃ for 30 minutes, and further stirred at 25 ℃ for 30 minutes. Then, the mixture was refluxed for 30 minutes by heating in an oil bath, and then naturally cooled to obtain SiO2Polysiloxane solution (1) having a concentration of 12% by mass as converted.
< Synthesis example 11 >
A solution of an alkoxysilane monomer was prepared by mixing ECS (29.0g), E1(11.5g) and E2(33.5g) in a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube. To this solution, a solution prepared by mixing ECS (14.0g), water (11.0g) and oxalic acid (0.50g) as a catalyst in advance was added dropwise at 25 ℃ for 30 minutes, and further stirred at 25 ℃ for 30 minutes. Then, the mixture was refluxed for 30 minutes by heating in an oil bath, and then naturally cooled to obtain SiO 2A polysiloxane solution (2) having a concentration of 12% by mass as converted.
The polysiloxane polymers obtained in synthesis examples 10 and 11 are shown in table 11.
[ Table 11]
Figure BDA0002684988800000371
Production of resin composition "
< Synthesis example 12 >
NMP (12.1g) was added to the polyamic acid solution (1) (5.40g) obtained by the method of Synthesis example 1, and the mixture was stirred at 25 ℃ for 1 hour. BCS (10.4g) and PB (2.98g) were then added thereto, and the mixture was stirred at 25 ℃ for 4 hours to obtain a resin composition (1).
< synthetic example 13 >
NMP (15.8g) was added to the polyimide powder (2) (1.20g) obtained by the method of Synthesis example 2, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the powder. BCS (4.32g) and PB (8.64g) were then added thereto, and the mixture was stirred at 25 ℃ for 4 hours to obtain a resin composition (2).
< Synthesis example 14 >
To the polyamic acid solution (3) (3.00g) obtained in Synthesis example 3 were added γ -BL (0.15g) and PGME (22.9g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (3).
< Synthesis example 15 >
To the polyamic acid solution (3) (3.00g) obtained in Synthesis example 3 were added γ -BL (0.15g), PGME (22.9g) and K2(0.042g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (4).
< Synthesis example 16 >
To the polyamic acid solution (3) (3.00g) obtained in Synthesis example 3 were added γ -BL (0.15g), PGME (22.9g), K2(0.042g) and N1(0.018g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (5).
< Synthesis example 17 >
To the polyamic acid solution (4) (3.00g) obtained in the method of Synthesis example 4 were added γ -BL (3.97g), PGME (19.1g) and K1(0.018g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (6).
< synthetic example 18 >
To polyamic acid solution (5) (3.00g) obtained by the method of Synthesis example 5 were added γ -BL (0.15g), PGME (22.9g), K2(0.060g) and N1(0.030g), and the mixture was stirred at 25 ℃ for 6 hours to obtain resin composition (7).
< synthetic example 19 >
NMP (13.6g) was added to polyamic acid solution (6) (5.40g) obtained by the method of Synthesis example 6, and the mixture was stirred at 25 ℃ for 1 hour. Then, PB (11.9g) and K2(0.054g) were added thereto, and the mixture was stirred at 25 ℃ for 4 hours to obtain a resin composition (8).
< synthetic example 20 >
NMP (15.8g) was added to the polyimide powder (7) (1.20g) obtained by the method of Synthesis example 7, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the powder. BCS (2.88g), PB (10.1g), K2(0.084g) and N1(0.036g) were then added thereto, and the mixture was stirred at 25 ℃ for 4 hours to obtain a resin composition (9).
< Synthesis example 21 >
To the polysiloxane solution (1) (10.0g) obtained by the method of Synthesis example 10, EC (3.93g) and PB (12.7g) were added, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (10).
< Synthesis example 22 >
To the polysiloxane solution (2) (10.0g) obtained by the method of Synthesis example 11 were added ECS (4.78g), PGME (25.2g) and N1(0.036g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (11).
< Synthesis example 23 >
NMP (12.1g) was added to polyamic acid solution (8) (5.40g) obtained by the method of Synthesis example 8, and the mixture was stirred at 25 ℃ for 1 hour. BCS (10.4g) and PB (2.98g) were then added thereto, and the mixture was stirred at 25 ℃ for 4 hours to obtain a resin composition (12).
< Synthesis example 24 >
To the polyamic acid solution (9) (3.00g) obtained by the method of Synthesis example 9 were added γ -BL (0.15g) and PGME (22.9g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (13).
The resin compositions obtained in Synthesis examples 12 to 24 were prepared in the manner shown in Table 12. The resin compositions obtained in these synthesis examples 12 to 24 were homogeneous solutions without any abnormality such as turbidity and precipitation.
In table 12, the values in parentheses for the specific crosslinkable compound and the specific initiator added to the resin composition represent the contents per 100 parts by mass of the specific polymer.
[ Table 12]
Figure BDA0002684988800000391
< preparation of liquid Crystal composition (A) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours 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 a specific compound. Then, the prepared solution of the polymerizable compound, a liquid crystal containing the specific compound, and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (A).
< preparation of liquid Crystal composition (B) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. On the other hand, S1(0.80g) and L1(5.20g) were mixed and stirred at 25 ℃ for 2 hours to prepare a liquid crystal containing a specific compound. Then, the prepared solution of the polymerizable compound, a liquid crystal containing the specific compound, and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (B).
< preparation of liquid Crystal composition (C) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. On the other hand, S2(0.40g) and L1(5.60g) were mixed and stirred at 25 ℃ for 2 hours to prepare a liquid crystal containing a specific compound. Then, the prepared solution of the polymerizable compound, liquid crystal containing the specific compound, and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (C).
< preparation of liquid Crystal composition (D) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. On the other hand, S1(0.20g), S2(0.10g) and L1(5.70g) were mixed and stirred at 25 ℃ for 2 hours to prepare a liquid crystal containing a specific compound. Then, the prepared solution of the polymerizable compound, a liquid crystal containing the specific compound, and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (D).
< preparation of liquid Crystal composition (E) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. Then, the prepared polymerizable compound solution, L1(6.00g) and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (E).
Production of liquid Crystal display element (glass substrate) "
The resin composition obtained by the method of the synthesis example was subjected to pressure filtration using a membrane filter having a pore size of 1 μm. The obtained solution was spin-coated on an ITO surface of an ITO electrode-equipped glass substrate (vertical: 100mm, horizontal: 100mm, thickness: 0.7mm) washed with pure water and IPA (isopropyl alcohol), and subjected to heat treatment on a hot plate at 100 ℃ for 5 minutes and a heat treatment in a thermal cycle type cleaning oven at 210 ℃ for 30 minutes to obtain an ITO substrate with a resin film having a film thickness of 100 nm. 2 pieces of the ITO substrate with resin film were prepared, and spacers (trade name: Micropearl, manufactured by waterlogging chemical Co., Ltd.) having a particle size of 15 μm were coated on the resin film surface of the 1 piece of the substrate. Then, the liquid crystal compositions (a) to (E) were dropped on the resin film surface of the substrate coated with the spacer by odf (one Drop filling) method, and then bonded so that the resin film surface of the other substrate was opposed to each other, to obtain a liquid crystal display element before treatment. In comparative example 1, a resin film was not formed, and a spacer having a particle size of 20 μm was coated on the ITO surface of the ITO substrate, and the liquid crystal composition was dropped and bonded by the same method as described above to form a liquid crystal display element before treatment.
The liquid crystal display element before the treatment was used at an illuminance of 20mW/cm2The halogenated metal lamp (2) is conducted by irradiating for 60 seconds with a wavelength of 350nm or less removedAnd (4) ultraviolet irradiation. Thus, a liquid crystal display element (glass substrate) was obtained.
Production of liquid Crystal display element (Plastic substrate) "
The resin composition obtained by the method of the synthesis example was subjected to pressure filtration using a membrane filter having a pore size of 1 μm. The obtained solution was applied to an ITO surface of a PET substrate (longitudinal: 150mm, lateral: 150mm, thickness: 0.1mm) with an ITO electrode, which had been washed with pure water, by means of a bar coater, and subjected to a heat treatment at 120 ℃ for 2 minutes by means of a thermal cycle oven, to obtain an ITO substrate with a resin film having a film thickness of 100 nm. 2 pieces of the ITO substrate with resin film were prepared, and the spacers of 20 μm were coated on the resin film surfaces of the 1 piece of the substrate. Then, the liquid crystal compositions (a) to (E) were dropped on the resin film surface of the substrate coated with the spacer by odf (one dropfilling) method, and then bonded so that the resin film surface of the other substrate was opposed to 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. In comparative example 2, a resin film was not formed, and a spacer having a particle size of 20 μm was coated on the ITO surface of the ITO substrate, and the liquid crystal composition was dropped and bonded by the same method as described above to form a liquid crystal display element before treatment.
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 stability test of irradiation with light to the liquid crystal display element, 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.
The results of Haze measurement after initial storage in a constant temperature and humidity chamber (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet ray) are summarized in tables 13 to 15.
Evaluation of adhesion between liquid Crystal layer and resin film (resin film 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). In examples 3 to 5, in addition to the standard test, the stress test was confirmed after the storage in a constant temperature and humidity chamber at 80 ℃ and 90% RH for 72 hours. The evaluation method was the same as described above.
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.) to obtain a liquid crystal display element2Ultraviolet ray (stability test of irradiation of light to the liquid crystal display element). Specifically, the peeling of the element does not occur, and the inside of the elementThe absence of the generation of bubbles was excellent in the present evaluation (good representation in the table).
The results of the adhesion (adhesion) between the resin film (resin film and electrode) and the liquid crystal layer after initial storage in the constant temperature and humidity chamber (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet rays) are summarized in tables 16 to 18.
< examples 1 to 15 and comparative examples 1 to 6 >
The production of a liquid crystal display element, the evaluation of optical properties (scattering properties and transparency), and the evaluation of adhesion between a liquid crystal layer and a resin film (resin film and electrode) were carried out by the methods described above using any of the resin compositions (1) to (13) obtained by the methods described in the synthesis examples and the liquid crystal compositions (a) to (E). In this case, the liquid crystal display elements were produced and evaluated using glass substrates in examples 1, 2, 11 to 13, comparative examples 1, 3 and 5, and plastic substrates were used in examples 3 to 10, 14 and 15, and comparative examples 2, 4 and 6. As described above, in comparative examples 1 and 2, liquid crystal display elements were produced without producing a resin film, and each evaluation was performed.
Further, in the evaluation of the adhesion between the liquid crystal layer and the resin film (resin film and electrode) in examples 3 to 5, the standard test was carried out, and as an emphasis test, the evaluation was carried out when the film was stored in a constant temperature and humidity chamber at a temperature of 80 ℃ and a humidity of 90% RH for 72 hours (other conditions were the same as the above conditions).
[ Table 13]
Figure BDA0002684988800000441
[ Table 14]
Figure BDA0002684988800000451
[ Table 15]
Figure BDA0002684988800000452
[ Table 16]
Figure BDA0002684988800000461
[ Table 17]
Figure BDA0002684988800000462
[ Table 18]
Figure BDA0002684988800000463
*1: a small amount of air bubbles was found in the cell.
*2: bubbles (more than 1) were found inside the element.
*3: many bubbles (more than 2) were found inside the element.
As described above, the liquid crystal display element of the example obtained good optical characteristics compared to the comparative example. That is, initially, the Haze in the state where no voltage is applied was low, and the change in Haze after storage in the constant temperature and humidity chamber and after ultraviolet irradiation was small. In particular, the Haze is reduced at lower voltages for the examples compared to the comparative examples. That is, in the embodiment, the driving voltage of the liquid crystal display element is reduced.
Further, in the examples, even after storage in the constant temperature and humidity chamber and after irradiation with ultraviolet rays, peeling of the liquid crystal display element and generation of bubbles were not observed.
These results are also the same when a plastic substrate is used as the substrate of the liquid crystal display element. Specifically, the results are compared between example 1 and comparative examples 1, 3 and 5, and between example 3 and comparative examples 2, 4 and 6.
In addition, when a specific crosslinkable compound is introduced into the resin composition, it is emphasized that, particularly after long-term storage in a constant temperature and humidity chamber in the test, the liquid crystal display element generates less bubbles. Specifically, example 3 is compared with example 4.
Further, when a specific generating agent is introduced into the resin composition in addition to the specific crosslinkable compound, it is emphasized that no bubble is generated in the liquid crystal display element in the test. Specifically, the comparison under the same conditions is a comparison between example 4 and example 5.
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. 2018-052663, which was filed 3/20/2018, are incorporated herein by reference as if they were disclosed in the specification of the present invention.

Claims (15)

1. A liquid crystal display element having a liquid crystal layer obtained by curing a liquid crystal composition containing a liquid crystal and a polymerizable compound, which is arranged between a pair of substrates provided with electrodes, by irradiating ultraviolet rays, and having a resin film on at least one of the substrates, wherein the liquid crystal display element is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied,
the liquid crystal has a positive dielectric anisotropy,
the liquid crystal composition contains a compound represented by the following formula [1], and
the resin film is obtained from a resin composition containing a polymer having at least one structure selected from the group consisting of the following formulas [2-a ] to [2-i ],
Figure FDA0002684988790000011
formula [1]In, X1Is represented by a formula [1-a ] selected from]-formula [1-j]Structure of the group consisting of, X2Represents a single bond, -O-, -NH-, -N (CH)3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-, X3Represents a single bond or- (CH)2)a-, wherein a is an integer of 1 to 15, X4Represents a single bond, -O-, -OCH2-, -COO-or-OCO-, X5Represents 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 X is a group represented by 6Represents a single bond, -O-, -CH2-、-OCH2-、-CH2O-, -COO-or-OCO-, X7Represents 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 X 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, Xm represents an integer of 0 to 4,
Figure FDA0002684988790000021
wherein, XARepresents a hydrogen atom or a benzene ring,
Figure FDA0002684988790000022
wherein, YARepresents a hydrogen atom or a benzene ring.
2. The liquid crystal display element according to claim 1, wherein the content of the compound represented by the formula [1] is 0.5 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal.
3. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal layer is a transparent layerFormula [1]X in (1)1Is represented by the formula [1-a]Formula [1-b ]]Formula [1-c ]]Formula [1-d]Formula [1-e]Or formula [1-f]。
4. 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-11],
Figure FDA0002684988790000031
Formula [1a-1]-formula [1a-4]In, Xarepresents-O-or-COO-, XbRepresents an alkyl group having 1 to 12 carbon atoms, p1 represents an integer of 1 to 10, p2 represents an integer of 1 or 2,
Figure FDA0002684988790000032
formula [1a-5]-formula [1a-8]In, XcRepresents a single bond, -COO-or-OCO-, XdRepresents an alkyl group or an alkoxy group having 1 to 12 carbon atoms, p3 represents an integer of 1 to 10, p4 represents an integer of 1 or 2,
Figure FDA0002684988790000041
formula [1a-9]-formula [1a-11]In, Xerepresents-O-or-COO-, XfRepresents a C17-51 2-valent organic group having a steroid skeleton, XgRepresents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, and p5 represents an integer of 1 to 10.
5. The liquid crystal display element according to any one of claims 1 to 4, wherein the resin composition contains at least one polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, a polyhydroxystyrene, a polyimide precursor, a polyimide, a polyamide, a polyester, a cellulose, and a polysiloxane.
6. The liquid crystal display element according to claim 5, wherein the resin composition contains a polyimide precursor or a polyimide obtained by using a diamine having a structure represented by any one of the formulae [2-a ] to [2-i ] as a part of a raw material.
7. The liquid crystal display element according to claim 6, wherein the diamine is a diamine having a structure represented by the following formula [2],
Figure FDA0002684988790000042
formula [2]]In, Y1Represents a single bond, -O-, -NH-, -N (CH)3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-, Y2Represents a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms and having a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, 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 is3Represents a single bond, -O-, -NH-, -N (CH)3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-, Y4Represents a group selected from the group consisting of the formula [2-a]-formula [2-i]And Ym represents an integer of 1 to 4.
8. The liquid crystal display element according to claim 7, wherein the diamine is a diamine represented by the following formula [2a ],
Figure FDA0002684988790000051
in the formula [2a ], Y represents the formula [2], and n represents an integer of 1 to 4.
9. The liquid crystal display element according to any one of claims 5 to 8, wherein the resin composition comprises a polyimide precursor or a polyimide obtained by using a tetracarboxylic acid component represented by the following formula [4] as a part of raw materials,
Figure FDA0002684988790000052
In the formula [4], Z represents the following formulas [4a ] to [4l ],
Figure FDA0002684988790000053
wherein Z isA～ZDRepresents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, ZEAnd ZFRepresents a hydrogen atom or a methyl group.
10. The liquid crystal display element according to claim 5, wherein the resin composition comprises a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1] or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1] and an alkoxysilane of the formula [ A2],
(A1)mSi(A2)n(OA3)p[A1]
formula [ A1]In (A)1Represents a compound having a formula selected from the group consisting of [2-a ] of]-formula [2-i]A C2-12 organic group in the structure of the group A2Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A3Represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, p represents an integer of 0 to 3, wherein m + n + p is 4,
(B1)nSi(OB2)4-n[A2]
formula [ A2]In (B)1Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B2Represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.
11. The liquid crystal display element according to any one of claims 1 to 10, wherein the resin composition contains a compound having an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group.
12. The liquid crystal display element according to any one of claims 1 to 11, wherein the resin composition contains at least one selected from the group consisting of 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and a solvent represented by any one of formulae [ D1] to [ D3],
Figure FDA0002684988790000061
wherein D is1And D2Represents an alkyl group having 1 to 3 carbon atoms, D3Represents an alkyl group having 1 to 4 carbon atoms.
13. The liquid crystal display element according to any one of claims 1 to 12, wherein the resin composition contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ -butyrolactone.
14. The liquid crystal display element according to any one of claims 1 to 13, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.
15. The liquid crystal display element according to any one of claims 1 to 14, wherein the liquid crystal display element is a light modulating window or shutter element.
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