CN111868616B - Liquid crystal display element - Google Patents

Liquid crystal display element Download PDF

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CN111868616B
CN111868616B CN201980019749.1A CN201980019749A CN111868616B CN 111868616 B CN111868616 B CN 111868616B CN 201980019749 A CN201980019749 A CN 201980019749A CN 111868616 B CN111868616 B CN 111868616B
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liquid crystal
carbon atoms
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benzene ring
coo
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CN111868616A (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

Abstract

Provided is a liquid crystal display element which can suppress peeling of the element, generation of bubbles, and degradation of optical characteristics even when exposed to a severe environment of high temperature, high humidity, and irradiation of light for a long period of time. A liquid crystal display element comprising a liquid crystal layer and a resin film provided on at least one of substrates, wherein the liquid crystal display element is in a scattering state when no voltage is applied and in a transparent state when a voltage is applied, the liquid crystal layer is formed by curing a liquid crystal composition containing a liquid crystal and a polymerizable compound, the liquid crystal composition being disposed between a pair of substrates provided with electrodes, the liquid crystal composition having positive dielectric anisotropy, the liquid crystal composition containing the following formula [1 ]]The compound is represented by the formula [2-a ] and the resin film is formed by a process comprising]-2-i]A resin composition of a polymer of at least one structure of the group consisting of. (the definition of the symbol in the formula is as described in the specification.)

Description

Liquid crystal display element
Technical Field
The present invention relates to a transmission scattering type liquid crystal display element which forms a transmission state when a voltage is applied.
Background
As a liquid crystal display element, a Twisted Nematic (TN) mode has been put to practical use. In this mode, light is switched by utilizing the optical characteristics of liquid crystal, and therefore, a polarizing plate is required. If a polarizing plate is used, the light utilization efficiency is lowered.
As a liquid crystal display element that does not use a polarizing plate, there is an element that switches between a transmissive state (also referred to as a transparent state) and a scattering state of liquid crystal. It is generally known to use a polymer dispersed liquid crystal (also referred to as PDLC (Polymer Dispersed Liquid Crystal)) or a polymer network type liquid crystal (also referred to as PNLC (Polymer Network Liquid Crystal)).
In these liquid crystal display elements, a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet light is disposed between a pair of substrates provided with electrodes, and the liquid crystal composition is cured by irradiation of ultraviolet light to form a composite of a liquid crystal and a cured product (for example, 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.
In a liquid crystal display element using PDLC or PNLC, when no voltage is applied, the liquid crystal is in a random direction, and therefore, the liquid crystal is in a cloudy (scattering) state, and when a voltage is applied, the liquid crystal is aligned in the electric field direction, and light is transmitted therethrough, thereby becoming a transmitted state (also referred to as a standard element). In this case, since the liquid crystal is random when no voltage is applied, a liquid crystal alignment film or alignment treatment for aligning the liquid crystal in one direction is not required. Accordingly, in this liquid crystal display element, the electrode is directly connected to the liquid crystal layer (composite of the liquid crystal and the cured product of the polymerizable compound) (see patent documents 1 and 2).
Prior art literature
Patent literature
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 effect of forming a polymer network and obtaining desired optical characteristics, and an effect of improving adhesion between the liquid crystal layer and the electrode. However, in order to realize them, it is necessary to form a tight polymer network, and thus driving of liquid crystal molecules for voltage application is hindered. Therefore, the driving voltage of the present element is higher than that of a liquid crystal display element such as a TN mode.
Further, since the present element uses an inorganic electrode such as Indium Tin Oxide (ITO) or the like, compatibility with a polymerizable compound of an organic substance, that is, adhesiveness tends to be lowered. If the adhesion is reduced, peeling of the element, generation of bubbles, and further reduction of optical characteristics 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 with light.
In view of the above, an object of the present invention is to provide a liquid crystal display element which exhibits good optical characteristics, has high adhesion between a liquid crystal layer and an electrode, and further has a reduced driving voltage. In particular, it is intended to provide a liquid crystal display element which can suppress peeling of the element, generation of bubbles, and degradation of optical characteristics even when exposed to a severe environment of high temperature, high humidity, and irradiation with light for a long period of time.
Solution for solving the problem
The present inventors have conducted intensive 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 in that the liquid crystal display element has a liquid crystal layer, which is formed by curing a liquid crystal composition containing a liquid crystal and a polymerizable compound, which is disposed between a pair of substrates having electrodes, by irradiation with ultraviolet rays, and has 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 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 formulas [2-a ] to [2-i ].
Figure BDA0002684988800000031
(X 1 The expression of the following formula [1-a ]]-1-j]。X 2 Represents a single bond, -O-, -NH-, -N (CH) 3 )-、-CH 2 O-、-CONH-、-NHCO-、-CON(CH 3 )-、-N(CH 3 ) CO-, -COO-or-OCO-. X is X 3 Represents a single bond or- (CH) 2 ) a - (a is an integer of 1 to 15). X is X 4 Represents a single bond, -O-, -OCH 2 -, -COO-or-OCO-. X is X 5 Represents a 2-valent cyclic group selected from the group consisting of benzene rings, cyclohexane rings and heterocyclic rings, or a 2-valent organic group having 17 to 51 carbon atoms of a steroid skeleton, any hydrogen atom on the cyclic group being optionally substituted with 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. X is X 6 Represents a single bond, -O-, -CH 2 -、-OCH 2 -、-CH 2 O-, -COO-or-OCO-. X is X 7 Represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, any hydrogen atom on these cyclic groups being optionally substituted with 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. X is X 8 Represents 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
(X A Represents a hydrogen atom or a benzene ring. )
Figure BDA0002684988800000041
(Y A Represents a hydrogen atom or a benzene ring. )
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a liquid crystal display element is obtained that exhibits good optical characteristics, has high adhesion between the liquid crystal layer and the electrode, and further has a reduced driving voltage. In particular, a liquid crystal display element is formed which can suppress peeling of the element, generation of bubbles, and degradation of optical characteristics even when exposed to a severe environment of high temperature, high humidity, and irradiation of light for a long period of time. Therefore, the element of the present invention can be used for a liquid crystal display, a light control window for controlling blocking and transmission of light, a shutter element, or the like for the purpose of illustration.
The mechanism by which 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 above formula [1 ]]The compounds shown (also referred to as specific compounds). The specific compound has a benzene ring, a site of a rigid structure such as cyclohexane ring, and the formula [1 ]]X in (2) 1 The site where polymerization reaction was carried out by ultraviolet rays is shown. Therefore, when the specific compound is contained in the liquid crystal composition, the position of the rigid structure of the specific compound improves the vertical alignment property of the liquid crystal, and the driving of the liquid crystal accompanied by the applied voltage is promoted, so that the driving voltage of the liquid crystal display element can be reduced. In addition, by the formula [1 ]]X in (2) 1 The sites of (a) react with the polymerizable compound, and the polymer network can be kept in a compact state.
The resin film used in 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 formulae [2-a ] to [2-i ].
In these specific structures, in the step of irradiating ultraviolet rays, which is a step of manufacturing a liquid crystal display element, photoreaction is performed with a reactive group of a polymerizable compound in a liquid crystal composition, and adhesion between a liquid crystal layer and a 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 an electrode is improved as compared with a liquid crystal layer formed of a low molecular weight polymerizable compound.
From the above, it is clear that the liquid crystal display element using the liquid crystal composition and the resin film of the present invention has excellent optical characteristics, high adhesion between the liquid crystal layer and the electrode, and further, a driving voltage of the liquid crystal display element is reduced. In particular, a standard element is formed which can suppress peeling of the element, generation of bubbles, and degradation of optical characteristics even when exposed to a severe environment of high temperature, high humidity, and irradiation of light for a long period of 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 ].
The liquid crystal may be nematic liquid crystal, discotic liquid crystal or cholesteric liquid crystal. Among them, in the present invention, positive dielectric anisotropy is exhibited. In addition, from the viewpoints 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 may be mixed and used according to the respective physical property values of the phase transition temperature, dielectric anisotropy and refractive index anisotropy.
In order to drive a liquid crystal display element as an active element such as a thin film transistor (TFT, thin Film Transistor), it is required that the liquid crystal has high resistance and high voltage holding ratio (also referred to as VHR). Therefore, fluorine-based or chlorine-based liquid crystals having high electric resistance and not causing 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 in which a dichroic dye is dissolved in a liquid crystal composition. In this case, an element which absorbs (scatters) when no voltage is applied and becomes transparent when voltage is applied is obtained. In this liquid crystal display element, the direction of the director of the liquid crystal (the direction of alignment) changes by 90 degrees according to the presence or absence of voltage application. Therefore, this liquid crystal display element obtains a higher contrast than a conventional host-guest type element in which switching is performed between random alignment and vertical alignment by utilizing the difference in light absorption characteristics of the dichroic dye. In the host-guest type element in which the dichroic dye is dissolved, the element becomes colored when the liquid crystal is oriented in the horizontal direction, and becomes opaque only in the scattering state. Therefore, an element which changes from colored opaque to colored transparent or colorless transparent when no voltage is applied can be obtained.
The polymerizable compound in the liquid crystal composition is used for forming a curable resin by performing a polymerization reaction by ultraviolet irradiation at the time of manufacturing a liquid crystal display element. Therefore, a polymer obtained by polymerizing a polymerizable compound in advance may be introduced into the liquid crystal composition. However, even when a polymer is formed, it is necessary to have a site where polymerization is performed by irradiation with ultraviolet rays. The polymerizable compound is preferably used in view of the treatment of the liquid crystal composition, that is, the suppression of the increase in viscosity of the liquid crystal composition and the solubility in 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, it is necessary that a part or all of the liquid crystal composition has a temperature at which a liquid crystal phase is exhibited. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is sufficient to visually confirm the liquid crystal display element and obtain substantially the same transparency and scattering characteristics as those of the entire inside of the element.
The polymerizable compound may be one that is polymerized by ultraviolet rays, and in this case, the curable resin may be formed by polymerizing in any reaction form. Specific examples of the reaction form include radical polymerization, cationic polymerization, anionic polymerization, and polyaddition.
Among them, the reactive form of the polymerizable compound is preferably radical polymerization from the viewpoint of the optical characteristics of the liquid crystal display element. In this case, as the polymerizable compound, the following radical type polymerizable compound or oligomer thereof can be used. 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 pages 69 to 71 of International publication No. 2015/146987.
The use ratio of the radical polymerizable compound or oligomer thereof 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 type polymerizable compound may be used in a mixture of 1 or 2 or more kinds depending on the respective characteristics.
In order to promote the formation of the curable resin, a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays is preferably introduced into the liquid crystal composition in order to promote radical polymerization of the polymerizable compound.
Specifically, the radical initiator described in pages 71 to 72 of International publication No. 2015/146987 is exemplified.
The ratio of the radical initiator to be used 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 and the electrode of the liquid crystal display element. More preferably 0.05 to 10 parts by mass. The radical initiator may be used in a mixture of 1 or 2 or more kinds depending on the respective characteristics.
The specific compound is a compound represented by the aforementioned formula [1 ].
[1 ]]Wherein X is 1 ～X 8 And Xm are as defined above, but among them, the following examples are preferable, respectively.
X 1 Preferably of the formula [1-a ]][1-b ]][1-c ]][1-d ]][1-e ]]Or [1-f]. More preferably [1-a ]][1-b ]][1-c ]]Or [1-e ]]. Most preferably [1-a ]]Or [1-b ]]。
X 2 Preferably a single bond, -O-, -CH 2 O-, -CONH-, -COO-or-OCO-. More preferably a single bond, -O-, -COO-or-OCO-.
X 3 Preferably 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).
X 4 Preferably a single bond, -O-or-COO-. More preferably-O-.
X 5 Preferably a benzene ring or cyclohexane ring, or a 2-valent organic group having 17 to 51 carbon atoms in a steroidal skeleton. More preferably a benzene ring or a 2-valent organic group having 17 to 51 carbon atoms in a steroidal skeleton.
X 6 Preferably a single bond, -O-, -COO-or-OCO-. More preferably a single bond, -COO-or-OCO-.
X 7 Preferably a benzene ring or cyclohexane ring.
X 8 Preferably 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 an alkoxy group having 1 to 12 carbon atoms.
Xm is preferably an integer of 0 to 2.
[1 ]]In (2) is preferably X 1 ～X 8 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
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-1a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-2a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-3a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-4a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-5a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-6a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-7a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-8a [1-a ]] Single key -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-9a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-10a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-11a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-12a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-13a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-14a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-15a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-16a [1-a ]] Single key -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-17a [1-a ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-18a [1-a ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-19a [1-a ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-20a [1-a ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
TABLE 2
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-21a [1-a ]] Single key -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-22a [1-a ]] Single key -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-23a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-24a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-25a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-26a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-27a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-28a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-29a [1-a ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-30a [1-a ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-31a [1-a ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-32a [1-a ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-33a [1-a ]] Single key -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-34a [1-a ]] Single key -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-35a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-36a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-37a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-38a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-39a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-40a [1-a ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
TABLE 3
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-41a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-42a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-43a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-44a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-45a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-46a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-47a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-48a [1-b ]] Single key -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-49a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-50a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-51a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-52a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-53a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-54a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-55a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-56a [1-b ]] Single key -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Carbon numberAlkyl of 1 to 12 2
1-57a [1-b ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-58a [1-b ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-59a [1-b ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-60a [1-b ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
TABLE 4
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-61a [1-b ]] Single key -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-62a [1-b ]] Single key -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-63a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-64a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-65a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-66a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-67a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-68a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-69a [1-b ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-70a [1-b ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-71a [1-b ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-72a [1-b ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-73a [1-b ]] Single key -(CH2)a- -O- Benzene ring -OCO- Cyclohexane (Cyclohexane)An alkane ring Alkyl of 1 to 12 carbon atoms 1
1-74a [1-b ]] Single key -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-75a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-76a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-77a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-78a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-79a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-80a [1-b ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
TABLE 5
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-81a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-82a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-83a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-84a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-85a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-86a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-87a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-88a [1-c ]] Single key -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-89a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-90a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-91a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-92a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-93a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Carbon numberAlkyl of 1 to 12 2
1-94a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-95a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-96a [1-c ]] Single key -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-97a [1-c ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-98a [1-c ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-99a [1-c ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-100a [1-c ]] Single key -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
TABLE 6
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-101a [1-c ]] Single key -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-102a [1-c ]] Single key -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-103a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-104a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-105a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-106a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-107a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-108a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-109a [1-c ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-110a [1-c ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-111a [1-c ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-112a [1-c ]] Single key -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-113a [1-c ]] Single key -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-114a [1-c ]] Single key -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-115a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-116a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-117a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-118a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-119a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-120a [1-c ]] Single key -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
TABLE 7
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-121a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-122a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-123a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-124a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-125a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-126a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-127a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key － Alkyl of 1 to 12 carbon atoms 0
1-128a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key － Alkoxy of 1 to 12 carbon atoms 0
1-129a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-130a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-131a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-132a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-133a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-134a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-135a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-136a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-137a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-138a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-139a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-140a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -COO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
TABLE 8
X 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 Xm
1-141a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-142a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-143a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-144a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-145a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 1
1-146a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 1
1-147a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkyl of 1 to 12 carbon atoms 2
1-148a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -OCO- Benzene ring Alkoxy of 1 to 12 carbon atoms 2
1-149a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-150a [1-e ]] -COO- -(CH2)a- -O- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-151a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-152a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring Single key Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-153a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-154a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-155a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-156a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -COO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-157a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-158a [1-e ]] -COO- -(CH2)a- -O- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
1-159a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 1
1-160a [1-e ]] -COO- -(CH2)a- -COO- Benzene ring -OCO- Cyclohexane ring Alkyl of 1 to 12 carbon atoms 2
TABLE 9
Figure BDA0002684988800000131
Among them, preferred are combinations of (1-3 a) to (1-8 a), (1-11 a) to (1-24 a), (1-27 a) to (1-36 a), (1-39 a), (1-40 a), (1-43 a) to (1-48 a), (1-51 a) to (1-64 a), (1-67 a) to (1-76 a), (1-79 a), (1-80 a), (1-83 a) to (1-88 a), (1-91 a) to (1-104 a), (1-107 a) to (1-116 a), (1-119 a), (1-120 a), (1-123 a), (1-124 a), (1-129 a), (1-130 a), (1-133 a), (1-134 a), (1-137 a), (1-138 a), (1-141 a), (1-142 a), (1-145 a), (1-146 a) or (1-149 a) to (1-172 a).
More preferably, (1-3 a) to (1-8 a), (1-11 a), (1-12 a), (1-15 a) to (1-18 a), (1-21 a), (1-22 a), (1-27 a) to (1-30 a), (1-33 a), (1-34 a), (1-39 a), (1-40 a), (1-43 a) to (1-48 a), (1-51 a), (1-52 a), (1-55 a) to (1-58 a), (1-61 a), (1-62 a), (1-67 a) to (1-70 a), (1-73 a), (1-74 a), (1-79 a), (1-80 a), (1-83 a) to (1-88 a), (1-91 a), (1-92 a), (1-95 a) to (1-98 a), (1-101 a), (1-102 a), (1-107 a) to (1-110 a), (1-113 a), (1-114 a), (1-119 a), (1-120 a), (1-123 a), and (1-123 a), (1-124 a), (1-129 a), (1-130 a), (1-133 a), (1-134 a), (1-137 a), (1-138 a), (1-141 a), (1-142 a), (1-145 a), (1-146 a) or combinations of (1-149 a) to (1-172 a).
Most preferred are combinations of (1-3 a) - (1-8 a), (1-15 a) - (1-18 a), (1-29 a), (1-30 a), (1-43 a) - (1-48 a), (1-55 a) - (1-58 a), (1-69 a), (1-70 a), (1-83 a) - (1-88 a), (1-95 a) - (1-98 a), (1-109 a), (1-110 a), (1-123 a), (1-124 a), (1-133 a), (1-134 a), (1-141 a), (1-142 a), (1-149 a) - (1-152 a) or (1-161 a) - (1-172 a).
Specific compounds include compounds represented by the following formulas [1a-1] to [1a-11], and those are preferably used.
Figure BDA0002684988800000141
X a represents-O-or-COO-. X is X b Represents 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
X c Represents a single bond, -COO-or-OCO-. X is X d Represents 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
X e represents-O-or-COO-. X is X f Represents a 2-valent organic group having 17 to 51 carbon atoms in a steroid skeleton. X is X g Represents 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 and the electrode of the liquid crystal display element. More preferably 0.5 to 20 parts by mass. Most preferably 1 to 10 parts by mass. In addition, 1 or 2 or more specific compounds may be used in combination according to each property.
As a method for producing the liquid crystal composition, a method in which a mixture of a polymerizable compound and a specific compound is added to a liquid crystal singly or in combination is exemplified; a method of adding a specific compound to a liquid crystal in advance to produce a mixture, and adding a single or a plurality of polymerizable compounds to the mixture.
When a plurality of polymerizable compounds are used, they may be heated depending on the solubility of the polymerizable compounds when mixed. The temperature at this time is preferably below 100 ℃. The same applies to the case of mixing the polymerizable compound with the specific compound and the case of mixing the liquid crystal with the specific compound.
< resin composition >
The resin film is obtained from a resin composition containing a polymer having a specific structure represented by the above formulae [2-a ] to [2-i ].
The specific structure is preferably the above-mentioned formula [2-a ] to formula [2-c ], formula [2-e ], formula [2-h ] or formula [2-i ]. 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 at least one polymer selected from the group consisting of acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses, and polysiloxanes is preferable. More preferably a polyimide precursor, polyimide or polysiloxane.
When a polyimide precursor or polyimide (also referred to collectively as polyimide-based polymer) is used as the specific polymer, it is preferable that the polyimide precursor or polyimide is obtained by reacting a diamine component with a tetracarboxylic acid component.
The polyimide precursor has the structure of the following formula [ A ].
Figure BDA0002684988800000161
R 1 Represents a 4-valent organic group. R is R 2 Represents a 2-valent organic group. A is that 1 And A 2 Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A is that 3 And A 4 Represents 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 the tetracarboxylic acid component includes a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound.
The polyimide-based polymer is preferably a polyamide acid of the structural formula containing a repeating unit of the following formula [ D ] or a polyimide obtained by imidizing the polyamide acid, because it can be obtained relatively easily by using a tetracarboxylic dianhydride of the following formula [ B ] and a diamine of the following formula [ C ] as raw materials.
Figure BDA0002684988800000171
R 1 And R is 2 Definition of (A) and formula [ A ]]The definition being the same.
Figure BDA0002684988800000172
R 1 And R is 2 Definition of (A) and formula [ A ]]The definition being the same.
The general synthesis method may be used to obtain the formula [ D ]]Is introduced into the polymer [ A ]]A in (2) 1 And A 2 Alkyl of 1 to 8 carbon atoms, and formula [ A ]]A in (2) 3 And A 4 Alkyl or acetyl of 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 the structure of the following formula [2] (also referred to as a specific diamine) is preferably used.
Figure BDA0002684988800000173
Y 1 Represents a single bond, -O-, -NH-, -N (CH) 3 )-、-CH 2 O-、-CONH-、-NHCO-、-CON(CH 3 )-、-N(CH 3 ) CO-, -COO-or-OCO-. Of these, preferred is a single bond, -O-, -CH 2 O-, -CONH-, -COO-, or-OCO-. More preferably a single bond, -O-, -CH 2 O-or-COO-.
Y 2 Represents a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms having a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, any hydrogen atom on these cyclic groups being optionally substituted with 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. Of these, preferred are a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring, and a cyclohexane ring. More preferably a single bond or an alkylene group having 1 to 12 carbon atoms.
Y 3 Represents a single bond, -O-, -NH-, -N (CH) 3 )-、-CH 2 O-、-CONH-、-NHCO-、-CON(CH 3 )-、-N(CH 3 ) CO-, -COO-or-OCO-. Of these, preferred are single bonds, -O-, -COO-, or-OCO-. More preferably a single bond or-OCO-.
Y 4 Represents a compound selected from the group consisting of the aforementioned formula [2-a ]]-2-i]A structure in the group consisting of. Of these, preferred is the formula [2-a ]]-2-e][2-h ]]Or [2-i ]]. More preferably [2-a ]][2-b ]][2-d ]][2-e ]]Or [2-i ]]. Most preferably [2-a ]][2-b ]]Or [2-i ]]. Ym represents an integer of 1 to 4. Among them, 1 or 2 is preferable.
The specific diamine is preferably a diamine of the following formula [2a ].
Figure BDA0002684988800000181
[2a ]]Wherein Y represents the above formula [ 2]]. In addition, the method of [2]Y in (3) 1 ～Y 4 And Ym and preferred combinations of the foregoing formula [ 2]]Said method.
Yn represents an integer of 1 to 4. Among them, 1 is preferable.
Specific diamines are more specifically represented by the following formulas [2a-1] to [2a-12], and these 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.
Of these, 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] are preferable. More preferably, the formula [2a-5] to the formula [2a-7], the formula [2a-11] or the formula [2a-12].
The ratio of the specific diamine to be used is preferably 10 to 70 mol% based on the total diamine component. More preferably 20 to 60 mol%. In addition, 1 kind or 2 or more kinds of specific diamines may be used in combination according to each characteristic.
As the diamine component for producing the polyimide-based polymer, a diamine of the following formula [3a ] (also referred to as a 2 nd diamine) is preferably also used.
Figure BDA0002684988800000201
W represents the following formula [3-a ] to formula [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.
W A And W is B Represents an alkyl group having 1 to 12 carbon atoms.
W C Represents 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 formulas [3a-1] and [3a-2].
Figure BDA0002684988800000203
Among them, 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] are preferable. 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 formula [2a ] and the formula [3a ] (also referred to as other diamines) may be used.
Specifically, other diamine compounds described in pages 27 to 30 of International publication No. WO2015/012368 and diamine compounds of formulae [ DA1] to [ DA14] described in pages 30 to 32 of International publication No. WO2015/012368 are exemplified. In addition, 1 kind or 2 or more kinds of diamines may be used in combination according to each characteristic.
As the tetracarboxylic acid component used for producing the polyimide-based polymer, it is preferable to use a tetracarboxylic dianhydride of the following formula [4], a tetracarboxylic acid as its tetracarboxylic acid derivative, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all of which will also be collectively referred to as a specific tetracarboxylic acid component).
Figure BDA0002684988800000211
Z represents the following formulas [4a ] to [4l ].
Figure BDA0002684988800000212
Z A ～Z D Represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z is Z E And Z F Represents a hydrogen atom or a methyl group.
Z in the formula [4] is preferably the formula [4a ], the formula [4c ], the formula [4d ], the formula [4e ], the formula [4f ], the formula [4g ], the formula [4k ] or the formula [4l ]. More preferably, formula [4a ], formula [4e ], formula [4f ], formula [4g ], formula [4k ] or formula [4l ]. Particularly preferred is formula [4a ], formula [4e ], formula [4f ], formula [4g ] or formula [4l ].
The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to the total tetracarboxylic acid components. More preferably 5 mol% or more. Particularly preferably 10 mol% or more. Most preferably 10 to 90 mole%.
In the present invention, the polyimide-based polymer may use a tetracarboxylic acid component other than the specific tetracarboxylic acid component. Examples of the other tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dicarboxylic acid dihalide compound, a dicarboxylic acid dialkyl ester compound, and a dialkyl ester dihalide compound shown below.
Specifically, other tetracarboxylic acid components described in pages 34 to 35 of International publication No. WO2015/012368 are exemplified.
The specific tetracarboxylic acid component and the other tetracarboxylic acid component may be used by mixing 1 or 2 or more kinds depending on each property.
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 pages 35 to 36 of International publication WO2015/012368 is exemplified.
The reaction of the diamine component with 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.
Specifically, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 1, 3-dimethyl-imidazolidinone, or the like can be cited. In addition, when the polyimide precursor has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent of the following formulas [ D1] to [ D3] can be used.
Figure BDA0002684988800000231
D 1 And D 2 Represents an alkyl group having 1 to 3 carbon atoms. D (D) 3 Represents an alkyl group having 1 to 4 carbon atoms.
In addition, they may be used alone or in combination. Further, even a solvent in which the polyimide precursor is not dissolved may be mixed with the solvent in a range where the polyimide precursor to be produced is not precipitated. Further, since moisture in the organic solvent suppresses polymerization reaction and causes hydrolysis of the polyimide precursor to be produced, it is preferable to use a dehydrated and dried organic solvent as the organic solvent.
The polyimide is a polyimide obtained by ring-closing a polyimide precursor, and the ring closure rate (also referred to as imidization rate) of an amide group in the 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 the solvent, it is preferably 30 to 80%. More preferably 40 to 70%.
The molecular weight of the polyimide-based polymer is preferably 5000 to 1000000, more preferably 10000 to 150000 in terms of Mw (weight average molecular weight) measured by the GPC (Gel Permeation Chromatography) method, in view of the strength of the resin film obtained therefrom, workability in forming the resin film, and film-coating property.
When a polysiloxane is used as the specific polymer, 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] is preferably used.
An alkoxysilane of the formula [ A1 ]:
(A 1 ) m Si(A 2 ) n (OA 3 ) p [A1]
A 1 is represented by the formula [2-a ] selected from the group consisting of]-2-i]An organic group having 2 to 12 carbon atoms in the structure of the group. Of these, preferred is the formula [2-a ]]-2-e][2-h ]]Or [2-i ]]. More preferably [2-a ]][2-b ]][2-d ]][2-e ]]Or [2-i ]]. Most preferably [2-a ]][2-b ]]Or [2-i ]]。
A 2 Is 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 is that 3 Alkyl groups having 1 to 5 carbon atoms are preferable, and alkyl groups having 1 to 3 carbon atoms are preferable. 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.
For example, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate or 3- (trimethoxysilyl) propyl methacrylate, preferably being used.
The alkoxysilane of the formula [ A1] may be used in an amount of 1 or 2 or more kinds thereof may be mixed according to each property.
An alkoxysilane of the formula [ A2 ]:
(B 1 ) n Si(OB 2 ) 4-n [A2]
B 1 is 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.
B 2 Alkyl groups having 1 to 5 carbon atoms are preferable, and alkyl groups having 1 to 3 carbon atoms are preferable. n is an integer of 0 to 3.
Specific examples of the alkoxysilane of the formula [ A2] include those of the formula [2c ] described in pages 24 to 25 of International publication WO 2015/008846.
Further, as the alkoxysilane in which n is 0 in the formula [ A2], tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane can be mentioned. As alkoxysilanes of the formula [ A2], preference is given to using these alkoxysilanes.
The alkoxysilane of the formula [ A2] may be used in an amount of 1 or 2 or more kinds thereof may be mixed according to each property.
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 them, from the viewpoints of reactivity of polycondensation and solubility of the polysiloxane-based polymer in a solvent, a polysiloxane obtained by polycondensing a plurality of alkoxysilanes is preferable. That is, it is preferable to use a polysiloxane obtained by polycondensing 2 kinds of alkoxysilanes of the formula [ A1] and the formula [ 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%, particularly preferably 1 to 30 mol%, based on the total alkoxysilane.
The alkoxysilane of the formula [ A2] is used in an amount of preferably 30 to 99 mol%, more preferably 50 to 99 mol%, particularly preferably 70 to 99 mol%, based on the total alkoxysilane.
The method for polycondensing the polysiloxane polymer is not particularly limited. Specifically, the method described in pages 26 to 29 of International publication WO2015/008846 is exemplified.
In the polycondensation reaction for producing the polysiloxane polymer, when a plurality of alkoxysilanes of the formulas [ A1] and [ A2] are used, the reaction may be performed using a mixture obtained by mixing a plurality of alkoxysilanes in advance, or may be performed while adding a plurality of alkoxysilanes in sequence.
In the present invention, the solution of the polysiloxane polymer obtained by the above method may be used as a specific polymer as it is, or the solution of the polysiloxane polymer obtained by the above method may be concentrated or diluted with a solvent if necessary, and replaced with another solvent to be used as a specific polymer.
The solvent used for dilution (also referred to as an additive solvent) may be a solvent used in 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 may be arbitrarily selected. Examples of such an additive solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvents used in the polycondensation reaction.
Further, in the case where a polysiloxane polymer and other polymers are used as the specific polymer, it is preferable that the alcohol produced during 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 other polymers mixed. In this case, the content of the other polymer is preferably 0.5 to 15 parts by mass based on 100 parts by mass of the specific polymer. More preferably 1 to 10 parts by mass. The other polymers include those not having a specific structure.
The solvent content in the resin composition may be appropriately selected from the viewpoints of the method of coating the resin composition and obtaining the target film thickness. Among them, the content of the solvent in the resin composition is preferably 50 to 99.9 mass% from the viewpoint of forming a uniform resin film by coating. Of these, 60 to 99 mass% is preferable. More preferably 65 to 99 mass%.
The solvent used in the resin composition is not particularly limited as long as it is a solvent for dissolving the specific polymer. Among them, in the case where the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or in the case where the solubility to a solvent is low in an acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose or polysiloxane, 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, dimethylsulfoxide, gamma-butyrolactone, 1, 3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or gamma-butyrolactone is preferable. In addition, they may be used alone or in combination.
In the case where the specific polymer is an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a cellulose or a polysiloxane, and further the specific polymer is a polyimide precursor, a polyimide, a polyamide or a polyester, the following solvent (also referred to as solvent B) can be used when the solubility of the specific polymer to the solvent is high.
Specific examples of the solvent B include solvents B described in pages 58 to 60 of International publication WO 2014/171493. Among them, preferred are 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 the aforementioned formulas [ D1] to [ D3].
In addition, when these solvents B are used, in order to improve the coatability of the resin composition, the aforementioned solvents A are preferably used in combination with N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or gamma-butyrolactone. More preferably gamma-butyrolactone.
These solvents B are preferably used in combination with the aforementioned solvents A, since they can improve the film-coating property and surface smoothness of the resin film when the resin composition is applied, and therefore, when a polyimide precursor, polyimide, polyamide or polyester is used as a specific polymer. In this case, the solvent B is preferably 1 to 99% by mass of the total solvent contained in the resin composition. Of these, 10 to 99 mass% is preferable. More preferably 20 to 95 mass%.
In order to improve the film strength of the resin film, a compound having an epoxy group, an isocyanate group, an oxetanyl group, a cyclic carbonate group, a hydroxyl group, a hydroxyalkyl group, or a lower alkoxyalkyl group (also collectively referred to as a specific crosslinkable compound) is preferably introduced into the resin composition. In this case, the compound is required to have 2 or more of these groups.
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 pages 63 to 64 of International publication WO 2014/171493.
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 WO 2011/132751.
Specific examples of the crosslinkable compound having a cyclic carbonate group include crosslinkable compounds of the formulae [5-1] to [5-42] described in pages 76 to 82 of International publication WO 2012/014898.
Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include melamine derivatives or benzoguanamine derivatives described in pages 65 to 66 of International publication No. 2014/171493 and crosslinkable compounds of the formulae [6-1] to [6-48] described in 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 based on 100 parts by mass of the total polymer components. In order to perform the crosslinking reaction and to exhibit the desired effect, the amount of the crosslinking agent is more preferably 0.1 to 50 parts by mass, and most preferably 1 to 30 parts by mass, based on 100 parts by mass of the total polymer component.
The resin composition is preferably introduced with at least one generator (specific generator) selected from the group consisting of a photoradical generator, a photoacid generator and a photobase generator.
Specific examples of the specific generating agent include those described in pages 54 to 56 of International publication No. 2014/171493. Among them, the specific generator is preferably a photoradical generator from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the electrode.
In the resin composition, a compound that improves the uniformity of film thickness and surface smoothness of a 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 that improves adhesion between the resin film and the substrate may be used.
Examples of the compound that improves 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 page 67 of International publication WO2014/171493 may be used. The use ratio is preferably 0.01 to 2 parts by mass based on 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 use ratio is preferably 0.1 to 30 parts by mass based on 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 above-mentioned compounds, a dielectric substance or a conductive substance which is an object of changing the dielectric constant, conductivity, or other electrical characteristics of the resin film may be added to the resin composition.
Method for producing resin film and liquid crystal display element
The substrate used in 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 further 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 addition, from the viewpoint of process simplification, a substrate formed with an ITO electrode, an indium zinc oxide (IZO, indium Zinc Oxide) electrode, an indium gallium zinc oxide (IGZO, indium Gallium Zinc Oxide) electrode, an organic conductive film, or the like for driving liquid crystal is preferably used. In the case of forming a reflective liquid crystal display element, a substrate having a metal such as a silicon wafer or aluminum, or a dielectric multilayer film formed thereon may be used only for one side substrate.
The liquid crystal display element has a resin film obtained from a resin composition having a specific polymer on at least one of the substrates. In particular, it is preferable that the resin films are present on both substrates.
The method of applying the resin composition is not particularly limited, and there are industrially available screen printing, offset printing, flexography, inkjet method, dipping method, roll coating method, slit coating method, spin coating method, spray method, and the like, and may be appropriately selected depending on the type of substrate and the film thickness of the target resin film.
After the resin composition is applied to the substrate, a heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven is used, and the temperature of the solvent used in the resin composition is preferably 30 to 300 ℃. More preferably 30 to 250 ℃, and the solvent is evaporated, thereby forming a resin film. In particular, when a plastic substrate is used as the substrate, the treatment is preferably performed 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, the reliability of the element may be lowered, and therefore, it is preferably 5 to 500nm. More preferably 10 to 300nm, particularly preferably 10 to 250nm.
The liquid crystal composition used in 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 examples thereof include the following methods. That is, when a glass substrate is used as the substrate, a pair of substrates on which a resin film is formed are prepared, a sealant is applied to a part of the 4 substrates on one side, and then the other substrate is bonded with the surface of the resin film on the inner side, thereby producing an empty cell. Then, the liquid crystal composition is injected under reduced pressure from a portion where the sealant is not applied, thereby obtaining a unit into which the liquid crystal composition is injected. Further, when a plastic substrate or a film is used as the substrate, a pair of substrates on which a resin film is formed are prepared, and a liquid crystal composition is dropped on one side of the substrates by ODF (One Drop Filling) method, inkjet method, or the like, and then the other side of the substrates is bonded to obtain a cell into which the liquid crystal composition is injected. In the liquid crystal display element of the present invention, the sealing agent may not be applied to 4 substrates because the adhesion between the liquid crystal layer and the electrode is high.
The gap of the liquid crystal display element can be controlled by the aforementioned spacers. As described above, the 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 plastic or film substrates, 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. Mu.m, more preferably 1 to 50. Mu.m. Particularly preferably 2 to 30. Mu.m. 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 curing of the liquid crystal composition is performed by irradiating the unit injected with the liquid crystal composition 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 light is preferably 250 to 400nm. Among them, 310 to 370nm is preferable. Further, after 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 is not limited thereto.
The shorthand used in the following is as follows.
< specific Compounds >)
Figure BDA0002684988800000301
< polymerizable Compound >)
R1: IBXA (manufactured by Osaka organic chemical industry Co., ltd.)
R2: methacrylic acid 2-hydroxy ethyl ester
R3: KAYARAD FM-400 (manufactured by Japanese Kai-drug Co., ltd.)
R4: EBECRYL 230 (DAICEL-ALLNEX LTD.)
R5: karenz MT PE1 (manufactured by Zhaoyao electric Co., ltd.)
< photo radical initiator >)
P1: IRGACURE 184 (BASF corporation)
< liquid Crystal >)
L1: MLC-3018 (Merck Ltd.)
< specific diamine >)
Figure BDA0002684988800000311
< 2 nd diamine >)
Figure BDA0002684988800000312
< other diamines >)
Figure BDA0002684988800000313
< specific tetracarboxylic acid component >
Figure BDA0002684988800000321
< monomer for producing polysiloxane Polymer >
E1: 3-methacryloxypropyl trimethoxysilane
E2: tetraethoxysilane
Specific crosslinkable Compound
Figure BDA0002684988800000322
< specific Generation agent >)
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
ECS: ethylene glycol monoethyl ether
EC: diethylene glycol monoethyl ether
[ molecular weight measurement of polyimide-based Polymer ]
The measurement was performed by using a normal temperature Gel Permeation Chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., ltd.) and a column (KD-803, KD-805) (manufactured by Shodex Co., ltd.).
Column temperature: 50 DEG C
Eluent: n, N' -dimethylformamide (as an additive, lithium bromide monohydrate (libr.h) 2 O) was 30 mmol/L, phosphoric acid/anhydrous crystals (orthophosphoric acid) was 30 mmol/L, tetrahydrofuran (THF) was 10ml/L
Flow rate: 1.0 ml/min
Standard curve preparation standard samples were used: 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 Rate of polyimide-based Polymer ]
20mg of polyimide powder was added to an NMR (nuclear magnetic resonance) sample tube (NMR sample tube standard, phi 5 (manufactured by Kagaku Co., ltd.), deuterated dimethyl sulfoxide (DMSO-d 6, 0.05% TMS (tetramethylsilane) mixture) (0.53 ml) was added, and the mixture was completely dissolved by applying ultrasonic waves. For this solution, proton NMR of 500MHz was measured by an NMR meter (JNW-ECA 500) (JEOL DATUM Ltd.). The imidization rate was determined by using a proton derived from a structure which did not change before and after imidization as a reference proton, and the peak accumulation value of the proton derived from the NH group of the amic acid which occurred in the vicinity of 9.5ppm to 10.0ppm were used and were obtained by the following formula.
Imidization ratio (%) = (1- α·x/y) ×100
(x is the proton peak accumulation value of NH group derived from amic acid, y is the peak accumulation value of reference proton, and α is the number ratio of 1 reference proton to NH group proton of amic acid when polyamic acid (imidization ratio is 0%))
Synthesis of polyimide-based Polymer "
Synthesis example 1 >
D2 (3.06 g, 12.2 mmol), A1 (4.10 g, 15.5 mmol) and C1 (1.68 g, 15.5 mmol) were mixed in NMP (33.2 g), reacted at 80 ℃ for 4 hours, and then D1 (3.60 g, 18.4 mmol) and NMP (16.6 g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (1) having a resin solid content of 20 mass%. The number average molecular weight (also referred to as Mn) of the polyamic acid was 18500, and the weight average molecular weight (also referred to as Mw) was 66100.
Synthesis example 2
To the polyamic acid solution (1) (30.0 g) obtained by the method of synthesis example 1, NMP was added to dilute it to 6 mass%, and acetic anhydride (3.60 g) and pyridine (2.30 g) were added as imidization catalysts, and then reacted at 60℃for 1.5 hours. The reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100℃to give polyimide powder (2). The polyimide had an imidization ratio of 51%, mn of 16100 and Mw of 43500.
Synthesis example 3 >
D4 (1.01 g, 5.10 mmol) and A1 (3.41 g, 12.9 mmol) were mixed in γ -BL (15.8 g), reacted at 60 ℃ for 6 hours, and then D1 (1.50 g, 7.65 mmol) and γ -BL (7.90 g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (3) having a resin solid content of 20 mass%. The polyamic acid had Mn of 10500 and Mw of 34700.
Synthesis example 4 >
D2 (1.70 g, 6.80 mmol), A2 (2.80 g, 13.8 mmol) and B1 (0.52 g, 3.44 mmol) were mixed in γ -BL (18.7 g), reacted at 60 ℃ for 6 hours, and then D1 (2.00 g, 10.2 mmol) and γ -BL (9.37 g) 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 (1.62 g, 6.46 mmol), A3 (2.32 g, 6.54 mmol), B1 (1.00 g, 6.54 mmol) and C1 (0.35 g, 3.27 mmol) were mixed in γ -BL (19.2 g), and after reaction at 60 ℃ for 6 hours, D1 (1.90 g, 9.69 mmol) and γ -BL (9.58 g) were added and reaction was carried out 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 (3.80 g, 17.0 mmol), A1 (2.72 g, 10.3 mmol), A2 (0.70 g, 3.44 mmol) and C1 (0.37 g, 3.43 mmol) were mixed in NMP (30.4 g) and reacted at 40 ℃ for 12 hours to obtain a polyamic acid solution (6) having a resin solid content concentration of 20 mass%. The polyamic acid had Mn of 15800 and Mw of 52500.
Synthesis example 7 >
To the polyamic acid solution (7) (30.0 g) obtained by the method of synthesis example 7, NMP was added to dilute it to 6 mass%, and acetic anhydride (3.60 g) and pyridine (2.35 g) were added as imidization catalysts, and then reacted at 60℃for 2 hours. The reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100℃to give polyimide powder (7). The polyimide had an imidization ratio of 48%, mn of 14600 and Mw of 40900.
Synthesis example 8
D2 (2.13 g, 8.50 mmol) and C1 (2.33 g, 21.5 mmol) were mixed in NMP (18.5 g), reacted at 80 ℃ for 4 hours, and then D1 (2.50 g, 12.8 mmol) and NMP (9.27 g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (8) having a resin solid content of 20 mass%. The polyamic acid had Mn of 22800 and Mw of 70200.
Synthesis example 9 >
D4 (1.35 g, 6.80 mmol), B1 (1.31 g, 8.61 mmol) and C1 (0.93 g, 8.61 mmol) were mixed in γ -BL (14.9 g), reacted at 60 ℃ for 6 hours, and then D1 (2.00 g, 10.2 mmol) and γ -BL (7.45 g) 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 polymer obtained in the synthesis example is shown in table 10.
In table 10, 1 represents a polyamic acid.
TABLE 10
Figure BDA0002684988800000361
Synthesis of polysiloxane Polymer "
< Synthesis example 10 >
A200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was mixed with EC (29.0 g), E1 (8.80 g) and E2 (36.2 g) to prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing EC (14.5 g), water (11.0 g) and oxalic acid (0.50 g) as a catalyst was added dropwise at 25℃for 30 minutes, and further stirred at 25℃for 30 minutes. Then, the mixture was heated in an oil bath for 30 minutes and refluxed, and then naturally cooled to obtain SiO 2 Polysiloxane solution (1) with a concentration of 12 mass%.
Synthesis example 11
A200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with ECS (29.0 g), E1 (11.5 g) and E2 (33.5 g) to prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by mixing ECS (14.0 g), water (11.0 g) and oxalic acid (0.50 g) as a catalyst at 25 ℃ for 30 minutes was added dropwise, and further stirred at 25 ℃ for 30 minutes. Then, the mixture was heated in an oil bath for 30 minutes and refluxed, and then naturally cooled to obtain SiO 2 Polysiloxane solution (2) with a concentration of 12 mass%.
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
To the polyamic acid solution (1) (5.40 g) obtained by the method of synthesis example 1, NMP (12.1 g) was added, and the mixture was stirred at 25℃for 1 hour. BCS (10.4 g) and PB (2.98 g) were then added, and stirred at 25℃for 4 hours to give a resin composition (1).
Synthesis example 13 >
NMP (15.8 g) was added to the polyimide powder (2) (1.20 g) obtained by the method of Synthesis example 2, and the mixture was stirred at 70℃for 24 hours to dissolve the polyimide powder. BCS (4.32 g) and PB (8.64 g) were then added, and stirred at 25℃for 4 hours, to give a resin composition (2).
Synthesis example 14
To the polyamic acid solution (3) (3.00 g) obtained by the method of synthesis example 3, γ -BL (0.15 g) and PGME (22.9 g) were added, 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) (3.00 g) obtained by the method of synthesis example 3, γ -BL (0.15 g), PGME (22.9 g) and K2 (0.042 g) were added, 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) (3.00 g) obtained by the method of synthesis example 3, γ -BL (0.15 g), PGME (22.9 g), K2 (0.042 g) and N1 (0.018 g) were added, 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) (3.00 g) obtained by the method of synthesis example 4, γ -BL (3.97 g), PGME (19.1 g) and K1 (0.018 g) were added, and the mixture was stirred at 25℃for 6 hours to obtain a resin composition (6).
Synthesis example 18 >
To the polyamic acid solution (5) (3.00 g) obtained by the method of synthesis example 5, γ -BL (0.15 g), PGME (22.9 g), K2 (0.060 g) and N1 (0.030 g) were added, and stirred at 25℃for 6 hours to obtain a resin composition (7).
Synthesis example 19 >
To the polyamic acid solution (6) (5.40 g) obtained by the method of synthesis example 6 was added NMP (13.6 g), and the mixture was stirred at 25℃for 1 hour. PB (11.9 g) and K2 (0.054 g) were then added, and stirred at 25℃for 4 hours, to give a resin composition (8).
Synthesis example 20 >
NMP (15.8 g) was added to the polyimide powder (7) (1.20 g) obtained by the method of Synthesis example 7, and the mixture was stirred at 70℃for 24 hours to dissolve the polyimide powder. BCS (2.88 g), PB (10.1 g), K2 (0.084 g) and N1 (0.036 g) were then added, and stirred at 25℃for 4 hours to give a resin composition (9).
Synthesis example 21 >
To the polysiloxane solution (1) (10.0 g) obtained by the method of Synthesis example 10, EC (3.93 g) and PB (12.7 g) were added, and the mixture was stirred at 25℃for 6 hours to obtain a resin composition (10).
Synthesis example 22 >
To polysiloxane solution (2) (10.0 g) obtained by the method of Synthesis example 11, ECS (4.78 g), PGME (25.2 g) and N1 (0.036 g) were added, and stirred at 25℃for 6 hours to obtain resin composition (11).
Synthesis example 23
To the polyamic acid solution (8) (5.40 g) obtained by the method of synthesis example 8, NMP (12.1 g) was added, and the mixture was stirred at 25℃for 1 hour. BCS (10.4 g) and PB (2.98 g) were then added, and stirred at 25℃for 4 hours to give a resin composition (12).
Synthesis example 24
To the polyamic acid solution (9) (3.00 g) obtained by the method of synthesis example 9, γ -BL (0.15 g) and PGME (22.9 g) were added, and the mixture was stirred at 25℃for 6 hours to obtain a resin composition (13).
The resin compositions obtained in the above synthetic examples 12 to 24 were prepared in the manner shown in Table 12. The resin compositions obtained in Synthesis examples 12 to 24 were homogeneous solutions without any abnormalities such as turbidity and precipitation.
In table 12, the numerical values in brackets for the specific crosslinkable compound and the specific generating agent added to the resin composition represent the content of 100 parts by mass relative to the specific polymer.
TABLE 12
Figure BDA0002684988800000391
Production of liquid Crystal composition (A)
R1 (1.20 g), R2 (0.30 g), R3 (1.20 g), R4 (0.90 g) and R5 (0.30 g) were mixed and stirred at 60℃for 2 hours to prepare a solution of the polymerizable compound. On the other hand, S1 (0.20 g) and L1 (5.80 g) 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 (0.10 g) were mixed and stirred at 25℃for 6 hours to obtain a liquid crystal composition (A).
Production of liquid Crystal composition (B)
R1 (1.20 g), R2 (0.30 g), R3 (1.20 g), R4 (0.90 g) and R5 (0.30 g) were mixed and stirred at 60℃for 2 hours to prepare a solution of the polymerizable compound. On the other hand, S1 (0.80 g) and L1 (5.20 g) 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 (0.10 g) were mixed and stirred at 25℃for 6 hours to obtain a liquid crystal composition (B).
Production of liquid Crystal composition (C)
R1 (1.20 g), R2 (0.30 g), R3 (1.20 g), R4 (0.90 g) and R5 (0.30 g) were mixed and stirred at 60℃for 2 hours to prepare a solution of the polymerizable compound. On the other hand, S2 (0.40 g) and L1 (5.60 g) 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 (0.10 g) were mixed and stirred at 25℃for 6 hours to obtain a liquid crystal composition (C).
Production of liquid Crystal composition (D)
R1 (1.20 g), R2 (0.30 g), R3 (1.20 g), R4 (0.90 g) and R5 (0.30 g) were mixed and stirred at 60℃for 2 hours to prepare a solution of the polymerizable compound. On the other hand, S1 (0.20 g), S2 (0.10 g) and L1 (5.70 g) 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 (0.10 g) were mixed and stirred at 25℃for 6 hours to obtain a liquid crystal composition (D).
Preparation of liquid Crystal composition (E)
R1 (1.20 g), R2 (0.30 g), R3 (1.20 g), R4 (0.90 g) and R5 (0.30 g) were mixed and stirred at 60℃for 2 hours to prepare a solution of the polymerizable compound. Then, the prepared solution of the polymerizable compound, L1 (6.00 g) and P1 (0.10 g) 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 pressure-filtered through a membrane filter having a pore diameter of 1. Mu.m. The obtained solution was spin-coated on an ITO surface of an ITO electrode-equipped glass substrate (vertical: 100mm, horizontal: 100mm, thickness: 0.7 mm) washed with pure water and IPA (isopropyl alcohol), and subjected to a heating treatment on a heating plate at 100℃for 5 minutes, and then subjected to a heating treatment at 210℃for 30 minutes by a thermal cycle type cleaning oven, to obtain an ITO substrate with a resin film having a film thickness of 100 nm. The ITO substrate with resin film 2 pieces was prepared, and spacers (trade name: micropearl, manufactured by Seattle chemical Co., ltd.) having a particle diameter of 15 μm were coated on the resin film surface of the 1 pieces of substrate. Then, the liquid crystal compositions (a) to (E) were dropped by ODF (One Drop Filling) method onto the resin film surface of the substrate coated with the spacers, and then the other substrate was bonded so that the resin film surface of the other substrate faced each other, thereby obtaining a liquid crystal display element before treatment. In comparative example 1, spacers having a particle diameter of 20 μm were coated on the ITO surface of the ITO substrate without forming a resin film, and the liquid crystal composition was dropped and bonded by the same method as described above, to produce a liquid crystal display element before the treatment.
The liquid crystal display element before the treatment was used with an illuminance of 20mW/cm 2 Removing wavelength of 350nm or less, and irradiating with ultraviolet rays for 60 secondsAnd (5) emitting. 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 pressure-filtered through a membrane filter having a pore diameter of 1. Mu.m. The obtained solution was applied to an ITO surface of a PET substrate (vertical: 150mm, horizontal: 150mm, thickness: 0.1 mm) with ITO electrodes washed with pure water by a bar coater, and heat-treated at 120℃for 2 minutes by a thermal cycle type oven to obtain an ITO substrate with a resin film having a film thickness of 100 nm. The resin film-coated ITO substrate 2 was prepared, and the resin film surface of the 1 substrate was coated with the 20 μm spacer. Then, the liquid crystal compositions (a) to (E) were dropped by ODF (One Drop Filling) method onto the resin film surface of the substrate coated with the spacers, and then the other substrate was bonded so that the resin film surface of the other substrate faced each other, thereby obtaining a liquid crystal display element before treatment. In addition, when dropping and bonding a liquid crystal composition by the ODF method, a glass substrate was used as a support substrate for a PET substrate with an ITO electrode. The support substrate is then removed prior to irradiation with ultraviolet light. In comparative example 2, spacers having a particle diameter of 20 μm were coated on the ITO surface of the ITO substrate without forming a resin film, and the liquid crystal composition was dropped and bonded by the same method as described above, to produce a liquid crystal display element before the treatment.
The liquid crystal display element (plastic substrate) before this treatment was obtained by irradiating ultraviolet rays in the same manner as in the production of the liquid crystal display element (glass substrate).
Evaluation of optical Properties (scattering Properties and transparency) "
The evaluation was performed by measuring Haze (Haze) of the liquid crystal display element (glass substrate and plastic substrate) in a state where no voltage was applied (0V) and in a state where a voltage was applied (ac drive: 10V to 50V). At this time, haze was measured by a Haze meter (HZ-V3, suga Test Instruments Co., ltd.) according to JIS K7136. In the present evaluation, the higher the Haze in the state where no voltage is applied, the more excellent the scattering property, and the lower the Haze in the state where voltage is applied, the more excellent the transparency.
Further, as a stability test in a high-temperature and high-humidity environment of the liquid crystal display element, measurement after 24 hours of storage in a constant temperature and humidity tank at a temperature of 80 ℃ and a humidity of 90% rh was also performed. Specifically, the smaller the change in Haze after storage in a constant temperature and humidity tank, the more excellent the evaluation was.
Further, as a stability test for light irradiation of the liquid crystal display element, irradiation of 5J/cm in 365nm was also performed using a desktop UV curing apparatus (HCT 3B28 HEX-1) (manufactured by Seattle corporation) 2 After ultraviolet light of (a) is emitted. Specifically, the smaller the change in Haze after ultraviolet irradiation, the more excellent the evaluation was.
The results of Haze measurements after initial storage in a constant temperature/humidity tank (constant temperature/humidity) and after ultraviolet irradiation (ultraviolet) are summarized in tables 13 to 15.
Evaluation of adhesion between liquid Crystal layer and resin film (resin film and electrode) "
The evaluation was performed by storing the liquid crystal display element (glass substrate and plastic substrate) in a constant temperature and humidity tank having 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 bubbles (as a stability test in a high temperature and high humidity environment of the liquid crystal display element). Specifically, the case where peeling of the element (the state where the liquid crystal layer and the resin film or the resin film and the electrode were peeled off) did not occur, and the case where no air bubbles were generated in the element were regarded as excellent in the present evaluation (good expression in the table). In this case, examples 3 to 5 were subjected to confirmation after storage in a constant temperature and humidity tank at a temperature of 80℃and a humidity of 90% RH for 72 hours as an emphasis test in addition to the standard test. The evaluation method was the same as that described above.
Further, a liquid crystal display device was also irradiated with 5J/cm light in 365nm conversion using a desktop UV curing device (HCT 3B28 HEX-1) (manufactured by Fahrenheit corporation) 2 After ultraviolet rays (as a stability test for light irradiation of the liquid crystal display element). Specifically, no peeling of the element occurs, and no peeling occurs in the elementThe case of the air bubbles was excellent in this evaluation (good in the table).
The results (adhesion) of the initial, constant temperature and humidity tank storage (constant temperature and humidity) and the adhesion of the liquid crystal layer to the resin film (resin film and electrode) after ultraviolet irradiation (ultraviolet) are summarized in tables 16 to 18.
Examples 1 to 15 and comparative examples 1 to 6 >
Using any one of the resin compositions (1) to (13) obtained by the method of the synthetic example and the liquid crystal compositions (a) to (E), the production of a liquid crystal display element, the evaluation of optical characteristics (scattering characteristics and transparency), and the evaluation of adhesion between a liquid crystal layer and a resin film (resin film and electrode) were performed by the method described above. In this case, the glass substrates were used in examples 1, 2, 11 to 13, 1, 3 and 5 to manufacture and evaluate the liquid crystal display elements, and the plastic substrates were used in examples 3 to 10, 14, 15, 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 above-mentioned standard test was performed, and the evaluation was also performed as an emphasis test when the film was stored in a constant temperature and humidity tank at a temperature of 80 ℃ and a humidity of 90% rh for 72 hours (other conditions were the same as the above-mentioned 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 bubbles were found in the cell.
*2: bubbles were found in the cell (more than 1).
*3: a number of bubbles (more than x 2) were found in the cell.
As described above, the liquid crystal display element of the example obtained good optical characteristics compared with the comparative example. That is, in the initial stage, the Haze is low in the state where no voltage is applied, and the change in Haze after storage in a constant temperature and humidity tank and after ultraviolet irradiation is reduced. In particular, the examples have reduced Haze at lower voltages than the comparative examples. That is, in the embodiment, the driving voltage of the liquid crystal display element is reduced.
Further, in the examples, peeling of the liquid crystal display element and generation of bubbles were not observed even after storage in a constant temperature and humidity tank and after irradiation with ultraviolet rays.
These results are also the same when a plastic substrate is used as the substrate of the liquid crystal display element. Specifically, the comparison of example 1 with comparative examples 1, 3 and 5 and the comparison of example 3 with comparative examples 2, 4 and 6 are described.
In addition, when a specific crosslinkable compound is introduced into the resin composition, the liquid crystal display element has few bubbles generated after being stored in a constant temperature and humidity tank for a long time, particularly in an emphasis test. Specifically, a comparison of example 3 and example 4 is made.
Further, in the case where a specific generating agent is introduced into the resin composition in addition to the specific crosslinkable compound, no bubble is generated in the liquid crystal display element in the stress test. Specifically, in the comparison under the same conditions, the comparison of example 4 and example 5 was performed.
Industrial applicability
The liquid crystal display element of the present invention can be suitably used as a standard element which is in a scattering state when no voltage is applied and in a transparent state when voltage is applied. The device can be used for a liquid crystal display intended for display, a light control window for controlling blocking and transmission of light, a shutter device, and the like, and a plastic substrate can be used as a substrate of the standard device.
The entire contents of the specification, claims, drawings, and abstract of japanese patent application No. 2018-052663 applied at 20/3/2018 are incorporated herein by reference as the disclosure of the specification of the present invention.

Claims (13)

1. A liquid crystal display element comprising a liquid crystal layer and a resin film provided 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 voltage is applied, wherein the liquid crystal layer is formed 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 irradiation with ultraviolet rays,
the liquid crystal has a positive dielectric anisotropy and,
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 FDA0004106981410000011
[1]]Wherein X is 1 Is selected from the following formula [1-a ]]-1-j]Structures, X, in the group consisting of 2 Represents a single bond, -O-, -NH-, -N (CH) 3 )-、-CH 2 O-、-CONH-、-NHCO-、-CON(CH 3 )-、-N(CH 3 ) CO-, -COO-or-OCO-, X 3 Represents a single bond or- (CH) 2 ) a -, wherein a is an integer of 1 to 15, X 4 Represents a single bond, -O-, -OCH 2 -, -COO-or-OCO-, X 5 Represents a 2-valent cyclic group selected from the group consisting of benzene rings, cyclohexane rings and heterocyclic rings, or a 2-valent organic group having 17 to 51 carbon atoms of a steroidal skeleton, any hydrogen atom on the cyclic group being optionally substituted with 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, X 6 Represents a single bond, -O-, -CH 2 -、-OCH 2 -、-CH 2 O-, -COO-or-OCO-, X 7 Represents a cyclic group selected from the group consisting of benzene rings, cyclohexane rings and heterocyclic rings, any hydrogen atom on these cyclic groups being optionally substituted with 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, X 8 Represents 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 FDA0004106981410000021
wherein X is A Represents a hydrogen atom or a benzene ring,
Figure FDA0004106981410000022
wherein Y is A Represents a hydrogen atom or a benzene ring,
the resin composition contains a polyimide precursor or polyimide obtained by using a diamine having the structure of the formulas [2-a ] to [2-i ] as a part of a raw material, or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1] and an alkoxysilane of the formula [ A2],
(A 1 ) m Si(A 2 ) n (OA 3 ) p [A1]
[ A1]]In (A) 1 Is represented by the formula [2-a ]]-2-i]An organic group having 2 to 12 carbon atoms of the structure in the group consisting of A 2 Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A 3 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,
(B 1 ) n Si(OB 2 ) 4-n [A2]
[ A2 ]]In (B) 1 Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B 2 An alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.
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 relative to 100 parts by mass of the liquid crystal.
3. The liquid crystal display element according to claim 1 or 2, wherein the formula [1]]X in (2) 1 Is of the formula [1-a ]][1-b ]][1-c ]][1-d ]][1-e ]]Or [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 formulas [1a-1] to [1a-11],
Figure FDA0004106981410000031
[1a-1]]-1 a-4]Wherein X is a represents-O-or-COO-, X b Represents an alkyl group having 1 to 12 carbon atomsP1 represents an integer of 1 to 10, p2 represents an integer of 1 or 2,
Figure FDA0004106981410000041
[1a-5 ]]-1 a-8]Wherein X is c Represents a single bond, -COO-or-OCO-, X d Represents 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 FDA0004106981410000042
[1a-9 ]]-1 a-11]Wherein X is e represents-O-or-COO-, X f Represents a C17-51 organic group having a steroid skeleton, X g Represents 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 claim 1 or 2, wherein the resin composition further contains at least one polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a polyamide, a polyester, and a cellulose.
6. The liquid crystal display element according to claim 1 or 2, wherein the diamine is a diamine having the structure of the following formula [2],
Figure FDA0004106981410000051
[2]]In (1), Y 1 Represents a single bond, -O-, -NH-, -N (CH) 3 )-、-CH 2 O-、-CONH-、-NHCO-、-CON(CH 3 )-、-N(CH 3 ) CO-, -COO-or-OCO-, Y 2 Represents a single bond, an alkylene group having 1 to 18 carbon atoms, or a carbon having a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycleOrganic groups having 6 to 24 carbon atoms, any hydrogen atom on these cyclic groups being 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, Y 3 Represents a single bond, -O-, -NH-, -N (CH) 3 )-、-CH 2 O-、-CONH-、-NHCO-、-CON(CH 3 )-、-N(CH 3 ) CO-, -COO-or-OCO-, Y 4 Represents a compound selected from the group consisting of the compounds represented by the formula [2-a ] ]-2-i]And Ym represents an integer of 1 to 4.
7. The liquid crystal display element according to claim 6, wherein the diamine is a diamine of the following formula [2a ],
Figure FDA0004106981410000052
in the formula [2a ], Y represents the formula [2], and n represents an integer of 1 to 4.
8. The liquid crystal display element according to claim 1 or 2, wherein the resin composition contains a polyimide precursor or polyimide obtained by using a tetracarboxylic acid component of the following formula [4] as a part of a raw material,
Figure FDA0004106981410000053
in the formula [4], Z represents the following formulas [4a ] to [4l ],
Figure FDA0004106981410000061
wherein Z is A ～Z D Represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, Z E And Z F Represents a hydrogen atom or a methyl group.
9. The liquid crystal display element according to claim 1 or 2, wherein the resin composition contains a compound having an epoxy group, an isocyanate group, an oxetane group, a cyclic carbonate group, a hydroxyl group, a hydroxyalkyl group, or a lower alkoxyalkyl group.
10. The liquid crystal display element according to claim 1 or 2, 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 solvents of the following formulas [ D1] to [ D3],
Figure FDA0004106981410000062
Wherein D is 1 And D 2 Represents an alkyl group having 1 to 3 carbon atoms, D 3 Represents an alkyl group having 1 to 4 carbon atoms.
11. The liquid crystal display element according to claim 1 or 2, 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.
12. The liquid crystal display element according to claim 1 or 2, wherein a substrate of the liquid crystal display element is a glass substrate or a plastic substrate.
13. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal display element is a dimming window or a shutter element.
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