JPWO2019181885A1 - Liquid crystal display element - Google Patents

Abstract

A pair of substrates equipped with electrodes that provide a liquid crystal display element that can suppress element peeling, bubble generation, and deterioration of optical characteristics even in a harsh environment exposed to high temperature and humidity or light irradiation for a long time. The liquid crystal composition containing the liquid crystal and the polymerizable compound arranged between them has a liquid crystal layer cured by irradiating with ultraviolet rays, and has a resin film on at least one of the substrates. A liquid crystal display element that becomes transparent when applied, the liquid crystal having positive dielectric anisotropy, the liquid crystal composition containing the compound of the following formula [1], and the resin film. A liquid crystal display element 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]. [Chemical formula 1] [Chemical formula 2] (Definition of symbols in the formula is as described in the specification.)

Description

The present invention relates to a transmission-scattering type liquid crystal display element that is in a transmission state when a voltage is applied.

As a liquid crystal display element, a TN (Twisted Nematic) mode has been put into practical use. In this mode, it is necessary to use a polarizing plate in order to switch light by utilizing the optical rotation characteristic of the liquid crystal. When a polarizing plate is used, the efficiency of light utilization 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 a liquid crystal. Generally, those using 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)) are known.

In these liquid crystal display elements, a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet rays is arranged between a pair of substrates provided with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays to be polymerizable with the liquid crystal. It forms a complex with a cured product of the compound (eg, a polymer network). Then, in this liquid crystal display element, the scattering state and the transmission state of the liquid crystal are controlled by applying a voltage.

A liquid crystal display element using PDLC or PNLC is in a cloudy (scattered) state because the liquid crystal is oriented in a random direction when no voltage is applied, and when a voltage is applied, the liquid crystals are arranged in the electric field direction and transmit light. (Also referred to as a normal type element). In this case, since the liquid crystal is random when no voltage is applied, there is no need for a liquid crystal alignment film or alignment treatment for aligning the liquid crystal in one direction. Therefore, in this liquid crystal display element, the electrode and the liquid crystal layer (composite of the liquid crystal and the cured product of the polymerizable compound) are in direct contact with each other (see Patent Documents 1 and 2).

Japanese Patent No. 3552328 Japanese Patent No. 4630954

The polymerizable compound in the liquid crystal composition has a role of forming a polymer network to obtain desired optical properties and a role of enhancing the adhesion between the liquid crystal layer and the electrode. However, in order to realize these, it is necessary to form a dense polymer network, so that the driving of the liquid crystal molecules with respect to the voltage application is hindered. for that reason. The drive voltage of this element is higher than that of a liquid crystal display element such as TN mode.

Further, since an inorganic electrode such as ITO (Indium Tin Oxide) is used for this element, the compatibility with the polymerizable compound of the organic substance, that is, the adhesion tends to be low. When the adhesion becomes low, the element may peel off or bubbles may be generated due to long-term use, especially in a harsh environment such as an environment exposed to high temperature and humidity or light irradiation, and the optical characteristics of the scattered state and the transparent state may be affected. It is easy to cause a drop.
From the above points, it is an object of the present invention to provide a liquid crystal display element that exhibits good optical characteristics, has high adhesion between the liquid crystal layer and electrodes, and further reduces the driving voltage of the liquid crystal display element. To do. In particular, it is an object of the present invention to provide a liquid crystal display element capable of suppressing peeling of an element, generation of bubbles, and deterioration of optical characteristics even in a harsh environment exposed to high temperature and high humidity or light irradiation for a long time.

（Ｘ^１は下記式［１−ａ］〜式［１−ｊ］を示す。Ｘ^２は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｘ^３は単結合又は−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）を示す。Ｘ^４は単結合、−Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｘ^５はベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる２価の環状基、又はステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシ基又はフッ素原子で置換されていてもよい。Ｘ^６は単結合、−Ｏ−、−ＣＨ_２−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｘ^７はベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシ基又はフッ素原子で置換されていてもよい。Ｘ^８は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシ基又は炭素数１〜１８のフッ素含有アルコキシ基を示す。Ｘｍは０〜４の整数を示す。）

（Ｘ^Ａは水素原子又はベンゼン環を示す。）

（Ｙ^Ａは水素原子又はベンゼン環を示す。）As a result of diligent research to achieve the above object, the present inventor has completed the present invention having the following gist.
That is, the present invention has a liquid crystal layer containing a liquid crystal and a polymerizable compound arranged between a pair of substrates provided with electrodes and cured by irradiating ultraviolet rays, and at least one of the substrates. A liquid crystal display element having a resin film on the surface, which is in a scattered state when no voltage is applied and becomes transparent when a voltage is applied.
The liquid crystal has a positive dielectric anisotropy, the liquid crystal composition contains a compound represented by the following formula [1], and the resin film has the following formulas [2-a] to [2]. A liquid crystal display device characterized by being obtained from a resin composition containing a polymer having at least one structure selected from the group consisting of 2-i].

(X ¹ represents the following formulas [1-a] to [1-j]. X ² is a single bond, -O-, -NH-, -N (CH ₃ )-, -CH ₂ O-,-. It indicates CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- or -OCO-. X ³ is a single bond _{or-(CH 2} ) _a- (a is. X ⁴ represents a single bond, -O-, -OCH _2- , -COO- or -OCO-. X ⁵ is a group consisting of a benzene ring, a cyclohexane ring and a heterocycle. A divalent cyclic group selected from the above, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and any hydrogen atom on the cyclic group has an alkyl group having 1 to 3 carbon atoms and a carbon number of carbon atoms. It may be substituted with an alkoxy group of 1 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. X ⁶ is 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 a benzene ring, a cyclohexane ring and a heterocycle, and these cyclic groups. Any hydrogen atom on the group can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or fluorine. It may be substituted with an atom. X ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Indicates a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Xm indicates an integer of 0 to 4.)

(X ^A indicates a hydrogen atom or a benzene ring.)

^{(Y A} represents a hydrogen atom or a benzene ring.)

According to the present invention, it is possible to obtain a liquid crystal display element that exhibits good optical characteristics, has high adhesion between the liquid crystal layer and electrodes, and further reduces the driving voltage of the liquid crystal display element. In particular, it is a liquid crystal display element capable of suppressing peeling of the element, generation of bubbles, and deterioration of optical characteristics even in a harsh environment exposed to high temperature and high humidity or light irradiation for a long time. Therefore, the element of the present invention can be used for a liquid crystal display for the purpose of display, a dimming window for controlling light blocking and transmission, an optical shutter element, and the like.

The mechanism by which the liquid crystal display element having the above-mentioned excellent characteristics can be obtained by the present invention is not necessarily clear, but it is presumed as follows.
The liquid crystal composition used in the present invention contains a liquid crystal having positive dielectric anisotropy, a polymerizable compound, and a compound represented by the above formula [1] (also referred to as a specific compound). Certain compounds have a site of rigid structure such as a benzene ring or a cyclohexane ring, and a portion of the polymerization reaction by ultraviolet rays represented by X ¹ in the formula [1]. Therefore, when such a specific compound is included in the liquid crystal composition, the portion of the rigid structure of the specific compound enhances the vertical orientation of the liquid crystal, promotes the drive of the liquid crystal when a voltage is applied, and lowers the drive voltage of the liquid crystal display element. it can. Further, since the sites of X ¹ in the formula [1] is reacted with a polymerizable compound, it is possible to maintain the polymer network dense state.

Further, the resin film used for the liquid crystal display element is a polymer having at least one structure (also referred to as a specific structure) selected from the group consisting of the above formulas [2-a] to [2-i] (also referred to as a specific structure). It is also obtained from a resin composition containing a specific polymer).
These specific structures photoreact with the reactive groups of the polymerizable compound in the liquid crystal composition in the step of irradiating ultraviolet rays, which is the step of manufacturing the liquid crystal display element, and the adhesion between the liquid crystal layer and the resin film is strong. It will be something like that. Further, since the resin film is obtained from a resin composition containing a specific polymer having a specific structure, it is considered that the adhesion to the electrode is higher than that of the liquid crystal layer made of a low molecular weight polymerizable compound.
From the above points, the liquid crystal display element using the liquid crystal composition and the resin film in the present invention has good optical characteristics, high adhesion between the liquid crystal layer and the electrodes, and further, the driving voltage of the liquid crystal display element is low. Become. In particular, it is a normal type device that can suppress peeling of the device, generation of bubbles, and deterioration of optical characteristics even in a harsh environment exposed to high temperature and high humidity or light irradiation for a long time.

The liquid crystal composition in the present invention has a liquid crystal, a polymerizable compound, and a specific compound represented by the above formula [1].
As the liquid crystal, a nematic liquid crystal, a smectic liquid crystal or a cholesteric liquid crystal can be used. Among them, in the present invention, it has a positive dielectric anisotropy. Further, from the viewpoint of low voltage drive and scattering characteristics, it is preferable that the dielectric constant has a large anisotropy and the refractive index has a large anisotropy. Further, as the liquid crystal, two or more kinds of liquid crystals can be mixed and used according to the respective physical property values of the phase transition temperature, the dielectric anisotropy and the refractive index anisotropy.
In order to drive a liquid crystal display element as an active element such as a TFT (Thin Film Transistor), it is required that the electric resistance of the liquid crystal is high and the voltage retention rate (also referred to as VHR) is high. Therefore, it is preferable to use a fluorine-based or chlorine-based liquid crystal having high electrical resistance and whose VHR is not lowered by active energy rays such as ultraviolet rays.

Further, the liquid crystal display element can be made into a guest host type element by dissolving a dichroic dye in the liquid crystal composition. In this case, an element that absorbs (scatters) when no voltage is applied and becomes transparent when a voltage is applied can be obtained. Further, in this liquid crystal display element, the direction (direction of orientation) of the director of the liquid crystal changes by 90 degrees depending on the presence or absence of voltage application. Therefore, this liquid crystal display element can obtain higher contrast than the conventional guest-host type element that switches between random orientation and vertical orientation by utilizing the difference in absorption characteristics of the dichroic dye. Further, in the guest host type device in which the dichroic dye is dissolved, the liquid crystal becomes colored when it is oriented in the horizontal direction and becomes opaque only in the scattered state. Therefore, as the voltage is applied, it is possible to obtain an element that switches from the colored opacity when no voltage is applied to the colored transparent and colorless transparent states.

The polymerizable compound in the liquid crystal composition is for forming a curable resin by a polymerization reaction by irradiation with ultraviolet rays at the time of producing 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 if it is a polymer, it is necessary to have a site that undergoes a polymerization reaction by irradiation with ultraviolet rays. As the polymerizable compound, it is preferable to use a liquid crystal composition containing the polymerizable compound from the viewpoint of handling the liquid crystal composition, that is, suppressing the increase in viscosity of the liquid crystal composition and the solubility in the liquid crystal.
The polymerizable compound is not particularly limited as long as it is dissolved in the liquid crystal, but it is necessary that a part or the whole of the liquid crystal composition has a temperature at which the liquid crystal phase is exhibited when the polymerizable compound is dissolved in the liquid crystal. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is sufficient that the liquid crystal display element is visually confirmed and the entire inside of the element has substantially uniform transparency and scattering characteristics.

The polymerizable compound may be any compound that is polymerized by ultraviolet rays, and at that time, the polymerization may proceed in any reaction form to form a curable resin. Specific reaction types include radical polymerization, cationic polymerization, anionic polymerization and polyaddition reaction.
Among them, the reaction type of the polymerizable compound is preferably radical polymerization from the viewpoint of the optical characteristics of the liquid crystal display element. At that time, as the polymerizable compound, the following radical type polymerizable compound or an oligomer thereof can be used. Further, as described above, a polymer obtained by polymerizing these polymerizable compounds can also be used.
Specific examples of the radical-type polymerizable compound or its oligomer include the radical-type polymerizable compound described on pages 69 to 71 of International Publication No. 2015/146987.

The ratio of the radical-type polymerizable compound or its oligomer used is preferably 70 to 150 parts by mass with respect 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, it is 80 to 110 parts by mass. Further, the radical type polymerizable compound may be used alone or in combination of two or more depending on each property.
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 introduced into the liquid crystal composition for the purpose of promoting radical polymerization of the polymerizable compound. Is preferable.
Specific examples thereof include radical initiators described on pages 71-72 of International Publication No. 2015/146987.

The ratio of the radical initiator used is preferably 0.01 to 20 parts by mass with respect 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, it is 0.05 to 10 parts by mass. Further, the radical initiator may be used alone or in combination of two or more, depending on each property.
The specific compound is a compound represented by the above formula [1].

Wherein ^[1], X 1 ~X ⁸ and Xm is as defined above, among others respectively, preferably from below.
X ¹ is the formula [1-a], Formula [1-b], Formula [1-c], Formula [1-d], wherein [1-e] or formula [1-f] are preferred. More preferred are formulas [1-a], formulas [1-b], formulas [1-c] or formulas [1-e]. The most preferable is the formula [1-a] or the formula [1-b].
X ² is preferably single bond, -O-, -CH ₂ O-, -CONH-, -COO- or -OCO-. More preferred are single bonds, -O-, -COO- or -OCO-.

X ³ is preferably single bond or − (CH ₂ ) _a − (a is an integer of 1 to 10). More preferred is − (CH ₂ ) _a − (a is an integer of 1-10).
X ⁴ is preferably single bond, -O- or -COO-. More preferred is -O-.
X ⁵ is preferably a benzene ring, a cyclohexane ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms. More preferably, it is a divalent organic group having 17 to 51 carbon atoms and having a benzene ring or a steroid skeleton.
X ⁶ is preferably single bond, -O-, -COO- or -OCO-. More preferred are single bonds, -COO- or -OCO-.
X ⁷ is preferably a benzene ring or a cyclohexane ring.
X ⁸ is 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 is preferable.
Xm is preferably an integer of 0 to 2.

A preferred combination of ^X 1 to X ⁸ and Xm in formula [1] are shown in Table 1-9 below. In Tables 1 to 9, a represents an integer of 1 to 10.

Among them, (1-3a) to (1-8a), (1-11a) to (1-24a), (1-27a) to (1-36a), (1-39a), (1-40a). , (1-43a) to (1-48a), (1-51a) to (1-64a), (1-67a) to (1-76a), (1-79a), (1-80a), ( 1-83a) to (1-88a), (1-91a) to (1-104a), (1-107a) to (1-116a), (1-119a), (1-120a), (1- 123a), (1-124a), (1-129a), (1-130a), (1-133a), (1-134a), (1-137a), (1-138a), (1-141a). , (1-142a), (1-145a), (1-146a) or combinations of (1-149a) to (1-172a) are preferred.

More preferred are (1-3a) to (1-8a), (1-11a), (1-12a), (1-15a) to (1-18a), (1-21a), (1- 22a), (1-27a) to (1-30a), (1-33a), (1-34a), (1-39a), (1-40a), (1-43a) to (1-48a). , (1-51a), (1-52a), (1-55a) to (1-58a), (1-61a), (1-62a), (1-67a) to (1-70a), ( 1-73a), (1-74a), (1-79a), (1-80a), (1-83a) to (1-88a), (1-91a), (1-92a), (1- 95a) to (1-98a), (1-101a), (1-102a), (1-107a) to (1-110a), (1-113a), (1-114a), (1-119a). , (1-120a), (1-123a), (1-124a), (1-129a), (1-130a), (1-133a), (1-134a), (1-137a), ( 1-138a), (1-141a), (1-142a), (1-145a), (1-146a) or a combination of (1-149a) to (1-172a).

Most preferred are (1-3a) to (1-8a), (1-15a) to (1-18a), (1-29a), (1-30a), (1-43a) to (1-). 48a), (1-55a) to (1-58a), (1-69a), (1-70a), (1-83a) to (1-88a), (1-95a) to (1-98a). , (1-109a), (1-110a), (1-123a), (1-124a), (1-133a), (1-134a), (1-141a), (1-142a), ( It is a combination of 1-149a) to (1-152a) or (1-161a) to (1-172a).

Ｘ^ａは、−Ｏ−又は−ＣＯＯ−を示す。Ｘ^ｂは、炭素数１〜１２のアルキル基を示す。ｐ１は、１〜１０の整数を示す。ｐ２は、１又は２の整数を示す。More specific specific compounds include compounds represented by the following formulas [1a-1] to [1a-11], and it is preferable to use these.

X ^a represents -O- or -COO-. 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.

Ｘ^ｃは、単結合、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｘ^ｄは、炭素数１〜１２のアルキル基又はアルコキシ基を示す。ｐ３は、１〜１０の整数を示す。ｐ４は、１又は２の整数を示す。

X ^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.

Ｘ^ｅは、−Ｏ−又は−ＣＯＯ−を示す。Ｘ^ｆは、ステロイド骨格を有する炭素数１７〜５１の２価の有機基を示す。Ｘ^ｇは、炭素数１〜１２のアルキル基又は炭素数２〜１８のアルケニル基を示す。ｐ５は、１〜１０の整数を示す。

X ^e indicates -O- or -COO-. X ^f represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms. 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 used is preferably 0.1 to 30 parts by mass with respect 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, it is 0.5 to 20 parts by mass. The most preferable is 1 to 10 parts by mass. Further, the specific compound may be used alone or in combination of two or more depending on each property.

As a method for preparing the liquid crystal composition, a method of adding a single or a mixture of a plurality of kinds of polymerizable compounds and a specific compound to the liquid crystal, or a method of preparing a liquid crystal to which a specific compound is added in advance and then singly or a plurality of kinds thereof. A method of adding the polymerizable compound of the above can be mentioned.
When a plurality of types of polymerizable compounds are used, they can be heated depending on the solubility of the polymerizable compounds when they are mixed. The temperature at that time is preferably less than 100 ° C. The same applies to the case where the polymerizable compound and the specific compound are mixed, and the case where the liquid crystal and the specific compound are mixed.

<Resin composition>
The resin film is obtained from a resin composition containing a polymer having a specific structure of the formulas [2-a] to [2-i].
As the specific structure, the above-mentioned formulas [2-a] to [2-c], formula [2-e], formula [2-h] or formula [2-i] are preferable. More preferred are formulas [2-a], formulas [2-b], formulas [2-h] or formulas [2-i].
The specific polymer having a specific structure is not particularly limited, but at least one selected from the group consisting of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. Seed polymers are preferred. More preferred are polyimide precursors, polyimides or polysiloxanes.

When a polyimide precursor or a polyimide (generally referred to as a polyimide-based polymer) is used as the specific polymer, they are preferably a polyimide precursor or a polyimide obtained by reacting a diamine component with a tetracarboxylic acid component.
The polyimide precursor has a structure of the following formula [A].

R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ and A ⁴ represent 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 two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic dianhydride compound, or a tetra. Examples thereof include a carboxylic acid dialkyl ester compound and a tetracarboxylic dianalkyl ester dihalide compound.

Ｒ^１及びＲ^２は、式［Ａ］で定義したものと同じである。The polyimide polymer of the following formula [D] can be obtained relatively easily by using the tetracarboxylic dianhydride of the following formula [B] and the diamine of the following formula [C] as raw materials. A polyamic acid having a structural formula of a repeating unit or a polyimide obtained by imidizing the polyamic acid is preferable.

R ¹ and R ² are the same as those defined by the formula [A].

Ｒ^１及びＲ^２は、式［Ａ］で定義したものと同じである。

R ¹ and R ² are the same as those defined by the formula [A].

Further, in the polymer of the formula [D] obtained above by a usual synthetic method, ^{an alkyl group having 1 to 8 carbon atoms of A 1} and A ^{2 in} the formula [A] and an alkyl group having 1 to 8 carbon atoms in the formula [A] are added. Alkyl groups or acetyl groups having 1 to 5 carbon atoms of A ³ and A ^{4 can also be introduced.}
As a method for introducing a specific structure into a polyimide-based polymer, it is preferable to use a diamine having a specific structure as a part of a raw material. In particular, it is preferable to use a diamine having the structure of the following formula [2] (also referred to as a specific diamine).

Y ¹ is a single bond, -O-, -NH-, -N (CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) Indicates CO-, -COO- or -OCO-. Of these, single bonds, -O-, -CH ₂ O-, -CONH-, -COO- or -OCO- are preferable. More preferred are single bonds, -O-, -CH ₂ O- or -COO-.
Y ² represents an organic group having 6 to 24 carbon atoms having a single bond, an alkylene group having 1 to 18 carbon atoms, or a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen on these cyclic groups. The atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. May be good. Of these, a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is preferable. More preferred are single bonds or alkylene groups with 1-12 carbon atoms.

Y ³ is a single bond, -O-, -NH-, -N (CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) Indicates CO-, -COO- or -OCO-. Of these, single bonds, -O-, -COO- or -OCO- are preferable. More preferred are single bonds or -OCO-.
Y ⁴ represents a structure selected from the group consisting of the above formulas [2-a] to [2-i]. Of these, formulas [2-a] to [2-e], formulas [2-h] or formulas [2-i] are preferable. More preferred are formulas [2-a], formulas [2-b], formulas [2-d], formulas [2-e] or formulas [2-i]. Most preferred are formulas [2-a], formulas [2-b] or formulas [2-i]. Ym represents an integer of 1 to 4. Of these, 1 or 2 is preferable.

式［２ａ］中、Ｙは前記式［２］を示す。また、式［２］におけるＹ^１〜Ｙ^４及びＹｍの詳細及び好ましい組み合わせは、前記式［２］の通りである。
Ｙｎは１〜４の整数を示す。なかでも、１が好ましい。As the specific diamine, it is preferable to use the diamine of the following formula [2a].

In the formula [2a], Y represents the above formula [2]. Further, details and preferred combinations of ^Y 1 to Y ⁴ and Ym in the formula [2] are the same as in the formula [2].
Yn represents an integer of 1 to 4. Of these, 1 is preferable.

ｎ１は、１〜１２の整数を示す。More specific specific diamines include the following formulas [2a-1] to [2a-12], and it is preferable to use these.

n1 represents an integer of 1 to 12.

ｎ２は０〜１２の整数を示す。ｎ３は、２〜１２の整数を示す。
なかでも、式［２ａ−１］、式［２ａ−２］、式［２ａ−５］〜式［２ａ−７］、式［２ａ−１１］又は式［２ａ−１２］が好ましい。より好ましいのは、式［２ａ−５］〜式［２ａ−７］、式［２ａ−１１］又は式［２ａ−１２］である。
特定ジアミンの使用割合は、ジアミン成分全体に対し１０〜７０モル％が好ましい。より好ましいのは、２０〜６０モル％である。また、特定ジアミンは、各特性に応じて、１種類又は２種類以上を混合して使用できる。

n2 represents an integer from 0 to 12. n3 represents an integer of 2 to 12.
Of these, formulas [2a-1], formulas [2a-2], formulas [2a-5] to [2a-7], formulas [2a-11] or formulas [2a-12] are preferable. More preferred are formulas [2a-5] to [2a-7], formulas [2a-11] or formulas [2a-12].
The ratio of the specific diamine used is preferably 10 to 70 mol% with respect to the entire diamine component. More preferably, it is 20 to 60 mol%. Further, as the specific diamine, one type or a mixture of two or more types can be used depending on each characteristic.

As the diamine component for producing the polyimide-based polymer, it is preferable to use the diamine of the following formula [3a] (also referred to as the second diamine).

ａは０〜４の整数を示す。なかでも、０又は１が好ましい。
ｂは０〜４の整数を示す。なかでも、０又は１が好ましい。
Ｗ^Ａ及びＷ^Ｂは、炭素数１〜１２のアルキル基を示す。
Ｗ^Ｃは炭素数１〜５のアルキル基を示す。W represents the following formulas [3-a] to [3-d].
Wm represents an integer of 1 to 4. Of these, 1 is preferable.

a represents an integer from 0 to 4. Of these, 0 or 1 is preferable.
b represents an integer from 0 to 4. Of these, 0 or 1 is preferable.
W ^A and ^{W B} is 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 second diamine include the following.
For example, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, In addition to 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and 3,5-diaminobenzoic acid, diamines of the following formulas [3a-1] and [3a-2] are used. Can be mentioned.

Among them, 2,4-diaminophenol, 3,5-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 preferred. More preferred are 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid or formula [3a-1].

As the diamine component for producing the polyimide-based polymer, diamines other than the diamines of the formulas [2a] and [3a] (also referred to as other diamines) can be used.
Specifically, other diamine compounds described on pages 27 to 30 of WO2015 / 012368 and diamine compounds of formulas [DA1] to [DA14] described on pages 30 to 32 of the same publication. Can be mentioned. In addition, other diamines may be used alone or in admixture of two or more depending on each characteristic.

Ｚは下記式［４ａ］〜式［４ｌ］を示す。Examples of the tetracarboxylic acid component for producing a polyimide-based polymer include the tetracarboxylic dianhydride of the following formula [4], its tetracarboxylic acid derivative tetracarboxylic acid, the tetracarboxylic acid dihalide compound, and the tetracarboxylic acid. It is preferable to use a dialkyl ester compound or a tetracarboxylic diandialkyl ester dihalide compound (all of which are also collectively referred to as a specific tetracarboxylic acid component).

Z represents the following formulas [4a] to [4l].

Ｚ^Ａ〜Ｚ^Ｄは、水素原子、メチル基、塩素原子又はベンゼン環を示す。Ｚ^Ｅ及びＺ^Ｆは、水素原子又はメチル基を示す。

Z ^{A to} Z ^D represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z ^E and ^{Z F} is a hydrogen atom or a methyl group.

As Z in the formula [4], 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] are preferable. .. More preferred are formulas [4a], formulas [4e], formulas [4f], formulas [4g], formulas [4k] or formulas [4l]. Particularly preferred are formulas [4a], formulas [4e], formulas [4f], formulas [4g] or formulas [4l].

The ratio of the specific tetracarboxylic acid component used is preferably 1 mol% or more based on the total tetracarboxylic acid component. More preferably, it is 5 mol% or more. Particularly preferred is 10 mol% or more. Most preferred is 10-90 mol%.

In the present invention, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide-based polymer. Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalides compounds, dicarboxylic acid dialkyl ester compounds and dialkyl ester dihalide compounds.
Specifically, other tetracarboxylic acid components described on pages 34 to 35 of International Publication No. WO2015 / 012368 can be mentioned.
The specific tetracarboxylic acid component and other tetracarboxylic acid components can be used alone or in admixture of two or more, depending on each property.

The method for synthesizing the polyimide polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. Specifically, the method described on pages 35 to 36 of International Publication No. WO2015 / 012368 can be mentioned.
The reaction between the diamine component and the tetracarboxylic acid component is usually carried out in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent used at that time is not particularly limited as long as it dissolves the produced polyimide precursor.

Specifically, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidi Non etc. can be mentioned. 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] may be used. it can.

Ｄ^１及びＤ^２は炭素数１〜３のアルキル基を示す。Ｄ^３は炭素数１〜４のアルキル基を示す。

D ¹ and D ² represent alkyl groups having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms.

Further, these may be used alone or in combination. Further, even if the solvent does not dissolve the polyimide precursor, it may be mixed with the above solvent and used as long as the produced polyimide precursor does not precipitate. Further, since the water content in the organic solvent inhibits the polymerization reaction and further causes the produced polyimide precursor to be hydrolyzed, it is preferable to use a dehydrated and dried organic solvent.
Polyimide is a polyimide obtained by ring-closing a polyimide precursor. In this polyimide, the ring closure rate (also referred to as imidization rate) of an amic acid group does not necessarily have to be 100%, and it depends on the application and purpose. Can be prepared arbitrarily. Of these, 30 to 80% is preferable from the viewpoint of solubility of the polyimide-based polymer in a solvent. More preferred is 40-70%.

The molecular weight of the polyimide-based polymer is Mw (weight average molecular weight) measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the resin film obtained from the polymer, the workability at the time of forming the resin film, and the coating film property. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
When polysiloxane is used as the specific polymer, polysiloxane obtained by polycondensing the alkoxysilane of the following formula [A1], or the alkoxysilane of the formula [A1] and the alkoxysilane of the following formula [A2] are polycondensed. It is preferable to use the polysiloxane obtained by.

Ａ^１は前記式［２−ａ］〜式［２−ｉ］からなる群から選ばれる構造を有する炭素数２〜１２の有機基を示す。なかでも、式［２−ａ］〜式［２−ｅ］、式［２−ｈ］又は式［２−ｉ］が好ましい。より好ましいのは、式［２−ａ］、式［２−ｂ］、式［２−ｄ］、式［２−ｅ］又は式［２−ｉ］である。最も好ましいのは、式［２−ａ］、式［２−ｂ］又は式［２−ｉ］である。
Ａ^２は水素原子又は炭素数１〜５のアルキル基であり、水素原子又は炭素数１〜３のアルキル基が好ましい。Ａ^３は炭素数１〜５のアルキル基であり、炭素数１〜３のアルキル基が好ましい。ｍは１又は２の整数であり、１が好ましい。ｎは０〜２の整数である。ｐは０〜３の整数であり、１〜３の整数が好ましく、２又は３の整数がより好ましい。ｍ＋ｎ＋ｐは４である。Alkoxysilane of formula [A1]:

A ¹ represents an organic group having 2 to 12 carbon atoms having a structure selected from the group consisting of the above formulas [2-a] to [2-i]. Of these, formulas [2-a] to [2-e], formulas [2-h] or formulas [2-i] are preferable. More preferred are formulas [2-a], formulas [2-b], formulas [2-d], formulas [2-e] or formulas [2-i]. Most preferred are formulas [2-a], formulas [2-b] or formulas [2-i].
A ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. A ³ is an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable. m is an integer of 1 or 2, preferably 1. n is an integer from 0 to 2. p is an integer of 0 to 3, preferably an integer of 1 to 3, and 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) propylmethacrylate, 3 -(Trimethoxysilyl) propylacrylate or 3- (trimethoxysilyl) propylmethacrylate, and it is preferable to use these.
The alkoxysilane of the formula [A1] can be used alone or in admixture of two or more depending on each characteristic.

Ｂ^１は水素原子又は炭素数１〜５のアルキル基であり、水素原子又は炭素数１〜３のアルキル基が好ましい。
Ｂ^２は炭素数１〜５のアルキル基であり、炭素数１〜３のアルキル基が好ましい。ｎは０〜３の整数である。Alkoxysilane of formula [A2]:

B ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
B ² is an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable. n is an integer from 0 to 3.

Specific examples of the alkoxysilane of the formula [A2] include the specific example of the alkoxysilane of the formula [2c] described on pages 24 to 25 of WO2015 / 008846.
In addition, examples of the alkoxysilane in which n is 0 in the formula [A2] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. As the alkoxysilane of the formula [A2], it is preferable to use these alkoxysilanes.
The alkoxysilane of the formula [A2] can be used alone or in combination of two or more, depending on each characteristic.

The polysiloxane-based polymer is a polysiloxane obtained by polycondensing the alkoxysilane of the formula [A1], or a polysiloxane obtained by polycondensing the alkoxysilane of the formula [A1] with the alkoxysilane of the formula [A2]. Is preferably used.
Of these, polysiloxane obtained by polycondensing a plurality of types of alkoxysilanes is preferable from the viewpoint of polycondensation reactivity and solubility of the polysiloxane-based polymer in a solvent. That is, it is preferable to use a polysiloxane obtained by polycondensing two types of alkoxysilanes of the formula [A1] and the formula [A2]. At that time, the proportion of the alkoxysilane of the formula [A1] is preferably 1 to 70 mol%, more preferably 1 to 50 mol%, and particularly preferably 1 to 30 mol% of all the alkoxysilanes.
The proportion of the alkoxysilane of the formula [A2] used is preferably 30 to 99 mol%, more preferably 50 to 99 mol%, and particularly preferably 70 to 99 mol% of all the alkoxysilanes.

The method for polycondensing the polysiloxane-based polymer is not particularly limited. Specifically, the method described on pages 26 to 29 of International Publication No. WO2015 / 008846 can be mentioned.
When multiple types of alkoxysilanes of the formulas [A1] and [A2] are used in the polycondensation reaction for producing a polysiloxane-based polymer, even if the reaction is carried out using a mixture of a plurality of types of alkoxysilanes in advance, a plurality of types may be used. The reaction may be carried out with the addition of seed alkoxysilanes in sequence.

In the present invention, the solution of the polysiloxane-based polymer obtained by the above method may be used as it is as the specific polymer, or if necessary, the solution of the polysiloxane-based polymer obtained by the above method may be used. It may be concentrated, diluted by adding a solvent, or replaced with another solvent to be used as a specific polymer.
The solvent used for dilution (also referred to as an addition solvent) may be a solvent used for the polycondensation reaction or another solvent. The additive solvent is not particularly limited as long as the polysiloxane-based polymer is uniformly dissolved, and one type or two or more types can be arbitrarily selected. Examples of such an additive solvent include a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and an ester solvent such as methyl acetate, ethyl acetate and ethyl lactate, in addition to the solvent used for the polycondensation reaction. ..

Further, when a polysiloxane-based polymer and a polymer other than the polysiloxane-based polymer are used as the specific polymer, before mixing the other polymer with the polysiloxane-based polymer, during the polycondensation reaction of the polysiloxane-based polymer. It is preferable to distill off the generated alcohol under normal pressure or reduced pressure.
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. At that time, two or more kinds of specific polymers can be used.
All of the polymer components in the resin composition may be specific polymers, or other polymers may be mixed. At that time, the content of the other polymer is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the specific polymer. More preferably, it is 1 to 10 parts by mass. Examples of other polymers include the above-mentioned polymers having no specific structure.

The content of the solvent in the resin composition can be appropriately selected from the viewpoint of the coating method of the resin composition and the desired film thickness. Among them, the content of the solvent in the resin composition is preferably 50 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. Of these, 60 to 99% by mass is preferable. More preferably, it is 65 to 99% by mass.
The solvent used in the resin composition is not particularly limited as long as it is a solvent that dissolves the specific polymer. Among them, when the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in a solvent is low, the following (Also also referred to as solvent A) is preferably used.

For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methylethylketone. , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone and the like. Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. Further, these may be used alone or in combination.

When the specific polymer is an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, cellulose or a polysiloxane, the specific polymer is a polyimide precursor, a polyimide, a polyamide or a polyester, and the specific polymer of these specific polymers. When the solubility in a polymer is high, the following polymer (also referred to as solvent B) can be used.
Specific examples of the solvent B include the solvent B described on pages 58 to 60 of WO2014 / 171493. Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone or the above formula [D1]. The formula [D3] is preferable.

When these solvents B are used, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone of the solvents A are used in combination for the purpose of improving the coatability of the resin composition. It is preferable to use it. More preferred is γ-butyrolactone.
Since these solvents B can enhance the coating film property and surface smoothness of the resin film when the resin composition is applied, when a polyimide precursor, a polyimide, a polyamide or a polyester is used as the specific polymer, the above-mentioned It is preferable to use it in combination with solvents A. At that time, the solvent B is preferably 1 to 99% by mass of the total solvent contained in the resin composition. Of these, 10 to 99% by mass is preferable. More preferably, it is 20 to 95% by mass.

The resin composition contains a compound having an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group or a lower alkoxyalkyl group (collectively, specific crosslinkability) in order to increase the film strength of the resin film. It is also preferable to introduce a compound). At that time, it is necessary to have two or more of these groups in the compound.
Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include the crosslinkable compound having an epoxy group or an isocyanate group described on pages 63 to 64 of WO2014 / 171493.
Specific examples of the crosslinkable compound having an oxetane group include crosslinkable compounds of formulas [4a] to [4k] published in WO2011 / 132751 on pages 58 to 59.

Specific examples of the crosslinkable compound having a cyclocarbonate group include the crosslinkable compounds of formulas [5-1] to [5-42] published in WO2012 / 014898 on pages 76 to 82.
Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group are described in WO2014 / 171493 on pages 65-66 of the melamine derivative or benzoguanamine derivative, and WO2011 / 132751 of WO2011 / 132751. Examples thereof include crosslinkable compounds of formulas [6-1] to [6-48], which are described on pages 62 to 66.

The content of the specific crosslinkable compound in the resin composition is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. In order for the cross-linking reaction to proceed and the desired effect to be exhibited, 0.1 to 50 parts by mass is more preferable with respect to 100 parts by mass of all the polymer components, and 1 to 30 parts by mass is most preferable. ..
It is preferable to introduce at least one generator (also referred to as a specific generator) selected from a photoradical generator, a photoacid generator, and a photobase generator into the resin composition.

Specific examples of the specific generator include the specific generator described on pages 54 to 56 of International Publication No. 2014/171493. Among them, it is preferable to use a photoradical generator as the specific generator from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the electrode.
As the resin composition, a compound that improves the uniformity of the film thickness and the surface smoothness of the resin film when the resin composition is applied can be used as long as the effects of the present invention are not impaired. Further, a compound or the like that improves the adhesion between the resin film and the substrate can also be used.

Examples of the compound for improving the uniformity of the film thickness and the surface smoothness of the resin film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specific examples thereof include surfactants described on page 67 of WO2014 / 171493. The proportion of the polymer used is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all the polymer components contained in the resin composition. More preferably, it is 0.01 to 1 part by mass.

Specific examples of the compound for improving the adhesion between the resin film and the substrate include the compounds described on pages 67 to 69 of WO2014 / 171493. Further, the ratio of use thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of all the polymer components contained in the resin composition. More preferably, it is 1 to 20 parts by mass.
In addition to the compounds other than the above, a dielectric or a conductive substance for which the purpose of changing the electrical properties such as the permittivity and conductivity of the resin film may be added to the resin composition.

<Method of manufacturing resin film and liquid crystal display element>
The substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, and a film thereof. Can be used. In particular, when used for a dimming window or the like, a plastic substrate or film is preferable. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, or the like is formed. .. Further, in the case of a reflective liquid crystal display element, if only one substrate is used, a substrate on which a metal such as a silicon wafer or aluminum or a dielectric multilayer film is formed can be used.

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 both substrates have a resin film.
The method for applying the resin composition is not particularly limited, but industrially, there are screen printing, offset printing, flexographic printing, inkjet method, dip method, roll coater method, slit coater method, spinner method, spray method and the like. It can be appropriately selected according to the type of substrate and the target thickness of the resin film.

After the resin composition is applied onto the substrate, the temperature is 30 to 300 ° C. depending on the type of substrate and the solvent used for the resin composition by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. The temperature is preferably. More preferably, the temperature is 30 to 250 ° C., and the solvent can be evaporated to form a resin film. In particular, when a plastic substrate is used as the substrate, it is preferable to treat it at a temperature of 30 to 150 ° C.
If the thickness of the resin film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the element may decrease. Therefore, the thickness is preferably 5 to 500 nm. More preferably, it is 10 to 300 nm, and particularly preferably 10 to 250 nm.

The liquid crystal composition used for the liquid crystal display element is the liquid crystal composition as described above, but a spacer for controlling the electrode gap (also referred to as a gap) of the liquid crystal display element can be introduced therein.
The method for 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 is prepared, and four pieces of the substrate on one side are coated with a sealant except for a part, and then the surface of the resin film is inside. In this way, an empty cell is produced by laminating the substrate on the other side. Then, a method of injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied to obtain a liquid crystal composition injection cell can be mentioned. Further, when a plastic substrate or a film is used as the substrate, a pair of substrates on which a resin film is formed is prepared, and a liquid crystal composition is applied onto one of the substrates by an ODF (One Drop Filling) method or an inkjet method. A method of dropping and then laminating the substrate on the other side to obtain a liquid crystal composition injection cell can be mentioned. In the liquid crystal display element of the present invention, since the adhesion between the liquid crystal layer and the electrodes is high, it is not necessary to apply a sealant to the four pieces of the substrate.

The gap of the liquid crystal display element can be controlled by the spacer or the like. Examples of the method include a method of introducing a spacer of a desired size into the liquid crystal composition, a method of using a substrate having a column spacer of the desired size, and the like. Further, when a plastic or film substrate is used as the substrate and the substrates are laminated by lamination, the gap can be controlled without introducing a spacer.
The size of the gap of the liquid crystal display element is preferably 1 to 100 μm. More preferably, it is 1 to 50 μm. Particularly preferred is 2 to 30 μm. If the gap is too small, the contrast of the liquid crystal display element decreases, and if it is too large, the drive voltage of the element increases.

The liquid crystal display element is obtained by curing the liquid crystal composition to form a liquid crystal layer. The liquid crystal composition is cured by irradiating the liquid crystal composition injection cell with ultraviolet rays. Examples of the light source of the ultraviolet irradiation device used at that time include a metal halide lamp and a high-pressure mercury lamp. The wavelength of ultraviolet rays is preferably 250 to 400 nm. Of these, 310 to 370 nm is preferable. Moreover, you may perform heat treatment after irradiating with ultraviolet rays. The temperature at that time is preferably 20 to 120 ° C. More preferably, it is 30 to 100 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
The abbreviations used below are as follows.
<Specific compound>

<Polymerizable compound>
R1: IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
R2: 2-Hydroxyethyl methacrylate R3: KAYARAD FM-400 (manufactured by Nippon Kayaku Co., Ltd.)
R4: EBECRYL 230 (manufactured by Daicel Ornex)
R5: Calends MT PE1 (manufactured by Showa Denko)
<Photoradical initiator>
P1: IRGACURE 184 (manufactured by BASF)
<LCD>

L1: MLC-3018 (manufactured by Merck & Co., Ltd.)
<Specific diamine>

＜その他のジアミン＞

<Second diamine>

<Other diamines>

＜ポリシロキサン系重合体を作製するためのモノマー＞
Ｅ１：３−メタクリロキシプロピルトリメトキシシラン
Ｅ２：テトラエトキシシラン<Specific tetracarboxylic acid component>

<Monomer for producing polysiloxane-based polymer>
E1: 3-Methyloxypropyltrimethoxysilane E2: Tetraethoxysilane

＜特定発生剤＞

<Specific crosslinkable compound>

<Specific generator>

<Solvent>
NMP: N-Methyl-2-pyrrolidone γ-BL: γ-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

"Measurement of molecular weight of polyimide polymer"
The measurement was carried out as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex).
Column temperature: 50 ° C
Eluent: N, N'-dimethylformamide ( _{30 mmol / L (liter) of lithium bromide-hydrate (LiBr · H 2} O) as an additive, 30 mmol of phosphoric acid / anhydrous crystal (o-phosphoric acid) / L, tetrahydrofuran (THF) is 10 ml / L)
Flow velocity: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about) 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidization rate of polyimide-based polymer"
20 mg of polyimide powder is placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku Co., Ltd.)) and deuterated dimethyl sulfoxide (DMSO-d 6,0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and ultrasonically applied to completely dissolve. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Datum). The imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid appearing near 9.5 ppm to 10.0 ppm. It was calculated by the following formula using the integrated value.
Imidization rate (%) = (1-α · x / y) × 100
(X is the integrated proton peak value derived from the NH group of amic acid, y is the integrated peak value of the reference proton, and α is the reference proton for one NH group proton of the amic acid in the case of polyamic acid (imidization rate is 0%). It is the number ratio of.)

"Synthesis of polyimide 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) and reacted at 80 ° C. for 4 hours. After that, D1 (3.60 g, 18.4 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 20% by mass. .. The number average molecular weight (also referred to as Mn) of this polyamic acid was 18,500, and the weight average molecular weight (also referred to as Mw) was 66,500.

<Synthesis example 2>
NMP was added to the polyamic acid solution (1) (30.0 g) obtained by the method of Synthesis Example 1 to dilute it to 6% by mass, and then acetic anhydride (3.60 g) and pyridine (2.30 g) were used as imidization catalysts. ) Was added, and the mixture was reacted at 60 ° C. for 1.5 hours. This reaction solution was put into methanol (450 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (2). The imidization ratio of this polyimide was 51%, Mn was 16,100, and Mw was 43,500.

<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 ° C. for 6 hours, and then D1 (1.50 g). , 7.65 mmol) and γ-BL (7.90 g) were added and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 20% by mass. The Mn of this polyamic acid was 10,500 and the Mw was 34,700.

<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) and 6 at 60 ° C. After the time reaction, D1 (2.00 g, 10.2 mmol) and γ-BL (9.37 g) were added and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (4) having a resin solid content concentration of 20% by mass. ) Was obtained. The Mn of this polyamic acid was 10,900 and the Mw was 35,100.

<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 added to γ-BL (19. After mixing in 2 g) and reacting at 60 ° C. for 6 hours, D1 (1.90 g, 9.69 mmol) and γ-BL (9.58 g) were added and reacted at 40 ° C. for 8 hours to obtain a resin solid content. A polyamic acid solution (5) having a concentration of 20% by mass was obtained. The Mn of this polyamic acid was 13,200, and the Mw was 45,100.

<Synthesis example 6>
NMP (30.4 g) for 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). The mixture was mixed in and reacted at 40 ° C. for 12 hours to obtain a polyamic acid solution (6) having a resin solid content concentration of 20% by mass. The Mn of this polyamic acid was 15,800 and the Mw was 52,500.

<Synthesis example 7>
NMP was added to the polyamic acid solution (7) (30.0 g) obtained by the method of Synthesis Example 7 to dilute it to 6% by mass, and then acetic anhydride (3.60 g) and pyridine (2.35 g) were used as imidization catalysts. ) Was added, and the mixture was reacted at 60 ° C. for 2 hours. This reaction solution was put into methanol (450 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (7). The imidization ratio of this polyimide was 48%, Mn was 14,600, and Mw was 40,900.

<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) and reacted at 80 ° C. for 4 hours before D1 (2.50 g, 12). .8 mmol) and NMP (9.27 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (8) having a resin solid content concentration of 20% by mass. The Mn of this polyamic acid was 22,800, and the Mw was 70,200.

<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) and 6 at 60 ° C. After the time reaction, D1 (2.00 g, 10.2 mmol) and γ-BL (7.45 g) were added and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (9) having a resin solid content concentration of 20% by mass. ) Was obtained. The Mn of this polyamic acid was 14,800 and the Mw was 43,200.

Table 10 shows the polyimide-based polymer obtained in the synthesis example.
In Table 10, * 1 represents a polyamic acid.

"Synthesis of polysiloxane-based polymers"
<Synthesis Example 10>
EC (29.0 g), E1 (8.80 g) and E2 (36.2 g) are mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of alkoxysilane monomer. did. A solution prepared by mixing EC (14.5 g), water (11.0 g) and oxalic acid (0.50 g) as a catalyst in advance with this solution was added dropwise at 25 ° C. over 30 minutes. Further, the mixture was stirred at 25 ° C. for 30 minutes. Then, it was heated using an oil bath and refluxed for 30 minutes, and then allowed to cool to obtain a polysiloxane solution (1) having _{a SiO 2 equivalent concentration of 12% by mass.}

<Synthesis Example 11>
ECS (29.0 g), E1 (11.5 g) and E2 (33.5 g) are mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of alkoxysilane monomer. did. A solution prepared by mixing ECS (14.0 g), water (11.0 g) and oxalic acid (0.50 g) as a catalyst in advance with this solution was added dropwise at 25 ° C. over 30 minutes. Further, the mixture was stirred at 25 ° C. for 30 minutes. Then, it was heated using an oil bath and refluxed for 30 minutes, and then allowed to cool to obtain a polysiloxane solution (2) having _{a SiO 2 equivalent concentration of 12% by mass.}

Table 11 shows the polysiloxane-based polymers obtained in Synthesis Examples 10 and 11.

"Manufacturing of resin composition"
<Synthesis Example 12>
NMP (12.1 g) was added to the polyamic acid solution (1) (5.40 g) obtained by the method of Synthesis Example 1, and the mixture was stirred at 25 ° C. for 1 hour. Then, BCS (10.4 g) and PB (2.98 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain 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 dissolved by stirring at 70 ° C. for 24 hours. Then, BCS (4.32 g) and PB (8.64 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain 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 ° C. for 6 hours to obtain a resin. The composition (3) was obtained.
<Synthesis Example 15>
Γ-BL (0.15 g), PGME (22.9 g) and K2 (0.042 g) were added to the polyamic acid solution (3) (3.00 g) obtained by the method of Synthesis Example 3 at 25 ° C. Stirring for 6 hours gave the resin composition (4).

<Synthesis Example 16>
Γ-BL (0.15 g), PGME (22.9 g), K2 (0.042 g) and N1 (0.018 g) were added to the polyamic acid solution (3) (3.00 g) obtained by the method of Synthesis Example 3. ) Was added, and the mixture was stirred at 25 ° C. for 6 hours to obtain a resin composition (5).
<Synthesis example 17>
Γ-BL (3.97 g), PGME (19.1 g) and K1 (0.018 g) were added to the polyamic acid solution (4) (3.00 g) obtained by the method of Synthesis Example 4 at 25 ° C. Stirring for 6 hours gave the resin composition (6).

<Synthesis Example 18>
Γ-BL (0.15 g), PGME (22.9 g), K2 (0.060 g) and N1 (0.030 g) were added to the polyamic acid solution (5) (3.00 g) obtained by the method of Synthesis Example 5. ) Was added, and the mixture was stirred at 25 ° C. for 6 hours to obtain a resin composition (7).
<Synthesis Example 19>
NMP (13.6 g) was added to the polyamic acid solution (6) (5.40 g) obtained by the method of Synthesis Example 6, and the mixture was stirred at 25 ° C. for 1 hour. Then, PB (11.9 g) and K2 (0.054 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain 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 dissolved by stirring at 70 ° C. for 24 hours. Then, BCS (2.88 g), PB (10.1 g), K2 (0.084 g) and N1 (0.036 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a resin composition (9). ..
<Synthesis example 21>
EC (3.93 g) and PB (12.7 g) are added to the polysiloxane solution (1) (10.0 g) obtained by the method of Synthesis Example 10 and stirred at 25 ° C. for 6 hours to prepare a resin composition. (10) was obtained.

<Synthesis Example 22>
ECS (4.78 g), PGME (25.2 g) and N1 (0.036 g) were added to the polysiloxane solution (2) (10.0 g) obtained by the method of Synthesis Example 11 and at 25 ° C. for 6 hours. Stirring gave the resin composition (11).
<Synthesis Example 23>
NMP (12.1 g) was added to the polyamic acid solution (8) (5.40 g) obtained by the method of Synthesis Example 8, and the mixture was stirred at 25 ° C. for 1 hour. Then, BCS (10.4 g) and PB (2.98 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain 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 ° C. for 6 hours to obtain a resin. The composition (13) was obtained.

Table 12 shows aspects of the resin compositions obtained in Synthetic Examples 12 to 24. The resin compositions obtained in these Synthesis Examples 12 to 24 were all uniform solutions with no abnormalities such as turbidity and precipitation.
In Table 12, the numerical values in parentheses for the specific crosslinkable compound and the specific generator added to the resin composition indicate the content with respect to 100 parts by mass of the specific polymer.

<Preparation 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) are mixed and stirred at 60 ° C. for 2 hours to obtain a polymerizable compound. The solution of was prepared. On the other hand, S1 (0.20 g) and L1 (5.80 g) were mixed and stirred at 25 ° C. for 2 hours to prepare a liquid crystal containing a specific compound. Then, the prepared solution of the polymerizable compound, the liquid crystal containing the specific compound, and P1 (0.10 g) were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal composition (A).

<Preparation 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) are mixed and stirred at 60 ° C. for 2 hours to obtain a polymerizable compound. The solution of was prepared. On the other hand, S1 (0.80 g) and L1 (5.20 g) were mixed and stirred at 25 ° C. for 2 hours to prepare a liquid crystal containing a specific compound. Then, the prepared solution of the polymerizable compound, the liquid crystal containing the specific compound, and P1 (0.10 g) were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal composition (B).

<Preparation 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) are mixed and stirred at 60 ° C. for 2 hours to obtain a polymerizable compound. The solution of was prepared. On the other hand, S2 (0.40 g) and L1 (5.60 g) were mixed and stirred at 25 ° C. for 2 hours to prepare a liquid crystal containing a specific compound. Then, the prepared solution of the polymerizable compound, the liquid crystal containing the specific compound, and P1 (0.10 g) were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal composition (C).

<Preparation 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) are mixed and stirred at 60 ° C. for 2 hours to obtain a polymerizable compound. The solution of was prepared. On the other hand, S1 (0.20 g), S2 (0.10 g) and L1 (5.70 g) were mixed and stirred at 25 ° C. for 2 hours to prepare a liquid crystal containing a specific compound. Then, the prepared solution of the polymerizable compound, the liquid crystal containing the specific compound, and P1 (0.10 g) were mixed and stirred at 25 ° C. 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) are mixed and stirred at 60 ° C. for 2 hours to obtain a polymerizable compound. The solution of was prepared. Then, the prepared solution of the polymerizable compound, L1 (6.00 g) and P1 (0.10 g) were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal composition (E).

"Manufacturing of liquid crystal display element (glass substrate)"
The resin composition obtained by the method of the above synthesis example was pressure-filtered with a membrane filter having a pore diameter of 1 μm. The obtained solution was spin-coated on the ITO surface of a glass substrate with an ITO electrode (length: 100 mm, width: 100 mm, thickness: 0.7 mm) washed with pure water and IPA (isopropyl alcohol), and placed on a hot plate. Heat treatment was carried out at 100 ° C. for 5 minutes at 210 ° C. for 30 minutes in a heat circulation type clean oven to obtain an ITO substrate with a resin film having a film thickness of 100 nm. Two ITO substrates with this resin film were prepared, and a spacer having a particle size of 15 μm (trade name: Micropearl, manufactured by Sekisui Chemical Co., Ltd.) was applied to the resin film surface of one of the substrates. Then, the liquid crystal compositions (A) to (E) are dropped onto the resin film surface coated with the spacer of the substrate by the ODF (One Drop Filling) method, and then the resin film surfaces of the other substrate face each other. The liquid crystal display element before processing was obtained. In Comparative Example 1, a spacer having a particle size of 20 μm was applied to 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. The liquid crystal display element of the above was manufactured.
^{A metal halide lamp having an illuminance of 20 mW / cm 2} was used for the liquid crystal display element before this treatment to cut wavelengths of 350 nm or less, and ultraviolet irradiation was performed with an irradiation time of 60 seconds. As a result, a liquid crystal display element (glass substrate) was obtained.

"Manufacturing of liquid crystal display element (plastic substrate)"
The resin composition obtained by the method of the above synthesis example was pressure-filtered with a membrane filter having a pore diameter of 1 μm. The obtained solution was applied to the ITO surface of a PET substrate with an ITO electrode (length: 150 mm, width: 150 mm, thickness: 0.1 mm) washed with pure water with a bar coater, and then placed in a heat circulation oven. Heat treatment was performed at 120 ° C. for 2 minutes to obtain an ITO substrate with a resin film having a film thickness of 100 nm. Two ITO substrates with the resin film were prepared, and the 20 μm spacer was applied to the resin film surface of one of the substrates. Then, the liquid crystal compositions (A) to (E) are dropped onto the resin film surface coated with the spacer of the substrate by the ODF (One Drop Filling) method, and then the resin film surfaces of the other substrate face each other. The liquid crystal display element before processing was obtained. When the liquid crystal composition was dropped and bonded by the ODF method, a glass substrate was used as a support substrate for the PET substrate with an ITO electrode. Then, the support substrate was removed before irradiating with ultraviolet rays. Further, in Comparative Example 2, a spacer having a particle size of 20 μm was applied to 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, and before the treatment. The liquid crystal display element of the above was manufactured.
The liquid crystal display element before this treatment was irradiated with ultraviolet rays by the same method as in the above-mentioned "Production of liquid crystal display element (glass substrate)" to obtain a liquid crystal display element (plastic substrate).

"Evaluation of optical characteristics (scattering characteristics and transparency)"
This evaluation was performed by measuring the haze (cloudiness) of the liquid crystal display element (glass substrate and plastic substrate) in the voltage-free state (0V) and the voltage-applied state (AC drive: 10V to 50V). At that time, Haze was measured with a haze meter (HZ-V3, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K 7136. In this evaluation, it was determined that the higher the haze in the no-voltage state, the better the scattering characteristics, and the lower the haze in the voltage-applied state, the better the transparency.
In addition, as a stability test of the liquid crystal display element in a high temperature and high humidity environment, measurement was also performed after storing the liquid crystal display element in a constant temperature and humidity chamber having a temperature of 80 ° C. and a humidity of 90% RH for 24 hours. Specifically, the smaller the change in Haze after storage in the constant temperature and humidity chamber with respect to the initial Haze, the better the evaluation.
Furthermore, as a stability test of the liquid crystal display element against light irradiation, observation after irradiation with ultraviolet rays ^{of 5 J / cm 2 in} terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite Co., Ltd.) is also possible. went. Specifically, the smaller the change in Haze after UV irradiation with respect to the initial Haze, the better the evaluation.
Tables 13 to 15 show the measurement results of Haze at the initial stage, after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after irradiation with ultraviolet rays (ultraviolet rays).

"Evaluation of adhesion between liquid crystal layer and resin film (resin film and electrode)"
In this evaluation, the liquid crystal display elements (glass substrate and plastic substrate) are stored in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH for 24 hours, and the peeling of the liquid crystal display elements and the presence or absence of air bubbles are confirmed. (As a stability test of the liquid crystal display element in a high temperature and high humidity environment). Specifically, the device in which the device is not peeled (the liquid crystal layer and the resin film or the resin film and the electrode are peeled off) and the device in which no bubbles are generated are excellent in this evaluation. (Good display in the table). At that time, in Examples 3 to 5, in addition to the above-mentioned standard test, as an emphasis test, confirmation was also performed after storage for 72 hours in a constant temperature and humidity chamber having a temperature of 80 ° C. and a humidity of 90% RH. The evaluation method is the same as described above.
In addition, confirmation was also performed after irradiating the liquid crystal display element with ultraviolet rays ^{of 5 J / cm 2 in} terms of wavelength 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite Co., Ltd.) (liquid crystal display element). As a stability test against light irradiation). Specifically, those in which the element was not peeled off and those in which no bubbles were generated in the element were considered to be excellent in this evaluation (good display in the table).
Tables 16 to 18 summarize the results (adhesion) of the adhesion between the liquid crystal layer and the resin film (resin film and electrode) at the initial stage, after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet rays (ultraviolet rays). Shown.

<Examples 1 to 15 and Comparative Examples 1 to 6>
Using any of the resin compositions (1) to (13) obtained by the method of the synthesis example and the liquid crystal compositions (A) to (E), a liquid crystal display element is produced by the above method. The optical characteristics (scattering characteristics and transparency) were evaluated, and the adhesion between the liquid crystal layer and the resin film (resin film and electrode) was evaluated. At that time, in Examples 1, Example 2, Examples 11 to 13, Comparative Example 1, Comparative Example 3 and Comparative Example 5, a liquid crystal display element was manufactured and evaluated using a glass substrate, and Examples 3 to 3 to 10. In Examples 14 and 15, Comparative Examples 2, 4 and 6, a plastic substrate was used. Further, as described above, in Comparative Examples 1 and 2, a liquid crystal display element was 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, in addition to the above standard test, as an emphasis test, a constant temperature and humidity chamber having a temperature of 80 ° C. and a humidity of 90% RH. Evaluation was also performed when the product was stored in the container for 72 hours (other conditions are the same as those described above).

＊１：素子内に少量の気泡が見られた。
＊２：素子内に気泡が見られた（＊１よりも多い）。
＊３：素子内に多くの気泡が見られた（＊２よりも多い）。

* 1: A small amount of air bubbles were found in the device.
* 2: Bubbles were found in the device (more than * 1).
* 3: Many bubbles were found in the device (more than * 2).

As can be seen from the above, the liquid crystal display element of the example obtained good optical characteristics as compared with the comparative example. That is, in the initial stage, the Haze in the state where no voltage was applied was low, and the change in the Haze after storage in the constant temperature and humidity chamber and after irradiation with ultraviolet rays was small. In particular, the examples had lower Haze at lower voltages than the comparative examples. That is, in the embodiment, the driving voltage of the liquid crystal display element became low.
Further, in the examples, peeling of the liquid crystal display element and generation of air bubbles were not observed even after storage in the constant temperature and humidity chamber and after irradiation with ultraviolet rays.
These results were the same even when a plastic substrate was used as the substrate of the liquid crystal display element. Specifically, it is a comparison between Example 1 and Comparative Examples 1, 3 and 5, and a comparison between Example 3 and Comparative Examples 2, 4 and 6.

Further, when the specific crosslinkable compound was introduced into the resin composition, the number of bubbles generated in the liquid crystal display element was small, especially after being stored in the constant temperature and humidity chamber for a long time performed in the emphasis test. Specifically, it is a comparison between Example 3 and Example 4.
Further, when a specific generator was introduced into the resin composition in addition to the specific crosslinkable compound, no bubbles were generated in the liquid crystal display element in the emphasis test. Specifically, it is a comparison between Example 4 and Example 5 in the comparison under the same conditions.

The liquid crystal display element of the present invention can be suitably used for a normal type element that is in a scattered state when no voltage is applied and is in a transparent state when a voltage is applied. This element can be used for a liquid crystal display for display purposes, a dimming window for controlling light blocking and transmission, an optical shutter element, and the like, and the substrate of this normal type element is made of plastic. A substrate can be used.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-052663 filed on March 20, 2018 are cited here as disclosure of the specification of the present invention. , Incorporate.

Claims (15)

A liquid crystal composition containing a liquid crystal and a polymerizable compound arranged between a pair of substrates provided with electrodes has a liquid crystal layer cured by irradiating with ultraviolet rays, and at least one of the substrates has a resin film. A liquid crystal display element that becomes a scattered state when no voltage is applied and becomes transparent when a voltage is applied.
The liquid crystal has positive dielectric anisotropy and
The liquid crystal composition contains a compound represented by the following formula [1] and contains.
A liquid crystal display device characterized in that 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]. ..

(X ¹ represents a structure selected from the group consisting of the following formulas [1-a] to [1-j]. X ² is 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 is a single bond or-(CH) ₂ ) _a − (a is an integer of 1 to 15). X ⁴ indicates a single bond, −O −, −OCH ₂ −, −COO− or −OCO−. X ⁵ indicates a benzene ring or cyclohexane. A divalent cyclic group selected from the group consisting of a ring and a heterocycle, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and any hydrogen atom on the cyclic group has 1 to 1 carbon atoms. It may be substituted with an alkyl group of 3, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. X ⁶ is a single bond. Indicates a bond, -O-, -CH _2- , -OCH _2- , -CH ₂ O-, -COO- or -OCO-. X ⁷ is a ring selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle. Any hydrogen atom on these cyclic groups represents a group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. It may be substituted with a fluorine-containing alkoxy group or a fluorine atom. X ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, and a carbon number of carbon atoms. Indicates an alkoxy group of 1 to 18 or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Xm indicates an integer of 0 to 4).

(X ^A indicates a hydrogen atom or a benzene ring.)

^{(Y A} represents a hydrogen atom or a benzene ring.) The liquid crystal display element according to claim 1, wherein the content of the compound represented by the formula [1] is 0.5 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal. ^{X 1} in the formula [1] is the formula [1-a], the formula [1-b], the formula [1-c], the formula [1-d], the formula [1-e] or the formula [1]. -F] The liquid crystal display element according to claim 1 or 2. The liquid crystal display device 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].

(X ^a represents -O- or -COO-. 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. Show.)

X ^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.

X ^e indicates -O- or -COO-. X ^f represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms. 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. Claim 1 in which the resin composition comprises at least one polymer selected from the group consisting of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. The liquid crystal display element according to any one of the items to 4. The liquid crystal display according to claim 5, wherein the resin composition contains a polyimide precursor or a polyimide obtained by using a diamine having a structure of the formulas [2-a] to [2-i] as a part of a raw material. element. The liquid crystal display element according to claim 6, wherein the diamine is a diamine having the structure of the following formula [2].

Y ¹ is a single bond, -O-, -NH-, -N (CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) Indicates CO-, -COO- or -OCO-. Y ² represents an organic group having 6 to 24 carbon atoms having a single bond, an alkylene group having 1 to 18 carbon atoms, or a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen on these cyclic groups. The atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. May be good. Y ³ is a single bond, -O-, -NH-, -N (CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) Indicates CO-, -COO- or -OCO-. Y ⁴ represents a structure selected from the group consisting of the above formulas [2-a] to [2-i]. Ym represents an integer of 1 to 4. The liquid crystal display element according to claim 7, wherein the diamine is a diamine of the following formula [2a].

Y represents the above formula [2]. n represents an integer of 1 to 4. The liquid crystal display device according to any one of claims 5 to 8, wherein the resin composition contains a polyimide precursor or a polyimide obtained by using a tetracarboxylic dian component of the following formula [4] as a part of a raw material.

Z represents the following formulas [4a] to [4l].

Z ^{A to} Z ^D represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z ^E and ^{Z F} is a hydrogen atom or a methyl group. The resin composition is obtained by polysiloxane obtained by polycondensing the alkoxysilane of the following formula [A1], or by polycondensing the alkoxysilane of the formula [A1] with the alkoxysilane of the following formula [A2]. The liquid crystal display element according to claim 5, which contains polysiloxane.

A ¹ represents an organic group having 2 to 12 carbon atoms having a structure selected from the group consisting of the above formulas [2-a] to [2-i]. A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ³ represents 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 from 0 to 3. However, m + n + p is 4.

B ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. B ² represents an alkyl group having 1 to 5 carbon atoms. n represents an integer from 0 to 3. The liquid crystal display according to any one of claims 1 to 10, wherein the resin composition contains a compound having an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group. element. The resin composition includes 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and the following. The liquid crystal display element according to any one of claims 1 to 11, which contains at least one selected from the group consisting of solvents of the formulas [D1] to [D3].

D ¹ and D ² represent alkyl groups having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms. The invention according to any one of claims 1 to 12, wherein the resin composition contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. Liquid crystal display element. The liquid crystal display element according to any one of claims 1 to 13, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate. The liquid crystal display element according to any one of claims 1 to 14, wherein the liquid crystal display element is a dimming window or an optical shutter element.