TW202104317A - Resin composition, resin film and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a liquid crystal display element which lowers the drive voltage of the liquid crystal display element and achieves favorable optical properties. A transmission/scattering-type liquid crystal display element having a liquid crystal layer in which a liquid crystal composition, which contains a polymerizable compound and liquid crystals arranged between a pair of substrates which are equipped with electrodes, is cured by applying active energy rays and/or heat thereto, said liquid crystal display element also being equipped with a resin film on at least one of the substrates, being configured so as to be in a scattering state when voltage is not applied thereto and in a transmitting state when voltage is applied thereto, and being characterized in that the resin film is obtained using a resin composition which contains a polymer which has one or more structures selected from formulas [1-1] and [1-2]. The definitions of the symbols in the formulas are as disclosed in the description.

Description

Resin composition, resin film and liquid crystal display element

The present invention relates to a transmissive scattering type liquid crystal display element that is in a scattering state when no voltage is applied, and is in a transmissive state when voltage is applied.

As a liquid crystal display element, the TN (Twisted Nematic) mode has been put into practical use. In this mode, in order to use the optical rotation characteristics of the liquid crystal to perform light switching (switching), it is necessary to use a polarizing plate. When a polarizing plate is used, the light utilization efficiency becomes low.

As a liquid crystal display element that does not use a polarizing plate, there is an element that switches between the transmission state (also called the transparent state) and the scattering state of the liquid crystal. Generally speaking, it is known to use polymer dispersed liquid crystal (also called PDLC (Polymer Dispersed Liquid Crystal)) or polymer network liquid crystal (also called PNLC (Polymer Network Liquid Crystal)). In these liquid crystal display elements, a liquid crystal composition containing a polymerizable compound polymerized by ultraviolet rays is arranged between a pair of substrates equipped with electrodes, and the liquid crystal composition is cured by ultraviolet irradiation to form a liquid crystal and A composite of hardened polymer compounds (such as polymer networks). In this liquid crystal display element, the scattering state and the transmission state of the liquid crystal are controlled by voltage application. In a liquid crystal display element using PDLC or PNLC, when no voltage is applied, the liquid crystal system faces a random direction, so it becomes a turbid (scattering) state. When voltage is applied, the liquid crystal system aligns in the direction of the electric field, allowing light to pass through. A liquid crystal display element in a transmissive state (also known as a normal element). At this time, since the liquid crystal is random when no voltage is applied, there is no need for a liquid crystal alignment film or alignment treatment to align 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 (see Patent Documents 1 and 2). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3552328 [Patent Document 2] Japanese Patent No. 4630954

[The problem to be solved by the invention]

The polymerizable compound in the liquid crystal composition plays a role in forming a polymer network to obtain desired optical properties, and in improving the adhesion between the liquid crystal layer and the electrode. However, in order to achieve this, it is necessary to form a dense polymer network, so the driving of liquid crystal molecules to the voltage application is hindered. Therefore, the driving voltage of this element is higher than that of liquid crystal display elements such as TN mode.

From the above viewpoints, the object of the present invention is to provide a liquid crystal display element that exhibits good optical characteristics and the driving voltage of the liquid crystal display element becomes low. [Means to solve the problem]

As a result of intensive research in order to achieve the aforementioned object, the inventors have completed the present invention having the following gist. That is, a liquid crystal display element having a liquid crystal layer that is cured by applying at least one of active energy rays and heat to a liquid crystal composition containing a liquid crystal and a polymerizable compound arranged between a pair of substrates provided with electrodes, Moreover, a resin film is provided on at least one of the substrates, and further, a transmissive scattering type liquid crystal display element that becomes a scattering state when no voltage is applied and becomes a transparent state when a voltage is applied, and is characterized by The aforementioned resin film is obtained by using a resin composition containing a polymer having at least one structure (also referred to as a specific structure (1)) selected from the following formula [1-1] and formula [1-2] .

X ¹ represents a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-,- N(CH ₃ )CO-, -COO- or -OCO-. X ² represents a single bond or -(CH ₂ ) _b- (b is an integer of 1-15). X ³ represents a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group with 17 to 51 carbon atoms having a steroid skeleton. Any hydrogen atom on the aforementioned cyclic group is also It can be substituted by alkyl groups with 1 to 3 carbons, alkoxy groups with 1 to 3 carbons, fluorinated alkyl groups with 1 to 3 carbons, fluorine-containing alkoxy groups with 1 to 3 carbons, or fluorine atoms. X ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom on these cyclic groups can also be passed through an alkyl group with 1 to 3 carbons and a carbon number of 1 ~3 alkoxy group, fluorine-containing alkyl group with carbon number 1 to 3, fluorine-containing alkoxy group with carbon number 1 to 3 or fluorine atom substitution. Xn represents an integer from 0 to 4. X ⁶ represents alkyl with 1 to 18 carbons, alkenyl with 2 to 18 carbons, fluorinated alkyl with 1 to 18 carbons, alkoxy with 1 to 18 carbons, or fluorine with 1 to 18 carbons Alkoxy.

X ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-. X ⁸ represents an alkyl group with 8 to 22 carbons or a fluorinated alkyl group with 6 to 18 carbons. [Effects of Invention]

According to the present invention, it is possible to obtain a liquid crystal display element having good optical characteristics and a low driving voltage of the liquid crystal display element. According to the present invention, the mechanism why a liquid crystal display element having the above-mentioned excellent characteristics can be obtained is not clear, but it is roughly estimated as follows. The specific structure (1) has parts such as a benzene ring or a cyclohexane ring, or a long-chain alkyl group. Therefore, it is considered that the resin film obtained from the resin composition containing the resin film can promote the driving of the liquid crystal accompanied by the voltage application, so that the driving voltage of the liquid crystal display element is low. In addition, the structure of the aforementioned formula [1-1] is a rigid structure, so even if the amount used is small, the aforementioned effect can be obtained. Therefore, the hydrophobic structure on the resin film can be reduced, so the adhesion between the liquid crystal layer and the resin film in the liquid crystal display element can be increased, and the reliability of the liquid crystal display element can be improved. In this manner, a liquid crystal display element using a resin composition containing a polymer having a specific structure (1) becomes a liquid crystal display element having the aforementioned characteristics. Therefore, the liquid crystal display element of the present invention can be used in a liquid crystal display for display purposes, or a dimming window or shutter element for controlling the blocking and transmission of light.

＜Specific structure (1)＞

Specific structure (1). It is the structure of the aforementioned formula [1-1] or formula [1-2]. In formula [1-1], X ¹ to X ⁶ and Xn are as defined above, and in particular, the following ones are preferred. From the viewpoint of availability of raw materials or ease of synthesis, X ^{1 is} preferably a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O- or -COO -. More preferably, it is a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O- or -COO-. X ^{2 is} preferably a single bond or -(CH ₂ ) _b- (b is an integer of 1-10). From the viewpoint of ease of synthesis, X ^{3 is} preferably a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO-. More preferably, it is a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O- or -COO-. From the viewpoint of ease of synthesis, X ^{4 is} preferably an organic group with 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton. X ^{5 is} preferably a benzene ring or a cyclohexane ring. X ^{6 is} preferably an alkyl group with 1 to 18 carbons, a fluorine-containing alkyl group with 1 to 10 carbons, an alkoxy group with 1 to 18 carbons, or a fluorine-containing alkoxy group with 1 to 10 carbons. More preferably, it is an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons. Particularly preferred ones are alkyl groups with 1 to 9 carbons or alkoxy groups with 1 to 9 carbons. From the viewpoint of availability of raw materials or ease of synthesis, Xn is preferably 0 to 3. More preferably, it is 0~2.

The preferred combination of X ¹ to X ⁶ and Xn can be cited as (2-1) to (2) disclosed in Table 6 to Table 47 on pages 13 to 34 of International Publication WO2011/132751 (published on October 27, 2011) -629) The same combination. Furthermore, in the tables in the International Publication, X ¹ ~ X ⁶ in the present invention are represented by Y1 ~ Y6, Xn is represented by n, Y1 ~ Y6 are regarded as X ¹ ~ X ⁶ , and n is regarded as Xn . In addition, in the tables (2-605) to (2-629) disclosed in the above-mentioned International Publications, the organic groups with 17 to 51 carbon atoms having a steroid skeleton in the present invention are expressed as carbon having a steroid skeleton An organic group with a number of 12 to 25 and an organic group with a carbon number of 12 to 25 with a steroid skeleton are regarded as an organic group with a carbon number of 17 to 51 with a steroid skeleton.

Among them, especially (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2-315) , (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615) combination is better. Particularly best ones are (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606) ), (2-607)~(2-609), (2-611), (2-612) or (2-624).

In the formula [1-2], X ⁷ and X ⁸ are as defined above, and the following ones are particularly preferred.

X ^{7 is} preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO-. More preferably, it is a single bond, -O-, -CONH- or -COO-. X ^{8 is} preferably an alkyl group having 8 to 18 carbon atoms.

The specific structure (1) of the present invention, as described above, can reduce the driving voltage of the liquid crystal display element more efficiently, and it is preferable to use the structure of formula [1-1]. The specific structure (1) is preferably a form contained in the repeating unit constituting the polymer. The repeating unit including the specific structure (1) preferably contains 0.1-60 mol%, and more preferably 1-30 mol%, relative to the entire repeating unit constituting the polymer. ＜Specific structure (2)＞ The polymer in the present invention preferably further has at least one structure selected from the following formula [2-a] to formula [2-i] (also referred to as a specific structure (2)).

Y ^A represents a hydrogen atom or a benzene ring. Among them, formula [2-a] ~ formula [2-f] are particularly preferred. More preferably, it is formula [2-a] ~ formula [2-e]. From the viewpoint of the adhesion between the liquid crystal layer and the resin film, the formula [2-a], the formula [2-b], the formula [2-d], or the formula [2-e] are particularly preferred. Furthermore, the resin composition in the present invention preferably further contains a polymer having a specific structure (2). By using the specific structure (2), it can be considered that in the step of ultraviolet irradiation or heating in the production of liquid crystal display elements, it undergoes photoreaction with the reactive groups of the polymerizable compound in the liquid crystal composition, and the liquid crystal layer and the resin film are closely adhered Sex becomes a strong one. <Polymer> The polymer is not particularly limited, but it is preferably composed of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyimide, At least one polymer selected from polyester, cellulose and polysiloxane. More preferably, it is a polyimide precursor, polyimide or polysiloxane. When using polyimide precursors or polyimine (also collectively referred to as polyimide-based polymers) as the polymer, these are preferably polyimide obtained by reacting a diamine component with a tetracarboxylic acid component Amine precursor or polyimide.

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 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ and A ⁴ respectively 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 with two primary or secondary amine groups in the molecule. The tetracarboxylic acid component includes tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic dihalide compounds, and tetracarboxylic dihalides. Alkyl ester compound or dialkyl tetracarboxylic acid dihalide compound.

Since the polyimide-based polymer can be easily obtained by using the tetracarboxylic dianhydride of the following formula [B] and the diamine of the following formula [C] as raw materials, it preferably contains the following The polyimide of the structural formula of the repeating unit of formula [D] or the polyimide obtained by imidizing the polyimide.

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

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

In addition, the polymer of formula [D] obtained above can also be introduced into ^{the alkyl group of A 1} and A ² in the formula [A] with carbon numbers of 1 to 8, and the formula [A] Among them, A ³ and A ⁴ are alkyl or acetyl groups with 1 to 5 carbon atoms. The method of introducing the specific structure (1) into the polyimide-based polymer is preferably to use a diamine having the specific structure (1) as a part of the raw material. Among them, it is particularly preferable to use a diamine having at least one structure selected from the aforementioned formula [1-1] and formula [1-2] (also referred to as a specific diamine (1)).

It is particularly preferable to use the diamine of the following formula [1a].

X represents the aforementioned formula [1-1] or formula [1-2]. In addition, ^{the details of X 1} to X ⁶ and Xn in formula [1-1], and preferred combinations, are as described in formula [1-1], X ⁷ and X in formula [1-2] ^{The details of 8} and the preferred combination are as described in the aforementioned formula [1-2]. Xm represents an integer from 1 to 4. Among them, 1 or 2 is particularly preferred. The specific diamine (1) of the formula [1-1], specifically, the formula [2-1] to the formula [2] described on pages 15 to 19 of International Publication WO2013/125595 (published on August 29, 2013) -6], the diamine compound of formula [2-9] ~ formula [2-36]. Further, according to International Publication WO2013 / 125595 of the formula [2-1] to the formula [2-3], and R ₂ in the formula [2-4] to Formula [2-6] in the R _4, represents C1-C18 alkyl group, C1-C18 fluorine-containing alkyl group, C1-C18 alkoxy group or C1-C18 fluorine-containing alkoxy group. _{In addition, A 4} in the formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms. _{In addition, R 3 in} formula [2-4] to formula [2-6] represents -O-, -CH ₂ O-, -COO- or -OCO-.

Among them, the particularly preferred diamine is the formula [2-1] ~ formula [2-6], formula [2-9] ~ formula [2-13] or formula [2-22] described in International Publication WO2013/125595 ~ The diamine compound of formula [2-31]. From the viewpoint of the optical characteristics of the liquid crystal display element, the diamine of the following formula [1a-32] to formula [1a-41] is more preferable.

R ¹ and R ² each represent an alkyl group having 3 to 12 carbon atoms.

R ³ and R ⁴ each represent an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. From the viewpoint of the optical characteristics of the liquid crystal display element, the best one is the diamine of the aforementioned formula [1a-35] to formula [1a-37], formula [1a-40] or formula [1a-41]. The specific diamine (1) of the formula [1-2], specifically, the diamine compound of the formula [DA1] to the formula [DA11] described on page 23 of International Publication WO2013/125595 (published on August 29, 2013) . Furthermore, in the description of International Publication WO2013/125595, A ₁ in formula [DA1] to formula [DA5] represents an alkyl group with 8 to 22 carbons or a fluorine-containing alkyl group with 6 to 18 carbons. From the viewpoint of the optical properties of the liquid crystal display element and the adhesiveness of the liquid crystal layer and the resin film, the use ratio of the specific diamine (1) is preferably 0.1-60 mol% with respect to the total diamine component. More preferably, it is 1-30 mol%. In addition, the specific diamine (1) can be used alone or in combination of two or more according to each characteristic. In the method of introducing a specific structure (2) to a polyimide-based polymer, it is preferable to use a diamine having a specific structure (2) as a part of the raw material. It is particularly preferable to use a diamine having a structure of the following formula [2] (also referred to as a specific diamine (2)).

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-. Among them, a single bond, -O-, -CH ₂ O-, -CONH-, -COO- or -OCO- is particularly preferred. Due to the availability of raw materials or ease of synthesis, the more preferable one is a single bond, -O-, -CH ₂ O- or -COO-. Y ² represents a single bond, an alkylene group with 1 to 18 carbon atoms, or an organic group with 6 to 24 carbon atoms having a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and these cyclic groups Any hydrogen atom above can also be passed through an alkyl group with 1 to 3 carbons, an alkoxy group with 1 to 3 carbons, a fluorinated alkyl group with 1 to 3 carbons, and a fluorinated alkoxy group with 1 to 3 carbons. Or fluorine atom substitution. Among them, a single bond, an alkylene ring with 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is particularly preferred. From the viewpoint of the adhesion between the liquid crystal layer and the resin film, a single bond or an alkylene group having 1 to 12 carbon atoms is more preferable. 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-. Among them, a single bond, -O-, -COO- or -OCO- is particularly preferred. More preferably, it is a single bond or -OCO-. Y ⁴ represents at least one structure selected from the aforementioned formula [2-a] to formula [2-i]. Among them, formula [2-a] ~ formula [2-f] are particularly preferred. More preferably, it is formula [2-a] ~ formula [2-e]. From the viewpoint of the adhesion between the liquid crystal layer and the resin film, the formula [2-a], the formula [2-b], the formula [2-d], or the formula [2-e] are particularly preferred. Yn represents an integer from 1 to 4. Among them, 1 or 2 is particularly preferred.

The specific diamine (2) is preferably a diamine of the following formula [2a].

Y represents the structure of the aforementioned formula [2]. In addition, ^{the details of Y 1} to Y ⁴ and Yn in formula [2], and preferred combinations, are as described in formula [2]. Ym represents an integer from 1 to 4. Among them, 1 is particularly preferred.

More specific specific diamine (2) includes the following formula [2a-1] to formula [2a-12], and these are preferably used.

n1 represents an integer of 2-12.

n2 represents an integer of 0-12. n3 represents an integer of 2-12.

Among them, formula [2a-1], formula [2a-2], formula [2a-5] ~ formula [2a-7], formula [2a-11] or formula [2a-12] are particularly preferred. More preferably, it is the formula [2a-5]~the formula [2a-7], the formula [2a-11] or the formula [2a-12]. From the viewpoint of the optical properties of the liquid crystal display element and the adhesion between the liquid crystal layer and the resin film, the use ratio of the specific diamine (2) is preferably 5 to 70 mol% with respect to the total diamine component. More preferably, it is 10-60 mol%. In addition, the specific diamine (2) can be used alone or in combination of two or more according to each characteristic. In order to produce the polyimide-based polymer, the diamine component may also use diamines other than the specific diamine (1) and the specific diamine (2) (also referred to as other diamines).

Specifically, other diamine compounds described on pages 27 to 30 of International Publication WO2015/012368 (published on January 29, 2015), and formulas [DA1] to [DA14] described on pages 30 to 32 of the same publication ] The diamine compound. In addition, other diamines can be used singly or in combination of two or more according to their characteristics.

In the present invention, it is preferable to use both the specific diamine (1) and the specific diamine (2) from the viewpoint of the optical properties of the liquid crystal display element and the adhesion between the liquid crystal layer and the resin film. The tetracarboxylic acid component used to make the polyimide polymer is preferably the tetracarboxylic dianhydride of the following formula [3], or its derivatives such as tetracarboxylic acid, tetracarboxylic dihalide, tetracarboxylic acid Dialkyl acid or dialkyl tetracarboxylic acid dihalide (all are also collectively referred to as specific tetracarboxylic acid components).

Z represents any of the following formula [3a] to formula [3l].

Z ^A to Z ^D respectively represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z ^E and Z ^F each represent a hydrogen atom or a methyl group). Among them, Z in formula [3], from the viewpoint of ease of synthesis or ease of polymerization reactivity during polymer production, formula [3a], formula [3c], formula [3d], and formula [ 3e], formula [3f], formula [3g], formula [3k] or formula [3l]. More preferably, it is formula [3a], formula [3e], formula [3f], formula [3g], formula [3k] or formula [3l]. From the viewpoint of the optical characteristics of the liquid crystal display element, the formula [3a], the formula [3e], the formula [3f], the formula [3g] or the formula [3l] are particularly preferred. The usage ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to all the tetracarboxylic acid components. More preferably, it is 5 mol% or more, and particularly preferably, it is 10 mol% or more. From the viewpoint of the optical characteristics of the liquid crystal display element, the best one is 10 to 90 mol%.

In the polyimide-based polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used. Examples of other tetracarboxylic acid components include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, or dialkyl ester dihalide compounds shown below. Specifically, other tetracarboxylic acid components described on pages 34 to 35 of International Publication WO2015/012368 (publication on 2015.1.29) can be cited. The specific tetracarboxylic acid component and other tetracarboxylic acid components can be used alone or in combination of two or more according to their characteristics. The method of synthesizing the polyimide-based polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Specifically, the method described on pages 35 to 36 of International Publication WO2015/012368 (published on January 29, 2015) can be cited.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent used at this time is not particularly limited as long as it can dissolve the polyimide precursor produced.

Specifically, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-di Methyl acetamide, dimethyl sulfide or 1,3-dimethyl-2-imidazolidinone, etc. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D1 ]~ The solvent of formula [D3].

D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group with 1 to 4 carbon atoms. Moreover, these can be used individually or in mixture. Furthermore, even if it is a solvent that does not dissolve the polyimide precursor, it can be used by mixing it with the aforementioned solvent in a range where the generated polyimine precursor does not precipitate. In addition, the moisture in the organic solvent will hinder the polymerization reaction, thereby causing the resulting polyimide precursor to be hydrolyzed. Therefore, the organic solvent is preferably dehydrated and dried. In the polymerization reaction of the polyimide precursor, when the total mole number of the diamine component is 1.0, the total mole number of the tetracarboxylic acid component is preferably 0.8 to 1.2. When the total mole number of the tetracarboxylic acid component is less than 1.0, that is, when the total mole number of the tetracarboxylic acid component is less than the mole number of the diamine component, it becomes a structure in which the terminal of the polymer is an amine group. When it is greater than 1.0, That is, when the total number of moles of the tetracarboxylic acid component is greater than the number of moles of the diamine component, it is a structure in which the end of the polymer is carboxylic anhydride or dicarboxylic acid. In the present invention, due to the higher effect of the aforementioned specific compound, it is preferable that the total molar number of the tetracarboxylic acid component is greater than 1.0, that is, the total molar number of the tetracarboxylic acid component is greater than the molar number of the diamine component number. Specifically, when the total molar number of the diamine components is 1.0, the total molar number of the tetracarboxylic acid components is preferably 1.05 to 1.20.

Polyimine is obtained by ring-closing a polyimine precursor. In the polyimide, the ring-closure rate of the amide acid group (also referred to as the imidization rate) does not necessarily have to be 100%, and can be adjusted arbitrarily according to the application or purpose. Among them, from the viewpoint of the solubility of the polyimide-based polymer to the solvent, 30 to 80% is particularly preferred. The better is 40~70%.

When considering the strength of the resin film thus obtained, and the workability and coating properties of the resin film when it is formed, the molecular weight of the polyimide polymer is Mw (weight) measured by the GPC (Gel Permeation Chromatography) method (Average molecular weight), preferably 5,000 to 1,000,000. More preferably, it is 10,000~150,000. When polysiloxane is used as the polymer, it is preferable to use polysiloxane obtained by polycondensation of alkoxysilane of the following formula [A1], or to combine the alkoxysilane of the formula [A1] with the following formula [A2] and/or polysiloxane obtained by polycondensation of alkoxysilane of formula [A3] (also collectively referred to as polysiloxane polymer). Alkoxysilane of formula [A1]:

A ¹ represents the aforementioned formula [1-1] or formula [1-2]. In addition, ^{the details of X 1} to X ⁶ and Xn in formula [1-1], and preferred combinations, are as described in formula [1-1], X ⁷ and X in formula [1-2] ^{The details of 8} and the preferred combination are as described in the aforementioned formula [1-2]. Among them, it is possible to reduce the driving voltage of the liquid crystal display element more efficiently, and it is particularly preferable to use the structure of formula [1-1]. A ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group with 1 to 3 carbon atoms is particularly preferred. A ³ represents an alkyl group with 1 to 5 carbon atoms. Among them, from the viewpoint of the reactivity of polycondensation, an alkyl group having 1 to 3 carbon atoms is particularly preferred. m represents an integer of 1 or 2. Among them, from the viewpoint of ease of synthesis, 1 is particularly preferred. n represents an integer from 0 to 2. p represents an integer from 0 to 3. Among them, from the viewpoint of the reactivity of polycondensation, 1 to 3 are particularly preferred. More preferably, it is 2 or 3. m+n+p is 4.

Specific examples of the alkoxysilane of the formula [A1] include the alkane of the formula [2a-1] to the formula [2a-32] described on pages 17 to 21 of International Publication WO2015/008846 (published on January 22, 2015) Oxysilane. Among them, the alkoxysilanes of formula [2a-9] ~ formula [2a-21], formula [2a-25] ~ formula [2a-28] or formula [2a-32] in the same bulletin are particularly preferred. The alkoxysilane of the formula [A1] can be used alone or in combination of two or more according to its characteristics. Alkoxysilane of formula [A2]:

B ¹ means that it has at least one selected from vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacrylic acid group, acrylic acid group, urea group, and cinnamon group. base. Among them, from the viewpoint of easy availability, an organic group having a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a urea group is particularly preferred. More preferably, it is an organic group having a methacryl group, an acryl group or a urea group. B ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group with 1 to 3 carbon atoms is particularly preferred. B ³ represents an alkyl group with 1 to 5 carbon atoms. Among them, from the viewpoint of the reactivity of polycondensation, an alkyl group having 1 to 3 carbon atoms is particularly preferred. m represents an integer of 1 or 2. Among them, from the viewpoint of ease of synthesis, 1 is particularly preferred. n represents an integer from 0 to 2. p represents an integer from 0 to 3. Among them, from the viewpoint of the reactivity of polycondensation, 1 to 3 are particularly preferred. More preferably, it is 2 or 3. m+n+p is 4.

Specific examples of the alkoxysilanes of the formula [A2] include specific examples of the alkoxysilanes of the formula [2b] described on pages 21 to 24 of International Publication WO2015/008846 (2015.1.22 publication). Among them, especially allyl triethoxy silane, allyl trimethoxy silane, diethoxy methyl vinyl silane, dimethoxy methyl vinyl silane, triethoxy vinyl silane, vinyl Trimethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, 3-(triethoxysilyl) propyl methacrylate, 3-(trimethoxysilyl) propyl acrylate, methyl methacrylate 3-(trimethoxysilyl) propyl acrylate, 3-glycidoxypropyl (dimethoxy) methyl silane, 3-glycidoxy propyl (diethoxy) methyl silane, 3-glycidoxypropyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is preferred.

The alkoxysilane of the formula [A2] can be used in one kind or in combination of two or more kinds according to the characteristics.

Alkoxysilane of formula [A3]:

D ¹ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group with 1 to 3 carbon atoms is particularly preferred. D ² represents an alkyl group with 1 to 5 carbon atoms. Among them, from the viewpoint of the reactivity of polycondensation, an alkyl group having 1 to 3 carbon atoms is particularly preferred. n represents an integer from 0 to 3.

Specific examples of the alkoxysilanes of the formula [A3] include specific examples of the alkoxysilanes of the formula [2c] described on pages 24 to 25 of International Publication WO2015/008846 (2015.1.22 publication).

In addition, in the formula [A3], n is 0 alkoxysilane, including tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane, and the alkoxysilane of formula [A3] As the base silanes, these alkoxysilanes are preferably used.

The alkoxysilane of the formula [A3] can be used alone or in combination of two or more according to its characteristics. Polysiloxane polymer is a polysiloxane obtained by polycondensation of alkoxysilane of formula [A1], or alkoxysilane of formula [A1] with formula [A2] and/or formula [A3] ] Polysiloxane obtained by polycondensation of alkoxysilane. That is, the polysiloxane-based polymer is a polysiloxane obtained by polycondensing only an alkoxysilane of formula [A1], and two types of alkoxysilanes of formula [A1] and formula [A2] are polymerized. Polysiloxane obtained by condensation, polysiloxane obtained by polycondensation of two kinds of alkoxysilanes of formula [A1] and formula [A3], and formula [A1], formula [A2] and formula [A3] Any one of the three polysiloxanes obtained by polycondensation of alkoxysilanes.

Among them, from the viewpoint of the reactivity of polycondensation or the solubility of polysiloxane-based polymers in solvents, polysiloxanes obtained by polycondensation of plural kinds of alkoxysilanes are particularly preferred. That is, it is preferable to use polysiloxane obtained by polycondensation of two types of alkoxysilanes of formula [A1] and formula [A2], and polysiloxanes of two types of alkoxysilanes of formula [A1] and formula [A3]. Polysiloxane obtained by condensation, and any one of polysiloxane obtained by polycondensation of three alkoxysilanes of formula [A1], formula [A2] and formula [A3].

When multiple types of alkoxysilanes are used in the production of polysiloxane-based polymers, the use ratio of the alkoxysilanes of formula [A1] is preferably 0.1-60 mol% among all alkoxysilanes. . More preferably, it is 1-30 mol%. In addition, the use ratio of the alkoxysilane of the formula [A2] is preferably 5 to 70 mol% among all the alkoxysilanes. More preferably, it is 10-60 mol%. Furthermore, the use ratio of the alkoxysilane of the formula [A3] is preferably 1 to 99 mol% among all the alkoxysilanes. More preferably, it is 1 to 80 mole%. The method of polycondensing the polysiloxane-based polymer is not particularly limited. Specifically, the method described on pages 26 to 29 of International Publication WO2015/008846 (published on January 22, 2015) can be cited.

In the polycondensation reaction of making polysiloxane-based polymers, when multiple types of alkoxysilanes of formula [A1], formula [A2] or formula [A3] are used, multiple types of alkoxysilanes can be used The mixture obtained by mixing in advance is reacted, and the reaction may be performed while adding plural kinds of alkoxysilanes in sequence. In the present invention, the solution of the polysiloxane polymer obtained by the aforementioned method can be used directly as the polymer, or the solution of the polysiloxane polymer obtained by the aforementioned method can be concentrated and diluted by adding a solvent as needed. , Or replaced with other solvents, used as a polymer.

The solvent used in the dilution (also referred to as the additive solvent) may be the solvent used in the polycondensation reaction or other solvents. The solvent is not particularly limited as long as it dissolves the polysiloxane-based polymer uniformly, and one type or two or more types can be arbitrarily selected. In addition to the solvent used in the aforementioned polycondensation reaction, additional solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as methyl acetate, ethyl acetate, and ethyl lactate. Solvents, etc.

Furthermore, when a polysiloxane-based polymer and other polymers are used as the polymer, it is preferable to preliminarily mix the polysiloxane-based polymer with the other polymers. The alcohol produced during the polycondensation reaction is distilled off under normal pressure or reduced pressure. ＜Resin composition＞ The resin composition contains a polymer having a specific structure (1), preferably a solution for forming a resin film, and is a solution containing a polymer having a specific structure (1) and a solvent. At this time, two or more types of polymers having the specific structure (1) can be used. The concentration of the polymer having the specific structure (1) in the resin composition is preferably 10-100% by mass, more preferably 20-100% by mass, and particularly preferably 30-100% by mass.

The polymer components contained in the resin composition may all be polymers having a specific structure (1). However, in the present invention, as mentioned above, it is preferable to have both a specific structure (1) and a specific structure (2). By. At this time, one polymer having both the specific structure (1) and the specific structure (2) may be used, or the polymer having the specific structure (1) and the polymer having the specific structure (2) may be used in combination. When used in combination, the use ratio of the polymer having the specific structure (2) is preferably 10 to 400 parts by mass relative to 100 parts by mass of the polymer having the specific structure (1). More preferably, it is 50 to 200 parts by mass. For polymers with specific structure (2), one type or two or more types can be used according to their characteristics.

In addition, the polymer component may be mixed with polymers other than the polymer having the specific structure (1) and the polymer having the specific structure (2). At this time, the use ratio of the polymer having no specific structure is preferably 10 to 200 parts by mass relative to 100 parts by mass of the entire polymer having the specific structure. More preferably, it is 10-100 parts by mass.

The content of the solvent in the resin composition can be appropriately selected from the viewpoint of the coating method of the resin composition or the objective film thickness. Among them, from the viewpoint of forming a uniform resin film by coating, the content of the solvent in the resin composition is particularly preferably 50 to 99.9% by mass. More preferably, it is 60 to 99% by mass. The best one is 65 to 99% by mass.

The solvent used in the resin composition is not particularly limited as long as it dissolves the polymer having a specific structure. Especially when the polymer is a polyimide precursor, polyimide, polyimide or polyester, or acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose or polyamide When the solubility of siloxanes in solvents is low, the following solvents (also referred to as solvent A) are preferably used.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl methacrylate Suspension, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, etc. . Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is particularly preferred. Moreover, these can be used individually or in mixture.

When the polymer is acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane, further, the polymer is a polyimide precursor, polyimide, or polysiloxane. When amines or polyesters, and these polymers have high solubility in solvents, the following solvents (also referred to as solvent B type) can be used.

A specific example of the solvent type B includes the solvent type B described on pages 58 to 60 of International Publication WO2014/171493 (published on October 23, 2014). Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexane are especially used. Ketone, cyclopentanone or the aforementioned formula [D1] to formula [D3] are preferred. In addition, when using these solvents of type B, it is preferable to use N-methyl-2-pyrrolidone and N-ethyl-2-pyrrole of the aforementioned solvent type A for the purpose of improving the coating properties of the resin composition. Pyridone or gamma-butyrolactone. It is more preferable to use γ-butyrolactone in combination.

Since these solvents B can improve the coating property or surface smoothness of the resin film when the resin composition is applied, polyimide precursors, polyimine, polyimide or polyester are used as the polymer At this time, it is preferably used in combination with the aforementioned solvent type A. In this case, the solvent type B is preferably 1 to 99% by mass of the total solvent contained in the resin composition. Among them, 10~99% by mass is particularly preferred. More preferably, it is 20-95% by mass. In order to increase the film strength of the resin film, it is preferable to introduce the resin composition with epoxy groups, isocyanate groups, oxetanyl groups, cyclocarbonate groups, hydroxyl groups, hydroxyalkyl groups, and lower alkoxyalkyl groups. At least one compound selected from the group (also collectively referred to as a specific crosslinkable compound). In this case, these groups must have two or more in the compound. Specific examples of crosslinkable compounds having epoxy groups or isocyanate groups include the crosslinkable compounds having epoxy groups or isocyanate groups described on pages 63 to 64 of International Publication WO2014/171493 (published on October 23, 2014) .

Specific examples of crosslinkable compounds having oxetanyl groups include the cross-links of formula [4a] to formula [4k] disclosed on pages 58 to 59 of International Publication WO2011/132751 (published on October 27, 2011) Linking compounds.

Specific examples of crosslinkable compounds having a cyclic carbonate group include formulas [5-1] to formula [5-42] disclosed on pages 76 to 82 of International Publication WO2012/014898 (published on February 2, 2012) The cross-linking compound.

Specific examples of crosslinkable compounds having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include the melamine derivatives or benzos described on pages 65 to 66 of International Publication 2014/171493 (published on October 23, 2014). Guanamine derivatives and crosslinkable compounds of formula [6-1] to formula [6-48] disclosed on pages 62 to 66 of International Publication WO2011/132751 (published on October 27, 2011).

The use ratio of the specific crosslinkable compound in the resin composition is preferably 0.1-100 parts by mass relative to 100 parts by mass of the total polymer components. Since the cross-linking reaction progresses and exhibits the purpose of the effect, it is more preferably 0.1-50 parts by mass. Particularly preferred is 1-30 parts by mass. For the resin composition, 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.

Specific examples of specific generating agents include specific generating agents described on pages 54 to 56 of International Publication 2014/171493 (published on October 23, 2014). Among them, among the specific generators, it is particularly preferable to use an optical radical generator from the viewpoint of the adhesion between the liquid crystal layer and the resin film. In the resin composition, a compound that improves the film thickness uniformity or surface smoothness of the resin film when the resin composition is applied can be used. Furthermore, a compound etc. which improve the adhesiveness of a resin film and a board|substrate can also be used. Compounds that improve the film thickness uniformity or surface smoothness of the resin film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specifically, the surfactant described on page 67 of International Publication WO2014/171493 (published on October 23, 2014) can be cited. In addition, the use ratio is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the total polymer components. More preferably, it is 0.01 to 1 part by mass.

Specific examples of compounds that improve the adhesion between the resin film and the substrate include the compounds described on pages 67 to 69 of International Publication WO2014/171493 (published on October 23, 2014). In addition, the use ratio is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total polymer components. More preferably, it is 1-20 parts by mass.

In the resin composition, in addition to the compounds other than the foregoing, a dielectric or conductive substance for the purpose of changing electrical properties such as the dielectric rate or conductivity of the resin film may be added. ＜Liquid crystal composition＞ The liquid crystal composition has a liquid crystal and a polymerizable compound. As the liquid crystal, nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal can be used. Among them, the liquid crystal display element of the present invention preferably uses liquid crystals with positive dielectric anisotropy. At this time, from the viewpoint of low-voltage driving and scattering characteristics, it is preferable that the anisotropy of the dielectric ratio is large and the anisotropy of the refractive index is large. In addition, in the liquid crystal, two or more types of liquid crystals can be mixed and used in accordance with the aforementioned phase transition temperature, dielectric anisotropy, and refractive index anisotropy. In order to drive the liquid crystal display element as an active element such as TFT (Thin Film Transistor), it is required that the resistance of the liquid crystal be high and the voltage retention rate (also called VHR) is high. Therefore, the liquid crystal is preferably a fluorine-based or chlorine-based liquid crystal that has high resistance and does not reduce VHR due to active energy rays such as ultraviolet rays.

Furthermore, the liquid crystal display element may be a guest-host type element by dissolving a dichroic dye in the liquid crystal composition. At this time, an element that absorbs (scatters) when no voltage is applied and is transparent when voltage is applied can be obtained. In addition, in this device, the direction of the molecular director of the liquid crystal (the direction of alignment) changes by 90 degrees depending on whether or not a voltage is applied. Therefore, the device utilizes the difference in the light absorption characteristics of the dichroic dyes, and can obtain high contrast compared with the conventional guest-host device that switches between random and vertical alignment. In addition, in the guest-host type device in which the dichroic dye is dissolved, the liquid crystal becomes colored when aligned in the horizontal direction, and becomes opaque only in the scattering state. Therefore, it is also possible to obtain a device that switches from a colored and opaque state when a voltage is not applied to a colored, transparent, and colorless and transparent state with the applied voltage.

The polymerizable compound in the liquid crystal composition is used to form a polymer network (also referred to as a curable resin) by polymerization reaction by active energy rays or heat during the production of the liquid crystal display element. The polymerization reaction in the present invention is preferably carried out by irradiating ultraviolet rays. For the polymerizable compound, a polymer obtained by polymerizing the polymerizable compound may be introduced into the liquid crystal composition in advance. However, the operation of the liquid crystal composition, that is, the suppression of the increase in the viscosity of the liquid crystal composition, or the effect of the liquid crystal composition From the viewpoint of solubility, it is preferable to use a liquid crystal composition containing a polymerizable compound. The polymerizable compound is not particularly limited as long as it is dissolved in the liquid crystal. When the polymerizable compound is dissolved in the liquid crystal, a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase must exist. Even when a part of the liquid crystal composition displays a liquid crystal phase, the liquid crystal display element can be confirmed by the naked eye, as long as substantially uniform transparency and scattering characteristics are obtained in the entire element.

The polymerizable compound may be a compound that is polymerized by ultraviolet rays or heat, and in this case, it may be polymerized to form a curable resin regardless of the form of the reaction. Specific reaction forms include radical polymerization, cationic polymerization, anionic polymerization, or addition polymerization.

Among them, the reaction form of the polymerizable compound, from the viewpoint of the optical properties of the liquid crystal display element, is particularly preferably radical polymerization. In this case, as the polymerizable compound, the following radical-type polymerizable compound or its oligomer can be used. In addition, as described above, a polymer obtained by subjecting these polymerizable compounds to a polymerization reaction can also be used.

Specific examples of the radical-type polymerizable compound or its oligomer include the radical-type polymerizable compounds described on pages 69 to 71 of International Publication No. 2015/146987 (published on October 1, 2015). The use ratio of the radical polymerizable compound or its oligomer, from the viewpoint of the adhesion between the liquid crystal layer and the resin film, is preferably 70 to 150 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition Copies. More preferably, it is 80 to 110 parts by mass. In addition, the radical-type polymerizable compound may be used alone or in combination of two or more according to its characteristics. For the purpose of promoting radical polymerization of polymerizable compounds, it is preferable to introduce a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays in the liquid crystal composition. Specifically, the radical initiators described on pages 71 to 72 of International Publication WO2015/146987 (published on October 1, 2015) can be cited. The use ratio of the radical initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition from the viewpoint of the adhesion between the liquid crystal layer and the resin film. More preferably, it is 0.05-10 parts by mass. Moreover, the radical initiator can also be used by using 1 type or mixing 2 or more types according to each characteristic. ＜Specific liquid crystal additive compound＞ In the liquid crystal composition, it is preferable to introduce a compound of the following formula [5a] (also referred to as a specific liquid crystal additive compound).

S ¹ represents any of the following formula [5-a] to formula [5-j]. Among them, formula [5-a], formula [5-b], formula [5-c], formula [5-d], formula [5-e] or formula [5-f] are particularly preferred. More preferably, it is formula [5-a], formula [5-b], formula [5-c] or formula [5-e]. Particularly preferred ones are formula [5-a] or formula [5-b].

S ^A represents a hydrogen atom or a benzene ring. S 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-. Among them, a single bond, -O-, -CH ₂ O-, -CONH-, -COO- or -OCO- is particularly preferred. More preferably, it is a single bond, -O-, -COO- or -OCO-. S ³ represents a single bond or -(CH ₂ ) _a- (a is an integer of 1-15). Among them, a single bond or -(CH ₂ ) _a- (a is an integer from 1 to 10) is particularly preferred. More preferably, it is -(CH ₂ ) _a- (a is an integer of 1-10). S ⁴ represents a single bond, -O-, -OCH ₂ -, -COO- or -OCO-. Among them, a single bond, -O- or -COO- is particularly preferred. The better one is -O-. S ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group with 17 to 51 carbon atoms having a steroid skeleton. Any hydrogen atom on the aforementioned cyclic group is also It can be substituted by alkyl groups with 1 to 3 carbons, alkoxy groups with 1 to 3 carbons, fluorinated alkyl groups with 1 to 3 carbons, fluorine-containing alkoxy groups with 1 to 3 carbons, or fluorine atoms. Among them, a benzene ring or a cyclohexane ring, or a divalent organic group with a carbon number of 17 to 51 with a steroid skeleton is preferred. More preferably, it is a benzene ring or a divalent organic group with a carbon number of 17 to 51 having a steroid skeleton. S ⁶ represents at least one selected from a single bond, -O-, -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, or -OCO-. Among them, a single bond, -O-, -COO- or -OCO- is particularly preferred. More preferably, it is a single bond, -COO- or -OCO-. S ⁷ represents a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom on these cyclic groups can also be passed through an alkyl group with 1 to 3 carbons and a carbon number of 1 to 3 The alkoxy group, C1-C3 fluorine-containing alkyl group, C1-C3 fluorine-containing alkoxy group or fluorine atom substitution. Among them, a benzene ring or a cyclohexane ring is particularly preferred. S ⁸ represents alkyl with 1 to 18 carbons, alkenyl with 2 to 18 carbons, fluorinated alkyl with 1 to 18 carbons, alkoxy with 1 to 18 carbons or fluorine with 1 to 18 carbons Alkoxy. Among them, an alkyl group or alkoxy group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms is preferred. More preferably, it is an alkyl group or an alkoxy group having 1 to 12 carbon atoms. Sm represents an integer from 0 to 4. Among them, 0~2 is particularly preferred. The specific liquid crystal additive compound has a site having a rigid structure such as a benzene ring or a cyclohexane ring, and a site ^{represented by S 1} in the formula [5a] that undergoes polymerization reaction by ultraviolet light or heat. Therefore, when the specific liquid crystal additive compound is contained in the liquid crystal composition, the rigid structure of the specific liquid crystal additive compound can improve the vertical alignment of the liquid crystal, promote the driving of the liquid crystal with voltage application, and reduce the driving voltage of the liquid crystal display element. ^{In addition, the S 1} site in the formula [5a] reacts with the polymerizable compound to keep the polymer network in a dense state. More specific specific liquid crystal additive compounds include compounds of the following formula [5a-1] to formula [5a-11], and these are preferably used.

S ^a represents -O- or -COO-, respectively. S ^b each represents an alkyl group having 1 to 12 carbon atoms. p1 represents an integer from 1 to 10 respectively. p2 represents an integer of 1 or 2 respectively.

S ^c represents a single bond, -COO- or -OCO-, respectively. S ^d represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms, respectively. p3 represents an integer from 1 to 10 respectively. p4 represents an integer of 1 or 2 respectively.

S ^e represents -O- or -COO-, respectively. S ^f respectively represents a divalent organic group with a carbon number of 17 to 51 having a steroid skeleton. S ^g represents an alkyl group with 1 to 12 carbons or an alkenyl group with 2 to 18 carbons, respectively. p5 represents an integer from 1 to 10 respectively. The use ratio of the specific liquid crystal additive 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 the adhesion between the liquid crystal layer and the resin film. More preferably, it is 0.5-20 parts by mass. Particularly preferred is 1-10 parts by mass. In addition, the specific liquid crystal additive compound may be used alone or in combination of two or more according to each characteristic. The method for preparing the liquid crystal composition includes a method of mixing a liquid crystal, a polymerizable compound, and a specific liquid crystal additive compound together, or a method of mixing a polymerizable compound and a specific liquid crystal additive compound beforehand and mixing with the liquid crystal. Among them, in the present invention, a method of mixing a polymerizable compound and a specific liquid crystal additive compound preliminarily mixed with a liquid crystal is particularly preferred. When preparing the liquid crystal composition as described above, heating may be performed according to the solubility of the polymerizable compound and the specific liquid crystal additive compound. The temperature at this time is preferably less than 100°C. <Method for manufacturing liquid crystal display element> The substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate. Glass substrates can be used, and acrylic substrates, polycarbonate substrates, PET (polyterephthalene) Ethylene formate) substrates and other plastic substrates, and then these films can be used. Especially when used in dimming windows, etc., it is preferably a plastic substrate or film. Furthermore, from the viewpoint of simplification of the manufacturing process, it is preferable to use a substrate on which ITO electrodes for liquid crystal driving, IZO (Indium Zinc Oxide) electrodes, IGZO (Indium Gallium Zinc Oxide) electrodes, organic conductive films, etc. are formed. In addition, as a reflective liquid crystal display element, as long as it is a single-sided substrate, a silicon wafer or a substrate formed with a metal such as aluminum or a dielectric multilayer film can be used. The liquid crystal display element has a resin film obtained from a resin composition containing a polymer having a specific structure (1) on at least one of the substrates. It is particularly preferred that both substrates have a resin film.

The coating method of the resin composition is not particularly limited. In terms of industry, there are screen printing, offset printing, flexographic printing, inkjet method, dipping method, roll coater method, and slit coater. The method, spinner method, spray method, etc. can be appropriately selected according to the type of substrate or the thickness of the target resin film.

After the resin composition is coated on the substrate, heating means such as a heating plate, a thermal cycle oven, an IR (infrared) oven, etc. can be used, depending on the type of substrate or the solvent used in the resin composition, at 30~300℃, Preferably, the temperature of 30 to 250°C evaporates the solvent to form a resin film. Especially when a plastic substrate is used for the substrate, it is better to process 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. If it is too thin, the reliability of the element may decrease, so it is preferably 5 to 500 nm. More preferably, it is 10~300nm. The best one is 10~250nm.

The liquid crystal composition used in the liquid crystal display element is the aforementioned liquid crystal composition, in which a spacer for controlling the electrode gap (also called a gap) of the liquid crystal display element can also be introduced.

The injection method of the liquid crystal composition is not particularly limited. For example, the following methods can be cited. That is, when a glass substrate is used as a substrate, a pair of substrates having a resin film formed thereon is prepared, and the sealant is applied to the four substrates on one side except for a part, and then the resin film is used as the inner side and the other is attached. One side of the substrate is used to make an empty cell. Then, from the place where the sealant is not applied, the liquid crystal composition is injected under reduced pressure to obtain a method of injecting the liquid crystal composition into the cell. Further, when a plastic substrate or a film is used as the substrate, a pair of substrates with a resin film formed thereon can be mentioned, and the liquid crystal composition is dropped on the single-sided substrate by the ODF (One Drop Filling) method or the inkjet method, etc., and then laminated On the other side of the substrate, the method in which the liquid crystal composition is injected into the unit cell is obtained.

The gap of the liquid crystal display element can be controlled by the aforementioned spacers and the like. As described above, the method includes a method of introducing a spacer of a target size into the liquid crystal composition, a method of using a substrate of a column spacer of a target size, and the like. In addition, when a plastic or film substrate is used for the substrate and the substrates are bonded by lamination, the gap can be controlled without introducing spacers.

The size of the gap of the liquid crystal display element is preferably 1-100 μm. More preferably, it is 1-50μm. The best one is 2~30μm. When the gap is too small, the contrast of the liquid crystal display element decreases, and when the gap is too large, the driving voltage of the element becomes higher.

The liquid crystal display element can be obtained by curing the liquid crystal composition to form a liquid crystal layer in a state where one part or the whole of the liquid crystal composition shows liquid crystallinity. The curing of the liquid crystal composition is performed by injecting the aforementioned liquid crystal composition into a cell, and irradiating it with ultraviolet rays or heating. In the present invention, as described above, ultraviolet irradiation is preferred.

The light source of the ultraviolet irradiation device used for ultraviolet irradiation includes, for example, a metal halide lamp or a high-pressure mercury lamp. In addition, the wavelength of ultraviolet rays is preferably 250 to 400 nm. Among them, 310~370nm is particularly preferred. In addition, heat treatment may be performed after irradiating ultraviolet rays. The temperature at this time is preferably 40 to 120°C. More preferably, it is 40~80°C. The device used for heating includes heating means used after coating the aforementioned resin composition on a substrate. In addition, the temperature at this time is appropriately selected depending on the temperature at which the reaction of the polymerizable compound proceeds or the type of substrate. Specifically, it is preferably 80 to 200°C. [Example]

Examples are listed below to illustrate the present invention in more detail, but are not limited to these. The abbreviations used below are as follows. "Compounds for polyimide polymers" ＜Specific Diamine (1)＞

＜Specific Diamine (2)＞

＜Other diamines＞

＜Specific tetracarboxylic acid component＞

"Compounds for polysiloxane-based polymers"

E2: Octadecyltriethoxysilane E3: 3-methacryloxypropyl trimethoxysilane E4: 3-ureidopropyl triethoxysilane E5: Tetraethoxysilane "Crosslinkable compound"

"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 "Compounds for liquid crystal compositions" ＜Specific liquid crystal additive compound＞

＜Polymerizable compound＞ R1: IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.) R2: 2-Hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) R3: KAYARAD FM-400 (manufactured by Nippon Kayaku Corporation) R4: EBECRYL 230 (manufactured by Daicel-Allnex) R5: Karenz MT PE1 (manufactured by Showa Denko) ＜Light radical initiator＞ P1: IRGACURE 184 (made by BASF) ＜LCD＞ L1: MLC-3018 (manufactured by Merck) "Molecular weight determination of polyimide-based polymers" Using a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Corporation) and a column (KD-803, KD-805) (manufactured by Shodex), the measurement was performed as follows.

Column temperature: 50℃ Eluent: N,N-dimethylformamide (containing lithium bromide monohydrate (LiBr･H ₂ O) 30mmol/L (liter), anhydrous phosphoric acid (o-phosphoric acid) 30mmol/L , Tetrahydrofuran (THF) 10ml/L as an additive) Flow rate: 1.0ml/min. Standard sample for calibration line preparation: TSK standard polyethylene oxide (molecular weight; approximately 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh) ) And polyethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories). "Measurement of the imidization rate of polyimide-based polymers" Put 20 mg of polyimide powder into an NMR (nuclear magnetic resonance) sample tube (NMR standard sampling tube, φ5 (manufactured by Kusano Scientific Co.)), and add Deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixture) (0.53ml), applied ultrasonic waves to completely dissolve it. This solution was measured for 500 MHz proton NMR using an NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM). The rate of imidization is determined by taking the protons derived from the unchanged structure before and after imidization as the reference protons. Using the following formula, using the peak integral value of the protons, it is derived from those near 9.5ppm~10.0ppm The proton peak integral value of the NH group of amide acid is obtained.

The imidization rate (%)=(1-α・x/y)×100 (x is the peak integral value of the proton derived from the NH group of the amide acid, y is the peak integral value of the reference proton, and α is the polyamide acid (the imidation rate is 0%), relative to the integral value of the amide acid For one NH proton, the ratio of the number of reference protons). "Synthesis of Polyimide Polymers" ＜Synthesis example 1＞ D2 (1.36g, 5.44mmol), A1 (1.05g, 2.76mmol) and C1 (1.19g, 11.0mmol) were mixed in NMP (10.4g), and after reacting at 80°C for 4 hours, D1 (1.60g, 8.16 mmol) and NMP (5.21 g) were reacted at 40°C for 6 hours to obtain a polyamide acid solution (1) with a resin solid content concentration of 25% by mass. The polyamide acid has a number average molecular weight (also referred to as Mn) of 21,500 and a weight average molecular weight (also referred to as Mw) of 64,700. ＜Synthesis example 2＞ Mix D2 (2.21g, 8.83mmol), A1 (1.71g, 4.49mmol), B1 (2.96g, 11.2mmol) and C1 (0.73g, 6.75mmol) in NMP (20.4g), and react at 80℃. 4 After hours, D1 (2.60 g, 13.3 mmol) and NMP (10.2 g) were added and reacted at 40° C. for 6 hours to obtain a polyamide acid solution (2) with a resin solid content concentration of 25% by mass. The Mn of the polyamide acid is 20,500, and the Mw is 61,000. ＜Synthesis example 3＞ To the polyamide acid solution (2) (20.0 g) obtained by the method of Synthesis Example 2, NMP was added and diluted to 6% by mass, and then acetic anhydride (1.65 g) and pyridine ( 1.00g), react at 60°C for 3 hours. The reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. This deposit was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (3). The imidization rate of this polyimide was 55%, Mn was 18,300, and Mw was 48,300. ＜Synthesis example 4＞ Mix D4 (0.74g, 3.73mmol), A2 (0.75g, 1.90mmol), B1 (1.50g, 5.68mmol) and C1 (0.21g, 1.94mmol) in γ-BL (8.60g), and mix at 60℃ After 4 hours of reaction, D1 (1.10 g, 5.61 mmol) and γ-BL (4.30 g) were added and reacted at 40° C. for 8 hours to obtain a polyamide acid solution (4) with a resin solid content concentration of 25% by mass. The Mn of this polyamic acid is 15,900 and the Mw is 47,600. ＜Synthesis example 5＞ Mix D4 (1.18g, 5.96mmol), A2 (0.51g, 1.29mmol) and B1 (1.94g, 7.34mmol) in γ-BL (8.25g), react at 60°C for 4 hours, add D1 (0.50 g, 2.55 mmol) and γ-BL (4.13 g) were reacted at 40°C for 8 hours to obtain a polyamide acid solution (5) with a resin solid content concentration of 25% by mass. The Mn of the polyamide acid is 13,300, and the Mw is 44,200. ＜Synthesis example 6＞ Mix D4 (0.74g, 3.73mmol), A3 (0.54g, 1.25mmol), B1 (1.66g, 6.28mmol) and C1 (0.54g, 4.99mmol) in NMP (10.4g), and react at 80°C. 4 After hours, D1 (1.70 g, 8.67 mmol) and NMP (5.18 g) were added and reacted at 40°C for 6 hours to obtain a polyamide acid solution (6) with a resin solid content concentration of 25% by mass. The Mn of the polyamide acid is 22,300, and the Mw is 68,500. ＜Synthesis example 7＞ D3 (2.00g, 8.92mmol), A2 (0.71g, 1.80mmol) and B2 (1.47g, 7.23mmol) were mixed in γ-BL (12.6g) and reacted at 40°C for 12 hours to obtain the resin solid content concentration 25% by mass polyamide acid solution (7). The Mn of the polyamide acid was 14,900, and the Mw was 41,900. ＜Synthesis example 8＞ Mix D3 (2.50g, 11.2mmol), A4 (0.28g, 0.57mmol), B1 (1.79g, 6.77mmol) and C1 (0.43g, 3.98mmol) in NMP (15.0g), and react at 40°C for 12 Within hours, a polyamide acid solution (8) having a resin solid content concentration of 25% by mass was obtained. The Mn of the polyamide acid is 16,100, and the Mw is 45,200. ＜Synthesis example 9＞ Mix D2 (1.11g, 4.44mmol), A5 (0.84g, 2.23mmol), B1 (1.48g, 5.60mmol) and C1 (0.36g, 3.33mmol) in NMP (10.2g), and react at 80°C. 4 After hours, D1 (1.30 g, 6.63 mmol) and NMP (5.10 g) were added and reacted at 40° C. for 6 hours to obtain a polyamide acid solution (9) with a resin solid content concentration of 25% by mass. The Mn of the polyamide acid is 19,900 and the Mw is 60,500. ＜Synthesis example 10＞ Mix D2 (1.53g, 6.11mmol) and C1 (1.68g, 15.5mmol) in NMP (10.0g), react at 80°C for 4 hours, add D1 (1.80g, 9.18mmol) and NMP (5.01g) And reacted at 40°C for 6 hours to obtain a polyamide acid solution (10) with a resin solid content concentration of 25% by mass. The Mn of this polyamic acid is 28,200, and the Mw is 73,900. ＜Synthesis example 11＞ Mix D4 (1.08g, 5.45mmol) and C1 (1.49g, 13.8mmol) in γ-BL (8.34g), and after reacting at 60°C for 4 hours, add D1 (1.60g, 8.16mmol) and γ-BL (4.17g), reacted at 40°C for 8 hours to obtain a polyamide acid solution (11) with a resin solid content concentration of 25% by mass. The Mn of this polyamic acid is 20,900 and the Mw is 58,400. Table 1 shows the polyimide-based polymer obtained in the synthesis example.

*1: Polyamide acid. "Synthesis of polysiloxane polymer"<Synthesis example 12> In a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube, mix ECS (28.3g), E1 (4.10g), and E3 (7.45g) And E5 (32.5g) to prepare a solution of alkoxysilane monomer. A solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was dropped into this solution over 30 minutes at 25°C, and further stirred at 25°C for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, a mixed solution of a methanol solution (1.20 g) and ECS (0.90 g) with a content of 92% by mass of E4 prepared in advance was added. After further refluxing for 30 minutes, it was left to cool to obtain a _{polysiloxane solution (1) having a SiO 2} conversion concentration of 12% by mass. <Synthesis Example 13> In a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube, EC (29.2g), E1 (4.10g) and E5 (38.8g) were mixed to prepare a solution of alkoxysilane monomer. A solution prepared by mixing EC (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst was dropped into this solution over 30 minutes at 25°C, and further stirred at 25°C for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, a mixed solution of methanol solution (1.20 g) and EC (0.90 g) with a content of 92% by mass of E4 prepared in advance was added. After further refluxing for 30 minutes, it was left to cool to obtain a _{polysiloxane solution (2) having a SiO 2} conversion concentration of 12% by mass. <Synthesis example 14> In a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube, ECS (28.3g), E2 (4.07g), E3 (7.45g) and E5 (32.5g) were mixed to prepare an alkoxy group A solution of silane monomer. A solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was dropped into this solution over 30 minutes at 25°C, and further stirred at 25°C for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, a mixed solution of a methanol solution (1.20 g) and ECS (0.90 g) with a content of 92% by mass of E4 prepared in advance was added. After further refluxing for 30 minutes, it was allowed to cool to obtain a _{polysiloxane solution (3) having a SiO 2} conversion concentration of 12% by mass.

Table 2 shows the polysiloxane-based polymers obtained in the synthesis example.

"Manufacturing of resin composition" <Example 1> To the polyamide acid solution (1) (10.0 g) obtained by the method of Synthesis Example 1, NMP (16.0 g) and BCS (15.7 g) were added, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (1) . In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 2> To the polyamide acid solution (2) (10.0 g) obtained by the method of Synthesis Example 2, NMP (16.0 g) and BCS (15.7 g) were added, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (2) . In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 3> To the polyimide powder (3) (2.50 g) obtained by the method of Synthesis Example 3, NMP (27.4 g) was added, and the mixture was stirred at 70°C for 24 hours to dissolve it. Then, BCS (7.83g) and PB (3.92g) were added, and it stirred at 25 degreeC for 6 hours, and obtained the resin composition (3). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 4> To the polyimide powder (3) (2.50 g) obtained by the method of Synthesis Example 3, NMP (27.4 g) was added, and the mixture was stirred at 70°C for 24 hours to dissolve it. Then, K1 (0.13g), BCS (7.83g), and PB (3.92g) were added, and it stirred at 25 degreeC for 6 hours, and obtained the resin composition (4). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 5> To the polyimide powder (3) (2.50 g) obtained by the method of Synthesis Example 3, γ-BL (5.88 g) was added, and the mixture was stirred at 60°C for 24 hours to dissolve it. Then, PGME (33.3g) was added, and it stirred at 25 degreeC for 6 hours, and obtained the resin composition (5). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 6> To the polyamide acid solution (4) (10.0 g) obtained by the method of Synthesis Example 4, γ-BL (0.33 g) was added, and the mixture was stirred at 25°C for 4 hours. Then, PGME (31.3g) was added, and it stirred at 25 degreeC for 6 hours, and obtained the resin composition (6). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 7> To the polyamide acid solution (4) (10.0 g) obtained by the method of Synthesis Example 4, γ-BL (0.33 g) was added, and the mixture was stirred at 25°C for 4 hours. Then, K2 (0.18g) and PGME (31.3g) were added, and it stirred at 25 degreeC for 6 hours, and obtained the resin composition (7). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 8> To the polyamide acid solution (5) (10.0 g) obtained by the method of Synthesis Example 5, γ-BL (0.33 g) was added, and the mixture was stirred at 25°C for 4 hours. Then, K2 (0.13g) and PGME (31.3g) were added, and it stirred at 25 degreeC for 6 hours, and obtained the resin composition (8). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 9> K1 (0.08g), NMP (19.9g) and PB (11.8g) were added to the polyamide acid solution (6) (10.0g) obtained by the method of Synthesis Example 6, and stirred at 25°C for 6 hours to obtain Resin composition (9). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 10> To the polyamide acid solution (7) (10.0 g) obtained by the method of Synthesis Example 7, γ-BL (0.33 g) was added, and the mixture was stirred at 25°C for 4 hours. Then, K2 (0.08g) and PGME (31.3g) were added, and it stirred at 25 degreeC for 6 hours, and obtained the resin composition (10). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 11> To the polyamide acid solution (8) (10.0 g) obtained by the method of Synthesis Example 8, NMP (16.0 g), BCS (7.83 g) and PB (7.83 g) were added, and the mixture was stirred at 25°C for 6 hours to obtain Resin composition (11). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 12> To the polyamide acid solution (9) (10.0 g) obtained by the method of Synthesis Example 9, NMP (16.0 g) and BCS (15.7 g) were added, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (12) . In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. <Example 13> ECS (12.5g) and BCS (7.52g) were added to the polysiloxane solution (1) (20.0g) obtained by the synthesis method of Synthesis Example 12, and stirred at 25°C for 6 hours to obtain a resin composition (13 ). It was confirmed that the resin composition did not see abnormalities such as turbidity or precipitation, and it was a uniform solution. <Example 14> EC (8.72g) and BCS (11.3g) were added to the polysiloxane solution (2) (20.0g) obtained by the synthesis method of Synthesis Example 13, and stirred at 25°C for 6 hours to obtain a resin composition (14 ). It was confirmed that the resin composition did not see abnormalities such as turbidity or precipitation, and it was a uniform solution. <Example 15> ECS (12.5g) and BCS (7.52g) were added to the polysiloxane solution (3) (20.0g) obtained by the synthesis method of Synthesis Example 14, and stirred at 25°C for 6 hours to obtain a resin composition (15 ). It was confirmed that the resin composition did not see abnormalities such as turbidity or precipitation, and it was a uniform solution. ＜Comparative example 1＞ To the polyamide acid solution (10) (10.0 g) obtained by the method of Synthesis Example 10, NMP (16.0 g) and BCS (15.7 g) were added, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (16) . In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. ＜Comparative example 2＞ To the polyamide acid solution (11) (10.0g) obtained by the method of Synthesis Example 11, γ-BL (0.33g) and PGME (31.3g) were added and stirred at 25°C for 6 hours to obtain a resin composition ( 17). In this resin composition, no abnormalities such as turbidity or precipitation were seen, and it was a uniform solution. The resin compositions obtained in Examples and Comparative Examples are shown in Tables 3 to 5.

*2: The value in parentheses indicates the amount of crosslinkable compound introduced (parts by mass) relative to 100 parts by mass of the polymer. "Production of liquid crystal composition" ＜Production of liquid crystal composition (A)＞ R1 (1.20g), R2 (0.30g), R3 (1.20g), R4 (0.90g), and R5 (0.30g) were mixed, and stirred at 60°C for 2 hours to prepare a polymerizable compound solution. After that, 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 (A). ＜Production of liquid crystal composition (B)＞ R1 (1.20g), R2 (0.30g), R3 (1.20g), R4 (0.90g), and R5 (0.30g) were mixed, and stirred at 60°C for 2 hours to prepare a polymerizable compound solution. On the other hand, S1 (0.20g) and L1 (5.80g) were mixed, and it stirred at 25 degreeC for 2 hours, and produced the liquid crystal containing a specific liquid crystal additive compound. After that, the prepared solution of the polymerizable compound, the liquid crystal containing the specific liquid crystal additive compound, and P1 (0.10 g) were mixed, and stirred at 25° C. for 6 hours to obtain a liquid crystal composition (B). ＜Production of liquid crystal composition (C)＞ R1 (1.20g), R2 (0.30g), R3 (1.20g), R4 (0.90g), and R5 (0.30g) were mixed, and stirred at 60°C for 2 hours to prepare a polymerizable compound solution. On the other hand, S2 (0.40g) and L1 (5.60g) were mixed and stirred at 25°C for 2 hours to produce a liquid crystal containing a specific liquid crystal additive compound. Then, the prepared solution of the polymerizable compound, the liquid crystal containing the specific liquid crystal additive compound, and P1 (0.10 g) were mixed, and stirred at 25° C. for 6 hours to obtain a liquid crystal composition (C). "Production of Liquid Crystal Display Elements (Glass Substrate)" The resin compositions obtained by the methods of the foregoing Examples and Comparative Examples were pressure-filtered with a membrane filter having a pore size of 1 μm. The resulting solution was spin-coated on the ITO surface of a 100×100mm glass substrate with ITO electrode (length: 100mm, width: 100mm, thickness: 0.7mm) washed with pure water and IPA (isopropyl alcohol) Heat treatment at 100°C on a hot plate for 5 minutes, and heat treatment at 210°C in a thermal cycle clean oven for 30 minutes to obtain an ITO substrate with a resin film with a thickness of 100nm. Two ITO substrates with a resin film were prepared, and a spacer of 20 μm was coated on the resin film surface of one of the substrates. After that, the above-mentioned liquid crystal composition (A)~(C) was dropped by ODF (One Drop Filling) method on the resin film surface of the substrate coated with spacers, and then the resin film surface of the other substrate was facing The method of bonding is performed to obtain the liquid crystal display element before processing.

For the liquid crystal display element before the treatment, a ^{metal halide lamp with an illuminance of 20 mW/cm 2 was} used to filter out wavelengths below 350 nm, and irradiated with ultraviolet light for an irradiation time of 60 seconds. Thereby, a liquid crystal display element (glass substrate) was obtained. "Production of Liquid Crystal Display Element (Plastic Substrate)" The resin composition obtained by the methods of the foregoing Examples and Comparative Examples was subjected to pressure filtration with a membrane filter with a pore size of 1 μm. Coat the resulting solution with a bar coater on the ITO surface of a 150×150mm PET substrate with ITO electrode (length: 150mm, width: 150mm, thickness: 0.1mm) washed with pure water, and heat cycled Heat treatment at 120°C for 2 minutes in a type oven to obtain an ITO substrate with a resin film with a thickness of 100 nm. Prepare two ITO substrates with resin film, and apply a 20μm spacer on the resin film surface of one of the substrates. Then, drop the liquid crystal composition (A)~(C) on the resin film surface of the substrate coated with spacers by ODF (One Drop Filling) method, and then face the resin film surface of the other substrate The method of bonding is performed to obtain the liquid crystal display element before processing. In addition, when dropping and bonding the liquid crystal composition by the ODF method, a glass substrate is used as a support substrate for the PET substrate with ITO electrode. Afterwards, the supporting substrate is removed before irradiating ultraviolet rays.

The liquid crystal display element before the treatment was irradiated with ultraviolet rays in the same manner as in the aforementioned "Production of the liquid crystal display element (glass substrate)" to obtain a liquid crystal display element (plastic substrate). "Evaluation of optical properties (scattering properties and transparency)" This evaluation is performed by measuring the Haze (haze) of the liquid crystal display element (glass substrate and plastic substrate) in the non-applied voltage state (0V) and the voltage applied state (AC drive: 10V~60V). At this time, Haze is measured with a haze meter (HZ-V3, manufactured by Suga Tester Co., Ltd.) in accordance with JIS K 7136. Furthermore, in this evaluation, the higher the Haze in the non-voltage state, the better the scattering characteristics, and the lower the Haze in the voltage 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, it is also measured after being stored in a constant temperature and humidity chamber at a temperature of 80°C and a humidity of 90%RH for 24 hours. Specifically, compared to the initial Haze, the smaller the change in Haze after storage in a constant temperature and humidity tank, the better this evaluation is.

Furthermore, as a stability test of the liquid crystal display element against light irradiation, a desktop UV curing device (HCT3B28HEX-1) (manufactured by SENLIGHT) was used, and observations after UV irradiation ^{at 365nm converted to 5J/cm 2 were also performed} . Specifically, compared to the initial Haze, the smaller the change in Haze after UV irradiation, the better this evaluation is.

In the initial stage, the measurement results of Haze after storage in a constant temperature and humidity tank (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet rays) are summarized in Table 6 to Table 8. <Example 16 to Example 31, Comparative Example 3, and Comparative Example 4> Using any one of the resin compositions (1) to (17) obtained by the methods of the foregoing examples and comparative examples, and the foregoing liquid crystal compositions (A) to (C), the liquid crystal display element was fabricated by the foregoing method and Evaluation of optical properties (scattering properties and transparency). At this time, Example 16 to Example 19, Example 25, Example 27, Example 28, Example 30, and Comparative Example 3 were made using glass substrates for the production and evaluation of liquid crystal display elements, and Example 20 to implementation In Example 24, Example 26, Example 29, Example 31, and Comparative Example 4, plastic substrates were used.

As mentioned above, the liquid crystal display element of the example using the resin composition containing the polymer having the specific structure (1) has lower Haze in the voltage applied state than in the comparative example not using it, and is The lower the voltage, the Haze is reduced. That is, in the embodiment, good optical characteristics (transparency) are exhibited, and the driving voltage of the liquid crystal display element becomes lower. Specifically, it is a comparison between Example 16 and Comparative Example 3, and a comparison between Example 21 and Comparative Example 4. In addition, when a specific diamine (2) having a specific structure (2) is used for the polymer, the change in Haze after storage in a constant temperature and humidity tank and after ultraviolet irradiation becomes small. Specifically, the comparison under the same conditions is a comparison between Example 16 and Example 17. Furthermore, when a specific crosslinkable compound is introduced into the resin composition, the change in Haze after storage in a constant temperature and humidity tank and after ultraviolet irradiation becomes smaller. Specifically, the comparison under the same conditions is a comparison between Example 18 and Example 19, and a comparison between Example 21 and Example 22. In addition, when a liquid crystal composition containing a specific liquid crystal additive compound is used, the Haze change in the voltage application state is lower than when it is not used, and the driving voltage is also changed lower. Specifically, the comparison under the same conditions is a comparison between Example 22 and Example 23. [Industrial availability]

By using a resin composition containing a polymer having a specific structure, a liquid crystal display element having good optical properties and a low driving voltage of the liquid crystal display element can be obtained.

In addition, the liquid crystal display element of the present invention can be suitably used as a normal type element that is in a scattering state when no voltage is applied, and becomes a transparent state when a voltage is applied. In addition, the device can be used for liquid crystal displays for display purposes, and further used for dimming windows or shutter devices for controlling the blocking and transmission of light. The substrate of the normal-type device can be a plastic substrate.

In addition, all the contents of the Japanese Patent Application No. 2019-042708, the scope of application, and the abstract of the Japanese Patent Application No. 2019-042708 filed on March 8, 2019 are cited here as the disclosure of the specification of the present invention.

Claims (17)

A liquid crystal display element having a liquid crystal layer hardened by applying at least one of active energy rays and heat to a liquid crystal composition containing a liquid crystal and a polymerizable compound arranged between a pair of substrates provided with electrodes, and on the substrate At least one of them is provided with a resin film, and further, a transmissive scattering type liquid crystal display element that becomes a scattering state when no voltage is applied and becomes a transparent state when a voltage is applied, characterized in that the resin film is made of Obtained from a resin composition of a polymer having at least one structure selected from the formula [1-1] and the formula [1-2];

X ¹ represents a single bond, -(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, At least one selected from -N(CH ₃ )CO-, -COO- or -OCO-; X ² represents a single bond or -(CH ₂ ) _b- (b is an integer from 1 to 15); X ³ represents Single bond, -(CH ₂ ) _c- (c is an integer of 1-15), _{at least one selected from -O-, -CH 2} O-, -COO- or -OCO-; X ⁴ represents a benzene ring , A bivalent cyclic group selected from a cyclohexane ring and a heterocyclic ring, or a divalent organic group with 17 to 51 carbon atoms with a steroid skeleton. Any hydrogen atom on the aforementioned cyclic group can also pass through a carbon number of 1 to 3 alkyl group, carbon number 1~3 alkoxy group, carbon number 1~3 fluorine-containing alkyl group, carbon number 1~3 fluorine-containing alkoxy group or fluorine atom substitution; X ⁵ means benzene ring, ring Cyclic groups selected from the hexane ring and heterocycles. Any hydrogen atom on these cyclic groups can also be passed through an alkyl group with 1 to 3 carbons, an alkoxy group with 1 to 3 carbons, and a carbon number of 1. ~3 fluorine-containing alkyl group, carbon number 1~3 fluorine-containing alkoxy group or fluorine atom substitution; Xn represents an integer of 0~4; X ⁶ represents carbon number 1~18 alkyl group, carbon number 2~18 Alkenyl, fluorine-containing alkyl group with 1 to 18 carbons, alkoxy group with 1 to 18 carbons or fluorine-containing alkoxy group with 1 to 18 carbons;

X ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-; X ⁸ represents an alkyl group with 8 to 22 carbons or a fluorinated alkyl group with 6 to 18 carbons. The liquid crystal display element of claim 1, wherein the aforementioned polymer further has at least one structure selected from the following formula [2-a] to formula [2-i];

Y ^A represents a hydrogen atom or a benzene ring. The liquid crystal display element of claim 1 or 2, wherein the aforementioned resin composition further contains a polymer having at least one structure selected from the following formula [2-a] to formula [2-i];

Y ^A represents a hydrogen atom or a benzene ring. Such as the liquid crystal display element of any one of claim 1 to claim 3, wherein the aforementioned polymer is composed of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, At least one selected from polyimide, polyamide, polyester, cellulose, and polysiloxane. The liquid crystal display element of claim 4, wherein the aforementioned polymer is a polyimide precursor obtained by the reaction of a diamine component and a tetracarboxylic acid component, or the polyimide precursor is imidized The obtained polyimide. The liquid crystal display element of claim 5, wherein the diamine component includes a diamine having at least one structure selected from the aforementioned formula [1-1] and formula [1-2]. The liquid crystal display element of claim 6, wherein the diamine having at least one structure selected from the aforementioned formula [1-1] and formula [1-2] is the following formula [1a];

X represents the aforementioned formula [1-1] or formula [1-2]; Xm represents an integer of 1-4. The liquid crystal display element of any one of claim 5 to claim 7, wherein the aforementioned diamine component includes a diamine having a structure of the following formula [2];

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 with 1 to 18 carbon atoms, or a cyclic group with 6 carbon atoms selected from a benzene ring, a cyclohexane ring and a heterocyclic ring ~24 organic groups, any hydrogen atoms on these cyclic groups can also pass through C1-C3 alkyl groups, C1-C3 alkoxy groups, C1-C3 fluorinated alkyl groups, Fluorine-containing alkoxy group or fluorine atom substituted with carbon number 1~3; Y ³ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-,- At least one selected from NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO-; Y ^{4 is} represented by the aforementioned formula [2-a] ~ formula [2- At least one structure selected from i]; Yn represents an integer from 1 to 4. The liquid crystal display element of claim 8, wherein the aforementioned diamine having the structure of formula [2] is the following formula [2a];

Y represents the structure of the aforementioned formula [2]; Ym represents an integer from 1 to 4. The liquid crystal display element of any one of claim 5 to claim 9, wherein the aforementioned tetracarboxylic acid component includes the tetracarboxylic dianhydride of the following formula [3];

Z represents any of the following formula [3a] ~ formula [3l];

Z ^A to Z ^D represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, ^{respectively; Z E} and Z ^F represent a hydrogen atom or a methyl group, respectively. The liquid crystal display element of claim 4, wherein the aforementioned polymer contains polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or an alkoxysilane of the formula [A1], and Polysiloxane obtained by polycondensation of alkoxysilanes of the following formula [A2] and/or formula [A3];

A ¹ represents the aforementioned formula [1-1] or formula [1-2]; A ² represents a hydrogen atom or an alkyl group with 1 to 5 carbons; A ³ represents an alkyl group with 1 to 5 carbons; m represents 1 or 2 N represents an integer from 0 to 2; p represents an integer from 0 to 3; however, m+n+p is 4;

B ¹ means that it has at least one selected from vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacrylic acid group, acrylic acid group, urea group, and cinnamon group. Group; B ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; B ³ represents an alkyl group with 1 to 5 carbon atoms; m represents an integer of 1 or 2; n represents an integer of 0 to 2; p represents 0 to 3 Is an integer; only, m+n+p is 4;

D ¹ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; D ² represents an alkyl group with 1 to 5 carbon atoms; n represents an integer of 0 to 3. Such as the liquid crystal display element of any one of claim 1 to claim 11, wherein the aforementioned liquid crystal composition contains a compound of the following formula [5a];

S ¹ represents any of the following formulas [5-a] to formula [5-j]; S 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-; S ³ represents a single bond or -(CH ₂ ) _a -(a is An integer from 1 to 15); S ⁴ represents a single bond, -O-, -OCH ₂ -, -COO- or -OCO-; S ⁵ represents a divalent ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring Alkyl group, or a divalent organic group with 17~51 carbons with a steroid skeleton, any hydrogen atom on the aforementioned cyclic group can also be passed through an alkyl group with 1 to 3 carbons and an alkoxy group with 1 to 3 carbons , Fluorine-containing alkyl groups with 1 to 3 carbons, fluorine-containing alkoxy groups with 1 to 3 carbons or fluorine atom substitution; S ⁶ represents a single bond, -O-, -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO- or -OCO-; S ⁷ represents a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom on these cyclic groups can also be Alkyl group with 1~3 carbon number, alkoxy group with carbon number 1~3, fluorine-containing alkyl group with carbon number 1~3, fluorine-containing alkoxy group with carbon number 1~3 or fluorine atom substitution; S ⁸ means carbon number 1 ~18 alkyl group, carbon number 2~18 alkenyl group, carbon number 1~18 fluorine-containing alkyl group, carbon number 1~18 alkoxy group or carbon number 1~18 fluorine-containing alkoxy group; Sm means Integer of 0~4;

S ^A represents a hydrogen atom or a benzene ring. The liquid crystal display element of claim 12, wherein the compound of the aforementioned formula [5a] is any one of the following formula [5a-1] to formula [5a-11];

S ^a represents -O- or -COO- ^{respectively; S b} represents an alkyl group with 1 to 12 carbons; p1 represents an integer of 1 to 10; p2 represents an integer of 1 or 2 respectively;

S ^c represents a single bond, -COO- or -OCO-, ^{respectively; S d} represents an alkyl group or alkoxy group with 1 to 12 carbons, respectively; p3 represents an integer of 1 to 10, and p4 represents an integer of 1 or 2 respectively;

S ^e stands for -O- or -COO- ^{respectively; S f} stands for a divalent organic group with 17~51 carbons with a steroid skeleton; S ^g stands for an alkyl group with 1 to 12 carbons or an alkyl group with 2 to 18 carbons Alkenyl; p5 each represents an integer of 1-10. Such as the liquid crystal display element of any one of claim 1 to claim 13, wherein the aforementioned resin composition further contains an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a hydroxyl group, and a hydroxyalkyl group. At least one cross-linkable compound selected from the group consisting of alkoxy groups and lower alkoxyalkyl groups. Such as the liquid crystal display element of any one of claim 1 to claim 14, wherein the substrate of the aforementioned liquid crystal display element is a glass substrate or a plastic substrate. A resin film used in the liquid crystal display element of any one of claims 1 to 15, which is composed of a polymer having at least one structure selected from the aforementioned formula [1-1] and formula [1-2] The resin composition of the object is formed. A resin composition for forming the resin film of claim 16, which contains a polymer having at least one structure selected from the aforementioned formula [1-1] and formula [1-2].